TWI605063B - Resin composition and display device - Google Patents

Description

Resin composition and display device

The present invention relates to a resin composition, a coating film and a pattern obtained from the resin composition, and a display device including the coating film and/or pattern.

A transparent film such as a color filter pixel pattern or a coating layer used in a display device (for example, a liquid crystal display device) is generally formed using a resin composition (particularly, a photosensitive resin composition). In the production of a coating layer and a pattern of a display device, a resin composition is generally applied onto a substrate by a spin coating method, a doctor blade spin coating method, or the like. Therefore, a resin composition which can form a uniform coating film having less spots is desired. In the past, as a photosensitive resin composition, for example, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent are known (Patent Document 1 and the like).

[Patent Document 1] JP-A-2008-181087

However, a coating film formed using a resin composition known in the past sometimes causes coating unevenness (unevenness). An object of the present invention is to provide a resin composition which can form a coating film having few spots.

The present invention provides a resin composition obtained by solving the above problems.

That is, the present invention provides the following [1] to [14].

[1] A resin composition comprising a resin, a polymerizable compound, a compound represented by the formula (F), and a solvent.

[In the formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group.

L ² and L ^{3 are} each independently and represent a trivalent C _2-8 aliphatic hydrocarbon group.

R ¹ and R ² each independently represent a monovalent C _1-8 aliphatic hydrocarbon group, and at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted by a fluorine atom.

m and n are each independent, and represent an integer of 0 or more and 22 or less. However, m+n is 3 or more and 22 or less]

[2] R ¹ and R ² each independently represent a resin composition as described in [1] of the formula (f1).

-C _p H _2p -C _q F _2q+1 (f1)

[In the formula (f1), p and q are each independent, and represent an integer of 1 or more and 4 or less]

[3] The resin composition according to [1] or [2] wherein R ¹ and R ² are a linear C _1-8 aliphatic hydrocarbon group.

[4] The resin composition as described in [2] or [3].

The compound of the formula (F) is a resin composition as described in any one of [1] to [4].

[In the formula (F1-1), m and n have the same meanings as described above. ]

[6] The resin composition according to any one of [1] to [5], wherein the m+n is 3 or more and 6 or less.

[7] The resin is a structural unit containing at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a monomer derived from a carbon-carbon double bond and a cyclic ether structure. (b) The resin composition according to any one of [1] to [6], which is a copolymer of the structural unit of the monomer (a).

[8] The monomer (b) is a resin composition described in [7] selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2).

In the formula (b1-1) and the formula (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and a hydrogen atom of the aliphatic hydrocarbon group may be substituted with a hydroxyl group.

L ⁴ represents a single bond or a C _1-6 aliphatic hydrocarbon group, and -CH ₂ - of the above aliphatic hydrocarbon group may be substituted by -O-, -S- or -NH-.

Further, each of R ³ and L ⁴ in the formula (b1-1) may be the same as or different from R ³ and L ⁴ in the formula (b1-2)]

[9] Further described in any one of [1] to [8] containing a polymerization initiator Resin composition.

[10] The polymerization initiator is a resin composition described in [9] containing a polymerization initiator of a bisimidazole compound.

[11] A coating film formed from the resin composition according to any one of [1] to [10].

[12] A pattern formed by using the resin composition described in [9] or [10].

[13] A liquid crystal display device comprising at least one selected from the group consisting of the coating film described in [11] and the pattern described in [12].

[14] An organic EL display device comprising at least one selected from the group consisting of the coating film described in [11] and the pattern described in [12].

[Formation of the Invention]

The resin composition of the present invention contains the resin (A), the polymerizable compound (B), the compound (F), and the solvent (H), and may optionally contain a polymerization initiator (C) and a polymerization initiation aid (D). ), polyfunctional thiol (E) and other additives (G).

Each of the above components may be used singly or in combination of two or more kinds, unless otherwise specified. Hereinafter, each component contained in the resin composition of the present invention will be described in order.

<Resin (A)>

The resin (A) is preferably soluble in a developing solution (particularly an alkaline developing solution). The resin soluble in the alkaline developing solution is, for example, selected from the group consisting of At least one monomer (a) in which the unsaturated carboxylic acid and the unsaturated carboxylic anhydride are grouped; and a copolymer having a carbon-carbon double bond and the monomer (a) as a different monomer (x). Each of the monomer (a) and the monomer (x) may be used alone or in combination of two or more. These are explained in order below.

Examples of the monomer (a) include (meth)acrylic acid, crotonic acid, cinnamic acid, o-, m-, p-vinylbenzoic acid, and succinic acid mono [2-(methyl)acryloxyloxy group. Ethyl], phthalic acid mono [2-(methyl) propylene oxiranyl ethyl], ω-carboxy polycaprolactone mono (meth) acrylate, 5-carboxy-5-methyl bicyclo [2.2 .1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5 - an unsaturated monocarboxylic acid such as carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydroortylene Dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, methyl-5-norbornene-2, An unsaturated dicarboxylic acid such as 3-dicarboxylic acid;

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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate (norbornene dianhydride) An unsaturated dicarboxylic acid anhydride or the like.

In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

The monomer (a) is preferably at least one compound selected from the group consisting of (meth)acrylic acid and maleic anhydride, and more preferably methacrylic acid, from the viewpoints of copolymerization reactivity, alkali solubility, and the like.

The monomer (x) is preferably one containing the monomer (b) having a carbon-carbon double bond and a cyclic ether structure. The monomer (b) may be used alone or in combination of two or more. Examples of the monomer (b) include a monomer (b1) having an epoxy group structure (i.e., an ethylene oxide structure), a monomer (b2) having an oxetane structure, and a tetrahydrofuran structure (ie, Monomer (b3) of oxolane structure). Among them, a monomer (b1) having an epoxy group structure and a monomer (b2) having an oxetane structure are preferred, and a monomer (b1) having an epoxy group structure is preferred.

The epoxy structure can be classified as

(1) a structure having a monocyclic oxirane ring (hereinafter referred to as "aliphatic epoxy structure"), and (2) a structure in which a ring of an aliphatic hydrocarbon is condensed with an oxirane ring (hereinafter referred to as a structure) It is "alicyclic epoxy structure"). The alicyclic epoxy group structure can be further classified into (2-1) a ring of an aliphatic hydrocarbon is a single ring (hereinafter referred to as "aliphatic monocyclic epoxy structure"), and (2-2) fat. The ring of the hydrocarbon is a polycyclic ring (hereinafter referred to as "aliphatic polycyclic epoxy structure"). Among them, an alicyclic epoxy group structure is preferred, and an aliphatic polycyclic epoxy group structure is more preferred.

Examples of the monomer (b1) having an aliphatic epoxy group structure include a glycidyl (meth)acrylate, a β-methylepoxypropyl (meth)acrylate, and a β-ethyl ring. Oxypropyl propyl (meth) acrylate, propylene propyl vinyl ether, a monomer represented by the formula (b1-3) described in JP-A-H07-248625, etc., in the formula (b1-3), R ⁴ ~R ^{6 is} each independently and represents a hydrogen atom or a C _1-10 alkyl group. M1 represents an integer from 1 to 5. }.

Examples of the monomer (b1-3) having an aliphatic epoxy group structure include o-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, and p-ethylene. Benzomethylepoxypropyl ether, α-methyl-o-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-methyl -p-vinylbenzyloxypropyl ether, 2,3-bis(epoxypropyloxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(epoxypropyloxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-cis (epoxypropyloxy) Methyl)styrene, 2,3,5-glycol(epoxypropyloxymethyl)styrene, 2,3,6-glycol(epoxypropyloxymethyl)styrene, 3,4, 5-glycol (epoxypropyloxymethyl)styrene, and 2,4,6-glycol(epoxypropyloxymethyl)styrene.

