JP2011002694A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition improved in adhesion to the substrate without degrading the alkaline developability.SOLUTION: The photosensitive resin composition includes: a photosensitive resin of a 20-140 mgKOH/g acid value having one or more radical polymerization unsaturated bonds and one or more carboxyl groups in one molecule; a polymer which includes one or more amide groups and one or more hydroxyl groups in 1 molecule and is 1,000-100,000 in average molecular weight when measured by a gel permeation method; a photopolymerization initiator; and a colorant.

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition for image formation suitably used for producing a color filter and the like.

  The photosensitive resin changes its shape when light is applied to the coated film. For example, the photosensitive resin has characteristics such that a portion irradiated with light is cured and other portions are soluble. Utilizing these characteristics, useful industries are becoming increasingly important with the development of so-called IT technology, which is used to manufacture display components and circuit boards for other electronic devices. Material. One of the important members formed by this is a color filter. The color filter is an indispensable member for a color liquid crystal display device and a color image pickup tube element, and has a fine colored resin layer for separating colors. As a method for producing a color filter, the current mainstream method is a method using a photosensitive resin composition, which usually contains an alkali-soluble resin as an essential component as a component that affects the plate-making characteristics in fine processing. In recent years, alkali-soluble resins imparted with photosensitivity by introducing not only alkali-soluble groups but also radical-polymerizable unsaturated bonds have been used to improve plate-making characteristics and reliability after curing. Yes.

  Conventionally, as a photosensitive resin composition used for production of a color filter, for example, an acid component monomer, one or more (meth) acrylate monomers, and a polyoxyalkylene chain-containing (meth) acrylate monomer are used as monomer components. A photocurable colored resin composition containing an acrylic copolymer containing as an alkali-soluble resin is disclosed (for example, Patent Document 1).

  On the other hand, a photosensitive resin composition containing a specific amide compound has been disclosed as a means for obtaining a resist having excellent film strength and alkali solubility (Patent Document 2).

JP-A-2005-70152 JP 2002-220422 A

  As described above, photosensitive resin compositions used for the production of color filters have been developed and improved, but with increasing demand for color filters and higher performance requirements, process time has been shortened. The demand for quality improvement is also increasing. For this reason, there is a demand for a resin with improved adhesion to the substrate.

  As a method for increasing the adhesion of the resin to the substrate, a method of adding an adhesion improver represented by silane is known. However, in order to further improve the adhesion, when the method of increasing the adhesion improver is taken, the undeveloped portion of the undeveloped portion is left undeveloped and an accurate pattern cannot be reproduced, and the required physical properties are satisfied. It didn't make it happen.

  The technique disclosed in Patent Document 2 is good in film strength and alkali solubility, but a high acid value compound is used for the purpose of removing the cured film by alkali dissolution after etching. When applied to the above, there was a problem that the cured coating film was missing.

  The present invention has been made in view of the above-described present situation, and provides a photosensitive resin composition that can be suitably used in the production of color filters and the like, with further improved adhesion to a substrate without reducing alkali developability. It is intended to do.

  As a result of intensive studies to solve the above problems, the present inventors have an acid value of 20 to 140 mgKOH / g having one or more radically polymerizable unsaturated bonds and one or more carboxyl groups in one molecule. A photosensitive resin (A) having one or more amide groups and one or more hydroxyl groups in one molecule, and having a weight average molecular weight of 1,000 to 100,000 as measured by gel permeation method (B) It has been found that by using a photosensitive resin composition containing a photopolymerization initiator (C), it is possible to improve the adhesion of the cured part to the substrate without reducing the alkali developability of the uncured part. The present invention has been achieved.

  That is, the photosensitive resin composition of the present invention is a photosensitive resin (A) having an acid value of 20 to 140 mgKOH / g having one or more radical polymerizable unsaturated bonds and one or more carboxyl groups in one molecule. A polymer (B) having one or more amide groups and one or more hydroxyl groups in one molecule, and having a weight average molecular weight of 1,000 to 100,000 measured by a gel permeation method, a photopolymerization initiator (C) contains the first gist, the photosensitive resin (A) is an acid-modified epoxy acrylate, and the photosensitive resin (A) is a modified copolymer. The fourth gist is that these photosensitive resin compositions contain a colorant (D).

