Reactive polycarboxylic acid compound, active energy ray-curable resin composition comprising same, cured product thereof, and use thereof

Abstract

The purpose of the present invention is to provide: an active energy ray-curable resin composition which allows for patterning by photolithography and has a low outgassing amount; and a cured product thereof.　The present invention was arrived at upon finding that the problem is solved by a resin composition comprising a reaction product of a specific epoxy resin, an unsaturated group-containing carboxylic acid and a specific polybasic acid anhydride.

Description

Reactive polycarboxylic acid compound, active energy ray curable resin composition using the same, cured product thereof, and uses thereof

[0001] The present invention relates to a novel reactive polycarboxylic acid compound (A), an active energy ray-curable resin composition containing the same, and a cured product thereof. In particular, the present invention relates to a novel reactive polycarboxylic acid compound suitable as a resist material that can also be used as a material for display devices such as organic EL display elements, an active energy ray-curable resin composition containing the same, and a cured product thereof.

[0002] Organic EL display elements, which utilize the electroluminescence of organic compounds, have many features, such as being self-luminous and not dependent on the viewing angle, having a fast response speed, and being able to be made thin and lightweight, and are therefore being actively developed for use in image display devices.

[0003] BACKGROUND ART Photolithographic pattern formation techniques are used to produce components of display devices such as organic EL displays, such as partition walls and planarizing layers, and active energy ray-curable resin compositions are used.

[0004] International Publication No. 2018 / 101314

[0005] In recent years, there has been a problem that outgassing from active energy ray-curable resin materials contaminates devices and manufacturing equipment, and therefore, there is a need for the development of active energy ray-curable resin materials with low outgassing. Therefore, an object of the present invention is to provide an active energy ray-curable resin composition that can be patterned by photolithography and has low outgassing, and a cured product thereof.

[0006] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that a resin composition using a reaction product of a specific epoxy resin with an unsaturated group-containing carboxylic acid and a specific polybasic acid anhydride solves the above-mentioned problems, and have arrived at the present invention.

[0007] That is, the present invention relates to the following: [1] A reactive polycarboxylic acid compound (A) obtained by reacting a reactive epoxy carboxylate compound (c) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, with a polybasic acid anhydride (d) represented by the following formula (2), the reactive polycarboxylic acid compound (A) having an acid value of solid content of 20 to 120 mg KOH / g:

[0008] (In the formula, n represents an average value and is a number from 0 to 10. G represents a glycidyl group.)

[0009]

[0010] [2] The reactive polycarboxylic acid compound (A) according to [1], wherein the carboxylic acid compound (b) is a monomer. [3] An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to [1] or [2]. [4] The active energy ray-curable resin composition according to [3], comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A). [5] The active energy ray-curable resin composition according to [3] or [4], comprising a photopolymerization initiator. [6] The active energy ray-curable resin composition according to [3] or [4], which is a material for a display device. [7] A cured product of the active energy ray-curable resin composition according to [3] or [4].

[0011] The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention can provide a cured resin product that has excellent developability, can be patterned by photolithography, and has a low outgassing amount.

[0012] The present invention will be described in detail below. The reactive polycarboxylic acid compound (A) of the present invention can be obtained by reacting an epoxy resin (a) having a structure represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule to obtain a reactive epoxy carboxylate compound (c), and then reacting the resulting compound with a polybasic acid anhydride (d) represented by the following formula (2):

[0013]

[0014] In the above formula (1), n ​​represents an average value and is a number from 0 to 10.

[0015] G represents a glycidyl group.

[0016]

[0017] First, the carboxylation step for imparting reactivity to a carboxylate compound to obtain a reactive epoxy carboxylate compound (c) will be described.

