TW201130905A - Resin composition - Google Patents

Abstract

To provide a resin composition which shows sufficient adhesiveness to a substrate and is excellent in storage stability. There is provided the resin composition showing good adhesiveness and storage stability, the resin composition including a resin, a polymerizable compound, a polymerization initiator, an isocyanato group-containing silane coupling agent, and a solvent, wherein the resin is a copolymer of at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; and a monomer (x) which has a carbon-carbon double bond and is different from the monomer (a).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a coating film and pattern obtained from the resin composition, and a display device including the coating film and/or pattern. [Prior Art] A pixel of a color concentrating sheet 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 color 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 the color pattern to form a pixel until the coloring pattern is heat-treated. Next, using the photosensitive resin composition of the remaining two colors in the same operation, 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, Patent Document 1 discloses the use of an amino group-containing decane compound in order to improve the adhesion to a glass substrate. [Patent Document 1] JP-A-2-3-567 No. [Invention] The use of an amine-containing decane The compound has a situation in which the substrate cannot be sufficiently adhered to -5 to 201130905. 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 it is an object of the invention 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 [1 2]. [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 an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. 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 (fi). OCN-L-SUR'UKR2)^^丨) (F1) [In the formula (F1), '1^ is C, .6 alkanediyl. ... is Cm alkyl, ml is 〇 or 1. However, the fact that ml is 0 means that R1 does not exist. ^ is ^^ alkoxy, and the plural R2 may be the same or different from each other. 〕 In the scope of this specification and the patent application, "Cx.y" means "the number of carbons is X or more and y or less". Further, the following "Chemical Formula -6 - 201130905" represented by the formula (F 1 ) 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]. Resin composition of any one of [1] to [4] in which the content of the isocyanate-containing decane compound is '% by mass to 1% by mass or less based on the solid content of the resin composition. Things. [6]. The resin composition of any one of [1] to [5] further containing a coloring agent [7]. The polymerization initiator is a biimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound. A resin composition of any one of [1] to [6] selected from the group. [8]. A resin composition containing any one of [1] to [7] having a compound having two or more sulfonyl groups. [9] A coating film formed using the resin composition of any one of [1] to [8]. [1 〇]. A pattern formed by using the resin composition of any one of [1] to [8]. [11] A liquid crystal display device of at least one selected from the group consisting of a coating film of [9] and a pattern of [1]. [12] An organic EL display device of at least one selected from the group consisting of the coating film of [9] and the pattern of [1]. BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), an isocyanatodecane-containing compound (F) 201130905, and a solvent (J). Further, a polymerization initiator (D) 'polyfunctional thiol (E), a colorant (G), and other additives (Η) may be contained as the case may be. Each of the above components may be used singly or in combination of two or more kinds without particular limitation. The resin (Α) is a copolymer containing a structural unit derived from 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 is mixed with a decane compound (i.e., a decane coupling agent), the resin is reacted to increase the viscosity, and the storage stability is lowered. Surprisingly, however, it has been found that the preservation stability is good by using the isocyanato-containing decane compound (F). 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 problem that the substrate cannot be sufficiently adhered (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 (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; and has a carbon-carbon double bond and a monomer (a) a copolymer of a different monomer (X):. 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, hydrazine, m-, p-ethylene-8 - 201130905 benzoic acid, succinic acid mono [2·(methyl) propylene oxime Ethyl ethyl], phthalic acid mono [2-(methyl) propylene oxiranyl ethyl], carboxy polycaprolactone mono (meth) acrylate, 5-carboxy-5-methyl bicyclo [2.2.1 ???Hept-2-ene' 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2_2.1]hept-2-ene' 5-carboxyl Unsaturated monocarboxylic acid such as -6-ethylbicyclo[2.2.1]hept-2-ene; maleic acid, maleic acid, citraconic acid, methyl fumaric acid, itaconic acid, 3_vinyl phthalic acid , 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid '丨, 4· Unsaturated dicarboxylic acids such as cyclohexene dicarboxylic 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, dimethyl Hydrogen anhydride, 5,6_-dicarboxy-bicyclo [2.2 1] hept-2-ene _ anhydride (nadic anhydride) and other unsaturated dicarboxylic acid anhydride and the like; 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 mono--9-201130905 (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 (bl), a monomer having an oxetane structure (b2), and a monomer having a tetrahydrofuran structure (b3). Wait. Among these, a monomer (b1) having an epoxy structure and a monomer (b2) having an oxetane structure are preferred, and a monomer (b1) having an epoxy structure is more preferable. The epoxy structure can be classified into (1) a monocyclic oxirane ring structure (ie, a structure in which an olefin is epoxidized) (hereinafter referred to as "structure (D"), and (2) an alicyclic hydrocarbon ring. Structure condensed with an oxirane ring (structure represented by the following formula (b); (hereinafter referred to as "structure (2)")

(b1-0) [In the formula (bl-Ο), WQ 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 (bl-〇), and the ring of the alicyclic hydrocarbon of WQ is a single ring) The structure (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 (bl-〇), it is a bridged ring Structure) (hereinafter referred to as "structure (2 _2) J ). In this case, structure (2) is preferred, structure (2-2) is better. Aspect (b) of structure (1), such as ring Oxypropyl (A-10-10 30,830,905) acrylate, 0-methylepoxypropyl (meth) acrylate, /3-ethylepoxypropyl (meth) acrylate vinegar, propylene oxide In the formula (b1 - 1) of the formula (b1 - 1), the radicals of the formula (b1 - 1), R3 to R5 each independently represent a hydrogen atom or a Ci-alkyl group. !12 is an integer from 1 to 5.}.

(b1-1) In terms of the monomer (b 1 -1 ) having the structure (1), such as 0-vinylbenzylepoxypropyl ether, m-ethylene decyl epoxypropyl ether, P-ethyl Alkyl epoxidized propyl ether, methyl-fluorene-vinylbenzyl epoxy propyl ether, α-methyl _ m-ethyl benzyl epoxide propyl propyl ether, methyl Ρ 乙 乙Epoxy epoxide, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidyl) Oxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene' 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5- Ginseng (glycidoxymethyl)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 (bl) having the structure (2-1), for example, i, 2·epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Chemical Industries Limited), 2, 3 - Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl propyl sulphuric acid vinegar (eg CYCLMER (registered trademark) A400; Daicel Chemical -11 - 201130905

Manufactured by Industries Limited., 3,4-epoxycyclohexylmethyl methacrylate (for example, CYC LMER (registered trademark) Ml 00; manufactured by Dai cel Chemical Industries Limited). 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., among these, a tricyclodecane ring is preferred. With respect to the monomer (bl) of the structure (2-2), for example, an epoxy norbornyl (meth) acrylate {for example, 3,4-epoxynorbornyl (meth) acrylate}, formula (bl- 2) the monomer represented and the monomer represented by the formula (bl-3). [Chemical 2] R6 Ο

Η2〇=0—C—O—L R6 Ο Η2〇=0°C—Ο In the formula (bl-2) and (bl-3), R6 is a hydrogen atom or a Cl_4 saturated aliphatic hydrocarbon group, and the aforementioned saturated fat The hydrogen atom of the group hydrocarbon group may be substituted with _0H. L1 is a single bond or a divalent Ci.6 saturated aliphatic hydrocarbon group, and the above-mentioned divalent saturated aliphatic hydrocarbon group -CH2· may be substituted with -0-, -S- or -NR7-, and the above R7 is a hydrogen atom or C丨-π»saturated aliphatic hydrocarbon group. Further, each of R6 and L1 in the formula (bl-2) may be the same as R6 and L1 in the formula (bl_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 other. And "_CH2·a divalent saturated aliphatic hydrocarbon group substituted by -0-, etc." means "on the surface of the divalent saturated aliphatic hydrocarbon group -CH2- is -O-, on the apparent -12-201130905, instead of "Actually, a two-valent saturated aliphatic group is synthesized;):] The base obtained by substituting -〇-etc." The "hydrogen atom is an aliphatic hydrocarbon group" and the like are also the same. R6 may also be a hydroxy-substituted saturated aliphatic hydrocarbon group, ethyl, propyl, isopropyl, butyl, sec-butylhydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-propyl, 3-hydroxypropyl, 1-hydroxy-1-methylethylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxyl and the like. R6 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group. A divalent saturated fat of L1 which may be substituted by -0 or the like such as methylene, ethylene, propane-1,3 -diyl, propane-1,4-diyl, butane-1,3-diyl , pentane-1,5-diyl, methyleneoxy (-CH2-indole), etidylene, propanedioxy {-((:112)3-0-, etc.), sub-ch2- S-), ethylenesulfanediyl {-(CH2)2-sulfanediyl {-((^2)3-3-yl}, methylene), ethyleneimine {- (CH2)2-NH-}, {-(CH2) 3,: "-etc}, etc. L1 is preferably a single bond group, a methyleneoxy group, an ethyleneoxy group or an ethylenesulfanediamine group, more preferably a single bond or an ethyleneoxy group. Each of the monomer (bl-2) and the monomer (bl-3) can be used in combination. Further, in the case of using a thiol group such as a monomer (b 1 -2 ) or the like, a saturated aliphatic group substituted with -ch2-0 fluorene may be used, for example, a methyl group, a t er t · butyl '-hydroxypropyl group. , 2-hydroxy ' 2 -hydroxy-1-methylbutyl, 4-hydroxybutyl:, 1-hydroxyethyl, a hydrocarbon group, which can be exemplified by a hospital-1,2-diyl, butyldiyl, hexane-1 ,6-{ - ( CH2 ) 2-0-methylsulfanediyl (-_ S - }, propanediylamino (-ch2-nh-propanediylimido, methylene, ethylene) Or a mixture of ethylene alone or 2 and a monomer (bl-3) -13- 201130905. Where such a mixture is used, monomer (b 1 -2 ) •• monomer (bl- 3) The molar ratio is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, and even more preferably 20: 80 to 80: 20. Preferred monomer (bl-2) (bl-2-l)~ is represented by any of the formulas (bl-2-15). In this case, the monomer (bl-2-l), the monomer (bI-2-3), and the monomer ( Bl-2-5), monomer (bl-2-7), monomer (bl-2-9), and monomer (bl-2_l 1 )~ monomer (bl-2-15) are better, single (bl-2-1), monomer (bl-2-7), monomer (bl-2-9), and monomer (bl-2-15 ) Better. -14- 0201130905 [Chemical 3 H2C=CH-C-0

