TW200832065A - Polymerizable resin composition - Google Patents

Abstract

A polymerizable resin composition comprising (A) a resin, (B) a polymerizable compound, (C) an initiator, (C-1) an initiation aid, (T) a polyfunctional thiol compound and (D) a solvent, wherein the initiation aid (C-l) contains a compound of the formula (V) : (in the formula (V), a dotted line depicted by X represents an aromatic ring, Y represents an oxygen atom or sulfur atom, R1 represents an alkyl group having 1 to 6 carbon atoms, R2 represents an alkyl group having 1 to 12 carbon atoms optionally substituted by a halogen atom, or an aryl group having 6 to 12 carbon atoms optionally substituted by a halogen atom.).

Description

200832065 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a polymerizable resin composition. ~ [Prior Art] It is recommended to form a spacer (φ photo spacer) between the color filter and the array substrate constituting the display (for example, a liquid crystal display or a touch panel) by using a photo-contact method. According to this method, the spacer can be formed at any position. Now, the high-intensity region of the spectrum of light emitted by a mercury lamp as a source of photo-etching method is usually about 43 6 nm, about 408 nm, about 3 65 nm, about 313 nm, about 315 nm. About 313 nm. A proximity exposure device and a walker are generally used as the exposure device used in the actual photo spacer formation method, and in many cases, the proximity exposure device has recently been used and short-wavelength light of less than 350 nm has been filtered out. In the walker, light of about 48 nm and about 365 nm is used. φ proposes a composition capable of exhibiting sufficient hardening properties, even when using an exposure apparatus that does not emit short-wavelength light of less than 350 nm, as in Patent Document 1 (JP-A No. 10-177108, 2nd) Page, column 2 in the left column to column 9 in the right column), Patent Document 2 (JP-A No. 2005-2083 60, page 2, column 2 to 9 in the left column), Patent Document 3 (JP-A No) .2006-133378, page 2, columns 2 to 17). In the composition, a compound having a maximum absorption wavelength in the range of 350 to 450 nm provides sufficient light sensitivity at about 4 3 6 nm, about 48 nm, and about 3 6 5 nm, even if exposed. The same is true when the device has removed the short 200832065 wavelength light below 305 nm. However, when the composition is used, although sufficient sensitivity is obtained, there is a problem in that since the maximum absorption wavelength is in the range of 350 to 450 nm, the light transmittance of the resulting coating film or pattern is lowered. Compounds having a maximum absorption wavelength in the range of 350 to 450 nm are widely used, but 4,4'-bis(N,N-diethylamino)benzophenone (also known as 4, is known). 4f-bis(N,N-diethylamine)benzophenone) has high sublimation properties. If the sublimation property is high, the inside of the oven is contaminated in the post-baking, resulting in a decrease in product yield. SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerizable resin composition which has sufficient sensitivity to light of about 436 nm, about 408 nm and about 365 nm and which can form a coating film having high light transmittance or pattern.

The present inventors have focused on the investigation and found that a polymerizable resin composition containing some types of hair auxiliaries can solve the aforementioned problems. That is, the present invention provides the following [1] to [6]. [1]. A polymerizable resin composition comprising (A) a resin, (B) a polymerizable compound, (C) an initiator, (C-1) an initiator, (T) a polyfunctional thiol compound And (D) a solvent, wherein the initiator (C-1) contains a compound of the formula (V): γ 〇 (xQc=ch-^r2 (v) R1 -5- 200832065 (in the formula (V), marked by X The dotted line represents an aromatic ring, Y represents an oxygen atom or a sulfur atom, R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 represents an alkyl group having 1 to 12 carbon atoms (which is optionally substituted by a halogen atom) Or an aryl group having 6 to 12 carbon atoms (which is optionally substituted by a halogen atom). [2] The polymerizable resin composition according to [1], wherein the initiator (C) contains The at least one compound selected from the group consisting of a diimidazole compound, an acetophenone compound, a triazine compound, a sulfonium phosphine phosphine compound, and a hydrazine compound. [3] The polymerizable resin composition according to [1] or [2] Wherein the resin (A) is a resin having an alkali-soluble group. [4] . A coated film which is polymerizable by using any one of [1] to [3] A lipid composition is formed. [5] . A pattern formed by using a coated film according to [4]. [6] A display comprising a pattern according to [5]. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described below. The polymerizable resin composition of the present invention is preferably a film for forming a display. The polymerizable resin composition of the present invention contains (A) a resin '(B) a polymerizable compound , (C) initiator, (C-1) initiator auxiliaries '(butyl) polyfunctional thiol compound dissolved or dispersed in (D) solvent. -6 - 200832065 Soluble alkali has a tree with 11 C In the middle, the composition of the group of fats and fats into the tree group RHW; the age of the lysate is combined with the accumulation of the material} • 1 C: The hair is as in this case, the 匕曰

