Unsaturated group-containing polycarboxylic acid resin and its production method, photosensitive resin composition containing unsaturated group-containing polycarboxylic acid resin and cured product thereof

Abstract

To provide a resin composition which has excellent photosensitivity to active energy rays and can form a fine image pattern by development with a dilute alkaline aqueous solution, in which the resulting cured film satisfies low curing shrinkage, adhesion and heat resistance required for a solder mask, and a cured product of the same.SOLUTION: There is provided an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) with a polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of an alicyclic isocyanurate polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an unsaturated group-containing polycarboxylic acid resin and a method for producing the same, a photosensitive resin composition containing the unsaturated group-containing polycarboxylic acid resin, and a cured product thereof. [Background technology]

[0002] In recent years, there has been a demand for printed wiring boards with higher precision and density in order to make portable devices smaller and lighter and to improve communication speeds. This has resulted in increasingly stringent requirements for the solder resist that covers the circuits themselves, and now solder resists are required to have better heat resistance and thermal stability than before while also providing excellent adhesion to the substrate, creating a demand for film-forming materials with tougher cured properties.

[0003] As such materials, carboxylate compounds obtained by reacting a general epoxy resin with a compound having a carboxylic acid and a hydroxyl group, and acrylic acid are known as materials having excellent developability despite their low acid value, and as examples of these, compositions using resins obtained by reacting a reaction product of a phenol novolac type epoxy resin or a cresol type epoxy resin with an unsaturated monobasic acid with an acid anhydride have been proposed (Patent Documents 1, 2, and 3). Although these photosensitive resin compositions have excellent developability, they do not satisfy the ever-increasing demand for heat resistance.

[0004] On the other hand, a composition using an acid group-containing acrylate resin obtained by reacting a reaction product of an amide-imide resin having a carboxylic acid and an acid anhydride group with a hydroxyl group-containing acrylate compound and an epoxy group-containing acrylate compound with a polycarboxylic acid anhydride and an isocyanate-containing acrylate compound has been proposed as a photosensitive resin composition having excellent heat resistance and adhesion (Patent Document 4). This acid group-containing acrylate resin has good heat resistance compared to conventionally used epoxy acrylate materials, but the shrinkage during curing becomes large, generating stress, which may cause cracks.

[0005] [Patent Document 1] Special Publication No. 7-67008 [Patent Document 2] Special Publication No. 7-17737 [Patent Document 3] Patent No. 2598346 [Patent Document 4] JP 2020-83968 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a resin composition and a cured product thereof which have excellent photosensitivity to active energy rays, which allows for the formation of a pattern of fine images by development with a dilute aqueous alkaline solution, and which produces a cured film which satisfies the low cure shrinkage, adhesion and heat resistance required for a solder mask. [Means for solving the problem]

[0007] The present invention has been made in consideration of the above-mentioned current situation, and is useful for various applications. An object of the present invention is to provide a resin composition and a cured product thereof, which is obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule, and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c), and which has excellent photosensitivity to active energy rays and from which a fine image can be patterned by development with a dilute aqueous alkali solution, and which provides a cured film that satisfies the low cure shrinkage, adhesion and heat resistance required for a solder mask.

[0008] That is, the present invention relates to the following [1] to [8]. [1] An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) to obtain a polyamide-imide resin (a3) ​​having terminal acid groups or acid anhydride groups, with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c). [2] The unsaturated group-containing polycarboxylic acid resin (A) according to [1], in which the molar ratio ((b) / (a2)) of the alicyclic tricarboxylic acid anhydride (a2) to the epoxy group-containing methacrylate compound (b) is 0.8 to 2.0. [3] The unsaturated group-containing polycarboxylic acid resin (A) according to [1] or [2], wherein the acid value of the solid content of the unsaturated group-containing polycarboxylic acid resin (A) is 40 to 140 mg·KOH / g. [4] A photosensitive resin composition comprising the unsaturated group-containing polycarboxylic acid resin (A) according to any one of [1] to [3], a crosslinking agent (B), a photopolymerization initiator (C) and a curing agent (D). [5] The photosensitive resin composition according to [4], which is a film-forming material for insulating purposes. [6] A photosensitive resin composition according to claim 4 or claim 5 for use as a permanent resist. [7] A cured product of the photosensitive resin composition according to any one of [4] to [6]. [8] A method for producing an unsaturated group-containing polycarboxylic acid resin (A), comprising the steps of: A step (1) of reacting an alicyclic isocyanurate polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2); The method includes a step (2) of reacting the polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group obtained in the step (1) with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c), The step (2) is a method for producing an unsaturated group-containing polycarboxylic acid resin (A), characterized in that a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) are added all at once to a polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group, and reacted simultaneously. Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition and a cured product thereof which have excellent photosensitivity to active energy rays, which enable the formation of a pattern of a fine image by development with a dilute alkaline aqueous solution, and which can form a cured film having low cure shrinkage, excellent adhesion, and heat resistance. BEST MODE FOR CARRYING OUT THEINVENTION

[0010] The unsaturated group-containing polycarboxylic acid resin (A) in the present invention is obtained by reacting a polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group, which is obtained by reacting a cyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c).

[0011] That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced by two reaction steps. The first step is to react a cyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) to obtain a polyamide-imide resin (a3). In the present invention, this step is called an amide-imidization step. Next, the resulting polyamide-imide resin (a3) ​​is reacted with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c). In the present invention, this step is referred to as a carboxylation step.

[0012] First, the amide-imidization step will be described in detail. The alicyclic isocyanurate type polyisocyanate (a1) used in the production of the polyamideimide resin (a3) ​​in the present invention can be obtained by isocyanurating a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst.

