TWI729161B - Pigment composition, colored composition and colored curable composition - Google Patents

Abstract

A pigment composition of the present invention comprises a compound represented by the formula (I) and at least one member selected from the group consisting of a quinophthalone compound, an isoindoline compound other than the compound represented by the formula (I), and a green colorant.

[In the formula, L¹represents -CO- or - SO₂-; R¹ to R⁵ and R¹² to R¹³ each independently represent a hydrogen atom, -CO-R¹⁰², -COO- R¹⁰¹, -OCO-R¹⁰², -COCO-R¹⁰², -O-R¹⁰², -SO₂-R¹⁰¹, -SO₂N(R¹⁰²)₂, -CON(R¹⁰²)₂、-N(R¹⁰²)₂、-NHCO-R¹⁰²、 -NHCO-N(R¹⁰²)₂、-NHCOOR¹⁰²、-OCON(R¹⁰²)₂、, a halogen atom, a cyano group, a nitro group, -SO₃M, -CO₂M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent; R² and R³, R³ and R⁴, R⁴ and R⁵, and R¹² and R¹³ may be bonded to each other to form a ring; R¹¹ and R¹⁰¹ each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent; R¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent; M represents a hydrogen atom or an alkali metal atom; when there are a plurality of R¹⁰¹, R¹⁰² and M, they may be the same or different; the wavy line represents the E form or the Z form.]

Description

Pigment composition, coloring composition, and coloring hardening composition

The present invention relates to a pigment composition, a coloring composition, and a coloring curable composition.

The coloring curable composition can be used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. In order to obtain a desired hue etc., the colored curable composition may contain two or more coloring agents with different colors.

For example, in Japanese Patent Application Laid-Open No. 2015-197677 (Patent Document 1), it is described that a coloring photosensitive composition for a green color filter contains CI Pigment Green 7, and CI Pigment Yellow 129 and CI Pigment Yellow 139 At least one yellow pigment of the group constituted.

【Description of the invention】

The present invention includes the following inventions.

[1] A pigment composition comprising a compound represented by the formula (I), and a group consisting of a quinoline yellow compound, an isoindoline compound other than the compound represented by the formula (I), and a green colorant At least one of them.

[In formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When ^{there are a plurality of R 101} , R ¹⁰² and M, their equivalence may be the same or different.

The wavy line represents the E body or the Z body. ]

[2] The pigment composition according to [1], wherein the compound represented by formula (I) is a compound represented by formula (I-a).

[In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. ]

[3] The pigment composition according to [2], wherein R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group.

[4] The pigment composition according to [2] or [3], wherein R ¹¹ and R ¹⁴ are independently an optionally substituted alkyl group having 1 to 40 carbon atoms, an optionally substituted phenyl group, An optionally substituted naphthyl group, an optionally substituted tetrahydronaphthyl group, an optionally substituted thienyl group, an optionally substituted furyl group or an optionally substituted pyridyl group.

[5] The pigment composition according to [1], wherein the compound represented by formula (I) is a compound represented by formula (I-b).

[In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ²⁰ and R ³⁰ are bonded to form ring Q.

The ring Q system may have a substituent, the constituent members of the ring are a ring with 5 to 7, and the ring Q system may be a hydrocarbon ring or a heterocyclic ring. The ring Q is bonded to a monocyclic ring selected from a hydrocarbon ring and a heterocyclic ring with a member number of 5 to 7, or a condensed ring formed by condensing the monocyclic ring. ]

[6] The pigment composition according to [5], wherein the compound represented by formula (I) is a compound represented by formula (I-c).

[In formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as the above.

R ⁶ and R ⁷ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) _2. Halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms or optionally substituted heterocyclic ring.

R ¹⁰¹ , R ¹⁰² and M have the same meaning as described above. ]

[7] The pigment composition according to any one of [1] to [6], wherein R ¹ is a hydrogen atom, and R ² to R ^{5 are} independently a hydrogen atom or a nitro group.

[8] A coloring composition comprising the pigment composition described in any one of [1] to [7] and a solvent.

[9] The colored composition as described in [8] further contains resin.

[10] The coloring composition according to any one of [8] to [9], further comprising the compound represented by formula (I), a yellow colorant or a green colorant.

[11] A colored curable composition comprising the colored composition described in any one of [8] to [10] and a polymerizable compound.

[12] The colored curable composition as described in [11], which further contains a polymerization initiator.

[13] A color filter formed of the colored composition or colored curable composition described in any one of [8] to [12].

[14] A liquid crystal display device comprising the color filter described in [13].

[15] A method for producing a colored composition comprising a compound represented by the formula (I), an isoindoline compound selected from the group consisting of a quinoline yellow compound, a compound other than the compound represented by the formula (I), and a green coloring agent At least one type of pigment composition, a solvent, and a coloring agent (A2) containing a colorant (A2) and a solvent are mixed with a liquid containing at least one type of the constituted group.

[In formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When ^{there are a plurality of R 101} , R ¹⁰² and M, their equivalent systems may be the same or different.

The wavy line represents the E body or the Z body. ]

[16] A production method according to [15], wherein the coloring agent (A2) is one or more coloring agents selected from the group consisting of a compound represented by formula (I), a green coloring agent, and a yellow coloring agent.

The present invention provides a pigment composition, a coloring composition, and a coloring curable composition that can be used to form a color filter with improved light resistance.

The pigment composition of the present invention includes: a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)), and isoindoline compounds selected from quinoline yellow compounds, compounds other than compound (I), and green At least one of the group of colorants.

Compound (I) also includes its tautomers and salts thereof.

Compound (I) can be used as a colorant.

The pigment composition of the present invention may contain one or more compounds (I).

At least one type selected from the group consisting of a quinoline yellow compound, an isoindoline compound other than the compound (I), and a green coloring agent can be used as a coloring agent.

The pigment composition of the present invention contains at least one selected from the group consisting of a quinoline yellow compound, an isoindoline compound other than the compound (I), and a green colorant.

The pigment composition of the present invention may contain a coloring agent other than the compound (I) and the quinophthalone compound (hereinafter, may be referred to as a coloring agent (A1-1)).

The pigment composition of the present invention may contain a coloring agent other than the compound (I) and an isoindoline compound other than the compound (I) (hereinafter, may be referred to as a coloring agent (A1-2)).

The pigment composition of the present invention may contain the compound (I) and a coloring agent other than the green coloring agent (hereinafter, may be referred to as a coloring agent (A1-3)).

The coloring composition of the present invention includes the above-mentioned pigment composition and solvent (E), that is, includes compound (I), isoindoline compounds selected from quinophthalone compounds, isoindoline compounds other than compound (I), and green colorants At least one of the group, and solvent (E). Moreover, it is preferable to disperse the compound (I), at least 1 sort(s) selected from the group which consists of a quinoline yellow compound, isoindoline compounds other than compound (I), and a green coloring agent in a solvent (E).

The colored composition system of the present invention may contain a resin (hereinafter, sometimes referred to as resin (B)).

The coloring composition system of the present invention may contain a coloring agent (hereinafter, sometimes referred to as a coloring agent (A2)).

The coloring agent (A2) may contain one or more coloring agents.

It is preferable that the coloring agent (A2) may contain the compound (I), a yellow coloring agent, or a green coloring agent.

In addition, the colored curable composition of the present invention includes the above-mentioned pigment composition, solvent (E), and polymerizable compound (C), that is, includes compound (I), selected from quinophthalone compounds, and other than compound (I) At least one of the group consisting of an isoindoline compound and a green colorant, a solvent (E), and a polymerizable compound (C).

The colored curable composition system of the present invention may contain a polymerization initiator (D).

The colored curable composition system of the present invention may contain a polymerization initiation assistant (D1).

The colored composition of the present invention may further contain a leveling agent (F) and an antioxidant.

<Compound (I)>

Compound (I) is a compound represented by formula (I).

[In formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When ^{there are a plurality of R 101} , R ¹⁰² and M, their equivalence may be the same or different.

The wavy line represents the E body or the Z body. ]

In this specification, the wavy line means E-body or Z-body. Specifically, the wavy line means E-body, Z-body or a mixture thereof.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, can A substituted hydrocarbon group having 1 to 40 carbon atoms or a heterocyclic group which may have a substituent is preferable.

L ¹ is preferably -CO-.

The carbon numbers of the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 are} from 1 to 40, preferably from 1 to 30, more preferably from 1 to 20, and even more preferably 1 to 15, and even better, 1 to 10.

The hydrocarbon groups of 1 to 40 carbons represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups may be saturated or Unsaturated, and may be chain or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 include: methyl, ethyl, propyl, butyl, pentyl} Straight-chain alkyl groups such as hexyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, heptadecyl, octadecyl, and eicosyl; Isopropyl, isobutyl, second butyl, tertiary butyl, (2-ethyl)butyl, isopentyl, neopentyl, tertiary pentyl, (1-methyl)pentyl, ( 2-methyl)pentyl, (1-ethyl)pentyl, (3-ethyl)pentyl, isohexyl, (5-methyl)hexyl, (2-ethyl)hexyl, and (3-ethyl)pentyl Alkyl) heptyl and other branched chain alkyl groups, etc.; vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butene Alkenyl, 1,3-butadienyl, (1-(2-propenyl)) vinyl, (1,2-dimethyl)propenyl, 2-pentenyl and other alkenyl groups; etc. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 8, Especially good series 1 to 5. Among them, a linear or branched alkyl group having a carbon number of 1 to 10, more preferably a carbon number of 1 to 8 is particularly preferred.

Examples of saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 include: cyclopropyl, 1-methylcyclopropyl, cyclopropyl} Butyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethyl ring Hexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl Hexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl Hexyl, 4,4-dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl and 3,3,5,5- Cycloalkyl groups such as tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl, etc.; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene ), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; norbornanyl, adamantyl, bicyclo[2.2.2]octane, etc. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 4 to 20, still more preferably 4 to 15, further preferably 5 to 15, particularly preferably 5 To 10. Among them, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl are particularly preferred.

Examples of the aromatic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-Dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tertiary butylphenyl, M-tert-butylphenyl, p-tert-butylphenyl, mesityl, 4-ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis(2 -Propyl)phenyl, 4-cyclohexylphenyl, 2,4,6-trimethylphenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, stilbyl, phenanthryl and aromatic hydrocarbon groups such as anthryl and pyrenyl; etc.

The carbon number of the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, and still more preferably 6-15.

The aromatic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be a combination of the above-mentioned hydrocarbon groups (for example, aromatic hydrocarbon groups, and chain hydrocarbon groups and alicyclic hydrocarbon groups At least one) of the group includes, for example, aralkyl groups such as benzyl, phenethyl, 1-methyl-1-phenylethyl, and arylalkenyl groups such as phenylvinyl (phenylvinyl) ; Phenylethynyl and other arylalkynyl groups; biphenyl, terphenyl and other phenyl groups bonded to one or more phenyl groups; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl) )Methyl)phenyl and the like.

In addition, ^{the groups represented by R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 are a combination} of the above-mentioned hydrocarbon groups (for example, chain hydrocarbon groups and alicyclic hydrocarbon groups), and may be, for example, Cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexyl An alkyl group bonded to one or more alicyclic hydrocarbon groups such as ethyl and adamantyl methyl groups.

The carbon number of these groups is preferably 4-30, more preferably 6-30, still more preferably 6-20, particularly preferably 6-15.

The hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have a substituent.} The substituent system may be monovalent or divalent. The divalent substituent is preferably one where two bonding sites are bonded to the same carbon atom to form a double bond.

Examples of the monovalent substituent system include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, and pentoxy. Group, hexyloxy, (2-ethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethyl) Hexyloxy, eicosyloxy, 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, o-tolyloxy, 2,3-dimethylphenoxy Group, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5- Dimethylphenoxy, 2,2-dicyanophenoxy, 2,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy , 2,6-dicyanophenoxy, 3,4-dicyanophenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy Group, 3-methoxyphenoxy, 4-ethoxyphenoxy, 2-ethoxyphenoxy and 3-ethoxyphenoxy, etc., and the groups shown in the following formula are in the single Side-bonded hydrocarbon groups with 1 to 20 carbons (preferably with 1 to 10 carbons) or derivatives thereof (for example, via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), carbon number 1 The oxy group of alkylsulfamoyl to 10 (preferably derived from octylsulfamoyl);

Methylthio, ethylthio, propylthio, butylthio, tertiary butylthio, pentylthio, hexylthio, (2-ethyl)hexylthio, heptylthio , Octylsulfanyl, nonylsulfanyl, decylsulfanyl, undecylsulfanyl, dodecylsulfanyl, eicosylsulfanyl, phenylsulfanyl and o-tolylsulfanyl bonds Sulfanyl group bound to a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms); epoxy group, oxetanyl group, tetrahydrofuranyl group, tetrahydropiperanyl group; methionyl group ; Acetyl, propionyl, butyryl, 2,2-dimethylpropionyl, pentyl, hexyl, (2-ethyl) hexyl, heptyl, octyl, nonyl, Decanoyl, undecanoyl, dodecanoyl, eicosanyl and benzyl, etc., and the groups shown in the following formulas are bonded with carbon number 1 to 20 (preferably carbon The number is 1 to 11) hydrocarbon group or its derivatives (e.g., via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfonyl with 1 to 10 carbon atoms (preferably (Octylsulfamoyl) and the like) the carbonyl group (when the carbonyl group is used as the alkane group, the carbon number is preferably from 2 to 12);

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tertiary butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, (2-ethyl)hexyloxycarbonyl, heptoxy Carbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, eicosyloxycarbonyl, phenoxycarbonyl, and o-tolyloxy Carbonyl, etc., and the groups represented by the following formulae are bonded to hydrocarbon groups with carbon numbers 1 to 20 (preferably carbon numbers 1 to 10) or derivatives thereof (for example, via carboxyl, sulfo, nitro, hydroxyl, halogen (Preferably a chlorine atom), an oxycarbonyl group derived from an alkylsulfasulfonyl group having 1 to 10 carbon atoms (preferably a group derived from an octylsulfasulfonyl group);

Amino; N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, N-propylamino, N,N-dipropylene Amine group, N-isopropylamino group, N,N-diisopropylamino group, N-butylamino group, N,N-dibutylamino group, N-isobutylamino group, N, N-diisobutylamino, N-second butylamino, N,N-disecond butylamino, N-tertiary butylamino, N,N-di-tertiary butylamino , N-pentylamino, N,N-dipentylamino, N-(1-ethylpropyl)amino, N,N-bis(1-ethylpropyl)amino, N-hexyl Amino, N,N-dihexylamino, N-(2-ethyl)hexylamino, N,N-bis(2-ethyl)hexylamino, N-heptylamino, N,N- Diheptylamino, N-octylamino, N,N-dioctylamino, N-nonylamino, N,N-dinonylamino, N-phenylamino, N,N -Diphenylamino, N,N-ethylmethylamino, N,N-propylmethylamino, N,N-isopropylmethylamino, N,N-butylmethylamino, N-decylamino, N,N-decylmethylamino, N-undecylamino, N,N-undecylmethylamino, N-dodecylamino, N ,N-Dodecylmethylamino, N-eicosylamino, N,N-eicosylmethylamino, N,N-tertiary butylmethylamino, N,N-benzene The base methyl amino group, etc., and the groups shown in the following formulae, etc. have 1 or 2 hydrocarbon groups with 1 to 20 carbons (preferably 1 to 10 carbons) or derivatives thereof (for example, through carboxyl, sulfo group). , Nitro, hydroxyl, halogen (preferably a chlorine atom), a C1-C10 alkylsulfasulfonyl (preferably octylsulfasulfonyl) and other derived amino groups);

Sulfamate; N-Methylsulfasulfonyl, N,N-Dimethylsulfasulfonyl, N-Ethylsulfasulfonyl, N,N-Diethylsulfasulfonyl, N-Propyl Sulfonamide, N,N-dipropyl sulfasulfonyl, N-isopropyl sulfasulfonyl, N,N-diisopropyl sulfasulfonyl, N-butyl sulfasulfonyl, N,N-dibutylsulfamate, N-isobutylsulfamate, N,N-diisobutylsulfamate, N-second butylsulfamate, N,N- Di second butyl sulfasulfonyl, N-tertiary butyl sulfasulfonyl, N,N-di-tertiary butyl sulfasulfonyl, N-pentyl sulfasulfonyl, N,N-dipentyl Sulfasulfonyl, N-(1-ethylpropyl)sulfasulfonyl, N,N-bis(1-ethylpropyl)sulfasulfonyl, N-hexylsulfasulfonyl, N,N -Dihexylsulfasulfonyl, N-(2-ethyl)hexylsulfasulfonyl, N,N-bis(2-ethyl)hexylsulfasulfonyl, N-heptylsulfasulfonyl, N, N-Diheptylsulfasulfonyl, N-octylsulfasulfonyl, N,N-dioctylsulfasulfonyl, N,N-octylmethylsulfasulfonyl, N-nonylsulfasulfon N,N-Dinonylsulfasulfonyl, N-phenylsulfasulfonyl, N,N-diphenylsulfasulfonyl, N,N-ethylmethylsulfasulfonyl, N , N-propyl methylsulfamate, N,N-isopropyl methylsulfamate, N,N-butyl methylsulfamate, N-decylsulfamate, N,N- Decylmethylsulfasulfonyl, N-undecylsulfasulfonyl, N,N-undecylmethylsulfasulfonyl, N-dodecylsulfasulfonyl, N,N- Dodecyl methyl sulfasulfonyl, N-eicosyl sulfasulfonyl, N,N-eicosyl methyl sulfasulfonyl, N,N-tertiary butyl methyl sulfasulfonyl, N,N-Phenylmethylsulfasulfonyl, etc., and the groups shown in the following formulas, etc. have 1 or 2 hydrocarbon groups with 1 to 20 carbon atoms (preferably from 1 to 10 carbon atoms) or their derivatives Group (e.g., derived from carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfasulfonyl with 1 to 10 carbons (preferably octylsulfasulfonyl), etc. Group) substituted sulfamoyl group;

Formylamino; Acetylamino, propylamino, butyrylamino, 2,2-dimethylpropanylamino, pentanylamino, hexylamino, (2- Ethyl) hexylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, eicosan Amino and benzylamino groups, etc., and the groups shown in the following formulae, etc. are bonded to hydrocarbon groups with carbon numbers 1 to 20 (preferably carbon numbers 1 to 12) or their derivatives (e.g., via Carboxy, sulfo, nitro, hydroxy, halogen (preferably a chlorine atom), alkyl sulfasulfonyl with 1 to 10 carbons, etc. (preferably a group derived from octylsulfasulfonyl), etc.) Carbonylamino group (when the carbonylamino group is used as the alkanoylamino group, the carbon number is preferably 1 to 12);

Hydroxyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxyl group, -CO ₂ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); sulfo group, -SO ₃ M ² ( M ² is an alkali metal, preferably lithium, sodium, potassium); nitro; cyano; formoxy; acetoxy, propoxy, butoxy, 2,2-dimethylpropane Acetyloxy, pentyloxy, hexyloxy, (2-ethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy Group, dodecyl oxy group, eicosane oxy group, benzyloxy group, etc., and the group shown in the following formula are bonded with carbon number 1 to 20 (preferably carbon number is 1 to 10) hydrocarbon group or its derivatives (e.g. via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkyl sulfonyl with 1 to 10 carbon atoms, etc. (preferably octylamine) Sulfonyl group), etc.) of the carbonyloxy group (when the carbonyloxy group is used as the alkoxy group, the carbon number is preferably 1 to 10);

Methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethyl)hexylsulfonyl, heptylsulfonyl Sulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, eicosylsulfonyl, phenylsulfonyl and The p-tolylsulfonyl group, etc., and the group represented by the following formula are bonded to a hydrocarbon group having 1 to 20 carbons (preferably 1 to 10 carbons) or its derivatives (e.g., via carboxyl, sulfo, Sulfonyl groups such as nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfasulfonyl with 1 to 10 carbon atoms (preferably derived from octylsulfonyl), etc.;

Carboxamide; N-methylcarboxamide, N,N-dimethylcarboxamide, N-ethylcarboxamide, N,N-diethylcarboxamide, N-propyl N, N, N-dipropylaminomethanyl, N, N-dipropylaminomethanyl, N-isopropylaminomethanyl, N,N-diisopropylaminomethanyl, N-butylaminomethanyl, N,N-dibutylaminomethanyl, N-isobutylaminomethanyl, N,N-diisobutylaminomethanyl, N-second butylaminomethanyl, N,N- Di-second butylamino formyl, N-tertiary butylamino formyl, N,N-di-tertiary butylamino formyl, N-pentylamino formyl, N,N-dipentyl Aminomethyl, N-(1-ethylpropyl)aminomethyl, N,N-bis(1-ethylpropyl)aminomethyl, N-hexylaminomethyl, N,N -Dihexylaminomethanyl, N-(2-ethyl)hexylaminomethanyl, N,N-bis(2-ethyl)hexylaminomethanyl, N-heptylaminomethanyl, N, N-Diheptylaminoformyl, N-octylaminoformyl, N,N-dioctylaminoformyl, N-nonylaminoformyl, N,N-octylmethylcarbamyl N, N, N-octyl butylamino formyl, N, N-dinonylamino formyl, N-phenylamino formyl, N, N-diphenylamino formyl, N , N-ethylmethylaminomethanyl, N,N-propylmethylaminomethanyl, N,N-isopropylmethylaminomethanyl, N,N-butylmethylaminomethanyl, N-decylaminoformyl, N,N-decylmethylaminoformyl, N-undecylaminoformyl, N,N-undecylmethylaminoformyl, N- Dodecylamine formyl, N,N-dodecylmethylamine formyl, N-eicosylamine formyl, N,N-eicosylmethylamine formyl, N,N-tertiary butylmethylaminoformyl, N,N-phenylmethylaminoformyl, etc., and the groups shown in the following formula, etc. have 1 or 2 carbon atoms from 1 to 20 (compared to Preferably a hydrocarbon group with 1 to 10 carbons or its derivatives (e.g. via carboxyl, sulfo, nitro, hydroxy, halogen (preferably a chlorine atom), alkylsulfonyl with 1 to 10 carbons (more Preferably octyl sulfasulfonyl) and other derived groups) substituted aminoformyl;

Trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, Perfluorodecyl, perfluoroundecyl, perfluorododecyl, perfluoroeicosyl, perfluorocyclohexyl, perfluorophenyl, etc. All hydrogen atoms are replaced by fluorine atoms and the carbon number is 1 to 20 The hydrocarbon group; perfluoroethylmethyl, perfluoropropylmethyl, perfluoroisopropylmethyl, perfluorobutylmethyl, perfluoropentylmethyl, perfluorohexylmethyl, perfluoroheptylmethyl, Perfluorooctylmethyl, perfluorononylmethyl, perfluorodecylmethyl, perfluoroundecylmethyl, perfluorododecylmethyl, perfluoroeicosylmethyl, etc. are all Hydrocarbon groups with 1 to 20 carbons substituted by straight-chain or branched alkyl groups with 1 to 20 carbon atoms substituted by fluorine atoms; 2-fluorophenyl, 3-fluorophenyl, 4-fluorobenzene And 2,4,6-trifluorophenyl and other hydrogen atoms are partially substituted by fluorine and carbon number 1 to 20 (preferably carbon number 1 to 10) hydrocarbon group; -CO-SH, -CO-S-CH ₃ , -CO-S-CH ₂ CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₂ -CH _3, etc. and carbon number 1 to 20 (Preferably carbon number 2 to 10) thiocarbonyl group bonded to an alkyl group, -CO-SC ₆ H _5, etc., thiocarbonyl group bonded to a carbon number 6 to 20 aryl group; as shown in the following formula * -COCO-R (in the formula, R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbons (for example, among the hydrocarbon groups listed above, those with 1 to 20 carbons), or its derivatives (for example, through carboxyl, sulfonic acid) Group, nitro group, hydroxyl group, halogen (preferably a chlorine atom), alkylsulfonamide (preferably a group derived from octylsulfonyl) and the like having 1 to 10 carbon atoms));

As shown in the following formula *-NRCONR ₂ (wherein R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms (for example, among the hydrocarbon groups listed above, those with 1 to 20 carbon atoms), or its derivative ( For example, a group derived from a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfasulfonyl group having 1 to 10 carbons (preferably an octylsulfasulfonyl group), etc.) , The R system may be the same or different from each other, and may be bonded to each other to form a ring) base;

As shown in the following formula *-OCONR ₂ (wherein R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbons (for example, those with 1 to 20 carbons among the hydrocarbon groups listed above), or its derivative ( For example, a group derived from a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfasulfonyl group having 1 to 10 carbons (preferably an octylsulfasulfonyl group), etc.) , The R systems can be the same or different from each other, and can be bonded to each other to form a ring) base;

As shown in the following formula *-NRCOOR (where R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms (for example, among the hydrocarbon groups listed above, those with 1 to 20 carbon atoms), or derivatives thereof (for example, A group derived from a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfasulfonyl group with a carbon number of 1 to 10 (preferably an octylsulfasulfonyl group), etc.), The R systems may be the same or different from each other, and may be bonded to each other to form a ring) base;

*-OP(O)(OCH ₃ ) ₂ etc. *-OP(O)(OR) ₂ (wherein, R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms (for example, among the hydrocarbon groups listed above, it satisfies C 1-20), or its derivatives (e.g. carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), C 1-10 alkylsulfonamide (preferably (Octylsulfamoyl), etc.), the R system may be the same or different from each other, and may be bonded to each other to form a ring); *-Si(CH ₃ ) ₃ , * -Si(CH ₂ CH ₃ ) ₃ , *-Si(C ₆ H ₅ ) ₃ and *-Si(CH(CH ₃ ) ₂ ) ₃ etc. *-SiR ₃ (where R is a hydrogen atom and carbon number is 1 Hydrocarbyl groups up to 20 (e.g. those with carbon numbers from 1 to 20 in the above-mentioned hydrocarbyl groups), or derivatives thereof (e.g. via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), carbon Alkylsulfasulfonyl groups (preferably derived from octylsulfasulfonyl groups) of 1 to 10), the R may be the same or different from each other, and may be bonded to each other to form a ring ) Of the base; etc.

Examples of divalent substituents include: imino groups substituted by pendant oxy groups, thioketone groups, imino groups, alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and 6 to 20 aryl substituted imino groups, etc. Examples of the imino group substituted by an alkyl group include CH ₃ -N=, CH ₃ -CH ₂ -N=, CH ₃ -(CH ₂ ) ₂ -N=, CH ₃ -(CH ₂ ) ₃ -N = Wait. Examples of the imino group substituted by an aryl group include C ₆ H ₅ -N= and the like.

The substituent of the hydrocarbon group having 1 to 40 carbon atoms is preferably a substituent of group s1. Derivative groups as shown below are preferably carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfonamide having 1 to 10 carbon atoms (preferably octylsulfonyl醯基) and other derived bases.

[群s1]

An oxy group with a hydrocarbon group with 1 to 20 carbons or a derivative thereof bonded on one side; a carbonyl group with a hydrocarbon group with 1 to 20 carbons or a derivative thereof bonded; a hydrocarbon group with 1 to 20 carbons or its derivative Derivative group of oxycarbonyl group; amine group; amine group substituted by one or two hydrocarbon groups with 1 to 20 carbons or derivatives thereof; sulfamoyl group; with 1 or 2 carbons from 1 to 20 Sulfonamide substituted by a hydrocarbon group or its derivative; a carbonylamino group bonded to a hydrocarbon group or its derivative with 1 to 20 carbon atoms; a hydroxyl group; a halogen atom; -CO ₂ M (M represents a hydrogen atom or an alkali metal atom , Preferably a hydrogen atom); -SO ₃ M (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); a nitro group; a cyano group; a hydrocarbon group with 1 to 20 carbon atoms or its derivatives A carbonyloxy group; a sulfonyl group bonded to a hydrocarbon group with 1 to 20 carbons or its derivative; carbamethanyl group; substituted by one or two hydrocarbon groups with 1 to 20 carbons or its derivative Carboxamide; a hydrocarbon group with 1 to 20 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms; a straight or branched chain alkyl group with 1 to 20 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms A hydrocarbon group with 1 to 20 carbons; a hydrocarbon group with 1 to 20 carbons in which a part of the hydrogen atom is replaced by fluorine; a pendant oxy group.

As the substituent of the hydrocarbon group having 1 to 40 carbon atoms, for example, the substituent of the group s2 is more preferable.