(b1-2-1) 〇h2c=ch-co-ch (b1-2-3) 0 h2c=ch-co-c2h4 (b1-2-5) 0 h2c=ch-co-c2h4o (b1-2- 7) 0 II H2C=C—C-0 1 I CH,

H2C=CH -C -〇 -C2H4S (b1-2-2) 0 H2C=CH-C-〇-C2H4NH (b1-2-4) 0 II h2c=c-c-o-c2h4s CH3 (b1-2-6)

(b1-2-9) H2C=C-C-〇-CH2 CH3 (b1-2-11)

0 0 h2c=c-c-o-c2h4nh

Ch3 o II

(b1-2-8)

H2c=c-c-oC2H5 (b1-2-10)

CH2OH (b1-2-12)

C2H4OH (b1-2-14)

O

II H2C=C-C-〇-C2H4 CH3 (b1-2-13)

O

II H2C=C-C-0-C2H40 CH3 (b1-2-15) The preferred monomer (bl-3) is represented by any of the formulae (bl-3-1) to (bl-3-15). Among these, monomer (bl-3-1), monomer (bl-3-3), monomer (bl-3-5), monomer (bl-3-7), monomer (bl- 3-9), and monomer (bl-3-11) ~ monomer (bl-3-15) is better, monomer (bl-3-1), monomer (bl-3-7), monomer (bl-3-9) and monomer (bl-3- 15) are even better. -15- 201130905

H2C=CH-C-〇-c2H4S (51-3-2) 0 H2C=CH-C-〇-c2H4^^ (b1-3-4)

化H2C=CH-C-0 (b1-3-1) H2C=CH-C-〇-CH2 (M-3-3) 0 H2C=CH-C-〇-C2H4 (b1-3- 5) ο

H2C=C-C-〇-C2H4S CH3 (b1-3-6) 0

H2c=?』-〇*c2H4NHtjX^b CH3 (b1-3-8) (b1-3-7)

0

H2C = C-C-0-C2H4 CH3 (b1-3-13)

0 II Λ h2c=c-c-o c2h4oh

(b1-3-14)

H2C=C-CO-C2H4O CH3 (51-3-15) with a monomer of the oxetane structure (b2) aspect 'for example, 3_(methyl)-propyl 醯oxymethyl oxetane' oxygen Methyl oxirane n 3_ethyl _3_(methyl) oxime oxiranyloxymethyl oxetane, 3-methyl-3-(methyl) propyl oxyalkyl] methyl oxygen Heterocyclobutane, 3-ethyl-3-[indolyl-(methyl)propenyloxy)methyloxetane, 3-methyl-3-[1-(methyl)propenyloxy Ethyl butane, 3-ethyl-3-[1-(methyl)propenyloxy)ethyloxetane, 2-phenyl-3-(methyl)propenyloxymethyl Oxetane, 2-tri-16-201130905 fluoromethyl-3-(methyl)propenyloxymethyloxetane, 2-pentafluoroethyl-3-(methyl)propene oxime Oxymethyloxetane, 3-methyl-3-(methyl)propenyloxyethyloxetane, 3-methyl-3-(methyl)propenyloxyethyl Oxetane, 2-phenyl-3-(methyl)propenyloxyethyloxetane, 2-trifluoromethyl-3-(methyl)propenyloxyethyloxy Cyclobutane or 2-pentafluoroethyl-3-(methyl)propenyloxyethyl Cyclobutane heteroaryl, 3- (meth) Bing Xixi oxetane group. Among these, 3-ethyl-3-(methyl)propenyloxymethyloxetane is preferred. In terms of a monomer (b 3 ) having a tetrahydrofuran structure, for example, tetrahydrofuranyl (meth) acrylate, tetrahydrofuranyl methoxyethyl (meth) acrylate, tetrahydrofuranyl methoxy propyl (methyl) Acrylic vinegar, etc. 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, and an unsaturated bond having a polymerizable side chain (carbon-carbon double bond or triple bond) An aromatic compound, a substituted vinyl compound, a 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 (methyl). Acrylate, benzyl (methyl) propylene vinegar, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (methyl) propylene Sour vinegar, bicyclo [5.2.1.0''6] decane-8-yl (meth) acrylate (a customary name for "dicyclopentyl (meth) acrylate" in this field), -17- 201130905 4 - Bicyclo [5.2.1.02'6] oxime-8-yl (meth) acrylate vinegar, 5-tricyclo [5.2.1.0''6] decene-8-yl (meth) acrylate , phenyl (meth) acrylate, amino ethyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate and other unsaturated carboxylic acid esters; acetic acid a carboxylic acid vinyl ester such as vinyl ester or vinyl propionate; an amide having a carbon-carbon double bond such as dimethyl (meth) acrylamide or isopropyl (meth) acrylamide; styrene Methylstyrene, B Alkyl toluene, p-methoxystyrene is equivalent to an aromatic compound having a polymerizable unsaturated bond in a side chain; a vinyl cyanide compound such as acrylonitrile, methacrylonitrile or α-chloro(meth)acrylonitrile; , halogenated ethylene compounds such as dichloroethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene, tetrafluoroethylene; Ν-methyl maleimide, Ν-ethyl maleimide, Ν- Butyl maleimide, fluorene-cyclohexylmaleimide, fluorene-benzyl maleimide, fluorenyl-phenylmaleimide, etc., substituted maleimide; Diene such as 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2 .1] hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.;!]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-ethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2 .1]Geng-2· -18- 201130905 Alkene, 5,6-bis(2'-hydroxyethyl)bicyclo[2·2.丨]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-ethylbicyclo[2_2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2_1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[ 2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2_ a polycyclic unsaturated compound such as an ene; In the monomer (c), benzyl acrylate, styrene 'N-cyclohexylmaleimide, N-benzyl maleimide, N-phenyl maleimide, bicyclo [2.2. 1] Hept-2-ene is preferred. The monomer (X)' may be used alone or in combination of either monomer (b) or monomer (c). The monomer (X) preferably contains the monomer (b). That is, the monomer (X) is preferably only monomer (b), or both of monomer (b) and monomer (c) is more preferably monomer only (b). The copolymer containing the monomer (b) is improved in heat resistance, light resistance, solvent resistance, enthalpy, growth, and mechanical properties of the coating film or pattern obtained by the composition of the tree. 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, the ratio is from 5 to 60% by mole, more preferably from 10 to 5% by mole, and the structural unit derived from the monomer (b) is preferably from 2 to 98% by mole (more preferably from -95% by mole). More preferably, it is 50 to 90% by mole). When it is 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. -19- 201130905 When the resin (A) is a copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) is 2 to 98 m in the entire structural unit of the copolymer. %, the structural unit derived from the monomer (c) is preferably from 2 to 98 mol%. If it is in this range, the tendency to maintain stability or heat resistance is 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 moles %. 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), in the entire structural unit of the copolymer, the structural unit derived from the monomer (a) is 2 to 97. 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. For the resin (A), for example, the method described in the document "Experimental method for polymer synthesis" (promulgated by Otsuka Ryokan, Ltd., 1st edition, 1st, 1st, 1st, 1st, 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 the reaction vessel 'in the absence of oxygen and in the absence of oxygen. The copolymer is produced by scrambling, heating -20-201130905, 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 structure enthalpy (d) having a carbon-carbon double bond in a side chain. The monotercene (d) is represented by the formula (dl) or the formula (d2), and preferably has a 1-alkyl-1-vinylcarbonyl group at the terminal, and more preferably has a (meth) acrylonitrile group at the terminal. 【化5】

In the formula (dl) and the formula (d2), R8 and R9 each independently represent a hydrogen atom or a hydrazine, a .6 alkyl group (preferably a hydrogen atom or a methyl group). Further, the * marks in the formula (dl) and the formula (d2) each indicate a bonding position in the structural unit (dl) 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), as in the method of JP-A-2005-189574, for example, adding a monomer (b) having a carbon-carbon double bond and a cyclic ether structure, It is preferably a monomer having a carbon-carbon double bond and an epoxy structure (bl) {for example, a monomer represented by the formula (bl-4) or the formula (bl_5) to form [formula (bl-4) or formula ( In bl_5), ... the same as above. 【化6】

