TW201139475A - Resin composition and display device - Google Patents

Abstract

The present invention relates to a resin composition containing a resin, a polymerizable compound, certain species of compound, and a solvent. The resin composition of the present invention has the excellent coating property and is capable of forming a coated film and pattern with less spots.

Description

201139475 VI. Description of the Invention: [Technical Field] The present invention relates to a resin composition, a coating film and pattern obtained from the resin composition, and a display device comprising the above coating film and/or pattern [previously A transparent film such as a color filter pixel pattern or a coating layer used in a display device (for example, a liquid crystal display device) is generally formed using a resin composition (particularly, a photosensitive resin composition). In the production of the coating layer and the pattern of the display device, the resin composition is usually applied onto the substrate by a spin coating method or a doctor blade spin coating method. Therefore, a resin composition which can form a uniform coating film having less spots is desired. In the past, as a photosensitive resin composition, for example, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent are known (Patent Document 1 and the like). [Patent Document 1] Japanese Unexamined Patent Publication (KOKAI) No. JP-A No. 2008-A. ). An object of the present invention is to provide a resin composition which can form a coating film having few spots. The present invention provides a resin composition obtained by solving the above problems. The present invention provides the following [1] to [14]. 201139475 [1] A resin composition containing a resin, a polymerizable compound, a compound represented by the formula (F), and a solvent.

[In the formula (F), L1 represents a divalent C2.8 aliphatic hydrocarbon group. L2 and L3 are each independently and represent a trivalent C2-8 aliphatic hydrocarbon group. R1 and R2 each independently represent a monovalent aliphatic hydrocarbon group, and at least three hydrogen atoms of the aliphatic hydrocarbon group are substituted by a fluorine atom. m and η are each independent, and represent an integer of 22 or more. However, m + n is 3 or more and 2 2 or less] [2JR1 and R2 are each independently, and the resin composition described in the formula (Η) is shown]. -C p Η 2 p - C q F 2 q + 1 (fl) [In the formula (fi), 'P and q are independent' means an integer of 1 or more and 4 or less] [3JR1 and R2 are linear C! The resin composition according to [1] or [2] of the aliphatic hydrocarbon group. [4] q is a resin composition as described in [2] or [3]. [5] The compound of the formula (F) is a resin composition as described in any one of [F1·1).

201139475 [In the formula (Fl-1), m and η have the same meanings as described above. [6] The resin composition according to any one of [1] to [5], wherein m + n is 3 or more and 6 or less. [7] The resin is a structural unit containing at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a monomer derived from a carbon-carbon double bond and a cyclic acid structure. (b) The resin composition according to any one of [5] to [6], which is a copolymer of a structural unit which is different from the monomer (a). [8] The monomer (b) is a resin composition described in [7] selected from the group consisting of a compound represented by the formula (bl-Ι) and a compound represented by the formula (bl-2). R3 0

(bM) (b1-2) Η2〇=〇—C—O —1_4 R3 〇

Η2〇=〇~CΟ1 [In the formula (bl-1) and the formula (bl-2), R3 represents a hydrogen atom or a Cm aliphatic hydrocarbon group. The hydrogen atom of the above aliphatic hydrocarbon group may be substituted by a hydroxyl group. L4 represents a single bond or a Cl-6 aliphatic hydrocarbon group, and -CH2- of the above aliphatic hydrocarbon group may be substituted by -〇-, -S- or -NH-. And R3 and L4 in the formula (bl-Ι) may be the same as or different from R3 and L4 in the formula (bl-2)] [9] further containing a polymerization initiator [川~[8] A resin composition of 201139475. [10] The polymerization initiator is a resin composition as described in [9] containing a polymerization initiator of a bisimidazole compound. [11] A coating film formed using the resin composition according to any one of [1] to Π 〇. [12] The pattern [13] formed by using the resin composition described in [9] or [10] contains a coating film selected from [11] and a pattern described in [12]. At least one type of liquid crystal display device. [14] An organic EL display device comprising at least one selected from the group consisting of the coating film described in [11] and the pattern described in [12]. [Form of the Invention] The resin composition of the present invention contains the resin (A), the polymerizable compound (B), the compound (F), and the solvent (Η), and may optionally contain a polymerization initiator (C), and polymerization. Start-up auxiliaries (D), polyfunctional thiols (Ε) and other additives (G). Each of the above components may be used singly or in combination of two or more kinds unless otherwise specified. Hereinafter, the components contained in the resin composition of the present invention will be described in order. <Resin (A) > Resin (A) is preferably soluble in a developing solution (particularly an alkaline developing solution). The resin which is soluble in the alkaline developing solution may, for example, be at least one monomer selected from the group consisting of -8 to 201139475 unsaturated carboxylic acid and unsaturated carboxylic anhydride (a and having a carbon-carbon double bond) The monomer (a) is a substance different from the monomer (X). The monomer (a) and the monomer (X) may be used alone or in combination of two or more. Examples of the body (a) include (meth)acrylic acid, acid, cinnamic acid, cerium-, m-, p-vinylbenzoic acid, succinic acid mono[methyl)acryloxyethyl], ortho-benzene. Dicarboxylic acid mono [2·(methyl)decyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, yl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-ylbicyclo[2.2.1]heptane- Unsaturated monocarboxylic acids such as 2-ene; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-ylphthalic acid, 4_vinylphthalic acid, 3,4 , 5,6-tetrahydroortic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, Base-5-norbornene-2,3-dicarboxylic acid and the like and dicarboxylic acids; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride '4-vinyl phthalic anhydride , 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic acid, 5,6-dicarboxybicyclo[ 2·2·1] An unsaturated form of an unsaturated dicarboxylic acid such as hept-2-ene anhydrate (norbornene di). In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of enoic acid and methacrylic acid. The expressions "(meth)propyl" and "(meth)acrylate" have the same meaning. Cocoa croton 2-( propylene 5-carboxy .2.1) 6 -ethylene

The unsaturated dicarboxylic anhydride anhydride is preferably selected from the group consisting of (meth)acrylic acid and maleic anhydride, from the viewpoint of copolymerization reactivity or alkali solubility, etc. from the viewpoint of copolymerization reactivity or alkali solubility, etc., more preferably Methacrylate. The monomer (X) is preferably one containing a monomer having a carbon-carbon double bond and (b). The monomer (b) can be used alone or in combination of one type. The monomer (b) may, for example, be a monomer (b1) having an epoxy oxyethylene structure, having an oxetane (b2), and having a tetrahydrofuran structure (i.e., an oxolane structure b3). Among them, a monomer having an epoxy group structure (a monomer having an oxetane structure (b2) is preferred, and a ring monomer (b 1 ) is also preferred. The epoxy group structure can be classified as ( 1) a structure having a monocyclic oxirane ring (having an aliphatic epoxy structure), and (2) a ring of an aliphatic hydrocarbon condensed with an oxirane ring, referred to as "alicyclic epoxy" Base structure"). The alicyclic ring is reclassified as (2-) the ring of the aliphatic hydrocarbon is a single ring (hereinafter, the simple group monocyclic epoxy group structure), and the ring of the (2_2) aliphatic hydrocarbon is a polycyclic ring ( The following simple polycyclic epoxy structure"). Among them, the alicyclic type is preferred, and the aliphatic polycyclic epoxy group structure is more preferable. As the monomer having an aliphatic epoxy group structure (bl), at least one cyclic ether structure of the epoxy propyl (meth) acrylate or the β-methyl propylene monomer (a) 5 may be used. The monomer (b) having a structure of 2 (i.e., a monomer of a ring structure) and the structure having an oxy structure are hereinafter referred to as "the structure (the structure of the oxy group may be referred to as "fat" as a fatty epoxy structure, for example, Ethyl (meth) -10- 201139475 Acrylate, β-ethylepoxypropyl (meth) acrylate, propylene propyl vinyl ether, and the formula described in JP-A-7-248 625 (bl) -3) The monomer or the like shown in the formula (bl-3), each of R4 to R6 is independently represented by a hydrogen atom or a Cl-ίο courtyard group. The ml represents an integer of 1 to 5.

Examples of the monomer (b 1 - 3 ) having an aliphatic epoxy group structure include fluorene-vinylbenzyloxypropyl ether, m-vinylbenzyloxypropyl ether, and P-. Vinylbenzyl epoxypropyl ether, α-methyl-indole-vinylbenzyloxypropyl ether, α-methyl-m-vinylbenzyloxypropyl ether, α-A Base-fluorene-vinylbenzyloxypropyl ether, 2,3-bis(epoxypropyloxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene , 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-paraxyl (epoxypropyloxy) Methyl)styrene, 2,3,5-glycol (epoxypropyloxymethyl)styrene, 2,3,6-glycol (epoxypropyloxymethyl)styrene, 3,4 5-quinone (epoxypropyloxymethyl)styrene, and 2,4,6-glycol(epoxypropyloxymethyl)styrene. As the monomer (b 1 ) having an aliphatic monocyclic cyclic oxy structure, for example, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; Daicel Chemical Industry Co., Ltd.) can be mentioned. , 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLOMER A400; Daicel Chemical Industry ( -11 - 201139475) (manufactured by the company), 3,4-epoxycyclohexylmethyl methacrylate (for example, CYCLOMER M100; manufactured by Daicel Chemical Industry Co., Ltd.). The monomer (bl) having an aliphatic polycyclic epoxy group structure may be a carbon-carbon double bond contained in a polycyclic aliphatic hydrocarbon group or may be contained in a side chain bonded to a ring. . Examples of the polycyclic ring include a norbornane ring and a tricyclodecane ring, and among them, a tricyclodecane ring is preferred. As the monomer (b1) having an aliphatic polycyclic epoxy group structure, for example, an epoxy group norbornyl group (meth) acrylate (for example, a 3,4-epoxynorbornyl group) Methyl) acrylate}, a monomer represented by the formula (bl-Ι), and a monomer represented by the formula (bl-2).

