TWI476240B - Resin composition - Google Patents

Description

Resin composition

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 pixel of a color filter used for a display device such as a liquid crystal is generally formed by photolithography (photolithography) using a photosensitive resin composition. Specifically, a photosensitive resin composition of any one of red, green, or blue is applied onto a substrate by using a coating device, and the volatile component is removed by heating or the like, and exposed through a mask, and then negatively formed. In the case where the unexposed portion is formed, if it is a positive type, the exposed portion is formed by removing the developing solution such as an aqueous alkali solution and developing it to form a color pattern, so that the colored pattern is heated to form a pixel. Next, using the same operation and the remaining two colors of the photosensitive resin composition, each of them was colored to form a color pattern, and finally a color filter having three colors of each pixel was formed.

The coloring pattern obtained from the above resin composition pursues good adhesion to the substrate. In order to improve the adhesion to the substrate, there is a case where a decane compound is added to the resin composition. For example, in Patent Document 1, in order to improve the adhesion to a glass substrate, it is disclosed that an amino group-containing decane compound is used.

[Patent Document 1] JP-A-2000-35670

When an amino group-containing decane compound is used, there is a case where sufficient adhesion to the substrate cannot be achieved. Further, in the resin composition containing an amino group-containing decane compound, there is a poor preservation stability. The present invention has been made in view of such a situation, and an object thereof is to provide a resin composition which has sufficient adhesion to a substrate and is excellent in storage stability.

That is, the present invention provides the following [1] to [12].

[1] A resin, a polymerizable compound, a polymerization initiator, an isocyanato-containing decane compound, and a solvent, wherein the resin is at least 1 selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. A resin composition of a monomer (a) and a copolymer of a monomer (x) having a carbon-carbon double bond and different from the monomer (a).

[2]. The monomer (x) contains the resin composition of [1] of the monomer (b) having a carbon-carbon double bond and a cyclic ether structure.

[3]. The monomer (x) comprises a resin composition of [2] having a carbon-carbon double bond and an epoxy structure monomer (b1).

[4] The isocyanatodecane compound is a resin composition of any one of [1] to [3] of the compound represented by the formula (F1).

OCN-L-Si(R ¹ ) _m1 (R ² ) _(3-m1) (F1)

(In the formula (F1), L is a C _1-6 alkanediyl group. R ¹ is a C _1-4 alkyl group, and m1 is 0 or 1. However, when m1 is 0, R ¹ is absent. R ² is C _{1- 4} alkoxy, plural R ² may be the same or different from each other.]

Further, in the scope of the present specification and the patent application, "C _xy " means "the number of carbons is x or more and y or less". Further, the "compound represented by the formula (F1)" below may be simply referred to as "compound (F1)". The compounds represented by the other formulae and the like are also referred to as abbreviations.

[5] A resin composition according to any one of [1] to [4], wherein the content of the isocyanate-containing decane compound is from 0.1% by mass to 15% by mass based on the solid content of the resin composition.

[6]. A resin composition according to any one of [1] to [5] which further contains a coloring agent.

[7] The polymerization initiator is a resin composition of any one of [1] to [6] selected from the group consisting of a biimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound.

[8]. A resin composition according to any one of [1] to [7] which further contains a compound having two or more sulfonyl groups.

[9] A coating film formed using the resin composition of any one of [1] to [8].

[10]. A pattern formed by using the resin composition of any one of [1] to [8].

[11] A liquid crystal display device comprising at least one selected from the group consisting of the coating film of [9] and the pattern of [10].

[12] At least one organic EL display device selected from the group consisting of the coating film of [9] and the pattern of [10].

Best form for implementing the invention

The resin composition of the present invention contains the resin (A), the polymerizable compound (B), the polymerization initiator (C), the isocyanatodecane-containing compound (F), and the solvent (J), and may be polymerized as the case may be. Starting auxiliaries (D), polyfunctional thiols (E), colorants (G) and other additives (H). Each of the above components may be used singly or in combination of two or more kinds without particular limitation.

The resin (A) contains a copolymer derived from a structural unit of at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and has a carboxyl group or a carbonyl oxygen which can form a carboxyl group. Alkylcarbonyl (carboxylic acid anhydride structure). When the resin (A) having a carboxyl group or the like and a decane compound (that is, a decane coupling agent) are mixed, they are mutually reacted to increase the viscosity, and the stability of storage stability is lowered. Surprisingly, however, it has been found that by using the isocyanato-containing decane compound (F), the preservation stability is good.

Among the amino group-containing decane compounds, there is also a case where the storage stability of the resin composition is not lowered. However, such an amino group-containing decane compound has a situation in which sufficient adhesion cannot be ensured to the substrate (refer to the following examples). In the case of using an isocyanato-containing decane compound, in addition to good storage stability, it is possible to ensure sufficient adhesion to the substrate.

Hereinafter, each component contained in the resin composition of the present invention will be described in order.

<Resin (A)>

The resin (A) is at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; (a); and a monomer having a carbon-carbon double bond and different from the monomer (a) (x); copolymer. Each of the monomer (a) and the monomer (x) may be used alone or in combination of two or more.

In terms of monomer (a), for example, (meth)acrylic acid, crotonic acid, cinnamic acid, o-, m-, p-vinylbenzoic acid, succinic acid mono[2-(methyl)acryloxyethyl] , phthalic acid mono [2-(methyl) propylene oxiranyl ethyl], ω-carboxy polycaprolactone mono (meth) acrylate, 5-carboxy-5-methyl bicyclo [2.2.1] g 2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 -Unsaturated monocarboxylic acids such as ethylbicyclo[2.2.1]hept-2-ene; maleic acid, fumaric acid, citraconic acid, methyl fumarate, itaconic acid, 3-vinyl phthalic acid, 4 -vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexane Unsaturated dicarboxylic acids such as enedicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4 - vinyl phthalic 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 (nadic anhydride) Unsaturated dicarboxylic anhydrides; and the like.

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

The monomer (a) is preferably at least one 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 a 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. The monomer (b) having a cyclic ether structure may, for example, be a monomer having an epoxy structure (b1), a monomer having an oxetane structure (b2), and a monomer having a tetrahydrofuran structure (b3). Wait. Among these, the monomer (b1) having an epoxy structure and the monomer (b2) having an oxetane structure are preferred, and the monomer (b1) having an epoxy structure is more preferable.

Epoxy construction can be classified as

(1) a structure in which a single ring has an oxirane ring (that is, a structure in which an olefin is epoxidized) (hereinafter referred to as "structure (1)"), and

(2) A structure in which an alicyclic hydrocarbon ring is condensed with an oxirane ring (structure represented by the following formula (b1-0)) (hereinafter referred to as "structure (2)").

(In the formula (b1-0), W ⁰ is a ring of an alicyclic hydrocarbon.]

Furthermore, the alicyclic epoxy structure can be classified into

(2-1) The ring of the alicyclic hydrocarbon is a single ring (the structure represented by the formula (b1-0), and W ⁰ is a structure of a ring of a monocyclic alicyclic hydrocarbon) (hereinafter referred to as "structure (2) -1)"), and

(2-2) The ring of the alicyclic hydrocarbon is a polycyclic ring (in the structure represented by the formula (b1-0), and W ⁰ is a structure of the bridged ring) (hereinafter referred to as "structure (2-2)")

. Among these, the structure (2) is preferred, and the structure (2-2) is more preferable.

For the monomer (b1) having the structure (1), for example, epoxy propyl (meth) acrylate, β-methyl propyl propyl (meth) acrylate, β-ethyl epoxypropyl group (A) In the formula (b1-1) of the formula (b1-1), which is represented by the formula (b1-1) of JP-A-H07-248625, R ³ to R ⁵ are each independently represented. A hydrogen atom or a C _1-10 alkyl group. M2 is an integer from 1 to 5. }.

【化1】

For the monomer (b1-1) having the structure (1), for example, o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, p-vinylbenzyloxypropyl Ether, α-methyl-o-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzyl epoxide Ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl) ) styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-para (epoxy Propyloxymethyl)styrene, 2,3,6-glycol (glycidoxymethyl)styrene, 3,4,5-glycol (glycidoxymethyl)styrene, and 2, 4,6-gin (glycidoxymethyl)styrene and the like.

In the aspect of the monomer (b1) having the structure (2-1), for example, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Chemical Industries Limited), 2, 3 Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLMER (registered trademark) A400; manufactured by Daicel Chemical Industries Limited), 3,4-ring Oxycyclohexylmethyl methacrylate (for example, CYCLMER (registered trademark) M100; manufactured by Daicel Chemical Industries Limited) or the like.