Examples of the monomer (b1) having an aliphatic monocyclic epoxy group structure include 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industry Co., Ltd.). , 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (eg, CYCLOMER A400; Daicel Chemical Industry) (manufactured by the company), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLOMER M100; manufactured by Daicel Chemical Industry Co., Ltd.).

The monomer (b1) having an aliphatic polycyclic epoxy group structure may be a carbon-carbon double bond contained in a polycyclic aliphatic hydrocarbon group or may be contained in a side chain bonded to a ring. . Examples of the polycyclic ring include a norbornane ring and a tricyclodecane ring, and among them, a tricyclodecane ring is preferred.

As the monomer (b1) having an aliphatic polycyclic epoxy group structure, for example, an epoxy group norbornyl group (meth) acrylate (for example, a 3,4-epoxynorbornyl group) can be mentioned. Methyl) acrylate}, a monomer represented by the formula (b1-1), and a monomer represented by the formula (b1-2).

In the formula (b1-1) and the formula (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and a hydrogen atom of the aliphatic hydrocarbon group may be substituted with a hydroxyl group.

L ⁴ represents a single bond or a divalent C _1-6 aliphatic hydrocarbon group, and -CH ₂ - of the above aliphatic hydrocarbon group may be substituted by -O-, -S- or -NH-.

Examples of the aliphatic hydrocarbon group which may be substituted by a hydroxyl group of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a hydroxymethyl group, and a 1-hydroxy group. Ethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1 - hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like. R ^{3 is} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

The divalent aliphatic hydrocarbon group which may be substituted by -O- or the like of L ⁴ may, for example, be a methyl group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group or a butane- 1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, methyloxy (-CH ₂ -O-) , Ethyloxy {-(CH ₂ ) ₂ -O-}, propane diyloxy {-(CH ₂ ) ₃ -O-, etc.}, methylsulfanyl diyl (-CH ₂ -S-) ), ethyl thiosulfanyl group {-(CH ₂ ) ₂ -S-}, propane diyl sulfanediyl {-(CH ₂ ) ₃ -S-, etc.}, methyl imino group (-CH) _2- NH-), ethyl imino group {-(CH ₂ ) ₂ -NH-}, propane diiminoimide group {-(CH ₂ ) ₃ -NH-, etc.} and the like. L ^{4 is} preferably a single bond, a methyl group, an ethyl group, a methyl group, a methyl group, an ethyl thiodiyl group, or an ethyl imino group, more preferably a single bond or Ethyloxy group.

Each of the monomer (b1-1) and the monomer (b1-2) may be used alone or in combination of two or more. A mixture of the monomer (b1-1) and the monomer (b1-2) can be further used. When using these mixtures, the monomer (b1-1): monomer (b1-2) has a molar ratio of preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20: 80~80:20.

The preferred monomer (b1-1) is one of the formula (b1-1-1) to the formula (b1-1-15). Among them, monomer (b1-1-1), monomer (b1-1-3), monomer (b1-1-5), monomer (b1-1-7), monomer (b1- 1-9), and monomer (b1-1-11)~monomer (b1-1-15) are preferred, and monomer (b1-1-1), monomer (b1-1-7), The monomer (b1-1-9) and the monomer (b1-1-15) are more preferred.

The preferred monomer (b1-2) is one of the formula (b1-2-1) to the formula (b1-2-15). Among these, monomer (b1-2-1), monomer (b1-2-3), monomer (b1-2-5), monomer (b1-2-7), monomer (b1-2) -9), and monomer (b1-2-11) ~ monomer (b1-2-15) is preferred, monomer (b1-2-1), monomer (b1-2-7), single The body (b1-2-9) and the monomer (b1-2-15) are more preferred.

Examples of the monomer (b2) having an oxetane structure include 3-(meth)acryloxymethyloxetane and 3-methyl-3-(meth)acryloxy group. Methyloxetane, 3-ethyl-3-(meth)acryloxymethyloxetane, 3-methyl-3-[1-(methyl)propenyloxy]methyl Oxetane, 3-ethyl-3-[1-(meth)acryloxy]methyloxetane, 3-methyl-3-[1-(meth)acryloxy] Ethyloxetane, 3-ethyl-3-[1-(methyl)propenyloxy]ethyloxetane, 2-phenyl-3-(methyl)acryloxymethyl Oxetane, 2-trifluoromethyl-3-(A Propyloxymethyloxetane, 2-pentafluoroethyl-3-(methyl)acryloxymethyloxetane, 3-methyl-3-(methyl)propeneoxy Ethyloxyoxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 2-phenyl-3-(methyl)propenyloxyethyloxene Butane, 2-trifluoromethyl-3-(meth)acryloxyethyloxetane or 2-pentafluoroethyl-3-(methyl)propenyloxyethyloxetane , 3-(meth)acryloxyoxetane, and the like. Among them, 3-ethyl-3-(meth)acryloxymethyloxetane is also preferred.

Examples of the monomer (b3) having a tetrahydrofuran structure include tetrahydroindenyl (meth) acrylate, furan methoxyethyl (meth) acrylate, and furan methoxy propyl (meth) acrylate. Ester and the like.

The monomer (x) may contain a monomer (c) different from the monomer (a) and the monomer (b). Examples of the monomer (c) include a carboxylic acid ester having a carbon-carbon double bond, an amide having a carbon-carbon double bond, and a polymerizable unsaturated bond (carbon-carbon double bond or a side chain). An aromatic compound, a substituted vinyl compound, an N-substituted maleimide, a diene, a polycyclic unsaturated compound, or the like. The monomer (c) may be used alone or in combination of two or more.

As the monomer (c), for example,

Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ring Hexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isodecyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (methyl Acrylate (the common name of "dicyclopentyl (meth) acrylate" is sometimes used in this field), 4-tricyclo[5.2.1.0 ^2,6 ]nonene-8-yl (methyl) Acrylate, 5-tricyclo[5.2.1.0 ^2,6 ]nonene-8-yl (meth) acrylate, phenyl (meth) acrylate, aminoethyl (meth) acrylate, Malay Unsaturated carboxylic acid esters such as diethyl acetate, diethyl fumarate, diethyl itaconate; vinyl carboxylates such as vinyl acetate or vinyl propionate; dimethyl (meth) propylene Amidoxime having a carbon-carbon double bond such as decylamine or isopropyl(meth)propenylamine; styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene equal to side chain An aromatic compound having a polymerizable unsaturated bond; acrylonitrile, methacrylonitrile or α-chloro (methyl) A vinyl cyanide compound such as a nitrile; a halogenated vinyl compound such as vinyl chloride, dichloroethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene or tetrafluoroethylene; N-methyl maleimide , N-ethyl maleimide, N-butyl maleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenyl malayan N-substituted maleimide such as amine; diene such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; bicyclo[2.2.1 Hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]heptane- 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[ 2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di (hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxy-5-ethylbicyclo[2.2.1]g- 2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy a polycyclic unsaturated compound such as carbonyl bicyclo[2.2.1]hept-2-ene or 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

In the monomer (c), phenyl methacrylate, styrene, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, bicyclo [ 2.2.1] Hept-2-ene is preferred.

As the monomer (x), either one of the monomer (b) or the monomer (c) may be used, or both of them may be used. The monomer (x) preferably contains the monomer (b). That is, the monomer (x) is preferably only the monomer (b), or both the monomer (b) and the monomer (c), and more preferably the monomer (b). The copolymer containing the monomer (b) can improve the heat resistance, light resistance, solvent resistance, and mechanical properties of the coating film or pattern obtained from the resin composition.