The structural unit (d) having a carbon-carbon double bond in the 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 by nitrogen to air, and is added relative to the amount of the monomer (a) used for the copolymerization. 5 to 80 moles of monomer (b). Next, a reaction catalyst (for example, dimethylaminomethyl group) of 0 _ 0 0 1 to 5 mass% is added to the total amount of the monomer (a) used in the copolymer and the monomer (b) used in the addition reaction. A phenol or the like and 0.001 to 5% by mass of a polymerization inhibitor (for example, hydroquinone or the like) are reacted 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 7 5 mol%, more preferably from 1 5 to 70, based on the amount of the monomer (a) used in the copolymerization. Moer%. In this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity is improved. -22- 201130905 Structural unit containing carbon-carbon double bonds in side chains (d) The copolymer can be used directly after the reaction solution' can also 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). If it is in this range, the solubility in the developer is improved, and the unexposed portion is easily dissolved. Here, the acid value is usually determined by titration with potassium hydroxide aqueous solution as measured by the amount (m g ) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer. 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). When it is 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 (?n)} is preferably from 1.1 to 6.0 (more preferably from 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 1 to 7 % by mass) based on the solid content of the resin composition. If it is in this range, the solubility in the developer is sufficient, and the 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 higher. Further, in the specification and the patent application, "solid content of the composition -23-201130905" means "the total amount of each component of the resin composition from which the solvent is removed". The solid component can be measured by a conventional means such as gas chromatography or liquid chromatography. <Polymerizable compound (B)> The polymerizable compound (B) is freely activated by a polymerization initiator (C) by heating or light irradiation. A compound which 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, and bis(2-hydroxyethyl)isocyanurate tris(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 trimethylpropane tri(meth)acrylate, caprolactone modified pentaerythritol di(meth) propylene Ester 'caprolactone modified ginseng (2-hydroxyethyl)iso-24- 201130905 cyanurate tri(meth) acrylate, caprolactone modified pentaerythritol tetrakis(methyl) acrylate vinegar, Vinegar modified pentaerythritol penta (methyl) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modification Tripentaerythritol penta (methyl) acrylate, caprolactone modified tripentaerythritol hexa(methyl) propionate, caprolactone modified tripentaerythritol hepta (methyl) propionate, caprolactone a reaction product of a trimellititol octa (meth) acrylate, a caprolactone-modified pentaerythritol tri(meth) acrylate and an acid anhydride, a caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, A reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride. 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. In the total of the resin (A) and the polymerizable compound (B), the content of the polymerizable compound (B) is preferably 5 to &lt; 75 mass% (more preferably 1 to 70 mass%, still more preferably 1 5~6 5 mass%). 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)> -25- 201130905 The polymerization initiator (c) is a compound which generates an active radical or an acid by heating or light irradiation, and starts polymerization, 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. The polymerization initiator (C) is, for example, a hydrazine compound, an acetophenone compound, a triazine compound, a mercaptophosphine oxide compound, an anthraquinone compound, a benzoin compound, a benzophenone compound or the like. Among these, a biimidazole compound, an acetophenone compound, an anthraquinone compound, and a triazine compound are preferred, and a biimidazole compound excellent in sensitivity is more preferable. The biimidazole compound may, for example, be 22'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole or 2,2'-bis(2,3-dichlorobenzene). 4,4',5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (dialkoxyphenyl)biimidazole, 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (eg special public Zhao An imidazole compound in which a phenyl group at the 4, 4', 5, 5' position is substituted with an alkoxycarbonyl group (-COOR) (for example, Japanese Patent Laid-Open No. Hei. No. 48-38403, No. Hei 62-174204, etc.) -] 〇 91 No. 3, etc. for reference). 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,-four Phenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole is preferred. -26- 201130905 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, hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2-methyl Benzyl)-2-dimethylamino-1(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4 -morpholinophenyl)-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-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl) -2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino) 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-morpholinobenzene Butyl ketone, 2-(4-bromobenzyl)-2-dimethylamino-b (4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2 -Dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholino Phenyl)-butanone, 2-(4-methoxy-27-201130905-benzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-( 2 -methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-bromobenzyl) -2-dimethylamino-indole_(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxyphenyl)-2-dimethylamino-1- ( 4 An oligomer of -morpholinophenyl)-butanone or 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one. The triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethyl). -6_(;4_methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6·piperonyl-1,3,5-triazine, 2,4 - bis(trichloromethyl)_6-(4-methoxythionyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)_6-[2-(5-methyl) Ethyl-2-yl)ethyl,-1,3,5-triazine, 2,4-bis(trichloromethyl)_6_[2-(furan-2-yl)ethylidene]-1, 3,5-trisyl, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-anthracene, 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 a quinone oxime compound, and specific examples thereof include, for example, 1-(4-phenylsulfonyl-phenyl)-butane-i,2-dione 1-oxime- 0-benzoate, 1-(4-phenylsulfonyl-phenyl).octane-1,2-dione 2-indole-0-benzoate, 1-[9-ethyl- 6-(2-Methylbenzylidene)-911-oxazol-3-yl]ethanone 1-0-acetate, 1-[9-ethyl-6-(2-methyl-4-) -28 - 201130905 (3,3-Methyl-2,4-oxocyclopentylmethoxy)benzimidyl)9}1_ 咔卩3·yl]ethanone I l_〇- Acetic acid vinegar and so on. For benzoin compounds, for example, benzoin, benzoin methyl ether, benzoic acid ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. In terms of benzophenone compounds, for example, benzophenone, methyl 0-benzylidene benzoate, 4-phenylbenzophenone, 4-phenylidene- 4,-methyldiphenyl sulfide 3,3',4,4'-tetra (tert_butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like. Further, as the polymerization initiator (C), 1 〇-butyl-2-chloroacridone, 2-ethyl hydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid can also be used. Methyl 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 No. 20-254-205205 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). A polymerization initiator having a group capable of generating a chain transfer, for example, a polymerization initiator represented by the formulae (C1) to (C6). -29 - _ I201130905 【化7 h2c

C-CH2-S-(CH2)3-S

0 CHi II . C~C—N H3COOC — ch3 h2c o wide, 0 ch3 CC-〇-(CH2)2-S-/^\-cC-N &gt;u I , (C1) c4h9-s-ch2 ch3 0 CHg 0 (C2)

C4H9-S-CH H2Cv 0 M ____u- ^ 6h3, (C3)

One 〇 ch3 -CH2-S-^^-c-C-NX ch3, (C4) h2. 0 ch2 ch \ h3cooc〆 p-CH2-S-(CH2)3-S-^^-c-C-3 (C5) CH, CH3 h2c

H3COOC P ^ o ch2 ru -CH2-S-(CH2)3-S-^-^-i_N^CH3i2H5, CH3 (C6) The content of the polymerization initiator (c) relative to the resins (A) and (B) In terms of 100 parts by mass, it is preferably 0.1 to more preferably 1 to 30 parts by mass. When it is in this range, the resin or heat becomes highly sensitive, and the coating strength or smoothness formed by using the resin composition tends to be improved. <Polymerization start aid (D)> The resin composition of the present invention may contain an auxiliary (D) as necessary. The polymerization starting assistant (D) can be usually used in combination with a poly-named one, and can be used to promote the polymerization initiator (C). 40 parts by mass of the polymerizable compound (the composition has a polymerization starting initiator for the film or pattern (C-polymerization and -30-201130905 when the polymerization initiator (D) is used, the content is relative to the resin The total amount of the polymerizable compound (B) and the polymerizable compound (B) is preferably 0.01 to 50 parts by mass (more preferably: 丨 to ... parts by mass). In the agent (D)', the sensitivity of the obtained resin composition to light or heat is further improved, and the productivity of the coating film or pattern formed using the resin composition tends to be improved. For example, an amine compound, a thioxanthone compound, a carboxylic acid compound, etc. The amine compound may, for example, be an aliphatic amine such as triethanolamine, methyldiethanolamine or triisopropanolamine; 4-dimethylammonium benzoate A Ester, 4-methylsulfonyl benzoic acid ethyl acetonate, monomethylammonium benzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylamine Ethyl ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino) Aromatic ketones (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, etc. Amine compounds, also available under the trade name "EAB-F" Commercial products such as Tugu Chemical Industry Co., Ltd., etc. For thioxanthone compounds, such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2 , dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. Examples of the carboxylic acid compound include (phenylthio)acetic acid, (methylphenylthio)acetic acid, (B) Phenylthio)acetic acid, (methylethylphenylthio)acetic acid, (dimethylphenylthio)acetic acid, (methoxyphenylthio)acetic acid, (dimethoxyphenylsulfuric acid) Acetate, (chlorophenylthio)acetic acid, (dichlorophenylthio)acetic acid, N-phenylglycine, phenoxy-31 - 201130905-based acetic acid, (naphthylthio)acetic acid, N- An aromatic heteroacetic acid such as naphthylglycine or the like. The polymerization initiation aid (D) can also be represented by the formula (D1) or naphthyloxyacetic acid.

