WO2010122777A1 - Colored composition, color filter, and color liquid crystal display element - Google Patents

Abstract

Disclosed is a colored composition which enables the production of a picture cell having a high contrast ratio even when a dispersant is contained in a small quantity, and which has excellent storage stability. The colored composition is characterized by comprising the following components (A), (B) and (C): (A) a coloring agent, (B) a (co)polymer having a group represented by formula (1); and (C) a solvent. In formula (1), R1 represents an alkylene group having 2 to 6 carbon atoms which may have a substituent; R2 and R3 independently represents a hydrogen atom, or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, wherein R2 and R3 may be bound to each other to form a cyclic structure; and "*" represents a bond.

Description

Coloring composition, color filter and color liquid crystal display element

The present invention relates to a novel compound that can be suitably used for a pigment dispersant, a surface treatment agent, and the like used in paints, printing inks, inkjet inks, color filter coloring compositions, electrophoretic display element coloring compositions, and the like, The present invention relates to a colored composition using the (co) polymer, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

The pigment has a clear color tone, excellent coloring power, heat resistance and light resistance, and is used in a wide range of fields. However, as the pigment becomes finer, it becomes difficult to disperse stably. In particular, in the field of color filters used in liquid crystal display devices and solid-state imaging devices, pigments used tend to become finer with the demand for higher brightness and higher contrast. In order to disperse stabilized pigments stably, research and development relating to dispersants and surface treatments are being actively conducted. For example, Patent Document 1 proposes the use of a pigment dispersant obtained by copolymerizing a vinyl monomer having a nitrogen-containing heterocyclic group. Patent Document 2 proposes the use of a polymer compound having a pigment adsorbing functional group.

JP 2003-26949 A JP 2008-83594 A

On the other hand, since the coloring composition used for the production of the color filter also requires functions such as photocurability and alkali developability, the content of the pigment dispersant and the surface treatment agent in the composition is small. Is preferred. Against this background, there is a strong demand for the development of a coloring composition that can form a pixel with a high contrast ratio and has excellent storage stability even when the content of the dispersant is small. Development of dispersants and surface treatment agents that can satisfy the requirements is desired.

Therefore, the subject of this invention is providing the novel compound which can be used as a dispersing agent and surface treating agent with extremely high affinity to a pigment.
Another object of the present invention is to provide a colored composition that can form a pixel with a high contrast ratio and has excellent storage stability even when the content of the dispersant is small.
Furthermore, the subject of this invention is providing the color liquid crystal display element which comprises the color filter provided with the pixel formed from the said coloring composition, and the said color filter.

Among various acidic compounds and basic compounds, the present inventors have used 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0]. A cyclic amidine compound such as non-5-ene (DBN) is a diketopyrrolopyrrole pigment. I. Pigment Red 254 (1,4-diketo-3,6-di (4-chlorophenyl) pyrrolo [3,4-c] pyrrole) and C.I. which is a phthalocyanine pigment. I. It was found that Pigment Green 36 (brominated chlorinated copper phthalocyanine) has a particularly high ability to dissolve and has an extremely high affinity for pigments. Based on such knowledge, the present inventors further modified the cyclic amidine compound. As a result, the novel compound represented by the following formula (6) has extremely high affinity for the pigment, and the (co) polymer thereof. It was found that the above-mentioned problems can be solved by using as a pigment dispersant, and the present invention has been completed.

That is, the present invention includes the following components (A), (B) and (C):
(A) a colorant,
(B) A (co) polymer having a group represented by the following formula (1) (hereinafter sometimes referred to as “(B) (co) polymer”), and (C) a solvent. A colored composition is provided.

[In Formula (1), R ¹ represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ² and R ³ each independently have a hydrogen atom or a substituent. An optionally substituted hydrocarbon group having 1 to 10 carbon atoms is shown. However, R ² and R ³ may be bonded to each other to form a cyclic structure. “*” Indicates a bond. ]

The present invention also provides a color filter comprising a colored layer formed using the above colored composition, and a color liquid crystal display device comprising the color filter. Here, the “colored layer” means a pixel, a black matrix, a black spacer, or the like used for a color filter.

Furthermore, the present invention provides a compound represented by the following formula (6) (hereinafter sometimes referred to as “compound (6)”) or a salt thereof.

[In Formula (6), R ¹ represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ² and R ³ each independently have a hydrogen atom or a substituent. Or a hydrocarbon group having 1 to 10 carbon atoms (wherein R ² and R ³ may combine with each other to form a cyclic structure), R ⁴ represents a hydrogen atom or a methyl group, and X represents — CO—, —C (═O) O — (*), —CONH — (*) or a phenylene group (where “*” is a bond bonded to Y), Y is a single bond or divalent Represents a linking group. ]

Furthermore, the present invention has a repeating unit represented by the following formula (2), characterized by (co) polymerizing a monomer containing the compound represented by the above formula (6) or a salt thereof. A method for producing a (co) polymer is provided.

[In Formula (2), R ¹ represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ² and R ³ each independently have a hydrogen atom or a substituent. Or a hydrocarbon group having 1 to 10 carbon atoms (wherein R ² and R ³ may combine with each other to form a cyclic structure), R ⁴ represents a hydrogen atom or a methyl group, and X represents — CO—, —C (═O) O — (*), —CONH — (*) or a phenylene group (where “*” is a bond bonded to Y), Y is a single bond or divalent Represents a linking group. ]

The novel compound of the present invention has extremely high affinity for the pigment, and can be suitably used as a pigment dispersant or surface treatment agent as it is. Moreover, since this novel compound has an ethylenically unsaturated bond, it can be used as a polymer dispersant by itself or by (co) polymerization with a vinyl monomer such as an acrylic monomer or a styrene monomer. .
Further, the colored composition of the present invention can form a pixel having a high contrast ratio even when the content of the dispersant is small, and is excellent in storage stability. Therefore, the colored composition of the present invention is used for various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. In addition to production, it can be used very suitably for paints, printing inks, inkjet inks, and coloring compositions for electrophoretic display elements.

