JP2010270208A - Novel polymer and photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel copolymer that is suitable as a binder resin for a resist forming a member for use in the field of electronic information and is excellent in photosensitivity, development rate with respect to an alkali, solvent resistance, pattern shape and adhesion and to form a high-quality color filter portion with a good yield by using a photosensitive resin composition including the resin. <P>SOLUTION: The copolymer produced by copolymerizing an itaconic acid and a monomer including an acrylic ester monomer is used as a binder resin. The photosensitive resin composition including as essential components the resin, a radically polymerizable compound, a photoinitiator and a solvent is used as a resist for a color filter. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a copolymer obtained by copolymerizing a monomer containing itaconic acid and an acrylate ester, and a photosensitive resin composition containing the copolymer. More specifically, the present invention relates to a copolymer suitable as a binder for color filters used in members in the field of electronic information, particularly color liquid crystal display panels and color imaging tube elements, and a photosensitive resin composition containing the copolymer.

  Conventionally, a photopolymer obtained by adding a compound having a functional group that binds to an acid group and a compound having a polymerizable double bond to a polymer obtained by copolymerizing (meth) acrylic acid as a polymer having excellent photopolymerizability with excellent alkali solubility. Resin is used. However, a copolymer obtained by copolymerizing (meth) acrylic acid has a maximum of 1 mol of polymerizable double bond capable of undergoing addition reaction with respect to 1 mol of acid groups in the polymer main chain. In some cases, the pattern shape may be insufficient particularly for color filter applications, so that improvement in performance has been demanded.

JP 2002-30119 A

  Therefore, the present invention provides a polymer and a photosensitive resin composition that are excellent in alkali solubility, have a high development rate for alkali, have good photosensitivity, and have excellent solvent resistance performance, pattern shape, and adhesion performance. For the purpose.

The present inventor has intensively studied to solve the above problems. As a result, it has been found that a copolymer obtained by using itaconic acid as an acid monomer and copolymerizing with an acrylate monomer can solve the above-mentioned problems all at once, thereby completing the present invention. That is, the polymer of the present invention is a copolymer essentially comprising itaconic acid and an acrylate monomer. The polymer of the present invention is preferably a side chain double bond-containing polymer having a polymerizable double bond in the side chain, more preferably by reacting glycidyl (meth) acrylate with the carboxyl group of the polymer to form a side chain. It is a polymer containing a side chain double bond in which a double bond is introduced into the chain.
Moreover, the photosensitive composition of this invention is a photosensitive composition containing the said polymer, a radically polymerizable compound, and a photoinitiator, Preferably it is a photosensitive colored composition containing a coloring agent.
Moreover, this invention is the hardened | cured material which hardened the said photosensitive composition, Preferably it can use for a color filter. Furthermore, this invention is a liquid crystal panel which has the hardened | cured material which hardened the said photosensitive composition.

  The resin of the present invention is excellent in alkali solubility, has a high development speed against alkali, has good photosensitivity, and has excellent solvent resistance performance, pattern shape, and adhesion performance.For example, a coating agent, an adhesive, It can be suitably used in photosensitive resin compositions used for adhesives, sealants, paints, inks, lenses, molding materials, particularly color filters used in liquid crystal displays and solid-state imaging devices.

(1) Copolymer The copolymer resin of the present invention will be described.

  The copolymer of the present invention is obtained by copolymerizing itaconic acid and an acrylate monomer. The copolymer of the present invention has a high development rate for alkali and is particularly excellent in adhesion performance. These performances are particularly good alkali developability by copolymerizing itaconic acid, a dibasic acid, so that the carboxylic acid present across the methylene group from the main chain works more flexibly than (meth) acrylic acid. It is considered that it also contributes to physical properties such as adhesion performance. The content of the itaconic acid monomer in the copolymer of the present invention may be appropriately set according to the purpose, application and molecular weight of the copolymer, but usually 1 to 90% by weight in all repeating structural units, Preferably it is 2-70 weight%, More preferably, it is 5-50 weight%. By setting the content of itaconic acid in the above range, the alkali solubility of the copolymer can be optimized.

  It is essential that the alkali-soluble copolymer of the present invention contains an acrylic ester. Itaconic acid is very poorly reactive with methacrylic acid ester, and when it is copolymerized with methacrylic acid ester, a large amount of itaconic acid monomer remains, and itaconic acid is not effectively incorporated into the copolymer, and the alkali solubility cannot be sufficiently exhibited. However, it has been found that by copolymerizing with an acrylate ester, the reaction of itaconic acid becomes very fast, the residual monomer of itaconic acid is extremely reduced, and the copolymer has excellent alkali solubility. .

  Examples of the acrylate monomer copolymerized with itaconic acid include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, and acrylic acid. t-butyl, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, tridecyl acrylate, cyclohexyl acrylate, cyclohexyl methyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate Benzyl acrylate, phenyl acrylate, isobornyl acrylate, adamantyl acrylate, tricyclodecanyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate , 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, acrylic acid, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate And acrylate esters such as glycidyl acrylate, β-methyl glycidyl acrylate, β-ethyl glycidyl acrylate, (3,4-epoxycyclohexyl) methyl acrylate, and N, N-dimethylaminoethyl acrylate. Among these acrylates, methyl acrylate, cyclohexyl acrylate, and benzyl acrylate are easy to balance heat resistance, colorant dispersibility, and dry redissolvability when used in an alkali developing resist described later. , Isobornyl acrylate, tricyclodecanyl acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, and the like are preferable. Particularly, the reactivity is high and the solubility in a solvent is high. Preferred are methyl acrylate, ethyl acrylate, n-butyl acrylate, benzyl acrylate, and cyclohexyl acrylate. Particularly preferred are methyl acrylate and benzyl acrylate. The copolymerization amount of the acrylate ester is preferably 10 to 99% by weight, more preferably 30 to 98% by weight, and most preferably 50 to 95% by weight. By setting the content of the acrylic acid ester within the above range, itaconic acid can be polymerized faster, the itaconic acid remaining can be reduced, and the alkali solubility of the copolymer can be improved. The ratio of itaconic acid and acrylic acid ester in the copolymer of the present invention is preferably 1/99 to 90/10, more preferably 2/98 to 70/30, for itaconic acid / acrylic acid ester. More preferably, it is 5 / 95-50 / 50.

  Furthermore, the alkali-soluble copolymer of the present invention can be copolymerized with other unsaturated group-containing monomers as necessary. Other unsaturated group-containing monomers include α-hydroxymethyl acrylates such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate; N, N-dimethylacrylamide, N-methylol acrylamide and the like Acrylamides; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, N-substituted maleimides such as phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc .; polystyrene, poly (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, poly Macromonomers having an acryloyl group at one end of a polymer molecular chain such as prolactam; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Vinyl esters; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, Vinyl ethers such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as nylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl acrylate and allyl isocyanate. These other copolymerizable monomers can be used alone or in combination of two or more.