  The photosensitive resin composition of the present invention comprises a photosensitive resin (A) having an acid value of 20 to 140 mgKOH / g having one or more radical polymerizable unsaturated bonds and one or more carboxyl groups in one molecule, one molecule. A polymer (B) having one or more amide groups and one or more hydroxyl groups therein and having a weight average molecular weight of 1,000 to 100,000 measured by gel permeation method, a photopolymerization initiator (C ). It has been found that this makes it possible to improve the adhesion of the cured part to the substrate without reducing the alkali developability of the uncured part.

  Therefore, the photosensitive resin composition of the present invention is an alkali-developable photosensitive resin composition for image formation, such as liquid crystal displays such as printing plate making, color filter protective film, color filter, black matrix, and photo spacer. It can be suitably used for various applications such as for plate production.

  The photosensitive resin composition of the present invention comprises a photosensitive resin (A) having an acid value of 20 to 140 mgKOH / g having one or more radical polymerizable unsaturated bonds and one or more carboxyl groups in one molecule, one molecule. A polymer (B) having one or more amide groups and one or more hydroxyl groups therein and having a weight average molecular weight of 1,000 to 100,000 measured by gel permeation method, a photopolymerization initiator (C ). This makes it possible to improve the adhesion of the cured part to the substrate without reducing the alkali developability of the uncured part.

  Hereinafter, the present invention will be described in detail.

(Photosensitive resin)
The photosensitive resin (A) used for obtaining the photosensitive resin composition of the present invention has an acid value of 20 to 140 mgKOH having one or more radically polymerizable unsaturated bonds and one or more carboxyl groups in one molecule. / G photosensitive resin. The acid value is more preferably 30 to 120 mgKOH / g, and still more preferably 40 to 100 mgKOH / g.

  By setting it as the acid value of such a range, in the specific composition of this application, the adhesiveness to the board | substrate of a hardened part and the alkali developability of an unhardened part become more favorable.

  Such a photosensitive resin (A) is obtained by reacting an unsaturated monobasic acid and a polybasic acid anhydride with an epoxy resin having two or more epoxy groups in one molecule as a starting material. It is obtained by reacting a carboxyl group-containing polymer obtained by copolymerizing an acid-modified epoxy acrylate or an unsaturated monobasic acid with a compound having a functional group capable of reacting with a carboxyl group and a radically polymerizable unsaturated group. A modified copolymer is mentioned.

  First, the acid-modified epoxy acrylate will be described.

(Acid-modified epoxy acrylate)
As long as it is obtained by reacting an unsaturated monobasic acid and a polybasic acid anhydride with an epoxy resin having two or more epoxy groups in one molecule as a starting material, the acid-modified epoxy acrylate The starting epoxy resin is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used. Bisphenol type epoxy resin; biphenyl type epoxy resin; Alicyclic epoxy resin; Polyfunctional glycidyl amine resin such as tetraglycidylaminodiphenylmethane; Multifunctional glycidyl ether resin such as tetraphenyl glycidyl ether ethane; Phenol novolac type epoxy resin and cresol novolac type epoxy resin; , M-cresol, naphth A reaction product of a polyphenol compound obtained by a condensation reaction of a phenol compound such as a phenol with an aromatic aldehyde having a phenolic hydroxyl group and epichlorohydrin; a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene Reaction product of polyphenol compound obtained by addition reaction and epichlorohydrin; Epoxidation of ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracid; Epoxy resin having heterocyclic ring such as triglycidyl isocyanurate; Phenol aralkyl type epoxy resin; and the like. Moreover, what extended | stretched the chain | strand by combining two or more molecules of each of these epoxy resins by reaction with chain extenders, such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol can also be used. Moreover, the homopolymer and copolymer of the monomer which has glycidyl groups like glycidyl (meth) acrylate may be sufficient. These can use 1 type (s) or 2 or more types.

  The acid-modified epoxy acrylate is a hydroxyl group formed by reacting an unsaturated monobasic acid with an epoxy group in the epoxy resin as a starting material to introduce a radical polymerizable unsaturated group and then opening the epoxy group. Can be obtained by reacting polybasic acid anhydrides to introduce carboxyl groups.

  The unsaturated monobasic acid in the present invention is a monobasic acid having one carboxyl group and one or more radically polymerizable unsaturated bonds. Specific examples include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxypropionic acid, hydroxyalkyl (meth) acrylate having one hydroxyl group and one (meth) acryloyl group, and dibasic acid anhydride. Reaction products, reaction products of polyfunctional (meth) acrylates having two hydroxyl groups and two or more (meth) acryloyl groups with dibasic acid anhydrides, caprolactone modified products of these monobasic acids, etc. 1 type, or 2 or more types can be used. Among them, preferred are those having a (meth) acryloyl group such as acrylic acid and methacrylic acid.