FIG. 1 is a diagram showing the measurement result of ¹ H-NMR of the compound (2a). FIG. 2 is a graph showing the results of ¹³ C-NMR measurement of compound (2a). FIG. 3 is a diagram showing a measurement result of an infrared spectrum of the compound (2a).

Hereinafter, the present invention will be described in detail.
(Coloring composition)
Hereinafter, the constituent components of the colored composition of the present invention will be described.

-(A) Colorant-
The (A) colorant in the present invention is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use such as a color filter. Specifically, any of pigments, dyes, and natural pigments can be used as the colorant. Of these, organic pigments and inorganic pigments are preferred because color filters are required to have heat resistance.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer and Colorists). Specific examples include those with the following color index (CI) numbers.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

In the present invention, the organic pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in JP-A-8-259876, and various commercially available pigment-dispersing polymers or oligomers. As the polymer coating method on the carbon black surface, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed.
In the present invention, the colorant (A) can be used alone or in admixture of two or more.

When the colored composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development, the colorant (A) is preferably a colorant having high color developability, specifically an organic pigment. Is preferably used.
On the other hand, when the colored composition of the present invention is used for forming a black matrix, the black matrix is required to have a light-shielding property. Therefore, an organic pigment or carbon black is preferably used as the colorant (A).

In the present invention, the content of (A) the coloring agent varies depending on the use of the coloring composition. For example, in the case of a thermosetting or radiation curable coloring composition used for the production of a color filter, it is colored from the point of forming a pixel having excellent transparency and color purity, or a black matrix having excellent light shielding properties. The total solid content of the composition is preferably 5 to 70% by mass, more preferably 5 to 60% by mass. Solid content here is components other than the (C) solvent mentioned later.

-(B) (Co) polymer-
The (B) (co) polymer in the present invention is a (co) polymer having a group represented by the above formula (1), but functions as a dispersant for the (A) colorant.
First, the definition of symbols in formula (1) will be described.
In the above formula (1), R ¹ represents an optionally substituted alkylene group having 2 to 6 carbon atoms. Such an alkylene group is preferably an alkylene group having 2 to 3 carbon atoms, specifically Is preferably an ethylene group, a trimethylene group or a methylethylene group.
R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Examples of such hydrocarbon groups include alkyl groups having 1 to 6 carbon atoms. An aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 16 carbon atoms are preferable.
R ² and R ³ may be bonded to each other to form a cyclic structure. The cyclic structure is preferably a 5- to 9-membered heterocyclic ring, particularly a 5- to 7-membered heterocyclic ring, and R ³ is In addition to the adjacent nitrogen atom, it may further have a hetero atom. Particularly preferable examples of the 5- to 9-membered heterocyclic ring include a pyrrolidine ring, a piperidine ring, and a hexamethyleneimine ring, and these heterocyclic rings are alkylenes having 2 to 6 carbon atoms in which R ² and R ³ are bonded to each other. It is formed by constructing a group.
Among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or R ² and R ³ are preferably a 5- to 9-membered heterocyclic ring formed by bonding to each other to form an alkylene group having 2 to 6 carbon atoms. In the present specification, examples of the “aryl group having 6 to 14 carbon atoms” include a phenyl group and a naphthyl group, and examples of the “aralkyl group having 7 to 16 carbon atoms” include a benzyl group and a phenylethyl group. Groups.
Examples of the substituent in R ¹ , R ² and R ³ include a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a carboxyl group, and an alkoxy group. Can do.
As the “hydrocarbon group having 1 to 6 carbon atoms” in the present specification, for example, a linear or cyclic alkyl group is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- Examples thereof include a butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group. The chain includes both linear and branched chains. In addition, examples of the “substituted amino group” in the present specification include an amino group having at least one alkyl group. Further, the “alkoxy group” in the present specification is preferably an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group. N-pentyloxy group and n-hexyloxy group.
Preferable specific examples of the group represented by the above formula (1) include groups represented by the following formulas (1-1) to (1-3).

[In formulas (1-1) to (1-3), “*” indicates a bond. ]

(B) The (co) polymer is not particularly limited as long as it has a group represented by the above formula (1), but the side chain of the (co) polymer has the above formula (1). Those having the group represented are preferred. Examples of the (B) (co) polymer include (co) polymers having a repeating unit represented by the following formula (2) (hereinafter referred to as “repeating unit (2)”).

[In the formula ^{(2), R 1 ~ R} 3 have the same meanings as R ¹ ~ R ³ in the above formula (1), R ⁴ represents a hydrogen atom or a methyl group, X is -CO -, - C (= O) represents O — (*), —CONH — (*) or a phenylene group (where “*” represents a bond bonded to Y), and Y represents a single bond or a divalent linking group. ]

In the above formula (2), examples of the divalent linking group for Y include a methylene group, an alkylene group, an oxymethylene group, an oxyalkylene group, a methyleneoxyalkylene group, an alkyleneoxyalkylene group, a dialkylsilylene group, and an alkylarylsilylene. Group, a diarylsilylene group, and these linking groups optionally have a substituent. Examples of the substituent include those similar to the substituents for R ¹ , R ² and R ³ .
The alkylene group, oxyalkylene group, methyleneoxyalkylene group and alkyleneoxy group of the alkyleneoxyalkylene group preferably have 2 to 6 carbon atoms. As the alkylene group, the same groups as those described above for R ¹ can be mentioned. Examples of the oxyalkylene group include an oxyethylene group, an oxytrimethylene group, an oxytetramethylene group, an oxypentamethylene group, and an oxyhexamethylene group. Examples of the methyleneoxyalkylene group include a methyleneoxyethylene group and a methyleneoxytrimethylene group. Examples of the alkyleneoxyalkylene group include an ethyleneoxyethylene group and an ethyleneoxytrimethylene group.
As the alkyl in the dialkylsilylene group and the alkylarylsilylene group, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
The aryl in the dialkylsilylene group, alkylarylsilylene group and diarylsilylene group is preferably an aryl group having 6 to 14 carbon atoms.
Among them, the divalent linking group in Y is preferably a methylene group or an alkylene group having 2 to 6 carbon atoms, particularly preferably a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a tetramethylene group, or a pentamethylene group.