(D1) C=CH-C-R11 R10 In the formula (D1), W1 is a C6.12 aromatic ring, and the above-mentioned sub-organic ring may be a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom L2 is an oxygen atom (- 0-) or a sulfur atom (-S - ). R1G is a chain or cyclic C, -6 aliphatic hydrocarbon group. R11 is a linear cyclic Ci_12 aliphatic hydrocarbon group or a C6.12 aromatic hydrocarbon group and The hydrogen atom of the aromatic hydrocarbon group may be substituted by a halogen atom, a chlorine atom or a bromine atom. The aromatic ring of W1 may, for example, be a benzene ring, a methylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene group, a cyclohexylbenzene ring, a naphthalene ring or a phenylbenzene ring. The halogen of W1 is, for example, a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a bromophenylbenzene ring, a chloronaphthalene ring, a bromonaphthalene ring or the like. W1 is a phenyl group or a naphthalene ring (naphthyl); R1 ° is an aliphatic hydrocarbon group, such as methyl, propyl, butyl, 2-butyl, 2-methylpropyl, tert-butylpentyl , 2-methylbutyl, 3-methylbutyl, i,l-dimethylsuccinylpropyl, 2,2-dimethylpropyl, hexyl, cyclopentyl aromatic ring, hydrogen atom, etc.) . Linear, branched, branched or branched, or the aforementioned aliphatic (for example, fluorine atom, dimethylbenzene ring, hexylbenzene cyclized aromatic ring, chlorophenyl benzene, preferably benzene ring) Base, iso-yl, pentyl, 2-propyl, 1,2-di, cyclohexyl, etc. -32- 201130905 RIC) is preferably methyl. R11 is an aliphatic hydrocarbon group, except for R1 (3 examples) Base, such as heptyl, octyl, decyl, decyl, undecyl, dodecyl, cycloheptyl, methylcyclohexyl, hexylcyclohexyl, norbornyl, adamantyl, etc. Halogenation of R11 Examples of the aliphatic hydrocarbon group are, 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, etc., and an aromatic hydrocarbon group of R11, for example Phenyl, methylphenyl, dimethylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, cyclohexylphenyl, naphthyl, biphenyl, etc. Further, in the case of a halogenated aromatic hydrocarbon group of R1 1, for example, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorophenylphenyl, bromophenylphenyl, chloronaphthyl, bromonaphthyl Etc. R 1 1 is preferably a phenyl group, a biphenyl group or a naphthyl group. In terms of a polymerization initiation aid (D 1 ), for example, 2-benzylidene-methylene-3-methylnaphtho[2, fluorene-d] Thiazoline, 2-benzylidylmethylene-3-methylnaphtho[l,2-d]thiazoline, 2-benzylidenemethylidene-3-methylnaphtho[2,3- d) thiazoline, 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(1-naphthylmethylidenemethylene)-3-methylbenzothiazoline , 2-(2-naphthylmethylidene methylene)-3-methyl-5-phenylbenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5- Phenylbenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-fluorobenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3 Methyl-5-fluorobenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(1-naphthylmethylidenemethyl) )-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-bromobenzothiazoline, 2-(1-naphthoquinone) Benzylmethyl)-3-methyl-5-bromobenzene-33- 201130905 thiazoline, 2-(4-phenylbenzylidenemethylidene)-3-methylbenzothiophene, 2- (4_phenyl Mercaptomethylidene)·3-methyl_5-phenylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methylnaphtho[2,1-d]m Porphyrin, 2-(2-naphthylmethylidene methylene)-3-methylnaphtho[1,2-(indolyl thiophene, 2-(4-phenylbenzimidylmethylene)-3 -methylnaphthyl] morpholine, 2-(4-phenylbenzimidylmethylene)-3-methylnaphtho[Hd]oxazoline, 2-(Ρ·fluorobenzhydrylmethylene )_3_methylnaphtho[2,1-d]oxazoline, 2-(p-fluorobenzhydrylmethylene)-3-methylnaphtho[1,2_ΐ]oxazoline, 2- Benzyl benzylidene-3-methylnaphtho[2,id], benzoyl benzylidene-3-methylnaphtho[Ud] 哩咐' 2 benzylene Methyl-3-methylnaphtho[2,3-d]oxazoline, 2-(2-naphthylmethylmethyl)-3-methylbenzoxazoline, 2-(1-naphthyl) Styrene methylene) methylbenzoxazoline, 2-(2-naphthylmethylidene methylene)_3_methyl-5-ylbenzoxazoline, 2-(1-naphthomethylphenyl) Methylene)_3·methyl_5·phenylbenzoxazoline, 2-(2-naphthylmethylidene methylene)methyl-5-fluorobenzoxazole, 2-(1-naphthoquinone) Kea methyl)_3·methyl_5_fluorobenzoxime Porphyrin, 2-(2-naphthylmethylidene methylene)methyl-5-chlorobenzoxazolidine, (1-naphthylmethylidene methylene)_3-methyl-5-chlorobenzoxazole Porphyrin, 2_( 2_methylmercaptomethylene)_3·methyl_5-bromobenzoxazoline, 2_(1-naphthylmethylmethylene)_3_methyl-5-bromobenzoxazoline , 2_(4_this basic methylmethylene)_3-methylbenzoxazoline, 2-(4-phenylbenzimidino)-3methyl-5-phenylbenzone Oxazoline, 2_(2 -Cai melanyl)-3-methylnaphtho[2,ld]oxazoline, 2_(2_naphthylmethylidene)-3-methylnaphtho[l , 2-d]oxazoline, 2-(4-phenyl-benzhydryl-pyrazole, thiazolidine, thiathiazol-2-ylidene 3-phenyl-benzoxazole 2-naphthoquinonemethyl-methyl-34- 201130905 -3 -Methylnaphtho[2,ld]oxazoline, 2-(4-phenylbenzylidenemethylene)-3-methylnaphtho[l,2-d]oxazoline , 2_(P-fluorobenzhydrylmethylene)-3-methylnaphtho[2,1-d]oxazoline, 2_(P-fluorobenzhydrylmethylene)-3-methyl Naphtho[l,2-d]oxazoline and the like. In the above, 2-(2-naphthylmethylidenemethylene)-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-phenylbenzimidylmethylene)-3- represented by formula (D1-3) Methylnaphtho[1,2-(1]thiazoline is preferred. α, 〇〇,)

[化9] s 〇 /:=CH_C

The resin composition containing the polymerization initiation aid (D 1 ) 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 (D 1 ) 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 (D 1 ) is preferably 50% by mass or more (more preferably 60% by mass) based on the content of the polymerization initiation aid (D). /35-201130905 More preferably, it is 65 mass% or more, and it is preferably 100 mass% or less. When the polymerization initiator (D1) is used in an amount in this range, the visible transmittance of the coating film becomes high, and the polymerization initiator (D) can also be a compound represented by the formula (D2) or ( ). . If light D3 [化1 0]