[0018] The epoxy resin (a) used in the present invention is an epoxy resin represented by the formula (1). Epoxy resins represented by the formula (1) are generally available under various trade names, such as EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 manufactured by Nippon Kayaku Co., Ltd., Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-690, Epicron N-695, Epicron N-665-EXP, and Epicron N-672-EXP manufactured by DIC Corporation, and YDCN-700-7, YDCN-700-10, YDCN-704, and YDCN-704A manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0019] In the present invention, a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule (hereinafter also referred to simply as "carboxylic acid compound (b)") is reacted to impart reactivity to actinic rays. There are no limitations on the number of ethylenically unsaturated groups and carboxyl groups, as long as there is at least one in the molecule.

[0020] Examples of the carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound, and the like, and the compound is preferably a monomer. Examples of the (meth)acrylic acids mentioned above include monocarboxylic acid compounds containing one carboxy group per molecule, such as (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, half esters which are equimolar reaction products of saturated or unsaturated dibasic acid anhydrides with (meth)acrylate derivatives having one hydroxyl group per molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids with monoglycidyl (meth)acrylate derivatives, as well as polycarboxylic acid compounds having multiple carboxy groups per molecule, such as half esters which are equimolar reaction products of (meth)acrylate derivatives having multiple hydroxyl groups per molecule, and half esters which are equimolar reaction products of saturated or unsaturated dibasic acids with glycidyl (meth)acrylate derivatives having multiple epoxy groups. Of these, (meth)acrylic acid is preferred.

[0021] Among these, in consideration of the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), the carboxylic acid compound (b) is preferably a monocarboxylic acid, and even when a monocarboxylic acid and a polycarboxylic acid are used in combination, the value expressed as the molar amount of the monocarboxylic acid / the molar amount of the polycarboxylic acid is preferably at least 15. Most preferred are (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, and cinnamic acid in terms of sensitivity when made into an active energy ray-curable resin composition.

[0022] The ratio of the epoxy resin (a) to the carboxylic acid compound (b) used in this carboxylation reaction should be appropriately adjusted depending on the intended use. That is, when all epoxy groups are carboxylated, no unreacted epoxy groups remain, resulting in a reactive epoxy carboxylate compound (c) with high storage stability. In this case, only the reactivity of the introduced double bond is utilized.

[0023] On the other hand, by reducing the amount of carboxylic acid compound (b) charged and leaving unreacted residual epoxy groups, it is possible to utilize the reactivity of the introduced unsaturated bond and the reaction of the residual epoxy groups, such as a polymerization reaction by a photocationic catalyst or a thermal polymerization reaction, in combination. However, in this case, care should be taken in examining the storage and production conditions of the reactive epoxy carboxylate compound (c).

[0024] When producing a reactive epoxy carboxylate compound (c) that does not leave any residual epoxy groups, the total amount of carboxylic acid compound (b) is preferably 90 to 120 equivalent percent relative to 1 equivalent of epoxy resin (a). This range allows production under relatively stable conditions. Adding more carboxylic acid compound than this is not preferred because excess carboxylic acid compound (b) and compound (c) remain.

[0025] Furthermore, when epoxy groups are to remain, the total amount of the carboxylic acid compound (b) is preferably 20 to 90 equivalent percent relative to 1 equivalent of the epoxy resin (a). Outside this range, the combined curing effect is diminished. Of course, in this case, sufficient care must be taken to prevent gelation during the reaction and to ensure the stability of the reactive epoxy carboxylate compound (c) over time.

[0026] The carboxylation reaction can be carried out without a solvent or by diluting with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

[0027] The amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but is preferably used so that the solid content is 90 to 20% by mass, more preferably 80 to 30% by mass.

[0028] Specific examples include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and mixtures thereof such as petroleum ether, white gasoline, and solvent naphtha, as well as ester solvents, ether solvents, and ketone solvents.

[0029] Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate.

[0030] Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran.

[0031] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0032] In addition, the curing can be carried out in a single organic solvent or a mixed organic solvent containing a reactive compound (B) other than the reactive polycarboxylic acid compound (A) described later (hereinafter, also simply referred to as "reactive compound (B)"), etc. In this case, when used as a curable resin composition, it can be used directly as a composition, which is preferable.