The monomer (b1) having the structure (2-2) may have a carbon-carbon double bond in the polycyclic aliphatic hydrocarbon group or a carbon-carbon double bond in the ring-bonded side chain. In the case of a polycyclic ring, for example, a norbornane ring, a tricyclodecane ring, etc., a tricyclodecane ring is preferred among these.

For the monomer (b1) having the structure (2-2), for example, an epoxy norbornene (meth) acrylate {for example, 3,4-epoxynorbornyl (meth) acrylate}, formula (b1- 2) a monomer represented by the formula and a monomer represented by the formula (b1-3).

[Chemical 2]

In the formula (b1-2) and the formula (b1-3), R ⁶ is a hydrogen atom or a C _1-4 saturated aliphatic hydrocarbon group, and the hydrogen atom of the saturated aliphatic hydrocarbon group may be substituted with -OH. L ¹ is a single bond or a divalent C _1-6 saturated aliphatic hydrocarbon group, and the above-mentioned divalent saturated aliphatic hydrocarbon group -CH ₂ - may be substituted by -O-, -S- or -NR ⁷ -, the aforementioned R ⁷ It is a hydrogen atom or a C _1-10 saturated aliphatic hydrocarbon group.

Further, each of R ⁶ and L ^{1 in the} formula (b1-2) may be the same as R ⁶ and L ¹ in the formula (b1-3), or may be different. Also, the symbols common to the other formulas in the present specification may be the same or different in each of the formulas. Further, "CH ₂ - a divalent saturated aliphatic hydrocarbon group substituted by -O- or the like" means "apparently, a group of a 2-valent saturated aliphatic hydrocarbon group-CH ₂ - is substituted by -O- or the like" Instead of "substantially synthesizing a divalent saturated aliphatic hydrocarbon group, the -CH ₂ - is substituted with -O- or the like" and the like. The "saturated aliphatic hydrocarbon group in which a hydrogen atom is substituted with -OH" is also the same.

R ⁶ may also be a hydroxy-substituted saturated aliphatic hydrocarbon group, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, hydroxymethyl, 1-hydroxyethyl , 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxyl Butyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like. R ^{6 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 saturated aliphatic hydrocarbon group which may be substituted with -O- or the like of L ¹ may, for example, be a methylene group, an ethylene 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, methyleneoxy (-CH ₂ -O-), Ethyleneoxy{-(CH ₂ ) ₂ -O-}, propanedioxy {-(CH ₂ ) ₃ -O-, etc.}, methylenesulfanediyl (-CH ₂ -S-), sub Ethylsulfanyldiyl {-(CH ₂ ) ₂ -S-}, propane diylsulfanyldiyl {-(CH ₂ ) ₃ -S-, etc.}, methyleneimido (-CH ₂ -NH) -), ethyleneimine {-(CH ₂ ) ₂ -NH-}, propane diiminoimide {-(CH ₂ ) ₃ -NH-, etc.}. L ^{1 is} preferably a single bond, a methylene group, an ethylene group, a methyleneoxy group, an ethyleneoxy group, an ethylenesulfanediyl group, or an ethyleneimine group, more preferably a single bond or an ethylene group. Oxygen.

Each of the monomer (b1-2) and the monomer (b1-3) may be used alone or in combination of two or more. Further, a mixture of the monomer (b1-2) and the monomer (b1-3) can also be used. When such a mixture is used, the monomer (b1-2): monomer (b1-3) preferably has a molar ratio of 5:95 to 95:5, more preferably 10:90 to 90:10, and more. Good for 20:80 ~ 80:20.

The preferred monomer (b1-2) is represented by any one of the formulae (b1-2-1) to (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) to monomer (b1-2-15) are better, monomer (b1-2-1), monomer (b1-2-7), monomer (b1-2-9) and monomer (b1-2-15) are even better.

[化3]

The preferred monomer (b1-3) is represented by any one of the formulae (b1-3-1) to (b1-3-15). Among these, monomer (b1-3-1), monomer (b1-3-3), monomer (b1-3-5), monomer (b1-3-7), monomer (b1- 3-9), and monomer (b1-3-11) to monomer (b1-3-15) are more preferable, monomer (b1-3-1), monomer (b1-3-7), monomer (b1-3-9) and monomer (b1-3-15) are even better.

【化4】

In the case of a monomer (b2) having an oxetane structure, for example, 3-(meth)acryloxymethyloxybutane, 3-methyl-3-(methyl)propenyloxymethyl Oxycyclobutane, 3-ethyl-3-(methyl)propenyloxymethyloxetane, 3-methyl-3-[1-(methyl)propenyloxy]A Oxycyclobutane, 3-ethyl-3-[1-(methyl)propenyloxy]methyloxetane, 3-methyl-3-[1-(methyl)propene oxime Oxy]ethyloxetane, 3-ethyl-3-[1-(methyl)propenyloxy]ethyloxetane, 2-phenyl-3-(methyl)propene醯oxymethyloxetane, 2-trifluoromethyl-3-(methyl)propenyloxymethyloxetane, 2-pentafluoroethyl-3-(methyl)propene醯oxymethyloxetane, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-methyl-3-(methyl)propenyloxy B Oxycyclobutane, 2-phenyl-3-(methyl)propenyloxyethyloxetane, 2-trifluoromethyl-3-(methyl)propenyloxyethyloxy Heterocyclic butane or 2-pentafluoroethyl-3-(methyl)propenyloxyethyloxetane, 3-(meth)acryloxyoxybutane and the like. Among these, 3-ethyl-3-(methyl)propenyloxymethyloxetane is preferred.

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

The monomer (x) may contain a monomer (a) and a monomer (c) different from the monomer (b). In the monomer (c) aspect, for example, a carboxylic acid ester having a carbon-carbon double bond, an amide having a carbon-carbon double bond, or a polymerizable unsaturated bond in a side chain (carbon-carbon double bond or triple bond) 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.

Specific examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate (a customary name for "dicyclopentyl (meth) acrylate" in this field), 4-tricyclic [5.2.1.0 ^2,6 ] 癸Alkene-8-yl (meth) acrylate, 5-tricyclo[5.2.1.0 ^2,6 ]nonene-8-yl (meth) acrylate, phenyl (meth) acrylate, aminoethyl Unsaturated carboxylic acid esters such as (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate; carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate ; decylamines having carbon-carbon double bonds such as dimethyl (meth) acrylamide, isopropyl (meth) acrylamide; styrene, α-methyl styrene, vinyl toluene, p- Methoxystyrene is equivalent to an aromatic compound having a polymerizable unsaturated bond in a side chain; acrylonitrile, methyl a vinyl cyanide compound such as an alkenonitrile or an α-chloro(meth)acrylonitrile; a halogenated vinyl compound such as vinyl chloride, dichloroethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene or tetrafluoroethylene; -methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N N-substituted maleimide such as phenylmaleimide; diene such as 1,3-butadiene, isoprene or 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] Hept-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- Alkene, 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-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2 .1]hept-2-ene, 5-hydroxy-5-B Bicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2 Polycyclic unsaturation such as olefin, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene Compound;

In monomer (c), benzyl acrylate, styrene, N-cyclohexylmaleimide, N-benzyl maleimide, N-phenyl maleimide, bicyclo [2.2. 1] Hept-2-ene is preferred.

For the monomer (x), only one of the monomer (b) or the monomer (c), or both, 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) has improved heat resistance, light resistance, solvent resistance, and mechanical properties of the coating film or pattern obtained in the resin composition.

When the resin (A) is a copolymer of the monomer (a) and the monomer (b), in the total constituent unit of the copolymer, the structural unit derived from the monomer (a) is preferably 2 to 98 mol% (more) Preferably, it is 5 to 60 mol%, more 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%). More preferably, it is 50 to 90% by mole). In this range, the storage stability and developability of the resin composition, and the residual film ratio and solvent resistance of the cured coating film or pattern tend to be improved.

When the resin (A) is a copolymer of the monomer (a) and the monomer (c), the total structural unit of the copolymer is 2 to 98 mol% based on the structural unit derived from the monomer (a), from the single The structural unit of the body (c) is preferably from 2 to 98 mol%. If it is in this range, the stability or heat resistance tends to be improved. 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 derived from the monomer (c) is 50 to 95% by mole. If it is in this range, the developability or the residual film ratio tends to be improved.

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 in the entire structural unit of the copolymer. The molar %, 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 in this range, the stability, heat resistance, and mechanical strength tend to be improved. 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 developability, residual film rate, or solvent resistance will also become favorable.

The resin (A) can be referred to, for example, the method described in the literature "Experimental method for polymer synthesis" (Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972). The literature is produced by polymerization of monomers. More specifically, a specific amount of the monomer (a), and the monomer (b) and/or the monomer (c), the polymerization initiator, and the solvent may be placed in a reaction vessel, and in the absence of oxygen by nitrogen substitution, The copolymer is produced by stirring, heating, and heat preservation. The operation method of the copolymerization or the reaction temperature may be appropriately adjusted in consideration of the heat generation amount by the production equipment or the polymerization.