  In the reaction between the epoxy resin and the unsaturated monobasic acid, the carboxyl group in the unsaturated monobasic acid is charged to 0.8 to 1.2 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin. It is preferable to make it react by 0.9, More preferably, it is 0.9-1.1 equivalent.

  The reaction conditions between the epoxy resin and the unsaturated monobasic acid are not particularly limited, but in the presence or absence of a diluent such as a radical polymerizable monomer or solvent described below, quinones such as hydroquinone, 2,6-di- -Tertiary phenols such as alkylphenols such as tert-butylphenol, N-oxyls such as phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, polymerization inhibitors such as oxygen, and triethylamine Quaternary ammonium salts such as amines, triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, tertiary phosphines such as triphenylphosphine, quaternary phosphonium salts such as benzyltriphenylphosphonium bromide, metal organics Acid or inorganic salt or chelate Coexistence of a reaction catalyst compound or the like may be performed in the usual 80 to 150 ° C..

  Polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6- Reaction of endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide with itaconic anhydride or maleic anhydride Dibasic acid anhydrides such as products; trimellitic anhydride; biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarbo Acid dianhydride, pyromellitic acid anhydride, aliphatic such as benzophenone tetracarboxylic acid dianhydride or aromatic tetracarboxylic acid dianhydride and the like, may be used alone or two or more of them.

  It does not specifically limit as a solvent at the time of polybasic acid anhydride addition reaction, All the solvents which can be used for reaction of an epoxy resin and unsaturated monobasic acid can be used. Industrially, following the reaction between the epoxy resin and the unsaturated monobasic acid, it is convenient to carry out an addition reaction by adding a polybasic acid anhydride to the reaction solution.

  A catalyst may be used in the addition reaction as necessary. Specific catalysts include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium bromide. , Metal carboxylates such as lithium acetate, and inorganic metal salts such as lithium carbonate.

  The polybasic acid anhydride is reacted so that the acid anhydride group in the polybasic acid anhydride is 0.1 to 1.1 mol per one chemical equivalent of the hydroxyl group generated by the ring opening of the epoxy group. It is preferably 0.2 to 0.9 mol. About reaction temperature, Preferably it is 60-150 degreeC, More preferably, it is 80-120 degreeC.

  Next, the modified copolymer will be described.

(Modified copolymer)
As a method for obtaining a modified copolymer, (a) a copolymer obtained by polymerization with another monomer using an epoxy group-containing ethylenically unsaturated compound as a monomer component, (meth) acrylic acid, etc. A method of reacting a polybasic acid anhydride with a hydroxyl group generated by ring opening of an epoxy group after addition of an unsaturated monobasic acid, (b) an unsaturated monobasic acid such as (meth) acrylic acid A method in which an epoxy group-containing ethylenically unsaturated compound is reacted with a copolymer obtained by polymerization with another monomer as a monomer component, and (c) a hydroxyl group such as 2-hydroxyethyl (meth) acrylate A carboxyl group is derived by reacting a hydroxyl group of a hydroxyl group-containing copolymer obtained by polymerization with another monomer using an ethylenically unsaturated compound having a monomer as a monomer component and reacting with a polybasic acid anhydride. And, a method of reacting an epoxy group-containing ethylenically unsaturated compounds, known techniques include respect further its carboxyl group.

  It is also possible to use an ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group such as an oxazolinyl group or an oxetanyl group instead of the epoxy group-containing ethylenically unsaturated compound.

  Monomers usable here are N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2) other than the unsaturated monobasic acids described above. , 6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) ) Maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-hydro N-substituted maleimide compounds such as cyphenyl) maleimide; aliphatic epoxy compounds such as glycidyl (meth) acrylate, allyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and fats such as 3,4-epoxycyclohexylmethyl (meth) acrylate Cyclic epoxy compounds; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol mono (meth) acrylate, di Pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono (meth) acrylate Salts, hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether, allyl alcohol, ethylenically unsaturated compounds having a hydroxyl group such as p-hydroxystyrene; styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc. Aromatic vinyl monomers; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; n- Alkyl vinyl ethers such as propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and the corresponding al Rubiniru (thio) ether; N- vinylpyrrolidone, N- vinyl-based monomer such as N- vinyloxazolidone and the like.