[0033] A catalyst is preferably used during the reaction to promote the reaction, and the amount of catalyst used is 0.1 to 10 parts by mass per 100 parts by mass of the total amount of reactants, i.e., epoxy resin (a), carboxylic acid compound (b), and optionally solvents and other components. The reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.

[0034] Furthermore, a thermal polymerization inhibitor may also be used, and examples of the thermal polymerization inhibitor that can be preferably used include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-tert-butyl-4-hydroxytoluene.

[0035] The carboxylation reaction is terminated when the acid value of the sample reaches 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling as appropriate.

[0036] The reactive epoxy carboxylate compound (c) thus obtained preferably has a weight average molecular weight, as measured by GPC in terms of polystyrene, of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. When the weight average molecular weight, as measured by GPC in terms of polystyrene, is in the range of 500 to 50,000, the cured product can exhibit sufficient toughness and good coatability.

[0037] If the molecular weight is smaller than this range, the toughness of the cured product will not be sufficient, and if it is larger than this range, the viscosity will be too high, making coating difficult.

[0038] Next, the acid addition step (hereinafter also referred to simply as "this acid addition reaction") will be described in detail. The acid addition step is carried out for the purpose of introducing a carboxy group, if necessary, into the reactive epoxy carboxylate compound (c) obtained in the previous step to obtain a reactive polycarboxylic acid compound (A). That is, a carboxy group is introduced via an ester bond by addition reaction of the polybasic acid anhydride (d) represented by the above formula (2) (hereinafter also referred to simply as "polybasic acid anhydride (d)").

[0039] The reactive polycarboxylic acid compound (A) of the present invention is synthesized using the polybasic acid anhydride (d) of the above formula (2). In some cases, other polybasic acid anhydrides (d) may be added. In this case, examples of the polybasic acid anhydride (d) include trimellitic anhydride and hydrogenated trimellitic anhydride. It is more preferable to add only the polybasic acid anhydride represented by the above formula (2).

[0040] The reaction of adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount of addition should be appropriately changed depending on the application.

[0041] For example, when the reactive polycarboxylic acid compound (A) of the present invention is used as an alkaline aqueous solution developable resist material, the amount of polybasic acid anhydride (d) added is preferably calculated so that the solids acid value (based on JIS K5601-2-1:1999) of the final reactive polycarboxylic acid compound (A) is preferably 20 to 120 mg KOH / g, more preferably 30 to 110 mg KOH / g, and even more preferably 35 to 100 mg KOH / g. When the solids acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good alkaline aqueous solution developability. In other words, there is good patterning property, a wide control range for overdevelopment, and no excess acid anhydride remains.

[0042] A catalyst is preferably used during the reaction to promote the reaction. The amount of catalyst used is 0.1 to 10 parts by mass based on the total amount of reactants, i.e., the epoxy compound (a), the reactive epoxy carboxylate compound (c) obtained from the carboxylic acid compound (b), and the polybasic acid anhydride (d), optionally including a solvent and other components. The reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.

[0043] This acid addition reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. Furthermore, when a solvent is used in the preceding carboxylation reaction, the product can be directly subjected to the subsequent acid addition reaction without removing the solvent, provided that the solvent is inert for both reactions. The solvent that can be used may be the same as that used in the carboxylation reaction.

[0044] The amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but is preferably used so as to be 70 to 30% by mass, more preferably 60 to 40% by mass, based on the solid content.

[0045] In addition, the reaction can be carried out in a single or mixed organic solvent of the reactive compound (B), etc. In this case, when used as a curable resin composition, it can be used directly as a composition, which is preferable.

[0046] It is preferable to use the same thermal polymerization inhibitors as those exemplified in the carboxylation reaction.

[0047] The acid addition reaction is terminated when the acid value of the reaction product falls within a range of ±10% of the set acid value, while sampling is carried out as appropriate.