The nature of A and the fat tree should be used as a counter-exhibition - less heat and light. The borrower is similar to the sexual class, and the if acid carboxy tree and the spoon are not a) dissolved and {the acid test has a carboxy body and the single satiety is less than the sub-case \) / • 1 self-selection} a Γν a (combined with 1 s and s.). Specific examples of at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, methyl-trans-butenedioic acid, itaconic acid An anhydride of the aforementioned unsaturated dicarboxylic acid; an unsaturated mono-((meth)acryloxy) group of di- or polyvalent carboxylic acids, such as succinic acid-[2-(methyl)propene a methoxyethyl]ester, a [2-(methyl) propylene oxyethyl] phthalate or the like; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl) acrylate And, similarly, from the viewpoints of copolymerization reactivity and alkali solubility, acrylic acid, methacrylic acid, maleic anhydride or the like is preferably used. Or two or more of them. Examples of the above-mentioned monomer (c) (except (a)) copolymerizable with (a) include alkyl (meth)acrylate such as methyl (meth)acrylate, (methyl) Ethyl acrylate, n-butyl (meth) acrylate 'dibutyl methacrylate, third butyl (meth) acrylate, etc.; cycloalkyl (meth) acrylate, such as (methyl) Cyclohexyl acrylate, 200832065 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02 6] oct-8-yl (meth) acrylate (commonly known as (meth) acrylate in this technology) Dicyclopentyl ester), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.; cycloalkyl acrylate such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, Tricyclo[5.2.1.02'6]oct-8-yl acrylate (commonly known as dicyclopentanyl acrylate in this technology), dicyclopentyloxyethyl acrylate, isobornyl acrylate or the like; An aryl acrylate such as phenyl (meth) acrylate, benzyl (meth) acrylate or the like; aryl acrylate such as phenyl acrylate , benzyl acrylate or the like; dicarboxylic acid diester, such as diethyl maleate, diethyl fumarate, diethyl itaconate; hydroxyalkyl esters, such as (meth)acrylic acid 2 - Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate or the like; monocyclic unsaturated compound such as bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] g? - alkene, 5-ethoxybicyclo[2.21]hept-2-ene, 5-hydroxybicyclo[2·2·1]hept-2-ene, 5-carboxybicyclo[221]hept-2-ene , 5-hydroxymethyl-cyclo[2 ·2·1]hept-2-ene, 5-(2,-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[ m]heptene, ethylbicycloalken, 5,6-dihydroxybicyclo[m]hept-2-ene, parent 6•dicarboxybicyclo[2.2.1]hept-2-ene, 5,6- Di(hydroxymethyl)bicyclo[2 21]heptene, 5 bis(2,-hydroxyethyl):cyclo, 5,6-dimethoxy-cyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.im-2-ene, Hong-8-200832065 cumyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5- Ethylbicyclo[2 · 2 · 1 ]hept-2-ene, 5-carboxy-5-methylbicyclo[2 · 2 ·pyrene]hept-2-ene, 5-carboxy-5-ethylbicyclo [2. 2.1] Geng-2·diluted, 5·hydroxymethyl_5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[221]hept-2-ene, %carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-di residue bicyclo [2.2.1] hept-2-yl anhydride, 5 - third Oxycarbonylbicyclo[2 ·2.1 ]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[221]hept-2-ene, 5-phenoxycarbonylbicyclo[2·2·1]hept_2 Alkenes, 5,6·bis(t-butylcarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[221]hept-2-ene Dicarbonyl quinone derivatives such as fluorenyl-phenylmaleimide, fluorene-cyclohexylmaleimide, fluorenyl-benzylmaleimide, anthracene-butanediamine -3-Malayimide benzoate, Ν-butanediamine-4-maleimide butyrate, hydrazine-butanediamine-6-maleimide Acid ester, Ν 丁 丁 醯 醯 imino-3 - maleimide propionate, ν - ( 9 - acridine) maleimide and the like; styrene, α-methyl phenyl hexene , m-methylphenylhexene, p-methylphenylhexene, vinyl toluene, p-methoxystyrene, acrylonitrile, methyl propyl Nitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-13-butadiene such as. From the viewpoints of copolymerization reactivity and alkali solubility, among them, preferred are styrene, fluorene-phenylmaleimide, fluorene-cyclohexylmaleimide, 1 benzylmaleimide, and bicyclol. [2.2.1] Hept-2-ene and the like. 200832065 These can be used alone or in combination with two or more. In the copolymer obtained by copolymerization of (a) and (c), the ratio of the components derived from the respective materials is preferably in the following range expressed by molar ratio. When the number of ears constituting the copolymer of the target II is 100 mol%, the fraction derived from (a): 2 to 40 mol% is derived from the component of (c): 60 to 9 8 mol% The ratio of the aforementioned components is preferably in the following range. Fraction derived from (a): 5 to 3 5 mol% Fraction derived from (c): 6 5 to 95 5 mol % When the aforementioned component ratio is within the above range, preservation stability, developability, and Excellent solvent resistance. The aforementioned resin (i) having a solubility test can be obtained, for example, from the literature "Kobunshi Gosei no Jikkenho (Experimental Method for Polymer Synthesis)" (Takayuki Ootsu, Kagaku Doj in KK 1 - st edition, 1-st print, March 1, 1) The method described in 972) and the literature listed in this document. Specifically, the selected amounts of units (a) and (c) constituting the copolymer, the polymerization initiator and the solvent are introduced into the reaction tank, stirred, heated and separated by oxygen-free oxygen in the absence of oxygen. Heat to get the polymer. The obtained copolymer may be used in the form of a solution after the reaction, may be used in the form of a concentrated or diluted solution, or may be taken out as a solid (powder) by a method (e.g., a reprecipitation method) before use. The weight average molecular weight of the aforementioned alkali-soluble resin (i) based on the polystyrene calibration standard is preferably 3,000 to 10 Å, preferably ,, and 5,000 to -10-200832065 5 0,0 00 is more preferable. The weight average molecular weight of the alkali-soluble resin (i) is preferably in the above range, so that the coating property is excellent, film loss is less likely to occur during development, and the developmental penetration of the non-image portion is excellent. Therefore. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η) of the alkali-soluble resin (i) is preferably from ΐ·ι to 6.0, and preferably from 1.2 to 4.0. Since the developability is excellent, the molecular weight distribution is preferably in the above range. The alkali-soluble resin (i) used in the polymerizable resin composition of the present invention is preferably contained in an amount of 5 to 90% by weight, preferably 1 to 70% by weight, based on the polymerizable resin composition. The weight of the solid component. The content of the alkali-soluble resin (i) is preferably in the above range, since the solubility in the developer is sufficient, the development slag is not easily formed on the substrate of the non-image portion, and the pixel portion of the exposed portion which is not easily developed is developed. The film loss occurs and the penetration of the non-exposed portion is excellent. The resin (ii) having alkali solubility and being reactive with at least one of light and heat may be (ii-Ι) the above (a) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. (c) a monomer copolymerizable with (a) (except (a)), and (b) a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond or a copolymer having an epoxybutyl group and a compound having an unsaturated bond, and (Π-2) the above (a) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (c) copolymerizable with (a) a copolymer of a monomer (other than (a)) derived from (a) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and having at least one group derived from the foregoing (b) selected from the group consisting of aliphatic rings The oxy group and the alicyclic epoxy group 11 - 200832065 are reacted with a compound having an unsaturated bond or a group derived from an epoxybutyl group and a compound having an unsaturated bond. In (b), specific examples of the compound having an aliphatic epoxy group and having an unsaturated bond are glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, (meth)acrylic acid, Β-ethyl glycidyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, glycidyl vinyl ether and the like. In (b), a specific example of a compound having an alicyclic epoxy group and having an unsaturated bond is vinylcyclohexyloxy-1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000) ; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, CYCLOMER A 4 0 0; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxy methacrylate A cyclohexylmethyl ester (for example, CYCLOMER M100; manufactured by Daicel Chemical Industries, Ltd.), or at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). r n R 0

In the formula (I) and the formula (II), R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is optionally substituted by a hydroxyl group. X independently represents a single bond or an alkylene group having 1 to 6 carbon atoms which optionally contains a hetero atom. Specific examples of R are a hydrogen atom; an alkyl group such as methyl, ethyl, n--12-200832065 propyl, isopropyl, n-butyl, t-butyl, t-butyl or the like; Alkyl group, such as: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxyisopropyl, 2 -hydroxyisopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl and the like. Of these, preferred are a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

X includes a single bond, an alkyl group such as a methyl group, an ethyl group, a propyl group or the like; an alkyl group having a hetero atom, such as an oxygen methyl group, an oxygen methyl group, an oxygen group propyl group, and a sulfur group. Methyl, sulfur extended ethyl, sulfur propyl, amine methyl, amino extended ethyl, amine extended propyl and the like. Among them, preferred are a single bond, a methyl group, an ethyl group, an oxygen group, an oxygen group, and more preferably a single bond and an oxygen group. The compound of the formula (I) may be a compound of the formula (1-1) to (1-15), and the formula (1-1), (1-3), (1-5), (1-7), (1- 9) ,

The compound of (1-15) is preferred, and the compounds of the formulae (1-1), (1-7), (1-9) and (I-1) are more preferred.

-13- 200832065 CH3 ο I II h2c=c一c—ο

CHq ο I II HgCasBC—C-Ό—CH】 ch3 o I II H2C—C—C—0 —C2H4 ch3〇 I II HgCssC--6—0—C2H4—O

C2h4oh o h2c=c- c one o

The compound of the formula (n) may be a compound of the formula (II-1) to (11-15) with the formulae (II-1), (II-1) to (II-3), (II-5), (II-7) 11-15) Compounds are preferred, and compounds of the formula (Π-1 II-9 ) (II-7 II-9 ) and (11-15 ) are preferred.