[群s2]

An oxy group bonded with a hydrocarbon group with 1 to 10 carbons or its derivative; a carbonyl group bonded with a hydrocarbon group with 1 to 10 carbons or its derivative; a hydrocarbon group bonded with 1 to 10 carbons or its derivative Oxycarbonyl group; amine group; amine group substituted by 1 or 2 hydrocarbon groups with 1 to 10 carbons or derivatives thereof; sulfamoyl group; amine group with 1 or 2 carbons 1 to 10 The sulfamsulfonyl group substituted by the hydrocarbon group or its derivatives; the carbonylamino group bonded to the hydrocarbon group or its derivatives with 1 to 10 carbon atoms; hydroxyl group; fluorine atom, chlorine atom, bromine atom; -CO ₂ M(M Represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO ₃ M (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); a nitro group; a cyano group; bonded with 1 to 10 carbon atoms The carbonyloxy group of the hydrocarbyl group or its derivative; the sulfonyl group bonded with the hydrocarbyl group of 1 to 10 carbons or its derivative; the carbamoyl group; the hydrocarbyl group of 1 or 2 carbons of 1 to 10 or The amine methyl group substituted by its derivative group; a hydrocarbon group with 1 to 10 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms; a straight or branched chain with 1 to 10 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms A hydrocarbon group of 1 to 10 carbons substituted by an alkyl group; a hydrocarbon group of 1 to 10 carbons in which a part of the hydrogen atom is replaced by fluorine; a pendant oxy group.

Examples of hydrocarbon groups having 1 to 40 carbon atoms having substituents represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 include those having monovalent or divalent substituents} A hydrocarbon group of 1 to 40, preferably a saturated or unsaturated chain hydrocarbon group of 1 to 30 carbons with a monovalent or divalent substituent, a saturated or unsaturated chain hydrocarbon group of 3 to 30 carbons with a monovalent or divalent substituent Unsaturated alicyclic hydrocarbon group, aromatic hydrocarbon group with 6 to 30 carbons or combination of hydrocarbon groups with monovalent or divalent substituent, and group with 1 to 30 carbons with monovalent or divalent substituent, more Preferred systems include, for example, a saturated or unsaturated chain hydrocarbon group with a carbon number of 1 to 20 having a substituent of group s1, a saturated or unsaturated alicyclic hydrocarbon group with a carbon number of 3 to 20 having a substituent of group s1, and The substituent of group s1 has an aromatic hydrocarbon group with 6 to 20 carbons or a combination of hydrocarbon groups, and a group with a substituent of group s1 has a group of 1 to 20 carbons. Particularly preferred ones include, for example, those with substituents of group s2 Saturated or unsaturated chain hydrocarbon group with 1 to 15 carbons, saturated or unsaturated alicyclic hydrocarbon group with 3 to 15 carbons having substituents of group s2, aromatics of 6 to 15 carbons with substituents of group s2 The group is a group of hydrocarbon group or a combination of hydrocarbon groups, and has a group of 1 to 15 carbons as a substituent of group s2.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be monocyclic or polycyclic, preferably containing heteroatoms as the constituent elements of the ring The heterocycle. Examples of the heteroatom system include a nitrogen atom, an oxygen atom, and a sulfur atom.

The carbon number of the heterocyclic group is preferably 3 to 30, more preferably 3 to 22, still more preferably 3 to 20, still more preferably 3 to 18, still more preferably 3 to 15, particularly preferably 3 to 14.

等單環系飽和雜環；2,5-二甲基吡咯等吡咯、2-甲基吡唑、3-甲基吡唑等吡唑、咪唑、1,2,3-三唑、1,2,4-三唑等5員環系不飽和雜環；吡啶、鄰二

(Pyridazine)、6-甲基嘧啶等嘧啶、吡

、1,3,5-三

等6員環系不飽和雜環；咪唑、二氫吲哚、異吲哚啉、吲哚、吲哚嗪、苯并咪唑、喹啉、異喹啉、5,6,7,8-四氫(3-甲基)喹

啉、3-甲基喹

啉等之喹

啉、喹唑啉、辛啉(Cinnoline)、酞嗪、萘啶(Naphthyridine)、卟啉、喋啶(pteridin)、苯并吡唑、苯并哌啶等縮合二環系雜環；咔唑、吖啶、啡

等縮合三環系雜環；等。 Examples of heterocyclic systems containing nitrogen atoms include aziridine, trimethyleneimine, pyrrolidine, piperidine, piperidine

Monocyclic saturated heterocycles; 2,5-dimethylpyrrole and other pyrroles, 2-methylpyrazole, 3-methylpyrazole and other pyrazoles, imidazole, 1,2,3-triazole, 1,2 ,4-Triazole and other 5-membered ring system unsaturated heterocycles; pyridine, o-di

(Pyridazine), 6-methylpyrimidine and other pyrimidines, pyridine

, 1,3,5-three

6-membered ring system unsaturated heterocyclic ring; imidazole, indoline, isoindoline, indole, indoleazine, benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl)quine

Morinoline, 3-methylquine

Quinoline

Condensed bicyclic heterocycles such as phyrin , quinazoline, octanoline, phthalazine, Naphthyridine, porphyrin, pteridin, benzopyrazole, benzopiperidine, etc.; carbazole, Acridine, phenanthrene

Condensed tricyclic heterocycles; etc.

烷、1,4-二

烷、1-環戊基二草酸酯等單環系飽和雜環；1,4-二

螺[4.5]癸烷、1,4-二

螺[4.5]壬烷等二環系飽和雜環；α-乙內酯、β-丙內酯、γ-丁內酯、γ-戊內酯及δ-戊內酯等內酯系雜環； 2,3-二甲基呋喃、2,5-二甲基呋喃等之呋喃等5員環系不飽和雜環；2H-吡喃、4H-吡喃等6員環系不飽和雜環；1-苯并呋喃、4-甲基苯并吡喃等苯并吡喃、苯并二

唑、二氫苯并吡喃、異二氫苯并吡喃等縮合二環系雜環；二苯并吡喃、二苯并呋喃等縮合三環系雜環；等。 Examples of heterocyclic systems containing oxygen atoms include ethylene oxide, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-di

Alkane, 1,4-bis

Monocyclic saturated heterocycles such as alkane, 1-cyclopentyl dioxalate, etc.; 1,4-di

Spiro[4.5]decane, 1,4-bis

Spiro[4.5]nonane and other bicyclic saturated heterocycles; α-hydantoin, β-propiolactone, γ-butyrolactone, γ-valerolactone and δ-valerolactone and other lactone heterocycles; 5-membered ring system unsaturated heterocycles such as furan such as 2,3-dimethylfuran and 2,5-dimethylfuran; 6-membered ring system unsaturated heterocycles such as 2H-pyran and 4H-pyran; 1 -Benzofuran, 4-methylbenzopyran and other benzopyrans, benzobis

Condensed bicyclic heterocycles such as azole, dihydrobenzopyran and isodihydrobenzopyran; condensed tricyclic heterocycles such as dibenzopyran and dibenzofuran; etc.

Examples of the sulfur atom-containing heterocyclic ring system include: 5-membered ring system saturated heterocyclic rings such as dithiolane; tetrahydrothiolane, 1,3-ditetrahydrothiolane, 2-methyl 1,3 -Ditetrahydrothiopyran and other 6-membered ring system saturated heterocycles; 5-members of 3-methylthiophene, 2-carboxythiophene and other thiophenes, 4H-thiopyran, chroman and other benzothiopyrans, etc. Ring system unsaturated heterocycle; benzothiophene and other condensed bicyclic heterocycles, etc.; Thianthrene, dibenzothiophene, etc. condensed tricyclic heterocycles; etc.

唑等

唑、2-甲基異

唑、3-甲基異

唑等之異

唑等單環系不飽和雜環；苯并

唑、苯并異

唑、苯并

、苯并

烷、苯并咪唑啉等縮合二環系雜環；二苯并噻

(Phenothiazine)等縮合三環系雜環；等。 Examples of heterocyclic systems containing nitrogen and oxygen atoms include morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, and 2-methyl-2-piperidine Monocyclic saturated heterocycles such as ketones; 4-methyl

Azoles etc.

Azole, 2-methyl iso

Azole, 3-methyl iso

The difference between azoles and others

Monocyclic unsaturated heterocycles such as azoles; benzo

Azole, benziso

Azole, benzo

Benzo

Alkyl, benzimidazoline and other condensed bicyclic heterocycles; dibenzothiol

(Phenothiazine) and other condensed tricyclic heterocycles; etc.

等縮合三環系雜環；等。 Examples of heterocyclic systems containing nitrogen and sulfur atoms include monocyclic heterocyclic rings such as thiazoles such as 3-methylthiazole and 2,4-dimethylthiazole; and condensed bicyclic heterocyclic rings such as benzothiazole; Dibenzothiazide

Condensed tricyclic heterocycles; etc.

The above-mentioned heterocyclic ring may be a group combining the above-mentioned hydrocarbon groups, and examples thereof include tetrahydrofurylmethyl and the like.

Other heterocyclic systems may be those represented by the following groups.

In addition, the above-mentioned heterocyclic group may be a heterocyclic group formed by two or more bonds ^{of R 1} to R ^5. Such a heterocyclic group has a ring structure of two or more rings together with the benzene ring to which ^{R 1} to R ^{5 are bonded.} Examples of the ring structure system having two or more rings include the structure of the following formula.

In addition, the above-mentioned bonding position of the heterocyclic ring is a part from which any hydrogen atom contained in each ring has been detached.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have a substituent.} Examples of the substituent system include the same substituents as the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² . In addition, when the aforementioned heterocyclic ring contains a nitrogen atom as its constituent element, the nitrogen atom may be bonded to the above-mentioned hydrocarbon group as a substituent.

Examples of preferable substituents include the same ones as the preferable substituents that the hydrocarbon group represented by ^{R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

Examples of the substituted heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include heterocyclic groups having monovalent or divalent substituents, and preferred For example, a heterocyclic group having a substituent of group s1 is mentioned, and more preferably, for example, a heterocyclic group having a substituent of group s2 is mentioned.

The above-mentioned hydrocarbon group or heterocyclic group may have one or more substituents (first substituent), and the two or more substituents are independently the same or different from each other. Furthermore, the hydrocarbon group contained in a part of the aforementioned first substituent may be bonded to another substituent (second substituent). The second substituent may be selected from the same groups as the first substituent.

The following describes the -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ^{101 of R 1} to R ⁵ , R ¹² , and R ¹³ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCON(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, -SO ₃ M, -CO ₂ M.

Examples of the -CO-R ¹⁰² system include formyl; acetyl, propionyl, butyryl, 2,2-dimethylpropionyl, pentamyl, hexyl, (2-ethyl) Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, eicosanyl, benzyl, etc., and groups represented by the following formula Etc. bonded with a hydrocarbon group with 1 to 40 carbon atoms (preferably with a carbon number of 1 to 20) or its derivatives (e.g. via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), carbon number The carbonyl group of 1 to 10 alkylsulfasulfonyl groups (preferably derived from octylsulfasulfonyl) and the like) (when the carbonyl group is used as the carbonyl group, the carbon number is preferably 2 to 41), and the table Among the compounds shown in Tables 1 to 8, Table 9(a), Table 9(b), and Tables 10 to 11, the group equivalent to -CO-R ¹⁰² , etc., more preferably, a bond with carbon number 1 The carbonyl group of a hydrocarbon group to 11 (more preferably a carbon number of 1 to 10) or a derivative thereof (when the carbonyl group is used as an alkane group, the carbon number is more preferably 2 to 12), and the following Tables 1 to 8, Among the compounds shown in Table 9(a), Table 9(b), and Table 10 to Table 11, the group is equivalent to -CO-R ¹⁰² .

Examples of the -COO-R ¹⁰¹ system include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2 -Ethyl)hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, twenty Alkoxycarbonyl, etc., and the groups shown in the above formula are bonded to hydrocarbon groups with carbon numbers 1 to 40 (preferably carbon numbers 1 to 20) or their derivatives (e.g. via carboxyl, sulfo, nitro, hydroxy) , Halogen (preferably a chlorine atom), a carbon number of 1 to 10 alkylsulfamoyl (preferably octylsulfamoyl) and the like derived from the oxycarbonyl group, and Tables 1 to 8 In the compounds shown in Table 9(a), Table 9(b) and Table 10 to Table 11, the group equivalent to -COO-R ¹⁰² , etc., more preferably, for example, a hydrocarbon group bonded with 1 to 10 carbon atoms ^{Or the oxycarbonyl group of its derivative group, and the group corresponding to -COO-R 102} in the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11, etc. .

Examples of the -OCO-R ¹⁰² system include: formoxy; acetoxy, propoxy, butoxy, 2,2-dimethylpropoxy, pentoxy, and hexoxy Oxy, (2-ethyl) hexyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, twenty Alkyloxy, benzyloxy, etc., and the groups shown in the following formulae, etc. are bonded to hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or their derivatives (e.g. via carboxyl , Sulfo, nitro, hydroxyl, halogen (preferably a chlorine atom), alkyl sulfasulfonyl with carbon number 1 to 10 (preferably a group derived from octylsulfasulfonyl), etc. carbonyl oxygen Group (when the carbonyloxy group is used as the carbonyloxy group, the carbon number is preferably from 2 to 41), and those shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 In the compound, the group equivalent to -OCO-R ¹⁰² , etc., more preferably, for example, a hydrocarbon group with 1 to 11 carbon atoms (more preferably a carbon number 1 to 10) or a carbonyloxy group (to When the carbonyloxy group is used as the carbonyloxy group, the carbon number is more preferably from 2 to 12), and the compounds shown in the following Tables 1 to 8, Table 9(a), Table 9(b), and Table 10 to Table 11 Medium is equivalent to the base of ^{-OCO-R 102, etc.}

Examples of the -COCO-R ¹⁰² system include: methyl oxalyl, ethyl oxalyl, propyl oxalyl, butyl oxalyl, pentyl oxalyl, hexyl oxalyl, (2-ethyl oxalyl) Base) hexyl glycidyl, heptyl glycidyl, octyl glycidyl, nonyl glycidyl, decyl glycidyl, undecyl glycidyl, lauryl glycidyl, eicosanyl Cyclopentyl glycidyl, cyclopentyl glycidyl, cyclohexyl glycidyl, phenyl glycidyl, p-tolyl glycidyl, etc., and the groups shown in the above formula are bonded with carbon number 1 to 40 ( Preferably it is a hydrocarbon group with 1 to 20 carbon atoms or its derivatives (e.g. via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably a chlorine atom), alkylsulfonamide with 1 to 10 carbon atoms ( Preferably it is the oxalyl group derived from the octylsulfamoyl group) and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11. It is equivalent to the base of ^{-COCO-R 102.}

Examples of -OR ¹⁰² series include: hydroxy; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, pentyl Oxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethyl)hexyloxy, eicosyloxy , 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2, 5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,2-dicyanobenzene Oxy, 2,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy, 2,6-dicyanophenoxy, 3,4 -Dicyanophenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-ethoxy Group phenoxy, 2-ethoxyphenoxy, 3-ethoxyphenoxy, etc., and the groups shown in the above formula are bonded with carbon number 1 to 40 (preferably carbon number 1 to 20) The hydrocarbon group or its derivative (for example, through carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfonamide having 1 to 10 carbon atoms (preferably octylsulfonamide) ), etc.), and the oxy group in the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11, etc., which ^{are equivalent to -OR 102, etc.} Preferable examples include, for example, an oxy group bonded to a hydrocarbon group with a carbon number of 1 to 10 or a derivative thereof, as shown in the following Tables 1 to 8, Table 9(a), Table 9(b), and Table 10 to Table 11. The compound is equivalent to ^{the base of -OR 102} and so on.

Examples of the -SO ₂ -R ¹⁰¹ system include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethylsulfonyl Base) hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, eicosane Sulfonyl, phenylsulfonyl, p-tolylsulfonyl, etc., and the groups represented by the above formula are bonded to hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or Derivative groups (e.g., carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfasulfonyl with 1 to 10 carbon atoms (preferably octylsulfasulfonyl), etc. _{Derivative groups) of the sulfonyl group, and the group equivalent to -SO 2} -R ¹⁰¹ in the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11, etc., More preferably, for example, a hydrocarbon group having 1 to 10 carbon atoms or a sulfonyl group bonded to a derivative thereof, and the following Tables 1 to 8, Table 9(a), Table 9(b) and Table 10 To the compounds shown in Table 11 are equivalent to -SO ₂ -R ¹⁰¹ groups.

Examples of -SO ₂ N(R ¹⁰² ) ₂ include: sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, and N-isopropyl N-butyl sulfasulfonyl, N-butyl sulfasulfonyl, N-isobutyl sulfasulfonyl, N-second butyl sulfasulfonyl, N-tertiary butyl sulfasulfonyl, N-pentyl Sulfonamide, N-(1-ethylpropyl) Sulfonamide, N-hexyl Sulfonamide, N-(2-Ethyl)hexyl Sulfonamide, N-heptyl Sulfonamide Group, N-octylsulfasulfonyl, N-nonylsulfasulfonyl, N-decylsulfasulfonyl, N-undecylsulfasulfonyl, N-dodecylsulfasulfonyl , N-eicosylsulfasulfonyl, N-phenylsulfasulfonyl, etc., and the groups shown in the above formula, etc. through 1 carbon number 1 to 40 (preferably carbon number 1 to 20) hydrocarbon group Or its derivatives (e.g. carboxyl, sulfo, nitro, hydroxy, halogen (preferably chlorine atom), alkylsulfasulfonyl with 1 to 10 carbon atoms (preferably octylsulfasulfonyl), etc. Derivatized group) substituted by the sulfamoyl group, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 are equivalent to -SO ₂ N(R ¹⁰¹ ) _{The base of 2} ; N,N-dimethylsulfasulfonyl, N,N-ethylmethylsulfasulfonyl, N,N-diethylsulfasulfonyl, N,N-propyl Methanesulfonyl, N,N-dipropylsulfamate, N,N-isopropylmethylsulfonyl, N,N-diisopropylsulfamethonyl, N,N- Tertiary butyl methyl sulfasulfonyl, N,N-diisobutyl sulfasulfonyl, N,N-di second butyl sulfasulfonyl, N,N-di-tertiary butyl sulfasulfonyl, N,N-butylmethylsulfasulfonyl, N,N-dibutylsulfasulfonyl, N,N-dipentylsulfasulfonyl, N,N-bis(1-ethylpropyl)sulfonyl N,N-Dihexylsulfasulfonyl, N,N-bis(2-ethyl)hexylsulfasulfonyl, N,N-Diheptylsulfasulfonyl, N,N-octylmethyl Sulfonamide, N,N-Dioctyl Sulfonyl, N,N-Dinonyl Sulfonyl, N,N-Decyl Methyl Sulfonyl, N,N-Undecane N, N,N-dodecylmethylsulfasulfonyl, N,N-eicosylmethylsulfasulfonyl, N,N-phenylmethylsulfasulfonyl , N,N-diphenylsulfasulfonyl, etc., and the groups shown in the above formula, etc. have 2 hydrocarbon groups with 1 to 40 (preferably carbon numbers 1 to 20) or derivatives thereof (for example, by Carboxy, sulfo, nitro, hydroxy, halogen (preferably chlorine atom), alkyl sulfamoyl with 1 to 10 carbons (preferably octyl sulfamoyl), etc.) substituted The sulfamoyl group, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 are equivalent to -SO ₂ N(R ¹⁰¹ ) ₂ groups, etc., More preferably, for example, sulfasulfonyl substituted with 1 or 2 hydrocarbon groups with 1 to 10 carbons or derivatives thereof, and the following Tables 1 to 8, Table 9(a), and Table 9(b) ) And the compounds shown in Table 10 to Table 11 are equivalent to- The base of SO ₂ N(R ¹⁰¹ ) ₂ and so on.

Examples of the -CON(R ¹⁰² ) ₂ system include: carboxamide; N-methyl carboxamide, N-ethyl carboxamide, N-propyl carboxamide, and N-isopropyl group. Aminoformyl, N-butylaminoformyl, N-isobutylaminoformyl, N-second butylaminoformyl, N-tertiary butylaminoformyl, N-pentyl Carboxylic, N-(1-ethylpropyl)carboxyl, N-hexylcarboxyl, N-(2-ethyl)hexylcarboxyl, N-heptylcarboxyl , N-octylamine methanoyl, N-nonyl amine methanoyl, N-decyl amine methanoyl, N-undecyl amine methanoyl, N-dodecyl amine methanoyl, N-eicosylamine methanoyl, N-phenylamine methanoyl, etc., and the groups shown in the above formula, etc. have 1 hydrocarbon group with 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) Or its derivatives (e.g. carboxyl, sulfo, nitro, hydroxy, halogen (preferably chlorine atom), alkylsulfasulfonyl with 1 to 10 carbon atoms (preferably octylsulfasulfonyl), etc. Derivative group) substituted amine methanoyl group, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 are equivalent to -CON(R ¹⁰² ) ₂ bases, etc.; N,N-dimethylaminoformyl, N,N-ethylmethylaminoformyl, N,N-diethylaminoformyl, N,N-propylmethyl Carboxamide, N,N-dipropylcarboxamide, N,N-isopropylmethylcarboxamide, N,N-diisopropylcarboxamide, N,N-third Butylmethylaminoformyl, N,N-diisobutylaminoformyl, N,N-disecondbutylaminoformyl, N,N-di-tertiarybutylaminoformyl, N, N-butylmethylaminoformyl, N,N-dibutylaminoformyl, N,N-butyloctylaminoformyl, N,N-dipentylaminoformyl, N,N- Di(1-ethylpropyl)aminomethanyl, N,N-dihexylaminomethanyl, N,N-bis(2-ethyl)hexylaminomethanyl, N,N-diheptylamine Formyl, N,N-octylmethylaminoformyl, N,N-dioctylaminoformyl, N,N-dinonylaminoformyl, N,N-decylmethylamine Formyl, N,N-undecylmethylaminoformyl, N,N-dodecylmethylaminoformyl, N,N-eicosylmethylaminoformyl, N , N-phenylmethylaminoformyl, N,N-diphenylaminoformyl, etc., and the groups shown in the above formula, etc. have 2 carbon numbers from 1 to 40 (preferably from 1 to 40 carbon atoms). 20) hydrocarbon group or its derivatives (e.g. via carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylsulfonamide having 1 to 10 carbon atoms (preferably octylsulfonyl) Aminoformyl group substituted by a group derived from sulfo group), and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11 are equivalent to -CON The group of (R ¹⁰² ) _{2 and} the like, and more preferable ones include, for example, an aminomethanyl group substituted with 1 or 2 hydrocarbon groups having 1 to 10 carbon atoms or derivatives thereof, and the following Tables 1 to 8, Tables 9(a), Table 9(b) and Table 10 to Table 11 The substance is equivalent to the base of -CON(R ¹⁰² ) ₂ and so on.

Examples of -N(R ¹⁰² ) ₂ series include: amino; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamine Group, N-isobutylamino, N-second butylamino, N-tertiary butylamino, N-pentylamino, N-hexylamino, N-(2-ethyl)hexyl Amino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-undecylamino, N-dodecylamino, N -Eicosylamino group, N-phenylamino group, etc., and the group represented by the above formula, etc. through 1 carbon number 1 to 40 (preferably carbon number 1 to 20) hydrocarbon group or its derivative ( For example, a group derived from a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfasulfonyl group having 1 to 10 carbons (preferably an octylsulfasulfonyl group), etc.) The substituted amine groups and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 are equivalent to -N(R ¹⁰² ) ₂ groups, etc.; N, N-dimethylamino, N,N-ethylmethylamino, N,N-diethylamino, N,N-propylmethylamino, N,N-dipropylamino, N,N-isopropylmethylamino, N,N-diisopropylamino, N,N-tertiary butylmethylamino, N,N-diisobutylamino, N,N-di The second butylamino group, N,N-di-tertiary butylamino group, N,N-butylmethylamino group, N,N-dibutylamino group, N,N-dipentylamino group, N, N-bis(1-ethylpropyl)amino, N,N-dihexylamino, N,N-bis(2-ethyl)hexylamino, N,N-diheptylamino, N, N-dioctylamino, N,N-dinonylamino, N,N-decylmethylamino, N,N-undecylmethylamino, N,N-dodecyl Methylamino, N,N-eicosylmethylamino, N,N-phenylmethylamino, N,N-diphenylamino, etc., and the groups represented by the above formula 2 hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or derivatives thereof (for example, carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), carbon 1 to 20) 10 alkylsulfasulfonyl (preferably octylsulfasulfonyl) and the like) substituted amine groups, and Table 1 to Table 8, Table 9 (a), Table 9 (b) and Among the compounds shown in Table 10 to Table 11, the group equivalent to -N(R ¹⁰² ) _{2 and} the like; more preferably, amines substituted with 1 or 2 hydrocarbon groups with 1 to 10 carbon atoms or derivatives thereof ^{Group, and the group corresponding to -N(R 102} ) ₂ in the compounds shown in the following Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11.

Examples of the -NHCO-R ¹⁰² system include: formamide; acetamide, acetamide, butyramide, 2,2-dimethyl acetamide, pentamido, and hexylamino Amino, (2-ethyl) hexamido, heptamido, octamido, nonamido, decanoamido, undecanoamido, dodecanoamido, 20 Alkylamino group, benzylamino group, etc., and the groups shown in the above formula, etc. are bonded to hydrocarbon groups with carbon numbers 1 to 40 (preferably carbon numbers 1 to 20) or their derivatives (e.g., via carboxy, The carbonylamino group of a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfasulfonyl group having 1 to 10 carbons (preferably a group derived from an octylsulfasulfonyl group), etc.) (When the carbonylamino group is used as the amide group, the carbon number is preferably 1 to 40), and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 Among them, the group corresponding to -NHCO-R ¹⁰² , etc., more preferably, for example, a carbonylamino group to which a hydrocarbon group with 1 to 10 carbon atoms or a derivative thereof is bonded (when the carbonylamino group is used as the alkaneamino group, the carbon More preferably, the number is 1 to 10), and the group ^{corresponding to -NHCO-R 102} among the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11.

Examples of -NHCON(R ¹⁰² ) ₂ series include the groups listed above, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11 are equivalent to -The ^{base of NHCONR 102} and so on.

Examples of the -NHCOOR ¹⁰² system include the groups listed above, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11, which are equivalent to -NHCOOR ¹⁰² Base and so on.

Examples of the -OCON(R ¹⁰² ) ₂ system include the bases listed above, and the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b), and Table 10 to Table 11 are equivalent to -The ^{base of OCONR 102} and so on.

The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

Examples of the M system of -SO ₃ M and -CO ₂ M include hydrogen atoms; alkali metal atoms such as lithium atoms, sodium atoms, and potassium atoms, and hydrogen atoms, sodium atoms, and potassium atoms are preferred.

In the above -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON( R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCON(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ contains the substituent (first substituent) system It may be one or two or more, and two or more substituents independently of each other may be the same or different.

Furthermore, the aforementioned first substituent may have another substituent (second substituent) bonded to the hydrocarbon group contained in a part thereof. The second substituent may be selected from the same groups as the first substituent.

啉、喹唑啉、辛啉、咔唑、咔啉、啡啶、吖啶、呸啶(Perimidine)、啡啉、啡

等之含氮縮合雜環及其部分還原體；3-氫苯并呋喃2-酮等之含氧縮合雜環及其部分還原體。 The ring system formed by R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ is condensed with the benzene ring of the isoindoline skeleton of formula (I). Examples of the condensed ring structure of the ring formed by R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ and the aforementioned benzene ring include indene, naphthalene, biphenyl, Indacene, acenaphthene, Phenalene, Phenalene, Phenanthrene, Anthracene, Benzoacenaphthene, Acephenanthrylene, Aceanthrylene, Triphenylene, Pyrene, Triphenylene, N-Methylphthalimide, N-( 1-Phenylethyl) phthalimide, fused tetrabenzene and other hydrocarbon-based condensed ring structures and their partial reductions (for example, 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.); Indole, isoindole, indazole, quinoline, isoquinoline, phthalazine, quinoline

Phenanthroline, quinazoline, octanoline, carbazole, carboline, phenanthridine, acridine, Perimidine, phenanthroline, phenanthrene

Condensed heterocyclic ring containing nitrogen and its partial reduction; 3-hydrobenzofuran 2-one and other condensed oxygen heterocyclic ring and its partial reduction.

When R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ form a ring, the ring system may have a substituent. Examples of the substituent system include the same substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have. The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

When R ³ and R ⁴ form a ring, R ² and R ⁵ are independently of each other and are preferably a hydrogen atom, an amino group or a hydroxyl group.

形成環之時，R⁴與R⁵係以不形成環為較佳，R⁴與R⁵為氫原子更佳。 R ² and R ³

The formation of a ring, R ⁴ and R ⁵ form a ring system of not preferred, R ⁴ and R ⁵ is more preferably a hydrogen atom.

And, R ⁴ and R ⁵ forming rings, R ² and R ³ form a ring system of not preferred for R ² and R ³ is more preferably a hydrogen atom.

For ^{example, the ring system formed by R 12} and R ^{13 is} _{bonded to the exomethylene (C=CH 2} ) outside the isoindoline skeleton of formula (I), and the ring formed by ^{R 12} and R ^{13 is included as} In addition, in the case of the structure of the methylene group (C=CH ₂ ), a structure in which various carbonyl groups of the following group A and group B are arranged in order, as well as exomethylene groups, and carbonyl groups can be exemplified. ** represents the bond to the isoindoline skeleton.