When the resin (A) is a copolymer of the monomer (a) and the monomer (b), the structural unit derived from the monomer (a) is preferably from 2 to 98 mol% in the total constituent unit of the copolymer (better) 5 to 60 mol%, particularly preferably 10 to 50 mol%), and the structural unit derived from the monomer (b) is preferably 2 to 98 mol%, more preferably 40 to 95 mol%, particularly preferably It is 50~90% by mole. When it is in this range, the storage stability and development properties of the resin composition, and the residual film ratio and solvent resistance of the coating film or pattern tend to be good.

When the resin (A) is a copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) in the total structural unit of the copolymer is from 2 to 98 mol%, derived from the monomer ( The structural unit of c) is preferably 2 to 98 mol%. When it is this range, it exists in the tendency which preserves stability and heat resistance. More preferably, in the total structural unit of the copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) is 5 to 50 mol%, and the structural unit of the monomer (c) It is 50~95% by mole. If it is this range, there is a tendency that the imaging property or the residual film ratio is also good.

When the resin (A) is a copolymer of the monomer (a), the monomer (b) and the monomer (c), the structural unit derived from the monomer (a) is 2 to 97 m in the entire structural unit of the copolymer. %, the structural unit derived from the monomer (b) is 2 to 97 mol%, and the structural unit derived from the monomer (c) is preferably 1 to 96 mol%. If it is this range, it has a tendency to maintain stability, heat resistance, and mechanical strength. More preferably, in the total structural unit of the copolymer of the monomer (a), the monomer (b) and the monomer (c), the structural unit derived from the monomer (a) is 10 to 50 mol%, derived from the monomer ( The structural unit of b) is 20 to 80 mol%, and the structural unit derived from monomer (c) is 10 to 70 mol%. If it is this range, the development property, the residual film rate, or the solvent resistance will become favorable.

The resin (A) is, for example, a method described in the reference "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972) and the literature. The cited literature can be made by polymerizing monomers. More specifically, the monomer (a), the monomer (b) and/or the monomer (c), the polymerization initiator, and the solvent are charged into the reaction vessel, and are carried out in the absence of nitrogen-substituted oxygen. stir The copolymer can be produced by mixing, heating and heat preservation. The charging method or the reaction temperature of the copolymerization may be appropriately adjusted in consideration of the production equipment or the calorific value of the polymerization or the like.

The resulting copolymer can be used as it is. In particular, when the solvent (H) described later is used as a polymerization solvent, the solvent can be removed from the copolymer solution after polymerization, and the resin composition can be used as it is, and the production steps can be simplified. Further, the copolymer solution may be concentrated or may be diluted. Further, a copolymer which is taken out as a solid (powder) in a method such as reprecipitation can be used.

The resin (A) may further have a structural unit (d) having a carbon-carbon double bond in a side chain. The structural unit (d) is preferably a 1-alkyl-1-vinylcarbonyl group at the terminal end as shown in the formula (d1) or the formula (d2), and more preferably has a (meth) acrylonitrile group at the terminal.

In the formula (d1) and the formula (d2), R ⁷ and R ⁸ each independently represent a hydrogen atom or a C _1-6 alkyl group (preferably a hydrogen atom or a methyl group). Further, each of the formulas (d1) and (d2) represents a bonding position in the structural unit (d1) and the structural unit (d2). The chemical formula is also the same.

The structural unit (d) having a carbon-carbon double bond in the side chain may be obtained by copolymerizing the monomer (a), and after the monomer (b) and/or the monomer (c), by the monomer (a) The carboxyl group or the carbonyloxycarbonyl group (carboxylate anhydride structure), for example, a monomer (b) having a carbon-carbon double bond and a cyclic ether structure is added in the same manner as described in JP-A-2005-189574. It is preferred to add a monomer (b1) having a carbon-carbon double bond and an epoxy structure {for example, a monomer represented by the formula (b1-4) or the formula (b1-5) to form [formula (b1-4)]. Or in the formula (b1-5), R ⁸ is the same as the above].

The structural unit (d) having a carbon-carbon double bond in the side chain is formed in the following manner in detail. After copolymerizing the monomer (a) and the monomer (b) and/or the monomer (c), the environment in the reaction vessel is replaced with nitrogen by air, and 5 is added to the amount of the monomer (a) used for copolymerization. ~80 mol% of monomer (b). Next, 0.001 to 5% by mass of a reaction catalyst (for example, dimethylaminomethylphenol) is added to the total amount of the monomer (a) used in the copolymer and the monomer (b) used in the addition reaction. And 0.001 to 5% by mass of a polymerization inhibitor (for example, hydroquinone), and the reaction is carried out at 60 to 130 ° C for 1 to 10 hours. In the addition reaction, in the addition reaction, the charging method or the reaction temperature may be appropriately adjusted in consideration of the production equipment or the calorific value of the addition reaction.

In the addition reaction, the amount of the monomer (b) used in the addition reaction is preferably from 10 to 75 mols for the amount of the monomer (a) used for the copolymerization. %, more preferably 15 to 70 mol%. In this range, there is a tendency to maintain stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity.

The copolymer containing the structural unit (d) having a carbon-carbon double bond in the side chain may be directly used as a solution after the reaction, or concentrated or diluted. Further, a copolymer which is taken out as a solid (powder) by a method such as reprecipitation can be further used.

The acid value of the resin (A) is preferably 50 to 150 (mgKOH/g), more preferably 60 to 135 (mgKOH/g), and particularly preferably 70 to 135 (mgKOH/g). When it is in this range, the solubility in the developing solution can be improved and the unexposed portion can be easily dissolved.

The measured value of the amount of potassium hydroxide (mg) required for neutralizing 1 g of the polymer having an acidic group is generally determined by titration with an aqueous potassium hydroxide solution.

The weight average molecular weight of the resin (A) is preferably from 2,000 to 100,000, more preferably from 2,000 to 50,000, particularly preferably from 3,000 to 30,000.

When it is this range, the coating property of the resin composition is good, and the high development speed can be obtained while maintaining the residual film ratio at the time of development. Further, the weight average molecular weight was determined by gel permeation chromatography using polystyrene as a standard.

The molecular weight distribution of the resin (A) {i.e., weight average molecular weight (Mw) / number average molecular weight (Mn)} is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When it is this range, it has a tendency for the imaging property to be excellent.

The content of the resin (A) in the resin composition is preferably from 5 to 90% by mass, more preferably from 10 to 70% by mass based on the solid content of the resin composition. %. In the case of this range, the solubility in the developing solution is sufficient, and the development residue is less likely to occur on the substrate of the non-exposed portion (non-pixel portion). Further, it is not easy to cause film reduction of the exposed portion (pixel portion) at the time of development, and the residual film ratio tends to be improved. In the present specification, the "solid content of the composition" is "the total amount of each component of the resin composition from which the solvent is removed", and the solid component can be measured by a known means such as gas chromatography or liquid chromatography.

<Polymerizable compound (B)>

The polymerizable compound (B) may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond. The polymerizable compound (B) is preferably a polymerizable compound having three or more carbon-carbon unsaturated bonds (hereinafter also referred to as "a trifunctional or higher polymerizable compound").

Examples of the trifunctional or higher polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and gin(2-hydroxyethyl)trimeric isocyanate tris(methyl). Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol (Meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride reactant, dipentaerythritol penta (meth) acrylate and anhydride Reaction product, reaction of tripentaerythritol hepta (meth) acrylate with anhydride, caprolactone modified trimethylolpropane tri(meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate , caprolactone modified ginseng (2-hydroxyethyl) trimer isocyanate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta (methyl) Acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified tripellitate tetra(meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, Lactone modified tripentaerythritol hexa(meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol Reaction of tri(meth)acrylate with anhydride, reaction of caprolactone-modified dipentaerythritol penta(meth)acrylate with anhydride, caprolactone-modified tripentaerythritol hepta(meth)acrylate and anhydride Reactant, etc.