0

Ch3o I II Η2〇==ό—C—Ο A C2H4-S

CH3 Ο I II Η2〇=ό—C Ο一C2H4

Ch3〇 I II Η〇0=ό—C —Ο A C2H4~~Ν Η

-14- 200832065 C2H4OH 〇 H2C=C-c-o

Ch3o I II ^ Η 2 〇 = ό - C - O - C2H4 - 至少 At least one of the compounds of the formula (I) and the compound of the formula (II) can be used individually. These compounds can be mixed in any ratio. In the case of mixing, the molar ratio of the formula (I): formula (II) indicates that the mixing ratio is preferably 5:95 to 95:5, 10:90 to 90:10 is better, and 20g is 80 to 80:20. Especially good. In (b), examples of the compound having an epoxybutyl group and having an unsaturated bond include: 3-methyl-3-methylpropenyloxymethylbutylene oxide, 3-methyl-3-propene oxime Oxymethyl butylene oxide, 3-ethyl-3-methylpropenyloxymethyl butylene oxide, 3-methyl-3-propenyloxymethyl butylene oxide, 3-methyl 3-methylpropenyloxyethyl butylene oxide, 3-methyl-3-propenyloxyethyl butylene oxide, 3-ethyl-3-methylpropenyloxyethyl Butylene oxide, 3-ethyl-3-propenyloxyethyl butylene oxide, and the like. In the copolymer (i-Ι), preferably, the ratio of the components derived therefrom relative to the total number of moles constituting the copolymer (i-1) is in the following range. The constituent unit derived from (a): 2 to 40 mol% The constituent unit derived from (c): 1 to 65 mol% The constituent unit derived from (b): 2 to 95 mol% of the aforementioned ratio of the constitution It is better in the following ranges. The constituent unit derived from (a): 5 to 35 mol% The constituent unit derived from (c): 1 to 60 mol% -15- 200832065 The constituent unit derived from (b): 5 to 80 mol% When the ratio of the aforementioned components is in the above range, storage stability, development, solvent resistance, heat resistance, and mechanical strength are excellent. The above-mentioned alkali-soluble resin (i-1) can be produced, for example: ''Kobunshi Gosei no Jikkenho (Takayuki Ootsu, Kagaku Dojin K. K. 1 - st edition, print, March 1, The method described in 1 972) and the disclosures in the literature. In particular, a selected amount of a derivative unit (a compound of a (c) and (b), a copolymerization initiator, and a solvent introduction tank, which constitute a copolymer, Stirring, heating and heat-free to obtain a polymer by oxygen-depleting with oxygen. The obtained copolymer may be used in the form of a solution after the reaction, may be used in the form of a concentrated or diluted solution, or may be used, for example, before use. A method such as a reprecipitation method, which is taken out as a solid (powder) as a resin which can be used in the present invention to exhibit reactivity by causing alkali solubility and by light and heat, copolymer (ii - 2 ) By using a copolymer (at least one (a) selected from the group consisting of unsaturated citric acid saturated carboxylic anhydride and monomer (c) copolymerizable with (a) ( (a) except for the unsaturated carboxylic acid and not At least one derivative selected from saturated carboxylic anhydride 'Reacting with the above-mentioned (b) compound having an aliphatic epoxy group or an alicyclic group and having an unsaturated bond or an epoxy group or epoxybutyl group derived from an epoxybutyl group and a compound having no bond. First, a copolymer is obtained by copolymerizing (a) and (c). The composition derived therefrom has a reaction with respect to the total number of moles of the copolymer of the foregoing copolymer. 5) π 1-st In the following range, the epoxy saturation composition of the formula is preferably -16-200832065. The constituent units derived from (a): 5 to 50 mol% are derived from The constituent unit of (c): 50 to 95 mol% The ratio of the aforementioned components is preferably in the following range. The constituent unit derived from (a): 10 to 45 mol% The constituent unit derived from (c): 55 to 90 Molar % is used to provide reactivity by light or heat, the carboxylic acid and carboxylic anhydride moiety of (a) (derived from copolymers obtained by copolymerizing (a) and (c)) and derived from (b) above Epoxy or epoxy butyl reaction. Based on the molar number of (a), the molar number of (b) is usually 5 to 80 mol%, 10 to 75 The ear % is better, preferably 15 to 70 mol%. The balance between preservation stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity is excellent. Resin (ii - 2 ) can be passed through two stages. It can be obtained by, for example, the literature 'Kobunshi Gosei no Jikkenho (Experimental Method for Polymer Synthesis)' (( Takayuki Ootsu, Kagaku Dojin KKl-st edition, 1-st print, March 1,1 972 ) The method described and the method described in JP-A Ν ο 200 1 -8 95 3 3. In particular, the method of the first stage will be described first. Selected amounts of compound-derived units (a) and (c) (constituting a copolymer by copolymerizing (a) and (c) (i.e., an alkali-soluble resin)), a polymerization initiator, and a solvent are introduced to the reaction In the tank, the mixture is stirred, heated, and insulated by oxygen-free oxygen in the absence of oxygen to obtain an alkali-soluble resin. The obtained resin may be used in the form of a solution after the reaction, and may be concentrated or diluted in the form of a solution -17-200832065, or may be taken out as a solid (powder) by a method (e.g., a reprecipitation method) before use. The weight average molecular weight of the foregoing resin based on the polystyrene calibration standard is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. The weight average molecular weight of the above resin is preferably in the above range, so that the coating property is excellent, film loss is less likely to occur during development, and the development visibility of the non-image portion is excellent. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] of the above resin is preferably from 1.1 to 6.0, and preferably from 1.2 to 4.0. Since the coatability and developability are excellent, the molecular weight distribution is preferably in the above range. The method of the second stage will be described later. Thereafter, the gas in the bottle is changed from nitrogen to air. Usually, the amount of component (b) is 5 to 80 mol% based on the mole of the component (a), and dimethylaminomethylphenol As a reaction catalyst for a carboxyl group and an epoxy group or an epoxybutyl group, the amount is 0.001 to 5% by weight based on the total of the monomers (a) to (c), and hydroquinone is used as a polymerization initiator. The amount is 〇〇1 to 5% by weight based on the total of the monomers (a) to (c), and these substances are introduced into the bottle and are usually from 60 to 130. After the reaction is carried out for 1 to 1 hour, the resin and the component (b) are reacted. The introduction method and the production temperature are appropriately adjusted similarly to the polymerization conditions, the production equipment of the visible polymerization reaction, the heat generation, and the like. The polymerizable compound (B) contained in the polymerizable resin composition of the present invention includes a monofunctional monomer, a difunctional monomer, and three or more polyfunctional monomers. Specific examples include nonylphenyl (meth) acrylate-18 - 200832065 carbitol, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbene (meth) acrylate Alcohol ester, 2-hydroxyethyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate , (meth) tetrahydrofuran acrylate, caprolactone (meth) acrylate, ethoxylated nonyl phenol (meth) acrylate, propoxylated nonyl phenol (meth) acrylate, N-vinyl pyrrole Specific examples of φ difunctional monomers include 1,3 - butanediol II Methyl) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di(meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate Ester, bis(acryloxyethyl)ether of bisphenol A, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, new ethoxylated Pentylene glycol di(meth) acrylate, 3-methyl pentanediol di(meth) acrylate, etc. Specific examples of three or more polyfunctional monomers include trimethylolpropane tris(A) Acrylate, pentaerythritol tri(meth)acrylate, bis(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate Propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate diquaternium Alcohol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate-19 - 200832065, the reaction product of tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate and anhydride, dipentaerythritol penta (meth) acrylate and anhydride Product, reaction product of tripentaerythritol hepta (meth) acrylate and anhydride, trimethylolpropane tri(meth) acrylate modified by caprolactone, pentaerythritol tri(meth) acrylate modified by caprolactone , hexamethylene phthalate modified (2-hydroxyethyl) isocyanurate tri(meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified Pentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified tripellitate tetrakis (meth) propylene Ester, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa(meth) acrylate, caprolactone-modified tripentaerythritol hepta(meth) acrylate, The reaction product of caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri(meth) acrylate and an acid anhydride, and caprolactone-modified dipentaerythritol penta (methyl) a reaction product of an acrylate and an acid anhydride, a reaction product of a caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride. Among them, it is preferred to use two or more polyfunctional monomers. These polymerizable compounds (B) may be used singly or in combination of two or more. The content of the polymerizable compound (B) is preferably from 1 to 70% by weight, preferably from 5 to 60% by weight, based on the total amount of the resin (A) and the polymerizable compound (B). The content of the polymerizable compound (b) is preferably in the above range. The sensitivity, strength, smoothness, reliability, and mechanical strength of the coating film and pattern are excellent -20-200832065. The compound which is contained in the polymerizable resin composition of the present invention is a compound which initiates polymerization by the action of light or heat. The azole compound, the acetophenone compound, the triazine compound, the sulfonium phosphine compound And hydrazine compounds, particularly preferred are diimidazole compounds, because of the excellent sensation. Examples of the aforementioned diimidazole compounds include 2,2f-bis(2-chlorophenyl)·4,4,5,5' -tetraphenyldiimidazole, 2,2,-bis(2,3-dichlorophenyl)-4,4,5,5,-tetraphenyldiimidazole (Reference, eg, ??-eight> ^〇.6-753 72 and 6-753 73), 2,2,-bis(2-chlorophenyl)-4,4f,5,5'-tetraphenyldiimidazole, 2,2'- Bis(2-chlorophenyl)-4,4,5,5-tetrakis(alkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5,-tetrakis(dialkyloxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole Reference, for example, JP-B No. 48-38403, JP-A No. 62-17 4204, an imidazole compound in which a phenyl group substituted at a 4,4\5,5'-position is substituted with a carboalkyloxy group ( Reference, for example, JP-A No· 7-1 0913 or the like), preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2, double (2, 3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4\5,5'- Tetraphenyldiimidazole. Examples of the aforementioned acetophenone compound include diethoxyethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-1_{4· [4-(2-hydroxy-2-methyl) Benzyl)-benzyl]-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2 -morpholine-21 - 200832065 propyl propan-1-one, 2-benzyl-2- dimethylamino-1-(4-morpholinylphenyl) butan-1-one, 2- (2- Methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1- (4-morpholinylphenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-methylinyl)-butyl, 2- (2 -ethylbenylmethyl)-2 - _^methylamino-1- 1-(4-morpholinylphenyl)-butanone, 2-(2-propylbenzene Methyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-butylbenzyl)-2·dimethylamino-1-( 4- Morpholinylphenyl)-butanone, 2-(2,3-dimercaptobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-( 2,4-Dimethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-chlorobenzyl)-2-yl Amino-1-( 4 -morphinylphenyl)-butan, 2·(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone , 2-(3-Chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamine 1-(4-morpholinylphenyl)-butanone, 2-(3.bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-Bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methylbenzyl)-2-dimethylamine -1-(4-morpholinylphenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone , 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-methoxybenzoate Base)-2- Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-n Base-2-methyl-l-[4-(1-methylethyl)-based]propan-1-revaluated low-22- 200832065 polymer, and the like.