R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -COCO-R ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ¹⁰⁴ and R ¹⁰⁵ preferably independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N (R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, which may have substituents A hydrocarbon group having 1 to 40 carbon atoms or a heterocyclic group which may have a substituent.

R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ show -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -COCO-R ¹⁰² , -SO ₂ -R ¹⁰¹ ,- SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , a halogen atom, -SO ₃ M and -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, for example, and R ¹ to R ⁵ , R ¹² And R ¹³ shows -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -COCO-R ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, -SO ₃ M, -CO ₂ M, and optionally substituted hydrocarbon groups having 1 to 40 carbon atoms or optionally substituted heterocyclic groups are the same.

Preferable examples of R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ include preferable groups among ^{R 1} to R ⁵ , R ¹² and R ^13.

R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ^{107 are} preferably independently methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, (2-ethyl) Hydrocarbon groups with 1 to 10 carbon atoms or hydrogen atoms such as hexyl, heptyl, octyl, nonyl, cyclohexyl, and phenyl.

The group A and the group B exemplified by the hydrogen atom bonded to the ring structure may be substituted by a substituent.

Examples of the substituent system include the same substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

Among the substituents, preferred ones include, for example, the same ones as preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have} .

R ¹ is a hydrogen atom, and R ² to R ^{5 are} each independently a hydrogen atom or a nitro group.

The aforementioned group A and group B are, for example, the rings shown in formula (QQ1) to formula (QQ25).

When R ¹² and R ¹³ do not form a ring, compound (I) is a compound represented by formula (Ia) (hereinafter, sometimes referred to as compound (Ia)), and a compound represented by formula (II) (hereinafter, sometimes Is referred to as compound (II)), compound represented by formula (II-a0) (hereinafter, sometimes referred to as compound (II-a0)), compound represented by formula (II-a1) (hereinafter, sometimes referred to as Compound (II-a1)) is preferred, and the compound represented by formula (Ia) is more preferred.

[In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. ]

As shown R ¹⁴ may have the carbon number of the substituent of the hydrocarbon group having 1 to 40 or a heterocyclic group which may have a substituent group of lines can be exemplified as the R ¹¹ and R ¹⁰¹ may be shown in the substituent group having a carbon number of 1 to 40 The hydrocarbon group or the heterocyclic group which may have a substituent is the same.

Preferred examples of R ¹⁴ include the same groups as the preferred groups of ^{R 11} and R ^101.

In compound (Ia), R ¹¹ and R ¹⁴ are preferably the same group.

Furthermore, ^{it is preferable that L 1} and L ² are the same group.

Preferably, R ¹¹ and R ^{14 are} independently an alkyl group having 1 to 40 carbon atoms, which may have a substituent, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a tetrahydronaphthyl group which may have a substituent. , Pyridyl which may be substituted, thienyl which may be substituted, furyl which may be substituted or pyridyl which may be substituted.

The carbon number of the alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-8.

The phenyl group, the naphthyl group, the tetrahydronaphthyl group, the pyridyl group, the thienyl group, the furyl group, and the alkyl group may have a substituent. These groups may be bonded to alkyl groups to replace substituents.

Examples of the substituent system include the same substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The alkyl group that can be bonded to the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridyl group, or the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thiophene group The substituents of the group, the furyl group and the pyridyl group are preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, (2-ethyl)hexyl and octyl and other carbons. Alkyl groups of 1 to 10; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; trifluoromethyl; oxycarbonyl to which hydrocarbon groups of 1 to 10 are bonded; nitro; hydroxyl; amine Sulfonyl; -SO ₃ M; -CO ₂ M.

The substituent of the alkyl group is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -SO ₃ M; -CO ₂ M.

L ¹ is preferably -CO-.

L ² is preferably -CO-.

R ¹ is preferably a hydrogen atom.

R ² to R ^{5 are} preferably a hydrogen atom, a halogen atom or a nitro group independently of each other. The halogen atom is preferably a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is more preferable. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

[In formula (II), R ¹ to R ⁵ , R ¹¹ to R ¹³ and the wavy line respectively represent the same meanings as described above. ]

R ^{11 is} preferably a phenyl group that may have a substituent, a naphthyl group that may have a substituent, a tetrahydronaphthyl group that may have a substituent, a pyridyl group that may have a substituent, a thienyl group that may have a substituent, and a substituted The furyl group or the alkyl group which may have a substituent. The carbon number of the alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-8.

The phenyl group, the naphthyl group, the tetrahydronaphthyl group, the pyridyl group, the thienyl group, the furyl group, and the alkyl group may have a substituent. These groups may be bonded to alkyl groups to replace substituents.

Examples of the substituent system include the same substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The alkyl group that can be bonded to the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridyl group, or the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thiophene group The substituents of the group, the furyl group and the pyridyl group are preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, (2-ethyl)hexyl and octyl and other carbons. Alkyl group of 1 to 10; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxycarbonyl group bonded to a hydrocarbon group with carbon number 1 to 10; nitro group; hydroxyl group; sulfonamide醯基; -SO ₃ M; -CO ₂ M.

The substituent of the alkyl group is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -SO ₃ M; -CO ₂ M.

R ¹ is preferably a hydrogen atom.

R ² to R ^{5 are} preferably a hydrogen atom, a halogen atom or a nitro group independently of each other. The halogen atom is preferably a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is more preferable. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . The R ¹² system is more preferably -CO-R ^102.

R ¹³ is preferably a cyano group.

R ¹⁰¹ and R ¹⁰² respectively have the same meaning as described above.

Compound (I) is preferably a compound represented by formula (II-a0) (hereinafter, sometimes referred to as compound (II-a0)).

[In formula (II-a0), R ¹ to R ⁵ , R ¹² to R ¹³ and the wavy line respectively have the same meaning as the above.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

However, when one of R ¹² and R ¹³ is a cyano group, and one of R ¹² and R ¹³ is a group represented by _{-SO 2} -R ²²³ , at least one of ^{R 2} to R ^{5 represents -CO} -R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M , -CO ₂ M, an optionally substituted hydrocarbon group with 1 to 40 carbon atoms or an optionally substituted heterocyclic group, when R ² and R ³ form a ring, R ⁴ and R ⁵ do not form a ring.

R ²²² represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

The R ²²³ series is the same as the ^{R 222.}

M represents a hydrogen atom or an alkali metal atom.

When ^{there are a plurality of R 101} , R ¹⁰² and M, their equivalent systems may be the same or different.

Examples of the hydrocarbon group having 1 to 40 carbons that may have a substituent represented by R ²²² include the same groups as the hydrocarbon group of 1 to 40 carbons that may have a substituent represented by ^{R 11.}

Examples of the preferable group of the hydrocarbon group having 1 to 40 carbons which may have a substituent represented by R ²²² include preferable groups of the hydrocarbon group of 1 to 40 carbons which may have a substituent represented by ^{R 11.}

R ^{222 is} preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent or an alkyl group which may have a substituent. The carbon number of the alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-8.

The phenyl group, the naphthyl group, the tetrahydronaphthyl group, and the alkyl group may have a substituent. These groups may be bonded to alkyl groups to replace substituents.

Examples of the substituent system include the same substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The substituents that can be bonded to the phenyl group, the naphthyl group, the tetrahydronaphthyl group, or the phenyl group, the naphthyl group, and the tetrahydronaphthyl group are preferably methyl, ethyl, propyl, C1-C10 alkyl groups such as isopropyl, butyl, tertiary butyl, hexyl, (2-ethyl)hexyl and octyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; three Fluoromethyl; oxycarbonyl bonded to a hydrocarbon group with 1 to 10 carbons; nitro; hydroxy; sulfamoyl; -SO ₃ M; -CO ₂ M.

The substituent of the alkyl group is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -SO ₃ M; -CO ₂ M.

R ¹ is preferably a hydrogen atom.

R ² to R ^{5 are} preferably a hydrogen atom, a halogen atom or a nitro group independently of each other. The halogen atom is preferably a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is more preferable. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . The R ¹² system is more preferably _{-SO 2} -R ^101.

R ¹³ is preferably a cyano group.

R ¹⁰¹ and R ¹⁰² respectively have the same meaning as described above.

Compound (I) is preferably a compound represented by formula (II-a1) (hereinafter, sometimes referred to as compound (II-a1)).

[In formula (II-a1), R ¹ to R ⁵ , R ¹² to R ¹³ and the wavy line respectively represent the same meanings as described above.

R ¹¹¹ represents a heterocyclic ring which may have a substituent. ]

Examples of the heterocyclic group represented by R ¹¹¹ that may have a substituent are the same as the heterocyclic group represented by ^{R 11 that may have a substituent.}

The preferable ones of the heterocyclic group which may have a substituent represented by R ¹¹¹ are the same as the preferable thing of the heterocyclic group which may have a substituent represented by ^{R 11, for example.}

R ¹¹¹ is preferably a pyridyl group, a thienyl group, and a furyl group which may have a substituent.

The pyridyl group, the thienyl group, and the furyl group may have a substituent. These groups may be bonded to alkyl groups to replace substituents.

Examples of the substituent system include the same groups as the substituents that the hydrocarbon group represented by ^{R 11 may have.}

Preferred examples of the substituent include, for example, preferred substituents that the hydrocarbon group represented by ^{R 11 may have.}

The alkyl group that can be bonded to the thienyl group, the furyl group and the pyridyl group, or the substituents of the thienyl group, the furyl group and the pyridyl group are preferably methyl, ethyl, propyl, isopropyl, C1-C10 alkyl groups such as butyl, tert-butyl, hexyl, (2-ethyl)hexyl and octyl; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; trifluoromethyl; An oxycarbonyl group bonded to a hydrocarbon group with 1 to 10 carbon atoms; nitro group; hydroxyl group; sulfamoyl group; -SO ₃ M; -CO ₂ M.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . The R ¹² system is more preferably _{-SO 2} -R ^101. R ¹⁰¹ and R ¹⁰² respectively have the same meaning as described above.

R ¹³ is preferably a cyano group.

R ¹ is preferably a hydrogen atom.

R ² to R ^{5 are} preferably a hydrogen atom, a halogen atom or a nitro group independently of each other. The halogen atom is preferably a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is more preferable. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

When R ¹² and R ¹³ form a ring, compound (I) is preferably a compound represented by formula (Ib) (hereinafter, sometimes referred to as compound (Ib)).

[In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ²⁰ and R ³⁰ are bonded to form ring Q.

The ring Q system may have a substituent, the constituent members of the ring are a ring with 5 to 7, and the ring Q system may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring selected from a hydrocarbon ring and a heterocyclic ring with a member number of 5 to 7, or a condensed ring formed by condensing the monocyclic ring.

The number of members of the ring is preferably 5 to 6 rings.

These single rings or condensed rings are preferably bonded to ring Q at two places to form condensed rings.

The ring Q and the ring system bonded to the ring Q with a single ring or a condensed ring can be exemplified by the same ones as the aforementioned group A and group B, preferably the ring represented by the formula (QQ1) to the formula (QQ25).

Among them, the ring represented by formula (Q1), formula (Q4), formula (Q7), formula (Q8), formula (Q18) is preferred (of formula (Q18), preferred is the ring represented by formula (QQ25)), More preferably, it is the ring represented by the formula (Q8) and the formula (Q18) (in the formula (Q18), the ring represented by the formula (QQ25)) is more preferable.

A monocyclic ring which may have substituents or a condensed ring formed by condensing two or more of the monocyclic ring whose constituent members are selected from the group consisting of ring Q, a hydrocarbon ring that can be condensed with ring Q, and a heterocyclic ring. The system may have a substituent. Examples of the substituent system are the same as the substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

Preferred examples of the substituent include, for example, preferred substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

Compound (I-b) is more preferably a compound represented by formula (I-c) (hereinafter, sometimes referred to as compound (I-c)).

[In formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as the above.

R ⁶ and R ⁷ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) _2. Halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms or optionally substituted heterocyclic ring.

R ¹⁰¹ , R ¹⁰² and M have the same meaning as described above. ]

R ⁶ and R ⁷ preferably independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N (R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, which may have substituents A hydrocarbon group having 1 to 40 carbon atoms or a heterocyclic ring which may have a substituent.

R ⁶ and R ⁷ show -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -COCO-R ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have substituents, and a heterocyclic group which may have substituents may be, for example, those represented by R ¹ to R ⁵ , R ¹² and R ¹³ -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -COCO-R ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, -SO ₃ M, -CO ₂ M. The hydrocarbon group having 1 to 40 carbon atoms which may have a substituent and the heterocyclic group which may have a substituent are the same.

Preferred examples of R ⁶ and R ^{7 are the same as the} preferred ones of R ¹ to R ⁵ , R ¹² and R ¹³ .

In compound (Ib) or compound (Ic), R ^{11 is} preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent group, a tetrahydronaphthyl group which may have a substituent group, a pyridyl group which may have a substituent group, An optionally substituted thienyl group, an optionally substituted furyl group or an optionally substituted alkyl group having 1 to 40 carbon atoms.

When R ¹¹ is an alkyl group that may have a substituent, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.

The phenyl group, the naphthyl group, the tetrahydronaphthyl group, the pyridyl group, the thienyl group, the furyl group, and the alkyl group may have a substituent. These groups may be bonded to alkyl groups to replace substituents.

Examples of the substituent system include the same substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

The alkyl group that can be bonded to the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridyl group, or the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thiophene group The substituents of the group, the furyl group and the pyridyl group are preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, (2-ethyl)hexyl and octyl and other carbons. Alkyl group of 1 to 10; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxycarbonyl group bonded to a hydrocarbon group with carbon number 1 to 10; nitro group; hydroxyl group; sulfonamide醯基; -SO ₃ M; -CO ₂ M.

The substituent of the alkyl group is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -SO ₃ M; -CO ₂ M.

R ¹ is preferably a hydrogen atom.

L ¹ is preferably -CO-.

R ² to R ^{5 are} preferably a hydrogen atom, a halogen atom or a nitro group independently of each other. The halogen atom is preferably a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom is more preferable. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ⁶ and R ^{7 are} preferably independent of each other ^{and are preferably the same as R 1} to R ⁵ , R ¹² , and R ¹³ , and more preferably independent of each other are methyl, ethyl, propyl, isopropyl, Butyl, tertiary butyl, pentyl, hexyl, (2-ethyl)hexyl, heptyl, octyl, nonyl, cyclohexyl, phenyl and other hydrocarbon groups with 1 to 10 carbon atoms or hydrogen atoms.

Specific examples of the compound (I) include, for example, in the formula (I-aa), compounds having the substituents shown in Tables 1 to 4 and Table 9(a) (compounds 1 to 360 and compounds 725 to 745) .

B ¹ B ² represents a partial structure of any one of formula (BB1) to formula (BB60).

B ¹ B ^{2 is} preferably formula (BB1), formula (BB6) or formula (BB19).

R ¹¹ and R ¹⁴ represent a partial structure of any one of formula (HH1) to formula (HH89).

In addition, specific examples of compound (I) include, for example, in formula (I-bb), compounds having substituents shown in Table 5 to Table 8, and Table 9(b) (Compounds 361 to 724 and Compounds 746 to 759).

B ¹ B ² represents a partial structure of any one of formula (BB1) to formula (BB60), and preferably represents formula (BB1), formula (BB6) or formula (BB19).

QQ represents a partial structure of any one of formula (QQ1) to formula (QQ25), preferably expression (QQ25).

R ¹¹ represents a partial structure of any one of formula (HH1) to formula (HH89).

As other specific examples of the compound (I), for example, the compound of the formula (I-aa) having the substituent shown in Table 10, and the compound of the formula (I-bb) having the substituent shown in Table 11 may be mentioned.

In Table 10 and Table 11, B ¹ B ² represents a part of any one of formula (BB1) to formula (BB60), formula (BBD1), formula (BBI1), formula (BBJ2), and formula (BBO10) structure. R ¹¹ and R ¹⁴ represent formula (HH1) to formula (HH89), formula (HHJ5), formula (HHJ6), formula (HHJ7), formula (HHJ10), formula (HHJ14), formula (HHJ15), formula (HHk5) , Partial structure of any one of formula (HHk6) and formula (HHk7).

QQ represents the partial structure of any one of formula (QQ1) to formula (QQ25).

The symbols in Tables 1 to 9(b) and Tables 10 to 11 indicate the following partial structures.

In addition, in the partial structure, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In addition, ※, B ¹ , B ² and ** respectively indicate the bonding location.

In each partial structure, even if the substituents substituted in the ring structure only represent the bonding of any one of ortho, para, and meta positions, the following examples include substitutions with ortho, para, and meta positions respectively. The 3 aspects.

Take compound 1 to compound 12, compound 100 to compound 360, compound 448 to compound 759, compound 01-10, compound 01-124, compound 01-138, compound 01-151, compound 01-24, compound 01-364, compound 01-37, compound 01-378, compound 01-391, compound 21-107, compound 21-108, compound 21-117, compound 21-118, compound 21-119, compound 21-13, compound 21-135, compound 21-14, compound 21-144, compound 21-15, compound 21-167, compound 21-168, compound 21-169, compound 21-185, compound 21-219, compound 21-292, compound 21-293, compound 21-294, compound 21-30, compound 21-31, compound 21-32, compound 21-34, compound 21-37, compound 21-38, compound 21-39, compound 21-4, compound 21-40, compound 21-43, compound 21-46, compound 21-48, compound 21-5, compound 21-53, compound 21-55, compound 21-87, compound 21-88, compound 21-89, compound 22-10, compound 22-1411, compound 22-1414, compound 22-1417, compound 22-1439, compound 22-1440, compound 22-3565, compound 22-3566, compound 22-3569, compound 22-3570, compound 22-4, compound 22-4961, compound 22-5, compound 22-6, compound 22-7, compound 22-8, compound 22-9, compound 51-28, compound 52-2436, compound 31-107, compound 31-31, compound 31-32, compound 31-34, compound 31-37, compound 31-38, compound 31-39, compound 31-40, compound 31-43, compound 31-46, compound 31-49, compound 31-5, compound 31-54, compound 32-1411, compound 32-1414, compound 32-1417, compound 41-842, compound 41-843, compound 41-845, compound 71-25, compound 71-30, compound 72-12 Preferably; compound 1 to compound 12, compound 100 to compound 273, compound 448 to compound 637, and compound 725 to compound 759 are more preferred; compound 1 to compound 12, compound 100 to compound 168, compound 186 to compound 255, compound 273, compound 448 to compound 532, compound 550 to compound 619, compound 63 7. Compound 725 to compound 726, compound 732 to compound 733, compound 739 to compound 740, compound 746 to compound 747, and compound 753 to compound 754 are even more preferable; from compound 100 to compound 168, compound 186 to compound 255, compound 273, compound 464 to compound 532, compound 550 to compound 619, compound 637, compound 732 to compound 733, compound 739 to compound 740, compound 746 to compound 747, and compound 753 to compound 754 are particularly preferred.

As a specific example of compound (I), for example, the compounds shown in Table 1 to Table 8, Table 9(a), Table 9(b) and Table 10 to Table 11 are bonded with 1 to 3 -SO ₃ M or -CO ₂ M compound. For example, the compound 102 in Table 2 in which 1 to 3 sulfo groups are bonded has the following structure. However, in the formula, (SO ₃ H) means replacing any hydrogen atom of compound 102.

For compound 1 to compound 12, compound 100 to compound 360, compound 448 to compound 759, compound 01-10, compound 01-124, compound 01-138, compound 01-151, compound 01-24, compound 01-364, Compound 01-37, Compound 01-378, Compound 01-391, Compound 21-107, Compound 21-108, Compound 21-117, Compound 21-118, Compound 21-119, Compound 21-13, Compound 21-135, Compound 21-14, Compound 21-144, Compound 21-15, Compound 21-167, Compound 21-168, Compound 21-169, Compound 21-185, Compound 21-219, Compound 21-292, Compound 21-293, Compound 21-294, Compound 21-30, Compound 21-31, Compound 21-32, Compound 21-34, Compound 21-37, Compound 21-38, Compound 21-39, Compound 21-4, Compound 21-40, Compound 21-43, Compound 21-46, Compound 21-48, Compound 21-5, Compound 21-53, Compound 21-55, Compound 21-87, Compound 21-88, Compound 21-89, Compound 22-10, Compound 22-1411, Compound 22-1414, Compound 22-1417, Compound 22-1439, Compound 22-1440, Compound 22-3565, Compound 22-3566, Compound 22-3569, Compound 22-3570, Compound 22-4, Compound 22-4961, Compound 22-5, Compound 22-6, Compound 22-7, Compound 22-8, Compound 22-9, Compound 51-28, Compound 52-2436, Compound 31-107, Compound 31-31, Compound 31-32, Compound 31-34, Compound 31-37, Compound 31-38, Compound 31-39, Compound 31-40, Compound 31-43, Compound 31-46, Compound 31-49, Compound 31-5, Compound 31-54, compound 32-1411, compound 32-1414, compound 32-1417, compound 41-842, compound 41-843, compound 41-845, compound 71-25, compound 71-30, compound 72-12 bond Compounds with 1 to 3 -SO ₃ M or -CO ₂ M are preferred; Compound 1 to compound 12, compound 100 to compound 273, compound 448 to compound 637, and compound 725 to compound 759 are bonded with 1 Up to 3 -SO ₃ M or -CO ₂ M compounds are more preferred; for compound 1 to compound 12, compound 100 to compound 168, Compound 186 to Compound 255, Compound 273, Compound 448 to Compound 532, Compound 550 to Compound 619, Compound 637, Compound 725 to Compound 726, Compound 732 to Compound 733, Compound 739 to Compound 740, Compound 746 to Compound 747, and Compound 753 Compounds with 1 to 3 -SO ₃ M or -CO ₂ M bonded to compound 754 are even more preferable; for compound 100 to compound 168, compound 186 to compound 255, compound 273, compound 464 to compound 532, compound From 550 to compound 619, compound 637, compound 732 to compound 733, compound 739 to compound 740, compound 746 to compound 747, and compound 753 to compound 754, the compounds in which 1 to 3 -SO ₃ M or -CO ₂ M are bonded are Especially good.

The compound (I) is preferably in the formula (I), L ¹ is -CO- or -SO ₂ -, preferably -CO-, R ¹ is a hydrogen atom or -SO ₃ M, R ² to R ⁵ Are independently hydrogen atom, nitro group, -SO ₃ M, or halogen atom, R ¹¹ is selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , a halogen atom, a cyano group and a nitro group consisting of an aromatic hydrocarbon group of 6 to 10 carbons which may have a substituent, and one of R ¹² and R ¹³ is a cyano group Group, one of R ¹² and R ¹³ is -CO-R ¹¹ or -SO ₂ -R ¹¹ , preferably -CO-R ¹¹ , R ¹⁰¹ and R ¹⁰² are each a hydrogen atom or a carbon number of 1 to The aliphatic hydrocarbon group of 8, M is a compound of hydrogen atom or alkali metal atom; more preferably, L ¹ is -CO- or -SO ₂ -, more preferably -CO-, R ¹ is hydrogen atom or -SO ₃ M , R ² to R ⁵ are each independently a hydrogen atom, a nitro group, -SO ₃ M, or a halogen atom, and R ¹¹ is selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ Substitutable phenyl group in the group consisting of M, -OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , halogen atom, cyano group and nitro group, one of R ¹² and R ¹³ is a cyano group , One of R ¹² and R ¹³ is -CO-R ¹¹ , -SO ₂ -R ^{11 is} preferably -CO-R ¹¹ , R ¹⁰¹ and R ¹⁰² are each a hydrogen atom or a carbon number of 1 to 8 Alkyl, M is a compound of hydrogen atom or alkali metal atom.

As a preferred compound (I), in addition to the above-mentioned compounds, the compound represented by formula (Ic) can also be exemplified, and L ¹ is -CO- or -SO ₂ -, preferably -CO-, R ¹ is hydrogen Atom or -SO ₃ M, R ² to R ⁵ are each independently a hydrogen atom, nitro group, -SO ₃ M, or halogen atom, R ⁶ to R ⁷ are each independently a hydrogen atom, -SO ₃ M, carbon number 1 to 4 alkyl, carbon 3 to 8 cycloalkyl or phenyl, R ¹¹ is selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , a halogen atom, a cyano group, and a nitro group consisting of an aromatic hydrocarbon group of 6 to 10 carbons that may have a substituent, and R ¹⁰¹ and R ¹⁰² are each a hydrogen atom, or Aliphatic hydrocarbon group with 1 to 8 carbon atoms, and M is a compound of hydrogen atom or alkali metal atom.

Compound (I) based R ¹ is a hydrogen atom, (PT1) of the compound represented by the formula can (hereinafter sometimes referred to as phthalonitrile compound) of a compound (the following formula (PT2), the alkyl may be referred to After the reaction of the oxide compound), the compound represented by the formula (pt3) and the compound represented by the formula (pt4) are further reacted in the presence of an acid to produce. When R ¹ is other than a hydrogen atom, the compound (I) can be further produced by reacting with the compound represented by formula (pt5).

[In formula (pt1) to formula (pt5) and formula (I), L ¹ , R ¹ to R ⁵ and R ¹¹ to R ^{13 have the} same meaning as described above.

R ⁷⁷⁷ represents an alkyl group having 1 to 20 carbons.

M ¹ represents an alkali metal atom.

LG represents a halogen atom, a methanesulfonyloxy group, a tosyloxy group, or a trifluoromethanesulfonyloxy group. ]

The alkyl group with 1 to 20 carbon atoms represented by R ⁷⁷⁷ can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl and tertiary butyl, etc., preferably Examples include alkyl groups having 1 to 6 carbon atoms.

The alkali metal atom system represented by M ¹ includes, for example, a lithium atom, a sodium atom, and a potassium atom.

Relative to 1 mol of the phthalonitrile compound, the usage amount of the alkoxide compound is usually 0.1 to 10 mol, preferably 0.2 to 5 mol, more preferably 0.3 to 3 mol, and still more preferably 0.4 to 2 mol. ear.

Relative to 1 mole of the phthalonitrile compound, the usage amount of the compound (pt3) is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and even more preferably 1 to 2 moles ear.

Relative to 1 mole of the phthalonitrile compound, the usage amount of the compound (pt4) is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and even more preferably 1 to 2 moles ear.

Examples of the acid system include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; acetic acid, Carboxylic acids such as citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acid, more preferably For example, acetic acid can be mentioned.

Relative to 1 mol of the phthalonitrile compound, the amount of acid used is usually 1 to 20 mols, preferably 1 to 10 mols, more preferably 1 to 8 mols, and still more preferably 1 to 6 mols.

The reaction system of the phthalonitrile compound, alkoxide compound, compound (pt3), and compound (pt4) is usually carried out in the presence of a solvent.

Examples of the solvent system include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; acetic acid Ester solvents such as ethyl; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as chlorinated methane and chloroform; N,N-dimethylformaldehyde and N-methylpyrrolidone Amine solvents; sulfite solvents such as dimethyl sulfite, preferably water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amine solvents and sulfite solvents , More preferably, water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methyl chloride, chloroform, N,N-dimethylformaldehyde, N-methylpyrrolidone and dimethyl sulfoxide, more preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol Alcohol, 1-octanol, acetone, methyl chloride, chloroform, N,N-dimethylformaldehyde, N-methylpyrrolidone and dimethyl sulfoxide, particularly preferred ones include water, acetonitrile, methanol, ethanol And 2-propanol.

The amount of the solvent used is usually 1 to 1000 parts by mass relative to 1 part by mass of the phthalonitrile compound.

The reaction temperature is usually 0 to 200°C, preferably 0 to 100°C, more preferably 0 to 70°C, and still more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

Relative to 1 mol of compound (I) in which R ¹ is a hydrogen atom, the usage amount of compound (pt5) is usually 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, and then More preferably, it is 1 to 2 moles.

When the compound (pt5) is reacted, it is preferable to coexist with a base. Examples of the base system include organic bases such as triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, and hexahydropyridine; sodium methoxide, sodium ethoxide, sodium tert-butoxide, tertiary butyl Metal alkoxides such as potassium alkoxide; organic metal compounds such as butyl lithium, tertiary butyl lithium and phenyl lithium; inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

Relative to 1 mol of compound (I) in which R ¹ is a hydrogen atom, the amount of base used is usually 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, and still more preferably 1 to 2 moles.

In addition, the reaction of the compound (pt5) is usually carried out in the presence of a solvent. The solvent can be selected from the same range as described above.

The amount of the solvent used is usually 1 to 1000 parts by mass relative to 1 part by mass of the compound (I) in which R ^{1 is not a hydrogen atom.} The reaction temperature of the compound (pt5) is usually -90 to 200°C, preferably -80 to 100°C, more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

When the compound (I) does not have a sulfo group or -SO ₃ M ² , by reacting the compound (I) with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid, a sulfo group or -SO ₃ M ² can be introduced.

M ² represents an alkali metal atom.

The alkali metal atom system represented by M ² includes, for example, a lithium atom, a sodium atom, and a potassium atom.

Relative to 1 mole of compound (I), the _{amount of SO 3} used in fuming sulfuric acid is usually 1 to 50 moles, preferably 5 to 40 moles, more preferably 5 to 30 moles, and even more preferably 5 to 25 moles.