Among these other copolymerizable monomers, aromatic vinyls such as styrene and vinyltoluene; N-substituted maleimides such as cyclohexylmaleimide, phenylmaleimide, and benzylmaleimide; polystyrene, polymethylacrylate, polycaprolactone, and the like Macromonomers having an acryloyl group at one end of the polymer molecular chain are preferred. The copolymerization amount of these other monomers is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and most preferably 5 to 15% by weight.
The alkali-soluble polymer of the present invention can be copolymerized with a methacrylic acid ester as necessary. However, as described above, if the copolymerization amount of the methacrylic acid ester is increased, the polymerizability of itaconic acid is extremely high. In order to decrease, the content of the methacrylic acid ester is preferably 30% by weight or less, more preferably 20% by weight or less, and most preferably not substantially contained. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate and the like.

  As the polymerization method of the monomer component, a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and it may be appropriately selected according to the purpose and application, but solution polymerization is industrially advantageous. Further, structural adjustment such as molecular weight is easy and preferable. As the polymerization mechanism, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is also industrially advantageous. ,preferable.

  As a method for initiating polymerization, energy necessary for initiating polymerization may be supplied to the monomer component from an active energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and a polymerization initiator is used in combination. This is preferable because the energy required for initiating the polymerization can be greatly reduced, and the reaction can be easily controlled.

  The molecular weight can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, and the type and amount of chain transfer agent.

  When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. The solvent may be appropriately set according to the polymerization conditions such as the amount, the polymerization temperature, the polymerization concentration, etc., but it is efficient and preferable to include a solvent to be used later when making the photosensitive resin composition.

  For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, glycol monoethers such as 3-methoxybutanol; ethylene glycol dimethyl ether; Ethylene glycol Diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Salts, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate, ethyl acetate , Propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Alkyl esters such as methyl, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone And the like. These may be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene are used because of the solubility of the copolymer, surface smoothness when forming a coating film, little influence on the human body and the environment, and easy industrial availability. Glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether are preferred.

  As a usage-amount of a solvent, 40-1000 weight part is preferable with respect to 100 weight part of all the monomer components, and 60-400 weight part is more preferable.

  When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy, depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate.

  For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate, azo Bisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), Examples thereof include peroxides such as hydrogen peroxide and persulfate, and azo compounds. These may be used alone or in combination of two or more. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

  The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20 parts is preferable and 0.5 to 15 parts is more preferable with respect to 100 parts of all monomer components.

  When the monomer component is polymerized by a radical polymerization mechanism, a chain transfer agent may be used as necessary, and it is more preferable to use it together with a radical polymerization initiator. When a chain transfer agent is used at the time of polymerization, there is a tendency that increase in molecular weight distribution and gelation can be suppressed. Specific examples of such chain transfer agents include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, N-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), di Mercaptocarboxylic esters such as pentaerythritol hexakis (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc. Alkyl mercaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 -Mercaptopropionyloxy) -ethyl] mercaptoisocyanurates such as isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; simple units such as α-methylstyrene dimer Monomeric dimers; alkyl halides such as carbon tetrabromide; Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercaptoalcohols, aromatic mercaptans; mercaptoisocyanurates in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. Compounds having a mercapto group, such as alkyls, are preferred, and alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic esters are most preferred. These may be used alone or in combination of two or more.

  The amount of chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of monomers used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.1 to 20 parts is preferable and 0.5 to 15 parts is more preferable with respect to 100 parts of all monomer components.

  The polymerization temperature when the monomer component is polymerized using a polymerization initiator that generates radicals by heat by a radical polymerization mechanism includes the type and amount of the monomer used, the type and amount of the polymerization initiator, etc. However, it is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.

  The copolymer of the present invention has an acid group for becoming alkali-soluble. The acid value of the copolymer of the present invention is set to a preferable value depending on the purpose and application, but is preferably 10 to 300 mgKOH / g, more preferably 15 to 250 mgKOH / g, and still more preferably. 20-200 mg KOH / g. By making it within the above range of the invention, good alkali solubility is expressed, and particularly when used for an alkali developing resist, good plate-making property can be exhibited.

  When the copolymer of the present invention is used for an alkali development type resist, it is more preferable to have a radically polymerizable unsaturated group because the plate-making property and reliability after curing can be improved. The content of the radically polymerizable unsaturated group may be appropriately set according to the purpose and application, but in order to obtain good coating strength, a radically polymerizable unsaturated bond equivalent (radical polymerizable unsaturated bond 1 The molecular weight per chemical equivalent) is preferably 200 to 5000, more preferably 250 to 4000, and still more preferably 400 to 2000.

  Examples of the radical polymerizable unsaturated group include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a methallyl group. The radical polymerizable unsaturated group may have only one kind or two or more kinds. Among these, an acryloyl group and a methacryloyl group are preferable in terms of reactivity. As a method for introducing a radically polymerizable unsaturated group, for example, a monomer having a functional group capable of reacting with a carboxylic acid after polymerizing a monomer component containing itaconic acid (the following is introduction of a side chain unsaturated group) (It may be called a monomer.) There is a two-stage introduction method of reacting. Examples of such a functional group capable of reacting with a carboxylic acid include a hydroxy group, an epoxy group, an oxetanyl group, and an isocyanate group. Among these, the combination of a carboxyl group and an epoxy group is preferable in terms of the speed of reaction with carboxylic acid, heat resistance, and transparency.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, and allyl glycidyl. Examples include ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like. These may be used alone or in combination of two or more.

  When using a monomer having an epoxy group, the step of reacting the carboxyl group and the epoxy group is preferably in the temperature range of 50 to 160 ° C. in order to ensure a good reaction rate and prevent gelation. Is carried out at 70 to 140 ° C, more preferably 90 to 130 ° C.

  In the step of reacting the carboxyl group and the epoxy group, in order to improve the reaction rate, it is preferable to use a basic catalyst and an acidic catalyst for esterification or transesterification as the catalyst, and the basic catalyst is preferable because of few side reactions. Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine and tetramethylethylenediamine, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethylammonium. Quaternary ammonium salts such as chloride, urea compounds such as tetramethylurea, alkylguanidines such as tetramethylguanidine, amide compounds such as dimethylformamide and dimethylacetamide, tertiary phosphines such as triphenylphosphine and tributylphosphine, tetraphenylphosphonium bromide And quaternary phosphonium salts such as benzyltriphenylphosphonium bromide. Among these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free. These catalysts may be used alone or in combination of two or more. The catalyst is used in an amount of 0.01 to 5.0 parts, preferably 0.1 to 3.0 parts, based on the copolymer of the present invention into which a radical polymerizable unsaturated bond has been introduced. It is preferable.