In the formula (D2) or the formula (D3), W2 and W3 each independently represent a C6 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. L3 and L4 each independently represent an oxygen atom or a sulfur atom (preferably an atom). R12 and R13 each independently represent a linear, branched or cyclic C12 aliphatic hydrocarbon group or a C6-12 aromatic hydrocarbon group. The aliphatic hydrocarbon and the hydrogen atom of the aromatic hydrocarbon group may be substituted by a halogen atom, a hydroxyl group or a (. 6 alkyl group. The aromatic ring and the hetero ring of W2 and W3, for example, a benzene ring, a furan ring thiophene ring, a pyrrole ring, an imidazole group a ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring, and combinations thereof (for example, a naphthalene ring, an isobenzofuran ring, a benzimidazole, etc.), a halogenated aromatic ring of W2 and W3, such as a gas benzene ring 'dichloro Ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromobenzene ring, chloronaphthalene ring, bromine ring, etc. W2 and W3 are each independently preferably a benzene or naphthalene ring. Cyclophenyl ring of oxy-oxygen oxide-36-201130905 The aliphatic hydrocarbon group of R12 and R13, the halogenated aliphatic hydrocarbon group, the aromatic radial group, and the halogenated aromatic hydrocarbon group, for example, those exemplified by R 1 1 , etc. RI 2 R 13-hydroxyl-substituted aliphatic hydrocarbon group, such as hydroxymethyl, _ethyl, hydroxy Or a hydroxybutyl group, etc., an aromatic hydrocarbon group substituted with a hydroxy group of R12 or R13, for example, a hydroxyphenyl group, a hydroxynaphthyl group, etc., an aspect of an aliphatic hydrocarbon group substituted with an alkoxy group, such as a methoxymethyl group. , methoxyethyl, methoxypropyl, methoxybutyl, butoxymethyl, ethoxyethyl, ethoxypropyl, propoxybutyl, etc. R12 or R13 to the alkane The oxy-substituted aromatic hydrocarbon group is, for example, a methoxyphenyl group, an ethoxynaphthyl group or the like. R12 and R13 are each independently preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. In the case of the auxiliary (D2) or (D3), for example, a dialkoxynaphthalene such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene or dibutoxynaphthalene: Dimethoxy oxime, diethoxy ruthenium, dipropoxy ruthenium, diisopropoxy ruthenium, dibutoxy ruthenium, dipentyl fluorene oxime, dihexyloxy ruthenium, methoxy ethoxy ruthenium , methoxypropoxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, ethoxybutoxy oxime Propoxyl a dialkoxy oxime such as oxindole, propoxy oxybutoxy fluorene or isopropoxy butyl hydrazine; dimethoxytetracene, diethoxytetracene, dipropoxy tetra a dialkoxytetracene such as benzene, diisopropoxytetracene or dibutoxytetracene; etc. -37- 201130905 <Polyfunctional thiol (E)> A resin composition of the present invention, A polyfunctional thiol (E) may be contained 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 may be added to the light or by a resin composition. The sensitivity of heat is good. In terms of polyfunctional thiol (E), such as hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, butanediol bis(3-sulfonyl) Propionate), butanediol bis(2-sulfonyl acetate), ethylene glycol bis(2-sulfonyl acetate), trimethylolpropane ginseng (2-sulfonyl acetate) ), butanediol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (2-sulfonylacetate) , pentaerythritol bismuth (3-sulfonyl propionate), penta Tetrahydrin (2-sulfonyl acetate), hydroxyethyl ginseng (3-sulfonyl propionate), pentaerythritol bismuth (3-sulfonyl butyl acrylate), 1,4-double (3- Sulfohydryl butyloxy) butane and the like. When the polyfunctional thiol (E) is used, the content thereof is preferably from 0.5 to 100 parts by mass, more preferably from 1 to 90 parts by mass, per 100 parts by mass of the polymerization initiator (C). When the polyfunctional thiol (E) is used in 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)> -38- 201130905 The resin composition of the present invention is characterized in that it contains both an isocyanato-containing decane compound (F) and a good storage stability and a substrate. Fully confidential. The resin (A) uses a monomer (a) containing an unsaturated carboxylic acid or the like, and a monomer having a carbon-carbon double bond and a cyclic ether structure (b) {especially an epoxy-structured monomer (bl) } 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 of 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 preservation 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 isocyanate-containing decane 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')ml(R2)(3-m.) (F1) -39- 201130905 [In the formula (FI), 'L is C,-6-alkyldiyl. ...is a C.4 alkyl group, mi is 〇 or 1. However, the fact that ml is 0 means that R1 does not exist. R2 is a C1-4 oxy group. The plural R2 may be the same or different from each other. L-alkanediyl' may, for example, be methylene, ethylene, propane-1 &gt; 3-diyl, propane-1,2-diyl, butane-i,4-diyl, butane-i , 3-diyl, pentylene-1,5-diyl, hexane-1,6-diyl, etc. ^L is preferably propane-1,3-diyl. The alkyl group of R1 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a butyl group (sec-butyl group) or a 2-methylpropyl group (isobutyl group). R1 is preferably a methyl group or an ethyl group. The alkoxy group of R2 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. R2 is preferably a methoxy group or an ethoxy group. Mm is preferably 0. Also, the plural R2 is preferably the same. In terms of the isocyanatodecane compound (F1), for example, isocyanatomethyltrimethoxydecane, 2-isoacylethyltrimethoxydecane, 3-isocyanatopropylmethyldimethoxy Basear, 3-isocyanatopropyltrimethoxydecane, 3-isocyanylpropylmethyldiethoxydecane '3-isocyanatepropyltriethoxydecane, 4-isocyanide Acid butyl trimethoxy decane, 5 · isocyanyl pentyl trimethoxy decane, and the like. Among these, 3-isocyanatopropyltrimethoxydecane and 3-isocyanatopropyltriethoxydecane are preferred. The content of the content of the isocyanatodecane compound (F) is preferably 〇·1% by mass or more and 15% by mass or less based on the solid content of the resin composition (more preferably 〇.2% by mass or more and 1 〇 by mass). %the following). If it is in this range, the storage stability of the resin composition and the adhesion of the coating film or the pattern are improved. -40-201130905 The tendency to develop residue is also difficult to see. <Colorant (G)> The resin composition of the present invention may further contain a colorant (G). For colorants (G), such as dyes and pigments. Dyes and pigments are all substances which can be used for coloring. However, in the specification and the scope of the patent application, those who are soluble in a solvent are defined as dyes, and those which are not in the valley are defined as pigments. 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). The pigment aspect is, for example, a compound classified as a pigment specifically in the Colour index (published by The Society of Dyers and Colourists). Details such as CI Pigment Yellow 1, 3, 1 2 ' 13; 14, 14, 16, 16, Π, '20, 24, 3 1 , 53 , 83 , 86 ' 93 , 94 , 109 , 11 〇 , 117 , 125, 128, 13, 7, '138, 139, 147, 148, 150, 153, 154' 166, 1 73, 194' ' 21 4 and other yellow pigments; CI Pigment Orange 1 3, 3 1, 36 ^ 38, 40 , 42 '43, 5 1 ' 5 5, 59, 61, 64, 65, 7 1, 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, 2 5 4, 2 5 5, 2 6 4, 2 6 5 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6,60 and other blue pigments CI pigment purple 1,19,23,29,32,36,38 and other purple pigments; -41 - 201130905 CI pigment green 7,36,58 and other green pigments; CI pigment brown 23,25, etc. Brown pigment; 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; is 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 dispersing agent may be used alone or in combination of two or more. In the case of using a pigment dispersant, the amount of the pigment 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, or an amphoteric type, and can be classified into an ester type, an amine type "acrylic type, an anthrone type, a fluorine type, etc." in the compound. These surfactants may be appropriately selected depending on the pigment or the like. In terms of surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl acids-42-201130905, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters , 3-grade amine modified polyurethanes, polyethyleneimine, and the like. Further, as a commercially available surfactant, for example, the trade name is KP (Shin-Etsu Chemical Co., Ltd.), P〇lyfl〇w (registered trademark) (Kyoei Chemical Co., Ltd.), EFTOP (registered trademark) (Mitsubishi Materials Electronic Chemicals Co., Ltd.) 'MEGAFACE (registered trademark) (DIC), Fluorad (registered trademark) (produced by Sumitomo 3M Limited), AsahiGuard (registered trademark) (asahi Glass) , Surflon (registered trademark) (manufactured by AGC SEIMI CHEMICAL CO., LTD.), SOLSPERSE (registered trademark) (Zeneca), EFKA (manufactured by C IB A), AJISPER (registered trademark) (Ajinomoto Fine-Techno) Co., Inc., Disperbyk (manufactured by BYK), and the like. 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 note (dyeing dyeing company) Dye. C. I. Solvent dyes, such as CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; C. I · Solvent Red 4 5, 4 9, 1 2 5, 1 3 0 ; C · I. Solvent Orange 2, 7, 11, 15, 26, 56; -43- 201130905 CI · Solvent Blue 35, 37, 59, 67; CI Solvent Green 1, 3 , 4, 5, 7, 28, 29, 32, 33, 34, 35 » and so on. C · I. Acid dyes, such as CI acid yellow 1, 3, 7, 9, 1 1 , 1 7 ' 23 ' 25 29 , 34 , 36 , 38 , 40 , 42 , 54 , 65 i ' 72 , 73 , 76 ' 79 , 98 , 99 , 111 ' 112 ' 113 ' 11 4 ' 1 16 , 119 , 123 , 128 , 134 , 135 , 138 , 139 , 140 , 144 , 150 ' 1 55 , 1 57 , 160 , 161 , 163, 168, 169, 172, 177, 178, 1 79 , 1 84 , 190 , 193 , 196 , 197 , 199 , 202 , 203 , 204 , 205 , 207 , 212 , 2 14 , 220 , 221 ' 228 , 230, 232, 235, 238, 240, 242, 243, 251; C. I. Acid red 1, 4, 8 &gt; 14, 17, 7, 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 , 15 1 , 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, 3 15 , 3 16 , 3 3 9 , 341 , 345 , 346 , 349 , 382 , 383 , 394 , 401 , 412 , 417 , 418 , 422 , 426 ; C. I. Lime 6, 7, 8 1 0,1 2,26,50,51,52,56,62,63,64,74,75,! 94, 95, 107, 108 ' 169, 173; CI Acid Blue 1, 7, 9, 15, 1 8, 23, 25 ' 27 , 29 , 40 , 42 , 45 , 51 , 62 , 70 , 74 , 80 , 83 ' 86 , 87 , 90 ' 92 , 96 , -44 - 201130905 103 , 112 , 113 , 120 , 129, 138, 147, 150 15 8' 17 1 ' 182, 192, 210, 242, 243, 256, 259, 267 &gt; 2 78, 2 80 , 285 , 290 , 296 , 315 , 324 : 1 , : 535 340; CI Acid Violet 6B, 7, 9 ' 17' 19; c · I. Acid Green 1, 3, 5, 9, 16 6 , 25 , 27 , 50 58 , 63 ' 65 , 80 , 104 , 105 ' 106' 109; and so on. CI direct dyes, such as C. I. Direct Yellow 2, 3 3, 34, 35, 38, 39, 43-47, 5 0, 54 , 58, 68, 69, 70, 71 , 86 , 93 , 94 , 95, 98, 102, 1 08, 109, 129, 136, 138 '14 1; c. I. Direct red 7 9 , 8 2 , 83 , 84 , 91 , 92 , 96 , 97 , 98 &gt; 99, 105 , 117, 182, 172 , 246, 2 5 0 ; C. I. Direct orange 3 4, 3 9 , 41 , 46 ' 50 ' 52 , 56 , 57 , 6 1 - 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, 1 09-113, 114, 115, 117 , 119, 137, 149, 150 15 3, 1 55 156, 158, 159, 160, 161, 162, 163, 164 - 166, 1 67 &gt; 170, 171, 172, 173, 188, 189, 190, 192 - 193, 194 196 198, 199, 200, 207, 209, 210, 212 2 13 , 2 14 222 &gt; 228 ' 229 , 237 , 238 ' 242 , 243 , 244 , 245 , 247 , -45 - 201130905 248 , 250 , 251 252, 256, 257, 259, 260' 268' 274, 275 '293; CI Direct Violet 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; For CI mord dyes, for example, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42 , 43 , 45 , 56 , 61 , 62 , 65 ; C · I. mordant red 1, 2, 3, 4, 9, 1 1 , 1 2, 1 4, 1 7 , 1 8 , 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 oranges 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 violet 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; -46- 201130905 In terms of dyes, for example, an amine salt of an acid dye having a group represented by any one of formulas (1) to (7), and an acid group having a group represented by formula (8) or formula (9) can be used. A sulfonamide derivative of a dye. Further, the sulfonamide derivative of the acid dye may have a group represented by the formula (1 〇 ) in addition to the group represented by the formula (8) or the formula (9). In the foregoing acid dyes, for example, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and anthraquinone dyes, etc. -(so3-)(Cn H2n+丨N + H 3) ( 1 ) -( so3 .) { ( C η H 2 n + 1 ) 2N+H2} ( 2 ) -( S03-) { ( CnH2n+1 ) 3N + H } ( 3 ) -( so3-) { ( C n H2 n+ 1 ) 4N+ } ( 4 ) -( sor) ( C〇H 2 0 + 1 〇C p H2pN + H3 ) ( 5 ) -( S〇3_ ) { ( CnH2n+ 1 ) (PhCH2) 2N + H } -( S03·) { ( C η H 2 n + 1 ) Py+ } ( 7) -so2nh ( C „ H2 n + 1 ) ( 8 ) - sc » 2nh ( Co h2 〇 + 1 0 C p H 2 p ) ( 9) -so3m (10) In the formulae (1) to (10), η is an integer of 1 or more and 20 or less. 〇 and p each independently represent an integer of 1 or more and 10 or less. Ph is a phenyl group. Py + is represented by the formula (H) Μ is a chlorine atom or a monovalent cation. [Chemical 1 1] A V^(CH3)q (1)) In the formula (11), q is 0 or 1 'q is 0 means that the methyl group does not exist in the formula ( The * mark in -47- 201130905 11 ) is the bonding position of Py+, and Py+ is a carbon atom bond with CnH2n + 1 in the formula (7) at the bonding position. η is preferably 1 or more and 10 or less ( More preferably an integer of 8 or less) 〇 and Ρ are each independently an integer of 1 or more and 8 or less (more preferably 6 or less). q is preferably 1. A monovalent cation aspect of ruthenium, such as lithium ion, sodium ion, potassium ion, or ammonium quaternary ammonium The ion {e.g., (C2H5) 3 ΗΝ + } or the like 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, it is 1 or less, and more preferably 8 or less. The number of groups represented by the formula (8) or the formula (9) in the sulfonamide derivative of the acid dye is preferably 1 or more and 8 or less (more) Preferably, the sulfonamide derivative of the acid dye may have 8 or less, more preferably 6 or less, and more preferably 5 or less The group represented by the following formula (10): In terms of an azo dye having a sulfonamide structure, for example, a dye represented by the formula (G 1 ). [Chemical 1 2] r16 R15