Relative to 1 mole of compound (I), the amount of sulfuric acid used in fuming sulfuric acid is usually 1 to 200 moles, preferably 10 to 100 moles, more preferably 10 to 75 moles, and even more preferably 10 moles. To 50 moles.

Relative to 1 mole of compound (I), the usage amount of chlorosulfonic acid is usually 1 to 500 moles, preferably 10 to 300 moles, more preferably 10 to 200 moles, and even more preferably 10 to 150 moles. ear.

The reaction temperature of sulfonation is usually -20 to 200°C, preferably -10 to 100°C, more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

The method for extracting the compound (I) from the reaction mixture is not particularly limited, and various known methods can be used for extracting. For example, after the reaction is completed, the compound (I) can be taken out by filtering the reaction mixture. Furthermore, after filtration, the resulting residue can also be subjected to column chromatography or recrystallization. In addition, after the reaction is completed, the solvent of the reaction mixture can be distilled off, and then purified by column chromatography.

<Quinoline Yellow Compound>

Examples of the quinophthalone compound contained in the pigment composition of the present invention include compounds represented by formula (K-1) to formula (K-17).

[R ^k1 to R ^k266 independently represent hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHSO ₂ -R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ H, -CO ₂ H _{, -SO 2 Cl, -SO-R} 102; -SO 3 H or -CO ₂ H of 1 to 3 valence polyvalent metal salt; -SO ₃ H or an alkyl ammonium salt of -CO ₂ H; may have a substituent group of A phthaliminomethyl group, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

Adjacent groups of R ^k1 to R ^{k266 are} integrated to form a ring which may have substituents.

R ¹⁰¹ independently represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

When ^{there are a plurality of R 101} and R ¹⁰² , their equivalence may be the same or different. ]

R to R ^K1 shown ^k266 of ^{-CO-R 102, -COO-R} 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102) 2, -CON ( R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , and the halogen atom system can be, for example, -CO-R ¹⁰² , -COO-R ^{shown by R 1} to R ⁵ , R ¹² , and R ^{13 101} , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , Halogen atoms are the same, these groups may further have substituents. Examples of such substituents include N,N-dimethylamino, N,N-diethylamino, amino, 4- Methyl-1-hexahydropyridyl, 4-ethyl-1-hexahydropyridyl, 1-hexahydropyridyl, 1-hexahydropyridylmethyloxy, 4-morpholinyl and the like.

基、4-乙基-1-哌

基、1-哌

基、1-哌

基甲基氧基、4-嗎福林基等。 The -NHSO ₂ -R ¹⁰² series represented by R ^k1 to R ^k265 include, for example, sulfonylamino; methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, butyl Sulfonylamino, pentylsulfonylamino, hexylsulfonylamino, (2-ethyl)hexylsulfonylamino, heptylsulfonylamino, octylsulfonylamino, Nonylsulfonylamino, decylsulfonylamino, undecylsulfonylamino, dodecylsulfonylamino, eicosylsulfonylamino, phenylsulfonyl Amino groups and p-tolylsulfonylamino groups are substituted by sulfonyl groups bonded with hydrocarbon groups having 1 to 20 carbon atoms. These groups may further have substituents. The substituents are Examples include N,N-dimethylamino, N,N-diethylamino, amino, 4-methyl-1-piperidine

Base, 4-ethyl-1-piper

Base, 1-Piperidine

Base, 1-Piperidine

Methyloxy, 4-morpholinyl and the like.

基、4-乙基-1-哌

基、1-哌

基、1-哌

基甲基氧基、4-嗎福林基等。 Examples of the -SO-R ¹⁰² system shown by R ^k1 to R k265 include methylsulfinyl, ethylsulfinyl, propylsulfinyl, ^{butylsulfinyl, and pentylsulfinyl.} Acetyl, hexylsulfinyl, (2-ethyl)hexylsulfinyl, heptylsulfinyl, octylsulfinyl, nonylsulfinyl, decylsulfinyl, ten Mono-alkylsulfinyl, dodecylsulfinyl, eicosylsulfinyl, phenylsulfinyl and p-tolylsulfinyl groups are bonded with 1 to 20 carbon atoms The sulfinyl group of the hydrocarbyl group may further have a substituent, and the substituent system may include, for example, N,N-dimethylamino, N,N-diethylamino, amino, 4 -Methyl-1-Piper

Radical, 4-ethyl-1-piperidine

Base, 1-Piperidine

Base, 1-Piperidine

Methyloxy, 4-morpholinyl and the like.

^Examples of the hydrocarbon group having 1 to 40 carbon atoms or the heterocyclic group that may have substituents represented by R ^k1 to R ^{k266 include those with R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , The hydrocarbon group having 1 to 40 carbon atoms or the heterocyclic group that may have a substituent represented by R ¹⁰¹ and R ^{102 are the same.}

The monovalent to trivalent metal salts of -SO ₃ H or -CO ₂ ^{H groups represented by R k1} to R ^k266 include, for example, alkali metal salts such as sodium salt and potassium salt; alkaline earth metals such as magnesium salt and calcium salt Salt; iron salt; aluminum salt; etc., -SO ₃ H or -CO ₂ H alkyl ammonium salt series can include, for example, monoalkyls having 1 to 40 carbon atoms such as octylamine, laurylamine, and stearylamine Ammonium salts derived from base amines; quaternary alkyl ammonium salts such as palmityl trimethyl ammonium, dilauryl dimethyl ammonium, distearyl dimethyl ammonium, etc.

In addition, when the valence of the metal ion _{forming the metal salt of -SO 3} H or -CO ₂ H is 2 or more, the ratio of the quinophthalone compound with _{-SO 3} ^- or -CO ₂ ^{-to the metal ion is} The method of maintaining electricity neutrality is adjusted according to the price.

Examples of the substituent system in the phthaliminomethyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) that may have a substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, neopentyl, n-hexyl, n-octyl, stearyl, 2-ethylhexyl and other linear or Branched chain alkyl with 1 to 20 carbons; trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3, Alkyl groups with 1 to 20 carbon atoms in which part or all of hydrogen atoms such as 3-tetrafluoropropyl are substituted by halogen atoms; 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, etc. Alkyl groups having 1 to 20 carbon atoms; phenyl, naphthyl, anthracenyl, p-tolyl, p-tertiary butylphenyl, p-bromophenyl, p-nitrophenyl, p- -Methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6- Aromatic hydrocarbon groups with 6 to 20 carbon atoms such as methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinone, 2-aminoanthraquinone and the like which may have substituents; benzyl Alkyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, etc. A group combined with an aromatic hydrocarbon group with 6 to 20 carbon atoms; methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy, new Pentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy Group, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy , 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy are equal to the oxy group with one side bonded to a hydrocarbon group with 1 to 20 carbon atoms; etc.

環、吡咯環、喹啉環、喹

啉環、呋喃環、苯 并呋喃環、噻吩環、苯并噻吩環、

唑環、噻唑環、咪唑環、吡唑環、吲哚環、咔唑環等。又，該環可具有之取代基係可舉例如與R¹至R⁵、R¹¹、R¹²、R¹³、R¹⁰¹及R¹⁰²所示之烴基可具有之取代基為相同者。該取代基之較佳者係可舉例如與R¹至R⁵、R¹¹、R¹²、R¹³、R¹⁰¹及R¹⁰²所示之烴基可具有之取代基的較佳者為相同者。 ^Among the groups shown by R ^k1 to R k266, adjacent groups are integrated, and may form a ring which may have a substituent. The ring system includes, for example, a saturated aliphatic hydrocarbon ring, an unsaturated hydrocarbon ring, an aromatic hydrocarbon ring, and an aromatic heterocyclic ring, and an aromatic hydrocarbon ring and an aromatic heterocyclic ring are preferred. Examples of aromatic hydrocarbon ring systems include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc., and aromatic heterocyclic ring systems include, for example, pyridine ring, piperidine ring, etc.

Ring, pyrrole ring, quinoline ring, quinoline

Phline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring,

Azole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring, etc. In addition, the substituent system that the ring may have includes, for example, the same substituents that the hydrocarbon group represented by ^{R 1} to R ^{5 , R 11} , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.} The preferred substituents include, for example, the same preferred substituents that the hydrocarbon groups represented by ^{R 1} to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may have.}

^Among the groups represented by R ^k1 to R k266, preferable groups include, for example, a halogen atom, a hydrocarbon group having 1 to 40 carbons which may have a substituent, -OR ¹⁰² , -SO ₃ H, -CO ₂ H,- SO ₃ H or -CO ₂ H to a monovalent metal salt of trivalent, -SO ₃ H or an alkyl ammonium salt -CO ₂ H, the phthalocyanine may have a substituent group of (PEI) methyl, -SO ₂ N ( R ¹⁰² ) ₂ , more preferred groups include halogen atoms, optionally substituted hydrocarbon groups with 1 to 40 carbon atoms, and -OR ¹⁰² , and even more preferred groups include halogen atoms.

Examples of the quinoline yellow compound contained in the pigment composition of the present invention include quinoline yellow dyes and quinoline yellow pigments, Color Index (published by The Society of Dyers and Colourists), and dyeing notes (color dyeing company). Known quinoline yellow dyes such as CI Acid Yellow 3, etc., CI Pigment Yellow 138, etc., which are described in Color Index (published by The Society of Dyers and Colourists), etc., are based on the formula (K-1- 1) To formula (K-1-2), formula (K-2-1) to formula (K-2-68), formula (K-3-1) to formula (K-3-23), formula ( K-4-1) to formula (K-4-6), formula (K-5-1) to formula (K-5-6), formula (K-6-1) to formula (K-6-50 ), formula (K-7-1) to formula (K-7-4), formula (K-8-1) to formula (K-8-2), formula (K-9-1) to formula (K -9-2), formula (K-10-1) to formula (K-10-6), formula (K-11-1) to formula (K-11-2), formula (K-12-1) To formula (K-12-2), formula (K-13-1) to formula (K-13-2), formula (K-14-1) to formula (K-14-6), formula (K- 15-1) to formula (K-15-2), formula (K-16-1) to formula (K-16-2) or formula (K-17-1) to formula (K-17-2) The compounds shown are preferred, such as CI Pigment Yellow 138, formula (K-1-1) to formula (K-1-2), formula (K-2-1) to formula (K-2-68), Formula (K-3-1) to Formula (K-3-23), Formula (K-4-1), Formula (K-6-1) to Formula (K-6-50), Formula (K-7 -1) to the compound represented by formula (K-7-4), formula (K-10-1), formula (K-12-1) or formula (K-14-1) is more preferred, CI pigment Yellow 138 is even better.

These quinophthalone compounds can be used alone or in combination of two or more kinds.

The pigment composition of the present invention may contain a coloring agent other than the compound (I) and the quinophthalone compound (hereinafter, sometimes referred to as a coloring agent (A1-1)).

<Colorant (A1-1)>

The colorant (A1-1) may be a dye or a pigment.

As the dye system, known dyes can be used, and examples thereof include dyes described in Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Dyers Company). Moreover, based on the chemical structure, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, and phthalocyanine dyes can be mentioned. These dye systems can be used alone or in combination of two or more kinds.

Specifically, for example, the following Color Index (C.I.) numbered dyes can be mentioned. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Lime 6, 7, 8, 10, 12 , 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Reactive Orange 16; CI Direct Orange 26, 34, 39 , 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83 , 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; CI Solvent Green 1, 3, 5, 28, 29, 32, 33; CI Acid Green 3, 5, 9, 25, 27, 28, 41; CI Basic Green 1; CI Bat Green 1, etc.

As the pigment system, known pigments can be used, for example, pigments classified as pigments by the Color Index (published by The Society of Dyers and Colourists). These can be used alone or in combination of two or more kinds.

Specifically, the system can include, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 129, 137, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209 , 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments ; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

As other colorants (A1-1), yellow dyes and yellow pigments (hereinafter, sometimes collectively referred to as "yellow colorants"), green dyes and green pigments (hereinafter, sometimes collectively referred to as "green colorants") ") is preferred, yellow pigments and green pigments are more preferred, and green pigments are even more preferred.

Examples of the yellow dye system include dyes in which the hue is classified as yellow among the above-mentioned dyes, and the yellow pigment system includes, for example, pigments in which the hue is classified as yellow among the above-mentioned pigments.

Among yellow pigments, metal-containing yellow pigments and isoindoline yellow pigments are preferred, CI Pigment Yellow 129, 139, 150, and 185 are more preferred, and CI Pigment Yellow 139, 150, and 185 are even more preferred. .

Examples of the green dye system include those in which the hue is classified as green among the above-mentioned dyes, and the green pigment system includes, for example, the pigments in which the hue is classified as green among the above-mentioned pigments.

Among the green pigments, phthalocyanine pigments are preferred, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, and is selected from CI Pigment Green 7, 36, 58 and At least one of the group of 59 is even better.

In the total amount of the pigment composition, the content of the compound (I) is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and the upper limit is 99.999 mass% or less, preferably 99.997 Mass% or less, more preferably 99.995% mass% or less.

In the total amount of the pigment composition, the content of the quinophthalone compound is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and the upper limit is 70 mass% or less, preferably 60 Mass% or less, more preferably 50 mass% or less.

Relative to 100 parts by mass of compound (I), the content of the quinophthalone compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, and 90 parts by mass or less. More preferably, it is 70 parts by mass or less, and still more preferably 50 parts by mass or less.

When the other coloring agent (A1-1) is contained, the content of the other coloring agent (A1-1) is preferably 10 parts by mass or more relative to 100 parts by mass of the total of the compound (I) and the quinophthalone compound, and more preferably It is 50 parts by mass or more, more preferably 100 parts by mass or more, preferably 10,000 parts by mass or less, and more preferably 5,000 parts by mass or less.

In 100 parts by mass of the pigment composition, the total content of compound (I) and quinoline yellow compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, particularly preferred 3 parts by mass or more.

<Isoindoline compounds other than compound (I)>

Examples of isoindoline compounds other than the compound (I) contained in the pigment composition of the present invention include isoindoline dyes and isoindoline pigments.

Specifically, the well-known isoindoline yellow dyes described in Color Index (published by The Society of Dyers and Colourists) and dyeing notes (color dyeing company), and Color Index (published by The Society of Dyers and Colourists) are preferred. Among the well-known isoindoline yellow pigments described in etc., yellow pigments such as CI Pigment Yellow 139 and 185 are more preferable, and CI Pigment Yellow 185 is even more preferable.

Isoindoline compounds other than these compounds (I) can be used alone or in combination of two or more kinds.

The pigment composition of the present invention may contain a coloring agent other than the compound (I) and an isoindoline compound other than the compound (I) (hereinafter, may be referred to as a coloring agent (A1-2)).

<Colorant (A1-2)>

The colorant (A1-2) may be a dye or a pigment.

As the dye system, well-known dyes can be used, and examples thereof include dyes described in the Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Dyers Company). Moreover, based on the chemical structure, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, and phthalocyanine dyes can be mentioned. These dye systems can be used individually or in combination of 2 or more types.

Specifically, for example, the following Color Index (C.I.) numbered dyes can be mentioned. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Lime 6, 7, 8, 10 , 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Reactive Orange 16; CI Direct Orange 26, 34 , 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79 , 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 1 32, 136, 139; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; CI Solvent Green 1, 3, 5, 28, 29, 32, 33; CI Acid Green 3, 5, 9, 25, 27, 28, 41; CI Basic Green 1; CI Bat Green 1 etc.

The pigment system can use well-known pigments, for example, pigments classified as pigments by the Color Index (published by The Society of Dyers and Colourists). These can be used individually or in combination of 2 or more types.

Specifically, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

Other colorants (A1-2) are preferably yellow dyes and yellow pigments (hereinafter, sometimes collectively referred to as "yellow colorants"), green dyes and green pigments (hereinafter, sometimes collectively referred to as "green colorants") ”), yellow pigments and green pigments are better, and green pigments are even better.

Examples of the yellow dye series include dyes in which the hue is classified as yellow among the above-mentioned dyes, and the yellow pigment series include, for example, pigments in which the hue is classified as yellow among the above-mentioned pigments.

Among the yellow pigments, quinoline yellow pigments and metal-containing yellow pigments are preferred, C.I. Pigment Yellows 129, 138, and 150 are more preferred, and C.I. Pigment Yellows 138, 150 are even more preferred.

Examples of the green dye system include those in which the hue is classified as green among the above-mentioned dyes, and the green pigment system includes, for example, the pigments in which the hue is classified as green among the above-mentioned pigments.

Among the green pigments, phthalocyanine pigments are preferred, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, and is selected from CI Pigment Green 7, 36, 58 At least one of the group consisting of and 59 is even more preferable.

In the total amount of the pigment composition, the content of isoindoline compounds other than compound (I) is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and the upper limit is 70 mass% % Or less, preferably 60% by mass or less, more preferably 50% by mass or less.

Relative to 100 parts by mass of compound (I), the content of isoindoline compounds other than compound (I) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, 90 parts by mass The amount is preferably not more than 70 parts by mass, more preferably not more than 70 parts by mass, and still more preferably not more than 50 parts by mass.

When other coloring agent (A1-2) is contained, the content of other coloring agent (A1-2) is 10 mass parts relative to the total of 100 parts by mass of compound (I) and isoindoline compounds other than compound (I) It is more preferably 50 parts by mass or more, still more preferably 100 parts by mass or more, more preferably 10000 parts by mass or less, and more preferably 5000 parts by mass or less.

In 100 parts by mass of the pigment composition, the total content of compound (I) and isoindoline compounds other than compound (I) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 Parts by mass or more, particularly preferably 3 parts by mass or more.

<Green colorant>

The green colorant contained in the pigment composition of the present invention may be a green dye or a green pigment.

As the green dye system, known green dyes can be used, and examples thereof include the green dyes described in the Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Color Dyeing Company).

These dye systems can be used individually or in combination of 2 or more types.

Specifically, for example, a green dye numbered by the following Color Index (C.I.) can be mentioned.

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Bat Green 1, etc.

The green pigments can use well-known pigments, for example, the green pigments described in the Color Index (published by The Society of Dyers and Colourists).

These can be used individually or in combination of 2 or more types.

Specifically, green pigments such as C.I. Pigment Green 7, 36, 58, 59, etc. can be mentioned.

The green colorant contained in the pigment composition of the present invention is preferably a green pigment. Among the green pigments, phthalocyanine pigments are preferred, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, and is selected from CI Pigment Green 7, 36, 58 At least one of the group consisting of and 59 is even more preferable.

These green colorants can be used alone or in combination of two or more kinds.

The pigment composition of the present invention may contain the compound (I) and a coloring agent other than the green coloring agent (hereinafter, sometimes referred to as a coloring agent (A1-3)).

<Colorant (A1-3)>

The colorant (A1-3) may be a dye or a pigment.

The dye system can use well-known dyes, for example, the dyes described in the Color Index (published by The Society of Dyers and Colourists) and the dyeing notes (color dyeing company). Furthermore, depending on the chemical structure, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, and phthalocyanine dyes can be mentioned. These dye systems can be used individually or in combination of 2 or more types.

Specifically, for example, the dyes numbered in the following Color Index (C.I.) can be mentioned. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Lime 6, 7, 8, 10 , 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Reactive Orange 16; CI Direct Orange 26, 34 , 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79 , 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 13 2, 136, 139; C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60, etc.

The pigment system can use well-known pigments, for example, pigments classified as pigments by the Color Index (published by The Society of Dyers and Colourists). These can be used individually or in combination of 2 or more types.

Specifically, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue Pigments: CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments.

Other coloring agents (A1-3) are preferably yellow dyes and yellow pigments (hereinafter, these are sometimes collectively referred to as "yellow colorants"), and yellow pigments are more preferred. Examples of the yellow dye series include those whose hue is classified as yellow among the above-mentioned dyes, and the yellow pigment series include, for example, those whose hue is classified as yellow among the above-mentioned pigments.

Among the yellow pigments, quinoline yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred, CI Pigment Yellow 129, 138, 139, 150, 185 are more preferred, and CI Pigment Yellow 138 , 139, 150, 185 are even better.

In the total amount of the pigment composition, the content of the green colorant is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and the upper limit is 99.999% by mass or less, preferably 99.997% by mass Below, it is more preferably 99.995% by mass or less.

Relative to 100 parts by mass of compound (I), the content of the green colorant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, preferably 10,000 parts by mass or less , More preferably 5,000 parts by mass or less, still more preferably 4,000 parts by mass or less.

When the other coloring agent (A1-3) is contained, the content of the other coloring agent (A1-3) is preferably 100 parts by mass or less relative to the total of 100 parts by mass of the compound (I) and the green coloring agent, and more preferably the system 90 parts by mass or less, more preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less, more preferably 0.001 parts by mass or more, more preferably 0.003 parts by mass or more.

In 100 parts by mass of the pigment composition, the total content of the compound (I) and the green colorant is preferably at least 50 parts by mass, more preferably at least 70 parts by mass, still more preferably at least 80 parts by mass, particularly preferably at least 90 Parts by mass or more.

The coloring composition of the present invention includes: a pigment composition containing compound (I), at least one selected from the group consisting of quinoline yellow compounds, isoindoline compounds other than compound (I), and green colorants , And solvent (E).

<Solvent (E)>

Solvents (E) include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule, and solvents without -COO-), alcohol solvents (containing OH in the molecule, without -O-, -CO- And -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.

Examples of the ester solvent system include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、苯甲醚、乙氧基苯及甲基苯甲醚等。 As the ether solvent system, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl ether Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol , 3-Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-di

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzyl Ether, ethoxybenzene and methyl anisole, etc.

Examples of the ether ester solvent system include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

Examples of the ketone solvent system include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of the alcohol solvent system include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As an aromatic hydrocarbon solvent system, benzene, toluene, xylene, trimethylbenzene, etc. are mentioned, for example.

Examples of the amide solvent system include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Two or more types of these solvents can be used in combination.

Relative to the total amount of the coloring composition, the content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass.

The coloring composition of the present invention contains compound (I) and at least one pigment composition selected from the group consisting of quinoline yellow compounds, isoindoline compounds other than compound (I), and green colorants , It is better to disperse in solvent (E).

The pigment composition can be implemented according to needs: rosin treatment, surface treatment using derivatives introduced with acidic or basic groups, etc., grafting treatment of the surface of the pigment composition with polymer compounds, etc., and sulfuric acid Micronization treatment by micronization method, etc., washing treatment by organic solvent or water to remove impurities, and removal treatment by ion exchange method for ionic impurities, etc. The particle size of the pigment composition is preferably approximately uniform. The pigment composition is dispersed by containing a dispersant, and the pigment composition can be uniformly dispersed in the dispersion liquid.

As the microdispersant system, for example, a surfactant, etc., can be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, for example, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc. may be mentioned. These dispersants can be used alone or in combination of two or more kinds. If the dispersant system is represented by a trade name, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca (Stock)), EFKA (manufactured by Registered trademark) (BASF (stock) system), Adisperse (registered trademark) (Ajinomoto Finetechno (stock) system), Disperbyk (registered trademark) (BYK Chemie (stock) system), BYK (registered trademark) (BYK Chemie ( Share) system) and so on.

When a dispersant is used, relative to 100 parts by mass of the pigment composition, the amount of the dispersant (solid content) used is preferably 300 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less. When the amount of dispersant used is within the aforementioned range, there is a tendency to obtain a colored composition with a more uniform dispersion state.

In the total amount of the coloring composition, the content of the pigment composition in the coloring composition is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass.

In the coloring composition, relative to the total solid content, the content of the pigment composition is usually 1% by mass to 90% by mass, preferably 1% by mass to 80% by mass, and more preferably 2% by mass Above 75% by mass.

The colored composition system of the present invention may contain a resin (hereinafter, sometimes referred to as resin (B)). By containing the resin (B), the colored composition can further improve the dispersion stability.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin and has a monomer (a) derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as The polymer of the structural unit of "(a)") is more preferable.

The resin (B) preferably has a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with a carbon number of 2 to 4 and an ethylenically unsaturated bond, And other structural unit copolymers.

As another structural unit system, for example, it is derived from the monomer (c) which can be copolymerized with the monomer (a) (However, it is different from the monomer (a) and the monomer (b). Hereinafter, it may be called " (c)") structural units, structural units having ethylenically unsaturated bonds, etc.

Examples of the (a) series include: acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acids such as ortho-, meta-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citracan Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxyl bicyclic ring [2.2. 1]Hept-2-ene, 5,6-dicarboxyl bicyclo[2.2.1]hept-2-ene, 5-carboxymethyl bicyclo[2.2.1]hept-2-ene and 5-carboxyethyl Bicyclic [2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; carboxylic acid anhydrides such as anhydrides of the above-mentioned unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid; succinic acid mono[ 2-(Meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] Alkyloxyalkyl] esters; such as α-(hydroxymeth)acrylic acid and unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity or the solubility of the resulting resin in an aqueous alkali solution.

(b) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of ethylene oxide, oxetane, and tetrahydrofuran rings) and an ethylenically unsaturated bond Polymeric compound. (b) A monomer having a cyclic ether with a carbon number of 2 to 4 and a (meth)acryloxy group is preferred.

Examples of the (b) system include monomers (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) having a saturated bond (hereinafter sometimes referred to as "(b2)") and the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

Examples of the (b1) system include monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxylated (hereinafter sometimes referred to as "(b1-1) ") and a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxylated.

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. (b1-1) Specifically, for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate Base ester, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)benzene Ethylene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl) Styrene, 2,3,4-gins (glycidoxymethyl) styrene, 2,3,5-gins (glycidoxymethyl) styrene, 2,3,6-gins (cyclo Oxypropyloxymethyl)styrene, 3,4,5-gins(glycidoxymethyl)styrene and 2,4,6-gins(glycidoxymethyl)styrene, etc.

Examples of the (b1-2) system include: vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; Daicell (Stock) Co., Ltd. ), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicell (stock)), 3,4-epoxycyclohexylmethyl (meth)acrylate Base ester (for example, Cyclomer (registered trademark) M100; manufactured by Daicell (Stock)), the compound represented by formula (BI), the compound represented by formula (BII), etc.

[Formula (BI) and the formula (BII), R ^a is and R ^b each independently represent a line a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms of the alkyl group contained in the system which may be substituted with hydroxy.

X ^a and X ^b each independently represent a single bond ^{lines, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

＊Denotes the bond with O. ]

Examples of the compound represented by formula (BI) include compounds represented by any one of formula (BI-1) to formula (BI-15), and the like. Among them, according to formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15) The compounds represented by) are preferred, and the compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15) are more preferred.

Examples of the compound represented by formula (BII) include compounds represented by any one of formula (BII-1) to formula (BII-15), etc. Among them, preferred ones include, for example, formula (BII-1) , Formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) to formula (BII-15), more preferably Examples include compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), and formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, respectively, or the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used in combination. When these are used in combination, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is calculated on a molar basis, preferably from 5:95 to 95:5, more preferably from 10:90 to 90:10, and even better, 20:80 to 80:20.

Examples of the (c) system include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, (meth) ) Tertiary butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, Cyclopentyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane (meth)acrylate -9-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene-9-yl Ester, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylate (Meth)acrylate such as propynyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; 2-(meth)acrylate Hydroxyl-containing (meth)acrylates such as hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diesters such as diethyl ester; bicyclic [2.2.1] hept-2-ene, 5-methyl bicyclic [2.2.1] hept-2-ene, 5-ethyl bicyclic [2.2 .1]Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyl Ethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene Ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di( 2'-Hydroxyethyl) bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy bicyclic Cyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept- 2-ene, 5-hydroxymethyl-5-methyl bicyclic [2.2.1]hept-2-ene, 5-tertiary butoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5- Cyclohexyloxycarbonyl bicyclic [2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl) Bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylbutane Endioximine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoic acid Ester, N- Succinimidyl-4-maleiminobutyrate, N-succinimidyl-6-maleiminohexanoate, N-succinimidyl-3- Dicarbonylimidine derivatives such as maleimide propionate and N-(9-acridinyl)maleimide; styrene, α-methylstyrene, vinyl toluene And p-methoxystyrene and other aromatic compounds containing vinyl; (meth)acrylonitrile and other vinyl-containing nitriles; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth)acrylamide Vinyl-containing amide; vinyl acetate and other esters; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene and other dienes; etc.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, ( Meth) acrylate tricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester, (meth)acrylic acid Ester tricyclic [5.2.1.0 ^2,6 ] decene-9-yl, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide Amide, bicyclo[2.2.1]hept-2-ene, benzyl (meth)acrylate, etc. are preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The resin system having such a structural unit can be in a polymer having a structural unit derived from (a) or (b), by adding to a group that can react with the group possessed by (a) or (b). Obtained from monomers with ethylenically unsaturated bonds.