[0048] The reactive polycarboxylic acid compound (A) thus obtained preferably has a weight average molecular weight, measured by GPC (gel permeation chromatography) in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000, in terms of polystyrene.

[0049] If the molecular weight is smaller than this range, the toughness of the cured product will not be sufficient, and if it is larger than this range, the viscosity will be too high, making coating difficult.

[0050] Specific examples of the reactive compound (B) that can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, other cationic reaction type epoxy compounds, and vinyl compounds that react with both of these.

[0051] Examples of acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, as well as epoxy acrylates, polyester acrylates, and urethane acrylates.

[0052] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0053] Examples of polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of an ε-caprolactone adduct of hydroxypivalic acid neopen glycol; poly(meth)acrylate of a reaction product of dipentaerythritol and ε-caprolactone; dipentaerythritol poly(meth)acrylate; trimethylolpropane tri(meth)acrylate; triethylolpropane tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate and its ethylene oxide adduct; dipentaerythritol hexa(meth)acrylate and its ethylene oxide adduct.

[0054] Usable vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

[0055] Furthermore, examples of so-called reactive oligomers include urethane acrylates which have both a functional group sensitive to active energy rays and a urethane bond in the same molecule, polyester acrylates which similarly have both a functional group sensitive to active energy rays and an ester bond in the same molecule, epoxy acrylates which are derived from epoxy resins and have both a functional group sensitive to active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

[0056] The cation-reactive monomer is not particularly limited as long as it is a compound generally having an epoxy group. Examples thereof include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., "Cyracure UVR-6110" manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" manufactured by Union Carbide), limonene dioxide (e.g., "Celloxide 3000" manufactured by Daicel Chemical Industries, Ltd.), and methyl glycidyl ether. Examples of epoxy cyclohexenes include 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (e.g., "Cyracure UVR-6128" manufactured by Union Carbide), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, and bis(3,4-epoxycyclohexyl)diethylsiloxane.

[0057] Of these, radical curing acrylates are most preferred as the reactive compound (B). In the case of cationic types, a two-component mixture is required because the carboxylic acid and the epoxy group react with each other.

[0058] The active energy ray-curable resin composition of the present invention can be obtained by mixing the reactive polycarboxylic acid compound (A) of the present invention with another reactive compound (B). At this time, other components may be added as appropriate depending on the application.

[0059] The active energy ray-curable resin composition of the present invention contains 97 to 5 parts by mass, preferably 87 to 10 parts by mass, of a reactive polycarboxylic acid compound (A) and 3 to 95 parts by mass, more preferably 3 to 90 parts by mass, of another reactive compound (B). If necessary, the composition may contain 0 to 80 parts by mass of other components.

[0060] In addition, in order to adapt the active energy ray-curable resin composition of the present invention to various applications, other components may be added to the composition in an amount of up to 70 parts by weight, such as a photopolymerization initiator, other additives, coloring materials, a thermosetting catalyst, and a volatile solvent added to adjust viscosity for the purpose of imparting coatability, etc.

[0061] The active energy ray-curable resin composition of the present invention can further contain a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator or a cationic photopolymerization initiator. Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and the like. Examples of known general radical photopolymerization initiators include anthraquinones such as quinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0062] Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine-based initiators, borate-based initiators, and other photoacid generators.

[0063] Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (e.g., San-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphonate (e.g., Cyracure UVI-6990 manufactured by Union Carbide) and triphenylsulfonium hexafluoroantimonate (e.g., Cyracure UVI-6974 manufactured by Union Carbide). Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate.