  In the step of reacting the carboxyl group and the epoxy group, it is desirable to add a polymerization inhibitor in the presence of a molecular oxygen-containing gas in order to prevent gelation. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel. As the polymerization inhibitor, a polymerization inhibitor for a radical polymerizable compound can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, Phenolic inhibitors such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), organic Examples include acid copper salts and phenothiazines. Among these, phenol-based inhibitors are preferable from the viewpoint of low coloration and ability to prevent polymerization. Among these, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), methoquinone, 6 -T-Butyl-2,4-xylenol and 2,6-di-t-butylphenol are preferred. These polymerization inhibitors may be used alone or in combination of two or more. As the amount of the polymerization inhibitor used, the copolymer of the present invention in which a radically polymerizable unsaturated bond is introduced is ensured from the viewpoint of ensuring sufficient polymerization prevention effect and curable when a photosensitive resin composition is used. And 0.001 to 1.0 part, preferably 0.005 to 0.5 part.

  When the side chain unsaturated group-introduced monomer is used, the amount of acid groups consumed for introducing the radical polymerizable unsaturated bond is consumed, and therefore the acid value of the side chain unsaturated group-introduced copolymer can be adjusted. preferable. As a method for adjusting the acid value, the amount (molar amount) of the side chain unsaturated group-introducing monomer is made smaller (small molar amount) than the amount (molar amount) of the acid group of the copolymer containing itaconic acid. Alternatively, the acid value can be adjusted by reacting the side chain unsaturated group-introducing monomer and then reacting a functional group having a polybasic acid anhydride group such as succinic anhydride.

  Specific examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, anhydrous Examples include trimellitic acid and pyromellitic anhydride, and one or more of these can be used.

  The copolymer of this invention may have 1 or more types chosen from an epoxy group, an oxetanyl group, and an alkoxy silyl group other than the said side chain unsaturated group. By having one or more selected from an epoxy group, an oxetanyl group, and an alkoxysilyl group, the crosslinking density can be improved in the thermosetting step. In the case of having one or more selected from an epoxy group, an oxetanyl group, and an alkoxysilyl group, among the alkali development resists described later, in particular, a color filter resist, a photospacer resist, a protective film transparent resist, and an interlayer insulating film resist It can be particularly suitably used for applications.

  As a method for obtaining the above-mentioned copolymer having an epoxy group, it can be produced by polymerizing a monomer composition containing itaconic acid, an acrylate ester and a monomer having an epoxy group. Moreover, it is also possible to mix | blend a polyfunctional monomer, a photoinitiator, a solvent, etc. with the obtained resin to make a photosensitive resin composition.

  As a method for obtaining the above copolymer having an oxetanyl group, it can be produced by polymerizing a monomer composition containing itaconic acid, an acrylate ester, and a monomer having an oxetanyl group. It is also possible to blend a quinonediazide compound, a polyhydric phenol compound, a solvent and the like with the obtained resin to obtain a positive photosensitive resin composition.

  A method for obtaining a copolymer having an alkoxysilyl group can be produced by polymerizing a monomer composition containing itaconic acid, an acrylate ester, and a monomer having an alkoxysilyl group. Moreover, it is also possible to mix | blend a polyfunctional monomer, a photoinitiator, a solvent, etc. with the obtained resin to make a photosensitive resin composition.

  The weight average molecular weight of the copolymer of the present invention may be appropriately set according to the purpose and use. However, in order to obtain good alkali solubility and plate making property of an alkali developing resist described later, 2000 to 250,000, preferably It is 3000-100000, More preferably, it is 4000-50000.

  Since the copolymer of the present invention is extremely excellent in alkali solubility, it is a cement hardening retarder, a surface lubricant treatment agent for metal plates, an alkali soluble adhesive / adhesive used for sticking container labels, a detergent soluble builder, and a resin impregnation. It is a material used in various industrial fields, from civil engineering and building materials to electronic information materials, such as paper, washing ink, and alkali developing resist. Among them, the copolymer of the present invention can be suitably used for an alkali developing resist.

  The copolymer in the alkali development type resist is a component that imparts coating film formability and developer solubility, and is also a component that affects various performances such as curability, adhesion, heat resistance, and dry redissolvability. . In particular, in an alkali development type resist containing a color material such as a color resist for a color filter, it also serves as a dispersion medium for the color material dispersed by the dispersant, and greatly affects the dispersibility of the color material. By using the copolymer of the present invention, a copolymer having a balanced performance can be obtained.

(2) Photosensitive resin composition This invention is also the photosensitive resin composition which contains the copolymer obtained by copolymerizing itaconic acid and the monomer containing an acrylic ester as an essential component. Below, the photosensitive resin composition of this invention is demonstrated.

  The photosensitive resin composition of the present invention comprises (A) a copolymer obtained by copolymerizing itaconic acid and a monomer containing an acrylate ester, (B) a radical polymerizable compound, and (C) a photoinitiator. It is a photosensitive resin composition contained as an essential component, and is suitable for an alkali developing resist for forming a member in the field of electronic information, particularly a color filter resist. In addition to the above-mentioned essential components, (F) other components depending on the use of (D) a solvent or (E) the use of a colorant to form a photosensitive colored resin composition, and depending on each application and purpose May be blended.

  Hereinafter, each constituent component of the photosensitive resin composition of the present invention will be described based on a color filter resist that can make the most of the characteristics of the copolymer of the present invention.

(A) Copolymer of the Present Invention The copolymer of the present invention is as described in the above (1), but the resist resin composition of the present invention is colored in addition to imparting coating film forming property and alkali solubility to the resist. When it contains a material, it also serves as a dispersion medium for the color material.
The copolymer of the present invention is particularly suitable for a color resist for a color filter. The color resist for color filters is usually prepared from a color material dispersion (mill base) comprising a color material, a dispersant, a binder resin, a solvent, and the like, and further from a radical polymerizable compound, a photoinitiator, a binder resin, a solvent, and the like. It is prepared by adding a transparent resist solution. The copolymer of the present invention is suitable as a binder resin for a mill base or a binder resin for a transparent resist solution, and may be used for both or only one of them. Moreover, you may mix and use binder resins other than the copolymer of this invention. The preferred structure of the copolymer of the present invention is as described above, but for colored resists, a structure having a radically polymerizable unsaturated group in the side chain is particularly preferred.