As such a structural unit system, for example, a structural unit obtained by adding (meth)acrylic acid glycidyl ester to a (meth)acrylic acid unit, and a maleic anhydride unit adding (meth)acrylic acid 2- The structural unit formed by hydroxyethyl ester and the structural unit formed by adding (meth)acrylic acid to the glycidyl (meth)acrylate unit. In addition, when these structural units have a hydroxyl group, a structural unit to which a carboxylic anhydride is further added can be exemplified as a structural unit having an ethylenically unsaturated bond.

The polymer system having the structural unit derived from (a) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, etc. are not particularly limited, and ordinary users in the field can be used. The polymerization initiator system may include, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (Benzoyl peroxide, etc.), the solvent should just be one that can dissolve each monomer.

In addition, the obtained polymer can be used directly after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation.

According to requirements, a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, ginseng (dimethylaminomethyl)phenol, etc.) and polymerization inhibitor (for example, hydroquinone, etc.) can be used.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxyl bicyclic [2.2.1]hept-2-ene anhydride, etc.

Specific examples of the resin (B) system include: (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy Tricyclic [5.2.1.0 ^2,6 ] decyl ester/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (Meth) glycidyl acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylate 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(former Base) acrylic acid/N-cyclohexyl maleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/ N-cyclohexyl maleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate Ester/(meth)acrylic acid/vinyltoluene copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/(meth) 2-Ethylhexyl acrylate copolymer, (meth)acrylate 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylate tricyclo[5.2.1.0 ^2,6 ]Decenyl ester/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/( Meth)acrylic acid/styrene copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, and Japanese Patent Application Publication No. 9-106071, Japanese Patent Application Publication No. 9-106071 Resins etc. described in the publications of 2004-29518 and Japanese Patent Application Publication No. 2004-361455.

Among them, the resin (B) is preferably a copolymer containing a structural unit derived from (a) and a structural unit derived from (b).

The resin (B) can be a combination of two or more types. In this case, the resin (B) preferably contains at least 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate /(Meth)acrylic acid copolymer; (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl maleic acid Imine/(meth)acrylic acid 2-hydroxyethyl ester copolymer; (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/ethylene Methyl toluene copolymer; (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/2-ethylhexyl(meth)acrylate copolymer One or more of them.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100.000, more preferably 5.000 to 50.000, and still more preferably 5.000 to 30.000. The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value (solid content conversion value) of the resin (B) is preferably 10 to 300 mg-KOH/g, more preferably 20 to 250 mg-KOH/g, and still more preferably 30 to 200 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be determined by titration using, for example, an aqueous potassium hydroxide solution.

In the coloring composition, relative to the total solid content, the content of the resin (B) is preferably 3 to 99% by mass, more preferably 5 to 99% by mass, and still more preferably 7 to 95% by mass.

The coloring composition system of the present invention may contain a coloring agent (hereinafter sometimes referred to as a coloring agent (A2)). The coloring agent (A2) may contain one or more coloring agents. The coloring agent (A2) preferably contains the compound (I), a yellow coloring agent, or a green coloring agent.

<Colorant (A2)>

The colorant (A2) may be a dye or a pigment. The dye system can use well-known dyes, for example, the dyes described in Color Index (published by The Society of Dyers and Colourists) and dyeing notes (Sei Dyesha). Moreover, based on the chemical structure, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, and phthalocyanine dyes can be mentioned. These dye systems can be used alone or in combination of two or more kinds.

Specifically, for example, the dyes numbered in the following Color Index (C.I.) can be mentioned. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Lime 6, 7, 8, 10 , 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Reactive Orange 16; CI Direct Orange 26, 34 , 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79 , 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 13 2, 136, 139; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; CI Solvent Green 1, 3, 5, 28, 29, 32, 33; CI Acid Green 3, 5, 9, 25, 27, 28, 41; CI Basic Green 1; CI Bat Green 1 etc.

The pigment system can use well-known pigments, for example, pigments classified as pigments by the Color Index (published by The Society of Dyers and Colourists). These can be used alone or in combination of two or more kinds.

Specifically, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue Pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

Other colorants (A2) are preferably compound (I), yellow dyes and yellow pigments (hereinafter sometimes collectively referred to as "yellow colorants"), green dyes and green pigments (hereinafter sometimes collectively referred to as "green Colorant"), preferably compound (I), yellow pigment and green pigment, and even more preferably compound (I) and green pigment.

Examples of the yellow dye system include dyes in which the hue is classified as yellow among the above-mentioned dyes, and yellow pigment systems include, for example, the pigments in which the hue is classified as yellow among the above-mentioned pigments.

Among the yellow pigments, quinoline yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred, CI Pigment Yellow 129, 138, 139, 150, 185 are more preferred, and CI Pigment Yellow 138 , 139, 150, 185 are even better.

Examples of the green dye system include those in which the hue is classified as green among the above-mentioned dyes, and the green pigment system includes, for example, the pigments in which the hue is classified as green among the above-mentioned pigments.

Among the green pigments, phthalocyanine pigments are preferred, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, and is selected from CI Pigment Green 7, 36, 58 and At least one of the group of 59 is even better.

When the coloring composition of the present invention contains a coloring agent (A2), a coloring agent (A2) containing liquid containing the coloring agent (A2) and a solvent (E) can be prepared in advance, and then the coloring agent (A2) containing liquid can be used to prepare coloring Composition. When the colorant (A2) is not dissolved in the solvent (E), the colorant (A2)-containing liquid system can be prepared by dispersing and mixing the colorant (A2) in the solvent (E). The colorant (A2) containing liquid system may be contained in part or all of the solvent (E) contained in the coloring composition.

The coloring composition of the present invention preferably comprises at least one selected from the group consisting of a compound represented by formula (I), a quinophthalone compound, an isoindoline compound other than compound (I), and a green coloring agent One type of pigment composition, solvent (E), and coloring agent (A2) containing liquid containing colorant (A2) and solvent (E) are mixed and manufactured. The aforementioned manufacturing method preferably contains a compound represented by formula (I), at least one pigment selected from the group consisting of a quinoline yellow compound, an isoindoline compound other than compound (I), and a green colorant The coloring composition and the solvent (E) are mixed by a bead mill or the like to prepare a coloring composition, and then the resulting coloring composition and the coloring agent (A2) containing the coloring agent (A2) and the solvent (E) are contained The method of mixing liquid.

The coloring agent (A2) preferably includes a compound represented by formula (I), and one or more coloring agents selected from a green coloring agent and a yellow coloring agent.

The coloring agent (A2) can be applied as needed: rosin treatment, surface treatment using coloring agent derivatives with acidic or basic groups introduced, etc., the surface treatment of the coloring agent (A2) with polymer compounds, etc. Branch treatment, micronization treatment by sulfuric acid micronization method, etc., washing treatment by organic solvent or water to remove impurities, removal treatment by ion exchange method for ionic impurities, etc. The particle size of the colorant (A2) is preferably approximately uniform. The coloring agent (A2) can be dispersed by containing a dispersing agent to form a state in which the coloring agent (A2) is uniformly dispersed in the coloring agent (A2)-containing liquid. The coloring agent (A2) system may be separately subjected to a dispersion treatment, or a plurality of types may be mixed and dispersed.

As the dispersant system, for example, a surfactant, etc., can be any one of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, for example, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc. may be mentioned. These dispersant systems can be used alone or in combination of two or more kinds. If the dispersant system is represented by a trade name, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca (Stock)), EFKA (manufactured by Registered trademark) (BASF (stock) system), Ajisper (registered trademark) (Ajinomoto Finetechno (stock) system), Disperbyk (registered trademark) (BYK Chemie (stock) system), BYK (registered trademark) (BYK Chemie ( Share) system) and so on.

In order to prepare the aforementioned colorant (A2) containing liquid, when using a dispersant, relative to 100 parts by mass of the colorant (A2), the amount of dispersant (solid content) used is preferably 300 parts by mass or less, more preferably 5 parts by mass Part or more and 100 parts by mass or less. When the amount of the dispersant used is in the aforementioned range, there is a tendency that a coloring agent (A2)-containing liquid with a more uniform dispersion state can be obtained.

In the total amount of the colorant (A2) containing liquid, the content of the coloring agent (A2) in the colorant (A2) containing liquid is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, more preferably 1 To 40% by mass.

In the colorant (A2) containing liquid, relative to the total solid content, the content of the colorant (A2) is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably It is 2 mass% or more and 75 mass% or less.

When the coloring composition of the present invention contains a resin (B), a coloring agent (A2) containing liquid containing a colorant (A2) and a solvent (E) is prepared in advance, and then the coloring composition (A2) containing liquid is used to prepare a coloring composition The colorant (A2) containing liquid may contain a part or all of the resin (B) contained in the coloring composition in advance, preferably a part of it. By preliminarily containing the resin (B), the dispersion stability of the colorant (A2)-containing liquid can be further improved.

Relative to 100 parts by mass of the colorant (A2), the content of the resin (B) in the colorant (A2) containing liquid is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass Copies.

In the coloring composition, relative to the total solid content, the content of the coloring agent (A) that combines the pigment composition and the coloring agent (A2) is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass % Or more and 80% by mass or less, more preferably 2% by mass or more and 75% by mass or less.

In the total amount of the colorant (A), the content of the compound (I) is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and the upper limit is 99.999% by mass or less, preferably 99.997% by mass or less, more preferably 99.995% by mass or less.

In the total amount of the coloring agent (A), the content of the quinophthalone compound is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and the upper limit is 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less.

Relative to 100 parts by mass of compound (I), the content of the quinophthalone compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 90 parts by mass or less , More preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.

When the other coloring agent (A2) is contained, the content of the other coloring agent (A2) is preferably 10 parts by mass or more, and more preferably 50 parts by mass relative to the total of 100 parts by mass of the compound (I) and the quinophthalone compound Part or more, more preferably 100 parts by mass or more, more preferably 10,000 parts by mass or less, and more preferably 5,000 parts by mass or less.

In 100 parts by mass of the colorant (A), the total content of the compound (I) and the quinophthalone compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, Particularly preferred is 3 parts by mass or more.

In the total amount of the coloring agent (A), the content of isoindoline compounds other than compound (I) is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and the upper limit is 70 mass% % Or less, preferably 60% by mass or less, more preferably 50% by mass or less.

Relative to 100 parts by mass of compound (I), the content of isoindoline compounds other than compound (I) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, 90 Part by mass or less is preferably, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.

When other coloring agent (A2) is contained, it is relative to 100 parts by mass of the total of isoindoline compounds other than compound (I) and compound (I), and the content of other coloring agent (A2) is 10 parts by mass or more. More preferably, it is more than 50 parts by mass, still more preferably more than 100 parts by mass, more preferably 10,000 parts by mass or less, and more preferably 5,000 parts by mass or less.

In 100 parts by mass of the coloring agent (A), the total content of the compound (I) and the isoindoline compound other than the compound (I) is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and still more preferably It is 2 parts by mass or more, particularly preferably 3 parts by mass or more.

In the total amount of the colorant (A), the content of the green colorant is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, and the upper limit is 99.999 mass% or less, preferably 99.997 mass% % Or less, more preferably 99.995% by mass or less.

Relative to 100 parts by mass of compound (I), the content of the green colorant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, preferably 10,000 parts by mass or less, more preferably It is 5000 parts by mass or less, and more preferably 4000 parts by mass or less.

較佳係4000質量份以下，0.001質量份以上為較佳、更佳係0.003質量份以上。 When the other coloring agent (A2) is contained, the content of the other coloring agent (A2) is preferably 10000 parts by mass or less, and more preferably 5000 parts by mass or less relative to the total of 100 parts by mass of the compound (I) and the green colorant ,more

Preferably it is 4000 parts by mass or less, more preferably 0.001 parts by mass or more, and more preferably 0.003 parts by mass or more.

The coloring and curable composition of the present invention includes compound (I), and at least one pigment composition selected from the group consisting of quinoline yellow compounds, isoindoline compounds other than compound (I), and green colorants Compounds, solvents (E) and polymerizable compounds (C).

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acid generated from the polymerization initiator (D), such as a compound having a polymerizable ethylenic unsaturated bond, etc., preferably (Meth)acrylate compound.

As a polymerizable compound with one ethylenically unsaturated bond, for example: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol Alcohol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b) and monomer (c).

Examples of polymerizable compounds having two ethylenically unsaturated bonds include: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di( Meth) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compound systems include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dixin Pentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, trineopentaerythritol octa (meth) acrylate, trineopentaerythritol hepta (meth) acrylate, Tetraneopentyl erythritol deca (meth) acrylate, tetraneopentyl erythritol nona (meth) acrylate, ginseng (2-(meth)acryloyloxyethyl) trimeric isocyanate, glycol modified Neopentyl erythritol tetra (meth) acrylate, ethylene glycol modified dineopentaerythritol hexa (meth) acrylate, propylene glycol modified neopentyl erythritol tetra (meth) acrylate, propylene glycol modified two Neopentylerythritol hexa(meth)acrylate, caprolactone-modified neopentaerythritol tetra(meth)acrylate, and caprolactone-modified dineopentaerythritol hexa(meth)acrylate, etc., preferably Department of dineopentaerythritol penta (meth) acrylate and dineopentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, and more preferably from 250 to 1,500.

In the coloring and curable composition, relative to the total solid content, the content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, and 5 to 55% by mass % Is even better.

The colored curable composition system of the present invention may contain a polymerization initiator (D).

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

化合物及醯基氧化膦化合物等。 The polymerization initiator (D) system can include, for example: O-acyl oxime compounds, alkyl phenone compounds, bisimidazole compounds, three

Compounds and phosphine oxide compounds, etc.

Examples of the O-acyl oxime compound system include: N-benzyloxy-1-(4-phenylhydrosulfanylphenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrosulfanylphenyl)butan-1-one-2-imine Acetyloxy-1-(4-phenylhydrosulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydrosulfanylbenzene) Yl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylhydrothiophenyl)-3-cyclopentylpropan-1-one -2-imine, N-acetoxy-1-(4-phenylhydrothiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1 -[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl Base-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxocyclopentylmethyloxy)benzyl} -9H-carbazol-3-yl]ethyl Alk-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentyl Propane-1-imine and N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-ring Pentyl propane-1-one-2-imine and so on. In addition, as the O-acetoxime compound, commercially available products such as Irgacure OXE01, OXE02 (all of the above are manufactured by BASF Co., Ltd.) and N-1919 (manufactured by ADEKA Co., Ltd.) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzene Methoxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylhydrothiophenyl) At least one of the group consisting of phenyl)-3-cyclopentylpropan-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylhydrosulfide (Phenyl)octane-1-one-2-imine.

Examples of the alkylphenone compound system include: 2-methyl-2-morpholinyl-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1 -(4-morpholinylphenyl)-2-benzylbutane-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-Mopholinyl)phenyl]butan-1-one and the like. As the alkylphenone compound, commercially available products such as Irgacure 369, 907, and 379 (all of the above are manufactured by BASF Co., Ltd.) can be used.

Examples of the alkyl phenone compound system include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethyl (Oxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer , Α,α-diethoxy acetonitrile and benzyl dimethyl ketal.

Examples of the bisimidazole compound system include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-di (Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkane) Oxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)bisimidazole, 2,2'-bis (2-Chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)bisimidazole (for example, refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62-174204 Etc.) and imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913 etc.).

化合物係可舉例如：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(5-甲基呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(4-二乙基胺基-2-甲基苯基)乙烯基〕-1,3,5-三

及2,4-雙(三氯甲基)-6-〔2-(3,4-二甲氧基苯基)乙烯基〕-1,3,5-三

等。 As three

The compound system may include, for example: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

Examples of the phosphine oxide compound system include 2,4,6-trimethylbenzyl diphenyl phosphine oxide.

As the polymerization initiator (D) system, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Azoin compound; benzophenone, o-benzoylbenzoic acid methyl, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3 ',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridine, benzyl, phenylglyoxylic acid methyl and titanocene compounds, etc.

These are preferably used in combination with the polymerization initiation aid (D1) (especially amines) described later.

化合物、醯基氧化膦化合物、O-醯基肟化合物及雙咪唑化合物所構成之群中之至少一種的聚合起始劑，更佳係含有O-醯基肟化合物之聚合起始劑。 The polymerization initiator (D) preferably contains selected from alkyl phenone compounds, three

A polymerization initiator of at least one of the group consisting of a compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a bisimidazole compound, and more preferably a polymerization initiator that contains an O-acyl oxime compound.

The content of the polymerization initiator (D) in the total amount of solid content in the colored curable composition is preferably 0.001 to 40% by mass, more preferably 0.01 to 30% by mass.

The colored curable composition system of the present invention may contain a polymerization initiation assistant (D1).

<Polymerization initiation aid (D1)>

The polymerization initiator (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is contained, it can usually be used in combination with the polymerization initiator (D).

Examples of the polymerization start aid (D1) system include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound system include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, and 4-dimethylaminobenzoic acid ethyl ester. 4-Dimethylaminobenzoic acid isoamyl ester, benzoic acid 2-dimethylaminoethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethyl) Methylamino)benzophenone, etc., preferably 4,4'-bis(diethylamino)benzophenone, for example. In addition, as the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

Examples of the alkoxyanthracene compound system include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound system include: 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorosulfur Heteroanthrone and 1-chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound system include: phenyl thio acetic acid, methyl phenyl thio acetic acid, ethyl phenyl thio acetic acid, methyl ethyl phenyl thio acetic acid, dimethyl phenyl Hydrosulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, dimethoxyphenyl sulfanyl acetic acid, chlorophenyl sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid, etc.

When using these polymerization initiation aids (D1), the content of the polymerization initiation aid (D1) is preferably 0.001 to 30% by mass in the total solid content in the colored curable composition, more preferably 0.01 to 20% by mass.

The colored composition system of the present invention may further contain a leveling agent (F) and an antioxidant.

<Leveling agent (F)>

The leveling agent (F) system includes, for example, silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These systems may have a polymerizable group in the side chain.

Examples of the polysiloxane-based surfactant system include a surfactant having a siloxane bond in the molecule, and the like. Specifically, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: TORAY Dow Corning Co., Ltd.) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan) )Wait.

Examples of the fluorine-based surfactant system include a surfactant having a fluorocarbon chain in the molecule, and the like. Specifically, for example, Flurad (registered trademark) FC430, Flurad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (DIC (stock) system), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Material Electronic Chemicals (stock) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute (stock)), etc.

Examples of the polysiloxane-based surfactant system having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, for example, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC (Stock)), etc. can be mentioned.

When the leveling agent (F) is contained, relative to the total amount of the coloring composition, the content of the leveling agent (F) is usually 0.0005 mass% to 1 mass%, preferably 0.001 mass% to 0.5 mass% , More preferably 0.001 mass% or more and 0.2 mass% or less, still more preferably 0.002 mass% or more and 0.1 mass% or less, particularly preferably 0.005 mass% or more and 0.1 mass% or less. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be improved.

<Antioxidant>

From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of two or more kinds. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like can be used.

-2,4,6(1H,3H,5H)-三酮，BASF(股)製)、Irganox 3790(Irganox 3790：1,3,5-參((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮，BASF(股)製)、Irganox 1035(Irganox 1035：硫二乙烯雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]，BASF(股)製)、Irganox 1135(Irganox 1135：苯丙烷酸、3,5-雙(1,1-二甲基乙基)-4-羥基、C7-C9側鏈烷基酯，BASF(股)製)、Irganox 1520L(Irganox 1520L：4,6-雙(辛基硫甲基)-鄰-甲酚，BASF(股)製)、Irganox 3125(Irganox 3125，BASF(股)製)、Irganox 565(Irganox 565：2,4-雙(正辛基硫)-6-(4-羥基3’,5’-二-第三丁基苯胺基)-1,3,5-三

，BASF(股)製)、Adekastab AO-80(Adekastab AO-80：3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯基氧基)-1,1-二甲基乙基)-2,4,8,10-四氧螺(5,5)十一烷，ADEKA(股)製)、Sumilizer BHT(住友化學(股)製)、Sumilizer GA-80(住友化學(股)製)、Sumilizer GS(z住友化學(股)製)、Cyanox 1790(Cytec(股)製)及維生素E(Eisai(股)製)等。 Examples of the phenol-based antioxidant system include: Irganox 1010 (Irganox 1010: neopentylerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF ( Stock), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF (Stock)), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-tertiary butyl-a,a',a''-(trimethylbenzene-2,4,6-triyl) three -P-cresol, manufactured by BASF (Stock)), Irganox 3114 (Irganox 3114: 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5- three

-2,4,6(1H,3H,5H)-Triketone, manufactured by BASF (Stock)), Irganox 3790 (Irganox 3790: 1,3,5-gin ((4-tertiary butyl-3-hydroxy- 2,6-Xylyl)methyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, made by BASF (stock)), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tertiary butyl-4) -Hydroxyphenyl) propionate], manufactured by BASF (Stocks), Irganox 1135 (Irganox 1135: phenylpropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7- C9 side chain alkyl ester, manufactured by BASF (stock), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF (stock)), Irganox 3125 (Irganox 3125) , Made by BASF (stock)), Irganox 565 (Irganox 565: 2,4-bis(n-octylsulfide)-6-(4-hydroxy 3',5'-di-tertiary butylanilino)-1, 3,5-Three

, BASF (Stock) system), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propane Oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxspiro(5,5)undecane, manufactured by ADEKA (Stock), Sumilizer BHT (Sumitomo Chemical (Stock) )), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of the phosphorus antioxidant system include Irgafos 168 (Irgafos 168: ginseng (2,4-di-tertiary butylphenyl) phosphite, manufactured by BASF (Stock)), Irgafos 12 (Irgafos 12: gin [ 2-[[2,4,8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]phosphoranyl-6-yl]oxy]ethyl]amine, BASF (Stock), Irgafos 38 (Irgafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl phosphite, BASF (Stock)) , Adekastab 329K (ADEKA (share) system), Adekastab PEP36 (ADEKA (share) system), Adekastab PEP-8 (ADEKA (share) system), Sandstab P-EPQ (Clariant company system), Weston 618 (GE company system) , Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphepin (manufactured by Sumitomo Chemical Co., Ltd.), etc.

Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl or distearyl dialkylthiodipropionate compounds, and tetrakis[methylene (3-dec Dialkyl thio) propionate] β-alkyl hydrogen thio propionate compound of polyhydric alcohols such as methane, etc.

<Other ingredients>

The coloring composition of the present invention can contain fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents and other additives known in the art as required.

Examples of adhesion promoting agents include: vinyl trimethoxysilane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethyl Oxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyl trimethoxysilane, 3-hydrothiopropyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N- 2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N- 2-(Aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl diethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane Wait.

<Color filter>

A color filter can be formed from the colored composition or colored curable composition of the present invention. As a method of forming a colored pattern, for example, a photolithographic etching method, an inkjet method, a printing method, etc. can be mentioned. Among them, the photolithography etching method is preferred. The photolithography etching method is a method in which the colored curable composition is applied to a substrate, dried to form a colored curable composition layer, and the colored curable composition layer is exposed and developed through a photomask. . In the photolithography etching method, it is preferable that the colored curable composition contains a polymerization initiator (D). In the photolithographic etching method, by not using a photomask and/or not developing an image during exposure, a colored coating film of the cured product of the colored curable composition layer can be formed. The colored pattern or colored coating film thus formed can be used as the color filter of the present invention.

The thickness of the color filter produced is not particularly limited, and can be appropriately adjusted according to the purpose or use, etc., for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate, a resin plate, silicon, or a substrate with aluminum, silver, silver/copper/palladium alloy film, etc. formed on the aforementioned substrate can be used. Other color filter layers, resin layers, transistors and circuits can be formed on these substrates.

The formation of the pixels of each color by the photolithography etching method can be performed by known or customary equipment or conditions. For example, it can be produced as follows.

First, the colored curable composition is coated on a substrate, heated and dried (pre-baking) and/or reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored curable composition layer.

The coating method includes, for example, a spin coating method, a die slit coating method, a die slit and spin coating method, and the like.

Next, the colored curable composition layer is exposed through a photomask for forming the intended colored pattern. In order to irradiate parallel light uniformly on the entire exposure surface, or perform correct alignment of the photomask and the substrate on which the colored curable composition layer is formed, it is preferable to use an exposure device such as a light aligner and a stepper.

By contacting the exposed colored curable composition layer with a developing solution for development, a colored pattern can be formed on the substrate. Through development, the unexposed part of the colored curable composition layer is dissolved in the developer solution and removed.

The developing solution is preferably aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide.

The imaging method may be any of paddle method, dipping method, spray method, and the like. Furthermore, it is also possible to tilt the substrate to an arbitrary angle during development.

The substrate after development is preferably washed with water.

Further, it is preferable to post-bak the obtained colored pattern.

The aforementioned color filters can be used as color filters for display devices (such as liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices, and among them, can be used as color filters for liquid crystal display devices.

[Example]

Hereinafter, the present invention will be explained more specifically with examples. However, the present invention is not limited by the following examples, and can be implemented with appropriate changes within the scope applicable to the meaning described above and below. All of them are included in the technical scope of the present invention. In addition, in the following, as long as there is no special statement, "parts" means "mass parts", and "%" means "mass%".

In the following synthesis examples, the structure of the compound was confirmed by NMR (JMECA-500; manufactured by JEOL Ltd.) or mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD6130 type).

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was performed by the GPC method under the following conditions.

Device: HLC-8120GPC (Tosoh (stock) system)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran

Flow rate: 1.0mL/min

Analysis of the solid content of the sample: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Tosoh (stock) system)

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene obtained above was taken as the degree of dispersion.

Synthesis example 1

11.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 91.5 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2°C, a mixture of 8.59 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 77.6 parts of methanol was dropped over 1 hour and 45 minutes, and stirred at 2°C for 6 Hours and 40 minutes. To the obtained mixture, 4.18 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 2°C for 1 hour and 45 minutes. While keeping the temperature of the obtained mixture below 4°C, 17.0 parts of acetic acid was added. 23.9 parts of trimethylacetoxyacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 87 hours. To the obtained mixture, 10.8 parts of trimethylacetoxyacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.40 parts of acetic acid were added, and the mixture was stirred at 40°C for 4 hours and 30 minutes. The obtained mixture was filtered, and the residue was washed with 360 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 22.8 parts of the compound (compound 101) represented by formula (I-1).

<Identification of the compound represented by formula (I-1) (compound 101)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 362

Exact Mass: 361

Synthesis Example 2

2.59 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.1 parts of methanol were mixed. While maintaining the temperature of the resulting mixture at 2°C, a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) 1.50 parts and 23.2 parts of methanol was dropped into the mixture over 1 hour and 10 minutes. The resulting mixture was stirred at 2°C for 2 hours and 20 minutes. While keeping the temperature of the obtained mixture below 3°C, 2.35 parts of acetic acid was added, and 4.13 parts of trimethylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the obtained mixture was stirred at room temperature. The mixture was stirred for 3 hours and 35 minutes at 40°C for 1 hour and 45 minutes. To the obtained mixture, 4.16 parts of trimethylacetoxyacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40°C for 1 hour and 30 minutes. The resulting mixture was stirred at room temperature for 37 hours. To the obtained mixture, 1.89 parts of trimethylacetoxyacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.24 parts of acetic acid were added, and the mixture was stirred at 40°C for 5 hours and 15 minutes. The obtained mixture was filtered, and the residue was washed with 198 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 5.58 parts of the compound (compound 188) represented by formula (I-2).

<Identification of the compound represented by formula (I-2) (compound 188)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 407

Exact Mass: 406

Synthesis Example 3

7.02 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 61.6 parts of methanol were mixed. While keeping the temperature of the resulting mixture at 2°C, a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) 8.20 parts and 74.6 parts of methanol was dropped over 1 hour and 30 minutes, and the mixture was stirred at 2°C. The resulting mixture was 6 hours and 15 minutes. While keeping the temperature of the obtained mixture below 4°C, 10.7 parts of acetic acid was added. To the obtained mixture, 17.6 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 44 hours. The obtained mixture was filtered, and the residue was washed with 800 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 18.0 parts of the compound (compound 102) represented by formula (I-3).

<Identification of the compound represented by formula (I-3) (compound 102)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Exact Mass: 401

Synthesis Example 4

4.12 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 37.2 parts of methanol were mixed. While keeping the temperature of the mixture at 2°C, a mixture of 4.82 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.2 parts of methanol was dropped over 1 hour, and the resulting mixture was stirred at 2°C 6 hour. While keeping the temperature of the obtained mixture below 4°C, 6.29 parts of acetic acid was added. 12.7 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at 2°C for 1 hour and at room temperature for 20 minutes. The resulting mixture was stirred at 40°C for 2 hours, at room temperature for 11 hours, and further stirred at 40°C for 5 hours and 40 minutes. To the obtained mixture, 3.18 parts of acetic acid and 6.45 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the obtained mixture was stirred at 40°C for 4 hours. Stir at room temperature for 62 hours. The obtained mixture was filtered, and the residue was washed three times with the same volume of methanol as the residue. The obtained residue was recrystallized with N,N-dimethylformamide. The obtained crystals were dried under reduced pressure at 60°C to obtain 9.99 parts of the compound represented by formula (I-4) (compound 112).