Examples of the aforementioned triazine compound include 2,4-bis(indolylchloromethyl)_6_(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)_6_ (4_methoxynaphthyl)-1,3,5-triazine, 2,4.bis(trichloromethyl)ylanyl-1,3,5·triazine, 2,4-bis(trichloromethane) -6-(4.methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2·(5-methylpyran- 2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2·(indol-2-yl)ethylidene]·1,3 ,5·2,2,4-bis(trichloromethyl) 6-[2 · (4-diethylamino-2-methylphenyl)vinyl, 5•trimium, 2,4-double (Trichloromethyl)-6-[2-(3,4.dimethoxyphenyl)ethylidene, 1,3,5-triazine, and the like. Examples of the aforementioned sulfonium phosphine phosphine initiator include bisphenylphosphine oxide or the like. Examples of the above hydrazine compound include hydrazine-ethoxycarbonyl, phenylpropan-1-one, a compound of the formula (III), a compound of the formula (IV) or the like.

The initiation aid (c 1) contained in the polymerizable resin composition of the present invention contains the compound of the formula (v). Preferably, the initiation aid () has a narrow, low sublimation property. -23- (V) 200832065

:C=CH-C-R2

In the formula (V), the dotted line indicated by X represents a square k' having 1 to 6 carbon atoms which is selectively substituted by a halogen atom. ¥ represents an oxygen atom or a sulfur atom.

Rl represents an alkyl group having from 1 to 6 carbon atoms. R2 represents an alkyl group having 1 to 12 carbon atoms (which is optionally substituted by a halogen atom) or an aryl group having 6 to 12 carbon atoms (which is optionally substituted by a halogen atom). The _ atom may be a fluorine atom, a chlorine atom, a bromine atom or the like. The aromatic ring having 6 to 12 carbon atoms may be a benzene ring or a naphthalene ring. Examples of the aromatic ring having 6 to 12 carbon atoms and optionally substituted by a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, and a butylbenzene group. Cyclo, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring Examples of the alkyl group having 1 to 6 carbon atoms such as a naphthalene ring, a chloronaphthalene ring, a bromine ring, and the like include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a 1-methyl-n-propyl group. Base, 2-methyl-n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl N-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl and the like. Examples of a hospital having from 1 to 12 carbon atoms and optionally substituted by a halogen atom -24-200832065 include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-propyl Base, 2-methyl-n-propyl, tert-butyl-n-pentyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, dimethyl-n-propyl 1,1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl, 3-chloro- N-butyl and the like. Examples of the aryl group having 6 to 12 carbon atoms and optionally substituted by a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, and a phenyl group. Phenyl, chlorobiphenyl, dichlorobiphenyl, bromobiphenyl, dibromobiphenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like. Specific examples of the compound of the formula (V) are 2-phenylhydrazinomethyl-3-methylnaphthalene [2,ld]thiazoline, 2-phenylhydrazinomethyl-3-methyl-naphthalene [l,2- d] thiazoline (V-2), 2-phenylhydrazinomethyl-3-methyl-naphthalene [2,3_d]thiazoline, 2-(2-naphthoquinonemethyl)-3-methylbenzo Thiazoline (V-1), 2-(1-naphthoquinonemethyl)-3-methylbenzothiazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-phenyl Benzothiazoline, 2-(1-naphthylquinonemethyl)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethyl)methyl-5- Fluorobenzothiazoline, 2-(1-naphthoquinonemethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2-naphthylmethyl)methyl-5- Chlorobenzothiazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylquinonemethyl)-3-methyl-5- Bromobenzothiazoline, 2-(b-naphthylmethyl)-3-methyl-5-bromobenzothiazoline, 2-(4-diphenylfluorenylmethyl)-3-methylbenzothiazole Porphyrin, 2-(4-diphenylfluorenylmethyl)-3--25- 200832065 methyl-5-phenylbenzothiazoline, 2-(2-naphthylquinonemethyl)-3-methyl -naphthalene [2,1-d]thiazoline, 2-(2-naphthylmethylidenemethyl)methyl-naphthoquinone, 2-d]thiazoline, 2-(4-diphenylfluorenylmethyl)methyl -naphthalene [2,led]thiazoline, 2-(4-biphenylfluorenylmethyl)methyl-naphthylthiazoline (V-3), 2-(p-fluorobenzhydrylmethylmethyl-naphthalene [2,Bu d]thiazoline, 2-(p-fluorobenzoylmethyl)methyl-naphthoquinone 1,2-"thiazoline, 2-benzylidene-methyl-3-methyl-naphthalene T2,1·01]oxazoline, 2_benzimidylmethyl-3-methyl-naphthalene, 1,_d]oxazoline, benzamidinemethyl-3-methyl-naphthalene [2,3 -d]oxazoline, 2_(2-naphthoquinonemethyl)-methylbenzoxazoline, 2-(b-naphthylmethyl)methylbenzoxazoline, 2-(2-naphthalene)醯Methoxy-5-phenylbenzoxazoline, 2·(1-naphthoquinonemethyl)-3-methyl-5-phenylbenzoxazoline, 2- (2 -Neptinylmethyl)_3-methyl-5-fluorobenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-fluorobenzoxazoline, 2·(2-naphthylmethyl)methyl-5-chlorobenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl-5-chlorobenzoxazoline, 2 - ( 2-naphthyl fluorenylmethyl)_3-methyl_5-bromobenzoxazoline, 2-(1-naphthoquinonemethyl)methyl-5-bromobenzoxazoline, 2_ (4-linked Phenylhydrazinomethyl)_3_methylbenzoxazoline, 2-('biphenylfluorenylmethyl)_3_methylphenylbenzoxazoline, 2-(indolizinylmethyl)- 3-methyl-naphthalene [2,1-d]oxazoline, 2-(2-naphthylfluorenylmethyl)_3_methyl-naphthalene [l,2-d]oxazoline, 2-(4 -biphenyl fluorenylmethyl) 3-methyl-naphthalene [2,1-d]oxazoline, 2-(4-biphenylfluorenylmethyl)-3-methyl-naphthalene [l,2-d Oxazoline (V-3), 2-(p-fluorobenzhydrylmethyl)-3-methyl-naphthalene [2,ld]oxazoline, 2-(p-fluorobenzhydryl) Base-26- 200832065)-3-methyl-naphthalene [l,2-d]oxazoline, and the like. Among them, preferred is 2-(2-phenylhydrazinomethyl)-3-methylbenzothiazoline of the formula (V-1), and 2-benzylidene-methyl-3 of (V-2). -methyl-naphthalene [l,2-d]thiazoline and 2-(4-biphenylfluorenylmethyl)-3-methyl-naphthalene[l,2-d]thiazoline of formula (V-3) 〇OC>=ch4_co (V-1) ch3