(A polymer having an amide group and a hydroxyl group and having a weight average molecular weight of 1,000 to 100,000 measured by gel permeation method)
The photosensitive resin composition of the present invention has one or more amide groups and one or more hydroxyl groups in one molecule, and the weight average molecular weight measured by gel permeation method is 1,000 to 100,000. By blending a certain polymer (B), it is possible to achieve both the adhesion of the cured portion to the substrate due to the amide group in the molecule and the alkali developability of the uncured portion due to the hydrophilicity of the amide group and the hydroxyl group.

  Such a polymer (B) is obtained by homopolymerizing a monomer (E) having one or more amide groups, one or more hydroxyl groups and one or more radically polymerizable unsaturated bonds in one molecule, or It can be obtained by copolymerization with other monomers. Specific examples of such monomers include 2-hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4- Examples thereof include hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5-hydroxypentyl (meth) acrylamide, 6-hydroxyhexyl (meth) acrylamide, and one or more of these can be used. .

  Other monomers that can be used when the polymer (B) is a copolymer include monomers used for obtaining the modified copolymer, that is, an epoxy group, an oxazolinyl group, an oxetanyl group, and the like. An ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group, an unsaturated monobasic acid such as (meth) acrylic acid, and an ethylenically unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate ( Except those having an amide group), N-substituted maleimide compounds, aliphatic or alicyclic epoxy compounds, aromatic vinyl monomers, vinyl ester monomers, (meth) acrylic monomers, alkyl vinyl (thio) It can be appropriately selected from ethers, N-vinyl monomers and the like.

  The polymer (B) is preferably a copolymer. When the polymer (B) is composed of 100 mol% of structural units, the content of the monomer (E) is preferably 10 to 60 mol% in terms of a molar ratio. By setting it as this range, the adhesiveness of the cured portion to the substrate and the alkali developability of the uncured portion become better balanced. A more preferred lower limit of the monomer (E) is 15 mol%, and a more preferred lower limit is 20 mol%. Moreover, a more preferable upper limit is 50 mol%, and a more preferable upper limit is 40 mol%.

  The method for obtaining the polymer (B) is not particularly limited, and conventionally known polymerization methods such as a solution polymerization method and a bulk polymerization method can be employed. Among these, a solution polymerization method is preferable because temperature control during the polymerization reaction is easy.

  The solvent for the solution polymerization is not particularly limited as long as it does not inhibit the polymerization or alter each component of the raw material monomer. Specific solvents that can be used include hydrocarbons such as toluene and xylene; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid (di) methyl, succinic acid (di) methyl, and adipine Esters such as acid (di) methyl, methyl acetate, ethyl acetate, butyl acetate, methyl propionate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, methyl-t-butyl ether, (di) ethyl Ethers such as glycol dimethyl ether; N, N-amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide and the like, can be used as a mixture of two or more thereof.

  Examples of the initiator that can be used in the polymerization reaction include ordinary radical polymerization initiators. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), Azo compounds such as 2,2′-azobis (2-methylisobutyronitrile); lauroyl peroxide, benzoyl peroxide, t-butylperoxyneodecanate, t-butylperoxypivalate, t- Organic peroxides such as butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, etc. can be mentioned, and selected as appropriate according to desired reaction conditions Use it.

  The amount of the initiator used is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of monomers used for the polymerization reaction.

  The specific method for obtaining the polymer (B) is not particularly limited, but a method in which all components are charged at once in a solvent for polymerization, and the remaining components are continuously added to a reaction vessel in which a solvent and a part of the components are previously charged. A method of polymerization by addition or sequential addition may be employed.

  There is no particular limitation on the pressure during the reaction, and the reaction may be performed under normal pressure or pressurized conditions. Regarding the temperature during the polymerization reaction, although it depends on the type and composition ratio of the raw material monomer used and the type of solvent used, it is usually preferably in the range of 20 to 150 ° C, more preferably 30 to 120 ° C. .

  During the polymerization reaction, it is preferable to set the amount of the solvent and each monomer component so that the final solid content concentration of the polymer solution is 10 to 70% by mass. By setting this range, both productivity and reaction rate are improved. A more preferable final solid content concentration is 20 to 65% by mass, and further preferably 30 to 60% by mass.

  Considering the properties as a resin composition, alkali developability, cured coating film properties, heat resistance, etc., the weight average molecular weight of the polymer (B) is a value when measured by gel permeation chromatography (GPC). 1,000 to 100,000 are preferable in terms of polystyrene. By setting it to 1,000 or more, tack before photocuring can be suppressed, and by setting it to 100,000 or less, the possibility of reduction in alkali developability can be reduced. A more preferred lower limit is 2,000, and a still more preferred lower limit is 3,000. A more preferred upper limit is 50,000, and a more preferred upper limit is 20,000.