The resulting copolymer can also be used directly as a solution after the reaction. In particular, when the solvent (J) described later is used as a polymerization solvent, the solvent can be directly used for the resin composition without removing the solvent from the copolymer solution after polymerization, and the production steps can be simplified. The copolymer solution can be concentrated or diluted. Further, a copolymer which is taken out as a solid (powder) by a method such as reprecipitation can also be used.

Further, the resin (A) may have a structural unit (d) having a carbon-carbon double bond in a side chain. The structural unit (d) is represented by the formula (d1) or the formula (d2), and preferably has a 1-alkyl-1-vinylcarbonyl group at the terminal, and more preferably a (meth)acryl fluorenyl group at the terminal.

【化5】

In the formula (d1) and the formula (d2), R ⁸ and R ⁹ each independently represent a hydrogen atom or a C _1-6 alkyl group (preferably a hydrogen atom or a methyl group). Further, the * marks in the formulas (d1) and (d2) each indicate the bonding position in the structural unit (d1) and the structural unit (d2). Other chemical formulas are the same.

The structural unit (d) having a carbon-carbon double bond in a side chain can be obtained from a monomer (a) by copolymerizing the monomer (a) and the monomer (b) and/or the monomer (c). a carboxyl group or a carbonyloxycarbonyl group (carboxylate structure), which is a monomer (b) having a carbon-carbon double bond and a cyclic ether structure, as described in JP-A-2005-189574, for example. a carbon-carbon double bond and an epoxy-structured monomer (b1) {for example, a monomer represented by the formula (b1-4) or the formula (b1-5) to form [formula (b1-4) or formula (b1-) 5), R ^{9 is the} same as above. ].

【化6】

The structural unit (d) having a carbon-carbon double bond in a side chain can be formed in the following manner. After the monomer (a) and the monomer (b) and/or the monomer (c) are copolymerized, the environment inside the reaction vessel is replaced with nitrogen by air, and is added relative to the amount of the monomer (a) used for the copolymerization. 5 to 80 mol% of the monomer (b). Next, 0.001 to 5% by mass of a reaction catalyst (for example, dimethylaminomethylphenol or the like) 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 or the like), and the reaction is carried out at 60 to 130 ° C for 1 to 10 hours. Further, similarly to the copolymerization, the addition reaction may take into consideration the calorific value of the production equipment or the addition reaction, and the operation method or the reaction temperature may be appropriately adjusted.

In the addition reaction, the amount of the monomer (b) used in the addition reaction is preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, based on the amount of the monomer (a) used in the copolymerization. . When it is in this range, the balance between the stability, the developability, the solvent resistance, the heat resistance, the mechanical strength, and the sensitivity tends to be improved.

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 may be concentrated or diluted. Further, a copolymer which is taken out as a solid (powder) by a method such as reprecipitation can also be used.

The acid value of the resin (A) is preferably from 50 to 150 (mgKOH/g), more preferably from 60 to 135 (mgKOH/g), still more preferably from 70 to 135 (mgKOH/g). In this range, the solubility in the developer is improved, and the unexposed portion is easily dissolved.

The acid value is a value measured by the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be usually 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, still more preferably from 3,000 to 30,000).

In this range, the coating property of the resin composition is good, and the residual film ratio at the time of development is maintained, and a high development speed tends to be obtained. Further, the weight average molecular weight was determined by colloidal permeation chromatography using polystyrene as a standard.

The molecular weight distribution of the resin (A) {that is, the 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). If it is this range, it is excellent in the developability.

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 this range, the solubility in the developer is sufficient, and development residue is less likely to occur on the substrate of the non-exposed portion (non-pixel portion). Further, there is a tendency that the film of the exposed portion (pixel portion) is less likely to be formed during development, and the residual film ratio tends to be high. In the specification and the patent application, the "solid content of the composition" means "the total amount of each component of the resin composition from which the solvent is removed". The solid fraction can be measured by a conventional means such as gas chromatography or liquid chromatography.

<Polymerizable compound (B)>

The polymerizable compound (B) is a compound which is polymerized by an active radical generated by a polymerization initiator (C) by heating or light irradiation, and is polymerized by an acid or the like, for example, 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 referred to as "a polymerizable compound having three or more functional groups").

In terms of a trifunctional or higher polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, gin(2-hydroxyethyl)isocyanurate tri(methyl) Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol five ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol VII ( a reaction of a methyl acrylate, a tripentaerythritol octa (meth) acrylate, a pentaerythritol tri(meth) acrylate with an acid anhydride, a reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, and a tripentaerythritol Reaction of acrylate with anhydride, caprolactone modified trimethylolpropane tri(meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, caprolactone modified ginseng (2 -hydroxyethyl)isocyanurate tri(meth)acrylate, Lactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified tripentaerythritol Tetrakis (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripellitate hexa(meth) acrylate, caprolactone modified tripentaerythritol hepta (methyl) Acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri(meth) acrylate and anhydride reactant, caprolactone modified dipentaerythritol penta (meth) acrylate A reaction product of an ester and an acid anhydride, a reaction product of a caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, and the like.

Among these, 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 more preferred.

The content of the polymerizable compound (B) is preferably 5 to 75% by mass (more preferably 10 to 70% by mass, still more preferably 15 to 65) in total of the resin (A) and the polymerizable compound (B). quality%). When it is in this range, it can be sufficiently hardened, and the film thickness can be prevented from decreasing before and after development, and the undercut tends to be less likely to be formed in the pattern, and the pattern adhesion tends to be improved. In addition, in this range, the sensitivity of the resin composition, the strength, smoothness, heat resistance, and chemical resistance of the coating film and the pattern tend to be improved.

<Polymerization initiator (C)>

The polymerization initiator (C) is a compound which generates an active radical or an acid by heating or light irradiation, and the polymerization is started, and a conventional polymerization initiator can be used. The resin composition of the present invention is preferably a photosensitive resin composition containing a photopolymerization initiator (C) which generates an active radical or an acid by light irradiation.

Examples of the polymerization initiator (C) include a biimidazole compound, an acetophenone compound, a triazine compound, a mercaptophosphine oxide compound, an anthraquinone compound, a benzoin compound, a benzophenone compound, and the like. Among these, a biimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound are preferable, and a biimidazole compound excellent in sensitivity is more preferable.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-double (2) -Chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example JP-A-48-38403, JP-A-62-174204, etc., and imidazole compounds in which a phenyl group at the 4, 4', 5, 5' position is substituted with an alkoxycarbonyl group (-COOR) (for example, Kaiping 7-10913, etc. for reference) and so on.

In this case, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole {especially 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole}, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole is preferred.

Examples of the acetophenone compound include diethoxyacetamidine, 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-propenyl) )-Benzyl]-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2- Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2-methylbenzyl) -2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholine Phenyl)butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethylbenzyl 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-dimethylamine 1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl -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-dimethylamino-1-(4-morpholino) Phenyl)-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-( An oligomer of 4-morpholinophenyl)-butanone or 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane) 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxythionyl)-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)vinyl -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.

The mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)phenylphosphine. Oxide, etc.

The hydrazine compound may, for example, be an O-mercapto fluorene-based compound, and specific examples thereof include 1-(4-phenylsulfonyl-phenyl)-butane-1,2-dione 2-indole- O-benzoate, 1-(4-phenylsulfonyl-phenyl)-octane-1,2-dione 2-indole-O-benzoate, 1-[9-ethyl- 6-(2-Methylbenzylidene)-9H-indazol-3-yl]ethanone 1-O-acetate, 1-[9-ethyl-6-(2-methyl-4- (3,3-Dimethyl-2,4-dioxolylmethoxy)benzylidene)-9H-indazol-3-yl]ethanone 1-O-acetate.

As the benzoin compound, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

In terms of benzophenone compounds, for example, benzophenone, methyl o-benzylidene benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Further, as the polymerization initiator (C), 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylate can also be used. Ester, titanocene compound, and the like.

Further, as the polymerization initiator (C), a polymerization initiator having a group capable of generating chain transfer as described in JP-A-2002-544205 can also be used. Further, a polymerization initiator having a group capable of generating chain transfer may be used as a structural unit of the resin (A) by copolymerization of the resin (A).

In the case of a polymerization initiator having a group capable of generating chain transfer, for example, a polymerization initiator represented by the formulae (C1) to (C6).

【化7】

The content of the polymerization initiator (C) is preferably 0.1 to 40 parts by mass (more preferably 1 to 30 parts by mass) based on 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). When it is in 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 improved.