  Since the copolymer of the present invention has good photosensitivity, solvent resistance, and a pattern shape can be obtained, it can be suitably used for a photospacer resist. When the copolymer of the present invention of the present invention is used for a resist for a photospacer, the preferred structure is as described above. In particular, a radically polymerizable unsaturated group, an epoxy group, an oxetanyl group, and an alkoxysilyl group are added to the side chain. The structure which has is preferable.

  The copolymer of the present invention is excellent in adhesion and transparency, and can be suitably used for a transparent resist for a protective film and a resist for an interlayer insulating film. When the copolymer of the present invention is used for a transparent resist for a protective film or a resist for an interlayer insulating film, a preferable structure is as described above, and in particular, a radical polymerizable unsaturated group, an epoxy group, an oxetanyl group, an alkoxy group in the side chain. A structure having one or more selected from silyl groups is preferred.

  The proportion of the copolymer (A) contained in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and application, but in the total amount of the above (A) to (C), It is 1-90 mass%, Preferably it is 3-80 mass%, More preferably, it is 5-70 mass%.

  (B) Radical polymerizable compound A radical polymerizable single compound is a low molecular compound having a radical polymerizable unsaturated group that is polymerized by irradiation with active energy rays such as electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.) and electron beams. Yes, imparting curability to the photosensitive resin composition of the present invention. Radical polymerizable compounds can be classified into monofunctional radical polymerizable compounds having only one radical polymerizable unsaturated group in the same molecule and polyfunctional radical polymerizable compounds having two or more radical curing compounds. From the viewpoint of properties, a polyfunctional radically polymerizable compound is preferred. Such radically polymerizable compounds may be appropriately selected from one or more according to the purpose and application.

  Examples of the monofunctional radically polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid. n-butyl, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, ( N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, (meth) acryl Octyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, (meth ) Phenyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-Ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β- (meth) acrylate β- Ethyl glycidyl, (meth) acrylic acid (3,4-epoxy (Meth) acrylic acid esters such as (cyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate; N, N-dimethyl (meth) (Meth) acrylamides such as acrylamide and N-methylol (meth) acrylamide; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, Unsaturated polyvalent carboxylic acids such as citraconic acid and mesaconic acid; chain extension between unsaturated groups and carboxyl groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate Unsaturated monocarboxylic acids; unsaturated acids such as maleic anhydride and itaconic anhydride Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, and naphthylmaleimide; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether N-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, Vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinyl N-vinyl compounds such as acetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate.

  Examples of the polyfunctional radical polymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and butylene glycol di (meth). Acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaene Thritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide Addition dipentaerythritol hexa (meth) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, propylene oxide addition ditrimethylolpropane tetra (meth) acrylate, propylene oxide addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipenta Erythritol hexa (meth) acrylate, ε-caprolac Ton-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, etc. Polyfunctional (meth) acrylates; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether , Trimethylolpropane trivinyl ether , Ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether Polyfunctional vinyl ethers such as ethylene oxide-added dipentaerythritol hexavinyl ether; (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth ) 2-vinyloxypropyl acrylate 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxy (meth) acrylate Vinyl ether groups such as methylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate Containing (meth) acrylic acid esters; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol dially Ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipenta Multifunctional allyl ethers such as erythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; (meth) Acrylic acid ants Allyl group-containing (meth) acrylic esters such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxy) Polyfunctional (meth) acryloyl group-containing isocyanurates such as ethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate; Many obtained by reaction with hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Ability urethane (meth) acrylate; polyfunctional aromatic vinyl compounds such as divinylbenzene, and the like.

  Among these polyfunctional radically polymerizable compounds, polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, (meth) acryloyl group-containing isocyanurates are selected from the viewpoints of reactivity, economy and availability. And a polyfunctional monomer having a (meth) acryloyl group, such as KAYARAD R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R- 551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), DPHA, DPHA-2C, D -310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-00 5 (manufactured by Nippon Kayaku); Aronix M-203S, M-208, M-211B, M-215, M-220, M-225, M-270, M-240, M-309, M-310 M-321, M-350, M-360, M-370, M-313, M-315, M-325, M-327, M-306, M-305, M-451, M-450, M -408, M-403, M-400, M-402, M-404, M-406, M-405, M-510, M-520 (above, manufactured by Toagosei); Light acrylate 3EG-A, 4EG- A, 9EG-A, DCP-A, BP-4EA, BP-4PA, HPP-A, PTMGA-250, G201PTMP-A, TMP-6EO-3A, TMP-3EO-A (manufactured by Kyoeisha Chemical), Wright Ester EG, 2 EG, 3EG, 4EG, 9EG, G101P, G201P, BP-2EM, BP-6EM, TMP (above, manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry) Etc.

  The molecular weight of the radically polymerizable compound of the present invention may be appropriately set according to the purpose and application, but 2000 or less is preferable because of low viscosity and good handleability.

  The amount of the radical polymerizable compound used may be appropriately set according to the type, purpose, and use of the radical polymerizable compound and binder resin to be used, but in order to obtain good plate making properties, the above (A) to ( In the total amount of C), it is usually 3 to 90% by mass, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.

  (C) Photoinitiator The photosensitive resin composition of this invention contains the photoinitiator which generate | occur | produces a polymerization initiation radical by irradiation of active energy rays, such as electromagnetic waves and an electron beam, and can use 1 type (s) or 2 or more types. Moreover, it is also preferable to add 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed.

  Specific examples of the photoinitiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl. Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) Alkyl] phenone compounds such as til] -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 2-carboxybenzophenone; Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (tri Loromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) Halomethylated triazine compounds such as -s-triazine; 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'- Benzomethyl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like halomethylated oxadiazole compounds; 2 , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichloro) Phenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 ′ -Biimidazole compounds such as tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [ Oxime ester compounds such as 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1 -Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium compounds such as titanium; p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc. Ikikosan ester compounds; acridine compounds such as 9-phenyl acridine; and the like.

  Sensitivity and curability can be improved by using a photosensitizer and a photoradical polymerization accelerator together with the photoradical initiator. Examples of such photosensitizers and photoradical polymerization accelerators include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; ethyl 4-dimethylaminobenzoate, 4-dimethylamino Examples include dialkylaminobenzene compounds such as 2-ethylhexyl benzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.

  The total amount of the radical polymerization initiator added may be appropriately set depending on the purpose and application, and is not particularly limited. However, from the viewpoint of balance between curability, adverse effects of decomposition products, and economy, the above (A) to In the total amount of (C), it is 0.1-30 mass%, Preferably it is 0.5-25 mass%, More preferably, it is 1-20 mass%.