  In order to adjust the molecular weight within this range, a chain transfer agent may be used during the polymerization reaction, if necessary. Usable chain transfer agents are not particularly limited as long as they do not adversely affect each monomer component used in the polymerization, and thiol compounds are usually used. Specifically, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan; aryl mercaptans such as thiophenol; mercapto group-containing aliphatic carboxylic acids such as mercaptopropionic acid and methyl mercaptopropionate and the like Ester etc. are mentioned as a preferable thing. The amount of the chain transfer agent used is not particularly limited, and may be appropriately adjusted so as to obtain a polymer (B) having a desired molecular weight. In general, the total number of moles of monomers used for polymerization. Is used in the range of 0.001 to 1.0 (molar ratio).

  In the photosensitive resin composition of the present invention, the polymer (B) having one or more amide groups and one or more hydroxyl groups in one molecule is 3 to 60 with respect to 100 parts by mass of the photosensitive resin (A). It is preferable to mix | blend in the range of a mass part, Especially preferably, it is the range of 5-50 mass parts. By setting it as such a range, the adhesiveness of the hardened | cured part to the board | substrate and the alkali developability of an unhardened part become a more favorable balance.

(Photopolymerization initiator)
As the photopolymerization initiator (C) of the present invention, known ones can be used, and benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like Anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzopheno , 4- (1-t-butyldioxy-1-methylethyl) benzophenone, benzophenones such as 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones .

  These photopolymerization initiators (C) are used as one type or a mixture of two or more types, and are 0 for a total of 100 parts by mass of the photosensitive resin (A), the polymer (B), and the radical polymerizable compound described later. It is preferable that 5-30 mass parts is contained. By using in this range, it is useful in both cured product characteristics and economy.

(Coloring agent)
The photosensitive resin composition of the present invention uses a dye / pigment as the colorant (D). From the viewpoint of heat resistance and light resistance, organic or inorganic pigments are preferable. Specifically, organic pigments such as organic compounds classified as pigments in the color index CI (published by The Society of Dyers and Colorists). And inorganic pigments such as metal oxides or composite oxides. These colorants (D) may be used alone or in combination.

  The colorant (D) is a total of 100 masses of the photosensitive resin (A), the polymer (B) having one or more amide groups and one or more hydroxyl groups in one molecule, and a radical polymerizable compound described later. It is preferable to use 10 to 150 parts by mass with respect to parts. More preferably, it is 20-100 mass parts.

  In the present invention, a monomer having one or more amide groups, one or more hydroxyl groups, and one or more radically polymerizable unsaturated bonds in one molecule used for obtaining the polymer (B) ( E) may be mixed as a radically polymerizable monomer. Such a photosensitive resin composition is preferable in that these monomers are involved in photopolymerization. Among these, 2-hydroxyethyl (meth) acrylamide is preferable from the viewpoint of compatibility with the photosensitive resin (A) and copolymerization at the time of curing.

  When using a monomer (E), it is preferable to mix | blend in the range of 50 mass parts or less with respect to 100 mass parts of photosensitive resin (A), Most preferably, it is the range of 30 mass parts or less. By setting it as such a range, the tack before photocuring resulting from a low molecular weight thing can be suppressed.

  The photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the photosensitive resin (A) and the monomer (E). Examples of the radical polymerizable compound include a radical polymerizable resin and a radical polymerizable monomer.

  As the radical polymerizable resin, unsaturated polyester, urethane acrylate, polyester acrylate, or the like can be used.

  As the radical polymerizable monomer, either a monofunctional monomer (one radical polymerizable double bond) or a polyfunctional monomer (two or more radical polymerizable double bonds) can be used. Since the radically polymerizable monomer is involved in photopolymerization, it can be used as a solvent for various reactions in addition to improving the properties of the resulting cured product, and can further adjust the viscosity of the photosensitive resin composition. . The preferable usage-amount in the case of using a radically polymerizable monomer is 300 mass parts or less with respect to 100 mass parts of photosensitive resin (A), More preferably, it is 150 mass parts or less.