R ⁴ is particularly preferably a hydrogen atom among a hydrogen atom and a methyl group.

X is particularly preferably a phenylene group among -CO-, -C (= O) O-(*), -CONH-(*) and a phenylene group. Specific examples include compounds represented by the following formula (7) or (8). Note that “*” indicates a bond that bonds with Y.

[In the formula (7), R ⁴ represents a hydrogen atom or a methyl group, Y ¹ represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and R ¹² represents a methylene group or an alkylene group having 2 to 6 carbon atoms. Show. ]

[In Formula (8), R ⁴ represents a hydrogen atom or a methyl group, Y ¹ represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and R ¹² represents a methylene group or an alkylene group having 2 to 6 carbon atoms. Show. ]

R ¹² is preferably an ethylene group, a trimethylene group or a tetramethylene group among a methylene group and an alkylene group having 2 to 6 carbon atoms.

The compound (6) that gives the repeating unit (2) and the compound (6) in which X is a phenylene group or —CO— is produced through, for example, Step 1 and Step 2, as shown in Scheme I below. be able to.

(In Scheme I, R ¹ , R ² , R ³ and Y have the same meanings as above. When X is a phenylene group, Z represents a group capable of nucleophilic reaction of compound (ii). When-, Y represents a single bond, and Z represents a halogen atom or a (meth) acryloyloxy group.)

When X is a phenylene group, Z in the formula (iii) is not particularly limited as long as the compound (ii) is a group capable of nucleophilic substitution reaction or nucleophilic addition reaction, and examples thereof include halogenated alkyl groups, alkoxysilyl groups. Group, glycidyloxyalkyl group, formyl group and the like.
In addition, when the compound of the formula (iii) is a halogenated alkyl group, the alkylene group represented by Y may be bonded to any of the ortho-position, meta-position and para-position of the phenylene group. Bonding is preferred.

In Scheme 1, Step 1 is a step of obtaining a compound (ii) by lithiation of the cyclic amidine compound (i).

Step 1 is performed by reacting 0.80 to 1.00 mol, preferably 0.90 to 0.95 mol of alkyllithium with 1 mol of the cyclic amidine compound (i) in a suitable solvent. As the cyclic amidine compound (i), for example, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, in the above formula (i), R ² and R ³ are bonded to each other to form tetramethylene. Compound formed as a group), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN, in the above formula (i), R ² and R ³ are bonded to each other to form an ethylene group) And the like).
Examples of the solvent used in Step 1 include ethers such as tetrahydrofuran, 1,4-dioxane, diethyl ether, and ethylene glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene, and xylene, and fats such as hexane and petroleum ether. Group hydrocarbons and the like. Examples of the alkyl lithium used in Step 1 include n-butyl lithium, s-butyl lithium, and t-butyl lithium.
The reaction temperature in Step 1 is −80 to 20 ° C., preferably −40 to 0 ° C. The reaction time in step 1 is appropriately set according to the reaction scale and the like, but is 1 to 12 hours, preferably 2 to 5 hours.

Step 2 is a step of reacting compound (ii) and compound (iii) to obtain compound (6) giving repeating unit (2).

Step 2 is performed by reacting 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol, of compound (iii) with respect to 1 mol of compound (ii).
When the compound (iii) is a styrene derivative having an electrophilic functional group, examples of the styrene derivative include o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and o- (1-chloroethyl) styrene. M- (1-chloroethyl) styrene, p- (1-chloroethyl) styrene, o- (2-chloroethyl) styrene, m- (2-chloroethyl) styrene, p- (2-chloroethyl) styrene, and the like. it can. Of these compounds, for example, p-chloromethylstyrene is sold by Tokyo Chemical Industry Co., Ltd.

On the other hand, in the compound (6) where X is —C (═O) O — (*), for example, the above compound (ii) is first reacted with an aldehyde or a ketone, and then the resulting alcohol is converted into (meth) acrylic acid. It can be produced by reacting with a halide, anhydrous (meth) acrylic acid or the like.

The reaction conditions in Step 2 can be appropriately set depending on the reaction substrate. For example, when compound (iii) is a styrene derivative, the reaction temperature is −80 to 40 ° C., preferably −20 to 30 ° C. 5 to 12 hours, preferably 0.5 to 3 hours.

A more specific reaction example in Step 2 is shown in Scheme II.

(In Scheme II, R ¹ , R ² , R ³ and R ⁴ have the same meanings as above. R ^a independently represents an alkyl group or an aryl group, and p represents an integer of 1 to 6. )

After Step 2, for example, the reaction solution is washed with water to remove unreacted compound (ii) and the like, and then reacted with carbon dioxide to temporarily form carbonate, and the carbonate is washed with an organic solvent. The compound (6) can be purified by decarboxylation of the carbonate in the presence of an alkali.
Organic solvents for washing carbonates include ethers such as tetrahydrofuran, 1,4-dioxane, diethyl ether and ethylene glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatics such as hexane and petroleum ether. Examples include hydrocarbons, esters such as methyl acetate, ethyl acetate, and propyl acetate. Examples of the alkali for decarboxylating the carbonate include sodium hydroxide and potassium hydroxide.