  The total amount of the photosensitizer and the radical photopolymerization accelerator may be appropriately set according to the purpose and application, and is not particularly limited, but from the viewpoint of balance between curability, adverse effects of decomposition products, and economic efficiency. The mass is 0.01 to 10 times, preferably 0.05 to 5 times, and more preferably 0.01 to 2 times by mass.

  (D) The solvent can be used for reducing the viscosity and improving the handleability, forming a coating film by drying, or forming a colorant dispersion medium. The solvent is a low-viscosity organic solvent or water that can dissolve or disperse each component in the photosensitive resin composition.

  Such a solvent may be appropriately selected according to the purpose and application. Specifically, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol Cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol glycol such as propylene glycol monobutyl ether and 3-methoxybutanol Ethers; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl Esters of glycol monoethers such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate Class: methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate Alkyl esters such as chill; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, and octane; dimethyl Examples include amides such as formamide, dimethylacetamide, and N-methylpyrrolidone, and water. These may be used alone or in combination of two or more. __ is preferable.

  What is necessary is just to set suitably as the usage-amount of the said solvent according to the objective and a use, 10-1000 mass parts with respect to 100 mass parts of total amounts of said (A)-(C), Preferably 20-400 mass parts It is.

  (E) The colorant coloring material is used to color the photosensitive resin composition of the present invention to further form a photosensitive colored resin composition, and pigments and dyes can be used. From the viewpoint of durability, the pigment ( Organic pigments and inorganic pigments) are preferred.

  Organic pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex System, diketopyrrolopyrrole, etc.), dye lake pigments, etc. can be used. Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium) , Yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), black pigment (carbon black, bone black, graphite, iron black, titanium black, etc.) Bright pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

  Examples of pigment colors that can be used include yellow, red, purple, blue, green, brown, black, white, and azo dyes.

Moreover, as a dye, the dye described in Unexamined-Japanese-Patent No. 2003-270428, Unexamined-Japanese-Patent No. 9-171108, Unexamined-Japanese-Patent No. 2008-50599 etc. can be used, for example.
The above-mentioned coloring materials can be used alone or in combination of two or more. As the above-mentioned colorant, those having an appropriate average particle diameter can be used according to the purpose and application. However, when transparency such as a color resist for color filters is required, it is as small as 0.1 μm or less. An average particle diameter is preferable, and when a concealing property such as a paint is required, a large average particle diameter of 0.5 μm or more is preferable. In addition, the above-described coloring material is subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application. Also good.

  The proportion of the coloring material in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and application, but in terms of balancing the coloring power and dispersion stability, the above (A) to (C) The total amount is usually 3 to 250 parts by mass, preferably 5 to 200 parts by mass, and more preferably 10 to 200 parts by mass.

  (F) Other components The photosensitive resin composition of the present invention comprises a filler, a binder resin other than the copolymer of the present invention, a dispersant, a heat resistance improver, and a development aid depending on the purpose and required characteristics of each application. , Plasticizer, polymerization inhibitor, UV absorber, antioxidant, matting agent, antifoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, thixotropic agent, thixotropic agent Components other than the above essential components such as coupling agents such as silane, aluminum, and titanium, quinonediazide compounds, polyhydric phenol compounds, cationic polymerizable compounds, and acid generators may be blended. Below, other components suitable when using the photosensitive resin composition of this invention as a resist for color filters are demonstrated.

  <Binder resin other than the copolymer of the present invention> A binder resin other than the binder resin of the present invention can be used for balance adjustment of various properties of the color filter resist and cost reduction of the resist. . Specific examples of such binder resins include (meth) acrylic acid / (meth) acrylic acid ester copolymers, (meth) acrylic acid / aromatic vinyl copolymers, (meth) acrylic acid / (Meth) acrylic acid ester / aromatic vinyl copolymer, (meth) acrylic acid / (meth) acrylic acid ester copolymer / N-substituted maleimide copolymer, (meth) acrylic acid / aromatic vinyl / N-substituted maleimide Copolymer, (meth) acrylic acid copolymer such as (meth) acrylic acid / (meth) acrylic ester / polystyrene macromonomer copolymer; radical polymerizable non-polymerizable in side chain of (meth) acrylic acid copolymer Saturated group-introduced; vinyl ester type copolymer such as (meth) acrylic acid added to epoxy resin and polybasic acid anhydride reacted It is.

  The amount of the binder resin other than the copolymer of the present invention may be appropriately set according to the purpose and application as long as the characteristics of the copolymer of the present invention are not impaired. ) To 20 mass times or less, preferably 10 mass times or less, and more preferably 5 mass times or less.

  <Dispersant> The dispersant is a desirable component to be blended together with the above essential components when a coloring material is added to the photosensitive resin composition of the present invention to form a photosensitive colored resin composition. The dispersant has an interaction site to the color material and an interaction site to the dispersion medium (solvent or binder resin), and has a function of stabilizing the dispersion of the color material in the dispersion medium. Generally, it is classified into a resin type dispersant (polymer dispersant), a surfactant (low molecular dispersant), and a pigment derivative.

  Specific examples of the resin-type dispersant include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide and salt formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) acrylic acid -Styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct And the like.

  In addition, as a structure, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a coloring material and the graft chain is a compatible chain having an interaction property with a dispersion medium, A resin having a compatible chain in a block structure is particularly preferably used.

  Specific examples of the surfactant include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, Anionic surfactants such as ammonium lauryl sulfate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate Nonionic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Thione surfactant; alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazoline, and the like.

  The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, an amide group, and a phthalimide group. Examples of the structure of the dye as a base include, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, and perylene. , Diketopyrrolopyrrole and the like.

  Although the commercially available dispersing agent which can be used is illustrated by a brand name below, the dispersing agent of this invention is not limited to these.

  For example, EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES), Anti-Terra-U, Ant -Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 (above, manufactured by Big Chemie), SOLPERSE 3000, 5000, 9000, 12000 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (manufactured by Nihon Lubrizol), Disperlon 7301, 325, 374, 234, 1 220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Enomoto Kasei), Ajisper PB-711, 821, 822, 880, PN-411, PA-111 (above, manufactured by Ajinomoto Fine Techno), KP series (Shin-Etsu) Chemical Industry), Polyflow Series (manufactured by Kyoeisha Chemical Co., Ltd.), Mega Fuck Series (manufactured by DIC), Dispaid Aid Series (manufactured by San Nopco), and the like.

  These dispersants can be used alone or in combination of two or more. The proportion of the dispersing agent in the photosensitive resin composition of the present invention may be appropriately set according to the purpose and application, but the dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency In order to balance, 0.01 to 60 parts by mass, preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass with respect to 100 parts of the color material.