In the formula (G1), R14 is a C2-2 decyl group, a C2-12 alkyl group substituted by a cyclohexyl group, and a C2 substituted by a cyclohexyl 'C2-i 2 alkoxy group substituted by a ^4 alkyl group. a phenyl group substituted with a -12 alkyl group, a C, .2Q alkyl group, a Ci.20 alkyl group substituted with a phenyl group, an alkylcarbonyloxyalkyl group represented by the formula (12), or represented by the formula (13) The alkoxycarbonylalkyl group (12) and the formula (13) wherein 'R19 is C2-l2 201130905 alkyl, and L4 is 0:2-12 alkanediyl. }. -L4-〇-CO-R19 (12) -L4-CO-〇-R'9 (13) In the formula (G1), R15 to R17 each independently represent a hydrogen atom, a methyl group, a hydroxyl group, an amine formazan group or a cyanogen group. base. 1118 is a Ci-4 alkyl group. The C2-2 0 alkyl group of R14, 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 C2_l2 alkyl group substituted by the cyclohexyl group of R14, for example, a cyclohexylethyl group, a 3-cyclohexylpropyl group, an 8-cyclohexyloctyl group or the like. The cyclohexyl group substituted by the oxime, such as 2-ethylcyclohexyl, 2-propylcyclohexyl and 2-butylcyclohexyl, etc. R14 (: 2.12 alkoxy substituted (: 2.12 alkyl aspect, for example 3-ethoxypropyl, 3-propoxypropyl, 4-propoxybutyl, 3-methylhexyloxyethyl and 2-ethylhexyloxy)propyl Et al. The phenyl aspect substituted by the Ci2 oxime group of R14, such as 〇-isopropylphenyl, etc. The phenyl group substituted by the phenyl group of R14, such as DL-1-phenylethyl, benzyl and 3 -Phenylbutyl group, etc. Rm's Cm-based aspect 'e.g. ethyl, propyl, hexyl, decyl, decyl, dodecyl, 2-ethylhexyl, 1,3-dimethylbutyl, 1 -methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl, etc. The C2.12 dibasic group of L4 may, for example, be an ethylene group and a hexanediyl group. Etc. 8 C, _4 alkyl aspect 'e.g. methyl, ethyl, propyl, isopropyl-49 - 201130905, butyl 'sec-butyl, isobutyl, tert-butyl. R14 is preferably Cm alkyl, more preferably 2-ethylhexyl. R15 is preferably a methyl group. R16 is preferably a cyano group. R17 is preferably a hydroxyl group. R18 is preferably methyl, ethyl, propyl or butyl, more preferably butyl. Dye (G1), the formula (G1-1) represented by the dyes are preferred. [Chemical 13]

02Η5 f^n-C4Hg so2nh (G1-1) Further, in terms of an azo dye having a sulfonamide structure, for example, a dye represented by the formula (G2 formula (G3) or formula (G4)).

An anthraquinone dye having a sulfonamide structure, for example, a dye represented by the formula (G5) -50-201130905. [化1 5]

(G5) In terms of a triphenylmethane dye having a sulfonamide structure, for example, a dye represented by the formula (G 6 ). 【化1 6】

In the case of a xanthene dye having a sulfonamide structure, for example, a dye represented by the formula (G 7 ). -51 - 201130905 hno2s 【化1 7】 c2h5

j^C4H9

In the case of an anthraquinone dye having a sulfonamide structure, for example, a dye represented by the formula (G8). [化1 8]

In the formula (G8), R20 to R23 each independently represent a hydrogen atom, -S02NH(ch2)3〇ch(CH3)2 group or sulfo group (-S03H). However, at least two of R2Q to R23 are - S02NH (CH2) 3OCH (CH3) 2 base. 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 to achieve the purpose of the spectrophotometry, the content thereof is preferably 2% by mass or more based on the colorant (G) (more preferably 5% by mass or more, 201130905 or more preferably 10% by mass or more). It is preferably 100 mass. /. The following (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 (Η)> The resin composition of the present invention may contain other additives (Η) as necessary. Other additives (Η) include, for example, a filler, a polymer compound other than the resin (A), an adhesion promoter, a surfactant, an antioxidant, an ultraviolet absorber, a photostabilizer, a chain transfer agent, and the like. For the filling agent, for example, glass, cerium oxide, aluminum oxide, and 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 0.0025 to 0.0250 by mass based on 100% by mass of the photosensitive resin composition excluding the surfactant. Preferably, it is from 0.0025 to 0.0200% by mass, more preferably from 0.005 to 0.0100% by mass. By including the surfactant in this range, in addition to making the flatness of the coating film good, it is possible to prevent the boiling of the solvent when it is dried. In the case of an anthrone-based surfactant, for example, a surfactant having a siloxane coupling. Specifically, for example, DC3PA, SH7PA, DC11PA, SH21PA, -53-201130905 SH28PA, same SH29PA, SH30PA, SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP 3 2 1 , KP 3 2 2, KP 3 2 3 , KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 ' TSF4452, TSF4460 ( Momentive