R3 Ο Η2〇=0一C—0~L R3 Ο I II H2C=C-C-〇-L

(b1-1) (b1-2) In the formula (bl-1) and the formula (bl-2), R3 represents a hydrogen atom or a c丨-4 aliphatic hydrocarbon group, and a hydrogen atom of the aliphatic hydrocarbon group may be substituted with a hydroxyl group. L4 represents a single bond or a divalent aliphatic hydrocarbon group, and -CH2 - of the above aliphatic hydrocarbon group may be substituted by -0, -S- or -NH-" as an aliphatic hydrocarbon group of R3 which may be substituted by a hydroxyl group, for example, Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2 -hydroxypropyl ' 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl , 4-hydroxy-12- 201139475 butyl, etc. R3 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group. The divalent aliphatic hydrocarbon group which may be substituted by -0- or the like of L4 may, for example, be a methyl group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group or a butane-1. ,4-diyl, butane-i,3-diyl, pentane-i,5-diyl, hexane-1,6-diyl, methyloxy (-CH2-0-), Ethyloxy {-(CH2)2-0-}, propanediyloxy {-((:112)3-0-, etc.), methylsulfanyldiyl (-CH2-S-), Ethylsulfanyldiyl {-(CH2)2-S-}, propanediylsulfanyldiyl {-(ch2)3-s-, etc., methylimido group (_ch2-nh-), extens Ethyleneimine (ch2)2-nh-}, propanediylimido {-(〇^2)3->^-, etc., etc. 14 is preferably a single bond, a methyl group, a stretch Ethyl, methyloxymethyl, ethyloxy*ethylthiodiyl, or ethylimido, more preferably a single bond or an ethyloxy group. Monomer (bl-Ι) Each of the monomers (bl-2) may be used singly or in combination of two or more. A mixture of a monomer (bl-Ι) and a monomer (bl-2) may be used. When these mixtures are used, Monomer (bl-Ι): Monomer (bl-2) molar is preferably 5: 95~95: 5, more preferably 10: 90~9〇: 10 ' Tejia 2 0: 80 to 80: 20. The preferred monomer (bl-Ι) is one of the formula (bl-1-l)~form (b), which is also a monomer ( Bl-1-l), monomer (bl·1·3), monomer (bl-1-5), monomer (bl-1-7), monomer (bl-1-9), and monomer (bl-1-ll) ~ monomer (b 1 1-15) is preferred, monomer (bl-1-l), monomer (bl-1-7), monomer (bl-1-9 ) and monomer (b 1 -1 -1 5 ) are more preferred. -13- 201139475 Ο H2C=CH-C-0 (b1-1-1) Ο II H2C=CH"C-0-CH2 (b1 -1-3) 0 h2c=ch-co-c2h4 (bM-5) O H2C=CH"C-0-C2H40 (bM-7) 0 II H2C=C—C—0 ch3 (b1-1-9) 0 II H 2〇=C ~C -0 -CH 2 CH3 (bM-11)

H2c=ch-c-o-c2h4s

H2C:

N H2C=CH-C-〇-C2H4NH (b1-1-4) 0 II ^2〇=?—CQC^HaS ch3 (b1-1-6) o H2C==?—C-0 - C2H4NH ch3 (b1 -1-8)

02H5 (b1-1-10)

Ch2oh (M-1-12)

C2H4OH (b1-1-14)

0

II H 2C =C ~C -Ο -〇2Η4 CH3 (bM-13) 0

II H2C=C~C-0-C2H4〇CH3 (bM-15) The preferred monomer (bl-2) is one of the formula (bl-2-1)~form (b 2-15) . Among these, monomer (bl-2-1), monomer (bl-2-3), monomer (bl-2-5), monomer (bl-2-7), monomer (bl-2) -9), and monomer (bl-2-ll) ~ monomer (bl-2-15) is preferred, monomer (bl-2-l), monomer (bl-2-7), single The body (bl-2-9) and the monomer (bl-2-15) are more preferred. -14- 201139475

H2C=CH-C-〇-C2H4, (b1-2-5) H2C=CH-C-〇-c2^S (b1-2-2) 0 H2C=CH-C-〇-c2H4r'1^ (b1 -2-4)

H2C=CH-Mang (b1-2-7) o HzC=C-C-〇-ch3 (b1-2-9)

H2C=C-C-〇-CH2 CH3 (b1-2-11)

i? H2C=C-C-〇-C2H4 CH3 (b1-2-13)

H2C=C-(5-〇-C2H4S CH3 (b1-2*6) 0 H2c=c -zhan-ο 咖CH3 (b1-2-8) 匕2Hs (b1-2-1〇) 0 II H2C=C —ό-. ch2oh (b1-2-12) 0 H2C=CC-0 C2H4OH

(b1-2-14) h2c=c-c-o-c2h4〇 Xu. n 4 r^\

^ ^ m ^ ^ mr h2 ), for example, ' ¥ & as a monomer (meth) acryloxymethyl oxetane, 3-methyl (meth) propylene having an oxetane structure Oxymethylpropane oxy]methyloxapropenyloxymethyloxetane, 3-ethyl-3-yloxybutane, 3-methyl-3-indole-(methyl) ring Butane, 3-ethyl-3-[1-(methyl)propaneoxy]methyloxetine, 3-methyl(meth)acryloxy]ethyloxetane, 3_Ethylmethyl)propenyloxy]ethyloxetan, 2_phenyl-3-(methyl)propenyloxymethyloxetane, 2-trifluoromethyl_3_( Methyl) -15- 201139475 Propenoxymethyloxetane, 2-pentafluoroethyl-3-(methyl)propenyloxymethyloxetane, 3-methyl-3-( Methyl)propenyloxyethyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 2-phenyl-3-(methyl)propenyloxy Ethyloxetane, 2-trifluoromethyl-3-(meth)acryloxyethyloxetane or 2-pentafluoroethyl-3-(meth)acryloxyethyl Oxetane, 3-(meth)acryloxy oxygen Heterocyclobutane and the like. Among them, 3-ethyl-3-(meth)acryloxymethyloxetane is also preferred. Examples of the monomer (b3) having a tetrahydrofuran structure include tetrahydroindenyl (meth) acrylate, furan methoxyethyl (meth) acrylate, and furan methoxy propyl (meth) acrylate. Ester and the like. The monomer (X) may contain a monomer (c) different from the monomer (a) and the monomer (b). Examples of the monomer (c) include a carboxylic acid ester having a carbon-carbon double bond, an amide having a carbon-carbon double bond, and a polymerizable unsaturated bond (carbon-carbon double bond or in a side chain). An aromatic compound, a substituted vinyl compound, an N-substituted maleimide, a diene, a polycyclic unsaturated compound, or the like. The monomer (C) may be used singly or in combination of two or more. Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isodecyl (meth) acrylate, tricyclo [5.2.1.02, 6 ] decane-8-yl (meth) acrylate (the common name of "dicyclopentyl (meth) acrylate" used in the field -16-201139475), 4_ three-ring [5.2.1. 〇2'6]decene-8-yl (meth) acrylate, 5-tricyclo[5·2·1_〇2'6]nonene-8-yl (meth) acrylate, phenyl ( Unsaturated carboxylic acid esters such as methyl acrylate, aminoethyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate; vinyl acetate or propyl acetate a vinyl carboxylate such as vinyl acetate; an amide having a carbon-carbon double bond such as dimethyl(meth)propenylamine or isopropyl(meth)propenylamine; -methyl benzene, ethylene Alkyl toluene, ρ-methoxystyrene is equivalent to an aromatic compound having a polymerizable unsaturated bond in a side chain; a cyanide ethyl compound such as acrylonitrile, methacrylonitrile or α-chloro(meth)acrylonitrile; chlorine Halogenated vinyl compounds such as ethylene, dichloroethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene, tetrafluoroethylene; Ν-methylmaleimide, Ν-ethylmaleimide , N-butyl maleimide, Ν-cyclohexylmaleimide, Ν-benzylmethylmaleimide, ν_phenylmaleimide, etc. - substituted maleimide ; 1,3-butadiene, isoprene, 2,3-dimethyl-; diene such as ι,3-butadiene; bicyclo[2·2·1]hept-2-ene, 5· Methylbicyclo[2 21]heptan-2-ene, 5 ethylbicyclo[2.2.1]hept-2-ene, 5·hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[ 2.2.1] Hept-2-ene, 5-(2,-hydroxyethyl)bicyclo[2 21]hept-2-y, 5-methoxybicyclo[2.2.1]heptane-2-Hui' 5 - Ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2_21]heptane-2·dilute, 5,6-di( -17- 201139475 hydroxymethyl)bicyclo[2.2.1 ] 2-ene, 5,6-bis(2,-hydroxyethyl)bicyclo[2.2.1]hept-2-diene, 5,6-dimethoxybicyclo[2.2.1]heptene-2, 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 a polycyclic unsaturated compound such as 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2,2.1]hept-2-ene, etc. In the monomer (C), phenyl methacrylate, styrene, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, double ring [2.2.1] Hept-2-ene is preferred. As the monomer (X), either one of the monomer (b) or the monomer (c) may be used, or both of them may be used. The monomer (X) preferably contains the monomer (b). That is, the monomer (X) is preferably only the monomer (b), or both the monomer (b) and the monomer (c), and more preferably the monomer (b). The copolymer containing the monomer (b) can improve the heat resistance, light resistance, solvent resistance, and mechanical properties of the coating film or pattern obtained from the resin composition. When the resin (A) is a copolymer of the monomer (a) and the monomer (b), the structural unit derived from the monomer (a) is preferably from 2 to 9 8 mol% in the total constituent unit of the copolymer (more) Good for 5~6 0mol%, especially good for 〇~5 〇莫耳%) 'The structural unit from monomer (b) is preferably 2~9 8 mol%, more preferably 40~95 mo Ear % 'extra good for 50~90 mol%. When it is in this range, the storage stability and development properties of the resin composition, and the residual film ratio and solvent resistance of the coating film or pattern tend to be good. -18 - 201139475 Resin (A) is a copolymer of monomer (a) and monomer (c). The total structural unit of the telomer, the structural unit derived from monomer (a) is 2 mol%, from monomer When the structural unit of (c) is 2 to 9 8 mol%, if it is in this range, it has good storage stability or heat resistance. More preferably, the total structure of the copolymer of the monomer (a) and the monomer (c) is from 5 to 50 mol% of the monomer (a), and the structural unit of the subunit is | 95% by mole. If it is in this range, there is a tendency that the apparent or residual film rate is also good. When the resin (A) is a monomer (a), a monomer (b), and a monomer (c), the unit of the monomer (a) in the total structural unit of the copolymer is 2 to 97 mol %, The structural unit derived from the monomer (b) is 2 to 8%, and the structural unit derived from the monomer (c) is preferably in the range of 1 to 9.6 mol%, and has stability in storage stability, heat resistance and mechanical strength. The tendency. More preferably, the structural unit derived from the monomer (a) in the entire structural unit of the monomer (a), the monomer (b) and the monomer (c) is 50 mol% from the monomer (b) The structural unit is 20 to 80 mol%. The structural unit of the monomer (c) is 1 〇 to 7 〇 mol%. If it is in this range, the development property, the residual film ratio, or the solvent resistance tend to be good. The resin (A) is, for example, the method described in the reference "The Reality of Polymer Synthesis" (issued by the Otsuka Bank of the Institute of Chemicals, the first edition of the first brush year, March 1) and the references cited in the document. The literature can be made from polymerized monomers. More specifically, the monomer (a), the monomer (b), and/or the monomer (c), the polymerization initiator, and the solvent are charged into the container, and stirred in the absence of nitrogen-substituted oxygen. Heating, a total of ~98 is good. The propensity bit I (C-like co-structure 97 mo. If a good total of 10 0 ~, come, there is a test 1972, borrowed and reverse, Bao -19- 201139475 can be made after the temperature of the copolymer. The copolymerization The charging method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the calorific value of the polymerization, etc., and the obtained copolymer can be directly used as the solution after the reaction. In particular, the solvent (H) described later is used as a polymerization solvent. When used, it is not necessary to remove the solvent from the copolymer solution after polymerization, and can be directly used in the resin composition, and the production steps can be simplified. Further, the copolymer solution can be concentrated or diluted, and can be further used in a method such as reprecipitation. a copolymer taken out as a solid (powder). The resin (A) may further have a structural unit (d) having a carbon-carbon double bond in a side chain. The structural unit (d) is a formula (d 1 ) or a formula (d2) As shown, it is preferred that the terminal has a 1-alkyl-1-vinylcarbonyl group, and more preferably has a (meth)acryloyl group at the terminal.