  <Heat resistance improver> The photosensitive resin composition of the present invention may contain an N- (alkoxymethyl) melamine compound, a compound having two or more epoxy groups or an oxetanyl group for the purpose of improving heat resistance and strength. it can. In particular, when a resist for a photospacer, a transparent resist for a protective film, or a resist for an interlayer insulating film is used, these are preferably used.

  <Leveling agent> A leveling agent can be added to the photosensitive resin composition of the present invention in order to improve leveling properties. As the leveling agent, a fluorine-based or silicon-based surfactant is preferable.

  <Coupling agent> A coupling agent can be added to the photosensitive resin composition of the present invention in order to improve adhesion. As the coupling agent, a silane coupling agent is preferable, and specific examples include epoxy, methacrylic, and amino silane coupling agents. Among these, an epoxy silane coupling agent is preferable.

  <Development aid> The photosensitive resin composition of the present invention is a monocarboxylic acid such as (meth) acrylic acid, acetic acid, propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, in order to improve developability. Polycarboxylic acids such as trimellitic acid; carboxylic acid anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride can be added as a development aid. .

  The photosensitive resin composition of the present invention is composed of the copolymer, radically polymerizable compound, photoinitiator, solvent, colorant, dispersant, other binder resin, leveling agent and other necessary components of the present invention. Can be prepared by mixing and dispersing using various mixers and dispersers.

  When the photosensitive resin composition of the present invention contains a color material, it is produced through a color material dispersion treatment step. For example, first, a predetermined amount of each of a coloring material, a dispersant, a binder resin, and a solvent are weighed, and the coloring material is dispersed in fine particles using a dispersing machine such as a paint conditioner, a bead mill, a roll mill, a ball mill, a jet mill, a homogenizer, a kneader, and a blender. Thus, a liquid colorant dispersion (mill base) is obtained. Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. To the obtained mill base, a transparent resist solution containing a radically polymerizable compound, a photoinitiator, a binder resin, a solvent, a leveling agent, etc., which has been separately stirred and mixed, is added and mixed to obtain a uniform dispersion solution. A resin composition is obtained. The obtained photosensitive colored resin composition is desirably filtered through a filter or the like to remove fine dust.

(3) Hardened | cured material This invention is also the hardened | cured material which hardened the said photosensitive resin composition. Since the cured product of the present invention is excellent in adhesion and mechanical properties, it is suitable for resist applications. The particularly preferable resist is illustrated in detail below about the curing method of the photosensitive resin composition of the present invention. Color filter resists include color filters such as colored resists (red, green, and blue pixels and black matrix forming resists), photospacer resists, protective film transparent resists, and interlayer insulation film resists. There is a resist corresponding to each part constituting, and the present invention is suitably used for any resist.

  Examples of the method for applying the photosensitive resin composition include spin coating, slit coating, roll coating, casting coating, and the like, but particularly when a resist is produced using the photosensitive resin composition of the present invention, A slit coating method is preferred. The coating conditions for slit coating differ depending on the slit-and-spin method and spinless method, the size of the transparent substrate, the target film thickness, etc., but can be applied by selecting the discharge rate from the nozzle and the moving speed of the slit head. is there. The lip width at the nozzle tip is preferably 30 to 500 μm, and the distance between the nozzle tip and the substrate is preferably 30 to 300 μm. In addition, the photosensitive resin composition of this invention is preferably applicable also to the method by spin coating, roll coating, and cast coating. The thickness of the coating film is preferably 0.3 to 3.5 μm in the case of a black matrix, a pixel and a protective film, and preferably 1 to 10 μm in the case of a photospacer.

  The coated film after application can be dried. As a drying method, a hot plate, an IR oven, a convection oven, or the like can be used. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but are preferably performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds. .

  The exposure is a step of irradiating the coating film with an actinic ray through a mask pattern as necessary and curing. Examples of active light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, argon ion lasers, YAG Laser light sources such as laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used. Examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.

  After the exposure, the film is developed with a developer to remove unexposed portions and form a pattern. As the developer, one that dissolves the photosensitive resin composition of the present invention is used, and an organic solvent or an alkaline aqueous solution is preferably used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Alkaline agents include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. ; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone or in combination of two or more; Also good. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonates, and the like. Anionic surfactants such as alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids. These may be used alone or in combination of two or more. Good. Examples of the organic solvent include alcohols such as isopropanol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol, and these may be used alone or in combination of two or more. The development treatment is performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.

  After the development, it is also preferably carried out by heating using a heating device such as a hot plate, a convection oven, a high-frequency heater and the like at a temperature of 150 to 250 ° C. for 5 to 60 minutes.

(4) Color filter This invention is also a color filter which has the hardened | cured material layer formed using the said photosensitive resin composition. The color filter in the present invention includes not only colored pixels but also each part, that is, black matrix, red, green, and blue pixels, a photo spacer, a protective layer, an orientation control rib, and the like. Examples of the method for forming the color filter portion of the present invention include a photolithography method, a printing method, an electrodeposition method, an ink jet method, and the like. As the photolithography method, a method using a negative acrylic photosensitive resin composition (photosensitive acrylic resin). Method) and a method using a non-photosensitive polyimide resin composition and a positive resist (non-photosensitive polyimide method). Specifically, in the photosensitive acrylic method, a negative photosensitive resin composition is applied onto a support substrate and dried, and then a photomask is overlaid on the formed coating film, and exposure is performed through this photomask. In this method, the exposed portion is photocured, the unexposed portion is developed, washed as necessary, and further heat-cured or photocured to form segments of each color filter. In particular, when the supporting substrate is large, coating by a slit coating device is preferable. When the photosensitive resin composition of the present invention is used as a negative photosensitive resin composition, high quality color filter segments can be formed with high yield. In addition, taking advantage of the excellent dry redissolvability of the copolymer and the photosensitive resin composition of the present invention, it can be preferably used for forming a segment of a color filter by an ink jet method.

  As a form of the color filter, pixels are formed on a transparent substrate in the case of a liquid crystal display device and on a photoelectric conversion element substrate in the case of an image pickup tube element, but each pixel is isolated as necessary. Forming a black matrix, forming a protective film on the pixel, forming a photo spacer on the black matrix area, forming a transparent electrode such as ITO on the pixel or the protective film, and controlling the alignment film and alignment It is also preferable to form a structural body. Further, a black matrix and pixels, and a protective film, a photospacer, and the like can be formed on a transparent substrate on which TFTs (thin film transistors) are formed.

  The color filter of the present invention only needs to have at least one segment formed using the photosensitive resin composition of the present invention, but preferably the color of all pixels, more preferably a black matrix. And a pixel is formed using the photosensitive resin composition of this invention. The photosensitive resin composition of the present invention is particularly suitable for a pixel and a black matrix that require coloring, but is also suitable for forming a segment that does not require coloring, such as a photospacer and a protective layer.