Performance Materials Japan contract company system) and so on. In the case of a fluorine-based surfactant, for example, a surfactant having a fluorocarbon chain. Specifically, such as Fluorinert (registered trademark) FC43 0, FC431 (made by Sumitomo 3M Limited), MEGAFACE (registered trademark) F142D, same as F171, same with F172, same with F173, with F177, with F183, with R30 (DIC) ), EFTOP (registered trademark) EF301, EF3 03, 冋EF351, EF3 5 2 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, same as S3 82, same as SC101, same as SC105 ( Manufactured by AGC SEIMI CHEMICAL CO., LTD., E5844 (manufactured by DAIKIN FINE CHEMICAL Research Institute), BM-1000, BM-1100 (all manufactured by BM Chemie Co., Ltd.). The fluorenone-based surfactant having a fluorine atom is, for example, a surfactant having a siloxane coupling and a fluorocarbon chain. Specifically, such as MEGAFACE (registered trademark) R08, with BL20, with F475, with F477, with F443 (DIC). Examples of adhesion promoters such as vinyl trimethoxy decane, vinyl diethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3-glycidoxypropyl trimethoxy decane ' 3_glycidoxypropylmethyl dimethyl-54- 201130905 oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyl-- Oxygen 5, 3-chloropropyl dimethoxy sand garden '3-methacryloxypropyltrimethoxydecane, 3-sulfonylpropyltrimethoxydecane, and the like. These may be used in combination with the isocyanato-containing decane compound (F). For antioxidants, for example, 2 -1 ert -butyl-6 - ( 3 -1 ert - 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-yl-5-methylphenyl)propanoxy}-1,1-dimethylethyl]-2,4, 8,10-Tetraoxaspiro[5.5]--alkane, 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 sulfonyl 3,3' -thiodipropionate, 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) -P-cresol, pentaerythritol oxime [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol In addition, the antioxidant is sold under the trade name "IRGANOX3114" by Ciba Japan Co., Ltd., etc. -55- 201130905 For UV absorbers, for example 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxyl 5-(-Chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[4-[(2-hydroxy-3-dodecyloxy)oxy]- 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl) Hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy- 4-butoxyphenyl)-6-( 2,4-bis-butoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonyl] Ethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(211-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, alkoxy Benzophenone and the like. 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 reaction 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-(l-cyclohexyloxy-2,2, 6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-l,3,5-triazine; bis(1,2,2,6,6- Pentamethyl-4-piperidinyl) sebacate; methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and the like. -56- 201130905 In terms of a chain transfer agent, for example, dodecyl mercaptan '2,4-diphenyl-4-methyl-1-pentene and the like. <Solvent (J)> The solvent (η is preferably such that the components such as the resin (a) are uniformly dissolved or dispersed and are not reacted with the respective components. From the viewpoint of coatability and drying properties, the boiling point is at 100 ° C. An organic solvent of 200 ° C is preferred. For the solvent (J ), for example, the following may be used: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol. Ethylene glycol monoalkyl ethers such as monobutyl ether: ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl Alkanediol alkyl ether acetates such as phenyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxypentyl acetate, etc. Propylene glycol monomethyl ether, propylene glycol Propylene glycol monoalkyl ethers such as monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol Propylene glycol dialkyl ethers such as methyl ether, propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol ethyl ether Propylene glycol alkyl ether propionates such as acid esters, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc. methoxybutyl alcohol, ethoxybutyl alcohol, propoxy butyl alcohol, butyl Butanediol monoalkyl ethers such as oxybutyl alcohol; -57- 201130905 methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxy Butanediol monoalkyl ether acetates such as acetoxyacetate; methoxybutyl propionate, ethoxybutyl propionate, propoxy butyl propionate, butoxybutyl propionic acid Butanediol monoalkyl ether propionate such as ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol methyl ethyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether. Aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone. B Acid propyl ester, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, glycolic acid Ester, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxyl Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxylate Methyl acetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propoxyacetic acid Butyl ester, methyl butoxyacetate, ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, butyl 2-methoxypropionic acid -58- 201130905 ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate 2-ethoxy Propyl propionate, butyl 2-ethoxypropionate, 2-butoxypropane Methyl ester, ethyl 2-butoxypropionate, propyl 2-butoxypropanoate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3·ethoxypropane Propyl acrylate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropane Esters such as butyl acrylate, 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 r-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 acid), vinegar (more Preferably, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate is preferred. The content of the solvent (J) is preferably 50% by mass based on the composition. /. The above (more preferably 60% by mass or more), preferably 9.5 mass% or less (more preferably 90% by mass or less). <Coating film, pattern, and display device> The coating film of the present invention can apply the resin composition to a substrate (for example, a substrate or a substrate on which a resin layer is formed), and then undergo thermal polymerization or photopolymerization-59-201130905 A coating film is formed. 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 by using an ink jet 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 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 aforementioned display device is preferably a liquid crystal display device, an organic EL display device or the like. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be more 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 invention described below. It is within the technical scope of the present invention. -60- 201130905 When it is not specifically noted, it is the following "%" and "{% by mass" and "parts by mass". 1 · Synthesis of resin (A) in a (four) bottle equipped with a reflux chiller's dropping funnel and a stirrer. Nitrogen was introduced into the nitrogen ring at 0.02 L/min, and diethylene glycol ethyl methyl group was added to 14 G parts. Heating to 7 () ι with stirring, then preparing 40 parts of methyl propylene acid; and a mixture of monomer (bl-2-l) and monomer (Μ-%)) &lt; monomer in the mixture (bi-2) -丨): Moth ratio of monomer = 50. 50} 360 parts of a solution of 19 parts by weight of diethylene glycol ethyl methyl ether, so that the solution was dripped for 4 hours to keep warm at 7 〇t inside the flask. 0 II =CH-C-0 (b1-3-1) [Chemical 1 9 0

H2c:

HjC^CH-C-0* (b1-2-1) On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in diethyl 2 A solution of 24 parts of alcohol ethyl methyl ether was dropped into the flask using another drop of the pump for 5 hours. After the completion of the dropwise addition of the polymerization initiator solution, it was maintained at 7 〇t for 4 hours, and then cooled to room temperature to obtain a copolymer having a solid content of 42.3% and an acid value of 60 mg-KOH / g. {Resin (A 1 ) Solution. 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 (??) of the obtained resin (A1) were measured by colloidal permeation chromatography under the following conditions. -61 - 201130905 Installation: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 mL/min Detector: RI Standard: polystyrene [Examples 1, 2, Comparative Examples 1 and 2] 2. Photosensitive resin composition Modulation (1) Preparation of photosensitive resin composition 1 (hereinafter referred to as "composition 1"): CI pigment green 36: 4.3 parts, CI pigment yellow 150: 1.9 parts, and propylene-based pigment dispersant 1.7 parts and propylene glycol monomethyl Ethyl ether acetate 35 parts mixed 'The pigment dispersion was prepared by sufficiently dispersing the pigment using a bead mill. 100.2 parts of the pigment dispersion liquid and the resin (A1) solution (42.4 parts in terms of solid content) and 42.4 parts of 2,2'-double (2) of dipentaerythritol hexaacrylate (KayaRAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) were mixed. Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd.) 3.4 parts, 2-(2-naphthoquinone) 4 parts of methylidene-3-methylbenzothiazolinium. 4 parts of pentaerythritol bismuth (3-sulfonylpropionate) (PEMP; manufactured by SC Organic Chemicals Co., Ltd.) 2.5 parts, 3-isocyanate Propyl triethoxy decane (KBE-9007; manufactured by Shin-Etsu Chemical Co., Ltd.) 〇·9 parts, polyether modified fluorenone oil of an anthrone-based surfactant (S Η 8 4 0 0 ; Dow Corning Toray -62- 201130905