<Identification of the compound represented by formula (I-4) (Compound 112)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

Synthesis Example 5

4.07 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 36.0 parts of methanol were mixed. While keeping the temperature of the mixture at 2°C, a mixture of 4.76 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 44.3 parts of methanol was dropped over 1 hour and 10 minutes, and the mixture was stirred at 2°C. The mixture was 5 hours and 25 minutes. While keeping the temperature of the obtained mixture below 3°C, 6.23 parts of acetic acid was added. 12.6 parts of 4-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at 40°C for 40 minutes. To the obtained mixture was added 456 parts of methanol, stirred at 40°C for 3 hours, and at room temperature for 37 hours. To the obtained mixture were added 3.14 parts of acetic acid and 4-chlorobenzylacetonitrile (Tokyo Chemical Industry Co., Ltd. ) 6.31 parts and 124 parts of methanol were stirred at 40°C for 6 hours and 40 minutes, and the resulting mixture was stirred at room temperature for 18 hours. The obtained mixture was filtered, and the residue was washed with 554 parts of methanol. 1740 parts of N,N-dimethylformamide was added to the obtained residue, and after stirring at 80 degreeC, it filtered while keeping it at 80 degreeC. Obtain the residue filtrate (ROE-1). The obtained residue was washed with 150 parts of N,N-dimethylformamide. Obtain the residue and lotion (SEN-1). The obtained residue was dried under reduced pressure at 60°C to obtain 4.88 parts of the compound (compound 114) represented by formula (I-5). Combine the obtained filtrate (ROE-1) and washing solution (SEN-1), and let stand at room temperature for 12 hours. The obtained mixture was filtered, and the residue was washed 3 times with the same volume of N,N-dimethylformamide as the residue. The obtained residue was dried under reduced pressure at 60°C to obtain 5.16 parts of the compound (compound 114) represented by formula (I-5).

<Identification of the compound represented by formula (I-5) (Compound 114)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

Synthesis Example 6

10.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 93 parts of methanol were mixed. While maintaining the temperature at 2°C, a mixture of 11.7 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 110 parts of methanol was dropped into the obtained mixture over 1 hour and 15 minutes. The resulting mixture was stirred at 5°C for 3 hours. While maintaining the temperature below 5°C, 7.71 parts of acetic acid and 8 parts of methanol were added to the obtained mixture. 11.4 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the obtained mixture was stirred at 2°C for 40 minutes and at room temperature for 17 hours and 40 minutes. 109 parts of methanol was added to the obtained mixture, stirred at room temperature for 1 hour and 20 minutes, and 6.41 parts of acetic acid, 10.1 parts of barbituric acid, and 16.0 parts of methanol were added to the obtained mixture. The resulting mixture was stirred at room temperature for 5 hours, and then stirred at 40°C for 2 hours. 344 parts of water was added to the obtained mixture. After the resulting mixture was stirred at 40°C for 3 hours and 25 minutes, it was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 1.55 parts of the compound (compound 466) represented by formula (I-6).

<Identification of the compound represented by formula (I-6) (Compound 466)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 385

Exact Mass: 384

Synthesis Example 7

5.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 42.0 parts of methanol were mixed. While maintaining at 2° C., a mixture of 5.83 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 52.5 parts of methanol was dropped into the obtained mixture over 1 hour and 30 minutes. The resulting mixture was stirred at 2°C for 6 hours. While keeping the temperature below 4°C, 7.59 parts of acetic acid was added to the obtained mixture. Further, 17.4 parts of 4-cyanoacetoxymethyl benzoate (synthesized according to the method described in JP 8-176154 A) and 682 parts of methanol were added. After stirring the resulting mixture at room temperature for 4 hours, it was stirred at 40°C for 48 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 2.21 parts of the compound represented by formula (I-7) (compound 139).

<Identification of the compound represented by formula (I-7) (compound 139)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Exact Mass: 517

Synthesis Example 8

8.10 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 69.0 parts of methanol were mixed. While keeping the temperature at 2°C, a mixture of 4.68 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.0 parts of methanol was dropped into the obtained mixture over 50 minutes. The resulting mixture was stirred at 2°C for 2 hours and 30 minutes. While maintaining at 2°C, 7.35 parts of acetic acid and 18.7 parts of phenylsulfonylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. After the resulting mixture was stirred at room temperature for 15 hours, it was stirred at 40°C for 50 hours. The obtained mixture was divided in half, and mixture 1 and mixture 2 were obtained.

After the solvent of the mixture 1 was distilled off with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.0273 part of the compound represented by formula (I-8) (compound 270).

To the mixture 2, 2.00 parts of acetic acid, 3.02 parts of barbituric acid, 50 parts of methanol, and 102 parts of water were added, and the mixture was stirred at 40°C for 12 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.0313 part of the compound represented by formula (I-9) (compound 634).

<Identification of the compound represented by formula (I-8) (compound 270)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 519

Exact Mass: 518

<Identification of the compound represented by formula (I-9) (compound 634)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 466

Exact Mass: 465

Synthesis Example 9

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 3-chlorobenzylacetonitrile (manufactured by Sigma Aldrich Japan), the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-10) (compound 113).

<Identification of the compound represented by formula (I-10) (Compound 113)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

Synthesis Example 10

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-cyanoacetoxybenzoic acid methyl ester, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I- 11) The compound shown (Compound 138).

<Identification of the compound represented by formula (I-11) (compound 138)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Exact Mass: 517

Synthesis Example 11

Except that methyl 4-cyanoacetoxybenzoate was substituted with phenylsulfonylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain The compound represented by formula (I-12) (Compound 183).

<Identification of the compound represented by formula (I-12) (Compound 183)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 474

Exact Mass: 473

Synthesis Example 12

Except that methyl 4-cyanoacetoxybenzoate was substituted with 2-methylbenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-13) (compound 103).

<Identification of the compound represented by formula (I-13) (compound 103)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact Mass: 429

Synthesis Example 13

Except that methyl 4-cyanoacetoxybenzoate was substituted with 3-methylbenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-14) (compound 104).

<Identification of the compound represented by formula (I-14) (compound 104)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact Mass: 429

Synthesis Example 14

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-methylbenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-15) (compound 105).

<Identification of the compound represented by formula (I-15) (compound 105)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact Mass: 429

Synthesis Example 15

Except that 4-cyanoacetoxybenzoic acid methyl ester was kept at its molar ratio and substituted with 2-nitrobenzylacetonitrile, the rest was carried out in the same manner as in Synthesis Example 7 to obtain the formula (I-16) The compound shown (Compound 140).

<Identification of the compound represented by formula (I-16) (compound 140)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Exact Mass: 491

Synthesis Example 16

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-nitrobenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-17) The indicated compound (Compound 141).

<Identification of the compound represented by formula (I-17) (compound 141)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Exact Mass: 491

Synthesis Example 17

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-nitrobenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain formula (I-18) The indicated compound (Compound 142).

<Identification of the compound represented by formula (I-18) (compound 142)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Exact Mass: 491

Synthesis Example 18

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 4-nitrobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-19) The indicated compound (Compound 121).

<Identification of the compound represented by formula (I-19) (compound 121)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 452

Exact Mass: 451

Synthesis Example 19

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-dimethylaminobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I -20) The compound shown in (Compound 147).

<Identification of the compound represented by formula (I-20) (compound 147)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 488

Exact Mass: 487

Synthesis Example 20

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 1-naphthoacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-21)的 compound (Compound 165).

<Identification of the compound represented by formula (I-21) (compound 165)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 502

Exact Mass: 501

Synthesis Example 21

Except that methyl 4-cyanoacetoxybenzoate was substituted with 2-naphthoacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-22)的 compound (Compound 166).

<Identification of the compound represented by formula (I-22) (compound 166)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 502

Exact Mass: 501

Synthesis Example 22

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 2-trifluoromethylbenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I- 23) The shown compound (Compound 106).

<Identification of the compound represented by formula (I-23) (compound 106)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Exact Mass: 537

Synthesis Example 23

Except that methyl 4-cyanoacetoxybenzoate is maintained at its molar ratio and substituted with 3-trifluoromethylbenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.), the rest is the same as Synthesis Example 7 The compound (Compound 107) represented by formula (I-24) is obtained by applying it in a suitable manner.

<Identification of the compound represented by formula (I-24) (compound 107)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Exact Mass: 537

Synthesis example 24

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-trifluoromethylbenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was the same as Synthesis Example 7 The compound (Compound 108) represented by the formula (I-25) was obtained by applying it in a suitable manner.

<Identification of the compound represented by formula (I-25) (compound 108)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Exact Mass: 537

Synthesis Example 25

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 2-fluorobenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.), the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-26) (compound 109).

<Identification of the compound represented by formula (I-26) (Compound 109)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Exact Mass: 437

Synthesis Example 26

Except that methyl 4-cyanoacetoxybenzoate was maintained at its molar ratio and substituted with 3-fluorobenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-27) The compound shown (Compound 110).

<Identification of the compound represented by formula (I-27) (compound 110)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Exact Mass: 437

Synthesis Example 27

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 4-fluorobenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.), the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-28) (compound 111).

<Identification of the compound represented by formula (I-28) (compound 111)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Exact Mass: 437

Synthesis Example 28

Except that methyl 4-cyanoacetoxybenzoate was maintained at its molar ratio and substituted with 2-bromobenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-29) The compound shown (Compound 115).

<Identification of the compound represented by formula (I-29) (compound 115)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Exact Mass: 557

Synthesis Example 29

Except that methyl 4-cyanoacetoxybenzoate was maintained at its molar ratio and substituted with 3-bromobenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-30) The compound shown (Compound 116).

<Identification of the compound represented by formula (I-30) (compound 116)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Exact Mass: 557

Synthesis Example 30

Except that methyl 4-cyanoacetoxybenzoate was replaced with 4-bromobenzylacetonitrile (manufactured by Sigma Aldrich Japan) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7. To obtain the compound represented by formula (I-31) (compound 117).

<Identification of the compound represented by formula (I-31) (compound 117)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Exact Mass: 557

Synthesis Example 31

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 2-methoxybenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-32 ) (Compound 125).

<Identification of the compound represented by formula (I-32) (compound 125)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Exact Mass: 461

Synthesis example 32

Except that methyl 4-cyanoacetoxybenzoate was substituted with 3-methoxybenzylacetonitrile while maintaining its molar ratio, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-33 ) (Compound 126).

<Identification of the compound represented by formula (I-33) (compound 126)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Exact Mass: 461

Synthesis Example 33

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-methoxybenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was the same as Synthesis Example 7 By application, the compound represented by formula (I-34) (compound 127) is obtained.

<Identification of the compound represented by formula (I-34) (compound 127)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Exact Mass: 461

Synthesis Example 34

13.8 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 115 parts of methanol were mixed. While maintaining the temperature at 2 to 3°C, a mixture of 7.94 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.0 parts of methanol was dropped into the obtained mixture over 40 minutes. The resulting mixture was stirred at 2 to 3°C for 4 hours. While keeping the obtained mixture at 3°C or lower, 12.5 parts of acetic acid was added, and then 25.4 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 parts of methanol were further added. After stirring the resulting mixture at room temperature for 18 hours, it was stirred at 43°C for 5 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 1.02 parts of the compound represented by formula (I-35) (compound 189).

<Identification of the compound represented by formula (I-35) (compound 189)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 447

Exact Mass: 446

Synthesis Example 35

Except that methyl 4-cyanoacetoxybenzoate is maintained at its molar ratio and substituted with 3,4-dichlorobenzylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.), the rest is the same as Synthesis Example 7 The compound (Compound 118) represented by formula (I-36) is obtained by applying it in a suitable manner.

<Identification of the compound represented by formula (I-36) (compound 118)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Exact Mass: 537

Synthesis example 36

Except that methyl 4-cyanoacetoxybenzoate kept its molar ratio and replaced it with (5,6,7,8-tetrahydro-2-naphthomethanoate)acetonitrile (manufactured by Sigma Aldrich Japan) Except for the above, the remaining system was applied in the same manner as in Synthesis Example 7 to obtain the compound represented by formula (I-37) (compound 167).

<Identification of the compound represented by formula (I-37) (compound 167)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 510

Exact Mass: 509

Synthesis Example 37

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 4-dimethylaminobenzylacetonitrile (manufactured by Sigma Aldrich Japan), the rest was the same as Synthesis Example 7 The same applies to obtain the compound represented by formula (I-38) (compound 148).

<Identification of the compound represented by formula (I-38) (Compound 148)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 488

Exact Mass: 487

Synthesis Example 38

Except that methyl 4-cyanoacetoxybenzoate was substituted with methylsulfonylacetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain The compound represented by formula (I-39) (Compound 182).

<Identification of the compound represented by formula (I-39) (Compound 182)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 350

Exact Mass: 349

Synthesis Example 39

Except that methyl 4-cyanoacetoxybenzoate was substituted with (4-bromophenylsulfonyl)acetonitrile (manufactured by Sigma Aldrich Japan Co., Ltd.) while maintaining its molar ratio, the rest was the same as Synthesis Example 7 The compound (Compound 184) represented by the formula (I-40) is obtained by applying it to the ground.

<Identification of the compound represented by formula (I-40) (Compound 184)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 630

Exact Mass: 629

Synthesis Example 40

Except that 4-cyanoacetylbenzoic acid methyl ester was kept at its molar ratio and substituted with 2-cyanoacetylbenzoic acid methyl ester, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I- 41) The compound shown in (Compound 137).

<Identification of the compound represented by formula (I-41) (compound 137)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Exact Mass: 517

Synthesis Example 41

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 4-sulfamoylbenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I- 42) The compound shown in (Compound 157).

Synthesis example 42

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 2-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-43) The indicated compound (Compound 134).

<Identification of the compound represented by formula (I-43) (compound 134)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

Synthesis Example 43

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-44) The indicated compound (Compound 135).

<Identification of the compound represented by formula (I-44) (compound 135)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

Synthesis example 44

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 4-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Synthesis Example 7 to obtain formula (I-45) The indicated compound (Compound 136).

<Identification of the compound represented by formula (I-45) (compound 126)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

Synthesis Example 45

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-cyanobenzoylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-46) The compound shown (Compound 120).

Synthesis Example 46

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 2-hydroxybenzoylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-47) The compound shown (Compound 122).

<Identification of the compound represented by formula (I-47) (compound 122)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Exact Mass: 433

Synthesis Example 47

Except that 4-cyanoacetoxybenzoate methyl ester was maintained at its molar ratio and substituted with 3-hydroxybenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-48) The compound shown (Compound 123).

<Identification of the compound represented by formula (I-48) (compound 123)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Exact Mass: 433

Synthesis Example 48

Except that methyl 4-cyanoacetoxybenzoate was kept at its molar ratio and substituted with 4-hydroxybenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-49) The compound shown (Compound 124).

<Identification of the compound represented by formula (I-49) (Compound 124)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Exact Mass: 433

Synthesis Example 49

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 2-aminobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-50) The indicated compound (Compound 143).

Synthesis Example 50

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 3-aminobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain formula (I-51) The indicated compound (Compound 144).

Synthesis Example 51

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-aminobenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain formula (I-52) The compound shown (Compound 145).

Synthesis Example 52

Except that 4-cyanoacetoxybenzoate methyl ester was maintained at its molar ratio and substituted with 4-acetoxybenzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 7 to obtain the formula (I-53 ) (Compound 133).

<Identification of the compound represented by formula (I-53) (compound 133)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 486

Exact Mass: 485

Synthesis Example 53

Except that 4-cyanoacetoxybenzoic acid methyl ester was maintained at its molar ratio and substituted with 4-diethylaminobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 7 to obtain the formula (I -54) (Compound 151).

Synthesis Example 54

Except that methyl 4-cyanoacetoxybenzoate was substituted with 4-methylthiobenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain formula (I-55 ) (Compound 130).

Synthesis Example 55

Except that methyl 4-cyanoacetamidobenzoate was substituted with (4-acetamidophenylsulfonyl)acetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain The compound represented by formula (I-56) (Compound 185).

Synthesis Example 56

Except that methyl 4-cyanoacetoxybenzoate was substituted with (2-pyridylsulfonyl)acetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Synthesis Example 7 to obtain formula (I-57 ) (Compound 186).

Synthesis Example 57

Except that methyl 4-cyanoacetoxybenzoate kept its molar ratio and replaced it with N-octyl-((4-cyanoacetoxy)phenyl)sulfonamide, the rest is the same as Synthesis Example 7 The same applies to obtain the compound represented by formula (I-58) (compound 164).

Synthesis Example 58

Except that 4-cyanoacetoxybenzoic acid methyl ester kept its molar ratio and replaced with N,N-dibutyl-((4-cyanoacetoxyphenyl)sulfonamide, the rest is with Synthesis Example 7 was applied in the same manner to obtain a compound represented by formula (I-59) (compound 160).

Synthesis Example 59

Except that methyl 4-cyanoacetoxybenzoate maintains its molar ratio and is substituted with N,N-diphenyl-((4-cyanoacetoxy)phenyl)sulfonamide, the rest is with Synthesis Example 7 was applied in the same manner to obtain a compound represented by formula (I-60) (compound 161).

Synthesis Example 60

While stirring 7.6 parts of fuming sulfuric acid (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) at 3°C, 0.513 parts of the compound represented by the formula (I-3) obtained in Synthesis Example 3 was added. To the obtained mixture, 3.8 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. While stirring the obtained mixture, the temperature was raised to 15°C over 3 hours and 30 minutes. 139 parts of ice water was added to the obtained mixture, and 38.2 parts of sodium chloride was further added. The obtained mixture was filtered, and the obtained residue was washed with 64 parts of 21.5% sodium chloride aqueous solution. The obtained residue was dried under reduced pressure at 60°C to obtain 1.02 parts of the compound represented by formula (I-61) (compound 102 with two sulfo groups bonded to it).

<Identification of the compound represented by formula (I-61) (compound 102 with 2 sulfo groups bonded)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 560

Exact Mass: 561

Synthesis Example 61

12.2 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 103 parts of methanol were mixed. While keeping the temperature at 4 to 6°C, drip a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries Co., Ltd.) and 130 parts of methanol in the resulting mixture over 2 hours and 10 minutes. The resulting mixture was stirred at °C for 6 hours. While keeping the temperature at 5°C or lower, 9.37 parts of acetic acid and 13.8 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The resulting mixture was stirred at room temperature for 15 hours. To the obtained mixture, 1.00 part of acetic acid and 1.39 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at room temperature for 3 hours and at 40°C for 2 hours and 30 minutes. 1.44 parts of acetic acid and 2.13 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at 40°C for 3 hours. 0.985 parts of acetic acid, 1.46 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 170 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 2 hours. 9.29 parts of acetic acid, 12.2 parts of barbituric acid, and 17 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 20 hours. 9.29 parts of acetic acid, 14.4 parts of barbituric acid, and 14 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 18 hours. The obtained mixture was filtered, and the obtained residue was washed twice with a mixture of 200 parts of water and 200 parts of methanol, once with a mixture of 219 parts of water and 219 parts of methanol, and once with 500 parts of water. The obtained residue was dried under reduced pressure at 60°C to obtain 31.3 parts of a mixture containing the compound represented by formula (I-3) (compound 102) and the compound represented by formula (I-6) (compound 466).

<Identification of the compound represented by formula (I-3) (compound 102)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Exact Mass: 401

<Identification of the compound represented by formula (I-6) (Compound 466)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 385

Exact Mass: 384

Synthesis Example 62

11.5 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 136 parts of methanol were mixed. While maintaining the temperature at 2 to 4°C, a mixture of 13.5 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 101 parts of methanol was dropped into the obtained mixture over 1 hour. While keeping the obtained mixture at 5°C or lower, it was stirred for 6 hours. While maintaining the temperature at 4 to 8°C, 8.88 parts of acetic acid, 3.2 parts of methanol, and 16.3 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The resulting mixture was stirred at room temperature for 16 hours. 1.02 parts of acetic acid, 1.64 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added to the obtained mixture, and the mixture was stirred at room temperature for 1.5 hours and at 40°C for 6 hours. To the obtained mixture, 1.35 parts of acetic acid, 2.44 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added, and the mixture was stirred at 40°C for 3 hours. To the obtained mixture, 1.16 parts of acetic acid, 2.03 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added, and the mixture was stirred at 40°C for 17 hours. 8.83 parts of acetic acid, 12.6 parts of barbituric acid, and 14 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 22 hours. To the obtained mixture, 4.40 parts of acetic acid, 5.75 parts of barbituric acid, and 14 parts of methanol were added, and the mixture was stirred at 40°C for 9 hours and at room temperature for 4 hours. The obtained mixture was filtered, and the obtained residue was washed once with 393 parts of methanol and once with a mixture of 393 parts of water and 393 parts of methanol. 800 parts of methanol was added to the obtained residue, and it stirred at 40 degreeC for 2 hours. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 40°C to obtain a compound containing a compound represented by formula (I-4) (compound 112) and a compound represented by formula (I-63) (compound 476) The mixture is 40.7 parts.

<Identification of the compound represented by formula (I-4) (Compound 112)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

<Identification of the compound represented by formula (I-63) (compound 476)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Exact Mass: 418

Synthesis Example 63

Except that 2-chlorobenzylacetonitrile was maintained at its molar ratio and substituted with 4-chlorobenzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 62 to obtain a compound represented by formula (I-5) A mixture of the compound (Compound 114) and the compound represented by Formula (I-64) (Compound 478).

<Identification of the compound represented by formula (I-5) (Compound 114)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

<Identification of the compound represented by formula (I-64) (Compound 478)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Exact Mass: 418

Synthesis example 64

Except that 2-chlorobenzylacetonitrile was kept at its molar ratio and substituted with trimethylacetonitrile, the rest was performed in the same manner as in Synthesis Example 62 to obtain a compound containing the formula (I-1) (Compound 101) and a mixture of the compound represented by formula (I-65) (Compound 465).

<Identification of the compound represented by formula (I-1) (compound 101)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 362

Exact Mass: 361

<Identification of the compound represented by formula (I-65) (Compound 465)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 365

Exact Mass: 364

Synthesis Example 65

Except that the phthalonitrile was maintained at its molar ratio and substituted with 4-nitrophthalonitrile, the remaining system was performed in the same manner as in Synthesis Example 62 to obtain a compound represented by formula (I-66) (compound 199) and formula ( A mixture of the compound shown in I-67) (Compound 563).

<Identification of the compound represented by formula (I-66) (compound 199)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Exact Mass: 514

<Identification of the compound represented by formula (I-67) (compound 563)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Exact Mass: 463

Synthesis Example 66

Except that phthalonitrile maintains its molar ratio and replaces it with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and replaces it with 4-chlorobenzylacetonitrile, the rest is related to synthesis Example 62 was similarly applied to obtain a mixture containing the compound represented by formula (I-68) (compound 201) and the compound represented by formula (I-69) (compound 565).

<Identification of the compound represented by formula (I-68) (compound 201)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Exact Mass: 514

<Identification of the compound represented by formula (I-69) (compound 565)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Exact Mass: 463

Synthesis Example 67

Except that phthalonitrile maintains its molar ratio and replaces it with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and replaces it with trimethylacetonitrile, the rest is the same as the synthesis example 62 is similarly applied to obtain a mixture containing the compound represented by formula (I-2) (compound 188) and the compound represented by formula (I-70) (compound 552).

<Identification of the compound represented by formula (I-2) (compound 188)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 407

Exact Mass: 406

<Identification of the compound represented by formula (I-70) (compound 552)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 410

Exact Mass: 409

Synthesis Example 68

Except that phthalonitrile maintains its molar ratio and is substituted with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and is substituted with benzylacetonitrile, the rest is the same as Synthesis Example 62 To obtain a mixture containing the compound represented by formula (I-35) (compound 189) and the compound represented by formula (I-72) (compound 553).

<Identification of the compound represented by formula (I-35) (compound 189)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 447

Exact Mass: 446

<Identification of the compound represented by formula (I-72) (compound 553)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact Mass: 429

Synthesis Example 69

Except that the barbituric acid was maintained at its molar ratio and substituted with benzylacetonitrile, the remaining system was performed in the same manner as in Synthesis Example 62 to obtain a compound represented by formula (I-4) (compound 112) and formula A mixture of the compound (Compound 7) shown in (I-73).

<Identification of the compound represented by formula (I-4) (Compound 112)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

<Identification of the compound represented by formula (I-73) (compound 7)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 436

Exact Mass: 435

Synthesis Example 70

Except that 2-chlorobenzylacetonitrile is kept at its molar ratio and substituted with 4-chloroacetonitrile, and barbituric acid is kept at its molar ratio and substituted with benzylacetonitrile, the rest is the same as Synthesis Example 62 To obtain a mixture containing the compound represented by formula (I-5) (compound 114) and the compound represented by formula (I-74) (compound 8).

<Identification of the compound represented by formula (I-5) (Compound 114)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

<Identification of the compound represented by formula (I-74) (compound 8)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 436

Exact Mass: 435

Synthesis Example 71

Except that phthalonitrile maintains its molar ratio and is substituted with 4-nitrophthalonitrile, and barbituric acid maintains its molar ratio and is substituted with benzoylacetonitrile, the rest is performed in the same manner as in Synthesis Example 62. A mixture containing the compound represented by formula (I-66) (compound 199) and the compound represented by formula (I-75) (compound 9) is obtained.

<Identification of the compound represented by formula (I-66) (compound 199)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Exact Mass: 514

<Identification of the compound represented by formula (I-75) (compound 9)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 481

Exact Mass: 480

Synthesis Example 72

In addition to maintaining its molar ratio of phthalonitrile and replacing it with 4-nitrophthalonitrile, 2-chlorobenzylacetonitrile maintains its molar ratio and replacing it with 4-chlorobenzylacetonitrile, and barbituric acid Except for maintaining its molar ratio and substituting for benzylacetonitrile, the rest was performed in the same manner as in Synthesis Example 62 to obtain a compound represented by formula (I-68) (compound 201) and formula (I-76) Mixture of the compound shown (Compound 10).

<Identification of the compound represented by formula (I-68) (compound 201)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Exact Mass: 514

<Identification of the compound represented by formula (I-76) (compound 10)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 481

Exact Mass: 480

Synthesis Example 73

Except that the barbituric acid was maintained at its molar ratio and substituted with dimethylcyclohexane dicopper (Dimedone) (manufactured by Tokyo Chemical Industry Co., Ltd.), the remaining system was performed in the same manner as in Synthesis Example 61 to obtain the containing formula ( A mixture of the compound represented by I-3) (Compound 102) and the compound represented by Formula (I-77) (Compound 454).

<Identification of the compound represented by formula (I-3) (compound 102)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Exact Mass: 401

<Identification of the compound represented by formula (I-77) (Compound 454)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 397

Exact Mass: 396

Synthesis Example 74

Except that methyl 4-cyanoacetoxybenzoate kept its molar ratio and substituted with 3-pendoxy-3-(2-thienyl)propionitrile (manufactured by Sigma Aldrich Japan), the rest of the system The procedure was carried out in the same manner as in Synthesis Example 7 to obtain a compound represented by formula (I-78) (compound 732).

<Identification of the compound represented by formula (I-78) (compound 732)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 414

Exact Mass: 413

Synthesis Example 75

Except that methyl 4-cyanoacetoxybenzoate was substituted with 2-furoylacetonitrile (manufactured by Sigma Aldrich Japan) while maintaining its molar ratio, the rest was the same as Synthesis Example 7 By application, the compound represented by formula (I-79) (compound 733) is obtained.

<Identification of the compound represented by formula (I-79) (compound 733)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 382

Exact Mass: 381

Synthesis Example 76

Except that the molar ratio of 2-chlorobenzylacetonitrile was maintained and it was substituted with 3-cyanoacetoxybenzoic acid, the remaining system was performed in the same manner as in Synthesis Example 62 to obtain the formula (I-44) A mixture of the compound (Compound 135) and the compound represented by Formula (I-80) (Compound 499).

<Identification of the compound represented by formula (I-44) (compound 135)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

<Identification of the compound represented by formula (I-80) (compound 499)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Exact Mass: 428

Synthesis Example 77

Except that the molar ratio of 2-chlorobenzylacetonitrile was maintained and it was substituted with 4-cyanoacetoxybenzoic acid, the rest of the system was performed in the same manner as in Synthesis Example 62 to obtain the formula (I-45) A mixture of the compound (Compound 136) and the compound represented by Formula (I-81) (Compound 500).

<Identification of the compound represented by formula (I-45) (compound 136)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

<Identification of the compound represented by formula (I-81) (compound 500)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Exact Mass: 428

Synthesis Example 78

Except that phthalonitrile maintains its molar ratio and replaces it with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and replaces it with 3-cyanoacetoxybenzoic acid, the rest is Synthesis Example 62 was similarly applied to obtain a mixture containing the compound represented by formula (I-82) (compound 222) and the compound represented by formula (I-83) (compound 586).