  Transparent substrates include glass, thermoplastic sheets such as polyesters, polycarbonates, polyolefins, polysulfones, cyclic olefin ring-opening polymers and their hydrogenated products, and thermosetting plastic sheets such as epoxy resins and unsaturated polyester resins. From the viewpoint of heat resistance, a glass plate and a heat resistant plastic sheet are preferable. The transparent substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.

  The black matrix is formed on a transparent substrate using a metal thin film or a photosensitive colored resin composition for black matrix. The black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide. In this case, first, the metal or metal / metal oxide thin film is formed on the transparent substrate by vapor deposition, sputtering, or the like. Next, after forming a positive photosensitive film thereon, the photomask is exposed and developed using the photomask to form a black matrix image. Thereafter, the thin film is etched to form a black matrix. When using the photosensitive coloring resin composition for black matrix, a black matrix can be formed according to the segment formation by the above-mentioned photosensitive acrylic method.

  The pixels are usually three colors of red, green, and blue. For example, first, green pixels are formed according to the above-described segment formation by the photosensitive acrylic method using a green photosensitive coloring composition. This operation is also performed for the remaining two colors, so that pixels of three colors can be formed.

  The protective film is formed on the pixels according to the above-described segment formation by the photosensitive acrylic method using the transparent photosensitive resin composition for the protective film after forming the pixels as necessary. In some cases, a protective film is not formed in order to reduce costs and simplify processes.

  When forming a transparent electrode on a pixel or a protective film, sputtering method, vacuum deposition method, CVD using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof. A thin film is formed by a method or the like, and if necessary, a predetermined pattern can be formed by etching using a positive resist or using a jig. In some liquid crystal driving methods such as a planar alignment driving method (IPS mode), a transparent electrode may not be formed.

  The photo spacer is formed directly on the black matrix according to the above-mentioned photosensitive acrylic method segment formation using the photosensitive resin composition for the photo spacer, if necessary, or a protective film or a transparent film in accordance with the black matrix region. Or formed on an electrode. It is also possible to maintain the cell gap with a particulate spacer without forming a photospacer.

(5) Color liquid crystal display panel The color liquid crystal display panel of the present invention is a liquid crystal display panel comprising the color filter of the present invention. The liquid crystal display panel of the present invention can be manufactured, for example, by forming an alignment film on the inner surface side of the color filter, and laminating a liquid crystal compound in a gap portion by bonding to a counter substrate.

  As the alignment film, a resin film such as polyimide is suitable, and usually a surface treatment is performed by ultraviolet treatment or rubbing treatment after coating and heat baking. The liquid crystal compound is not particularly limited, and conventionally known liquid crystal compounds can be used. The counter substrate is preferably a TFT substrate, and a substrate manufactured by a normal method can be used. The bonding gap between the color filter and the counter substrate is usually in the range of 2 to 8 μm. After the opposing substrates are bonded together, the liquid crystal display panel is completed by sealing with a sealing material.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these Examples. Unless otherwise specified, “parts” means “parts by weight”.
In the following examples, various physical properties and the like were measured as follows.

<Weight average molecular weight>
Weight average molecular weight was measured by a GPC (gel permeation chromatography) method using HLC-8120GPC (manufactured by Tosoh Corp.) and column TSKgel SuperHZM-M (manufactured by Tosoh Corp.) using polystyrene as a standard substance and eluent as tetrahydrofuran.

<Acid value>
3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone / 10 g of water, titrated with 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid content was determined from the concentration of the solid content.

Example 1
<Synthesis of resin solution>
(A) A separable flask with a cooling tube as a reaction vessel was charged with 48 parts of itaconic acid, 135 parts of propylene glycol monomethyl ether acetate (PGMEA) and 58 parts of propylene glycol monomethyl ether (PGME), and the temperature was 90 ° C. in a nitrogen atmosphere. After the temperature was increased to 29 parts, benzyl maleimide 29 parts, itaconic acid 32 parts, methyl acrylate 100 parts, benzyl acrylate 86 parts, PGMEA 311 parts, PGME 133 parts, perbutyl O (trade name, manufactured by NOF Corporation) 6 As a part and a dropping system 2, 10 parts of n-dodecyl mercaptan, 35 parts of PGMEA, and 15 parts of PGMEA were continuously supplied over 3 hours. Thereafter, after maintaining at 90 ° C. for 30 minutes, 2 parts of perbutyl O was added, and after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours. The polymerization rate was calculated from the amount of unreacted monomer sampled by gas chromatography and sampled from the polymerization solution. The reaction rate of each monomer was 98% for benzylmaleimide, 99% for itaconic acid, and methyl acrylate. 96% and benzyl acrylate was 96% by weight.
Next, 75 parts of glycidyl methacrylate, 1 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor (trade name “ANTAGE W400”, Kawaguchi Chemical Industries, Ltd.) Resin solution 1 was obtained by adding 0.6 part) and continuing reaction for 6 hours, bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%).
When various physical properties of the obtained resin solution 1 were measured, the weight average molecular weight was 10,800, the solid concentration obtained by drying at 160 ° C. under vacuum was 29.2%, and the solid content determined by the titration method The per acid value was 121 mgKOH / g.

<Adjustment of photosensitive resin composition>
12 parts of resin solution 1, 8 parts by weight of dipentaerythritol pentaacrylate, 0.3 part by weight of Irgacure 369 (manufactured by Ciba-Gaigi) as a photopolymerization initiator, and 79.7 parts by weight of PGMEA are mixed, and photosensitive resin composition 1 Got.

<Evaluation of developability and surface smoothness>
The obtained photosensitive resin composition was spin-coated on a glass substrate and dried at 120 ° C. for 3 minutes to form a coating film 1 having a thickness of 2.0 μm.

The coating film 1 was exposed to 50 mJ / cm ² of UV light through a line and space photomask having a line width of 15 μm with a UV exposure apparatus (TME-150RNS manufactured by Topcon), and a spin developing machine (manufactured by Actes Co., Ltd.). ADE-3000S) was developed with a 0.05% aqueous potassium hydroxide solution for 20 seconds. The pattern shape was very good, no unexposed residue was observed, and the developability was also good.