[0064] Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (e.g., Trigonal PI manufactured by AKZO Corporation), 2,2-dichloro-1-4-(phenoxyphenyl)ethanone (e.g., Sandray 1000 manufactured by Sandoz Corporation), and α,α,α-tribromomethylphenyl sulfone (e.g., BMPS manufactured by Seitetsu Kagaku Co., Ltd.). Triazine initiators include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (e.g., Triazine A manufactured by Panchim Corporation), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (e.g., Triazine PMS manufactured by Panchim Corporation), and 2,4-trichloromethyl-(pipronyl)-6-triazine (e.g., Triazine PMS manufactured by Panchim Corporation). Examples of suitable bis(trichloromethyl)-s-triazine include Triazine PP manufactured by Panchim, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B manufactured by Panchim, etc.), 2[2'(5-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd., etc.), and 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

[0065] Examples of the borate-based photopolymerization initiator include NK-3876 and NK-3881 manufactured by Nippon Kanko Dyes Co., Ltd., and other examples of the photoacid generator include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (e.g., Biimidazole manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis(2-amino-propane) dihydrochloride (e.g., V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane]dihydrochloride (e.g., V50 manufactured by Wako Pure Chemical Industries, Ltd.), and 2,2-azobis[2-(imidazolin-2-yl)propane]dihydrochloride (e.g., V50 manufactured by Wako Pure Chemical Industries, Ltd.). [eta-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,eta)-(methylethyl)-benzene]iron(II) hexafluorophosphonate (Irgacure 261 manufactured by CibaGeigy, etc.), and bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyr-1-yl)phenyl]titanium (CGI-784 manufactured by CibaGeigy, etc.).

[0066] In addition, azo-based initiators such as azobisisobutyronitrile, heat-sensitive peroxide-based radical initiators such as benzoyl peroxide, etc. may be used in combination. Also, both radical and cationic photopolymerization initiators may be used in combination. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0067] Among these, radical photopolymerization initiators are particularly preferred in consideration of the properties of the reactive polycarboxylic acid compound (A) of the present invention.

[0068] Furthermore, the active energy ray-curable resin composition of the present invention may contain a coloring pigment. Examples of the coloring pigment include those not intended for coloring, so-called extender pigments. Examples of the coloring pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, and carbon black.

[0069] Furthermore, the active energy ray-curable resin composition of the present invention may contain other additives as needed, such as a thermosetting catalyst such as melamine, a thixotropy-imparting agent such as Aerosil, a silicone-based or fluorine-based leveling agent or antifoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, etc.

[0070] In addition, resins that do not exhibit reactivity to active energy rays (so-called inert polymers) can also be used, such as other epoxy resins, phenolic resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof, which are preferably used in an amount of up to 40 parts by mass in the resin composition.

[0071] In particular, when using a reactive polycarboxylic acid compound (A) for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not exhibit reactivity to active energy rays. This is because carboxy groups derived from the reactive polycarboxylic acid compound (A) remain even after reaction and curing with active energy rays, resulting in poor water resistance and hydrolysis resistance of the cured product. Therefore, by using an epoxy resin, the remaining carboxy groups are further carboxylated, forming a stronger crosslinked structure. The known general epoxy resin can use the above-mentioned cation-reactive monomer.

[0072] Depending on the intended use, a volatile solvent may be added to the resin composition in an amount of up to 50 parts by mass, more preferably up to 35 parts by mass, for the purpose of adjusting the viscosity.

[0073] The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and laser beams, and particle beams such as alpha rays, beta rays, and electron beams. Among these, ultraviolet rays, laser beams, visible light, and electron beams are preferred in consideration of the preferred uses of the present invention.

[0074] In the present invention, the material for a display device is a material used in display elements such as liquid crystal display devices, organic EL devices, and electronic paper. Specific applications include spacers, protective films, planarizing films, interlayer insulating films, and partition materials. Among these, the display device according to one embodiment of the present invention is preferably an organic EL device.

[0075] The present invention also includes a cured product obtained by irradiating the above-mentioned curable resin composition with active energy rays, and also includes a multi-layer material having a layer of the cured product.

[0076] Furthermore, it is also preferable to use the unreacted reactive polycarboxylic acid compound (A) as an alkaline water developable resist material composition by taking advantage of the characteristic that the unreacted reactive polycarboxylic acid compound (A) is soluble in an alkaline aqueous solution.