^(manufactured by Ciba Japan Co., Ltd.) 0.04 parts, IRGANOX 31 14 k H deuterium from diethylene glycol ethyl) 0.2 parts, and a solvent to obtain a composition 1 ° @ θ alcohol monomethyl ether acetate Ester, methyl ether, diethylene glycol butyl methyl ether, 芮 / η: 3 〇: 17: 13, and the mass ratio of the composition and dipropylene glycol dimethyl ether is 3 3 % of the solid content of ΡΧ 1 mixing. (2) Preparation of Photosensitive Resin Composition 2 (hereinafter referred to as "Component 2") The composition 2 was prepared 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 and the like are as shown in Table 1 below. -63- 201130905 [Table 1] Composition 1 Composition 2 Resin (Α) Resin (Α1) 42.4 parts 涸) 46.1 parts (solid content) Polymerizable compound (Β) Dipentaerythritol hexaacrylate 42.4 parts 46.1 parts polymerization Starting agent (C) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole 3_4 parts 3.7 parts polymerization start! 1(D) 2-(2-naphthylmethylidenemethyl)-3-methylbenzothiazoline 0.4 part 0.5 part polyfunctional thiol (Ε) pentaerythritol 肆 (3-sulfonyl propionate) 2.5 2.8 parts of isocyanatodecane coupling agent 3-isocyanate propyl triethoxy decane 0.9 parts 0.9 parts coloring agent (G) CI pigment green 36 4.3 parts CI pigment yellow 150 1.9 parts _ other additives (Η) Propylene pigment dispersant 1.7 parts Polyether modified anthrone oil 0.04 parts 0.04 parts IRGANOX3114 0.2 parts 0.2 parts solvent (J) • Diethylene glycol ethyl methyl ether • Diethylene glycol butyl methyl ether • Propylene glycol monomethyl Ether acetate • Dipropylene glycol dimethyl ether (mass ratio: 4〇: 3〇: 17: 13) Mixed in such a manner that the solid content of the composition is 33%, and the solid content of the composition is 33%. (3) The preparation of the photoreceptor composition Η 1 (hereinafter referred to as "composition η丨") is carried out except that 3-isoacyl propyl triethoxy decane is substituted with 3-aminopropyltrimethoxy decane The substance 1 similarly modulates the composition Η 1. However, the components are mixed and the composition 胶 1 is colloidalized. Therefore, it is impossible to evaluate the adhesion and the like. (4) Preparation of photosensitive resin composition Η2 (hereinafter referred to as "composition η2") -64 - 201130905 In addition to substitution of 3-isocyanatopropyltriethoxydecane to N-phenyl-3-amino group The composition Η 2 was prepared in the same manner as in the composition 1 except for the propyltrimethoxy sand. 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 for 4 days at 2 3 t. The viscosity was measured using a viscometer manufactured by Toki Sangyo Co., Ltd. (乂13€14£丁£111'乂-30). The enthalpy change (%) of the formula (I) is good (〇) in the range of 98 to 102%, and is evaluated as poor (X) outside the range. The results are shown in Table 2. Viscosity change (%) = 100x viscosity after storage (mPa · s) / viscosity before storage (mPa · s) (I) (2) Evaluation of adhesion The adhesion of the tantalum nitride substrate is evaluated as follows . First, a 5 cm x 5 cm tantalum nitride substrate was sequentially washed with a neutral detergent, water and alcohol, and then dried. On the substrate, spin coating was carried out in such a manner that the film thickness after baking of the composition was 3 · 0 μηη. Subsequently, the pressure reduction was carried out by a vacuum dryer (VCD Microtek Co., Ltd.) to reduce the pressure to 1 _ 0 t0 r r to form a coating film. The coating film was prebaked in a hot plate at 90 ° C for 2 minutes. -65- 201130905 Then use the exposure machine (TME-150RSK; TOPCON (light source), light source; ultra-high pressure mercury lamp), under the atmospheric environment, with an exposure of 100mJ/cm2 (4〇5nm basis), after prebaking The film is exposed. This exposure is performed by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (LU0 400; 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 heated at 235 ° C with a hot plate. After 1 minute, it was baked to obtain a hardened coating film having a film thickness of 3 μm. In the hardened coating film, a cutter and a Super Cutter Guide (made by Taiyo Machinery Co., Ltd.) were used to add the cuts at intervals of 1 mm to make 100 units of 1 mm x 1 mm. The hardened coating film having a 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 single digits remaining on the substrate without the peeling of the cured coating film was visually calculated. The results are shown in Table 2. (3) Residue and resolution of pattern development by photolithography (3 -1) Pattern development The glass substrate of 5 cm X 5 cm 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.Οηη. Subsequently, the pressure was reduced to a reduced pressure of 1 · Torr Torr by a vacuum dryer (manufactured by -66 - 201130905 VCDMicrotek 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 a exposure machine (TME-1 50RSK; TOPCON (light source), light source; ultrahigh pressure mercury lamp), the pre-baked coating film was exposed to an exposure amount of 50 mJ/cm 2 (405 nm reference) in an atmospheric atmosphere. 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, the exposure is performed using a quartz glass mask which forms a line pattern of line widths of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, ΙΟμηι, 2〇μηι '3 0 μιη ' 40 μπι, 50 μΓη, and ΙΟΟμηι. The distance between the substrate and the reticle is 1 Ομηι. The exposed coating film was immersed in a tetramethylammonium hydroxide aqueous solution (containing 0.20 parts of tetramethylammonium hydroxide in 1 part of an aqueous solution) at 27 ° C for 120 seconds, and then developed, washed with water, and heated. After baking at 235 ° C for a minute, it was baked to form a line/pitch pattern with a film thickness of 3 μm. (3-2) Residue evaluation The non-exposure portion of the pattern was observed by a microscope (VF7510; manufactured by KEYENCE Co., Ltd.; magnification: 1 250×), and it was evaluated as good (〇) when no attachment from the composition was observed. The observed condition was evaluated as poor (x). 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. 'Knot-67- 201130905 is shown in Table 2. [Table 2] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Photosensitive resin composition composition 1 Composition 2 Composition Η1 Composition Η2 Storage stability 〇〇X*1 〇Adhesiveness 100 100 _ 0 Residue 〇〇X resolution 5μτη 5μηι - ΙΟμηι *1 Composition H1 is a mixture of components and colloidalized. [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 were obtained (hereinafter referred to as "composition 3" and "composition 4". ). [Examples 5 and 6] Each of the components described in Table 3 was mixed to obtain photosensitive resin compositions 5 and 6 (hereinafter referred to as "composition 5" and "composition 6"). -68- 201130905 [Table 3] Composition 3 Composition 4 Composition 5 Composition 6 Resin (8) Resin A (l) 42.1 parts (solids) 41.7 parts (solids) 45.7 parts (solids) 45.2 parts (solids) Polymerizable compound (B) Dipentaerythritol hexaacrylate 42.1 parts 41.7 parts 45.7 parts 45.2 parts 2,2'-bis(2-chlorophenyl)-polymerization initiator (C) 4,4',5,5' -tetraphenyl-1,2'-linked 3.4 parts 3.3 parts 3.7 parts 3.6 parts azole polymerization starting aid (D) 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazole Porphyrin 0.4 parts 0.4 parts 0.5 parts 0.5 parts polyfunctional thiol (E) Pentaerythritol bismuth (3-sulfonyl propyl vinegar) 2_5 parts 2.5 parts 2.8 parts 2.7 parts of isocyanatodecane compound (F) 3-isocyanide Acid propyl triethoxy decane 1.7 parts 2.5 parts 1.8 parts 2.7 parts coloring agent (G) CI pigment green 36 4.3 parts 4.3 parts. 诵CI pigment yellow 150 1.9 parts 1.9 parts. . propylene pigment dispersant 1.7 parts 1.7 Ingredients Other Ingredients (H) Polyether modified anthrone oil 0.04 parts 0.04 parts 0.04 parts 〇.〇4 parts IRGNOX3114 0.2 parts 0.2 parts 0.2 parts 0.2 parts diethylene glycol ethyl methyl ether diethylene The solvent of the composition of the composition of the composition of the butyl methyl ether composition (J) The solid content of the propylene glycol monomethyl ether acetate is 33% solids, 33% solids, and 33% solids. The mixture was evaluated in the same manner as in Example 1 using a photosensitive resin composition of 3 to 6 in a mass ratio of 40:30:17:13 in a mixture of 33% dipropylene glycol dimethyl ether mixed mixed type. The results are shown in Table 4. -69 - 201130905 [Table 4] Example 3 Example 4 Example 5 Example 6 Photosensitive resin composition Composition 3 Composition 4 Composition 5 Composition 6 Preservation stability 〇〇〇〇 adhesion 100 100 100 100 Residue 〇〇. 〇〇 resolution 7μηι 7μιη 5μηι 5μτη Using the composition HI of 3-aminopropyltrimethoxydecane, the storage stability is poor, and the components are mixed and colloidalized. 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-isocyanatopropyltriethoxynonane are excellent in both storage stability and adhesion. Further, the compositions 1 to 6 were formed, and no residue was observed in the non-exposed portion during development of the pattern, and the development property was also excellent. Industrial Applicability The resin composition of the present invention can form a cured coating film and a pattern having good storage stability and 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. -70-

Claims (1)

201130905 VII. Patent application scope: 1 . A resin composition characterized by containing a resin, a polymerizable compound, a polymerization initiator, an isocyanatodecane-containing compound, and a solvent, and the resin is an unsaturated carboxylic acid and A copolymer of at least one monomer (a) selected from the group consisting of unsaturated carboxylic anhydrides and a monomer (X) having a carbon-carbon double bond and different from the monomer (a). 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. 3. The resin composition of claim 2, wherein the monomer (X) comprises a monomer (bl) having a carbon-carbon double bond and an epoxy structure. 4. The resin composition of claim 1, wherein the isocyanatodecane-containing compound is a compound represented by the formula (F1), OCN-L-Si(R') ml(R2)(3.mi) ( F1) [In the formula (F1), L is a Cm alkanediyl group, ... is an alkyl group, and ml is 0 or 1, but when ml is 0, it means that R1 does not exist, "is an alkoxy group, plural" The resin composition of claim 1, wherein the content of the isocyanato-containing decane compound is '〇. 1% by mass relative to the solid content of the resin composition. The above-mentioned 15% by mass or less. 6. The resin composition of claim 1 which further contains a colorant. 7. The resin composition of claim 1 wherein the polymerization initiator is a biimidazole compound, Acetylbenzene compounds, antimony compounds and triazine compounds -71 - 201130905 Selected in groups 8. j or more sulfonium sulfonium 9. - formed. 10. formed. 11. Membrane and request 12. Coating and at least The resin composition of claim 1 further comprising a compound having two groups. The coating film is characterized in that the resin composition of claim 1 is used. The pattern is characterized in that the resin composition of claim 1 is used in a liquid crystal display device, and the feature includes at least one selected from the group consisting of the pattern of the coating item 10 of claim 9. The EL display device is characterized in that it contains at least one selected from the group consisting of the pattern of the claim 10 of the claim 9. -72- 201130905 The four designated representative maps: (1) The representative map of the case is: none. The symbol of the symbol of this representative figure is simple: no 201130905 If there is a chemical formula in the case of this case, please reveal the chemical formula that best shows the characteristics of the invention: none