Comparative Example 1
(A) In a separable flask with a cooling tube as a reaction tank, 508 parts of PGMEA and 127 parts of PGME were charged and heated to 90 ° C. in a nitrogen atmosphere, and then 30 parts of benzylmaleimide and 108 parts of methacrylic acid as a dropping system 1 Methyl acrylate 72 parts, benzyl acrylate 90 parts, PGMEA 24 parts, PGME 6 parts, dropping system 2 as dimethyl 2,2′-azobis (2-methylpropinate) (trade name “V-601”, manufactured by Wako Pure Chemical Industries, Ltd. ) 26 parts, 28 parts of PGMEA, and 7 parts of PGME were each continuously supplied over 3 hours. Then, after maintaining 90 degreeC for 30 minutes, it heated up to 115 degreeC and superposition | polymerization was continued for 1.5 hours. The reaction rate calculated from the amount of unreacted monomer measured by gas chromatography after sampling the polymerization solution is 97% for benzylmaleimide, 95% for methacrylic acid, 96% for methyl acrylate, and benzyl acrylate. 94%.
Subsequently, 74 parts of glycidyl methacrylate, 1 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor (trade name “ANTAGE W400”, Kawaguchi Chemical Industries, Ltd.) Resin solution 2 was obtained by adding 0.6 part) and continuing reaction for 6 hours, bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%).
When various physical properties of the obtained resin solution 2 were measured, the weight average molecular weight was 12,000, the solid concentration obtained by drying at 160 ° C. under vacuum was 31.2%, and the solid content determined by the titration method The per acid value was 118 mgKOH / g.

  Further, except that the resin solution 2 was used, the same operation as in Example 1 was performed to obtain a photosensitive resin composition 2, and the same operation as in Example 1 was performed to measure the developability. The developability was poor.

Comparative Example 2
(A) A separable flask with a cooling tube as a reaction vessel was charged with 48 parts of itaconic acid, 135 parts of propylene glycol monomethyl ether acetate (PGMEA) and 58 parts of propylene glycol monomethyl ether (PGME), and the temperature was 90 ° C. in a nitrogen atmosphere. After the temperature was increased to 29 parts, benzyl maleimide 29 parts, itaconic acid 32 parts, methyl methacrylate 100 parts, benzyl methacrylate 86 parts, PGMEA 311 parts, PGME 133 parts, perbutyl O (trade name, manufactured by NOF Corporation) 6 As a part and a dropping system 2, 10 parts of n-dodecyl mercaptan, 35 parts of PGMEA, and 15 parts of PGMEA were continuously supplied over 3 hours. Thereafter, after maintaining at 90 ° C. for 30 minutes, 2 parts of perbutyl O was added, and after maintaining at 90 ° C. for 30 minutes, the temperature was raised to 115 ° C. and polymerization was continued for 1.5 hours. The reaction rate calculated from the amount of unreacted monomer measured by gas chromatography after sampling the polymerization solution is 95% for benzylmaleimide, 50% for itaconic acid, 92% for methyl acrylate, and benzyl acrylate. It was 95% by weight. Since a large amount of itaconic acid remained, 1 part of perbutyl O was further added and the reaction was continued for another 30 minutes. However, the reaction rate of itaconic acid increased only to 62%.
Next, 75 parts of glycidyl methacrylate, 1 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor (trade name “ANTAGE W400”, Kawaguchi Chemical Industries, Ltd.) Resin solution 3 was obtained by adding 0.6 part), and continuing reaction for 6 hours, bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%).
When various physical properties of the obtained resin solution 3 were measured, the weight average molecular weight was 10,800, the solid concentration obtained by drying at 160 ° C. under vacuum was 29.4%, and the solid content determined by the titration method The per acid value was 120 mgKOH / g.

  Further, the same operation as in Example 1 was carried out except that the resin solution 3 was used to obtain a photosensitive resin composition 3, and the developability was measured by performing the same operation as in Example 1. The alkali developability was poor. The pattern could not be formed.

Example 2
<Adjustment of photosensitive coloring composition>
1.6 parts of resin solution 1, 7.2 parts of PGMEA, 0.7 parts of Disperkbyk 2001 as a dispersant, 1.3 parts of Irgafore Red BT-CF as a red pigment were mixed and dispersed for 3 hours using a paint shaker. Thereafter, 3.6 parts of the resin solution 1, 1.2 parts by weight of dipentaerythritol pentaacrylate, 0.2 parts by weight of Irgacure 369 (manufactured by Ciba-Gigi) as a photopolymerization initiator, and 9.7 parts of PGMEA are mixed again. Dispersed for 1.5 hours in a paint shaker. A photosensitive coloring composition 1 was obtained by mixing 0.2 parts by weight of Irgacure 369 (manufactured by Ciba Gaigi Co., Ltd.) as a photopolymerization initiator in the obtained dispersion.

<Evaluation of developability and surface smoothness>
The obtained photosensitive coloring composition was spin-coated on a glass substrate and dried at 120 ° C. for 3 minutes to form a coating film 2 having a thickness of 2.0 μm.

The coating film 2 was exposed to 50 mJ / cm ² of UV light through a line and space photomask having a line width of 15 μm with a UV exposure apparatus (TME-150RNS manufactured by Topcon), and a spin developing machine (manufactured by Actes) ADE-3000S) was developed with a 0.05% aqueous potassium hydroxide solution for 20 seconds. The pattern shape was very good, no unexposed residue was observed, and the developability was also good.
Comparative Example 3
Except that the resin solution 2 was used, the same operation as in Example 2 was performed to obtain a photosensitive colored composition 2, and the developability was measured by performing the same operation as in Example 2. As a result, the pattern line was severely thin. The developability was poor.

  From the Examples and Comparative Examples described above, it can be seen that the photosensitive resin composition using the unsaturated group-containing resin of the present invention is excellent in alkali developability and adhesion.

The copolymer of the present invention and the photosensitive resin composition using the resin are excellent in photosensitivity, alkali developability and adhesion, and resists for forming members in the field of electronic information, such as solder resists, etching resists, It is suitable for interlayer insulating materials, plating resists, color filter resists, and is excellent in colorant dispersibility and platemaking properties, and is particularly suitable for forming a colored layer of a color filter.

Claims (8)

A copolymer obtained by copolymerizing itaconic acid and a monomer containing an acrylate ester. 2. A side chain double bond-containing copolymer, wherein the polymer according to claim 1 has a polymerizable double bond in the side chain. The side chain double bond containing copolymer which introduced the double bond into the side chain by making glycidyl (meth) acrylate react with the carboxyl group of the side chain double bond containing polymer of Claim 2. The photosensitive resin composition containing the copolymer in any one of Claims 1-3, a radically polymerizable compound, and a photoinitiator. Furthermore, the photosensitive coloring composition of Claim 4 containing a coloring agent. Hardened | cured material formed by hardening | curing the photosensitive composition of Claim 4 or 5. A color filter, wherein the cured product according to claim 6 is formed on a substrate.
A liquid crystal panel, wherein the cured product according to claim 6 is formed on a substrate.