The compound (6) may be in the form of a salt. Examples of the salt of the compound (6) include inorganic acid salts such as hydrochloride, sulfate, nitrate, and carbonate, and organic acid salts such as acetate and citrate. Is mentioned.

Compound (6) or a salt thereof has a cyclic amidine structure and therefore has a very high affinity for the pigment, and can be suitably used as a pigment dispersant or a surface treatment agent as it is. In addition, since the compound (6) has an ethylenically unsaturated bond, a polymer dispersant can be obtained alone or by (co) polymerization with a vinyl monomer such as an acrylic monomer or a styrene monomer. it can.

The compound (6) giving the repeating unit (2) can be used alone or in admixture of two or more.

In the (B) (co) polymer, the content of the repeating unit (2) is usually 1% by mass or more, preferably 1 to 80% by mass, more preferably from the viewpoint of obtaining a desired effect. 1 to 50% by mass.

The (B) (co) polymer, together with the repeating unit (2), is represented by, for example, a repeating unit represented by the following formula (3) (hereinafter referred to as “repeating unit (3)”) or a following formula (4). At least one selected from the group consisting of a repeating unit (hereinafter referred to as “repeating unit (4)”) and a repeating unit represented by the following formula (5) (hereinafter referred to as “repeating unit (5)”): Can have.

[In Formula (3), R ⁵ has a hydrogen atom, a chain or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁶ represents a hydrogen atom or a methyl group. ]

[In the formula (4), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n is an integer of 0 to 5 Indicates. ]

[In the formula (5), R ⁹ represents an ethylene group and / or a propylene group, R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, and m represents 1 to 20 Indicates an integer. ]

In the above formula (3), examples of the substituent of the alkyl group represented by R ⁵ include a halogen atom and an alkoxy group having 1 to 6 carbon atoms. Examples of the substituent for the aryl group and aralkyl group include a chain-like alkyl group having 1 to 6 carbon atoms, a halogen atom, and an alkoxy group having 1 to 6 carbon atoms. The chain alkyl group includes both linear and branched chains.
R ⁵ in the above formula (3) is preferably a chain alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms, such as a methyl group, an ethyl group, or propyl group. Particularly preferred are a group, butyl group, 2-ethylhexyl group, phenyl group, benzyl group and phenylethyl group.

In the above formula (4), n is preferably 0 or 1, and when n is 1, R ⁸ is preferably a hydroxyl group.
R ¹⁰ in the above formula (5) is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group or a butyl group. M is preferably 1 to 10, and more preferably 1 to 5.

Examples of the monomer that gives the repeating unit (3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, and the like. These can be used alone or in admixture of two or more. Here, “(meth) acrylate” in the present specification means “acrylate or methacrylate”.

Monomers that give the repeating unit (4) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-vinylphenol, m-vinylphenol, Examples thereof include p-vinylphenol and p-hydroxy-α-methylstyrene. These can be used alone or in admixture of two or more.

Monomers that give the repeating unit (5) include 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, And methoxydipropylene glycol (meth) acrylate. These can be used alone or in admixture of two or more.

The (B) (co) polymer is an AB block copolymer or BAB having an A block having the repeating unit (2) and a B block not having the repeating unit (2) from the viewpoint of enhancing a desired effect. More preferably, it is a block copolymer. The (B) (co) polymer is a graft copolymer in which an A block having a repeating unit (2) is a polymer main chain, and a B block having no repeating unit (2) is branched from the polymer main chain. It may be a polymer. The copolymerization ratio (mass ratio) of A block / B block in such a block copolymer or graft copolymer is preferably 1/99 to 80/20, particularly preferably 1/99 to 50/50.

Examples of the monomer that gives the graft copolymer include N, N-methylenebisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and bisphenol A dimethacrylate. These can be used alone or in admixture of two or more.

The weight average molecular weight of the (B) (co) polymer in the present invention is preferably 1,000 to 30,000. By setting it within such a range, the colorant can be more stably dispersed.

In the A block, two or more repeating units (2) may be contained in one A block. In that case, each repeating unit may be contained in any form of random copolymerization or block copolymerization in the A block.

The B block has, for example, at least one selected from the group consisting of the repeating unit (3), the repeating unit (4), and the repeating unit (5). The repeating unit may be contained in any mode of random copolymerization and block copolymerization. Each repeating unit may be contained in one B block in two or more. In that case, each repeating unit may be contained in the B block in any form of random copolymerization and block copolymerization. In addition, the copolymerization ratio of a repeating unit (3), a repeating unit (4), and a repeating unit (5) can be set suitably.

Such a (B) (co) polymer can be produced, for example, by subjecting the above-mentioned monomer giving each repeating unit to living polymerization. Examples of the living polymerization method include JP-A-9-62002; JP-A-2002-31713; Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984); C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981); Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985); Hatada, K .; Ute, et al, Polym. J. et al. 18, 1037 (1986); Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989); Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985); Y. Sogoh, W .; R. Hertler et al., Macromolecules, 20, 1473 (1987); Polym. Sci. Part A Polym. Chem. 47, 3773-3794 (2009); Polym. Sci. Part A Polym. Chem. 47, 3544-3557 (2009), etc., can be used.

In the present invention, a dispersant other than the (B) (co) polymer may be used in combination with the (B) (co) polymer. (B) Examples of the dispersant other than the (co) polymer include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polyethylene glycol diester. Examples thereof include a dispersant, a sorbitan fatty acid ester dispersant, a fatty acid-modified polyester dispersant, an acrylic dispersant, and a pigment derivative.
Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK (BYK)), Disparon (manufactured by Enomoto Kasei Co., Ltd.), Solsperse ( Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (Tochem Products Co., Ltd.), Mega Fuck (Dainippon Ink Chemical Co., Ltd.) , Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.
These dispersants can be used alone or in admixture of two or more.