  As radical polymerizable monomers, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-chlorophenyl) ) Maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tribromophenyl) maleimide, N -[3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2,4,6-trichlorophenyl) N) such as maleimide, N- (4-hydroxyphenyl) maleimide Substituted maleimide group-containing monomers; aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, diallyl phthalate, diallylbenzenephosphonate; vinyl acetate, Vinyl ester monomers such as vinyl adipate; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) ) Acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, (Meth) acrylic such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acryloyloxyethyl] triazine, dendritic acrylate Monomer: n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether (Hydroxy) alkyl vinyl (thio) ethers such as 2-ethylhexyl vinyl ether and 4-hydroxybutyl vinyl ether; 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxy) (meth) acrylate ) Vinyl having a radical polymerizable double bond such as ethyl, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate (thio) ) Ether; monomers containing acid anhydride groups such as maleic anhydride or monomers obtained by ring-opening modification of acid anhydride groups with alcohols, amines, water, etc .; N-vinylpyrrolidone, N-vinyloxazolidone N-vinyl monomers such as allyl alcohol, triallyl Examples thereof include compounds having one or more double bonds capable of radical polymerization such as cyanurate.

  These are suitably selected according to the use and required characteristics of the photosensitive resin composition, and can be used alone or in combination of two or more.

  From the viewpoint of workability when the composition of the present invention is applied to a substrate, a solvent may be blended in the composition. The solvent is not particularly limited as long as it does not hinder the reaction or cause deterioration of each component of the raw material. The hydrocarbons, esters, alcohols, ketones, ethers, amides, sulfoxides described above Various solvents, such as a kind, are mentioned, These 1 type (s) or 2 or more types can be mixed and used.

  If necessary, the photosensitive resin composition of the present invention further includes a filler such as talc, clay, barium sulfate, an antifoaming agent, a coupling agent, a leveling agent, a sensitizer, a release agent, a lubricant, a plasticizer. Known additives such as agents, antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners, metal organic acid salts, inorganic salts, or chelate compounds may be added.

  Among these, the addition of a metal organic acid salt, an inorganic salt, or a chelate compound improves the physical properties after post-curing. Among these, metal chelate compounds are preferable, and for example, compounds described in JP-A No. 2004-177498 (0035) and (0036) are listed, and those of Al, Ti, and Zn are particularly preferable as metal atoms.

  These chelate compounds are used as one type or a mixture of two or more types, and 0.01-100 parts by mass with respect to 100 parts by mass in total of the photosensitive resin (A), the polymer (B), and the aforementioned radical polymerizable compound. It is preferably contained, more preferably 0.1 to 50 parts by mass. By using in this range, it is useful in both cured product characteristics and economy.

  When using the photosensitive resin composition of this invention for image formation, after apply | coating to a base material by a well-known method, a prebaking is performed and a solvent is evaporated and a coating film is formed. Subsequently, after exposing this coating film through a photomask, an unexposed portion is dissolved in an alkaline aqueous solution to perform alkali development. Next, after washing as necessary, post-baking is performed. Thus, a predetermined pattern is formed through application of the composition, pre-baking, exposure, development processing, and post-baking.

  Specific examples of alkalis that can be used for development include alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; ammonia; monomethylamine and dimethylamine Water-soluble organic amines such as trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, These 1 type (s) or 2 or more types can be used.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the present invention are within the technical scope of the present invention. Is included. In the following description, “part” represents “part by mass” and “%” represents “mass%” unless otherwise specified.

Synthesis Example 1: Synthesis of photosensitive resin solution 1 (acid-modified epoxy acrylate type) Cresol novolak type epoxy resin “YDCN-704” (manufactured by Tohto Kasei, epoxy equivalent 207.1) in 207.1 parts, acrylic acid 73 parts, 186 parts of propylene glycol monomethyl ether acetate, 0.8 part of triphenylphosphine, and 0.03 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl are added to obtain a homogeneous solution. It was made to react for time, and it confirmed that the acid value of the reaction material was set to 7.2 mgKOH / g. Next, 66 parts of tetrahydrophthalic anhydride was added to this solution and reacted at 100 ° C. for 5 hours. A propylene glycol monomethyl ether acetate solution 1 containing 65% of a photosensitive resin (acid-modified epoxy acrylate type) having an acid value of 81 mg / KOH was obtained.

Synthesis Example 2: Synthesis of photosensitive resin solution 2 (acid-modified epoxy acrylate type) 207.1 parts of the same cresol novolac type epoxy resin “YDCN-704” used in Synthesis Example 1 with 73 parts of acrylic acid and propylene glycol Add 178 parts of monomethyl ether acetate, 0.8 part of triphenylphosphine, 0.03 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl to make a homogeneous solution, and react at 120 ° C. for 15 hours. The acid value of the reaction product was confirmed to be 7.3 mg KOH / g. Next, 51 parts of succinic anhydride was added to this solution and reacted at 100 ° C. for 5 hours. A propylene glycol monomethyl ether acetate solution 2 containing 65% of a photosensitive resin (acid-modified epoxy acrylate type) having an acid value of 98 mg / KOH was obtained.