<Identification of the compound represented by formula (I-82) (compound 222)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Exact Mass: 534

<Identification of the compound represented by formula (I-83) (Compound 586)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Exact Mass: 473

Synthesis Example 79

Except that phthalonitrile maintains its molar ratio and replaces it with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and replaces it with 4-cyanoacetoxybenzoic acid, the rest is with Synthesis Example 62 was similarly applied to obtain a mixture containing the compound represented by formula (I-84) (compound 223) and the compound represented by formula (I-85) (compound 587).

<Identification of the compound represented by formula (I-84) (Compound 223)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Exact Mass: 534

<Identification of the compound represented by formula (I-85) (compound 587)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Exact Mass: 473

Synthesis Example 80

Except that the molar ratio of 2-chlorobenzylacetonitrile was maintained and replaced with 2-cyanoacetoxybenzoic acid, the rest of the system was applied in the same manner as in Synthesis Example 62 to obtain the formula (I-43) A mixture of the compound (Compound 134) and the compound represented by Formula (I-86) (Compound 498).

<Identification of the compound represented by formula (I-43) (compound 134)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Exact Mass: 489

<Identification of the compound represented by formula (I-86) (compound 498)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Exact Mass: 428

Synthesis Example 81

Except that phthalonitrile maintains its molar ratio and replaces it with 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile maintains its molar ratio and replaces it with 2-cyanoacetoxybenzoic acid, the rest is with Synthesis Example 62 was applied in the same manner to obtain a mixture containing the compound represented by formula (I-87) and the compound represented by formula (I-88).

<Identification of the compound represented by formula (I-87) (compound 221)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Exact Mass: 534

<Identification of the compound represented by formula (I-88) (compound 585)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Exact Mass: 473

Raw material synthesis example 1

Acetonitrile with a molar number of 4 times the molar number of 10 parts of methyl 4-(carboxymethyl)benzoate and methyl 4-(carboxymethyl)benzoate with a molar number of 4-(carboxymethyl)benzoic acid can be obtained at a temperature of -78℃ 10 parts of a mixture of 3 times the number of moles of lithium bis(trimethylsilyl)amide and 130 parts of tetrahydrofuran. To this mixture, a mixture of 10 parts of methyl 4-(carboxymethyl)benzoate and 90 parts of tetrahydrofuran was added, and the mixture was stirred at a temperature from -78°C to room temperature for 16 hours. The obtained mixture was purified to obtain 8 parts of 4-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 4-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Exact Mass: 203

Raw material synthesis example 2

At a temperature of -78°C, acetonitrile with a molar number of 33 parts of methyl 4-(2-carboxyethyl)benzoate 6 times the molar number and a molar number of 4-(2-carboxyethyl) was obtained. ) A mixture of 890 parts of lithium bis(trimethylsilyl)amide and 890 parts of tetrahydrofuran that is 5.5 times the molar number of 33 parts of methyl benzoate. To this mixture, 33 parts of methyl 4-(2-carboxyethyl)benzoate was added, and the mixture was stirred at -78°C for 30 minutes. The obtained mixture was purified to obtain 29 parts of 4-(2-carboxyethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 4-(2-carboxyethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 216

Exact Mass: 217

Raw material synthesis example 3

At a temperature of -78°C, acetonitrile with a molar number of 30 parts of 2-(carboxymethyl)benzoic acid methyl ester 4 times the molar number and a molar number of 2-(carboxymethyl)benzoic acid methyl ester are obtained A mixture of 270 parts of lithium bis(trimethylsilyl)amide and 270 parts of tetrahydrofuran which is 3 times the molar number of 30 parts of ester. To this mixture, a mixture of 30 parts of methyl 2-(carboxymethyl)benzoate and 270 parts of tetrahydrofuran was added, and the mixture was stirred at a temperature of -78°C to room temperature for 3 hours. The obtained mixture was purified to obtain 27 parts of 2-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 2-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Exact Mass: 203

Raw material synthesis example 4

At a temperature of -78°C, acetonitrile with a molar number of 34 parts of 4-(2-(methoxycarbonyl)ethyl)benzoic acid 6 times the molar number of 4-(2-(methoxycarbonyl)ethyl)benzoic acid and a molar number of 4-(2- (Methoxycarbonyl) ethyl) benzoic acid 5.5 times the molar number of 34 parts of lithium bis(trimethylsilyl)amide and 1200 parts of tetrahydrofuran mixture. To this mixture, 34 parts of 4-(2-(methoxycarbonyl)ethyl)benzoic acid was added, and the mixture was stirred at -78°C for 1 hour. The obtained mixture was purified by recrystallization using ethyl acetate and hexane to obtain 30 parts of 4-(2-(cyanomethylcarbonyl)ethyl)benzoic acid.

<Identification of 4-(2-(cyanomethylcarbonyl)ethyl)benzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 216

Exact Mass: 217

Raw material synthesis example 5

Acetonitrile with a molar number of 5.5 times the molar number of 28 parts of 4-(methoxycarbonylmethyl)benzoic acid and a molar number of 4-(methoxycarbonylmethyl) at a temperature of -78°C A mixture of 28 parts of benzoic acid 5 times the molar number of n-butyl lithium and 1100 parts of tetrahydrofuran. To this mixture was added 28 parts of 4-(methoxycarbonylmethyl)benzoic acid, and stirred at -78°C for 15 minutes. The obtained mixture was purified by column chromatography to obtain 22 parts of 4-(cyanomethylcarbonylmethyl)benzoic acid.

<The identification of 4-(cyanomethylcarbonylmethyl)benzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Exact Mass: 203

Raw material synthesis example 6

Acetonitrile with a molar number of 4-(methoxycarbonyl)-3-methoxybenzoic acid 4 times the molar number of 18 parts of 4-(methoxycarbonyl)-3-methoxybenzoic acid and a molar number of 4-(methoxy) at a temperature of -78℃ Carbonyl)-3-methoxybenzoic acid is a mixture of 3 times the molar number of 18 parts of lithium bis(trimethylsilyl)amide and 160 parts of tetrahydrofuran. A mixture of 18 parts of 4-(methoxycarbonyl)-3-methoxybenzoic acid and 160 parts of tetrahydrofuran was added to this mixture, and the mixture was stirred at a temperature of -78°C to room temperature for 16 hours. The obtained mixture was purified to obtain 15 parts of 4-(cyanomethylcarbonyl)-3-methoxybenzoic acid.

<The identification of 4-(cyanomethylcarbonyl)-3-methoxybenzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 218

Exact Mass: 219

Raw material synthesis example 7

Acetonitrile with a molar number of 4-(methoxycarbonyl)-2-methoxybenzoic acid 4 times the molar number of 14 parts of 4-(methoxycarbonyl)-2-methoxybenzoic acid and a molar number of 4-(methoxy) at a temperature of -78℃ A mixture of lithium bis(trimethylsilyl)amide and 120 parts of tetrahydrofuran, three times the molar number of 14 parts of carbonyl)-2-methoxybenzoic acid. To this mixture, a mixture of 14 parts of 4-(methoxycarbonyl)-2-methoxybenzoic acid and 120 parts of tetrahydrofuran was added, and the mixture was stirred at a temperature of -78°C to room temperature for 16 hours. The obtained mixture was purified to obtain 13 parts of 4-(cyanomethylcarbonyl)-2-methoxybenzoic acid.

<Identification of 4-(cyanomethylcarbonyl)-2-methoxybenzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 218

Exact Mass: 219

Synthesis Example 82

Mix 5 parts of 4-aminophthalonitrile and 40 parts of methanol. While maintaining the temperature below 5°C, a 25% sodium methoxide methanol solution containing 0.5 times the molar number of 5 parts of 4-aminophthalonitrile of sodium methoxide was added to the obtained mixture. The mixture was stirred at 5°C for 3 hours and at room temperature for 16 hours. Benzylacetonitrile and 5.3 parts of acetic acid were added to the obtained mixture with a molar number of 2.2 times the molar number of 5 parts of 4-aminophthalonitrile. The mixture was stirred at room temperature for 32 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-89) (compound 21-55).

<Identification of the compound represented by formula (I-89) (compound 21-55)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 417

Exact Mass: 416

Synthesis Example 83

Mix 5 parts of 4-(N-acetamido)phthalonitrile and 40 parts of methanol. While keeping the temperature below 5°C, add 25% sodium methoxide containing sodium methoxide 0.5 times the number of moles of 5 parts of 4-(N-acetamido)phthalonitrile to the resulting mixture Methanol solution. The mixture was stirred at 5°C for 3 hours and at room temperature for 16 hours. Benzylacetonitrile and 5.3 parts of acetic acid were added to the obtained mixture with a molar number of 2.2 times the molar number of 5 parts of 4-(N-acetamido)phthalonitrile. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.2 part of the compound represented by formula (I-90) (compound 21-185).

<Identification of the compound represented by formula (I-90) (compound 21-185)>

(Quality analysis) Ionization mode=ESI+: m/z=[MH] ⁺ 459

Exact Mass: 458

Synthesis example 84

Mix 3 parts of 4-carboxyphthalonitrile and 32 parts of ethanol. A 21% sodium ethoxide ethanol solution containing 2.1 times the molar number of 3 parts of 4-carboxyphthalonitrile to sodium ethoxide was added to the resulting mixture at room temperature. The mixture was stirred at 60°C for 16 hours. Benzylacetonitrile having a molar number 2.3 times the molar number of 3 parts of 4-carboxyphthalonitrile and 9.4 parts of acetic acid were added to the obtained mixture. The mixture was stirred at 90°C for 20 hours. 9.4 parts of acetic acid was added to the obtained mixture. The mixture was stirred at 90°C for 72 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.5 part of the compound represented by formula (I-91) (compound 21-135).

<Identification of the compound represented by formula (I-91) (compound 21-135)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Exact Mass: 445

Synthesis Example 85

Mix 3 parts of 4-carboxyphthalonitrile and 47 parts of ethanol. A 25% sodium methoxide methanol solution containing 2 times the number of moles of 3 parts of 4-carboxyphthalonitrile of 4-carboxyphthalonitrile was added to the obtained mixture at room temperature. The mixture was stirred at 60°C for 16 hours. 9.4 parts of acetic acid, 2.3 times the number of moles of 3 parts of 4-carboxyphthalonitrile, 4-cyanoacetoxybenzoic acid, and 120 parts of methanol were added to the obtained mixture. The mixture was stirred at 70°C for 96 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.2 part of the compound represented by formula (I-92) (compound 21-144).

<Identification of the compound represented by formula (I-92) (compound 21-144)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 532

Exact Mass: 533

Synthesis Example 86

Mix 3 parts of 4,5-dichlorophthalonitrile and 48 parts of methanol. While keeping the temperature at 0°C, a 25% sodium methoxide methanol solution containing 3 parts of 4,5-dichlorophthalonitrile in moles of sodium methoxide was added to the obtained mixture. The mixture was stirred at room temperature for 16 hours. 6.3 parts of acetic acid, 2.2 times the number of moles of 3 parts of 4,5-dichlorophthalonitrile, 4-cyanoacetoxybenzoic acid, and 160 parts of methanol were added to the obtained mixture. The mixture was stirred at room temperature for 48 hours and at 50°C for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-93) (compound 21-40).

<Identification of the compound represented by formula (I-93) (compound 21-40)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Exact Mass: 557

Synthesis Example 87

Mix 5 parts of 4-methoxyphthalonitrile and 79 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 2.5 times the mol number of 5 parts of 4-methoxyphthalonitrile of sodium methoxide was added to the obtained mixture. The mixture was stirred at room temperature for 3 hours and at 65°C for 3 hours. To the resulting mixture were added 4-cyanoacetoxybenzoic acid 2.2 times the number of moles of 5 parts of 4-methoxyphthalonitrile, 160 parts of methanol, and 21 parts of acetic acid. The mixture was stirred at room temperature for 64 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-94) (compound 21-169).

<Identification of the compound represented by formula (I-94) (compound 21-169)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Exact Mass: 519

Synthesis Example 88

Mix 5 parts of 4-methoxyphthalonitrile and 79 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing sodium methoxide twice the number of moles of 5 parts of 4-methoxyphthalonitrile was added to the obtained mixture. The mixture was stirred at 70°C for 5 hours, and 3-cyanoacetoxybenzoic acid and methanol were added 2.5 times the number of moles of 5 parts of 4-methoxyphthalonitrile to the resulting mixture. 160 parts and 21 parts of acetic acid. The mixture was stirred at room temperature for 68 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-95) (compound 21-168).

<Identification of the compound represented by formula (I-95) (compound 21-168)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Exact Mass: 519

Synthesis Example 89

Mix 8 parts of 4-methoxyphthalonitrile and 95 parts of methanol. At room temperature, a 25% sodium methoxide methanol solution containing 2.5 times the mol number of 8 parts of 4-methoxyphthalonitrile of sodium methoxide was added to the resulting mixture. The mixture was stirred at 65°C for 3 hours, and 2-cyanoacetoxybenzoic acid and acetic acid were added with a molar number 2.2 times the molar number of 8 parts of 4-methoxyphthalonitrile to the resulting mixture. 34 copies. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.4 part of the compound represented by formula (I-96) (compound 21-167).

<Identification of the compound represented by formula (I-96) (compound 21-167)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Exact Mass: 519

Synthesis Example 90

Mix 2 parts of 4-carboxyphthalonitrile and 32 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing sodium methoxide twice the number of moles of 2 parts of 4-carboxyphthalonitrile was added to the obtained mixture. The mixture was stirred at 60°C for 6 hours, and 4.2 parts of acetic acid, 4-(carboxymethyl)-1 whose molar number was 2.2 times the molar number of 2 parts of 4-carboxyphthalonitrile, was added to the resulting mixture. -95 parts of (cyanomethylcarbonyl)benzene and methanol. The mixture was stirred at 70°C for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-97) (compound 22-4961).

<Identification of the compound represented by formula (I-97) (compound 22-4961)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 560

Exact Mass: 561

Synthesis Example 91

6.51 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 58 parts of methanol were mixed. While maintaining the temperature below 5°C, a mixture of 7.61 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 71 parts of methanol was dropped into the obtained mixture over 1 hour and 30 minutes. The mixture was stirred below 5°C for 12 hours. While maintaining the temperature at 5°C or lower, 15.0 parts of acetic acid was added to the obtained mixture, and 30.2 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 927 parts of methanol were further added. After the resulting mixture was stirred at room temperature for 4 hours, it was stirred at 40°C for 96 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.882 parts of the compound represented by formula (I-4) (compound 112).

<Identification of the compound represented by formula (I-4) (Compound 112)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Exact Mass: 469

Synthesis Example 92

5.44 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 64 parts of methanol were mixed. While maintaining the temperature below 5°C, a mixture of 6.37 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 48 parts of methanol was dropped into the obtained mixture over 1 hour and 30 minutes. While keeping the obtained mixture at 5°C or lower, it was stirred for 12 hours. While keeping the temperature at 5°C or lower, 4.20 parts of acetic acid, 742 parts of methanol, and 7.69 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The resulting mixture was stirred at room temperature for 36 hours. To the obtained mixture, 0.482 parts of acetic acid and 0.775 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at room temperature for 3 hours and at 40°C for 12 hours. 0.638 parts of acetic acid and 1.15 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at 40°C for 6 hours. 0.549 parts of acetic acid and 0.958 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at 40°C for 36 hours. 4.17 parts of acetic acid and 5.96 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 48 hours. To the obtained mixture, 2.08 parts of acetic acid and 2.72 parts of barbituric acid were added, and the mixture was stirred at 40°C for 24 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.283 parts of the compound represented by formula (I-63) (compound 476).

<Identification of the compound represented by formula (I-63) (compound 476)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Exact Mass: 418

Synthesis Example 93

7.51 parts of 4,5-dichlorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 parts of methanol were mixed. While keeping the temperature at 0°C, 7.41 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into the obtained mixture over 1 hour and 30 minutes. The resulting mixture was stirred at room temperature for 16 hours. 16.0 parts of acetic acid, 670 parts of methanol, and 7.27 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture at room temperature. The resulting mixture was stirred at room temperature for 12 hours and at 50°C for 12 hours. 0.433 parts of acetic acid and 0.733 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture, and the mixture was stirred at 50°C for 6 hours. 0.573 parts of acetic acid and 1.09 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture, and the mixture was stirred at 50°C for 6 hours. 0.493 parts of acetic acid and 0.906 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture, and the mixture was stirred at 50°C for 12 hours. 3.75 parts of acetic acid and 5.35 parts of barbituric acid were added to the obtained mixture, and it stirred at 50 degreeC for 24 hours. 1.87 parts of acetic acid and 2.44 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 50°C for 24 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.252 parts of the compound represented by formula (I-98) (compound 31-40).

<Identification of the compound represented by formula (I-98) (compound 31-40)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 495

Exact Mass: 496

Synthesis Example 94

Except for keeping 2-chlorobenzylacetonitrile at its molar ratio and replacing it with 4-cyanoacetoxybenzoic acid, and keeping barbituric acid at its molar ratio and replacing it with benzylacetonitrile, the rest is The procedure was carried out in the same manner as in Synthesis Example 92 to obtain a compound represented by formula (I-99) (compound 01-10).

<Identification of the compound represented by formula (I-99) (compound 01-10)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Exact Mass: 445

Synthesis Example 95

In addition to maintaining the molar ratio of phthalonitrile and substituting 4-nitrophthalonitrile, 2-chlorobenzylacetonitrile maintains its molar ratio and substituting 4-cyanoacetonitrile to 4-cyanoacetoxybenzoic acid, and the barbi Except that uric acid maintains its molar ratio and is substituted with benzylacetonitrile, the rest is applied in the same manner as in Synthesis Example 92 to obtain a compound represented by formula (I-100) (compound 01-364).

<Identification of the compound represented by formula (I-100) (compound 01-364)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Exact Mass: 490

Synthesis Example 96

Except that the barbituric acid was substituted with benzylacetonitrile while maintaining its molar ratio, the remaining system was performed in the same manner as in Synthesis Example 93 to obtain a compound represented by formula (I-101) (compound 01-124).

<Identification of the compound represented by formula (I-101) (compound 01-124)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Exact Mass: 513

Synthesis Example 97

Except for keeping 2-chlorobenzylacetonitrile at its molar ratio and replacing it with 2-cyanoacetoxybenzoic acid, and keeping barbituric acid at its molar ratio and replacing it with benzylacetonitrile, the rest is The procedure was carried out in the same manner as in Synthesis Example 92 to obtain a compound represented by formula (I-102) (compound 01-37).

<Identification of the compound represented by formula (I-102) (compound 01-37)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Exact Mass: 445

Synthesis Example 98

In addition to maintaining its molar ratio of phthalonitrile and replacing it with 4-nitrophthalonitrile, 2-chlorobenzylacetonitrile maintains its molar ratio and replacing it with 2-cyanoacetoxybenzoic acid, and the Except that uric acid maintains its molar ratio and is substituted with benzylacetonitrile, the rest is applied in the same manner as in Synthesis Example 92 to obtain a compound represented by formula (I-103) (compound 01-391).

<Identification of the compound represented by formula (I-103) (compound 01-391)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Exact Mass: 490

Synthesis Example 99

In addition to keeping 4-cyanoacetoxybenzoic acid at its molar ratio and replacing it with 2-cyanoacetoxybenzoic acid, and keeping barbituric acid at its molar ratio and replacing it with benzylacetonitrile, The rest was performed in the same manner as in Synthesis Example 93 to obtain the compound represented by formula (I-104) (compound 01-151).

<Identification of the compound represented by formula (I-104) (compound 01-151)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Exact Mass: 513

Synthesis Example 100

Mix 3 parts of 4-bromophthalonitrile and 24 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 0.5 times the number of moles of 3 parts of 4-bromophthalonitrile of sodium methoxide was added to the obtained mixture. The mixture was stirred at 0°C for 3 hours, and 3.1 parts of 4-cyanoacetoxybenzoic acid with a molar number of 2.2 times the molar number of 3 parts of 4-bromophthalonitrile and 3.1 parts of acetic acid were added to the resulting mixture. . The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-105) (compound 21-294).

<Identification of the compound represented by formula (I-105) (compound 21-294)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 566

Exact Mass: 567

Synthesis Example 101

Mix 5 parts of 3,4-dicyanobenzenesulfonic acid and 79 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 0.5 times the number of moles of 5 parts of 3,4-dicyanobenzenesulfonic acid of sodium methoxide was added to the obtained mixture. The mixture was stirred at 0°C for 6 hours, and 4-cyanoacetoxybenzoin was added to the resulting mixture with a molar number of 2.2 times the molar number of 5 parts of 3,4-dicyanobenzenesulfonic acid. 5.2 parts of acid and acetic acid. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.4 part of the compound represented by formula (I-106) (compound 21-219).

<Identification of the compound represented by formula (I-106) (compound 21-219)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 568

Exact Mass: 569

Synthesis Example 102

Mix 2 parts of phthalonitrile and 16 parts of methanol. While maintaining the temperature at 5°C, a 25% sodium methoxide methanol solution containing sodium methoxide whose molar number is 0.5 times the molar number of 2 parts of phthalonitrile is added to the obtained mixture. The mixture was stirred at 5°C for 3 hours, and N-acetyl-4-(cyanoacetoxy)aniline with a molar number of 2.2 times the molar number of 2 parts of phthalonitrile was added to the resulting mixture And 2.2 parts of acetic acid. The mixture was stirred at room temperature for 16 hours and at 50°C for 48 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-107) (compound 154).

<Identification of the compound represented by formula (I-107) (compound 154)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 516

Exact Mass: 515

Synthesis Example 103

Mix 2 parts of 4-(trifluoromethyl)phthalonitrile and 32 parts of methanol. While maintaining at 0°C, a 25% sodium methoxide methanol solution containing 2 parts of 4-(trifluoromethyl)phthalonitrile in moles of sodium methoxide 0.8 times the number of moles was added to the resulting mixture. The mixture was stirred at 10°C for 2 hours, and 4-cyano groups with a molar number of 4.4 parts of acetic acid and 2.2 times the molar number of 2 parts of 4-(trifluoromethyl)phthalonitrile were added to the resulting mixture. Acetyl benzoic acid. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-108) (compound 21-119).

<Identification of the compound represented by formula (I-108) (compound 21-119)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Exact Mass: 557

Synthesis Example 104

Mix 2 parts of 4-(trifluoromethyl)phthalonitrile and 32 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 4 parts of 4-(trifluoromethyl)phthalonitrile in moles of sodium methoxide 0.5 times the number of moles was added to the obtained mixture. The mixture was stirred at 0°C for 3 hours, and 3-cyanoacetoxybenzoin was added to the resulting mixture with a molar number of 2.2 times the molar number of 4 parts of 4-(trifluoromethyl)phthalonitrile. 4.4 parts of acid and acetic acid. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-109) (compound 21-118).

<Identification of the compound represented by formula (I-109) (compound 21-118)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Exact Mass: 557

Synthesis Example 105

Mix 2.5 parts of 4-(trifluoromethyl)phthalonitrile and 32 parts of methanol. While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 2.5 parts of 4-(trifluoromethyl)phthalonitrile in moles of sodium methoxide 0.5 times the number of moles was added to the resulting mixture. The mixture was stirred at 0°C for 3 hours, and 2-cyanoacetoxybenzoin was added to the resulting mixture with a molar number of 2.5 parts of 4-(trifluoromethyl)phthalonitrile and 2.2 times the molar number. 3 parts of acid and acetic acid. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.1 part of the compound represented by formula (I-110) (compound 21-117).

<Identification of the compound represented by formula (I-110) (compound 21-117)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Exact Mass: 557

Synthesis Example 106

Mix 2 parts of phthalonitrile and 16 parts of methanol. While maintaining the temperature at 5°C, a 25% sodium methoxide methanol solution containing sodium methoxide whose molar number is 0.5 times the molar number of 2 parts of phthalonitrile is added to the obtained mixture. The mixture was stirred at 5°C for 3 hours and at room temperature for 16 hours. To the resulting mixture was added 4-sulfasulfonyl benzyl whose molar number was 2.2 times the molar number of 2 parts of phthalonitrile. 2.2 parts of acetonitrile and acetic acid. The mixture was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-42) (compound 157).

<Identification of the compound represented by formula (I-42) (Compound 157)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 560

Exact Mass: 559

Synthesis Example 107

4.1 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 48 parts of methanol were mixed. While keeping the temperature at 5°C, a mixture of 4.8 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 36 parts of methanol was dropped into the obtained mixture over 1 hour and 30 minutes, and the obtained mixture The mixture was kept below 5°C while stirring for 12 hours. While keeping the temperature at 5°C or lower, 5.1 parts of acetic acid, 750 parts of methanol, and 7.2 parts of 4-sulfamoylbenzylacetonitrile were added to the obtained mixture. The mixture was stirred at room temperature for 36 hours. To the obtained mixture, 0.56 parts of acetic acid and 0.73 parts of 4-sulfamoylbenzylacetonitrile were added, and the mixture was stirred at room temperature for 3 hours and at 40°C for 12 hours. To the obtained mixture, 0.77 parts of acetic acid and 1.1 parts of 4-sulfamoylbenzylacetonitrile were added, and the mixture was stirred at 40°C for 6 hours. 0.66 parts of acetic acid and 0.90 parts of 4-sulfamoylbenzylacetonitrile were added to the obtained mixture, and the mixture was stirred at 40°C for 36 hours. 3.1 parts of acetic acid and 4.5 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 48 hours. 1.6 parts of acetic acid and 2.0 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 24 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.21 part of the compound represented by formula (I-111) (compound 521).

<Identification of the compound represented by formula (I-111) (compound 521)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Exact Mass: 463

Synthesis Example 108

Except that phthalonitrile was substituted with 4-nitrophthalonitrile while maintaining its molar ratio, the procedure was carried out in the same manner as in Synthesis Example 107 to obtain the compound represented by formula (I-112) (compound 608).

<Identification of the compound represented by formula (I-112) (Compound 608)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 509

Exact Mass: 508

Synthesis Example 109

Except that phthalonitrile was substituted with 4-nitrophthalonitrile while maintaining its molar ratio, the remaining system was performed in the same manner as in Synthesis Example 102 to obtain the compound represented by formula (I-113) (compound 241).

<Identification of the compound represented by formula (I-113) (compound 241)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 561

Exact Mass: 560

Synthesis Example 110

Except that phthalonitrile was substituted with 4-nitrophthalonitrile while maintaining its molar ratio, the remaining system was performed in the same manner as in Synthesis Example 106 to obtain the compound represented by formula (I-114) (compound 244).

<Identification of the compound represented by formula (I-114) (compound 244)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 605

Exact Mass: 604

Synthesis Example 111

Except that 4-cyanoacetoxybenzoic acid was maintained at its molar ratio and substituted with 2-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Synthesis Example 100 to obtain the formula (I-115) Compounds (Compounds 21-292).

<Identification of the compound represented by formula (I-115) (compound 21-292)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 566

Exact Mass: 567

Synthesis example 112

Except that 4-cyanoacetoxybenzoic acid was maintained at its molar ratio and substituted with 3-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Synthesis Example 100 to obtain the formula (I-116) Compounds (Compounds 21-293).

<Identification of the compound represented by formula (I-116) (compound 21-293)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 566

Exact Mass: 567

Synthesis Example 113

Except that the barbituric acid was maintained at its molar ratio and substituted with Dimedone (manufactured by Tokyo Chemical Industry Co., Ltd.), the rest of the system was performed in the same manner as in Synthesis Example 93 to obtain the formula (I -117) (Compounds 41-843).

<Identification of the compound represented by formula (I-117) (compound 41-843)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 507

Exact Mass: 508

Synthesis example 114 to synthesis example 165

In addition to substituting phthalonitrile for the compound represented by the formula (PPA-1) using the group shown in the column ^{"B 1} B ^{2 "of Table 12, the 2-chlorobenzylacetonitrile was substituted with "Lk} Except for the compound represented by the formula (PPA-2) of the group shown in the "Hd" column, the rest was carried out in the same manner as in Synthesis Example 91, and the compound shown in the "Compound" column of Table 12 was obtained.

The compound obtained in each synthesis example is a compound represented by formula (PPA-3), ^{and the groups shown in the "B 1} B ² ", "Lk" and "Hd" columns of Table 12 are used.

The identification of compounds is carried out by mass analysis.

When the "Ionization Mode" column of Table 12 is "1", the (mass analysis) ionization mode = ESI +: m/z = [M+H] ^{+ the} detected value will be shown in the "Detection" of Table 12 Value" column.

When the "Ionization Mode" column of Table 12 is "-1", the (mass analysis) ionization mode = ESI-: m/z=[MH] ^-The detected value will be shown in the "Detection value" of Table 12 "column.

The value of Exact.Mass. is shown in the "Exact.Mass." column of Table 12.

In Table 12, ^{the symbols (HH35, BB19, etc.) in the “B 1} B ² ”column and the “Hd” column are defined in the same way as the symbols in Table 1 to Table 9(b) and Table 10 to Table 11 in the specification of this case .

Synthesis example 166 to synthesis example 181

Except that 4-cyanoacetoxybenzoic acid is substituted with the compound represented by the formula (PPA-2) using the groups shown in the "Lk" and "Hd" columns of Table 13, the rest is the same as in Synthesis Example 86 It was implemented practically to obtain the compounds shown in the "Compounds" column of Table 13.