(V_2) > (V-3) When these compounds are used, the resulting polymerizable resin composition exhibits high sensitivity, and therefore, it is preferred to form a coating film or pattern by using this, which results in production of a coating film and a pattern. Improvements. For example, 4,4'-bis(N,N-diethylamino)benzophenone (EAB-F) is used as an example to enhance the penetration of the coating film by sublimation under the heating of the coating film. Light, the inside of the oven will be contaminated by sublimated substances, preferably with the compound of formula (V), because it will not sublimate in the post-baking heating of the film and only by the action of either light or heat. Fading to improve light transmission. The photopolymerization initiator can be further used without impairing the effects of the present invention. Examples of the photopolymerization initiator include benzoin -27-200832065, a benzophenone compound, an oxysulfide Pill compound, a hydrazine compound and the like. More specifically, the compounds are as described below, and these may be used individually or in combination of two or more. Examples of the aforementioned benzoin compound include benzoin, benzoin methyl ether, 'benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. Examples of the aforementioned benzophenone compound include benzophenone, methyl p-benzoyl benzoate, 4-phenyl benzophenone, 4-benzylidene-4^methyl φ biphenyl sulfonate. 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone or the like. Examples of the above oxysulfonium di compound include 2-isopropyl oxysulfonium di, 4-isopropyloxysulfonate, 2,4-diethyloxysulfonate, and 2,4-dichlorothiazide. Mountain, 1-chloro-4-propoxy oxysulfonate and the like. Examples of the above hydrazine compound include 9,10-dimethoxy hydrazine, 2-ethyl-9,10-monomethoxy hydrazine, 9,10-diethoxy fluorene, 2-ethyl-9,10- Diethoxy hydrazine and the like. • In addition, ' 10-butyl-2-chloroacridone, 2-ethyl benzopyridone, diphenylethylenedione, 9,10-morphine, camphorquinone, methyl phenylglyoxylate, A titanocene compound or the like can be used as a photopolymerization initiator. Further, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2002-544205 can be used as a photopolymerization initiator having a group capable of initiating chain transfer. The photopolymerization initiator having a group capable of initiating chain transfer may be, for example, a photopolymerization initiator of the following formulas (5) to (1 〇 ). -28- 200832065 Η义 { HaCOOC7Η弋 F C4H9-S-CH2 h2c -g-S^CHa^S-^

0 ch3 Factory 11 1 / \ II 1 .: c-C-N 1 \- > (5) ch3 0 ch3 Plant II 1 / \ 4 - C - N / ° (6) ch3 ? HV C - C - N,