<Polymerization starter (D)>

The resin composition of the present invention may contain a polymerization initiation aid (D) as necessary. The polymerization starting assistant (D) can be usually used in combination with the polymerization initiator (C), and can be used for promoting the polymerization of the polymerization initiator (C).

When the polymerization initiator (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 starting aid (D) in this range is used, the sensitivity to light or heat of the obtained resin composition is further improved, and the productivity of the coating film or pattern formed using the resin composition tends to be improved.

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

Examples of the amine compound include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate; 4-Dimethylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N,N-dimethyl pair- Aromatic amines such as toluidine, 4,4'-bis(dimethylamino)benzophenone (generalized as: methyl ketone), 4,4'-bis(diethylamino)benzophenone . A commercially available product such as the trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used as the amine compound.

In terms of thioxanthone compounds, for example 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 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 Methylphenylthio)acetic acid, (methoxyphenylthio)acetic acid, (dimethoxyphenylthio)acetic acid, (chlorophenylthio)acetic acid, (dichlorophenylthio)acetic acid And aromatic polyacetic acids such as N-phenylglycine, phenoxyacetic acid, (naphthylthio)acetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The compound represented by the formula (D1) can also be used as the polymerization initiation aid (D).

【化8】

In the formula (D1), W ¹ is a C _6-12 aromatic ring, and a hydrogen atom of the above aromatic ring may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like). L ² is an oxygen atom (-O-) or a sulfur atom (-S-). R ¹⁰ is a linear, branched chain or cyclic C _1-6 aliphatic hydrocarbon group. R ¹¹ is a linear, branched chain 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 be a halogen atom (for example, fluorine). Substituted by an atom, a chlorine atom, a bromine atom, or the like.

The aromatic ring of W ¹ , such as benzene ring, methyl benzene ring, dimethyl benzene ring, ethyl benzene ring, propyl benzene ring, butyl benzene ring, pentyl benzene ring, hexyl benzene ring, cyclohexyl benzene ring , naphthalene ring, phenylbenzene ring and the like. The halogenated aromatic ring of W ¹ may, for example, be a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a chloronaphthalene ring or a bromine ring. W ^{1 is} preferably a benzene ring (phenylene) or a naphthalene ring (naphthyl).

An aliphatic hydrocarbon group of R ¹⁰ such as methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, cyclopentyl, Cyclohexyl and the like. R ^{10 is} preferably a methyl group.

The aliphatic hydrocarbon group of R ¹¹ is, in addition to the group exemplified for R ¹⁰ , for example, heptyl, octyl, decyl, decyl, undecyl, dodecyl, cycloheptyl, methylcyclohexyl, hexyl ring Hexyl, norbornyl, adamantyl and the like. The halogenated aliphatic hydrocarbon group of R ¹¹ is, for example, a trifluoromethyl group, a 1-chlorobutyl group, a 2-chlorobutyl group, a 3-chlorobutyl group, a 1-bromohexyl group, a 2-bromododecyl group or the like. The aromatic hydrocarbon group of R ¹¹ , such as phenyl, methylphenyl, dimethylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, cyclohexylbenzene Base, naphthyl, biphenyl, and the like. Further, in the case of the halogenated aromatic hydrocarbon group of R ¹¹ , for example, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorophenylphenyl, bromophenylphenyl, chloronaphthyl, bromonaphthyl, etc. . R ^{11 is} preferably a phenyl group, a biphenyl group, or a naphthyl group.

In terms of polymerization initiation aid (D1), for example, 2-benzylidenemethylene-3-methylnaphtho[2,1-d]thiazoline, 2-benzylidenebenzylidene-3-methyl Naphtho[1,2-d]thiazoline, 2-benzylidenebenzylidene-3-methylnaphtho[2,3-d]thiazoline, 2-(2-naphthylmethylidene) 3-methylbenzothiazoline, 2-(1-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3 -methyl-5-phenylbenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethyl) Methylene)-3-methyl-5-fluorobenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2- Naphthylmethylidene methylene)-3-methyl-5-chlorobenzothiazoline, 2-(1-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzothiazoline, 2 -(2-naphthylmethylidene methylene)-3-methyl-5-bromobenzothiazoline, 2-(1-naphthylmethylidenemethylene)-3-methyl-5-bromobenzo Thiazoline, 2-(4-phenylbenzylidenemethylene)-3-methylbenzothiazoline, 2-(4-phenylbenzylidenemethylene)-3-methyl-5 -Phenylbenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methylnaphtho[2,1-d]thiazoline, 2-(2-naphthalene Methylmercaptomethyl)-3-methylnaphtho[1,2-d]thiazolin, 2-(4-phenylbenzylidenemethylidene)-3-methylnaphtho[2, 1-d]thiazoline, 2-(4-phenylbenzylidenemethylene)-3-methylnaphtho[1,2-d]thiazoline, 2-(p-fluorobenzhydryl) Methyl)-3-methylnaphtho[2,1-d]thiazoline, 2-(p-fluorobenzhydrylmethylene)-3-methylnaphtho[1,2-d]thiazoline 2-Benzylmercaptobenzyl-3-methylnaphtho[2,1-d]oxazoline, 2-benzylidenemethylidene-3-methylnaphtho[1,2-d Oxazoline, 2-benzylidenemethylidene-3-methylnaphtho[2,3-d]oxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl Benzooxazoline, 2-(1-naphthylmethylidene methylene)-3-methylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5 -Phenylbenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethylidenemethyl) )-3-methyl-5-fluorobenzoxazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-fluorobenzoxazoline, 2-(2-naphthalene) Mercaptomethylidene-3-methyl-5-chlorobenzoxazoline, 2-(1-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzoxazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-5- Benzooxazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-bromobenzoxazoline, 2-(4-phenylbenzimidylmethylene)- 3-methylbenzoxazoline, 2-(4-phenylbenzimidylmethylene)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethyl) Methylene)-3-methylnaphtho[2,1-d]oxazoline, 2-(2-naphthylmethylidenemethyl)-3-methylnaphtho[1,2-d] Oxazoline, 2-(4-phenylbenzylidenemethylene)-3-methylnaphtho[2,1-d]oxazoline, 2-(4-phenylbenzimidylmethylene -3-methylnaphtho[1,2-d]oxazoline, 2-(p-argonbenzylidenemethylene)-3-methylnaphtho[2,1-d]oxazoline , 2-(p-fluorobenzhydrylmethylene)-3-methylnaphtho[1,2-d]oxazoline or the like.

In the above, 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline represented by the formula (D1-1), 2-benzoyl represented by the formula (D1-2) Mercaptomethyl-3-methylnaphtho[1,2-d]thiazoline, and 2-(4-phenylbenzimidyl)-3- represented by formula (D1-3) Methylnaphtho[1,2-d]thiazoline is preferred.

【化9】

The resin composition containing the polymerization initiation aid (D1) tends to have high sensitivity, and the productivity of the coating film or pattern tends to be improved. The polymerization initiation aid (D1) does not sublimate even in the post-baking step when the coating film or pattern is formed, and the contamination in the baking furnace can be suppressed. Further, since the polymerization initiation aid (D1) is discolored by the action of light or heat, the visible light transmittance of the coating film or pattern can be improved by using it.

The content of the polymerization initiation aid (D1) is preferably 50% by mass or more (more preferably 60% by mass or more, and still more preferably 65% by mass or more) based on the content of the polymerization initiation aid (D). It is preferably 100% by mass or less. When the polymerization initiation aid (D1) is used in an amount in this range, the visible light transmittance of the coating film becomes high.

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

【化10】

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 above heterocyclic ring may be substituted with a halogen atom. L ³ and L ⁴ each independently represent an oxygen atom or a sulfur atom (preferably an oxygen atom). R ¹² and R ¹³ 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 may be Substituted by a halogen atom, a hydroxyl group or a C _1-6 alkoxy group.

The aromatic ring and the heterocyclic ring of W ² and W ³ , such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, etc., and the like (for example, a naphthalene ring, Isobenzofuran ring, benzimidazole ring, etc.). Halogenated aromatic rings of W ² and W ³ , such as chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, chloronaphthalene ring , bromine naphthalene ring and the like. W ² and W ³ are each independently preferably a benzene ring or a naphthalene ring.

Examples of the aliphatic hydrocarbon group, the halogenated aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the halogenated aromatic hydrocarbon group of R ¹² and R ¹³ are, for example, those exemplified as R ¹¹ . The aliphatic hydrocarbon group substituted with a hydroxyl group of R ¹² or R ¹³ is, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group or the like. The aromatic hydrocarbon group substituted with a hydroxyl group of R ¹² or R ¹³ , for example, a hydroxyphenyl group, a hydroxynaphthyl group or the like. An aliphatic hydrocarbon group substituted with an alkoxy group for R ¹² or R ¹³ , such as methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, butoxymethyl, ethoxy Ethyl ethyl, ethoxypropyl, propoxybutyl and the like. The aromatic hydrocarbon group in which R ¹² or R ¹³ is substituted with an alkoxy group, for example, a methoxyphenyl group, an ethoxynaphthyl group or the like. R ¹² and R ¹³ are each independently preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.