(B) The content of the (co) polymer is usually 1 to 200 parts by mass with respect to 100 parts by mass of the (A) colorant. In addition, in this invention, even if content of (B) (co) polymer is 30 mass parts or less with respect to 100 mass parts of (A) colorants, it can improve the dispersion stability of a colored composition. it can.

-(C) Solvent-
The colored composition of the present invention contains (C) a solvent as an essential component in addition to (A) the colorant and (B) (co) polymer. (C) As a solvent, components (A) and (B) constituting the colored composition and other components described later are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is, it can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy -3-methylbutanoic acid methyl, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, (C) solvent can be used individually or in mixture of 2 or more types.

In addition to the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

(C) Although the content of the solvent is not particularly limited, the total concentration of each component excluding the solvent from the colored composition is from the viewpoint of applicability, stability and the like of the obtained colored composition. Usually, an amount of 5 to 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly desirable.

-(D) Binder resin-
The coloring composition of the present invention can contain (D) a binder resin. Thereby, alkali developability and the binding property to a board | substrate can be provided to a coloring composition. Such a binder resin is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (D1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as“ unsaturated monomer (d2) ”) are preferred.

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). An acrylate etc. can be mentioned. These unsaturated monomers (d1) can be used alone or in admixture of two or more.
In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (d1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Further, as the unsaturated monomer (d2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene and p-hydroxy-α-methylstyrene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide of paracumylphenol Unsaturated carboxylic esters such as modified (meth) acrylates;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.
These unsaturated monomers (d2) can be used alone or in admixture of two or more.

Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-10-31308, and JP-A-10-300922. And copolymers disclosed in JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like.

In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-11-140144, JP-A-2008-181095, etc. As disclosed, a carboxyl group-containing copolymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of (D) binder resin in the present invention is usually 1,000 to 300,000. Preferably, it is 3,000 to 100,000. If the Mw is too small, when a colored layer is formed using the colored composition of the present invention, the residual film ratio of the resulting colored layer is reduced, the pattern shape and heat resistance are impaired, and the electrical properties are reduced. On the other hand, if it is too large, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

Further, the ratio (Mw / Mn) of Mw of (D) binder resin in the present invention and polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). ) Is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

The (D) binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can also be controlled by the method used.
In this invention, (D) binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the (D) binder resin (solid content) is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(E) Multifunctional monomer-
The coloring composition of the present invention can contain (E) a polyfunctional monomer. Thereby, thermosetting or radiation sclerosis | hardenability can be provided to a coloring composition. As used herein, “(E) polyfunctional monomer” refers to a monomer having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (E) polyfunctional monomer is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl groups include aliphatic polyhydroxy compounds and esters of (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and alkylene oxide-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-containing (meth) acrylate and polyfunctional isocyanate, carboxyl group obtained by reacting hydroxyl-containing (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate etc. which have can be mentioned.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide-modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide-modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl). ) Benzoguanamine, N, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid esters, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, carboxyl groups Preferred are polyfunctional (meth) acrylates having N, N, N, N, N, N-hexa (alkoxymethyl) melamine and N, N, N, N-tetra (alkoxymethyl) benzoguanamine. Trivalent or higher aliphatic polyhydroxy compound from the viewpoint that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and it is difficult for stains and film residue to occur on the unexposed substrate and the light shielding layer. And (meth) acrylic acid ester are preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyfunctional (meth) acrylate having a carboxyl group is penta A compound obtained by reacting erythritol triacrylate and succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are preferred.
In this invention, (E) polyfunctional monomer can be used individually or in mixture of 2 or more types.

In the present invention, the content of the (E) polyfunctional monomer is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight, with respect to 100 parts by weight of the (A) colorant. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

-(F) Photopolymerization initiator-
The coloring composition of the present invention can contain (F) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. In this specification, “radiation” is a concept including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The photopolymerization initiator (F) used in the present invention is obtained by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a functional monomer.
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like.
In this invention, (E) photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Specific examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include '5,5'-tetraphenyl-1,2'-biimidazole.

In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

Specific examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Triazine compounds having a halomethyl group such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Specific examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

In the present invention, when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, the content of the (F) photopolymerization initiator is preferably 0.01 to 120 parts by weight, particularly preferably 1 to 100 parts by weight, with respect to 100 parts by weight of the (E) polyfunctional monomer. . In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to peel easily from a board | substrate at the time of image development.

-Additive-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, anionic surfactants, and the like Surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-chloropropylmethyldimethoxy Adhesion promoters such as lan, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Anticoagulant such as sodium acrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3 -Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-a Residue improvers such as -1,2-butanediol; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono Examples include developability improvers such as (meth) acrylate.

When imparting curability or alkali developability to the colored composition of the present invention, the colored composition can be prepared by an appropriate method. The following method can be mentioned as a preparation method of a preferable coloring composition. That is, (A) a colorant in (C) a solvent, in the presence of (B) (co) polymer and other dispersant added as needed, optionally with part of (D) component, for example Using a bead mill, a roll mill or the like, a dispersion is prepared by mixing and dispersing while pulverizing. Next, components (D) to (F) and, if necessary, additional (C) solvent and additives are added to the dispersion and mixed.
According to the coloring composition thus prepared, a pixel having a high contrast ratio can be formed, and the coloring composition is also excellent in storage stability and alkali developability.