II C4H9-s——ch2

H — c — N — CH 2 — s

(7) h2c,

CH3 \; one ch2 one s

Ch3

H3COOC H2 ~ ΠΤ3 (9) CH, CH3

H2C

H3COOC 〇ch2 /ch3 C-NI Vm C2H5 ch3 --- U 丫 ",2;_r^s_Q_4 N; (10) The photopolymerization initiator having a group capable of initiating chain transfer can also be used as the copolymer Fraction (A3). The obtained copolymer can be used as a binder resin as a binder resin in the polymerizable resin composition of the present invention, and can be used. The hydroxyl compound and the following carboxylic acid compound can also be used. In the case where the effect of the present invention is impaired, it is used as an initiation aid. Specific examples of I. ft #% include aliphatic amine compounds (e.g., triethanol feel ' ¥ X n & II amine, triisopropanolamine And arylamine compounds ( -29- 200832065 eg, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate , 2-ethylhexyl 4-dimethylhexyl benzoate, 2, dimethylaminoethyl benzoate, hydrazine, hydrazine-dimethyl-p-toluidine, 4,4f-bis (dimethyl Amino)benzophenone (common name: Mi chi eir ketone), 4,4'-bis(diethylamino)benzophenone, etc. Specific examples of carboxylic acid compounds include aromatic hetero An acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenyl Thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycerol, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycerol The content of the initiator (C) is preferably from 0.1 to 40% by weight, based on the total amount of the resin (A) and the polymerizable compound (B), and is preferably from 1 to 40% by weight, based on the total amount of the resin (A) and the polymerizable compound (B). 30% by weight is more preferable. Based on the same standard as described above, the content of the initiation aid (C-1) is preferably from 0.01 to 50% by weight, more preferably from 1 to 40% by weight. The content of the compound of the formula (V) is preferably from 50 to 100%, more preferably from 60 to 100%, still more preferably from 65 to 100%, based on the content of (C-1). The content of the compound of the formula (V) is within the above range. Preferably, when the coating film is formed by using the polymerizable resin composition containing the film, the light transmittance of the coating film is good. The total amount of the initiator (C) is preferably in the above range, which makes it possible. The resin composition has high sensitivity and the coating film or pattern strength formed by using the above polymerizable resin composition and the flatness of the flat film on the surface of the above-mentioned coating film or pattern are excellent. The amount of the auxiliary agent (c-1) is preferably in the above range because the resulting polymerizable resin composition exhibits higher sensitivity and the production property of the pattern substrate formed using the aforementioned polymerizable resin composition is obtained. The polyfunctional thiol compound (T) used in the polymerizable resin composition of the present invention is a compound having two or more thiol groups in the molecule, wherein two or more aliphatic sulfurs are present. The alcohol-based compound is preferred because the polymerizable resin composition of the present invention has a high sensitivity. Specific examples of the polyfunctional thiol compound (T) are hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, butanediol dithiopropionate, butanediol dithio Glycolate, ethylene glycol dithioglycolate, trimethylolpropane thioglycolate, butanediol dithiopropionate, trimethylolpropane thiopropionate , trimethylolpropane thioglycolate, pentaerythritol thiopropionate, pentaerythritol thioglycolate, hydroxyethyl thiopropionate, pentaerythritol bismuth (3- Mercaptobutyrate, 1,4-bis(3-decylbutoxy)butane, and the like. The content of the polyfunctional thiol compound (τ) is preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, based on the weight of the initiator (C). The content of the polyfunctional thiol compound (T) is preferably in the above range, because the sensitivity is improved and the developability is excellent. A specific example of the polymerizable resin composition used in the present invention as a solvent (D) is an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monopropyl ether. , ethylene glycol monobutyl ether, etc.; diethylene glycol dialkyl ether, for example: diethylene glycol dimethyl ether, diethylene di-31 - 200832065 alcohol diethyl ether, diethylene glycol dipropyl ether, two Diol dibutyl ether, diethylene glycol ethyl methyl ether or the like; ethylene glycol alkyl ether acetate, such as · methyl fibrin acetate, ethyl fibrin acetate, etc.; Alcohol alkyl ether acetate, for example: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, etc.; Φ aromatic a hydrocarbon such as benzene, toluene, xylene, mesitylene or the like; a ketone such as methyl ethyl ketone, acetone, methyl amyl, methyl isobutyl ketone, cyclohexanone, cyclopentanone or the like; For example: ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, methoxybutanol, ethoxybutanol, glycerin, etc.; ester For example, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or the like; cyclic ester such as γ-butyrolactone or the like. In the above solvent, an organic solvent having a boiling point of from 1 Torr to 200 ° C is preferred, and this is a viewpoint of coatability and dryness. Specific examples of the organic solvent having a boiling point of 100 to 200 ° C are an alkylene glycol alkyl ether acetate, an alcohol (e.g., methoxybutanol, ethoxybutanol or the like), a ketone (e.g., cyclohexanone). And esters (e.g., ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc.), preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone , methoxybutanol, methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These solvents (D) may be used singly or in combination of two or more. The content of the solvent (D) in the polymerizable resin composition of the invention is preferably from 60 to 90% by weight, more preferably from 65 to 85% by weight, based on the weight of the polymerizable resin composition. The content of the solvent (D) is preferably in the above range because of the coating device (e.g., spin coater, slit and spin coater, slit coater (also known as die coater, curtain flow) Coating machine, inkjet, roll coater, dip coater, etc.) are excellent in coating properties when applied. In the polymerizable resin composition of the present invention, the additive (F) may be used as needed, for example, dip, other polymer compound, colorant, pigment dispersant, tight adhesion promoter, antioxidant, Ultraviolet light absorber, light stabilizer, chain transfer agent and the like. Specific examples of the coating include glass, vermiculite, alumina, etc. Specific examples of other polymer compounds are curable (thermosetting) resins (e.g. • T®. • Oxygenated resin, maleic imide resin) Such as) 'thermoplastic resin (such as: polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether polyfluoride acrylate, polyester, polyurea, etc.). As a coloring agent, a compound classified as a pigment according to a color index (Society (3f Dyes and Colo ur ists): a specific one is a yellow pigment, for example, C. I. P igment Yellow "1 3, 12, 13 , 14 > 15 , 16 , 17 , 20 , 24 , 31 , 53 ^ 83 86 , 93 94 ' 109 , 1 10 丨 , 117 , 125 , 128 , 137 , 138 ^ 1 39 147 ' , 148 , 150 , • 153, 154, 166, 173, 194, 2 1 4; orange pigments, eg, C. I. Pigment Orange 13, 31, 36 38, 40 42, 43, 5, 55, 59, 61, 64, Red pigments such as 65, 71, 73, such as C. I. Pigment Red 9, 97, 105 > 1 22 -33- 200832065 123, 144, 149, 166, 168, 176, 177, 180, 192, 209 , 215, 216, 224, 242, 254, 255, 264, 265; blue pigments, such as CIPigment Blue 15, 15:3, 15:4, 1 5: 6, 60; purple pigments, For example, CIPigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as CIPigment G Reen 7, 36 or the like; brown pigments, such as CIPigment Brown 23, 25; black pigments, such as CIPigment Black 1, 7, etc. Commercially available surfactants can be used as pigment dispersants. Examples include anthrone, fluorine, ester, cationic, anionic, nonionic and zwitterionic surfactants, which may be used alone or in combination of two or more. Specific examples of the aforementioned surfactant include polyether oxygenated Alkyl, polyoxyethylene ethyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane, poly Ethylenediamine or the like; in addition, the registered names are: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Kagaku Co., Ltd.), EFTOP (Tochern Products), and MEGAFAC (Dainippon Inc and Chemicals, Incorporated), FLORAD (manufactured by Sumitomo 3M), ASAHI GUARD, SURFRON (all manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS), PB821 (Aji) Nomoto Co., Inc. manufactured). Specific examples of the adhesion promoter include vinyl trimethoxy-34-200832065 base sand, vinyl trimethoxy decane, vinyl ginseng (2-methoxyethoxy) sand, N-(2-amine Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3- Glycidyloxypropyltrimethoxy_"End '3 - glycidyloxypropyl'-methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloro Propylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethylsulfoxane or the like. Specific examples of antioxidants are 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1- (2-hydroxy-3 5 5 -di-third amylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, 6-[3-(3-tert-butyl- 4-hydroxy-5-methylphenyl)propoxybu 2,4,8,10-tetrabutylbutylbenzene [(1, £][1,3,2] bismuth phosphate • 3,9-bis[3_{3·(Tertiary butyl_4_hydroxy-5-methylphenyl)propoxybu 1,1·dimethylethyl]-2,4,8,10 - tetraoxaspiro[5·5] eleven, 2,2'-extended methyl bis(6-t-butyl-4-methylphenol), 4,4'-butylene double (6- Tributyl-3-methylate), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-t-butyl- 4-methylphenol), 3,3 _ thio-propionic acid monolauryl ester, 3,3, thiopropionic acid dimyristate, 3,3'·thiopropionate distearate, hydrazine (3_laurylthiopropionic acid) -35- 200832065 Pentaerythritol ester, 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5- Triazine e-2,4,6 ( 1H,3H,5H )-trione 3,3,,3,,,5,5,,5"-sixth butyl-&,&,,&"-(mesitylene-2,4,6-triyl) three -p-cresol, hydrazine [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, 2,6-di-tert-butyl-4-methylphenol Specific examples of ultraviolet light absorbers are 2-(2-hydroxy-5-t-butylphenyl)-211-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)oxyhydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisyl, 2,4-bis(2-hydroxy-4 -butoxyphenyl)-6-( 2,4-dibutoxyphenyl)-1,3,5-trisyl, 2-(2-pyridyl-4-[1-octyloxy) Ethoxy]phenyl)- 4.6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(2^1-benzotriazin-2-yl)-4,6- Bis(1·methyl-1-phenylethyl)phenol, 2_(2H-benzodiindenyl)-6-bis(1-methyl-1-phenylethyl)tetramethylbutylphenol ,twenty three- Tributyl-2-hydroxy-5-methylphenyl) _5_ chlorobenzene and oxadiazole, benzophenone and the like alkoxy groups. Specific examples of light stabilizers are polymers of succinic acid and (4-transyl-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)triazine·2·yl)-4,7 - diazepine-I,10.diamine; hydrazine acid, (2.2.6.6-tetramethyl-1_(octyloxy)_4-piperidinyl) ester, and 1,1 methoxy-36- 200832065 Reaction product of ethyl hydrogen peroxide; bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethyl) malonate Benzyl)-4-hydroxyphenyl]methyl]butyl; 2,4-bis[N-butylcyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Amino]-6-(2-hydroxyethylamine)-1,3,5-triazine; bis(1,2,2,656-pentamethyl-4-piperidyl)sebacate; methyl ( 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or the like. As the chain transfer agent, it may be a dodecyl mercaptan or 2,4 · diphenyl-4-methyl-1-pentene. The polymerizable resin composition is formed by, for example, coating on a glass substrate, a film substrate, a color filter or a substrate having a driving circuit thereon, photohardening and developing, thereby forming a pattern. By. First, the polymerizable resin composition is applied to a substrate (usually glass) or a layer composed of a solid component of a previously formed polymerizable resin composition, and the coated polymerizable resin composition layer is coated. Bake in advance to remove volatile components, such as solvents, to obtain a smooth, uncured coating film. At this stage, the unhardened film thickness is about 1 to 6 microns. The unhardened coating thus obtained is irradiated with ultraviolet light emitted from a mercury lamp or light emitted from a diode through a photomask for forming a desired pattern. In the pattern formation, the line width is appropriately controlled depending on the size of the mask. In recent exposure devices, filters that filter out this wavelength range are used to filter out light below 350 nm, or light bands that pass through these wavelength ranges are used to pass the filter, about 436 nm, about 408 nm, and about 365 Nai. The light of the meter is selectively selected to be uniformly illuminated by the parallel beams over the entire exposed portion. In this procedure, preferably, the device (e.g., reticle straightener, step -37-200832065 shifter, etc.) is used to properly adjust the position of the reticle and substrate. Further, after that, the coating film is contacted with an alkaline aqueous solution to dissolve the unexposed portion after completion of irradiation with light, and development is carried out to obtain a desired coating film or pattern form. The development method may be a liquid stirring method (so-called agitating method), a soaking method, a spraying method or the like. Further, the substrate can be tilted at any angle during development. The developer used in the development after exposure forming the pattern is usually an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of inorganic and organic basic compounds. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, carbonic acid. Sodium, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic base compounds may be used singly or in combination of two or more. The concentration of the basic compound in the alkaline developer is preferably from 0.01 to 1.0% by weight, preferably from 0.03 to 5% by weight. The surfactant in the alkaline developer can be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specific examples of the nonionic surfactant include polyoxyethylidene group, polyoxyethylene ethyl aryl ether, polyoxyalkylene aryl ether, other polyoxyethylene derivatives, and epoxy B. Alkane/propylene oxide copolymer, sorbitan fatty ester, polyoxyethylene sorbitan fatty ester, polyoxyethylene ethyl ester 38 - 200832065 sorbitol fatty ester, glycerol fatty ester, polyoxygen extension Ethyl fatty ester, polyoxyethylene extended amine amine and the like. Specific examples of the anionic surfactant include high-carbon alcohol sulfate salts (e.g., 'sodium lauryl sulfate, sodium oleate sulfate, etc.), alkyl sulfates (e.g., 'sodium lauryl sulfate, ammonium lauryl sulfate, etc.) Alkyl aryl sulfonate (e.g., sodium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfonate, etc.) ° Specific examples of cationic surfactants include amine salts or quaternary ammonium salts ( Such as 'stearylamine hydrogen chloride, lauryl trimethyl ammonium chloride) and the like. These interfacial agents can be used individually or in combination of two or more. The surfactant concentration in the alkaline developer is preferably from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, more preferably from 0.1 to 5% by weight. After development, it is washed with water, and, if necessary, post-baking can be carried out at 150 to 230 ° C for 10 to 180 minutes. The polymerizable resin composition of the present invention can be used to form a pattern on the substrate of the color filter substrate by the aforementioned method. This pattern can be used as a light spacer or a pattern top coat which is used in a liquid crystal display. Further, if a mask for hole formation is used for forming a pattern on an unhardened coating film, a hole can be formed, and therefore, it can function as an interlayer insulating film. Further, the entire surface may be exposed and hardened by heat, or may be hardened only by heat, but the photomask is not used in the exposure on the uncured coating film, thereby forming a light transmissive film which can be used as an outer coating. And can also be used for touch panels. The coating film thus obtained can be incorporated into a display (e.g., a liquid crystal display) to produce an excellent quality display in a high yield manner. -39 - 200832065. According to the present invention, there is provided a polymerizable resin composition which exhibits sufficient sensitivity to light of about 436 nm, about 408 nm and about 3 65 nm upon exposure, and is capable of forming A film with a high light transmittance. EXAMPLES The present invention will be explained in more detail by the following examples, but it goes without saying that the invention is not limited to these examples. In the examples, the % and parts of the representative amounts and amounts are by weight unless otherwise stated. Synthesis Example 1 In a 1 liter bottle equipped with a return condenser, a dropping funnel, and a stirrer