As the polymerization starting assistant (D2) or (D3), for example, a dialkoxy group such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene or dibutoxynaphthalene Naphthalenes; dimethoxy hydrazine, diethoxy hydrazine, dipropoxy hydrazine, diisopropoxy hydrazine, dibutoxy fluorene, dipentyl fluorene, dihexyloxy fluorene, methoxy Oxime, methoxypropoxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, ethoxylated a dialkoxy anthracene such as oxyanthracene, propoxy oxime oxime, propoxy methoxy oxime or isopropoxy butyl oxime; dimethoxytetracene, diethoxy tetra a dialkoxytetracene such as acenes, dipropoxytetracene, diisopropoxytetracene or dibutoxytetracene; and the like.

<Multifunctional thiol (E)>

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

In the polyfunctional thiol (E), two or more compounds having a sulfonyl group bonded to a carbon atom of an aliphatic hydrocarbon group are preferred because they improve the sensitivity of the resin composition to light or heat.

In terms of polyfunctional thiol (E), such as hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, butanediol bis(3-sulfonylpropionate), butanediol Bis(2-sulfonyl acetate), ethylene glycol bis(2-sulfonyl acetate), trimethylolpropane ginseng (2-sulfonyl acetate), butanediol double (3) -sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (2-sulfonylacetate), pentaerythritol oxime (3-sulfonate) Propionate), pentaerythritol bismuth (2-sulfonyl acetate), hydroxyethyl ginseng (3-sulfonyl propionate), pentaerythritol bismuth (3-sulfonyl butyl acrylate), 1, 4 - bis(3-sulfonylbutenyloxy)butane or the like.

When the polyfunctional thiol (E) is used, the content thereof is preferably 0.5 to 100 parts by mass, more preferably 1 to 90 parts by mass, per 100 parts by mass of the polymerization initiator (C). When the polyfunctional thiol (E) is used in an amount in this range, the sensitivity is high and the developability tends to be improved. Further, the polyfunctional thiol (E) is preferably used in combination with the biimidazole compound of the polymerization initiator (C). When this combination is used, there is a tendency that the sensitivity is high.

<Isocyanate-containing decane compound (F)>

The resin composition of the present invention is characterized in that it contains both an isocyanato-containing decane compound (F) and good storage stability and sufficient adhesion to a substrate.

The resin (A) uses a monomer (a) derived from an unsaturated carboxylic acid or the like, and a monomer (b) having a carbon-carbon double bond and a cyclic ether structure (especially an epoxy-structured monomer (b1)} In the case of a copolymer of a structural unit, when an amino group-containing decane compound is used, the preservation stability is extremely deteriorated. For example, as shown in the following examples, the resin (A) having a carboxyl group and a cyclic ether structure (especially an epoxy structure) and an amino group-containing decane compound may be added to each other to increase the viscosity. This is considered to be because the conventional amine-containing decane compound is used as an amine catalyst for promoting the reaction between a carboxyl group and a cyclic ether structure. In the case where the isocyanatodecane-containing compound (F) is used, the reaction between the carboxyl group and the cyclic ether structure can be prevented, and good storage stability can be achieved.

Further, among the conventional amino group-containing decane compounds, there are many cases in which the storage stability of the resin composition is not lowered. However, such an amino group-containing decane compound does not have sufficient adhesion to the substrate. When the isocyanatodecane-containing compound (F) is used for this, sufficient adhesion can be ensured for the substrate. As described above, the present invention is characterized in that it has good storage stability and sufficient adhesion to a substrate by using an isocyanato-containing decane compound in the resin composition.

The isocyanatodecane compound (F) is preferably represented by the formula (F1).

OCN-L-Si(R ¹ ) _m1 (R ² ) _(3-m1) (F1)

[In the formula (F1), L is a C _1-6 alkanediyl group. R ¹ is C _1-4 alkyl and ml is 0 or 1. However, the fact that ml is 0 means that R ¹ does not exist.

R ² is a C _1-4 alkoxy group, and the plural R ^{2 's} may be the same or different from each other. ]

The alkanediyl group of L may, for example, be a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group or a butane-1. 3-diyl, pentane-1,5-diyl, hexane-1,6-diyl and the like. L is preferably a propane-1,3-diyl group.

The alkyl group of R ¹ is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group) or the like. R ^{1 is} preferably a methyl group or an ethyl group.

The alkoxy group of R ² is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group or the like. R ^{2 is} preferably a methoxy group or an ethoxy group.

Mm is preferably 0. Further, the plural R ² is preferably the same.

In terms of the isocyanatodecane compound (F1), for example, isocyanatomethyltrimethoxydecane, 2-isocyanatoethyltrimethoxydecane, 3-isocyanatopropylmethyldimethoxy Basear, 3-isocyanatopropyltrimethoxydecane, 3-isocyanatopropylmethyldiethoxydecane, 3-isocyanatopropyltriethoxydecane, 4-isocyanide Acid butyl trimethoxy decane, 5-isocyanyl pentyl trimethoxy decane, and the like. Among these, 3-isocyanatepropyltrimethoxydecane and 3-isocyanatopropyltriethoxydecane are preferred.

The content of the isocyanate-containing decane compound (F) is preferably 0.1% by mass or more and 15% by mass or less (more preferably 0.2% by mass or more and 10% by mass or less) based on the solid content of the resin composition. When it is in this range, the storage stability of the resin composition and the adhesion of the coating film or the pattern tend to be good, and the development residue tends to be less likely to be seen.

<Colorant (G)>

The resin composition of the present invention may also contain a coloring agent (G). In terms of colorants (G), such as dyes and pigments. Dyes and pigments are all substances which can be used for coloring, but in the specification and the scope of the patent application, those which are soluble in a solvent are defined as a dye, and those which are insoluble in a solvent are defined as a pigment. Both the dye and the pigment may be used alone or in combination of two or more. Further, a combination of a dye and a pigment can also be used as the colorant (G).

In terms of pigments, for example, compounds which are specifically classified as pigments in the Colour Index (published by The Society of Dyers and Colourists). The details are, 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, Yellow pigments such as 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, Red pigments such as 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 Such as purple pigment; 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; Further, in the present specification, "C.I. Pigment Yellow" or the like is described only in the first pigment, and only the same pigment is described. The dye is also the same.

Among the above pigments, CI Pigment Yellow 138, 139, 150; CI Pigment Red 177, 209, 242, 254; CI Pigment Violet 23; CI Pigment Blue 15:3, 15:6; and CI Pigment Green 7, 36, 58; better.

The pigment may be subjected to rosin treatment if necessary; surface treatment using a pigment derivative or a pigment dispersant or the like which introduces an acidic group or a basic group; graft treatment of the surface of the pigment with a polymer compound or the like; and microparticulation with sulfuric acid The micronization treatment, the removal treatment of the impurities by an organic solvent or water, the removal of ionic impurities by an ion exchange method or the like;

It is preferred to use a pigment having a uniform particle size. Further, in the case of using a pigment, it is preferred to uniformly disperse the pigment in a solvent using a pigment dispersant. The pigment dispersant may be used alone or in combination of two or more. When the pigment dispersant is used, the amount of the pigment used is preferably 0.05 parts by mass or more and 1 part by mass or less (more preferably 0.5 parts by mass or less) per 1 part by mass of the pigment. When the pigment dispersant is used in an amount in this range, there is a tendency that a uniformly dispersed pigment dispersion liquid can be obtained.

A surfactant can be used as the pigment dispersant. The surfactant can be classified into a cationic type, an anionic type, a nonionic type, and an amphoteric type, and can be classified into an ester type, an amine type, an acryl type, an anthrone type, a fluorine type, and the like. These surfactants may be appropriately selected depending on the pigment or the like. In terms of surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines Modified polyurethanes, polyethyleneimines, and the like. Further, as a commercially available surfactant, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (registered trademark) (manufactured by Kyoei Chemical Co., Ltd.), and EFTOP (registered trademark) (Mitsubishi Materials) may be used. Electronic Chemicals Co., Ltd., MEGAFACE (registered trademark) (made by DIC), Fluorad (registered trademark) (manufactured by Sumitomo 3M Limited), AsahiGuard (registered trademark) (asahi Glass), Surflon (Login) Trademark) (made by AGC SEIMI CHEMICAL CO., LTD.), SOLSPERSE (registered trademark) (made by Zeneca), EFKA (made by CIBA), AJISPER (registered trademark) (made by Ajinomoto Fine-Techno Co., Inc. ), Disperbyk (made by BYK), etc.