Synthesis Example 3: Synthesis of photosensitive resin solution 3 (modified copolymer type) 260 parts of propylene glycol monomethyl ether acetate as a solvent in a vessel equipped with a stirrer, thermometer, reflux condenser, gas introduction tube and dropping funnel After charging and replacing the inside of the container with nitrogen gas, the container was heated with stirring until the internal temperature reached 110 ° C. Separately, two dropping funnels were prepared, one of which was 113.1 parts N-phenylmaleimide, 141.6 parts 2-hydroxyethyl methacrylate, 45.3 parts styrene, and 200 parts propylene glycol monomethyl ether acetate as a solvent. The solution obtained by mixing was charged. Another example is 6 parts of 2,2′-azobis (2-methylbutyronitrile) [V-59; manufactured by Wako Pure Chemical Industries, Ltd.] as a polymerization initiator and 60 parts of propylene glycol monomethyl ether acetate as a solvent. A solution obtained by partial mixing was charged.

  The temperature in the container was maintained at 110 ° C., and the solutions in the two dropping funnels were each dropped over 2 hours for polymerization in a nitrogen atmosphere. After completion of the dropping, the solution was aged at 110 ° C. for 3 hours. After completion of the aging, the introduced gas was switched from nitrogen to a mixed gas of nitrogen / air = 1/1 (vol.%), Heated to 120 ° C. and maintained for 1 hour to deactivate the polymerization initiator.

  A solution containing 36.6% of a copolymer of N-phenylmaleimide: 2-hydroxyethyl methacrylate: styrene = 30: 50: 20 (molar ratio) was obtained. The weight average molecular weight of this polymer was 45,000.

  Subsequently, as a carboxyl group introduction reaction, 149 parts of tetrahydrophthalic anhydride and 0.24 part of benzyltriethylammonium chloride as a catalyst were added, and at 120 ° C. under a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). The reaction was performed for 4 hours. A solution containing 46.3% of a copolymer into which a carboxyl group having an acid value of 122 mgKOH / g was introduced was obtained.

  Next, as a double bond introduction reaction, 100 parts of the copolymer solution introduced with this carboxyl group, 4.12 parts of glycidyl methacrylate, 0.03 part of methylhydroquinone, 0.02 part of benzyltriethylammonium chloride, propylene 1.03 parts of glycol monomethyl ether acetate was charged, and an unsaturated double bond introduction reaction was performed by reacting at 110 ° C. for 6 hours in a mixed gas atmosphere of nitrogen / air = 1/1 (vol.%). A propylene glycol monomethyl ether acetate solution 3 containing 48% of a photosensitive resin (modified copolymer type) having an acid value of 81 mg / KOH was obtained.

Synthesis Example 4: Synthesis of Photosensitive Resin Solution 4 (Acid-Modified Epoxy Acrylate Type) 207.1 parts of the same cresol novolac type epoxy resin “YDCN-704” used in Synthesis Example 1 with 73 parts of acrylic acid and propylene glycol Add 202 parts of monomethyl ether acetate, 0.8 part of triphenylphosphine, 0.03 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl to obtain a homogeneous solution, and react at 120 ° C. for 15 hours. The acid value of the reaction product was confirmed to be 6.9 mgKOH / g. Next, 95 parts of succinic anhydride was added to this solution and reacted at 100 ° C. for 5 hours. A propylene glycol monomethyl ether acetate solution 4 containing 65% of a photosensitive resin (acid-modified epoxy acrylate type) having an acid value of 152 mg / KOH was obtained.

Synthesis Example 5: Synthesis of polymer having amide group and hydroxyl group 60 parts of propylene glycol monomethyl ether as a solvent was charged in a container equipped with a stirrer, a thermometer, a reflux condenser, a gas introduction pipe and a dropping funnel. After replacing with nitrogen gas, the mixture was heated with stirring until the internal temperature reached 90 ° C. Separately, two dropping funnels were prepared, and one of them was 44 parts of N-phenylmaleimide, 43.9 parts of N-hydroxyethylacrylamide, 112.1 parts of benzylmaleimide, and t-butylperoxy-2 as a polymerization initiator. -A solution obtained by mixing 10 parts of ethylhexanoate [Perbutyl O; manufactured by NOF Corporation] and 120 parts of propylene glycol monomethyl ether acetate as a solvent was charged. Another solution was prepared by mixing 6 parts of n-dodecyl mercaptan as a chain transfer agent and 20 parts of propylene glycol monomethyl ether acetate as a solvent.