[0077] In the present invention, the resist material composition refers to an active energy ray-sensitive composition that is prepared by forming a coating layer of the composition on a substrate, then partially irradiating the substrate with active energy rays such as ultraviolet rays, and utilizing the difference in physical properties between the irradiated and unirradiated areas to perform patterning. Specifically, the composition is used for the purpose of removing the irradiated or unirradiated areas by some method, such as dissolving them with a solvent or alkaline solution, and then performing patterning.

[0078] The active energy ray-curable resin composition, which is a resist material composition of the present invention, can be applied to various materials that can be patterned. For example, it is particularly useful as a solder resist material and an interlayer insulating material for a build-up method, and can also be used as an optical waveguide in electrical, electronic, and optical substrates such as printed wiring boards, optoelectronic substrates, and optical substrates.

[0079] Particularly suitable applications include photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, color resists, color filters, black matrices, and other applications requiring a resin composition, taking advantage of the properties of good heat resistance and developability.

[0080] Furthermore, the resin composition can also be suitably used for a resin composition for an insulating layer of a multilayer printed wiring board (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed wiring board in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer), a resin composition for plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition), etc.

[0081] Patterning using the active energy ray-curable resin composition of the present invention can be carried out, for example, as follows: A coating film can be formed by applying the curable resin composition of the present invention to a substrate in a film thickness of 0.1 to 200 μm by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, or spin coating, and drying the coating film at a temperature of usually 50 to 110° C., preferably 60 to 100° C. Thereafter, high-energy rays such as ultraviolet rays are irradiated directly or indirectly onto the coating film through a photomask having an exposure pattern formed thereon at a dose of usually 10 to 2000 mJ / cm. ２ The desired pattern can be obtained by irradiating the film with an intensity of about 1000 nm and using a developer described below, for example, by spraying, immersing with vibration, puddling, brushing, or the like.

[0082] The aqueous alkali solution used for the development may be an inorganic aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, etc., or an organic aqueous alkali solution such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, etc. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0083] In addition, it is particularly suitable for use in dry films that require mechanical strength before a curing reaction with active energy rays. That is, since the balance between the hydroxyl group and the epoxy group in the epoxy resin (a) used in the present invention is within a specific range, the reactive polycarboxylic acid compound (A) of the present invention can exhibit good developability despite having a relatively high molecular weight.

[0084] The method for forming the film is not particularly limited, and any of various coating methods can be used, including intaglio printing methods such as gravure, relief printing methods such as flexography, stencil printing methods such as silk screen printing, lithographic printing methods such as offset printing, and methods using a roll coater, knife coater, die coater, curtain coater, spin coater, etc.

[0085] The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays and curing it.

[0086] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, % means % by mass unless otherwise specified.

[0087] The softening point, epoxy equivalent, and acid value were measured under the following conditions. 1) Epoxy equivalent: Measured according to a method in accordance with JIS K7236:2001. 2) Softening point: Measured according to a method in accordance with JIS K7234:1986. 3) Acid value: Measured according to a method in accordance with JIS K0070:1992. 4) GPC (gel permeation chromatography) measurement conditions are as follows: Model: TOSOH HLC-8220GPC Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C Detector: RI (differential refractometer) Molecular weight standard: Polystyrene

[0088] Synthesis Example 1: Synthesis of reactive epoxy carboxylate compound (c) 218 ​​g of cresol novolac epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., softening point 92°C, epoxy equivalent 218 g / eq.) and 72.0 g of acrylic acid (AA) as carboxylic acid compound (b) were added. 1.25 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 70 mass%, and the mixture was reacted at 100°C for 24 hours to obtain a reactive epoxy carboxylate compound (c) solution.