As the dye, a conventional dye such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, a sulfonamide derivative of an acid dye, or the like can be used. In terms of dyes, for example, compounds classified as dyes by the Colour Index (published by The Society of Dyers and Colourists) (for example, CI solvent dyes, CI acid dyes, CI direct dyes, CI mordant dyes, etc.) or dyeing notes (dyeing dyes) are described. Dye.

For CI solvent dyes, for example, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 45, 49, 125, 130; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue 35, 37, 59, 67; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; .

For CI acid dyes, for example, CI Yolk 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98 , 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177 , 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI limes 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64 , 74, 75 , 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI acid violet 6B, 7, 9, 17, 19; CI acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109; and so on.

CI direct dyes, such as CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250; CI Direct Orange 34, 39, 41, 46, 50 , 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Purple, 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct green 25, 27, 31, 32 , 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

CI mordant dyes, such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2 , 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46 , 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24 , 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20 , 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI mordant purple 1, 2 , 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant green 1, 3, 4, 5, 10 , 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

As the dye, for example, an amine salt of an acid dye having a group represented by any one of the formulae (1) to (7), and a sulfonium sulfonate having an acid dye represented by the formula (8) or the formula (9) can be used. Amine derivative. Further, the sulfonamide derivative of the acid dye may have a group represented by the formula (10) in addition to the group represented by the formula (8) or the formula (9). Examples of the acid dyes include azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and anthraquinone dyes.

-(SO ₃ ^- )(C _n H _2n+1 N ⁺ H ₃ ) (1)

-(SO ₃ ^- ){(C _n H _2n+1 ) ₂ N ⁺ H ₂ } (2)

-(SO ₃ ^- ){(C _n H _2n+1 ) ₃ N ⁺ H} (3)

-(SO ₃ ^- ){(C _n H _2n+1 ) ₄ N ⁺ } (4)

-(SO ₃ ^- )(C _o H _2o+1 OC _p H _2p N ⁺ H ₃ ) (5)

-(SO ₃ ^- ){(C _n H _2n+1 )(PhCH ₂ ) ₂ N ⁺ H} (6)

-(SO ₃ ^- ){(C _n H _2n+1 )Py ⁺ } (7)

-SO ₂ NH(C _n H _2n+1 ) (8)

-SO ₂ NH(C _o H _2o+1 OC _p H _2p ) (9)

-SO ₃ M (10)

In the formulae (1) to (10), n is an integer of 1 or more and 20 or less. o and p each independently represent an integer of 1 or more and 10 or less. Ph is a phenyl group. Py ⁺ is a group represented by the formula (11). M is a hydrogen atom or a monovalent cation.

【化11】

In the formula (11), q is 0 or 1, and q is 0 means that the methyl group does not exist. Formula (11) The symbol * is bonding position Py ^+, Py ⁺ for the C in the bonding position of formula (7) _n H _{2n + 1} carbon atom knot.

n is preferably an integer of 1 or more and 10 or less (more preferably 8 or less). Each of o and p is preferably an integer of 1 or more and 8 or less (more preferably 6 or less). q is preferably 1. The monovalent cation aspect of M, such as a lithium ion, a sodium ion, a potassium ion, a 4-stage ammonium ion {e.g., (C ₂ H ₅ ) ₃ HN ⁺ }, etc., is preferably a sodium ion.

The number of the groups represented by any one of the formulae (1) to (7) contained in the amine salt of the acid dye is preferably 1 or more and 20 or less (more preferably 10 or less, still more preferably 8 or less). The number of the groups represented by the formula (8) or the formula (9) in the sulfonamide derivative of the acid dye is preferably an integer of 1 or more and 8 or less (more preferably 6 or less, still more preferably 5 or less). Further, the sulfonamide derivative of the acid dye is preferably a group represented by the formula (10) which may have 8 or less, more preferably 6 or less, and more preferably 5 or less.

In the case of an azo dye having a sulfonamide structure, for example, a dye represented by the formula (G1).

【化12】

In the formula (G1), R ¹⁴ is a C _2-20 alkyl group, a C _2-12 alkyl group substituted by a cyclohexyl group, a cyclohexyl group substituted by a C _1-4 alkyl group, or a C _2-12 alkoxy group. a C _2-12 alkyl group, a phenyl group substituted by a C _1-20 alkyl group, a C _1-20 alkyl group substituted by a phenyl group, an alkylcarbonyloxyalkyl group represented by the formula (12), or a formula (13) In the alkoxycarbonylalkyl group represented by the formula (12) and the formula (13), R ¹⁹ is a C _2-12 alkyl group, and L ⁴ is a C _2-12 alkanediyl group. }.

-L ⁴ -O-CO-R ¹⁹ (12)

-L ⁴ -CO-OR ¹⁹ (13)

In the formula (G1), R ¹⁵ to R ¹⁷ each independently represent a hydrogen atom, a methyl group, a hydroxyl group, an amine carbenyl group or a cyano group. R ¹⁸ is a C _1-4 alkyl group.

a C _2-20 alkyl group of R ¹⁴ , such as ethyl, propyl, isopropyl, hexyl, decyl, decyl, dodecyl, 2-ethylhexyl, 1,3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl and the like. The C _2-12 alkyl group substituted by the cyclohexyl group of R ¹⁴ is, for example, a cyclohexylethyl group, a 3-cyclohexylpropyl group, an 8-cyclohexyloctyl group or the like. Examples of the cyclohexyl group substituted with a C _1-4 alkyl group of R ¹⁴ include, for example, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-butylcyclohexyl group and the like. The R C ¹⁴ _2-12 alkoxy C _2-12 alkyl group substituted by aspects such as 3-ethoxypropyl, 3-propoxypropyl, 4-propoxybutyl, 3-methyl Hexyloxyethyl and 3-(2-ethylhexyloxy)propyl and the like. A phenyl group substituted with a C _1-20 alkyl group of R ¹⁴ , for example, an o-isopropylphenyl group or the like. The C _1-20 alkyl group substituted with a phenyl group of R ¹⁴ may, for example, be a DL-1-phenylethyl group, a benzyl group or a 3-phenylbutyl group.

C _2-12 alkyl aspect of R ¹⁹ , such as ethyl, propyl, hexyl, decyl, decyl, dodecyl, 2-ethylhexyl, 1,3-dimethylbutyl, 1-methyl Butyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl and the like. The C _2-12 alkanediyl group of L ⁴ may, for example, be an ethylene group or a hexanediyl group.

The C _1-4 alkyl group of R ¹⁸ is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl.

R ^{14 is} preferably a C _2-10 alkyl group, more preferably a 2-ethylhexyl group.

R ^{15 is} preferably a methyl group. R ^{16 is} preferably a cyano group. R ^{17 is} preferably a hydroxyl group. R ^{18 is} preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a butyl group. Among the dyes (G1), a dye represented by the formula (G1-1) is preferred.

【化13】

Further, in the case of the azo dye having a sulfonamide structure, for example, a dye represented by the formula (G2), the formula (G3) or the formula (G4).

【化14】

In the case of an anthraquinone dye having a sulfonamide structure, for example, a dye represented by the formula (G5).

【化15】

In the case of a triphenylmethane dye having a sulfonamide structure, for example, a dye represented by the formula (G6).

【化16】

The oxonium dye having a sulfonamide structure is, for example, a dye represented by the formula (G7).

【化17】

In the case of an anthraquinone dye having a sulfonamide structure, for example, a dye represented by the formula (G8).

【化18】

In the formula (G8), R ²⁰ to R ²³ each independently represent a hydrogen atom, -SO ₂ NH(CH ₂ ) ₃ OCH(CH ₃ ) ₂ group or a sulfo group (-SO ₃ H). However, at least two of R ²⁰ to R ²³ are -SO ₂ NH(CH ₂ ) ₃ OCH(CH ₃ ) ₂ groups.

When the coloring agent (G) is used for the coating film or the pattern to achieve the purpose, the content of the coloring agent (G) is preferably 60% by mass or less, more preferably 55% by mass or less based on the solid content of the resin composition. More preferably, it is 50% by mass or less.

When the pigment is used for the purpose of the purpose, the content of the pigment is preferably 2% by mass or more (more preferably 5% by mass or more, still more preferably 10% by mass or more) based on the coloring agent (G). It is preferably 100% by mass or less (more preferably 98% by mass or less, still more preferably 95% by mass or less). When the pigment is used in an amount in this range, excellent heat resistance and light resistance can be achieved.

<Other Additives (H)>

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

Examples of the other additive (H) include a filler, a polymer compound other than the resin (A), an adhesion promoter, a surfactant, an antioxidant, an ultraviolet absorber, a photostabilizer, and a chain transfer agent.