  The temperature in the container was maintained at 90 ° C., and the solutions in the two dropping funnels were each dropped over 2 hours for polymerization in a nitrogen atmosphere. After completion of the dropping, the solution was aged at 90 ° C. for 3 hours. After completion of aging, the introduced gas was switched from nitrogen to a mixed gas of nitrogen / air = 1/1 (vol.%), Heated to 110 ° C. and maintained for 3 hours to deactivate the polymerization initiator.

  N-phenylmaleimide: N-hydroxyethylacrylamide: benzyl methacrylate = 20: 30: 50 (molar ratio) solution containing 50.0% of a polymer having an amide group and a hydroxyl group (propylene glycol monomethyl ether and propylene glycol monomethyl ether) A mixed solvent of acetate) was obtained. The weight average molecular weight of this polymer was 7,000.

Examples 1-6 and Comparative Examples 1-3
Using the resin solutions obtained in Synthesis Examples 1 to 5, photosensitive resin compositions having the composition shown in Table 1 were prepared (numbers are parts by mass). Evaluation was performed by the following method, and the results are shown in Table 1.

[Developability]
Each photosensitive resin composition was spin-coated on a glass substrate (dry film thickness of about 5 μm) and pre-dried at 80 ° C. for 5 minutes. Thereafter, the film was immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 30 seconds, and the remaining degree of the coating film was evaluated according to the following criteria.
○: Completely developed.
X: Deposits remain.

[Photocurability]
The dry coating film obtained in the same manner as in the evaluation of developability was irradiated with 200 mJ / cm ² of ultraviolet rays using an ultraviolet exposure device. Then, it was immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 60 seconds and washed with water. After air drying, photocurability was evaluated according to the following criteria.
○: No peeling on the coating film.
X: There exists peeling in a coating film.

[Adhesion]
The dry coating film obtained in the same manner as in the evaluation of the developability was irradiated with 200 mJ / cm ² of ultraviolet rays through a pattern mask using an ultraviolet exposure device. Then, it was immersed in 1% sodium carbonate aqueous solution at 30 ° C. for 60 seconds to dissolve the uncured resin, and then washed with water. After air drying, it was post-baked at 230 ° C. for 1 hour and 2 hours, and the adhesion was evaluated by pattern shape observation based on the following criteria.
A: There is no defect in the pattern after 2 hours of post-baking.
◯: There is no defect in the pattern after 1 hour of post baking, but there is a defect after 2 hours of post baking.
X: There is a defect in the pattern after 1 hour of post-baking.

表１から明らかなように、本発明の感光性樹脂組成物（実施例１〜６）は、現像性、光硬化性、塗膜の密着性において優れており、単量体（Ｅ）やキレート化合物を添加することでさらに密着性が向上することが判る。

As is clear from Table 1, the photosensitive resin compositions of the present invention (Examples 1 to 6) are excellent in developability, photocurability, and adhesion of the coating film, and are monomer (E) or chelate. It can be seen that the adhesion is further improved by adding the compound.

  On the other hand, a resin composition not containing a polymer having an amide group and a hydroxyl group in one molecule (Comparative Examples 1 and 2), or a resin composition using a high acid value resin even if this polymer is contained (Comparative Example) In 3), the coating film had poor adhesion.

  The photosensitive resin composition of this invention has confirmed that it was excellent in developability, photocurability, and the adhesiveness of a cured coating film. Therefore, the photosensitive resin composition of the present invention is an alkali-developable photosensitive resin composition for image formation, such as liquid crystal displays such as printing plate making, color filter protective film, color filter, black matrix, and photo spacer. It can be suitably used for various applications such as for plate production.

Claims (4)

Photosensitive resin (A) having an acid value of 20 to 140 mgKOH / g having one or more radically polymerizable unsaturated bonds and one or more carboxyl groups in one molecule, one or more amide groups and one in one molecule A photosensitivity comprising a polymer (B) having at least one hydroxyl group and a weight average molecular weight of 1,000 to 100,000 measured by gel permeation method, and a photopolymerization initiator (C). Resin composition. The photosensitive resin composition according to claim 1, wherein the photosensitive resin (A) is an acid-modified epoxy acrylate. The photosensitive resin composition according to claim 1, wherein the photosensitive resin (A) is a modified copolymer. The photosensitive resin composition according to claim 1, further comprising a colorant (D).