Nitrogen gas was passed at 0.02 L/min to provide a nitrogen atmosphere, and 2 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of 3-methoxybutyl acetate were introduced and heated to 7 〇 while stirring. C. Thereafter, 5 5 parts by weight of methacrylic acid, 175 parts by weight of 3,4-epoxytricyclo[5.2.1.〇2_6]decyl acrylate (formula (1-1) compound and formula (II-1) a compound having a molar ratio of 50:50) and 70 parts by weight of N-cyclohexylmaleimide dissolved in 14 parts by weight of 3-methoxybutyl acetate to prepare a solution. Using a drip pump, the solution was dropped into an insulated bottle at 7 ° C for 4 hours.

Ο

On the other hand, '30 parts by weight of a polymerization initiator 2,2'-azobis(2,4-methylammonium Sb) is dissolved in 225 parts by weight of 3-methoxybutyl acetate. With another drop of liquid, drop into the bottle -40 in 5 hours

In 200832065. After the polymerization initiator solution was completely dropped, the mixture was heated at 7 ° C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin ( ) solution having a solid content of 32·6 by weight of lanthanum is 34·3. The weight average molecular weight (Mw) of the obtained tree Aa is 13,600, the average molecular weight (?n) is 5,400, and the degree of dispersion is 2.5. The aforementioned weight average molecular weight (Mw) and number average molecular weight ( ) of the copolymer are It was measured by the GPC method under the following conditions: Equipment: K2479 (manufactured by Shimadzu Corp.)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml/min. Detector: RI The ratio of the weight average molecular weight based on the polystyrene calibration standard to the number average molecular weight obtained above is called the degree of dispersion (Mw/Mn). Plus i) grams Μη to

Example 1 69 parts (solid content: 55 parts) Resin solution (A) containing the tree (1) obtained in Synthesis Example 1, 45 parts of dipentaerythritol hexaacrylate), 4 parts of 2,2'-bis (2-chloro) Phenyl)-4,4,5,5'-tetraphenyldiimidazole) (2 -Nylanylmethyl)-3-methylbenzoindole D sitting (1), 4 parts of thiol Pentaerythritol propionate (τ), 56 parts of propylene glycol monoether acetate (D) and 40 parts of 3-ethoxyethyl propionate were mixed to obtain a polymerized resin composition 1. Fat (Β C (C C-甲可 -41 - 200832065

Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Polymerizable resin composition 1 Polymerizable resin composition 2 Polymerizable resin composition 3 Polymerizable resin composition 4 Polymerizable resin composition 5 Measurement (A) shed Aa only solid content) 55 55 55 55 55 polymerizable compound (B) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co" Ltd" KAYARAD DPHA 45 45 45 45 45 initiator (C) 2, 2f-bis(o-chlorophenyl)_ 4,5,4',5'-tetraphenyl-l,2f-diimidazole, manufactured by Hodogaya Chemical Co., Ltd., B-CIM 4 4 4 4 4 Additive (C-1) 2-(2-naphthylfluorenylmethyl)-3·methylbenzothiazoline Compound (V-1) 0.5 0.5 0.5 4,4f-bis(N,N-diethylamine Base) Dibenzoate, Hodogaya Chemical Co., Ltd., EAB-F Manufacture 0.5 Thiol Compound (7) Pentaerythritol thiopropionate, manufactured by Osaka Organic Chemistry Industry Ltd., POS-405 4 4 4 肆 (3-锍-butyric acid) pentaerythritol ester, manufactured by Showa Denko KK, Karenz MT PE-1 4 1,4-bis(3-5 alkoxybutoxy) Dingyuan, Showa Denko KK , Karenz MTDB-1 4 Solvent (D) Propylene glycol monomethyl ether acetate 56 56 56 56 56 3-ethoxyethyl propionate 40 40 40 40 40 Self-resin (8) Incorporated 3-methoxy-1-butene Alcohol + 3-methoxybutyl acetate 114 114 114 114 114 -42· 200832065 2 inch square glass substrate (# 1 73 7; manufactured by Corning) is washed sequentially with natural detergent, water and alcohol, followed by drying . The polymerizable resin composition 1 was spin-coated on the glass substrate and exposed to an exposure amount of 200 mJ/cm 2 (45 nm), developed, and washed with water so that the film thickness after baking was 3 · 0 μm, then pre-bake at 1 ° C for 3 minutes in a clean oven. After cooling, the interval between the substrate coated with the polymerizable resin composition and the quartz glass reticle was set to 1 〇 micrometer, and in a hot environment, an exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: Ultra-high pressure mercury lamp), the exposure is 2 〇〇mJ/cm 2 (405 nm). It is used to irradiate the polymerizable resin composition so that the light emitted by the ultra-high pressure mercury lamp is passed through an optical filter (MC4 05; Asahi Bunko Κ·Κ·; center wavelength 405 nm, half-height width 10 nm, penetration The rate is 60%), and about 405 nm of light is selectively used. As the photomask, a photomask having a pattern formed on the same plane (10 μm square for the transparent portion and 100 μm between the squares) is used. After the illumination, the coating film is immersed in an aqueous developer at 26 ° C ( It was contained in a 2% nonionic surfactant and 〇.〇5 % potassium hydroxide for 80 minutes for development, washed with water, and then post-baked in an oven at 23 ° C for 40 minutes. &lt;Pattern formation&gt; Using a scanning electron microscope (S-4 1〇0; manufactured by Hitachi, Ltd.), the exposure was 1 〇〇mJ/cm 2 and the temperature was 2 3 0 -43 to 200832065. . The cross-sectional shape of the pattern obtained by post-baking in a condition of (:: 〇 is (lower bottom size - higher bottom size), x is (lower bottom size &lt; higher bottom size) The results are shown in Table 2. &lt;Residual film sensitivity&gt; The same operation as the evaluation pattern formation was performed, and the exposure amount of the pattern was 100 mJ/cm 2 and 200 mJ/cm 2 . The surface shape measurement system (Micromap MM527N-PS-M100; manufactured by Ryoka Systems Inc.) measures the height of each pattern after baking. The residual film sensitivity is calculated according to the following formula. The results are shown in Table 2. Membrane residual sensitivity (%) = l 〇〇x (the exposure is 1〇〇mJ/cm2)/(the exposure is 200mJ/cm2) The higher the film residual sensitivity (°/〇), the height and exposure of the pattern The smaller the dependence of the amount, the wider the degree of freedom of processing, that is, the higher the residual sensitivity of the film. &lt;Line width&gt; The two-dimensional non-contact surface shape measuring system (Micro map MM527N-PS-M100; Ryoka) Systems lnc. manufactured) The line width of the pattern obtained by the light penetrating illuminating exposure amount of 100 mJ/cm 2 is shown in Table 2. <Transmission rate> -44- 200832065 Using a polymerizable resin composition 丨The film is cured so that the film thickness after baking is 3 · 0 μm. During the manufacturing of the cured film, a microspectroscopy apparatus (OSP-SP200; manufactured by OLYMPUS) is used after prebaking, after exposure, and after baking. The light transmittance (%) at 4 Å was measured. The results are shown in Table 2. The increase in light transmittance means a decrease in absorption enthalpy. Example 2 φ In the same manner as for the polymerizable resin composition 1 The polymerizable resin composition 2 was obtained to provide the composition shown in Table 1 and evaluated. The results are shown in Table 2. Example 3 In the same manner as in Example 1, a polymerizable resin composition 3 was obtained. The compositions shown in Table 1 were provided and evaluated. The results are shown in Table 2 〇 Comparative Example 1 In the same manner as in Example 1, except that EAB-F was used instead of the compound of the formula (V) to obtain a polymerizable resin composition. Compound 4 was provided to provide the compositions shown in Table 1 and evaluated. The results are shown in Table 2. Comparative Example 2 In the same manner as in Example 1, but without the compound of the formula (V), a polymerizable resin composition 5 was obtained to provide the blend shown in Table 1, -45-200832065 and The results are shown in Table 2. Table 2 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Polymerizable resin composition 1 2 3 4 5 Pattern formation residual film sensitivity (%) 99.0 97.3 95.0 97.0 91.0 Line width (micron) 23.3 22.1 20.3 22.0 18.6 Transmittance (after prebaking) (%) '41.7 42.2 42.6 69.8 Vertical light transmittance after Tengguang) 67.6 68.3 69.1 78.8 - Light transmittance (post baking) Thereafter) (%) 92.0 93.0 94.0 87.0 95.0 From the results of Examples 1 to 3 shown in Table 2, it is understood that the pattern and the coating film are used when the polymerizable resin composition of the present invention containing the initiator having a specific structure is used. It has an excellent pattern shape and excellent balance between sensitivity and transmittance. In contrast, Comparative Examples 1 and 2 did not give a polymerizable resin composition having a high residual film sensitivity and a high light transmittance. Reference Example 1 &lt;heating weight loss&gt; 2-(β-naphthylmethylidenemethyl)-3-methylbenzothiazoline and 4,4'-di(N,N-diethylamino)benzol The ketone (EAB-F) was measured for weight change when heated under the following conditions, and the results are shown in Table 3. Since the larger number means less weight change (weight before measurement: 1 〇〇%), it is judged that the sublimation is small and it shows an excellent condition. Equipment: Differential thermogravimetric synchronization measuring device TG/DTA220 ( Seiko

Instruments manufactured by KK) -46- 200832065 Reference: tin oxide environment: air (flow rate: 200 ml / min) Measurement conditions: 23 0 ° C / maintenance for 1 hour Table 3 % 2-(β-naphthyl fluorenylmethyl) -3-methylbenzothiazoline 98.6 4,4'-bis(N,N-diethylamino)benzophenone 86.4

The polymerizable resin composition of the present invention is capable of forming a pattern and a coating film having an excellent pattern shape and exhibiting an excellent balance between sensitivity and light transmittance, and is suitable for forming a light-transmissive film or pattern (the constitution thereof) A portion of the color filter, such as a light transmissive film or pattern of the photo spacer, an outer coating, an insulating film, a liquid crystal pointing control projection, a microscope sheet, a material of a coating for adjusting the film thickness of the color pattern. Further, this composition is suitable for a color filter or array substrate provided with the aforementioned light transmissive film and a liquid crystal display equipped with a color filter or an array substrate. -47-

Claims (1)

200832065 X. Patent Application 1 · A polymerizable resin composition comprising (A) resin, (b) polymerizable compound, (C) initiator, (C-1) initiator, (T) polyfunctional a thiol compound and (D) a solvent, wherein the initiation aid (C-1) contains a compound of the formula (V): , C=CH—C—R2 ΟII (V) (In the formula (V), the dotted line indicated by X represents an aromatic ring, γ represents an oxygen atom or a sulfur atom, R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 represents 1 to 12 carbons. An alkyl group of an atom (which is optionally substituted by a halogen atom) or an aryl group having 6 to 12 carbon atoms (which is optionally substituted by a halogen atom)) 2. The polymerizable resin composition of claim 1, wherein the initiator (C) comprises a compound selected from the group consisting of a diimidazole compound, an acetophenone compound, a triazine compound, a sulfonium phosphine oxide compound, and a hydrazine compound. At least one compound of the group. 3. If you apply for a patent scope! Or a polymerizable resin composition of 2' wherein the resin (A) is a resin having an alkali-soluble group. 4. A coated film formed by using the polymerizable resin composition of any one of claims 1 to 3. 5 - A pattern formed by using the coated film of the fourth application of the patent application. 6. A type of display containing the pattern of item 5 of the patent application. -48 - 200832065 VII. Designated representative map (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: formula (V)