Among them, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Methyl) acrylate is preferred, and dipentaerythritol hexa(meth) acrylate is preferred.

The content of the polymerizable compound (B) is preferably from 5 to 75% by mass, more preferably from 10 to 70% by mass, particularly preferably from 15 to 65 by mass, based on the total of the resin (A) and the polymerizable compound (B). %. If it is this range, hardening is sufficient, and the film thickness reduction before and after development can be prevented, and it is difficult to generate a relief in a pattern, and the adhesiveness of a pattern will become favorable. Also, if it is the range, there is The sensitivity of the resin composition, the strength of the coating film and the pattern, the smoothness, the heat resistance, and the chemical resistance tend to be good.

<Polymerization initiator (C)>

The resin composition of the present invention may contain a polymerization initiator (C) as necessary, and preferably contains a photopolymerization initiator (C). The polymerization initiator (C) is a compound which initiates polymerization by generating an active radical or an acid or the like by heating or light irradiation, and a known polymerization initiator can be used.

Examples of the polymerization initiator (C) include a bisimidazole compound, an acetophenone compound, a triazine compound, a mercaptophosphine oxide compound, an anthraquinone compound, a benzoin compound, and a benzophenone compound. Among them, a bisimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound are preferred, and a diimidazole compound having excellent sensitivity is preferred.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, and 2,2'-bis(2,3-di). Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-double (2) -Chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example The phenyl group at the 4,4', 5,5' position of the phenyl group at the 4,4', 5,5' position may be substituted with an alkoxycarbonyl group (-COOR) (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.). , refer to Japanese Patent Publication No. 7-10913, etc.).

Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole {2,2'-bis(2-chlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-bisimidazole}, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-four Phenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole is preferred.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy- 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propyl) Mercapto)-benzyl}-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2 -morpholinopropan-1-one, 2-benzyl-2-ylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2-methylbenzoate 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-? Oleinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethyl Benzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4) -morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2, 3-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-di Methylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzene 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholine Phenyl)butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl) )-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamine 1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-Methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2- Dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl) )-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2- Methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 - a ketone oligomer or the like.

As the triazine compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethane) are mentioned. 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene 1,1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

Examples of the mercaptophosphine oxide compound include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

The ruthenium compound may, for example, be an O-indenyl ruthenium compound, and as a specific example, 1-(4-phenylsulfonyl-phenyl)-butane-1,2-dione 2- 肟-O-benzoate, 1-(4-phenylsulfonyl-phenyl)-octane-1,2-dione 2-indole-O-benzoate, 1-[9-B 5-(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone 1-O-acetate, 1-[9-ethyl-6-(2-methyl- 4-(3,3-Dimethyl-2,4-bishexacyclopentylmethyloxy)benzylidene)-9H-indazol-3-yl]ethanone 1-O-acetate Wait.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, o-benzylidene benzoic acid methyl, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Base sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Further as a polymerization initiator (C), 10-butyl-2-chloroacridone, 2-ethyl hydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid can be used. Acid methyl, titanocene compound, and the like.

Further, as the polymerization initiator (C), a polymerization initiator having a group causing linkage movement as described in JP-A-2002-544205 can be used. Further, a polymerization initiator having a group causing linkage movement can be used for copolymerization of the resin (A) and inserted into the resin (A) as a structural unit.

Examples of the polymerization initiator having a group which causes linkage movement include a polymerization initiator represented by the formulae (C1) to (C6).

When the polymerization initiator (C) is used, the content is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). . When it is this range, the resin composition has high sensitivity to light or heat, and the strength or smoothness of the coating film or pattern formed using the resin composition tends to be good.

<Polymerization Starter (D)>

The toxic resin composition of the present invention may contain a polymerization initiation aid (D) as necessary. The polymerization initiation aid (D) is generally used in combination with a polymerization initiator (C) for promoting polymerization initiated by the polymerization initiator (C).

When the polymerization start-up aid (D) is used, the content is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40% by mass based on 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). Share. When the polymerization initiation aid (D) in this range is used, the light or heat sensitivity to the obtained resin composition can be further improved, and the productivity of the coating film or pattern formed using the resin composition is improved. The tendency.

Examples of the polymerization initiation aid (D) include an amine compound, a thioxanthone compound, and a carboxylic acid compound.

The amine compound may, for example, be an aliphatic amine such as triethanolamine, methyldiethanolamine or triisopropanolamine; 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyltoluidine, 4,4'- Aromatic amines such as bis(dimethylamino)benzophenone (commonly known as: mazulone) and 4,4'-bis(diethylamino)benzophenone. Further, as the amine compound, a commercial product such as "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxene. Ketone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the carboxylic acid compound include (phenylthio)acetic acid, (methylphenylthio)acetic acid, (ethylphenylthio)acetic acid, (methylethylphenylthio)acetic acid, and (dimethylphenylsulfonate)acetic acid, ( Methoxyphenylthio)acetic acid, (dimethoxyphenylthio)acetic acid, (chlorophenylthio)acetic acid, (dichlorophenylthio)acetic acid, N-phenylglycine, phenoxyacetic acid, (naphthylsulfide) Acetic acid, N-naphthylglycine, An aromatic heteroacetic acid such as naphthoxyacetic acid.

As the polymerization initiation aid (D), a compound represented by the formula (D1) can be used.

In the formula (D1), W ¹ represents a C _6-12 aromatic ring, and a hydrogen atom of the above aromatic ring may be substituted by a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like). L ⁵ represents -O- or -S-. R ⁹ represents a linear, branched or cyclic C _1-6 aliphatic hydrocarbon group.

R ¹⁰ represents a linear, branched or cyclic C _1-12 aliphatic hydrocarbon group or a C _6-12 aromatic hydrocarbon group, and the hydrogen atom of the aliphatic hydrocarbon group and the aromatic hydrocarbon group may also be a halogen atom (for example, Substituted by a fluorine atom, a chlorine atom, a bromine atom or the like.

Examples of the aromatic ring of W ¹ include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, and a cyclohexyl group. Benzene ring, naphthalene ring, phenylbenzene ring, and the like. Examples of the halogenated aromatic ring of W ¹ include a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a chloronaphthalene ring, a bromine naphthalene ring, and the like. . W ^{1 is} preferably a benzene ring (phenylene) or a naphthalene ring (naphthyl).

Examples of the aliphatic hydrocarbon group of R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a 2-methylpropyl group, a tert-butyl group, a pentyl group, and a 2-pentyl group. Base, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, cyclopentyl Base, cyclohexyl and the like. R ^{9 is} preferably a methyl group.

Examples of the aliphatic hydrocarbon group of R ¹⁰ include a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a cycloheptyl group, and a methyl ring in addition to the groups exemplified for R ⁹ . Hexyl, hexylcyclohexyl, norbornyl, adamantyl and the like. Examples of the halogenated aliphatic hydrocarbon group of R ¹⁰ include a trifluoromethyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, 1-bromohexyl group, and 2-bromododecyl group. Examples of the aromatic hydrocarbon group of R ¹⁰ include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, and a hexylphenyl group. Cyclohexylphenyl, naphthyl, biphenyl, and the like. Further, examples of the halogenated aromatic hydrocarbon group of R ¹⁰ include a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorophenylphenyl group, a bromophenylphenyl group, a chloronaphthyl group, and a bromine group. Naphthyl and the like. R ^{10 is} preferably a phenyl group, a biphenyl group or a naphthyl group.