In the formula (dl) and the formula (d2), R7 and R8 each independently represent a hydrogen atom or a ci-6 group (preferably a hydrogen atom or a methyl group). Further, the *prints in the formula (dl) and the formula (d2) each represent a bonding position in the structural unit (dl) and the structural unit (d2). The chemical formula is also the same. The structural unit (d) having a carbon-carbon double bond in the side chain may be obtained by copolymerizing monomer (a), and monomer (b) and/or monomer (c), and by 201139475 from monomer ( The carboxyl group or the carbonyloxycarbonyl group (carboxylate anhydride structure) of a) is added, for example, in the same manner as described in JP-A-2000-185 The monomer (b) of the ether structure 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) } and [formula (bl-4) or formula (bl-5), R8 is the same as described above]. Ο

(b1-4) R8 Y^ch2

(b1-5) The structural unit (d) having a carbon-carbon double bond in the side chain is formed in the following manner in detail. After copolymerizing the monomer (a) and the monomer (b) and/or the monomer (c), the environment in the reaction vessel is replaced with nitrogen by air, and 5 is added to the amount of the monomer (a) used for copolymerization. ~80 mol% of monomer (b). Next, 0.001 to 5% by mass of a reaction catalyst (for example, dimethylaminomethylphenol) is added to the total amount of the monomer (a) used in the copolymer and the monomer (b) used in the addition reaction. And 0.001 to 5% by mass of a polymerization inhibitor (for example, hydroquinone), and the reaction is carried out at 60 to 130 ° C for 1 to 1 hour. Further, in the addition reaction, the charging method or the reaction temperature may be appropriately adjusted in consideration of the production equipment or the calorific value by the addition reaction, as in the case of the copolymerization. In the addition reaction, the amount of the monomer (b) used in the addition reaction is preferably from 1 to 75 mol % -21 to 201139475 for the amount of the monomer (a) used for the copolymerization. Good for I5~70 mol%. If it is in this range, there is a tendency to maintain stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity. The copolymer containing the structural unit (d) having a carbon-carbon double bond in the side chain may be directly used as a solution after the reaction, or concentrated or diluted. Further, a copolymer which is taken out as a solid (powder) by a method such as reprecipitation can be further used. The acid value of the resin (A) is preferably from 50 to 150 (mgKOH/g), more preferably from 60 to 135 (mgKOH/g), particularly preferably from 70 to 135 (mgKOH/g). If it is in this range, the solubility in the developing solution can be improved and the unexposed portion can be easily dissolved. The measurement of the amount of potassium hydroxide (mg) required for the neutralization of the polymer lg having an acidic group is generally determined by titration with an aqueous potassium hydroxide solution. The weight average molecular weight of the resin (A) is preferably from 2,000 to 1,00,000, more preferably from 2,000 to 50,000, particularly preferably from 3,000 to 30,000. If it is in this range, the coating property of the resin composition is good, and a high development speed can be obtained while maintaining the residual film ratio at the time of development. Further, the weight average molecular weight was determined by gel permeation chromatography using polystyrene as a standard. The molecular weight distribution of the resin (A) {i.e., weight average molecular weight (Mw) / number average molecular weight (?n)} is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When it is this range, it has a tendency for the imaging property to be excellent. The content of the resin (A) in the resin composition is preferably from 5 to 90% by mass, more preferably from 10 to 70% by mass, based on the solid content of the resin composition, from -22 to 201139475. When it is in this range, the solubility in the developing solution is sufficient, and the development residue is less likely to occur on the substrate of the non-exposed portion (non-pixel portion). Further, it is not easy to cause film reduction of the exposed portion (pixel portion) at the time of development, and the residual film ratio tends to increase. In the present specification, the "solid content of the composition" is "the total amount of each component of the resin composition from which the solvent is removed", and the solid component can be measured by a known means such as gas chromatography or liquid chromatography. Compound (B) > The polymerizable compound (B) may, for example, be a compound having a polymerizable carbon-carbon unsaturated bond. The polymerizable compound (B) is preferably a polymerizable compound having three or more carbon-carbon unsaturated bonds (hereinafter also referred to as "a trifunctional or higher polymerizable compound"). Examples of the trifunctional or higher polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and gin(2-hydroxyethyl)trimeric isocyanate tris(methyl). Acrylate, ethoxylated trimethylolpropane tri(meth) acrylate 'propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Reaction of (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with anhydride, dipentaerythritol penta (methyl) acrylate and anhydride -23- 201139475 Reactant, tripent of pentaerythritol hepta(meth) acrylate and anhydride, caprolactone modified trimethylolpropane tri(meth) acrylate, caprolactone pentaerythritol Tris(meth)acrylate, caprolactone modified ginseng (2-hydroxyethyl)trimeric isocyanate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, Ester-modified dipentaerythritol pentamethyl acrylate, caprolactone modified dipentaerythritol hexa(methyl) propionate, caprolactone modified tripellitate tetrakis(meth) acrylate, hexyl ester modified tripentaerythritol (Meth) acrylate, caprolactone modified tripentaerythritol hexa(meth) acrylate, caprolactone modified tripentaerythritol heptamethyl acrylate 'caprolactone modified tripentaerythritol VIII (methyl) Propionate, caprolactone modified pentaerythritol tri(meth)acrylate and anhydride reactant, caprolactone modified dipentaerythritol penta(meth)acrylate and anhydride reactant, caprolactone modified tripellitate A reaction product of (meth)acrylic acid and an acid anhydride. Among them, pentaerythritol tri(meth)acrylate 'trimethylolpropane tri(meth)acrylate, pentaerythritol tetrakis(meth)acrylate dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) acrylate Acrylate is preferred, and dipentaerythritol hexa(meth)acrylate is preferred. The content of the polymerizable compound (B) is preferably from 5 to 75% by mass, more preferably from 10 to 5% by mass, particularly preferably from 15 to 65 by mass, based on the total of the resin (A) and the polymerizable compound (B). %. If it is in this range, it has a hardening component, and the film thickness reduction before and after development can be prevented, and it is difficult to produce a pattern in the pattern, and the adhesion of the pattern tends to be good. In addition, if it is in this range, it is changed to the base season (the inner season of the vinylene ester group (the ethyl ester ester ester group is 70-filled and floated with -24 - 201139475), the sensitivity of the resin composition, and the strength and smoothness of the coating film and pattern. The heat resistance and the chemical resistance tend to be good. <Polymerization initiator (C) > The resin composition of the present invention may contain a polymerization initiator (C) as necessary, preferably containing photopolymerization Agent (C). Polymerization initiator (C) A compound which initiates polymerization by heating or light irradiation to generate an active radical or an acid, etc., and a known polymerization initiator can be used. As a polymerization initiator (C), Examples thereof include a bisimidazole compound, an acetophenone compound, a triazine compound, a mercaptophosphine oxide compound, an anthraquinone compound, a benzoin compound, a benzophenone compound, etc. Among them, a diimidazole compound and a phenylethyl group are also mentioned. The ketone compound, the oxime compound and the triazine compound are preferred, and the biimidazole compound having excellent sensitivity is more preferable. As the biimidazole compound, 2,2,-bis(2-chlorophenyl)-4,4',5 may be mentioned. , 5'-tetraphenylbisimidazole, 2,2,-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2,-bis (2) -Chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)bisimidazole, 2,2,_bis(2-chlorophenyl)-4,4',5,5' -tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example The phenyl group in which the phenyl group at the 4,4', 5,5' position may be substituted by an alkoxycarbonyl group (-coor) is described in Japanese Patent Publication No. Sho 48-3 8403, JP-A-62-1 74204, and the like. (e.g. 'Refer to JP-A-7-1091, etc.), etc. They also use 2,2,-bis(2-chlorophenyl)-4,4,5,5,-tetraphenyl.基双-25- 201139475 Imidazole {2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole}, 2,2' - Bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-tetraphenylbisimidazole is preferred. As the acetophenone compound, diethoxyacetophenone, 2-hydroxy-2- 1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1 a ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 - (4-morpholinophenyl)butan-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone , 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-di Methylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butyl Ketone, 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-?-deuterated benzene Butyl ketone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzene Methyl)-2- Methylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butyl Ketone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone , 2-(4-bromobenzyl)-2-dimethylamino-1-( -26- 201139475 4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl) _2_Dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholino Phenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl- 4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2- Dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-? Oligomers of phenylphenyl)-butanone, 2-hydroxy-2-methyl-l-[4-(l-methylvinyl)phenyl]propan-1-one, and the like. 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-piperidin-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3 , 5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1, 3,5-triazine, and the like. The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide. Examples of the ruthenium compound include a 0-fluorenyl fluorene compound, and specific examples thereof include 1-(4-phenylsulfonyl-phenyl)-butane-1,2-dione 2-oxime. -0-benzoate, 1-(4-phenylsulfonyl-phenyl)-octane-1,2-dione-27-201139475 2-indole-0-benzoate, 1-[ 9-Ethyl-6-(2-methylbenzhydryl)-91 oxazol-3-yl]ethanone 1-0·acetate, 1-[9-ethyl·6- (2-A 4-(3,3-dimethyl-2,4-bishexacyclopentylmethyloxy)benzylidenyl)-9-indazol-3-yl]ethanone 1-0-B Acid esters, etc. Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether as benzophenone. Examples of the compound include benzophenone, fluorenyl-benzoyl benzoic acid methyl, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, and 3 , 3', 4, 4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Further as a polymerization initiator (C), 10 - butyl-2-chloroacridone, 2-ethyl hydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylacetaldehyde can be used. Acid acid methyl, titanocene compound, and the like. Further, as the polymerization initiator (C), a polymerization initiator having a group which causes a linkage shift as described in JP-A-2002-544205 can be used. Further, a polymerization initiator having a group which causes a chain shift can be used for copolymerization of the resin (A) and inserted into the resin (A) as a structural unit. As the polymerization initiator having a group which causes the chain shift, for example, a polymerization initiator represented by the formulae (C1) to (C6) can be mentioned. -28- 201139475