For the filler, for example, glass, cerium oxide, aluminum oxide, or the like.

Examples of the polymer compound include a curable resin such as an epoxy resin or a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyamine. A thermoplastic resin such as a formate.

The surfactant is, for example, at least one selected from the group consisting of an anthrone-based surfactant, a fluorine-based surfactant, and an anthrone-based surfactant having a fluorine atom. The surfactant is preferably 0.0025 to 0.0250% by mass, more preferably 0.0025 to 0.0200% by mass, even more preferably 0.005 to 0.0100% by mass, based on 100% by mass of the photosensitive resin composition other than the surfactant. By including the surfactant in this range, the flatness of the coating film can be improved, and at the same time, the boiling of the solvent can be prevented.

In the case of an anthrone-based surfactant, for example, a surfactant having a siloxane coupling. Specifically, such as DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, with SH29PA, SH30PA, SH8400 (trade name: Dow Corning Toray), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry ( ()), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

In the case of a fluorine-based surfactant, for example, a surfactant having a fluorocarbon chain. Specifically, for example, Fluorinert (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, and R30 (DIC) EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, same as S382, same as SC101, and SC105 (AGC SEIMI CHEMICAL CO. , Ltd.), E5844 (manufactured by DAIKIN FINE CHEMICAL Co., Ltd.), BM-1000, and BM-1100 (all manufactured by BM Chemie Co., Ltd.).

Examples of the fluorenone-based surfactant having a fluorine atom include a surfactant having a siloxane coupling and a fluorocarbon chain. Specifically, it is MEGAFACE (registered trademark) R08, the same BL20, the same F475, the same F477, the same F443 (DIC system).

Examples of adhesion promoters such as vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3-glycidoxypropyl trimethoxy decane , 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-sulfonylpropyltrimethoxydecane, and the like.

These may be used in combination with the isocyanato-containing decane compound (F).

In terms of antioxidants, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 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-butyldiphenyl[d,f][1,3,2]dioxaphosphepine, 3,9 - bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylene bis(6-tert- Butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4 -methylphenol), dilauryl 3,3'-thiodipropionate, di(tetradecyl) 3,3'-thiodipropionate, distearyl 3,3'-sulfur Dipropionate, pentaerythritol bismuth (3-laurylthiopropionate), 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a "-(Trimethyl-2,4,6-triyl)tri-p-cresol, pentaerythritol quinone [ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, etc. Further, the antioxidant is Ciba Japan and other companies sell them under the trade names "IRGANO X 3114".

In terms of ultraviolet absorbers, for example, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-( 5-Chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[4-[(2-hydroxy-3-dodecyloxy)oxy]-2-hydroxybenzene 4-[6,6-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- Butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-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-chlorobenzotriazole, alkoxybiphenyl Ketones, etc.

In terms of light stabilizers, for example, 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-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7 - diazepine-1,10-diamine; decane dibasic acid and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester a reactant of 1,1-dimethylethylhydroperoxide; bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-((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-piperidinyl sebacate; methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and the like.

As the chain transfer agent, for example, dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, and the like.

(Solvent (J)>

The solvent (J) is preferably one in which the components such as the resin (A) are uniformly dissolved or dispersed and are not reacted with the respective components. From the viewpoints of coatability and drying properties, an organic solvent having a boiling point of from 100 ° C to 200 ° C is preferred. As the solvent (J), 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 methoxybutyl alcohol, ethoxybutyl alcohol, propoxy butyl alcohol, butoxybutyl alcohol; methoxybutyl acetate, ethoxylated Butanediol monoalkyl ether acetates such as acetoxyacetate, propoxybutyl acetate, butoxybutyl acetate; methoxybutyl propionate, ethoxybutyl propionic acid Butanediol monoalkyl ether propionate such as ester, propoxy butyl propionate or 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 trimethylbenzene; 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 propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -propyl ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxy Methyl propionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxyl Propyl propionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 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 ethers, diethylene glycol dialkyl ethers (more preferably diethylene glycol ethyl methyl ether), esters (more Preferably, it is ethyl 3-ethoxypropionate or methyl 3-methoxypropionate.

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

<Coating film, pattern and display device>

In the coating film of the present invention, the resin composition can be applied to a substrate (for example, a substrate or a substrate on which a resin layer is formed), and then formed into a coating film by thermal polymerization or photopolymerization. The coating method for forming the coating film is not particularly limited, and a conventional method such as a spin coating method can be used.

The pattern of the present invention can be formed by, for example, applying a resin composition of the present invention to a pattern shape using an inkjet machine or the like, followed by thermal polymerization or photopolymerization. Further, when the photosensitive resin composition of the present invention containing the photopolymerization initiator (C) is used, a pattern can be formed even by photolithography. In the photolithography technique, coating, solvent removal, pre-exposure heating (prebaking), exposure, development, post-development heating (post-baking), and various steps are usually performed by the photosensitive resin composition. .

By using an isocyanato-containing decane compound instead of the conventional amino group-containing decane compound, the (cured) coating film and the pattern obtained by the resin composition of the present invention have sufficient adhesion to the substrate, and excellent storage stability can be achieved. .

The coating film and the pattern of the present invention are suitable for, for example, a transparent film of a component such as a color filter or an array substrate of a display device, a color pattern of a color filter, a spacer, a protective film, an insulating film, and a liquid crystal alignment control. Protrusions, microlenses, coating layers, and the like. The coating film and the pattern of the present invention are particularly suitable for a coating film or pattern formed on the substrate because of sufficient adhesion to the substrate. The display device is preferably a liquid crystal display device, an organic EL display device or the like.

Example

The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples, and may be appropriately modified without departing from the spirit and scope of the inventions described below. .

In addition, the "%" and "parts" of the component amount are "% by mass" and "parts by mass" when not specifically noted.

1. Synthesis of resin (A)

Nitrogen was introduced into a nitrogen atmosphere at 0.02 L/min in a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and 140 parts of diethylene glycol ethyl methyl ether was added thereto, and the mixture was heated to 70 ° C with stirring. Then, 40 parts of methacrylic acid; and a mixture of the monomer (b1-2-1) and the monomer (b1-3-1) {monomer (b1-2-1) in the mixture: monomer (b1-3) -1) Mohr ratio = 50:50} 360 parts of a solution of 190 parts of diethylene glycol ethyl methyl ether, the solution was dripped, and it took 4 hours to drip into a flask kept at 70 ° C .

【化19】

On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 240 parts of diethylene glycol ethyl methyl ether was used to additionally drip the pump. It took 5 hours to drip into the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer {resin (A1)} having a solid content of 42.3% and an acid value of 60 mg-KOH/g. The obtained resin (A1) had a weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw/Mn) of 1.91.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin (A1) were measured by colloidal permeation chromatography under the following conditions.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

Standard: Polystyrene

[Examples 1, 2, and Comparative Examples 1 and 2] 2. Modulation of photosensitive resin composition (1) Modulation of photosensitive resin composition 1 (hereinafter referred to as "composition 1")

36:4.3 parts of CI Pigment Green, 150:1.9 parts of CI Pigment Yellow, and 1.7 parts of propylene-based pigment dispersant were mixed with 35 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill to prepare a pigment. Dispersions. 100.2 parts of the pigment dispersion liquid, the resin (A1) solution (42.4 parts in terms of solid content), 42.4 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 2,2'-double (2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Baotu Valley Chemical Co., Ltd.) 3.4 parts, 2-(2-naphthoquinone) 0.4 parts of benzylidene-3-methylbenzothiazoline, bismuth pentaerythritol (3-sulfonylpropionate) (PEMP; manufactured by SC Organic Chemicals Co., Ltd.) 2.5 parts, 3-isocyanatopropyl 0.9 parts of a polyether modified fluorenone oil (SH8400; manufactured by Dow Corning Toray Co., Ltd.) of 0.9 parts of a triethoxy decane (KBE-9007; manufactured by Shin-Etsu Chemical Co., Ltd.) and an anthrone-based surfactant. 0.2 parts of IRGANO X 3114 (manufactured by Ciba Japan Co., Ltd.) and a solvent were used to obtain a composition 1. The solvent is composed of diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol dimethyl ether in a mass ratio of 40:30:17:13, and The solid content of the composition 1 was mixed in a manner of 33%.

(2) Modulation of photosensitive resin composition 2 (hereinafter referred to as "composition 2")

The composition 2 was prepared almost in the same manner as the composition 1 except that the colorant and the propylene-based pigment dispersant were not used. The components of the compositions 1 and 2 are as shown in Table 1 below.