As the polymerization initiation aid (D1), for example, 2-benzylpyridylmethyl-3-methylnaphtho[2,1-d]thiazoline, 2-benzylidenemethyl-3-methyl Methylnaphtho[1,2-d]thiazoline, 2-benzylidene extended methyl-3-methylnaphtho[2,3-d]thiazoline, 2-(2-naphthoquinonemethyl) 3-methylbenzothiazoline, 2-(1-naphthylquinonemethyl)-3-methylbenzothiazoline, 2-(2-naphthylquinonemethyl)-3-methyl-5- Phenylbenzothiazoline, 2-(1-naphthylfluorenylmethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethyl)methyl- 5-fluorobenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2-naphthoquinonemethyl)-3-methyl- 5-chlorobenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylquinonemethyl)-3-methyl- 5-bromobenzothiazoline, 2- (1-Naphthylfluorenylmethyl)-3-methyl-5-bromobenzothiazoline, 2-(4-phenylbenzylidenemethyl)-3-methylbenzothiazoline, 2-( 4-phenylbenzimidylmethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethyl)-3-methylnaphtho[2,1-d Thiazoline, 2-(2-naphthylmethylidenemethyl)-3-methylnaphtho[1,2-d]thiazoline, 2-(4-phenylbenzhydrylmethyl)-3-methyl Naphtho[2,1-d]thiazoline, 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[1,2-d]thiazoline, 2-(p-fluoro Benzopyridylmethyl)-3-methylnaphtho[2,1-d]thiazoline, 2-(p-fluorobenzhydrylmethyl)-3-methylnaphtho[1,2-d Thiazoline, 2-benzylidene-methyl-3-methylnaphtho[2,1-d]oxazoline, 2-benzylidene-methyl-3-methylnaphtho[1,2- d] oxazoline, 2-benzylidene-methyl-3-methylnaphtho[2,3-d]oxazoline, 2-(2-naphthylmethyl)methyl-3-phenylbenzoate Oxazoline, 2-(1-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzone Oxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylfluorenylmethyl)-3-methyl-5-fluoro Benzo Oxazoline, 2-(1-naphthylquinonemethyl)-3-methyl-5-fluorobenzoxazoline, 2-(2-naphthylmethyl)methyl-5-chloride Benzooxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-chlorobenzoxazoline, 2-(2-naphthoquinonemethyl)-3-methyl-5 -Bromobenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-bromobenzoxazoline, 2-(4-phenylbenzylidenemethyl)-3 -methylbenzoxazoline, 2-(4-phenylbenzylidenemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethyl) 3-methylnaphtho[2,1-d]oxazoline, 2-(2-naphthoquinonemethyl)-3-methylnaphtho[1,2-d]oxazoline, 2-( 4-phenylbenzimidylmethyl)-3-methylnaphthyl [2,1-d]oxazoline, 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[1,2-d]oxazoline, 2-(p-fluorobenzene Methyl fluorenylmethyl)-3-methylnaphtho[2,1-d]oxazoline, 2-(p-fluorobenzhydrylmethyl)-3-methylnaphtho[1,2-d Oxazoline and the like.

In the above, 2-(2-naphthylfluorenylmethyl)-3-methylbenzothiazoline represented by the formula (D1-1), 2-benzylidene group represented by the formula (D1-2) 3-methylnaphtho[1,2-d]thiazoline, and 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[1] represented by formula (D1-3) , 2-d] thiazoline is preferred.

The resin composition containing the polymerization initiation aid (D1) tends to have high sensitivity and has a tendency to improve the productivity of the coating film or the pattern. The polymerization initiation aid (D1) is discolored by the action of light or heat, so that only the use of this can increase the visible light transmittance of the coating film or pattern.

The content of the polymerization initiation aid (D1) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more, more preferably in an amount of the polymerization initiation aid (D). 100% by mass or less is preferred. By using the polymerization initiation aid (D1) in this range, the visible light transmittance of the coating film can be improved.

Further, as the polymerization initiator (D), a compound represented by the formula (D2) or the formula (D3) can be used.

In the formula (D2) or the formula (D3), W ² and W ³ each independently represent a C _6-12 aromatic ring or a heterocyclic ring, and the aromatic ring and the hydrogen atom of the aforementioned hetero ring may be substituted by a halogen atom. L ⁶ and L ^{7 are} each independently and represent -O- or -S- (preferably -S-). R ¹¹ and R ¹² each independently represent a linear, branched or cyclic C _1-12 aliphatic hydrocarbon group or a C _6-12 aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the hydrogen atom of the aromatic hydrocarbon group are also It may be substituted by a halogen atom, a hydroxyl group or a C _1-6 alkoxy group.

Examples of the aromatic ring and the hetero ring of W ² and W ³ include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring, and the like (for example, Naphthalene ring, isobenzofuran ring, benzimidazole ring, etc.). Examples of the halogenated aromatic ring of W ² and W ³ include a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a phenylbenzene ring, a chlorophenylbenzene ring, and a bromophenylbenzene ring. Chlorophthalene ring, bromine ring, and the like. W ² and W ^{3 are} each independently, and preferably a benzene ring or a naphthalene ring is preferred.

Examples of the aliphatic hydrocarbon group of R ¹¹ and R ¹² , the halogenated aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the halogenated aromatic hydrocarbon group are those exemplified as R ¹⁰ . The aliphatic hydrocarbon group substituted with the hydroxyl group of R ¹¹ or R ¹² may, for example, be a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group. The aromatic hydrocarbon group substituted with the hydroxyl group of R ¹¹ or R ¹² may, for example, be a hydroxyphenyl group or a hydroxynaphthyl group. Examples of the aliphatic hydrocarbon group substituted by the alkoxy group of R ¹¹ or R ¹² include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, and a butoxymethyl group. Ethoxyethyl, ethoxypropyl, propoxybutyl and the like. Examples of the aromatic hydrocarbon group substituted by the alkoxy group of R ¹¹ or R ¹² include a methoxyphenyl group and an ethoxynaphthyl group. R ¹¹ and R ^{12 are} each independently and preferably represent a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.

As the polymerization initiation aid (D2) or (D3), for example,

a dialkoxynaphthalene such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene or dibutoxynaphthalene; dimethoxy oxime, diethoxy ruthenium, Dipropoxy ruthenium, ruthenium diisopropoxide, ruthenium dibutoxide, ruthenium pentoxide, bishexaoxy ruthenium, methoxyethoxy ruthenium, methoxypropoxy ruthenium, methoxy Isopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, ethoxybutoxy oxime, propoxyisopropoxy oxime, propoxy a dialkoxy anthracene such as bismuthoxy oxime or isopropoxy butyl oxime; dimethoxytetracene, diethoxytetracene, dipropoxytetracene, diisopropyloxy a dialkoxytetracene such as a tetracene, a dibutoxytetracene or the like;

<Multifunctional thiol (E)>

The resin composition of the present invention may contain a polyfunctional thiol as necessary (E).

The term "polyfunctional thiol" means "a compound having two or more sulfonyl groups in the molecule". In the polyfunctional thiol (E), a compound having two or more sulfonyl groups bonded to a carbon atom of an aliphatic hydrocarbon group is preferred because it can improve the sensitivity of the resin composition.

Examples of the polyfunctional thiol (E) include hexanedithiol, decanedithiol, 1,4-dimethylhydrothiobenzene, and butanediol bis(3-sulfonylpropionate). ), butanediol bis(2-sulfonyl acetate), ethylene glycol bis(2-sulfonyl acetate), trimethylolpropane ginseng (2-sulfonyl acetate), butyl Diol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (2-sulfonylacetate), pentaerythritol quinone (3-sulfonylpropionate), pentaerythritol bismuth (2-sulfonylacetate), hydroxyethyl ginseng (3-sulfonylpropionate), pentaerythritol bismuth (3-sulfonylbutyric acid) Ester), 1,4-bis(3-sulfonylbutenyloxy)butane, and the like.