The compound obtained in each synthesis example is a compound represented by formula (I-93a), and the group shown in the column "Lk" and "Hd" in Table 13 is used.

The identification of compounds is carried out by mass analysis.

When the "Ionization Mode" column of Table 13 is "1", the (mass analysis) ionization mode = ESI +: m/z = [M+H] ^{+ the} detected value will be shown in the "Detected value" of Table 13 "column. Table "ionization mode" of column 13 is "-1" when the system will be (mass spectrometry) ionization mode = ESI-: m / z = [ MH] - represents the value detected "in Table 13 of the detection value "column.

The value of Exact.Mass. is shown in the "Exact.Mass." column of Table 13.

In Table 13, the symbols (HH35 etc.) described in the "Hd" column are defined in the same way as the symbols in Table 1 to Table 9(b) and Table 10 to Table 11 in the specification of this case.

Synthesis examples 182 to 223

In addition to substituting phthalonitrile for the compound represented by the formula (PPA-1) using the group shown in the column ^{"B 1} B ^{2 "of Table 14, the 2-chlorobenzylacetonitrile was substituted with "Lk} Except for the compound represented by the formula (PPA-2) of the group shown in the "Hd" column, the rest was carried out in the same manner as in Synthesis Example 92, and the compound shown in the "Compound" column of Table 14 was obtained.

The compound obtained in each synthesis example is a compound represented by formula (I-63a), ^{and the groups shown in the "B 1} B ² ", "Lk" and "Hd" columns of Table 14 are used.

The identification of compounds is carried out by mass analysis.

When the "Ionization Mode" column of Table 14 is "1", the (mass analysis) ionization mode = ESI +: m/z = [M+H] ^{+ the} detected value will be shown in the "Detected value" of Table 14 "column.

When table-based "ionization mode" column 14 of the "-1" will be satisfied (mass spectrometry) ionization mode = ESI-: m / z = [ MH] - the value detected are shown in Table "14 of the detection value "column.

The value of Exact.Mass. is shown in the "Exact.Mass." column of Table 14.

In Table 14, ^{the symbols described in the "B 1} B ² "column and the "Hd" column are defined in the same way as the symbols in Table 1 to Table 9(b) and Table 10 to Table 11 in the specification of this case.

Synthesis example 224 to synthesis example 237

Except that 4-cyanoacetoxybenzoic acid is substituted with the compound represented by the formula (PPA-2) using the groups shown in the "Lk" and "Hd" columns of Table 15, the rest is the same as in Synthesis Example 93 It was carried out to obtain the compounds shown in the "Compounds" column of Table 15.

The compound obtained in each synthesis example is a compound represented by formula (I-98a), and the group shown in the column "Lk" and "Hd" in Table 15 is used.

The identification of compounds is carried out by mass analysis.

When the "Ionization Mode" column of Table 15 is "1", the (mass analysis) ionization mode = ESI +: m/z = [M+H] ^{+ the} detected value will be shown in the "Detected value" of Table 15 "column.

When the "Ionization Mode" column of Table 15 is "-1", it will be (mass analysis) Ionization Mode = ESI-: m/z=[MH] ^-The detected value is shown in the "Detection Value" of Table 15 "column.

The value of Exact.Mass. is shown in the "Exact.Mass." column of Table 15.

In Table 15, the symbols in the "Hd" column are defined in the same way as the symbols in Table 1 to Table 9(b) and Table 10 to Table 11 in the specification of this case.

Synthesis example 238 to synthesis example 240

In addition to substituting phthalonitrile with the compound represented by formula (PPA-1) using the group shown in the column ^{"B 1} B ^{2 "in Table 16, the 2-chlorobenzylacetonitrile was substituted with "Lk} "" column is the same as Synthesis Example 92 except that the compound represented by the formula (PPA-2) of the group shown in the "Hd" column and substituted barbituric acid with dimethylcyclohexanedicopper (Dimedone) It was implemented practically to obtain the compounds shown in the "Compounds" column of Table 16.

The compound obtained in each synthesis example is a compound represented by formula (I-63a), ^{and the groups shown in the "B 1} B ² ", "Lk" and "Hd" columns of Table 16 are used.

The identification of compounds is carried out by mass analysis.

When the "Ionization Mode" column of Table 16 is "1", the (mass analysis) ionization mode = ESI +: m/z = [M+H] ^{+ the} detected value will be shown in the "Detected value" of Table 16 "column.

When table-based "ionization mode" column 16 of the "-1" will be satisfied (mass spectrometry) ionization mode = ESI-: m / z = [ MH] - represents a detected value of the "detected value in the Table 16 "column.

The value of Exact.Mass. is shown in the "Exact.Mass." column of Table 16.

In Table 16, ^{the symbols described in the "B 1} B ² "column and the "Hd" column are defined in the same way as the symbols in Table 1 to Table 9(b) and Table 10 to Table 11 in the specification of this case.

Synthesis Example 241

Except for keeping 2-chlorobenzylacetonitrile at its molar ratio and replacing it with 3-cyanoacetoxybenzoic acid, and keeping barbituric acid at its molar ratio and replacing it with benzylacetonitrile, the rest In the same manner as in Synthesis Example 92, the compound represented by formula (I-118) (Compound 01-24) was obtained.

<Identification of the compound represented by formula (I-118) (compound 01-24)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Exact Mass: 445

Synthesis Example 242

In addition to maintaining the molar ratio of phthalonitrile and substituting 4-nitrophthalonitrile, 2-chlorobenzylacetonitrile maintains its molar ratio and substituting 3-cyanoacetonitrile with 3-cyanoacetonitrile, and the barbi Except that uric acid maintains its molar ratio and is substituted with benzylacetonitrile, the rest is the same as in Synthesis Example 92 to obtain the compound represented by formula (I-119) (compound 01-378).

<Identification of the compound represented by formula (I-119) (compound 01-378)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Exact Mass: 490

Synthesis Example 243

Except for keeping 4-cyanoacetoxybenzoic acid at its molar ratio and replacing it with 3-cyanoacetoxybenzoic acid, and keeping barbituric acid at its molar ratio and replacing it with benzylacetonitrile, Otherwise, the compound represented by formula (I-120) (compound 01-138) was obtained in the same manner as in Synthesis Example 93.

<Identification of the compound represented by formula (I-120) (compound 01-138)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Exact Mass: 513

Resin synthesis example 1

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was placed, and heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxy tricyclo [5.2. 1.0 ^2,6 ] A mixed solution of 289 parts of mixture of decane-9-yl ester and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dripping was completed, the solution was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin B1) with a solid content of 35.0%. The weight average molecular weight of the obtained resin B1 was 8800, the dispersion degree was 2.1, and the acid value of the solution was 28 mg-KOH/g.

Resin synthesis example 2

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, replaced with a nitrogen atmosphere, and 350 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85°C while stirring. Then, 70 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate or/and 3,4-epoxy tricyclo[ 5.2.1.0 ^{A mixed solution of 202 parts of 2,6} ]decane-9-yl ester mixture, 78 parts of vinyl toluene (isomer mixture), and 100 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 167 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the starter solution was dropped, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of the copolymer (resin B5) with a solid content of 38.1%. The weight average molecular weight of the obtained resin B5 was 10400, the degree of dispersion was 2.03, and the acid value of the solution was 53 mg-KOH/g.

Resin synthesis example 3

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, replaced with a nitrogen atmosphere, and 362 parts of propylene glycol monomethyl ether acetate was placed and heated to 80°C while stirring. Then, 58 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate or/and 3,4-epoxytricyclo[ 5.2.1.0 ^{A mixed solution of 167 parts of a mixture of 2,6} ]decane-9-yl ester, 65 parts of 2-ethylhexyl acrylate, and 111 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 210 parts of propylene glycol monomethyl ether acetate was dissolved in which 27 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved was dropped over 5.5 hours. After the starter solution was dropped, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of the copolymer (resin B6) with a solid content of 29.8%. The weight average molecular weight of the obtained resin B6 was 10900, the dispersion degree was 2.25, and the acid value of the solution was 44 mg-KOH/g.

Comparative example 1

Mixed

Pigment: C.I. Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts

, Use a bead mill to prepare a pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed. In addition,

Mixed

Pigment: 22 parts of C.I. Pigment Yellow 138, 7.1 parts of dispersant, 9.3 parts of resin, and solvent (E): 140 parts of propylene glycol monomethyl ether acetate. The pigment was dispersed using a bead mill to obtain a pigment dispersion.

Then, mix the total amount of the obtained pigment dispersion (colorant (A2) containing liquid); the total amount of the obtained pigment dispersion; resin (B): 48 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 11 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.7 parts;

The polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE- 01; BASF Corporation) 4.5 parts; Adhesive promoter: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.57 parts; Solvent (E): 4-hydroxy-4 -85 parts of methyl-2-pentanone; solvent (E): 330 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (TORAY polysiloxane SH8400; TORAY Dow Corning (Stock) System) 0.090 parts; mixed to obtain a comparatively colored curable composition 1.

[Creation of coloring patterns]

On a 2 inch square glass substrate (EagleXG; manufactured by Corning), the comparatively colored curable composition 1 was applied by a spin coating method, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the distance between the substrate on which the colored curable composition layer was formed and the quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon (Stock)) was used. Under the atmosphere, the distance was 80 mJ/cm ^{Exposure of 2} (365nm standard) exposure. In addition, the photomask used a pattern formed with a row pitch of 100 μm. The colored coating film after exposure was immersed in an aqueous solution containing 0.12% of a non-ionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds for development, and washed with water. The colored coating film was post-baked at 230°C for 30 minutes to obtain a colored pattern.

The film thickness of the obtained colored pattern was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The film thickness of the colored pattern is shown in the column of "film thickness" in Table 17.

[Measurement of initial brightness]

For the obtained coloring pattern, use a color measuring machine (OS vs-S vs-200; Olympus (stock) system) to measure the spectroscopy, and use the characteristic function of the C light source to determine the xy chromaticity coordinates in the XY Z color system of CIE ( x, y) and stimulus value Y. The larger the value of Y, the higher the brightness.

[Lightfastness evaluation]

A UV cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA (share); intercepting light below 380nm) is placed on the colored pattern obtained, and a light resistance tester (Sun-Test CPS+: manufactured by Toyo Seiki Co., Ltd.) Carry out the light fastness test of irradiating xenon lamp for 15 hours. When the stimulus value Y before the light resistance test (the initial brightness obtained above) is taken as 100%, the relative value (%) of the stimulus value Y after the light resistance test is shown in the column of "Brightness change rate" in Table 17 . The closer the brightness change rate is to 100%, the higher the light resistance.

Example 1-1

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, the total amount of the pigment composition composed of coloring agent (A): 20 parts of the compound represented by formula (I-1) and coloring agent (A): CI Pigment Yellow 138 2.2 parts, dispersant (BYK- LPN6919; manufactured by BYK Chemie Japan Co., Ltd.) 26 parts, resin (B): resin B1 solution 44 parts, and solvent (E): propylene glycol monomethyl ether acetate 350 parts, using a bead mill to make A pigment composition composed of the compound shown in (I-1) and CI Pigment Yellow 138 is dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (TORAY polysiloxane SH8400; TORAY Dow Corning ( (Stock) system) 0.090 parts; to obtain a colored curable composition 1-1.

Except that the comparatively colored curable composition 1 was replaced with the colored curable composition 1-1, the remaining system was applied in the same manner as in Comparative Example 1 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 17.

Example 1-2 to Example 1-60

Except that the compound represented by formula (I-1) was substituted with the compound shown in the column of "XXXXX" in Table 17, the rest was performed in the same manner as in Example 1-1 to obtain the "coloring" in Table 17 Color the curable composition shown in the "curable composition" column to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 17.

Example 1A-1

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mix the total amount of the pigment composition composed of coloring agent (A): 20 parts of compound 136, and coloring agent (A): CI Pigment Yellow 138 2.2 parts, 26 parts of dispersant solution (solid content 60%), resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead grinder to disperse the pigment composition containing compound 136 and CI Pigment Yellow 138 to obtain color Composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (TORAY polysiloxane SH8400; TORAY Dow Corning ( (Stock) system) 0.090 parts; to obtain a colored curable composition 1A-1.

Except that the comparative colored curable composition 1 was replaced with the colored curable composition 1A-1, the remaining system was performed in the same manner as in Comparative Example 1, and a colored pattern was obtained. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the "Film Thickness" and "Luminance Change Rate" columns in Table 18.

Example 1A-2 to Example 1A-231

Except for substituting compound 136 with the compound shown in the column of "XXXXX" in Table 18 to Table 21, the procedure was carried out in the same manner as in Example 1A-1 to obtain the "coloring curability" in Table 18 to Table 21. The colored curable composition shown in the column of "Composition" obtains a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 18 to Table 21.

Comparative example 2

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mixed pigment: CI Pigment Yellow 138 22 parts, dispersant 7.1 parts, resin 9.3 parts, and solvent (E): propylene glycol monomethyl ether acetate 140 parts, using a bead mill to disperse the pigment to obtain the pigment Dispersions.

Then, mix the total amount of the obtained pigment dispersion (colorant (A2) containing liquid); the total amount of the obtained pigment dispersion; resin (B): 48 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 11 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.7 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.5 parts; Adhesion promoter: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.57 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 330 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; and comparatively colored curable composition 2 was obtained.

[Creation of coloring patterns]

On a 2-inch square glass substrate (EagleXG; manufactured by Corning Corporation), the comparatively colored curable composition 2 was applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the distance between the substrate on which the colored curable composition layer was formed and the quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon (Stock)) was used. Under the atmosphere, the distance was 80 mJ/cm ^{Exposure of 2} (365nm standard) exposure. In addition, the photomask used a pattern formed with a row pitch of 100 μm. The colored coating film after exposure was immersed in an aqueous solution containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds to develop, and then washed with water. The colored coating film was post-baked at 230°C for 30 minutes to obtain a colored pattern.

The film thickness of the obtained colored pattern was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The film thickness of the colored pattern is shown in the column of "film thickness" in Table 22.

[Measurement of initial brightness]

Regarding the obtained coloring pattern, a color measuring machine (OS vs-S vs-200; Olympus (stock) system) was used to measure the spectroscopy, and the characteristic function of the C light source was used to determine the xy chromaticity coordinates in the XY Z color system of CIE ( x, y) and stimulus value Y. The larger the value of Y, the higher the brightness.

[Lightfastness evaluation]

A UV cut filter (COLORED OPTICAL GLASS L38; made by HOYA (share); intercepting light below 380nm) is placed on the colored pattern obtained, and a light resistance tester (Sun-Test CPS+: manufactured by Toyo Seiki Seisakusho) is used. Carry out the light fastness test of irradiating xenon lamp for 15 hours. When the stimulus value Y before the light resistance test (the initial brightness obtained above) is taken as 100%, the relative value (%) of the stimulus value Y after the light resistance test is shown in the column of "Brightness change rate" in Table 22 . The closer the brightness change rate is to 100%, the higher the light resistance.

Example 2-1

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, the total amount of the pigment composition composed of coloring agent (A): 20 parts of the compound represented by formula (I-1) and coloring agent (A): CI Pigment Yellow 185 2.2 parts, dispersant (BYK- LPN6919; manufactured by BYK Chemie Japan Co., Ltd.) 26 parts, resin (B): resin B1 solution 44 parts, and solvent (E): propylene glycol monomethyl ether acetate 350 parts, using a bead mill to make the inclusion formula The compound shown in (I-1) and the pigment composition of CI Pigment Yellow 185 are dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; a colored curable composition 2-1 was obtained.

Except that the comparative colored curable composition 2 was replaced with the colored curable composition 2-1, the remaining system was applied in the same manner as in Comparative Example 2 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 22.

Example 2-2 to Example 2-60

Except that the compound represented by formula (I-1) was substituted with the compound shown in the column of "XXXXX" in Table 22, the rest was performed in the same manner as in Example 2-1 to obtain the "coloring" in Table 22 Color the curable composition shown in the "curable composition" column to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 22.

Example 2A-1

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mix the total amount of the pigment composition composed of coloring agent (A): 20 parts of compound 136, and coloring agent (A): CI Pigment Yellow 185 2.2 parts, 26 parts of dispersant solution (solid content 60%), resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead grinder to disperse the pigment composition containing compound 136 and CI Pigment Yellow 185 to obtain color Composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; to obtain a colored curable composition 2A-1.

Except that the comparatively colored curable composition 2 was replaced with the colored curable composition 2A-1, the remaining system was performed in the same manner as in Comparative Example 2 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 23.

Example 2A-2 to Example 2A-231

Except that compound 136 was replaced with the compound shown in the column of "XXXXX" in Table 23 to Table 26, the rest was performed in the same manner as in Example 2A-1 to obtain the "coloring and hardening" in Table 23 to Table 26. Color the curable composition shown in the column of "Sexual composition" to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 23 to Table 26.

Comparative example 3

Mixed

Pigment: CI Pigment Green 58 47 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mixed pigment: CI Pigment Yellow 138 22 parts, dispersant 7.1 parts, resin 9.3 parts, and solvent (E): propylene glycol monomethyl ether acetate 140 parts, using a bead mill to disperse the pigment to obtain the pigment Dispersions.

Then, mix the total amount of the obtained pigment dispersion (colorant (A2) containing liquid); the total amount of the obtained pigment dispersion; resin (B): 48 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 11 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.7 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Co., Ltd.) 4.5 parts; Adhesive promoting agent: 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) 0.57 parts; Solvent (E): 4-hydroxy- 85 parts of 4-methyl-2-pentanone; solvent (E): 330 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; TORAY Dow Corning ( (Stock) system) 0.090 parts; and comparatively colored curable composition 3 was obtained.

[Creation of coloring patterns]

On a 2 inch square glass substrate (EagleXG; manufactured by Corning Corporation), the comparatively colored curable composition 3 was applied by a spin coating method, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the distance between the substrate on which the colored curable composition layer was formed and the quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon (Stock)) was used. Under the atmosphere, the distance was 80 mJ/cm ^{Exposure of 2} (365nm standard) exposure. In addition, the photomask used a pattern formed with a row pitch of 100 μm. The colored coating film after exposure was immersed in an aqueous solution containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds to develop, and then washed with water. The colored coating film was post-baked at 230°C for 30 minutes to obtain a colored pattern.

The film thickness of the obtained colored pattern was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The film thickness of the colored pattern is shown in the column of "film thickness" in Table 27.

[Measurement of initial brightness]

Regarding the obtained coloring pattern, a color measuring machine (OS vs-S vs-200; Olympus (stock) system) was used to measure the spectroscopy, and the characteristic function of the C light source was used to determine the xy chromaticity coordinates in the XY Z color system of CIE ( x, y) and stimulus value Y. The larger the value of Y, the higher the brightness.

[Lightfastness evaluation]

A UV cut filter (COLORED OPTICAL GLASS L38; made by HOYA (share); intercepting light below 380nm) is placed on the colored pattern obtained, and a light resistance tester (Sun-Test CPS+: manufactured by Toyo Seiki Seisakusho) is used. Carry out the light fastness test of irradiating xenon lamp for 15 hours. When the stimulus value Y before the light resistance test (the initial brightness obtained above) is taken as 100%, the relative value (%) of the stimulus value Y after the light resistance test is shown in the column of "Brightness change rate" in Table 22 . The closer the brightness change rate is to 100%, the higher the light resistance.

Example 3-1

Mixed

Pigment: CI Pigment Green 58 46 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder In addition, a pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, the total amount of the pigment composition composed of the coloring agent (A): 21 parts of the compound represented by the formula (I-1) and 1.1 parts of the pigment: CI Pigment Green 58 is mixed, and the dispersant (BYK-LPN6919; BYK Chemie 26 parts made by Japan Co., Ltd., resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead mill to include formula (I-1) The compound shown and the pigment composition of CI Pigment Green 58 are dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toraay Silicone SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; to obtain a colored curable composition 3-1.

Except that the comparative colored curable composition 3 was replaced with the colored curable composition 3-1, the remaining system was applied in the same manner as in Comparative Example 3 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 27.

Example 3-2 to Example 3-60

Except that the compound represented by formula (I-1) was substituted with the compound shown in the column of "XXXXX" in Table 27, the rest was performed in the same manner as in Example 3-1 to obtain the "coloring" in Table 27 Color the curable composition shown in the "curable composition" column to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 27.

Example 3A-1

Mixed

Pigment: CI Pigment Green 58 46 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder In addition, a pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mix the total amount of the pigment composition consisting of coloring agent (A): Compound 136 21 parts, and pigment: CI Pigment Green 58 1.1 parts, dispersant solution (solid content 60%) 26 parts, resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead mill, the pigment composition containing compound 136 and CI Pigment Green 58 was dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (TORAY polysiloxane SH8400; TORAY Dow Corning ( (Stock) system) 0.090 parts; to obtain a colored curable composition 3A-1.

Except that the comparative colored curable composition 3 was replaced with the colored curable composition 3A-1, the remaining system was performed in the same manner as in Comparative Example 3 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 28.

Example 3A-2 to Example 3A-231

Except that compound 136 was substituted with the compound shown in the column of "XXXXX" in Table 28 to Table 31, the rest was performed in the same manner as in Example 3A-1 to obtain the "coloring and hardening property" in Table 28 to Table 31. The colored curable composition shown in the column of "Composition" obtains a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 28 to Table 31.

Example 3B-1

Mixed pigment: CI Pigment Green 58 46 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, grinding with beads The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared by the machine. In addition, mix the total amount of the pigment composition composed of coloring agent (A): compound 136 21 parts, and pigment: CI Pigment Green 59 1.1 parts, dispersant solution (solid content 60%) 26 parts, resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead mill, the pigment composition containing compound 136 and CI Pigment Green 58 was dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; to obtain a colored curable composition 3B-1.

Except that the comparatively colored curable composition 3 was replaced with the colored curable composition 3B-1, the remaining system was applied in the same manner as in Comparative Example 3 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 32.

Example 3B-2 to Example 3B-231

Except that compound 136 was substituted with the compound shown in the column of "XXXXX" in Table 32 to Table 35, the rest was performed in the same manner as in Example 3B-1 to obtain the "coloring hardening property" in Table 32 to Table 35. The colored curable composition shown in the column of "Composition" obtains a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 32 to Table 35.

Example 3C-1

Mixed

Pigment: CI Pigment Green 58 46 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B5 solution 57 parts, and solvent (E): propylene glycol monomethyl ether acetate 220 parts, using a bead grinder The pigment dispersion liquid (colorant (A2) containing liquid) in which the pigment is dispersed is prepared. In addition, mix the total amount of the pigment composition composed of coloring agent (A): compound 136 21 parts, and pigment: CI Pigment Green 7 1.1 parts, dispersant solution (solid content 60%) 26 parts, resin (B): 44 parts of resin B1 solution, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, using a bead mill, the pigment composition containing compound 136 and CI Pigment Green 58 was dispersed to obtain a colored composition.

Then, mix the total amount of the obtained pigment dispersion liquid (colorant (A2) containing liquid); the total amount of the obtained coloring composition; resin (B): 8.3 parts of resin B6 solution; polymerizable compound (C): polymerizable Compound (A9570W; manufactured by Shinnakamura Chemical Industry Co., Ltd.) 9.9 parts; polymerization initiator (D): compound represented by the following formula (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 5.0 parts;

Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; BASF Corporation) 4.0 parts; Adhesive promoting agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.50 parts; Solvent (E): 4-hydroxy-4- 85 parts of methyl-2-pentanone; solvent (E): 110 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silionce SH8400; TORAY Dow Corning (stock) Preparation) 0.090 parts; to obtain a colored curable composition 3C-1.

Except that the comparatively colored curable composition 3 was replaced with the colored curable composition 3C-1, the remaining system was applied in the same manner as in Comparative Example 3 to obtain a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 36.

Example 3C-2 to Example 3C-231

Except that compound 136 was substituted with the compound shown in the column of "XXXXX" in Table 36 to Table 39, the rest was performed in the same manner as in Example 3C-1 to obtain the "coloring hardening property" in Table 36 to Table 39 The colored curable composition shown in the column of "Composition" obtains a colored pattern. In addition, the initial brightness measurement and light resistance evaluation were performed. The results are shown in the columns of "Film Thickness" and "Luminance Change Rate" in Table 36 to Table 39.

From the above results, it can be seen that the colored pattern formed by the colored hardenable composition containing the pigment composition of the present invention can improve the light resistance.

[Industrial Utilization Possibility]

The pigment composition, coloring composition, and coloring curable composition of the present invention can be used to form a color filter with improved light resistance, so it can be suitably used in display devices such as color filters or liquid crystal display devices.

Claims (16)

A pigment composition comprising: a compound represented by formula (I), an isoindoline compound selected from the group consisting of quinophthalone compounds, compounds represented by formula (I), and a green colorant At least 1 species of the group;

In formula (I), L ¹ represents -CO- or -SO ₂ -; R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ ,- OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO -R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, which may have substituents A hydrocarbon group with 1 to 40 carbon atoms or a heterocyclic group that may have substituents; R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring; R ¹¹ and R ¹⁰¹ each independently represent a hydrocarbon group with 1 to 40 carbon atoms or a heterocyclic group ^{that may have substituents; R 102} represents a hydrogen atom, a hydrocarbon group with 1 to 40 carbons that may have substituents Or a heterocyclic group that may have a substituent; M represents a hydrogen atom or an alkali metal atom; ^{when there are plural R 101} , R ¹⁰² and M, their equivalent systems may be the same or different; the wavy line represents the E body or Z body. The pigment composition described in item 1 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ia);

In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above, L ² represents -CO- or -SO ₂ -, and R ¹⁴ represents the number of carbon atoms that may have a substituent. Hydrocarbyl groups up to 40 or heterocyclic groups which may have substituents. The pigment composition as described in item 2 of the scope of patent application, wherein R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group. The pigment composition described in item 2 or 3 of the scope of the patent application, wherein R ¹¹ and R ¹⁴ are independently an alkyl group having 1 to 40 carbon atoms which may have a substituent, a phenyl group which may have a substituent, and Substituent naphthyl, optionally substituted tetrahydronaphthyl, optionally substituted thienyl, optionally substituted furyl or optionally substituted pyridyl. The pigment composition described in item 1 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ib);

In formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as the foregoing; R ²⁰ and R ³⁰ are bonded to form ring Q; ring Q may have substituents, A ring with 5 to 7 members, the ring Q may be a hydrocarbon ring or a heterocyclic ring; in the ring Q, it may be a ring with a member selected from the group consisting of a hydrocarbon ring and a heterocyclic ring. The ring or the single ring is condensed to form a condensed ring bond. The pigment composition according to item 5 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ic);

In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above; R ⁶ and R ⁷ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, may have The substituent is a hydrocarbon group with 1 to 40 carbon atoms or a heterocyclic ring which may have a substituent; R ¹⁰¹ , R ¹⁰² and M have the same meaning as described above. The pigment composition according to any one of items 1 to 3, 5, and 6 in the scope of the patent application, wherein R ¹ is a hydrogen atom, and R ² to R ^{5 are} independently a hydrogen atom or a nitro group. A coloring composition containing the pigment composition described in any one of items 1 to 7 of the scope of patent application and a solvent. The coloring composition described in item 8 of the scope of patent application further contains resin. The coloring composition described in item 8 of the scope of patent application further contains the compound represented by formula (I), a yellow colorant or a green colorant. A coloring and curable composition containing the coloring composition and polymerizable compound described in item 8 of the scope of patent application. The coloring composition described in item 11 of the scope of patent application further contains a polymerization initiator. A color filter is formed by the colored composition described in item 8 of the scope of patent application or the colored hardenable composition described in item 11 of the scope of patent application. A liquid crystal display device containing the color filter described in item 13 of the scope of patent application. A method for producing a colored composition that contains a compound represented by the formula (I) and a group consisting of a quinophthalone compound, an isoindoline compound other than the compound represented by the formula (I), and a green coloring agent At least one of the pigment composition, solvent, and colorant (A2) containing liquid containing colorant (A2) and solvent are mixed;

In formula (I), L ¹ represents -CO- or -SO ₂ -; R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ ,- OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO -R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, which may have substituents A hydrocarbon group with 1 to 40 carbon atoms or a heterocyclic group that may have substituents; R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring; R ¹¹ and R ¹⁰¹ each independently represent a hydrocarbon group with 1 to 40 carbon atoms or a heterocyclic group ^{that may have substituents; R 102} represents a hydrogen atom, a hydrocarbon group with 1 to 40 carbons that may have substituents Or a heterocyclic group that may have a substituent; M represents a hydrogen atom or an alkali metal atom; ^{when there are more than one R 101} , R ¹⁰² and M, their equivalent systems may be the same or different; the wavy line represents the E body Or Z body. The manufacturing method described in claim 15, wherein the coloring agent (A2) is one or more coloring agents selected from the group consisting of compounds represented by formula (I), green coloring agents, and yellow coloring agents.