H2C\ _ 0 ch3 C-CH2-S-(CH2)3-S-^~^—CC—N, H3COOG w ch3 h2c 0 „ 0 ch3 ,c«—(CH^-S 乂hC-9—N, C4h9-s-ch2 w CH (C1) c. (C2) h2cs c4h9-s-ch2 0 0 CH, (C3) H,C 0 CH3 — (C4) (C5)

-ch2-s-^ ^-c-c-n ^0 ch3 9 H2c, _ 0 CH2 PL, )c-ch2-s-(ch2)3-sh〇>-c-c-n^ 3 H3COOC W CH, CH3

HaCOOC〆 0 CH, -CH2-S-(CH2)3-S-^~^-C-C-

-N c2h5 , h3 "ch3 (C6) When the polymerization initiator (c) is used, the content is _ 40 parts by mass, more preferably 1 for the total of 100 parts by mass of the polymerizable compound (B). ~30 parts by mass. If the composition of the range is highly sensitive to light or heat, the strength or smoothness of the coating film or the pattern of the resin composition tends to be good. <Polymerization Start Aid (D) > The toxic resin composition of the present invention may contain a polymerization term as necessary. Polymerization initiation aid (D) is a combination polymerization initiator which is used to promote the polymerization initiator (C). When the polymerization initiation aid (D) is used, the content is 隹f fat. (A) and U Gui are 0.1~, formed by resin