When the polyfunctional thiol (E) is used, the content is preferably from 0.5 to 100 parts by mass, more preferably from 1 to 90 parts by mass, per 100 parts by mass of the polymerization initiator (C). When the polyfunctional thiol (E) is used in this range, the sensitivity can be improved and the development property tends to be good. Further, it is preferred that the polyfunctional thiol (E) is used in combination with the biimidazole compound of the polymerization initiator (C). If this combination is used, there is a tendency to improve the sensitivity.

<compound (F)>

The resin composition of the present invention is a compound containing a compound represented by the formula (F) Characterized by 1. By using the compound (F), it is possible to produce a film and a pattern which are less and uniformly coated. Further, the resin composition of the present invention can also form a coating film having high heat resistance.

The basis of the formula (F) will be described below in order.

In the formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group. Examples of L ¹ include an ethylidene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, and a butane-1,4-diene group. Base, 2,2-dimethylpropane-1,3-diyl, butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane Alkyl-1,4-diyl, heptane-1,7-diyl, octane-1,8-diyl and the like. Among them, 2,2-dimethylpropane-1,3-diyl is also preferred.

In the formula (F), L ² and L ^{3 are} each independently and represent a trivalent C _2-8 aliphatic hydrocarbon group.

Examples of L ² and L ³ include a group represented by the formula (f2-1) to the formula (f2-11), and those of the formula (f2-1) are also preferred. And the *print in the following formula represents a bonding position at which an oxygen atom in the formula (F) is bonded.

In the formula (F), R ¹ and R ² each independently represent a monovalent C _1-8 aliphatic hydrocarbon group, and at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted by a fluorine atom. Examples of R ¹ and R ² include at least 3 hydrogen atoms in the linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Substituted (eg, trifluoromethyl, etc.); such as 2-methylethyl, 2-methylpropyl, 2,2-dimethylethyl, 2-butyl, 2-pentyl, 2- At least a branched aliphatic hydrocarbon group of methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl or 2,2-dimethylpropyl 3 hydrogen atoms are replaced by fluorine atoms (for example, 2-trifluoromethylpropyl); at least 3 of cycloaliphatic, cyclohexyl, methylcyclohexyl, ethylcyclohexyl cyclic aliphatic hydrocarbon groups A hydrogen atom is replaced by a fluorine atom (for example, pentafluoroethylcyclohexyl). Among them, a linear one is preferred, and an ethyl group, a propyl group, a butyl group and a hexyl group having at least three fluorine atoms are preferred.

R ¹ and R ^{2 are} each independently, and the group represented by the formula (f1) is preferably: -C _p H _2p -C _q F _2q+1 (f1)

In the formula (f1), p and q are each independently, and represent an integer of 1 or more and 4 or less. p, preferably 1 or 2, more preferably 2. q, preferably 3 or 4, more preferably 4. Further, the group represented by the formula (f1) is preferably a linear chain. In the group represented by the formula (f1), ₂ , ₂ , 3, 3, 4, 4, 5, 5, ₅ -hexafluoropentyl {n-CF ₃ (CF ₂ ) ₃ CH ₂ -}, 3, 3,4,4,5,5,6,6,6-nonafluorohexyl{n-CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ -}, 4,4,5,5,6,6,7 7,7-nonafluoroheptyl {n-CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ -}, 5,5,6,6,7,7,8,8,8-nonafluorooctyl { More preferably, n-CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₄ -} is more preferably 3,3,4,4,5,5,6,6,6-hexafluorohexyl.

In the formula (F), m and n are each independently, and preferably 0 or more is preferable, preferably 1 or more, more preferably 2 or more, and most preferably 22 or less, more preferably 10 or less, still more preferably 6 or less. . However, m+n is preferably 3 or more, preferably 4 or more, 22 or less, more preferably 10 or less, still more preferably 6 or less.

The compound (F) is preferably represented by the formula (F1). [In the formula (F1), m, n, p and q have the same meanings as described above. The description of the group represented by -C _p H _2p -C _q F _{2q+1 is the same} as the description of the group represented by the formula (f1)].

In the compound (F1), a compound represented by the formula (F1-1) to the formula (F1-3) is preferred, and a compound (F1-1) is preferred, and a compound having m+n of 3 or more and 6 or less (F1- 1) It is more preferable [in the formula (F1-1) to the formula (F1-3), m and n have the same meanings as described above. -C ₄ F ₉ in the formula (F1-1) is preferably a linear chain. ]

The content of the compound (F) is preferably 0.001 to 0.15% by mass, more preferably 0.01 to 0.1% by mass, even more preferably 0.02 to 0.1% by mass, based on the solid content of the resin composition. When the content of the compound (F) is in this range, a coating film having less spots can be easily obtained.

Compound (F) can be produced by various reaction routes. For example, the preferred compound (F1) can be etherified by using a compound of the formula (f3) and a compound of the formula (f4) (i.e., 2,2-dimethyl-1,3-propanediol). And manufacturing. Still preferably the compound (F1) by OMNOVA Company available PolyFox ^TM PF-7002 and the like.

<Other additives (G)>

The resin composition of the present invention may contain other additives (G) as necessary.

Examples of the other additive (G) include a colorant, a pigment dispersant, a filler, a polymer compound different from the resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain. A moving agent, a surfactant, and the like.

As the coloring agent, a compound classified as a coloring matter by a color index (published by The Society of Dyers and Colourists) can be cited. For details, 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, 137, 138, 139 Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigments orange 13, 13, 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, Red pigments such as 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; CI pigment blue 15, 15, 3, 15:4, 15:6 , 60 such as blue pigment, CI pigment purple 1,19,23,29,32,36,38 and other purple pigments; CI pigment green 7,36,58 and other green pigments; CI pigment brown 23,25 and other brown pigments; CI Pigment black 1, 7 and other black pigments.

In the present specification, only "C.I. Pigment Yellow" or the like is described for the first pigment, and only the number is described for the same pigment.

As the pigment dispersant, a surfactant can be used. The surfactants can be classified into cationic, anionic, nonionic, and amphoteric, and can be classified into esters, amines, acrylics, and polyoxygens. Examples of the surfactant include polyethylene oxide alkyl ethers, polyethylene oxide alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polycondensates. Ester, tertiary amine modified polyurethane, polyethyleneimine, and the like. Further, for the surfactant to be sold, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Poly-Flow (registered trademark) (manufactured by Kyoei Chemical Co., Ltd.), and SOLSPERS (registered trademark) (Zeneca) can be used. (share) system, EFKA (manufactured by CIBA Co., Ltd.), AJISPER (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (BKY company), and the like.

Examples of the filler include glass, cerium oxide, and aluminum oxide. Wait.

Examples of the polymer compound include an epoxy resin (for example, an o-methyl novolone type epoxy resin), a curable resin such as a maleimide resin, a polyvinyl alcohol, a polyacrylic acid, and a polyethylene glycol monoalkane. Thermoplastic resins such as alkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, and 3-aminopropyl trimethoxy decane. , N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3 - Hydrogenthiopropyltrimethoxydecane, and the like.