[Color filter]
The color filter of the present invention comprises a colored layer formed using the colored composition of the present invention.
As a method for forming a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a liquid composition of the radiation-sensitive colored composition of the present invention in which a red colorant is dispersed is applied on this substrate, and then prebaked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.
Then, using the liquid composition of each radiation-sensitive colored composition in which a green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. A green pixel array and a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.
The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation coloring composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition of the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. In particular, spin coating and slit die coating are preferable.

Pre-baking is usually performed by combining vacuum drying and heat drying. The vacuum drying is usually performed at 0.1 to 1 Torr. The conditions for heat drying are usually about 70 to 110 ° C. and about 1 to 10 minutes.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm, as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5. An aqueous solution of -diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.
The post-baking conditions are usually 180 to 280 ° C. and about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Further, as a second method of forming a color filter, a method of obtaining pixels of each color by an ink jet method can be mentioned. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the colored composition of the present invention in which, for example, a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.
Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using a liquid composition of each coloring composition in which a green or blue colorant is dispersed, in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.
In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. The film thickness is usually 1 to 3 μm. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the film thickness of the partition wall.
A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has a high contrast ratio, it is extremely useful particularly for a color liquid crystal surface element represented by TV.

[Color LCD device]
The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other through a liquid crystal layer. It can also take a structure. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
<Synthesis of the monomer represented by the following formula (2a)>
A monomer represented by the following formula (2a) was synthesized by the following method.

In a reaction flask purged with nitrogen, 10 g (65.7 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was dissolved in 80 mL of the solvent tetrahydrofuran, and − Cooled to 20 ° C. To this, 39.2 mL (62.3 mmol) of a 1.59 M n-butyllithium hexane solution was added dropwise over 1 hour. Then, it stirred at the same temperature for 3 hours.
Next, 11 g (72.1 mmol) of p-chloromethylstyrene was dissolved in 60 mL of a solvent tetrahydrofuran and cooled to 0 ° C. under normal pressure in another reaction flask subjected to nitrogen substitution. The reaction solution was added dropwise to this solution over 1 hour and stirred at the same temperature for 30 minutes.
After adding 10 mL of methanol to the obtained reaction solution and stirring for 30 minutes, unreacted DBU and lithium chloride were removed by washing with 1N aqueous sodium hydroxide solution. Thereafter, drying was performed using anhydrous sodium hydroxide. Sodium hydroxide was removed by filtration, 2 mL of water was added to the resulting solution, and carbon dioxide gas was bubbled to precipitate a white precipitate. Diethyl ether was added to the precipitated white precipitate and stirred for 1 hour, followed by decantation to remove unreacted p-chloromethylstyrene and by-products. 100 mL of 1N sodium hydroxide aqueous solution was added to the precipitate after decantation, and the mixture was stirred until no carbon dioxide gas was generated, followed by extraction with diethyl ether. After the diethyl ether layer was dried over anhydrous sodium hydroxide, the sodium hydroxide was removed by filtration and concentrated under reduced pressure to obtain a very pale yellow viscous liquid (yield 48.9%).

As a result of performing GC analysis about the obtained product, purity was 98.0%. Further, as a result of analysis by ¹ H-NMR (trade name: Unity INOVA 400, manufactured by Varian) using deuterated chloroform as a measurement solvent, it was confirmed to be the target compound.
The result of ¹ H-NMR is shown in FIG. 1, the result of ¹³ C-NMR is shown in FIG. 2, and the infrared spectrum is shown in FIG.

Example 2
<Synthesis of polymer (B1)>
The following copolymer was synthesize | combined using the compound represented by the said Formula (2a) obtained.
In a flask equipped with a stir bar, methyl methacrylate 40 g (400 mmol), n-butyl methacrylate 20 g (141 mmol), 2-ethylhexyl methacrylate 20 g (101 mmol), benzyl methacrylate 20 g (114 mmol), 2,2′-azobisisobutyrate 1.63 g (9.93 mmol) of ronitrile and 4.22 g (20.0 mmol) of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 100 mL of propylene glycol monomethyl ether, and nitrogen bubbling was performed for 30 minutes. . Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization.
Next, 8.95 g (93.1 mmol) of methanesulfonic acid was dissolved in a state where the reaction solution was cooled to 0 ° C. with an ice bath, and 25 g (93.1 mmol) of the monomer represented by the above formula (2a) was dissolved. It was dripped. After the reaction solution was warmed to room temperature, 2,2′-azobisisobutyronitrile (2.0 g, 12.2 mmol) was charged, and nitrogen substitution was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization. The obtained copolymer solution was reprecipitated using a 1 mol / L sodium hydroxide aqueous solution, then washed with water and dried to obtain the target block copolymer. The obtained copolymer is referred to as “(co) polymer (B1)”. The polymer (B1) has an A block having a repeating unit derived from the monomer represented by the formula (2a), and a repeating unit derived from methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. It was an AB type block copolymer consisting of B blocks.

Example 3
<Synthesis of polymer (B2)>
In a flask equipped with a stirrer, 100 g (703 mmol) of n-butyl methacrylate, 1.63 g (9.93 mmol) of 2,2′-azobisisobutyronitrile and cyano (dimethyl) methyl pyrazole-1-dithiocarboxylate 4.22 g (20.0 mmol) of the ester was dissolved in 100 mL of propylene glycol monomethyl ether, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization.
Next, 8.95 g (93.1 mmol) of methanesulfonic acid was dissolved in a state where the reaction solution was cooled to 0 ° C. with an ice bath, and 5 g (18.6 mmol) of the monomer represented by the above formula (2a) was dissolved. It was dripped. The reaction solution was warmed to room temperature, and then charged with 0.4 g (2.44 mmol) of 2,2′-azobisisobutyronitrile and purged with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization. The obtained copolymer solution was reprecipitated using a 1 mol / L sodium hydroxide aqueous solution, then washed with water and dried to obtain the target block copolymer. The obtained copolymer is referred to as “polymer (B2)”. The polymer (B2) is an AB type block copolymer comprising an A block having a repeating unit derived from the monomer represented by the formula (2a) and a B block having a repeating unit derived from n-butyl methacrylate. Met.