[0089] (Example 1-1): Preparation of reactive polycarboxylic acid compound (A-1) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 2.61 g of maleic anhydride as the polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 50%, and an acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-1) solution with a solid acid value of 38.0 mg KOH / g. The solid acid value (mg KOH / g) was measured as a solution and converted to a value based on the solid content.

[0090] (Example 1-2): Preparation of reactive polycarboxylic acid compound (A-2) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 4.08 g of maleic anhydride as the polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 50%, and an acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-2) solution with a solid acid value of 60.0 mg KOH / g. The solid acid value (mg KOH / g) was measured as a solution and converted to a value based on the solid content.

[0091] (Example 1-3): Preparation of reactive polycarboxylic acid compound (A-3) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 7.19 g of maleic anhydride as the polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 50%, and an acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-3) solution with a solid acid value of 98.0 mg KOH / g. The solid acid value (mg KOH / g) was measured as a solution and converted to a value based on the solid content.

[0092] (Comparative Example 1-1): Preparation of reactive polycarboxylic acid compound (A-4) To 50.0 g of the reactive epoxy carboxylate compound (c) solution obtained in Synthesis Example 1, 4.11 g of phthalic anhydride as the polybasic acid anhydride (d) and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content was 50%, and an acid addition reaction was carried out at 100°C to obtain a reactive polycarboxylic acid compound (A-4) solution with a solid acid value of 40.6 mg KOH / g. The solid acid value (mg KOH / g) was measured as a solution and converted to a value based on the solid content.

[0093] (Example 3 and Comparative Example 3): Preparation of resin composition and evaluation of developability, evaluation of outgassing amount 2.00 g of the reactive polycarboxylic acid compound (A) obtained in Examples 1-1 to 1-3 and Comparative Example 1-1, 0.67 g of DPHA (trade name: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.) as another reactive compound (B), 0.08 g of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator, and 1.63 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added and dispersed uniformly to obtain a resin composition.

[0094] Each evaluation item will be described in detail.

[0095] Evaluation of developability (abbreviation in the table: developability) The above resin composition was applied to a glass substrate using a spin coater, and then dried for 5 minutes in a hot air dryer at 80°C. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution (spray pressure 0.2 MPa), and the time until the coating film completely dissolved, the so-called break time, was used to evaluate the developability (unit: seconds). ×...Swelling peeling: For "swelling peeling", if the coating film swelled and peeled during development rather than being dissolved and developed, it was evaluated as × rather than the break time. For developability, a development time of 30 seconds or less is preferred.

[0096] Evaluation of outgassing amount (abbreviations in the table: outgassing) The photosensitive resin composition was applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Nippon Mining & Metals Corporation) using an applicator to a thickness of 10 μm, and the coating film was dried in a hot air dryer at 80°C for 30 minutes. After that, it was irradiated with an ultraviolet ray (manufactured by GS YUASA: CS 30L-1) at 500 mJ / cm ２ Thereafter, the copper foil was removed with iron (III) chloride 45° Baume (manufactured by Junsei Chemical Co., Ltd.) to obtain a cured product.

[0097] The cured product was heated in a heating oven at 230°C for 30 minutes, and the amount of outgassing was measured using a P&T-GC (purge and trap gas chromatograph) according to the following analytical method: Measuring equipment: P&T / JTD-505III (manufactured by Japan Analytical Industry) GC / G1530A (manufactured by Agilent Technologies) Purge: 230°C / 30 min Trap: -40°C Column: HP-5MS 30 m x 0.25 mm i.d. , df = 0.25 μm (manufactured by Agilent Technologies) Carrier gas: He 1.2 mL / min (Constant flow mode) Detector temperature: 300°C Oven: 50°C (2 min) - 300°C (13 min), temperature increase 10°C / min Injection: Split (10:1) Detector: FID (manufactured by Agilent Technologies) Sample amount: 4 mg