(3) Modulation of photosensitive resin composition H1 (hereinafter referred to as "composition H1")

The composition H1 was prepared in the same manner as in the composition 1 except that 3-isocyanatopropyltriethoxydecane was substituted with 3-aminopropyltrimethoxydecane. However, when the components are mixed, the composition H1 is colloidalized. Therefore, it is impossible to evaluate the adhesion and the like.

(4) Modulation of photosensitive resin composition H2 (hereinafter referred to as "composition H2")

The composition H2 was prepared in the same manner as in the composition 1 except that 3-isocyanatopropyltriethoxydecane was substituted with N-phenyl-3-aminopropyltrimethoxynonane.

3. Evaluation

The stability and adhesion of the composition, and the residue and resolution of the pattern development of the photolithography technique were evaluated as follows.

(1) Evaluation of preservation stability

The composition was measured for viscosity before and after storage at 23 ° C for 4 days. For the viscosity measurement, a viscometer (VISCMETER TV-30) manufactured by Toki Sangyo Co., Ltd. was used. When the value of the viscosity change (%) represented by the formula (I) is in the range of 98 to 102%, it is good (○), and outside the range, it is evaluated as defective (×). The results are shown in Table 2.

Viscosity change (%) = 100 × viscosity after storage (mPa ‧ s) / viscosity before storage (mPa ‧ s) (I)

(2) Evaluation of adhesion

The adhesion to the tantalum nitride substrate was evaluated as follows. First, a 5 cm × 5 cm tantalum nitride substrate was sequentially washed with a neutral detergent, water, and alcohol, followed by drying. Spin coating was performed on the substrate so that the film thickness after baking of the composition was 3.0 μm. Then, the pressure was reduced to 1.0 torr by a vacuum dryer (VCD Microtek Co., Ltd.) to remove the solvent to form a coating film. The coating film was prebaked in a hot plate at 90 ° C for 2 minutes. Then, using an exposure machine (TME-150RSK; TOPCON (light source), light source; ultra-high pressure mercury lamp), the pre-baked coating film was exposed to an exposure amount of 100 mJ/cm ² (405 nm basis) in an atmospheric environment. . This exposure is performed by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (LU0400; Asahi Separation Co., Ltd.). The exposed coating film was immersed in a tetramethylammonium hydroxide aqueous solution (containing 0.20 parts of tetramethylammonium hydroxide in 100 parts of an aqueous solution) at 27 ° C for 120 seconds, washed with water, and then subjected to a hot plate at 235 ° C for 11 minutes. After baking, a hardened coating film having a film thickness of 3 μm was obtained.

In the hardened coating film, a cutter was used and a cut was added at intervals of 1 mm using a Super Cutter Guide (manufactured by Taisho Machinery Co., Ltd.) to make 100 units of 1 mm × 1 mm. The hardened coating film having the cut was treated with a highly accelerated life tester (manufactured by Tabai espec Co., Ltd.) under the conditions of a temperature of 120 ° C, a humidity of 100%, and a pressure of 2.1 at a pressure of 2 hours. Then, a 24 mm wide tape (registered trademark) (manufactured by Nichiban Co., Ltd.) was attached to the unit of the cut film of the hardened coating film, and the tape was attached to the hardened coating film by an eraser on the tape, and the tape was held at the end of 2 minutes. Department, maintain a right angle with the film surface, and remove it in one breath. Thereafter, the number of units in which the cured coating film was not peeled off and remained on the substrate was visually counted. The results are shown in Table 2.

(3) Residue and resolution of pattern development of photolithography (3-1) Graphic development

The 5 cm × 5 cm glass substrate was washed with a neutral detergent, water and alcohol in order, and then dried. On the substrate, spin coating was carried out so that the film thickness after baking of the resin composition was 3.0 μm. Subsequently, the pressure was reduced to a reduced pressure of 1.0 Torr by a vacuum dryer (manufactured by VCD Microtek Co., Ltd.) to remove the solvent to form a coating film. The coating film was prebaked in a hot plate at 90 ° C for 2 minutes. Next, the pre-baked coating film was exposed to light at an exposure amount of 50 mJ/cm ² (405 nm basis) in an atmosphere using an exposure machine (TME-150RSK; TOPCON system, light source; ultrahigh pressure mercury lamp). This exposure is performed by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (LU0400; Asahi Separation Co., Ltd.). Further, as the exposure, a quartz glass reticle for forming a line pattern having line widths of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm is used, and the substrate and the light are used. The interval between the covers is 10 μm. The exposed coating film was immersed in a tetramethylammonium hydroxide aqueous solution (containing 0.20 parts of tetramethylammonium hydroxide in 100 parts of an aqueous solution) at 27° C. for 120 seconds, and then subjected to water washing, followed by heating at 235° C. After baking for 11 minutes, a line/pitch pattern having a film thickness of 3 μm was formed.

(3-2) Residue evaluation

The non-exposed portion of the pattern was observed with a microscope (VF7510; manufactured by Keyence Corporation; magnification: 1250 times), and when the deposit from the composition was not observed, it was evaluated as good (○), and when it was observed, it was evaluated as poor (×). . The results are shown in Table 2.

(3-3) Resolution evaluation

The pattern obtained by a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.) was observed, and the minimum line width of the pattern separation was taken as the resolution. The results are shown in Table 2.

[Examples 3 and 4]

In the same manner as in Example 1, except that the amount of each component used was changed to the amount shown in Table 3, photosensitive resin compositions 3 and 4 (hereinafter referred to as "composition 3" and "composition 4") were obtained.

[Examples 5 and 6]

Each of the components described in Table 3 is mixed to obtain photosensitive resin compositions 5 and 6 (hereinafter referred to as "composition 5" and "composition 6").

The photosensitive resin compositions 3 to 6 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

The composition H1 of 3-aminopropyltrimethoxydecane was used, and the stability of storage was poor, and the components were mixed to be colloidal. Further, the composition H2 containing N-phenyl-3-aminopropyltrimethoxydecane has good storage stability, but has poor adhesion to a tantalum nitride substrate. For this reason, the compositions 1 to 6 containing 3-isocyanatopropyltriethoxydecane are excellent in both storage stability and adhesion. Further, in the compositions 1 to 6, no residue was observed in the non-exposed portion during pattern development, and the developability was also excellent.

Industrial use possibility

The resin composition of the present invention can form a cured coating film and a pattern which are excellent in storage stability and have sufficient adhesion to a substrate. Further, the photosensitive resin composition of the present invention containing a photopolymerization initiator can form a pattern without development residue. The resin composition of the present invention can produce a color pattern of a high-quality transparent film or a color filter, and can improve the yield of the display device constituting the component.

Claims (12)

A resin composition comprising a resin, a polymerizable compound, a polymerization initiator, an isocyanato-containing decane compound, and a solvent selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides a copolymer of at least one monomer (a) and a monomer (x) having a carbon-carbon double bond and different from the monomer (a), wherein the acid value of the resin is 50 to 150 (mgKOH/g). The weight average molecular weight of the resin is 2,000 to 50,000, and the content of the resin is 10 to 70% by mass based on the solid content of the resin composition, and the content of the polymerizable compound is in the resin and the polymerizable compound. The total amount of the polymerization initiator is from a biimidazole compound, an acetophenone compound, a triazine compound, a mercaptophosphine oxide compound, an anthraquinone compound, a benzoin compound, a benzophenone compound, and a 10- to 65% by mass. At least 1 selected from the group consisting of butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compound Kind of compound. The resin composition of claim 1, wherein the monomer (x) comprises a monomer (b) having a carbon-carbon double bond and a cyclic ether structure. The resin composition of claim 2, wherein the monomer (x) comprises a monomer (b1) having a carbon-carbon double bond and an epoxy structure. The resin composition of claim 1, wherein the isocyanatodecane-containing compound is a compound represented by the formula (F1), OCN-L-Si(R ¹ ) _m1 (R ² ) _(3-m1) (F1) [In the formula (F1), L is a C _1-6 alkanediyl group, R ¹ is a C _1-4 alkyl group, and m1 is 0 or 1, but when m1 is 0, it means that R ¹ is absent and R ² is C. _1-4 alkoxy, plural R ² may be the same or different from each other. The resin composition of claim 1, wherein the content of the isocyanatodecane-containing compound is 0.1% by mass or more and 15% by mass or less based on the solid content of the resin composition. The resin composition of claim 1, which further contains a colorant. The resin composition of claim 1, wherein the polymerization initiator is at least one selected from the group consisting of a biimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound. The resin composition of claim 1, which further contains a compound having two or more sulfanyl groups. A coating film characterized by using the resin composition of claim 1. A pattern characterized by the use of the resin composition of claim 1. A liquid crystal display device characterized by comprising at least one selected from the group consisting of the coating film of claim 9 and the pattern of the request item 10. An organic EL display device characterized by comprising at least one selected from the group consisting of a coating film of the claim 9 and a pattern of the request item 10.