The antioxidant may, for example, be 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate or 2-[ 1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl) 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxin Heterogene, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy}-1,1-dimethylethyl ]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-extended methyl bis(6-tert-butyl-4-methylphenol), 4,4'-Adenine Bis (6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-sulfur double (6-tert -butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol bismuth (3-laurel thiopropyl) Acid ester), 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-Triketone, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl Tri-p-cresol, pentaerythritol 肆 [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methyl Further, as the antioxidant, a trade name such as "IRGANOX 3114" available from Ciba Japan Co., Ltd., or the like can be used.

Examples of the ultraviolet absorber include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole and octyl-3-[3-tert-butyl-4-hydroxy- 5-(5-Chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy] -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2') -ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis (2 -hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1 -octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(2H-benzotriazol-2-yl -4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) 4-(1,1,3,3-tetramethylbutyl)phenol, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriene Azole, alkoxybenzophenone, and the like.

Examples of the photosensitizer include a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol; N, N', N" ,N'"-肆(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethyl) Piperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine; decane dibasic acid, bis(2,2,6,6 -tetramethyl-1-(octyloxy)-4-piperidinyl ester, a reaction with 1,1-dimethylethylhydroperoxide; double (1,2,2,6,6 -pentamethyl-4-piperidine)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate; 2,4- Bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)- 1,3,5-triazine; bis(1,2,2,6,6-pentamethyl-4-piperidine) sebacate; methyl (1,2,2,6,6-penta Keto-4-piperidine) sebacate and the like.

Examples of the chain shifting agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

As a surfactant, a polyoxyl surfactant is mentioned, for example. As the polyoxymethylene surfactant, a surfactant having a decane bond can be mentioned.

Specifically, Toray polyoxyl DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified polyoxyl SH8400 (trade name: Dow Corning Toray) System, KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan) Contract company system) and so on.

The content of the surfactant is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass, based on the curable resin composition. The upper portion is 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less. When the surfactant is contained in the above range, the flatness of the coating film can be improved.

Further, the above surfactant is different from the above pigment dispersant.

<Solvent (H)>

As the solvent (H), those which can be uniformly dissolved or dispersed in each component such as the resin (A) and which do not react with each component are used. From the viewpoint of coatability and dryness, an organic solvent having a boiling point of from 100 ° C to 200 ° C is preferred. As the solvent (H), for example, the following can be used.

Ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; ethylene glycol monomethyl ether acetate Ester, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate An alkanediol alkyl ether acetate such as methoxypentyl acetate.

Propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, Propylene glycol dialkyl ether such as propylene glycol dipropyl ether propylene glycol propyl methyl ether or propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, Propylene glycol alkyl ether propionate such as propylene glycol butyl ether propionate.

Butanediol monoalkyl ethers such as methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol; methoxybutyl acetate, ethoxybutyl acetate Butanediol monoalkyl ether acetates such as propoxy butyl acetate and butoxybutyl acetate; methoxybutyl propionate, ethoxybutyl propionate, propoxy Butanediol monoalkyl ether propionates such as butyl propionate and butoxybutyl propionate.

Diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol methyl ethyl ether Dipropylene ethers; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether.

An aromatic hydrocarbon such as benzene, toluene, xylene or mesitylene; a ketone such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone.

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxyl Propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxy Butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxy Propyl acetate, butyl oxyacetate, methyl butoxyacetate, butoxyacetate Ester, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxy Methyl propyl propionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propyl propyl propionate, butyl 3-ethoxypropionate, 3. methyl propoxy propionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

a cyclic ether such as tetrahydrofuran or pyran; or a cyclic ester such as γ-butyrolactone.

Among the above, alkylene glycol alkyl ether acetates (more preferably propylene glycol monomethyl ether acetate), ketones (more preferably cyclohexanone), butanediol monoalkyl ether acetates ( More preferably methoxybutyl acetate), butanediol monoalkyl ether (more preferably methoxybutanol), diethylene glycol dialkyl ether (more preferably diethylene glycol B) Methyl ether), an ester (more preferably ethyl 3-ethoxypropionate or methyl 3-methoxypropionate) is preferred.

The content of the solvent (H) is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 95% by mass or less, and still more preferably 90% by mass or less based on the resin composition.

<Coating film, pattern, display device>

In the coating film of the present invention, the resin composition is applied to a substrate (for example, a substrate such as glass, tantalum, metal, or plastic, or a substrate formed of a resin layer or an inorganic compound layer), and then coated. Thermal polymerization and/or photopolymerization can form a coating film. The coating method for forming the coating film is not particularly limited, and a known method such as a spin coating method can be used.

The pattern of the present invention can be formed, for example, by using a spray machine or the like, and after the resin composition of the present invention is applied to a pattern, it can be formed by thermal polymerization or photopolymerization. Further, when a photosensitive resin composition of the present invention containing a photopolymerization initiator (C) is used, a pattern can be formed by photolithography. In the photoetching method, the patterning is generally carried out by application of a photosensitive resin composition, solvent removal, heating (pre-bake) before exposure, exposure, development, heating after development (post-baking), and each step.

The resin composition of the present invention containing the compound (F) can form a coating film having less spots. Therefore, it is possible to manufacture a coating layer and a pixel pattern for a large display device.

The coating film and pattern of the present invention can be applied, for example, to a transparent film of a constituent element such as a color filter or an array substrate of a display device, a color filter coloring pattern, a photoresist spacer, an ultra-coating film, an insulating film, and a liquid crystal. Orientation protrusions, microlenses, coating layers, and the like. Since the coating film and the pattern of the present invention exhibit sufficient adhesion to the substrate, it is particularly useful as a coating film or pattern formed on the substrate. As the display device, a liquid crystal display device, an organic EL display device, or the like is preferable.

[Examples]

The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples, and it is undoubtedly described above. The scope of the following gist of the subject matter can be appropriately changed and implemented, and they are all included in the technical scope of the invention.

In addition, the "%" and "parts" of the following components are not specifically described, and indicate "% by mass" and "parts by mass".

1. Synthesis of resin (A)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare a nitrogen atmosphere, and 130 parts of 3-methoxybutyl acetate and 3-methoxy-1-butin were placed. 110 parts of alcohol was heated to 80 ° C while stirring. Next, 40 parts of methacrylic acid, a mixture of monomer (b1-1-1) and monomer (b1-2-1) {monomer (b1-1-1) in the mixture: monomer (b1-2- 1) Mohr ratio = 50: 50} 360 parts, and 36 parts by weight of azobisdimethylvaleronitrile are dissolved in 210 parts of 3-methoxybutyl acetate and 3-methoxy-1-butene A mixed solution of 170 parts of alcohol was added dropwise over 5 hours, and after aging for 3 hours, it was cooled to room temperature to obtain a solution of a copolymer having a solid content of 43.1% and an acid value of 60 mg-KOH/g. This copolymer was used as the resin (A1). The obtained resin (A1) had a weight average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 1.95.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (A1) were carried out under the following conditions using a GPC method.

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

Standard: Polystyrene

2. Modulation of resin composition

The components shown below were mixed in the amounts shown in Table 1 to obtain resin compositions 1 to 6.

Resin (A): Resin (A1) solution (Table 1 shows the amount of the resin (A1) in terms of solid content)

Polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (C): 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (B-CIM; Baotu Valley Chemical (share) system)

Polymerization initiation aid (D): 2-(2-naphthoquinonemethyl)-3-methylbenzothiazoline polyfunctional thiol (E): pentaerythritol bismuth (3-sulfonylpropionate) PEMP; SC organic chemistry (share) system)

Compound (F): PolyFox ^TM PF-7002 represented by formula (F1-1-1) (manufactured by OMNOVA, formula (F1-1-1), m'+n'≒4~5)

Other additives (G)

(G1): o-methyl phenolic epoxy resin (Sumi epoxy ESCN-195XL-80; manufactured by Sumitomo Chemical Co., Ltd.)