Example 4
<Synthesis of polymer (B3)>
In a flask equipped with a stirrer, 100 g (703 mmol) of n-butyl methacrylate, 1.63 g (9.93 mmol) of 2,2′-azobisisobutyronitrile and cyano (dimethyl) methyl pyrazole-1-dithiocarboxylate 4.22 g (20.0 mmol) of the ester was dissolved in 100 mL of propylene glycol monomethyl ether acetate, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization. The reaction solution was cooled to room temperature, and after bubbling with nitrogen again for 30 minutes, 33.8 g (140 mmol) of diethylene glycol dimethacrylate was charged. While strongly stirring the reaction solution, a solution prepared by dissolving 6.1 g of triethylamine and 6.1 g of hexylamine in 20 g of propylene glycol monomethyl ether acetate was added dropwise to the reaction solution, and the reaction was performed for 24 hours. The obtained polymer was reprecipitated using methanol and then dried to obtain a macromonomer represented by the following formula (9).

In a flask equipped with a stirrer, 80 g of the macromonomer, 25 g (93.1 mmol) of the monomer represented by the formula (2a), and 0.40 g of 2,2′-azobisisobutyronitrile (2. 43 mmol) was dissolved in 100 mL of propylene glycol monomethyl ether, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform radical polymerization. The obtained copolymer solution was reprecipitated using n-hexane and then dried to obtain the intended graft copolymer. The obtained copolymer is referred to as “polymer (B3)”. The polymer (B3) has an A block having a repeating unit derived from the monomer represented by the formula (2a) as a polymer main chain, and has a repeating unit derived from n-butyl methacrylate from the polymer main chain. It was a graft copolymer in which the B block was branched.

Example 5
<Synthesis of polymer (B4)>
In a flask equipped with a stirrer, methyl methacrylate 40 g (400 mmol), n-butyl methacrylate 20 g (141 mmol), 2-ethylhexyl methacrylate 20 g (101 mmol), benzyl methacrylate 20 g (114 mmol), represented by the above formula (2a) 25 g (93.1 mmol) of the monomer and 2.50 g (15.2 mmol) of 2,2′-azobisisobutyronitrile were dissolved in 250 mL of propylene glycol monomethyl ether and subjected to nitrogen bubbling for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform radical polymerization. The obtained copolymer solution was reprecipitated using n-hexane and then dried to obtain the desired random copolymer. The obtained copolymer is referred to as “polymer (B4)”. The polymer (B4) was a random copolymer of methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and a monomer represented by the above formula (2a).

Synthesis example 1
<Synthesis of polymer (b1)>
In a flask equipped with a stir bar, methyl methacrylate 40 g (400 mmol), n-butyl methacrylate 20 g (141 mmol), 2-ethylhexyl methacrylate 20 g (101 mmol), benzyl methacrylate 20 g (114 mmol), dimethylaminoethyl methacrylate 25 g (159 mmol) and 2.50 g (15.2 mmol) of 2,2′-azobisisobutyronitrile was dissolved in 250 mL of propylene glycol monomethyl ether, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform radical polymerization. The obtained copolymer solution was reprecipitated using n-hexane and then dried to obtain the desired random copolymer. The obtained copolymer is referred to as “polymer (b1)”. The polymer (b1) was a random copolymer of methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and dimethylaminoethyl methacrylate.

Synthesis example 2
<Synthesis of polymer (b2)>
N- [3- (1H-imidazol-1-yl) propyl] methacrylamide was synthesized according to the description in paragraphs [0101] to [0102] of JP-A-2003-26949. A random copolymer was prepared in the same manner as in Comparative Synthesis Example 1 except that N- [3- (1H-imidazol-1-yl) propyl] methacrylamide was used instead of dimethylaminoethyl methacrylate in Comparative Synthesis Example 1. Got. The obtained copolymer is referred to as “polymer (b2)”.

Synthesis example 3
<Synthesis of binder resin>
A flask equipped with a condenser and a stirrer was charged with 2 g of 2,2′-azobisisobutyronitrile and 200 g of propylene glycol monomethyl ether acetate, followed by 20 g of methacrylic acid, 15 g of 2-hydroxyethyl methacrylate, 15 g of N-phenylmaleimide, Charge 12 g of styrene, 10 g of benzyl methacrylate, 28 g of 2-ethylhexyl methacrylate and 3 g of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) as a molecular weight regulator for 30 minutes. Replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 6,000. This binder resin solution is referred to as “binder resin solution (D1)”.

Example 6
Preparation of colorant dispersion C.I. I. 10 parts by weight of Pigment Red 254, 2.5 parts by weight of the polymer (B1) as a dispersant, 82.5 parts by weight of propylene glycol monomethyl ether acetate and 5 parts by weight of propylene glycol monomethyl ether as a solvent were mixed for 12 hours by a bead mill. -Dispersed to prepare a colorant dispersion (A-1).

Preparation of Radiation Sensitive Coloring Composition 100 parts by weight of the resulting colorant dispersion (A-1), 30 parts by weight of binder resin solution (D1) as the binder resin, and dipentaerythritol hexaacrylate 15 as the polyfunctional monomer Parts by weight, 4 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1 part by weight of 4,4′-bis (diethylamino) benzophenone as a photopolymerization initiator, and Propylene glycol monomethyl ether acetate was mixed as a solvent to prepare a radiation-sensitive colored composition (CR1) having a solid concentration of 15% by mass.
The radiation-sensitive colored composition (CR1) was evaluated according to the following procedure.