Start with the additive (D C) and use it. It is 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the total of the resin (A -29-201139475) and the polymerizable compound (B). When the polymerization initiation aid (D) is used, the sensitivity to light or heat of the resultant product can be further improved, and the productivity of the pattern formed by using the resin composition tends to be improved. Examples of the polymerization initiation aid (D) include an amine compound compound and a carboxylic acid compound. The amine compound may, for example, be an aliphatic amine such as triethanolamine or methyldiisopropanolamine; Amino benzoic acid methylamino benzoic acid ethyl, 4-dimethylamino benzoic acid isovaleryl benzoic acid 2-ethylhexyl, benzoic acid 2-dimethylamine N, N-dimethyltoluidine , 4,4'-bis(dimethylamino)diphenyl:miqierone), 4,4'-bis(diethylamino)benzophenone, and the like. Further, as the amine compound, a commercial product such as "EAB-F" (manufactured by Chemical Industries, Ltd.) can be used. Examples of the thioxanthone compound include 2-isopropylthioxo-4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-ketone, and 1-chloro-4-. Propoxy thioxanthone and the like. Examples of the carboxylic acid compound include (phenylthio)acetic acid, () acetic acid, (ethylphenylthio)acetic acid, (methylethylbenzenesulfonyl)dimethylbenzenesulfuric acid), and (methoxyphenylsulfonate)acetic acid. , (dithio)acetic acid, (chlorophenylthio)acetic acid, (dichlorophenylthio)acetic acid glycine, phenoxyacetic acid, (naphthylthio)acetic acid, N-naphthylglyoxyacetic acid, etc. . Preferably, the coating film of the resin group of the range or thioxanthone, trisyl, 4-diyl, 4-diylethyl, ketone (commonly known as aromatic amine (preservative gluten, two) Chlorothioxylmethylbenzenethioacetic acid, (methoxybenzene, N-phenylamine acid, naphthalene-30-201139475) As a polymerization initiation aid (D), a compound of the formula (D1) can be used. C=CH -C-R10 (D1) R9 In the formula (D1), W1 represents a C6-12 aromatic ring, and the hydrogen atom of the above aromatic ring may be substituted by a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.). 0 - or - S-. R9 represents a linear, branched or cyclic Cha aliphatic hydrocarbon group. R1() represents a linear, branched or cyclic (^-12 aliphatic hydrocarbon group, or C6. u The aromatic hydrocarbon group 'The aliphatic hydrocarbon group and the hydrogen atom of the aromatic hydrocarbon group may be substituted by a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom). Examples of the aromatic ring of W1 include a benzene ring and a group. Alkylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, naphthalene , phenylbenzene ring, etc.. As a dentate aromatic ring of ', a chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a chlorophenyl benzene ring, a bromophenyl benzene ring, a chloronaphthalene ring, a bromine ring, etc. W1 is preferably a benzene ring (phenylene) or a naphthalene ring (naphthyl). Examples of the aliphatic hydrocarbon group of R9 include a methyl group, an ethyl group, a propyl group and an isopropyl group. Base, butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-pentyl '2-methylbutyl, 3-methylbutyl, dimethylpropyl 1>2_dimethylpropyl, 2,2-dimethylpropyl, hexyl, cyclopentyl, cyclohexyl, etc. -31 - 201139475 R9 is preferably a methyl group. As an aliphatic hydrocarbon group of R1G, Other than the groups exemplified in R9, heptyl, octyl, decyl, decyl, undecyl, dodecyl, cycloheptyl, methylcyclohexyl, hexylcyclohexyl, norbornyl And adamantyl group. Examples of the halogenated aliphatic hydrocarbon group of R1g include a trifluoromethyl group, a 1-chlorobutyl group, a 2-chlorobutyl group, a 3-chlorobutyl group, a 1 bromohexyl group, and a 2-bromo-10- Dialkyl or the like. Examples of the aromatic hydrocarbon group of R1C) include a phenyl group and a methylbenzene group. , dimethylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, cyclohexylphenyl, naphthyl, biphenyl, etc. Also, as a halogen of R1G Examples of the aromatic hydrocarbon group include a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorophenylphenyl group, a bromophenylphenyl group, a chloronaphthyl group, a bromonaphthyl group, etc. R1() Preferably, it is a phenyl group, a biphenyl group, or a naphthyl group. As the polymerization initiation aid (D 1 ), for example, 2-benzylidene-methyl-3-methylnaphtho[2,1- d] thiazoline, 2-benzylidene-methyl-3-methylnaphtho[l,2_d]thiazoline, 2-benzylidene-methyl-3-methylnaphtho[2,3-d] Thiazoline, 2-(2-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methylbenzothiazolyl, 2-(2 -naphthyl fluorenylmethyl)-3-methyl-5-phenylbenzothiazolium, 2_(丨_naphthylmethyl)methyl-3-phenylbenzothiazoline, 2-( 2-naphthyl fluorenylmethyl)-3-methyl-5-fluorobenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-fluorobenzothiazoline, 2- (2 -naphthyl fluorenylmethyl)-3_methylchlorobenzo Oxazoline, 2-(1-naphthylfluorenylmethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-bromobenzo Thiazoline, 2-(1-naphthylquinonemethyl)-3-methyl-5-bromobenzothiazoline, 2-(4-phenylbenzene-32-201139475 formazanylmethyl)-3- Benzothiazoline, 2-(4-phenylbenzylidenemethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethyl)methyl-3- Naphtho[2,1-d]thiazoline, 2-(2.naphthylmethyl)methyl 3-methylnaphtho[1,2-(1]thiazoline, 2-(4-phenylbenzene Methyl hydrazinomethyl)-3-methylnaphtho[2, Ι-d]thiazoline, 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[l,2-d Thiazoline, 2-(p-fluorobenzhydrylmethyl)-3-methylnaphtho[2,ld]thiazoline, 2·(ρ-fluorobenzhydrylmethyl)-3-methyl Naphtho[l,2-d]thiazoline, 2-benzylidene-methyl-3-methylnaphtho[2,1-d]oxazoline, 2-benzylidene-methyl-3- Naphtho[1,2-d]oxazoline, 2-benzylidene-methyl-3-methylnaphtho[2,3-d]oxazoline, 2-(2.naphthylmethyl)- 3-methylbenzoxazoline, 2 -(1-naphthylfluorenylmethyl)_3-methylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzoindole porphyrin, 2 -(1-naphthyl fluorenylmethyl)-3-methylphenylbenzoindole quinone, 2-(2-naphthyl fluorenylmethyl)-methyl-winning and astringent porphyrin, 2-( 1-naphthyl fluorenylmethyl)_3 -methylfluorobenzopyry porphyrin, 2-(2-naphthyl fluorenylmethyl)_3·methyl-5_gas benzopyrene, 2_ (1_蔡酿Methyl)-3-methyl-5-chlorobenzoacetophenone, 2-(2-naphthylquinonemethyl)_3_methyl-5-bromobenzoxazoline, 2-(1-naphthalene)醯Methyl-3-methyl-5-bromobenzoxazoline, 2-(4-phenylbenzylidenemethyl)methylbenzoxazoline, 2-(4-phenylbenzene Methyl hydrazinomethyl)-3-methyl-5-phenylbenzoxazoline '2-(2-naphthyl phenylmethyl). 3-methylnaphtho[2,1_d]oxazoline, 2-(2-naphthyl fluorenylmethyl)_3·methylnaphtho[1,2_d]oxazoline, 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[2,1_d] Oxazoline, 2-(4-phenylbenzylidenemethyl)methyl-3-naphtho[1,2_<1]oxazole-33 - 201139475 porphyrin, 2-(p-fluorobenzhydryl) Methyl)-3-methylnaphtho[2,ld]oxazoline, 2-(p-fluorobenzhydrylmethyl)-3-methylnaphtho[l,2-d]oxazoline, etc. In the above, '2-(2-naphthylfluorenylmethyl)-3-methylbenzothiazoline represented by formula (D1-1), 2-benzylidene-methyl group represented by formula (Dl_2) 3-methylnaphtho[1,2-(1]thiazoline, and 2-(4-phenylbenzylidenemethyl)-3-methylnaphtho[2] l, 2-d] thiazoline is preferred.

The resin composition containing the polymerization initiation aid (D1) tends to have high sensitivity and has a tendency to improve the productivity of the coating film or the pattern. Since the polymerization initiation aid (D1) is discolored by the action of light or heat, the visible light transmittance of the coating film or pattern can be improved by using only this. The content of the polymerization initiation aid (D1) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more, more preferably in an amount of the polymerization initiation aid (D). 100% by mass or less is preferred. By using the polymerization initiation aid (D1) in this range, the visible light transmittance of the coating film can be improved. Further, as the polymerization initiator (D), a compound represented by the formula (D2) or the formula (201139475 D3) can be used.

In the formula (D2) or the formula (D3), W2 and W3 are each independently an aromatic ring or a heterocyclic ring, and the aromatic ring and the hydrogen atom of the above heterocyclic ring are substituted. L6 and L7 are each independently and represent -〇- or -S- (preferably R11 and R12 are each independently, and represent a linear, branched or cyclic aliphatic hydrocarbon group, or a C6.12 aromatic hydrocarbon group, the aforementioned aliphatic hydrocarbon group. The hydrogen atom of the aromatic hydrocarbon group may be substituted by a halogen atom, a hydroxyl group or a Ci-e. Examples of the aromatic ring and the hetero ring of W2 and W3 include a benzene ring, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, and a pyrimidine ring. Etc., and combinations thereof (for example, a naphthalene ring, an isobenzofuranocyclazole ring, etc.). As the halogenated aromatic ring of W2 and W3, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, or a benzene can be mentioned. a benzene ring, a chlorine, a bromophenyl benzene ring, a chloronaphthalene ring, a bromine ring, etc. W2 and W3 each preferably represent a benzene ring or a naphthalene ring. As an aliphatic hydrocarbon group of R11 and R12, a halogenated aliphatic aromatic hydrocarbon group The halogenated aromatic hydrocarbon group may, for example, be an aliphatic hydrocarbon group in which R1 () is substituted with a hydroxyl group of R11 or R12, and

Base, hydroxyethyl, hydroxypropyl, hydroxybutyl and the like. As R-35-, it is not C 6 - 1 2 and halogen can be -S -). The C 1 - 1 2 is intended to be the same as the above-mentioned aryl; oxime, furan ring and pyrazine ring, benzopyrene chlorobenzene ring phenyl benzene ring independently, the list of hydrocarbon groups, aromatics. Examples of the aromatic hydrocarbon group substituted by the hydroxyl group of the hydroxyl group 11 or R12 of 201139475 include a hydroxyphenyl group and a hydroxynaphthyl group. Examples of the aliphatic hydrocarbon group substituted by the alkoxy group of R11 or R12 include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, and an ethoxy group. Ethyl ethyl, ethoxypropyl, propoxybutyl and the like. The aromatic hydrocarbon group substituted by the alkoxy group of R11 or R12 may, for example, be a methoxyphenyl group or an ethoxynaphthyl group. R11 and R12 are each independently and preferably represent a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. Examples of the polymerization initiation assistant (D2) or (D3) include dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, and dibutoxynaphthalene. Alkoxynaphthalenes; dimethoxy hydrazine, diethoxy hydrazine, dipropoxy hydrazine, diisopropoxy hydrazine, dibutoxy fluorene, bispentaoxy fluorene, bis hexaoxy fluorene, A Oxyethoxy ruthenium, methoxypropoxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxyisopropoxy oxime, B a dialkoxy oxime such as oxybutoxy fluorene, propoxy oxyhydroxy fluorene, propoxy oxy fluorene, isopropoxy butyl hydrazine; dimethoxytetracene, diethyl a dialkoxytetracene such as oxytetracene, dipropoxytetracene, diisopropoxytetracene or dibutoxytetracene; etc. <Multifunctional thiol (E) > The resin composition of the present invention may contain a polyfunctional thiol (E) as needed -36-201139475 This "polyfunctional thiol" means "a compound having two or more sulfonyl groups in the molecule". In the polyfunctional thiol (E), a compound having two or more sulfonyl groups bonded to a carbon atom of an aliphatic hydrocarbon group is preferred because it can improve the sensitivity of the resin composition. Examples of the polyfunctional thiol (E) include hexanedithiol, decanedithiol, 1,4-dimethylhydrothiobenzene, and butanediol bis(3-sulfonylpropionate). ), butanediol bis(2-sulfonyl acetate), ethylene glycol bis(2-sulfonyl acetate), trimethylolpropane ginseng (2-sulfonyl acetate) Diol bis(3-sulfonylpropionate), trimethylolpropane ginseng (3-sulfonylpropionate), trimethylolpropane ginseng (2-sulfonyl acetate), pentaerythritol quinone (3-sulfonylpropionate), pentaerythritol bismuth (2-sulfonyl acetate), hydroxyethyl ginseng (3_sulfonylpropionate), pentaerythritol bismuth (3-sulfonylbutyric acid) When a polyfunctional thiol (E) is used as the oxime or 1,4-bis(3-sulfonylbutenyloxy)butane, the content is 100 parts by mass of the polymerization initiator (C). Preferably, it is 0.5 to 100 parts by mass, more preferably 1 to 90 parts by mass. When the polyfunctional thiol (E) is used in this range, the sensitivity can be improved and the development property tends to be good. Further, a polyfunctional thiol (E) is preferably used in combination with a diimidazole compound of a polymerization initiator (C). If this combination is used, there is a tendency to improve the sensitivity. <Compound (F) > The resin composition of the present invention is characterized by containing a compound represented by the formula (F). By using compound (F), it is possible to produce less and uniform spots. 37-201139475 Coating film or pattern. Further, the resin composition of the present invention can also form a coating film having high heat resistance. The basis of the formula (F) will be described below in order.