[0098] Next, the components of the outgassed cured product were analyzed using a thermal desorption GC-MS (gas chromatograph mass spectrometer) according to the following method. Measuring equipment: Thermal desorption / JCI-22 (manufactured by Japan Analytical Industry) GC-MS / JMS-Q1500GC (manufactured by JEOL) Column: HP-5MS 30 m x 0.25 mm i.d., df = 0.25 μm (manufactured by Agilent Technologies) Carrier gas: He 1.0 mL / min (constant flow mode) Thermal desorption temperature: 315°C Thermal desorption time: 15 sec. Oven: 50°C (2 min) - 300°C (3 min), temperature increase 10°C / min Injection: Split (30:1) Ionization: EI

[0099] Thermal desorption GC-MS revealed that polybasic acid anhydride (d) was generated as outgassing derived from the reactive polycarboxylic acid compound (A). The peak area of ​​the peak assigned to polybasic acid anhydride (d) was determined by P&T-GC and used as an index of the amount of outgassing (Area / mg).

[0100]

[0101] An FID detector, which is sensitive to carbon atoms, was used to quantify the amount of outgassing. To compare the outgassing amounts of different polybasic acid anhydrides (d), the concept of relative sensitivity (effective carbon number) in the FID detector was introduced. Specifically, the peak area was divided by the total effective carbon number of the corresponding polybasic acid anhydride (d) measured by the FID detector, and the amount of outgassing was calculated. The amount of outgassing divided by the effective carbon number of the polybasic acid anhydride is shown in Table 3. The effective carbon number was calculated from the type and number of functional groups in Table 2, which was compiled based on the following reference: (Reference: Umezawa Yoshio, Sawada Tsuguro, Nakamura Hiroshi (eds.); "Latest Separation, Purification, and Detection Methods," NTS (1997), p. 35).

[0102]

[0103] In addition, since the acid value of the reactive polycarboxylic acid compound (A) used in each example and comparative example was different, the amount of outgassing per acid value was calculated and shown in Table 3.

[0104]

[0105] From the above results, it can be said that the active energy ray-curable resin composition using the reactive polycarboxylic acid compound (A) of the present invention has a smaller amount of outgassing per acid value and is also excellent in developability, compared to the comparative resin composition.

Claims

1. A reactive polycarboxylic acid compound (A) is obtained by reacting a reactive epoxy carboxylate compound (c) obtained by reacting an epoxy resin (a) represented by the following formula (1) with a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and then reacting the resulting reactive epoxy carboxylate compound (c) with a polybasic acid anhydride (d) represented by the following formula (2), the reactive polycarboxylic acid compound (A) having an acid value of solid content of 20 to 38.0 mg KOH / g. 【Chemistry 1】 (In the formula, n represents an average value and is a number from 0 to 10. G represents a glycidyl group.) 【Chemistry 2】

2. The reactive polycarboxylic acid compound (A) according to claim 1, wherein the carboxylic acid compound (b) is a monomer.

3. An active energy ray-curable resin composition comprising the reactive polycarboxylic acid compound (A) according to claim 1.

4. The active energy ray-curable resin composition according to claim 3 , further comprising a reactive compound (B) other than the reactive polycarboxylic acid compound (A).

5. An active energy ray-curable resin composition comprising a reactive polycarboxylic acid compound (A) having a solid acid value of 20 to 120 mg KOH / g, and dipentaerythritol hexaacrylate as a reactive compound (B) other than the reactive polycarboxylic acid compound (A), the reactive polycarboxylic acid compound (A) being obtained by reacting a carboxylic acid compound (b) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule with an epoxy resin (a) represented by the following formula (1): 【Transformation 3】 (In the formula, n represents an average value and is a number from 0 to 10. G represents a glycidyl group.) 【Chemistry 4】

6. The active energy ray-curable resin composition according to claim 4 or claim 5, further comprising a photopolymerization initiator.

7. The active energy ray-curable resin composition according to claim 4 or 5, which is a material for a display device.

8. A cured product of the active energy ray-curable resin composition according to claim 4 or 5.

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