Evaluation of Contrast Ratio The radiation-sensitive colored composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after these substrates were cooled to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 J / m ² using a high-pressure mercury lamp. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) on these substrates, and shower development was performed for 1 minute. . Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a cured film for evaluation.
With respect to the obtained three cured films, chromaticity coordinate values (x, y) in the CIE color system were measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view. . Furthermore, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range 380 to 780 nm) from the back side, and a luminance meter (Minolta Co., Ltd.) The maximum value and the minimum value of the light intensity transmitted through LS-100) were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value x = 0.650 was obtained. The evaluation results are shown in Table 1.

Evaluation of storage stability The viscosity immediately after the preparation of the radiation-sensitive colored composition (CR1) was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). In addition, the light-sensitive colored composition (CR1) was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). . Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “A”, when 5% or more and less than 10%, “B”, 10% or more The case was evaluated as “C”. The evaluation results are shown in Table 1.

Examples 7 to 19 and Comparative Examples 1 to 5
In Example 6, the colorant dispersion (A-2) was prepared in the same manner as in Example 6 except that the colorant and / or dispersant used in the preparation of the colorant dispersion was changed to those shown in Table 1. ) And (A-19) were prepared, and then radiation sensitive coloring compositions (CR2) to (CR19) were prepared. Next, various evaluations were performed in the same manner as in Example 6 except that the radiation-sensitive colored compositions (CR2) to (CR19) were used instead of the radiation-sensitive colored composition (CR1). The red radiation-sensitive colored composition has a contrast ratio at a chromaticity coordinate value x = 0.650, and the green radiation-sensitive colored composition has a chromaticity coordinate value y = 0.600. Contrast ratios for the blue radiation-sensitive colored composition were respectively determined for the chromaticity coordinate value y = 0.100. The evaluation results are shown in Table 1.

Claims (13)

The following components (A), (B) and (C):
(A) a colorant,
(B) A coloring composition comprising a (co) polymer having a group represented by the following formula (1), and (C) a solvent.

[In Formula (1), R ¹ represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ² and R ³ each independently have a hydrogen atom or a substituent. Or a hydrocarbon group having 1 to 10 carbon atoms. However, R ² and R ³ may be bonded to each other to form a cyclic structure. “*” Indicates a bond. ] The coloring composition according to claim 1, wherein the component (B) is a (co) polymer having a repeating unit represented by the following formula (2).

[In the formula (2), R ¹ to R ³ are as defined above, R ⁴ represents a hydrogen atom or a methyl group, X represents —CO—, —C (═O) O — (*), — CONH — (*) or a phenylene group (where “*” is a bond bonded to Y), and Y represents a single bond or a divalent linking group.] The component (B) is further selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5). The coloring composition according to claim 2, which is a (co) polymer having one kind.

[In Formula (3), R ⁵ has a hydrogen atom, a chain or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. R ⁶ represents a hydrogen atom or a methyl group. ]

[In the formula (4), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and n is an integer of 0 to 5 Indicates. ]

[In the formula (5), R ⁹ represents an ethylene group or a propylene group, R ¹⁰ represents an alkyl group having 1 to 5 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 20 Indicates. ] The colored composition according to any one of claims 1 to 3, further comprising a binder resin (excluding the (B) (co) polymer) as the component (D). The colored composition according to any one of claims 1 to 4, further comprising a polyfunctional monomer as component (E). The coloring composition according to claim 5, further comprising a photopolymerization initiator as component (F). A color filter comprising a colored layer formed using the colored composition according to any one of claims 1 to 6. A color liquid crystal display element comprising the color filter according to claim 7. The compound or its salt represented by following formula (6).

[In Formula (1), R ¹ represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ² and R ³ each independently have a hydrogen atom or a substituent. Or a hydrocarbon group having 1 to 10 carbon atoms (wherein R ² and R ³ may combine with each other to form a cyclic structure), R ⁴ represents a hydrogen atom or a methyl group, and X represents — CO—, —C (═O) O — (*), —CONH — (*) or a phenylene group (where “*” is a bond bonded to Y), and Y is a single bond or divalent Represents a linking group. ] The compound or its salt of Claim 9 whose compound represented by said Formula (6) is a compound represented by following formula (7).

[In Formula (7), R ⁴ represents a hydrogen atom or a methyl group, Y ¹ represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and R ¹² represents a methylene group or an alkylene group having 2 to 6 carbon atoms. Show. ] The compound or its salt of Claim 9 whose compound represented by said Formula (6) is a compound represented by following formula (8).

[In Formula (8), R ⁴ represents a hydrogen atom or a methyl group, Y ¹ represents a methylene group or an alkylene group having 2 to 5 carbon atoms, and R ¹² represents a methylene group or an alkylene group having 2 to 6 carbon atoms. Show. ] The compound or a salt thereof according to claim 10 or 11, wherein R ¹² is an ethylene group, a trimethylene group or a tetramethylene group. Production of a (co) polymer having a repeating unit represented by the following formula (2), wherein the monomer containing a compound represented by the following formula (6) or a salt thereof is (co) polymerized. Method.

[In the formulas (2) and (6), R ¹ represents an optionally substituted alkylene group having 2 to 6 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a substituent. A hydrocarbon group having 1 to 10 carbon atoms which may have a structure (provided that R ² and R ³ may combine with each other to form a cyclic structure), and R ⁴ represents a hydrogen atom or a methyl group , X represents —CO—, —C (═O) O — (*), —CONH — (*) or a phenylene group (where “*” represents a bond bonded to Y), and Y represents a single bond. A bond or a divalent linking group is shown. ]

Images