HO

In the formula (F), L1 represents a divalent C2-8 aliphatic hydrocarbon group. Examples of L1 include an ethylidene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, and a butane-1,4-diyl group. , 2,2-dimethylpropane-1,3-diyl, butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane -1,4-diyl, heptane-17-diyl, octane-1,8-diyl and the like. Among them, 2,2-dimethylpropane-U·diyl is also preferred. In the formula (F), each of L2 and L3 independently represents a trivalent C2-8 aliphatic hydrocarbon group as L2 and L3, and examples thereof include a formula (f2-1) to a formula (f2-l1). The base is also represented by the formula (f2-l). And the * in the following formula shows the bonding position at which the oxygen atom in the formula (F) is bonded.

-38 - 201139475 In the formula (F), R1 and R2 are each independently, and represent a monovalent (:1.8 aliphatic hydrocarbon group '. At least three hydrogen atoms of the aliphatic hydrocarbon group are substituted by a fluorine atom. For R1 and R2, for example, At least three hydrogen atoms in a linear aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl are substituted by a fluorine atom (for example, trifluoromethyl) Etc.; such as 2-methylethyl, 2-methylpropyl, 2,2-dimethylethyl, 2-butyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl At least 3 hydrogen atoms in the branched aliphatic hydrocarbon group of 1,1,1-dimethylpropyl, 1,2-dimethylpropyl and 2,2-dimethylpropyl are replaced by fluorine atoms (eg, 2-trifluoromethylpropyl); such as cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl cyclic aliphatic hydrocarbon groups wherein at least 3 hydrogen atoms are replaced by fluorine atoms (eg And pentafluoroethylcyclohexyl). Among them, a linear one is preferred, and an ethyl group having at least 3 fluorine atoms, a propyl group, a butyl group and a hexyl group are preferred. R1 and R2 are each independently represented. Expression (Π) Preferably, -CpH2p-CqF2q+1 (fl) In the formula (fl), p and q are each independently, and represent an integer of 1 or more and 4 or less. P, preferably 1 or 2, more preferably 2. q, preferably. It is 3 or 4, more preferably 4. Further, the group represented by the formula (fl) is preferably a linear chain. The base of the formula (Π) is also 2, 2, 3, 3, 4, 4, 5 ,5,5-nonafluoropentyl {n-CF3(CF2)3CH2-}, 3.3.4.4.5.5.6.6.6- nonafluorohexyl {η - CF 3 (CF 2) 3 (C Η 2) 2 - }, 4.4.5.5.6.6.7.7.7- nonafluoroheptyl {η - CF 3 (CF 2) 3 (C Η 2) 3 -}, 5.5.6.6.7.7.8.8.8- nonafluorooctyl { 11-0?3(€?2)3((:112)4-} is better, with -39 - 201139475 3,3,4,4,5,5,6,6,6-nonafluorohexyl for In the formula (F), m and η are each independently, and preferably 0 or more, more preferably i or more, more preferably 2 or more, more preferably 22 or less, more preferably 1 or less, still more preferably 6 The following integers are preferable: m + n is preferably 3 or more, more preferably 4 or more, and most preferably 22 or less, more preferably 10 or less, still more preferably 6 or less. Compound (F), preferably Formula (F1) In the formula [F1], m, η, p, and q have the same meanings as described above. The description of the group represented by -CpH2p-CqF2q + 1 and the group represented by the formula (Π) Ming same].

The compound (F1) is preferably a compound represented by the formula (F1-1) to the formula (F1-3), and the compound (F1-1) is preferably a compound having a 'm + n of 3 or more and 6 or less (F1- 1) It is more preferable that 'm and η in the formula (F1-1) to the formula (F1-3) have the same meanings as described above. _C4F9' in the formula (F1-1) is preferably linear. ]

OH (F1-1) -40- 201139475

〇,cf3 O CF3 ch2 \ / CH2 \ CH2〇Η·|〇Η2«Η2-〇·)-〇Η2-?-αΗ2 十Ο-0Η2-々-0Η·^-0Η (F1-3) CH3 CH, The content of the compound (F) is preferably 0.001 to 0.15% by mass, more preferably 0.01 to 0.1% by mass, even more preferably 0.02 to 0.1% by mass, based on the solid content of the resin composition. When the content of the compound (F) is in this range, a coating film having less spots can be easily obtained. Compound (F) can be produced by various reactions. For example, a preferred compound (F 1 ) can be etherified by using a compound of the formula (f3) and a compound of the formula (f4) (i.e., 2,2-dimethyl-1,3-propanediol). Manufactured by reaction. Further preferred compound (F1) is available from OMNOVA Corporation as PolyFoxTM PF-7002 and the like. ^/CpH2p-CqF2q+i h2c-c-ch2\ 9H2

(m+n) | | I + H〇-CH2-C-CH2-〇H °-CH^ / in3 (f4)

O (f3) Q^CpH2p-CqF2q+i ✓CpH2p-CqF2q+i / ?h2 \ 9h2 / 9Hz \ OH~[CH2-C-CH2-〇j-CH2-C-CH2 十0-CH2-C-CH Tetra-OH ^ CH3 CH3 ^ CH3 n (F1) -41 - 201139475 <Other Additives (G) > The resin composition of the present invention may optionally contain other additives (G) as other additives (G), for example, Examples thereof include a colorant, a pigment dispersant, a chelating agent, a polymer compound different from the resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a photostabilizer, a chain shifting agent, and a surfactant. As the coloring agent, a compound classified as a coloring matter by a color index (published by The Society of Dyei >s and Colourists) can be cited. Specifically, for example, CI·pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 2, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigment orange 13, 13, 36, 38, 40, 42, 43, 51, Orange pigments such as 55, 59, 61, 64, 65, 71, 73; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176' 177, 180, 192, 209, 215 , 216, 224, 242 '254, 255, 264, 265 and other red pigment; CI pigment blue 15, 15: 3' 15: 4, 15: 6, 60 and other blue pigment; CI pigment purple 1, 19, 23 , 29, 32, 36, 38 and other purple pigments -42- 201139475 cl pigment green 7,36,58 and other green pigments; CI pigment brown 23,25 and other brown pigments; CI pigment black 1,7 and other black pigments. In the present specification, only "C.I. Pigment Yellow" or the like is described for the first pigment, and only the number is described for the same pigment. As the pigment dispersant, a surfactant can be used. The surfactants can be classified into cationic, anionic, nonionic, and amphoteric, and can be classified into esters, amines, acrylics, and polyoxygens. Examples of the surfactant include polyethylene oxide alkyl ethers, polyethylene oxide alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polycondensates. Ester, tertiary amine modified polyurethane, polyethyleneimine, and the like. Further, for the surfactant to be sold, for example, KP (Shin-Etsu Chemical Co., Ltd.), p〇ly-Fl〇w (registered trademark) (Kyoei Chemical Co., Ltd.), SOLSPERSE (registered) can be used. Trademarks) (Zeneca), EFKA (manufactured by CIBA), AJISPER (registered trademark) (Ajinomoto Fine-Techno), Disperbyk (BKY). Examples of the chelating agent include hydrazine such as glass, cerium oxide, and aluminum oxide, and examples thereof include an epoxy group resin (for example, an o-methyl phenol type epoxy resin) and a maleimide. A thermoplastic resin such as a curable resin such as a polyvinyl alcohol, a polyacrylic acid, a polyethylene glycol monoalkyl ether, a polyfluoroalkyl acrylate 'polyester, or a polyurethane. Examples of the adhesion promoter include vinyl trimethoxy decane, -43-201139475 vinyl triethoxy decane, vinyl ginate (2-methoxyethoxy) decane, and 3-aminopropyl group. Trimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Alkane, 3-hydrothiopropyltrimethoxydecane, and the like. The antioxidant may, for example, be 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate or 2-[ 1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3- ( 3-tert-butyl) 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra46^-butyldibenzo[(1,[1,3,2]dioxin Heterogenin, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxydimethylethyl]-2,4, 8,10-tetraoxaspiro[5.5]undecane, 2,2'-extended methyl bis(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, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, Pentaerythritol bismuth (3-lauro thiopropionate), 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-461^-butyl-a,a , a"-(homotriene-2,4,6-triyl)tri-P-cresol, pentaerythritol 肆[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid Ester], 2,6-di-tert--44 - 201139475 butyl-4-methylphenol, etc. Further, 'antioxidant can be used under the trade name "IRGAN0X3 1 14" available from Cib a Japan Co., Ltd., etc. Examples of the ultraviolet absorber include 2_(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5- (5-Chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2 -hydroxyphenyl]_4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl) Hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy- 4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyl Oxycarbonylcarbonyl]phenyl)-4,6-bis(4-phenylphenyl)_1,3,5-triazine, 2-(2!1-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotris-11-yl-2-yl)-6- (1-methylphenylethyl)·4-(l,l,3,3-tetramethylbutyl)phenol, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl ) · 5-Chlorobenzotriazine, alkoxy benzophenone, etc. Examples of the photosensitizer include a polymer obtained from succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol; 扎1^', > ^',1^'"-肆(4,6-bis(butyl-(1^-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazine- 2-yl)-4,7-diazanonane-l,i〇-diamine: decane dibasic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy) a reaction of 4-piperidinyl ester with 1, dimethylethylhydroperoxide; bis( 1,2,2,6,6-pentamethyl-4-piperidine)-[[ 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate; 2,4-bis[N-butyl-N-(1-ring) Hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethyl-45-201139475 amide)-1,3,5-triazine; Bis(1,2,2,6,6-pentamethyl-4-piperidine) sebacate; methyl (1,2,2,6,6-pentamethyl-4-piperidine) anthracene Examples of the chain shifting agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene. Examples of the surfactant include polyfluorene oxide. Interface activator. As a polyoxo-based surfactant The surfactant having a decane bond may be mentioned. Specifically, Toray polyoxyl DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, and the polyether modified poly sand may be mentioned. Oxygen oil SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP 3 22, KP3 23, KP3 24, KP326, KP 340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400 'TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 ( Momenti ve Performance