(G2): IRGANOX3114 (manufactured by Ciba Japan)

(G3): 3-aminopropyltrimethoxydecane (KBM-903; Shin-Etsu Chemical Co., Ltd.)

(G4): Polyether modified polyoxyxide oil (SH8400 manufactured by Dow Corning Toray Co., Ltd.)

Solvent (H)

(H1): ethyl 3-ethoxypropionate

(H2): 3-methoxy-1-butanol

(H3): 3-methoxybutyl acetate

(H4): propylene glycol monomethyl ether acetate

(H5): diethylene glycol ethyl methyl ether

1 The value of the resin (A) to other additives (G) indicates the amount of each component (parts by mass).

2 Solvent (H) is the solid content of the mixed composition to the above (% by mass).

The value of the solvent components (H1) to (H5) in the solvent (H) represents the mass ratio in the solvent (H).

3. Evaluation of resin composition

The striation and unevenness of the coating film obtained in the above compositions 1 to 7 were evaluated as follows.

Moreover, the heat resistance of the coating film obtained by each of the composition 4 and the composition 6 was evaluated as follows.

(1) Stripe evaluation

To evaluate the streaks of the coating films obtained by the compositions 1 to 7, first, using the colored resin composition of the composition shown in Table 2, a color pattern is formed on the crucible substrate. Next, using the compositions 1 to 7, a coating film was formed on the substrate on which the color pattern was formed. Here, the streak indicates a radial spot of the coating film from the step of the coloring pattern.

The 4 inch crucible substrate was washed successively with a neutral detergent, water and 2-propanol, and dried. On the substrate thus obtained, the film thickness after spin coating of the colored resin composition to post-baking was 3.0 μm. Next, the spin-coated colored resin composition layer was prebaked in a dust-free oven for 3 minutes at 90 °C. After cooling, the distance between the substrate on which the colored resin composition layer was applied and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; TOPCON, light source; ultrahigh pressure mercury lamp) was used, and the atmosphere was 100 mJ. The exposure amount of /cm ² (365 nm reference) was exposed. Further, at this time, the exposure of the colored resin composition layer was carried out by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (UV-35; Asahi Techno GLASS Co., Ltd.). Further, as a photomask, a mask (having a light-transmitting portion having a square length of 10 mm and a square of 100 mm) was formed on the same plane. After the exposure, the colored resin composition layer exposed to a water-based developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide was immersed at 23 ° C for 80 seconds, and after water washing, the oven was at 220. After baking for 20 minutes at ° C, a color pattern of 10 mm side length was formed on the substrate.

The composition 1 to 6 was applied under the conditions of a film thickness of the coloring pattern formed by spin coating and a film thickness after hardening of 2.0 μm. Thereafter, the pressure was reduced to a reduced pressure of 1.0 Torr (about 1.3 × 10 ² Pa) by a vacuum dryer (manufactured by VCD Microtek Co., Ltd.) and dried. Next, it was pre-baked on a hot plate set at 90 ° C for 2 minutes to form a coating film. After cooling, the surface of the coating film was irradiated with a Na lamp, and the surface of the coating film was visually confirmed. When the streaks were not confirmed on the substrate, it was evaluated as good (○) (very good), and when it was not confirmed, it was evaluated as poor (×) (bad). The results are shown in Table 3.

(2) Cloud fog assessment

In the same manner as in the evaluation of the stripes, a coating film was formed on the substrate on which the coloring pattern was not formed, and the surface of the coating film was visually confirmed by irradiating the surface of the coating film with a Na lamp. When the uneven cloud-like plaque was not confirmed on the coating film, it was evaluated as good (○) (very good), and when the cloud-like plaque was slightly confirmed, it was a level (?) which was not practical, and it was confirmed to be cloudy. Spot time was evaluated as poor (x) (bad). The results are shown in Table 3.

(3) Heat resistance evaluation

A glass substrate (Eagle 2000; manufactured by Corning) having a length of 2 inches was washed with a neutral detergent, water, and 2-propanol, followed by drying. The composition 4 or the composition 6 was applied on the glass substrate by a spin coating method, baked in a dust-free oven at 100 ° C for 3 minutes, and further baked at 220 ° C for 20 minutes to form a coating film. The coating film thus formed was heated in a dust-free oven at 240 ° C for 4 hours, and the transmittance (%) of the coating film at a wavelength of 400 nm was performed by a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.). Determination, the retention of transmittance is obtained from formula (i):

Permeability retention rate (%) = 100 × transmittance after heating (%) / transmittance before heating (%) (i)

The results are shown in Table 3. When the retention of the transmittance is 90% or more, the heat resistance of the coating film can be judged to be good.

From the results shown in Tables 1-3, the composition containing the compound (F) 1~ 4 and 7 For the compositions 5 and 6 which do not contain the compound (F), a coating film having less spots can be formed. Further, the coating film obtained from the composition 4 has a higher transmittance and a higher heat resistance than the coating film obtained from the composition 6.

[Industrial availability]

The resin composition of the present invention containing the compound (F) is a coating film and a pattern which are excellent in coatability and have few spots. Therefore, when the resin composition of the present invention is used, a high-quality display device can be produced at a high yield. In particular, the resin composition of the present invention is suitable for use in the production of coating layers and pixel patterns of large display devices.

Claims (11)

A resin composition comprising a resin, a polymerizable compound, a compound represented by the formula (F), and a solvent; [In the formula (F), L ¹ represents a divalent C _2-8 aliphatic hydrocarbon group; and L ² and L ³ each independently represent a trivalent C _2-8 aliphatic hydrocarbon group; and R ¹ and R ² each independently represent a formula ( F1) The group shown; -C _p H _2p -C _q F _2q+1 (f1) [In the formula (f1), p represents an integer of 1 or more and 4 or less, and q represents an integer of 4], and m and n are independent, An integer of 0 or more and 22 or less is shown; however, m+n is 3 or more and 22 or less]. The resin composition of claim 1, wherein the compound represented by the formula (F) is a compound represented by the formula (F1-1); [In the formula (F1-1), m and n have the same meanings as described above]. The resin composition of claim 1, wherein m+n is 3 or more and 6 or less. The resin composition of claim 1, wherein the resin is a structural unit containing at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and derived from having carbon-carbon A copolymer of structural units of a monomer (b) having a double bond and a cyclic ether structure which is different from the monomer (a). The resin composition of claim 4, wherein the monomer (b) is at least one selected from the group consisting of a compound represented by the formula (b1-1) and a compound represented by the formula (b1-2); In the formula (b1-1) and the formula (b1-2), R ³ represents a hydrogen atom or a C _1-4 aliphatic hydrocarbon group, and a hydrogen atom of the above aliphatic hydrocarbon group may be substituted with a hydroxyl group; L ⁴ represents a single bond or C _{1 -6} aliphatic hydrocarbon group, -CH ₂ - of the above aliphatic hydrocarbon group may be substituted by -O-, -S- or -NH-; and R ³ and L ⁴ in the formula (b1-1) may each be a formula (b1-2) R ³ and L ^{4 are the} same or different]. The resin composition of claim 1, further comprising a polymerization initiator. The resin composition of claim 6, wherein the polymerization initiator is a polymerization initiator containing a diimidazole compound. A coating film characterized by using the first item of the patent application scope It is formed by a resin composition. A pattern characterized by being formed using a resin composition as in claim 6 of the patent application. A liquid crystal display device comprising at least one selected from the group consisting of a coating film of claim 8 and a pattern of claim 9 of the patent application. An organic EL display device characterized by comprising at least one selected from the group consisting of a coating film of claim 8 and a pattern of claim 9 of the patent application.