Materials Japan contract company) and so on. The content of the surfactant is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less, of the curable resin composition. . When the surfactant is contained in the above range, the flatness of the coating film can be made good. Further, the above surfactant is different from the above pigment dispersant. <Solvent (Η) > As the solvent (Η), a component which can be uniformly dissolved or dispersed in a resin (-46 - 201139475 A) and which does not react with each component is used. From the viewpoint of coatability and dryness, an organic solvent having a boiling point of from 1 〇〇 t to 200 ° C is preferred. As the solvent (Η), for example, the following can be used. Ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; ethylene glycol monomethyl ether acetate Ester, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate An alkanediol alkyl ether acetate such as methoxypentyl acetate. Propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, Propylene glycol dialkyl ether such as propylene glycol dipropyl ether propylene glycol propyl methyl ether or propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, Propylene glycol alkyl ether propionate such as propylene glycol butyl ether propionate. Butanediol monoalkyl ethers such as methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol; methoxybutyl acetate, ethoxybutyl acetate Butanediol monoalkyl acid acetates such as propoxy butyl acetate and butoxybutyl acetate; methoxybutyl propionate, ethoxybutyl propionate, propoxy Butanediol monoalkyl acid propionates such as butyl propionate and butoxybutyl propionate. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol B-47- 201139475 methyl ether, diethylene glycol butyl methyl ether, diethylene glycol methyl ethyl ether, etc. Diethylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether. An aromatic hydrocarbon such as benzene, toluene, xylene or mesitylene; a ketone such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone. Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxyl Propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxy Butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxy Propyl acetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -propyl ethoxypropionate, butyl 2-ethoxypropionate Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid-48- 201139475 Ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropane Propyl acrylate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, 3-butoxypropane An ester such as butyl acrylate. a cyclic ether such as tetrahydrofuran or pyran; or a cyclic ester such as γ-butyrolactone. Among the above, alkylene glycol alkyl ether acetates (more preferably propylene glycol monomethyl ether acetate), ketones (more preferably cyclohexanone), butanediol monoalkyl ether acetates ( More preferably methoxybutyl acetate), butanediol monoalkyl ether (more preferably methoxybutanol), diethylene glycol dialkyl ether (more preferably diethylene glycol B) Preferably, the methyl ether) and the ester (more preferably ethyl 3-ethoxypropionate or methyl 3-methoxypropionate) are preferred. The content of the solvent (Η) is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 95% by mass or less, and still more preferably 90% by mass or less based on the resin composition. <Coating film, pattern, and display device> The coating film of the present invention is obtained by applying the resin composition to a substrate (for example, a substrate such as glass, ruthenium, metal, or plastic, or a resin layer or an inorganic compound layer) After coating the formed substrate or the like, a coating film can be formed by thermal polymerization and/or photopolymerization. The coating method for forming the coating film is not particularly limited, and a known method such as a spin coating method can be used. The pattern of the present invention can be formed, for example, by using a spray machine or the like, and after coating the resin composition of the present invention in a pattern, it can be formed by thermal polymerization or photopolymerization -49-201139475. Further, when a photosensitive resin composition of the present invention containing a photopolymerization initiator (C) is used, a pattern can be formed by photolithography. In the photolithography method, patterning is generally carried out by application of a photosensitive resin composition, solvent removal, heating before exposure (prebaking), exposure, development, heating after development (post-baking), and each step. The resin composition of the present invention containing the compound (F) can form a coating film having less spots. Therefore, it is possible to manufacture a coating layer and a pixel pattern for a large display device. The coating film and pattern of the present invention can be applied, for example, to a transparent film of a constituent element such as a color filter or an array substrate of a display device, a color filter coloring pattern, a photoresist spacer, an ultra-coating film, an insulating film, and a liquid crystal. Orientation protrusions, microlenses, coating layers, and the like. Since the coating film and the pattern of the present invention exhibit sufficient adhesion to the substrate, it is particularly useful as a coating film or pattern formed on the substrate. As the display device, a liquid crystal display device, an organic EL display device, or the like is preferable. [Embodiment] [Embodiment] The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples, and it is undoubtedly possible to appropriately change the scope of the above-mentioned subject matter. And implementation, they are included in the technical scope of the invention. In addition, "%" and "parts" of the following components are not specifically described, and indicate "mass ° /." and "parts by mass". -50-201139475 1 . Synthesis of Resin (A) In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare a nitrogen atmosphere, and 3-methoxybutyl acetate was placed. 130 parts and 10 parts of 3-methoxy-1-butanol were heated to 80 ° C while stirring. Next, 40 parts of methacrylic acid, a mixture of monomer (bl-1-l) and monomer (bl-2-l) {monomer (bl-1-l) in the mixture: monomer (bl-2- l) Mohr ratio = 50: 50} 360 parts, and 36 parts by weight of azobisdimethylvaleronitrile dissolved in 210 parts of 3-methoxybutyl acetate and 3-methoxy-1-butene A mixed solution of 70 parts of alcohol was added dropwise over 5 hours, and after aging for 3 hours, it was cooled to room temperature to obtain a solution of a copolymer having a solid content of 43.1% and an acid value of 60 mg-KOH/g. This copolymer was used as the resin (A1). The obtained resin (A1) had a weight average molecular weight (Mw) of 78 00 and a molecular weight distribution (Mw/Mn) of 1.95.重量 Ο H2C=CH-C-O^^Y^y° The weight average molecular weight (Mw) and the number average molecular weight (?) of the obtained resin (Al) were carried out under the following conditions using a G P C method. Device; Κ2479 (made by Shimadzu Corporation)

Pipe column; SHIMADZU Shim-pack GPC-80M column temperature; 40 °C solvent; THF (tetrahydrofuran) flow rate; 1.0mL/min -51 - 201139475

Detector; RI standard: Polystyrene 2. Preparation of resin composition The components shown below were mixed in the amounts shown in Table 1 to obtain resin compositions 1 to 6. Resin (A): Resin (A1) solution (Table 1 shows the amount of the resin (A1) in terms of solid content) Polymerizable compound (B): Dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Chemical Co., Ltd.) Preparation) polymerization initiator (C): 2,2'-bis(2-chlorophenyl)·4,4',5,5'-tetraphenyl-1,2'-bisimidazole (B-CIM; Baotu Valley Chemical Co., Ltd.) Polymerization Starter Aid (D): 2-(2-Naphthoquinonemethyl)-3-methylbenzothiazoline Polyfunctional Mercaptan (E): Pentaerythritol (3-) Sulfhydrylpropionate) (PEMP; SC Organic Chemicals Co., Ltd.) Compound (F): P〇lyFoxTM PF-7002 represented by formula (F1-1-1) (manufactured by OMNOVA, formula (F1-1- 1) medium, m, +n' and 4 to 5) Other additives (G) (G1): o-methyl phenolic epoxy resin (Sumi epoxy ESCN-195XL-80; Sumitomo Chemical Co., Ltd.) (G2) : IRGANOX3114 (manufactured by Ciba Japan Co., Ltd.) (G3): 3-aminopropyltrimethoxydecane (KB M-903; manufactured by Shin-Etsu Chemical Co., Ltd.) -52- 201139475 (G 4 ): Polyether Modified polysand oil (SH8400 manufactured by Dow Corning Toray Co., Ltd.) Solvent (Η) (HI): 3-ethoxyl Ethyl acetate (H2): 3-methoxy-1-butanol (H3): 3-methoxybutyl acetate (H4): propylene glycol monomethyl ether acetate (H5): diethylene Alcohol ethyl methyl ether 〇^\/n'C4F9 ch2 \ ch2

OH~fCH2-C-CH2-〇f-CH2-C-CH2 十 O CH·:

-53- 201139475 [Table i] Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Composition 6 Composition 7 Resin (A) 46. 2 46.2 46.2 53.5 46.2 59.9 46.2 Polymerizable compound (B) 46.2 46.2 46.2 35.7 46.2 39.9 46. 2 Polymerization starter (c) 3.7 3.7 3.7 — 3.7 3.7 Polymerization starter auxiliaries (D) 0.9 0.9 0.9 0.9 a 0.9 polyfunctional thiol (E) 2.8 2.8 2.8 2.8 2.8 Miscellaneous (F) 0.01 0.04 0.09 0. 06 I— 0. 03 Other Additives (G) (G1) ' 8.9 I—(G2) 0.2 0.2 0.2 0.9 0_ 2 0.2 0.2 (G3) — One 0.9 — — (G4) One to one — 0.01 Solvent (H) (H1) 45 45 45 One 45 One 45 (H2) 15 15 15 30 15 30 15 (H3) 40 40 40 — 40 — 40 (H4) — One — 40 — 40 — (H5) — — A solid composition of a composition of 30 to 30: %) 33 33 33 18 33 18 33 1 The amount of each component (parts by mass) is represented by 树月(A) to other additives (G). 2 Solvent (H) is the solid content of the mixed composition to the above (% by mass). The solvent component (H1) to (H5) in the solvent (H) represents the mass ratio in the solvent (H). 3. Evaluation of Resin Composition The stripe and the unevenness of the coating film obtained in the above compositions 1 to 7 were evaluated as follows. Further, the heat resistance of each of the coating films obtained by the composition 4 and the composition 6 was evaluated as follows. (1) Streak evaluation To evaluate the streaks of the coating films obtained in the compositions 1 to 7, first, using the colored resin composition of the composition shown in Table 2, a color pattern was formed on the ruthenium substrate, -54-201139475, followed by the composition 1 ～7, a coating film is formed on the substrate on which the color pattern is formed. Here, the streak indicates a radial spot of the coating film from the step of the coloring pattern. [Table 2] Component amount CI pigment blue 15 : 6 5.5 parts CI pigment purple 23 0.4 parts pigment dispersant 2.0 parts benzyl methacrylate / methacrylic acid copolymer (mass composition ratio: 65/35, polyphenylene) Ethylene-equivalent weight average molecular weight: 25000) 7.4 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) 7.4 parts of 2-benzyl-2-dimethylamino-1-(4-morpholine) Butyl phenyl) butanone, (IRUGACUR369; manufactured by Ciba Japan) 1.8 parts 4, heart diethylaminobenzophenone (FAB-F; made by Baotu Valley Chemical Co., Ltd.) 0.6 parts organic modified oil (SH8400) Dow Coming Toray (stock) 0_01 parts 3-ethyl ethoxypropionate 15 parts propylene glycol monomethyl ether acetate 60 parts 4 inch 矽 substrate with neutral detergent, water and 2-propene The alcohol is washed successively and then dried. On the substrate thus obtained, the film thickness after spin coating of the colored resin composition to post-baking was 3·0 μm. Next, the spin-coated colored resin composition layer was subjected to 9 (pre-baking of TC for 3 minutes in a dust-free oven. After cooling, the distance between the substrate on which the colored resin composition layer was applied and the quartz glass reticle was 10 ( ^111, use exposure machine (Ding 1^£-15 0113 〖; 7'0? (: 0> 1 (share) system, light source; ultra-high pressure mercury lamp), exposure to 100 mJ/cm2 in atmospheric environment (3 65 nm In the case of exposure to the colored resin composition layer, the emitted light from the ultrahigh pressure mercury lamp was passed through an optical-55-201139475 filter (UV-35; Asahi Techno GLASS Co., Ltd.). Further, as a photomask, a mask having a pattern (having a light-transmitting portion of a square having a length of 1 mm and a square of the square, and the interval between the squares is 〇〇mm) is formed on the same plane. After exposure, it contains a non-ionic interface activity. Agent 〇.1 2% and potassium hydroxide 0.04% of the aqueous imaging solution exposed to the colored resin composition layer after immersion at 23 ° C for 80 seconds, after water washing, in the oven at 220 ° C for 20 minutes After baking, a color pattern of 10 mm side length is formed on the sand substrate. Then, the composition was coated with the composition 1 to 6 under the condition that the film thickness after hardening was 2.0 μm by spin coating. Thereafter, the pressure was reduced to a reduced pressure by a vacuum dryer (manufactured by VCD Microtek Co., Ltd.). To l.OTorr (about 1.3×10 2 Pa) and dried. Secondly, pre-bake on a hot plate set at 90 ° C for 2 minutes to form a coating film. After cooling, the surface of the coating film was irradiated with a Na lamp, and the coating film was visually confirmed. The surface was evaluated as good (〇) when no streaks were confirmed on the substrate, and was evaluated as bad (X) (bad) when not confirmed. The results are shown in Table 3. (2) Cloud plaque evaluation and streak evaluation In the same manner, 'the coating film was formed using the composition 1 to 6 on the substrate on which the coloring pattern was not formed.' After the surface of the coating film was irradiated with a Na lamp, the surface of the coating film was visually confirmed. No coating was confirmed on the coating film. When the uniform cloud-like plaque was evaluated as good (〇) (very g〇od )', it was confirmed that the cloud-like plaque was a level (△) (good) with no practical problem, and it was evaluated as bad when the cloud-like plaque was confirmed ( X ) ( bad ). The results are shown in Table 3 -56- 201139475 (3) Heat resistance evaluation A 2 inch long glass substrate (Eagle 2000; manufactured by Corning Co., Ltd.) was sequentially washed with a neutral detergent, water, and 2-propanol, and dried. The composition 4 or the composition 6 was rotated on the glass substrate. The coating method was applied, and the mixture was baked in a dust-free oven at 3 ° C for 3 minutes, and then baked at 220 ° C for 20 minutes to form a coating film. The coating film thus formed was placed in an ovenless oven. 〇 ° C was heated for 4 hours, and the transmittance (%) of the coating film at a wavelength of 400 nm was measured by a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.), and the transmittance was obtained from the formula (i). Retention rate: transmittance retention rate (%) = 1 transmittance after heating (%) / transmittance before heating (%) (i) The results are shown in Table 3. When the transmittance retention ratio is 90% or more, the heat resistance of the coating film can be judged to be good. [Table 3] Retention rate of fringe cloud spot transmittance (%) Composition 1 〇 △ One composition 2 〇〇 one composition 3 〇〇 - Composition 4 〇〇 95 Composition 5 XX Discussion composition 6 XX 79 Composition From the results shown in Tables 1 to 3, it was found that the composition containing the compound (ρ) 1 to -57-201139475 4 and 7 can form a plaque for the compositions 5 and 6 which do not contain the compound (F). Less coating film. Further, the coating film obtained from the composition 4 has a higher transmittance and a higher heat resistance than the coating film obtained from the composition 6. [Industrial Applicability] The resin composition of the present invention containing the compound (F) is a coating film and a pattern which are excellent in coating property and have few spots. Therefore, when the resin composition of the present invention is used, a high-quality display device can be produced at a high yield. In particular, the resin composition of the present invention is suitable for use in the production of coating layers and pixel patterns of large display devices. -58-

Claims (1)

201139475 VII. Patent application scope: 1. A resin composition characterized by containing a resin, a polymerizable compound, a compound represented by the formula (F), and a solvent; [In the formula (F), L1 represents a divalent C2-8 aliphatic hydrocarbon group; L2 and L3 each independently represent a trivalent C2-8 aliphatic hydrocarbon group; and R1 and R2 are each independently, and represent a monovalent C, -8 aliphatic hydrocarbon group. At least three of the hydrogen atoms of the aliphatic hydrocarbon group are substituted by a fluorine atom; m and η are each independently represent an integer of 0 or more and 22 or less; but 'm + n is 3 or more and 22 or less. 2. The resin composition of claim 1 wherein R & R are independent, meaning that formula (fl) is not based, -CpH2p-CqF2q + i (fl) [in formula (fi), P and q Each of the independent integers represents an integer of 1 or more and 4 or less. 〇3. The resin composition of the first aspect of the patent application, wherein R and R represent a linear chain <^.8 aliphatic® S ° 4 . In the resin composition of item 2 or 3, q is 4. 5 · Resin composition as claimed in item 1 of the patent's formula (the compound shown is a compound of the formula (F 2 ); -59 - 201139475 OH (F1-1) OH [wherein m and n in the formula (FI-1) have the same meaning as described above]. 6. The resin composition of claim 1 wherein m + n is 3 or more and 6 or less. 7. The resin composition of claim 1, wherein the resin is a structural unit containing at least one monomer (a) selected from the group consisting of unsaturated decanoic acid and + @% carboxylic anhydride; A copolymer of a structural unit of a carbon-carbon double bond and a cyclic ether structure monomer (b) G denier 'different from monomer (a)}. 8. The resin composition according to claim 7, wherein the monomer (b) is at least one selected from the group consisting of a compound represented by the formula (bl-1) and a compound represented by the formula (bl-2); [In the formula (bl-Ι) and the formula (bl-2), R3 represents a hydrogen atom or a C,-4 aliphatic hydrocarbon group, and a hydrogen atom of the above aliphatic hydrocarbon group may be substituted with a hydroxyl group; and L4 represents a single bond or an aliphatic hydrocarbon group, -60-201139475 CH2 - of the above aliphatic hydrocarbon group may be substituted by -〇_, -S- or ·ΝΗ-; and R3 and l4 in the formula (bl-1) may be of the formula (b) R3 and L4 are the same or different]. 9. The resin composition of claim 1, further comprising a polymerization initiator. 10. The resin composition of claim 9, wherein the polymerization initiator is a polymerization initiator containing a diimidazole compound. A coating film which is formed by using a resin composition as in the first aspect of the patent application. 12. A pattern characterized by being formed using a resin composition as in claim 9 of the patent application. A liquid crystal display device characterized by comprising at least one selected from the group consisting of a coating film of claim 11 and a pattern of claim 12 of the patent application. An organic EL display device comprising at least one selected from the group consisting of a coating film of claim 11 and a pattern of claim 12 of the patent application. -61 - 201139475 IV. Designation of Representative Representatives (1) The representative representative of the case is: No (2) A simple description of the symbol of the representative of the representative figure··No 201139475 If there is a chemical formula in the case, please reveal the best invention Chemical formula of the feature: none