[0013] Examples of diisocyanates containing alicyclic diisocyanate compounds include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0014] The trimerization catalyst is not particularly specified, and examples thereof include amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate, and quaternary ammonium salts of carboxylic acids. Commercially available products include DABCO P15 (manufactured by Sankyo Air Products), DABCO K15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by Perlon), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), and U-CAT 18X ​​(manufactured by San-Apro).

[0015] Examples of the alicyclic isocyanurate polyisocyanate (a1) include alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from isophorone diisocyanate, alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated tolylene diisocyanate, alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated xylene diisocyanate, isocyanurate triisocyanate (including polymers such as pentamer) synthesized from norbornane diisocyanate, alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated diphenylmethane diisocyanate, etc. Among them, alicyclic isocyanurate isocyanate synthesized from isophorone diisocyanate is preferred. By using an alicyclic isocyanurate type polyisocyanate synthesized from isophorone diisocyanate, it has excellent tackiness and curing shrinkage.

[0016] Examples of the alicyclic tricarboxylic anhydride (a2) used in the production of the polyamideimide resin (a3) ​​in the present invention include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which has excellent tackiness and cure shrinkage, is preferred.

[0017] The reaction between the alicyclic isocyanurate type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) is preferably such that the total of the acid anhydride group and the carboxylic acid is 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and still more preferably 1.4 mol to 2.6 mol, per 1 mol of the isocyanate group possessed by the alicyclic isocyanurate type polyisocyanate (a1). When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the residual of the isocyanate group can be prevented, the increase in molecular weight can be suppressed, and the developability becomes good. When the total of the acid anhydride group and the carboxylic acid is lower than 3.0 mol, the residual of the alicyclic tricarboxylic anhydride can be prevented, and the development residue can be suppressed.

[0018] The amide-imidization step can be carried out in a solventless manner or in an organic solvent not having a hydroxyl group, specifically, for example, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, and other polyethylene glycol monoalkyl ether acetates; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, and other propylene glycol dialkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, and other polypropylene glycol dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and other propylene glycol monoalkyl ether acetates;Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, and tripropylene glycol monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers, and monoacetate monoalkyl ethers of copolymerized polyether glycols; or alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols, and further crosslinking agents (B) not having a hydroxyl group among the crosslinking agents (B) described below, can be reacted alone or in a mixed organic solvent;

[0019] The amide-imidization reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate polyisocyanates (a1) and one or more of the alicyclic tricarboxylic acid anhydrides (a2) in a solvent or without a solvent, and raising the temperature while stirring.

[0020] The reaction temperature of the amide-imidization reaction is preferably in the range of 50°C to 250°C, and particularly preferably in the range of 70°C to 180°C. By setting the reaction temperature in this range, the reaction rate is increased. In the reaction, an anhydride group and an isocyanate group form an imide group while accompanying decarbonation, and a carboxylic acid group and an isocyanate group form an amide group. During the reaction, an antioxidant, a leveling agent, an antifoaming agent, a surfactant, etc. can be used as necessary.

[0021] The progress of the reaction can be followed by analytical means such as infrared spectroscopy, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. In infrared spectroscopy, the characteristic absorption of isocyanate groups at 2250 cm -1 decreases with the reaction and further increases to 1860cm -1and 850cm -1 The acid anhydride group, which has a characteristic absorption at 1780cm, is decreased. -1 and 1720cm -1 The absorption of the imide group increases at 2250 cm, which is the characteristic absorption of the isocyanate group. -1 It is preferable to allow the reaction to proceed until disappearance of the reaction product, since this makes it easier to control the reaction.

[0022] The polyamideimide resin (a3) ​​having terminal acid groups or acid anhydride groups obtained by reacting the cyclic isocyanurate polyisocyanate (a1) with the alicyclic tricarboxylic anhydride (a2) has a preferred molecular weight range, in terms of polystyrene, measured by GPC, of ​​1000 to 20,000, more preferably 1,500 to 15,000, and particularly preferably 2000 to 10,000.

[0023] Next, the carboxylation step will be described in detail. As the (meth)acrylate (b) having epoxy in one molecule used for producing the unsaturated group-containing polycarboxylic acid resin (A) in the present invention, the specific structure is not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. Examples of such compounds include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, a (meth)acrylate compound having one epoxy group is preferred because the reaction is easily controlled, and glycidyl methacrylate and epoxycyclohexylmethyl methacrylate are preferred from the viewpoints of reactivity and curability. In addition, from the viewpoints of cure shrinkage and sensitivity, it is preferred that the molar ratio ((b) / (a2)) of the (meth)acrylate (b) having an epoxy group in one molecule to the alicyclic tricarboxylic anhydride (a2) is in the range of 0.8 to 2.0. It is more preferred that the molar ratio is 0.9 to 1.80, and even more preferred that the molar ratio is 1.0 to 1.5.

[0024] Examples of the aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c) used in the production of the unsaturated group-containing polycarboxylic acid resin (A) in the present invention include succinic anhydride, tetrahydrophthalic anhydride, 1,2-cyclopropane dicarboxylic anhydride, 2,2-dimethylsuccinic anhydride, caronic anhydride, 1,2-cyclohexane dicarboxylic anhydride, butylsuccinic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, n-octylsuccinic anhydride, decylsuccinic anhydride, and dodecylsuccinic anhydride. Examples of the aliphatic tricarboxylic anhydride include tricarboxylic anhydrides having a linear aliphatic structure and tricarboxylic anhydrides having an alicyclic structure. Examples of the tricarboxylic anhydride having a linear aliphatic structure include propane tricarboxylic anhydride. Examples of the tricarboxylic anhydride having an alicyclic structure include the same compounds as those exemplified in the alicyclic tricarboxylic anhydride (a2). Among these, aliphatic dicarboxylic anhydrides are preferred from the viewpoint of electrical properties. Also, tricarboxylic anhydrides having an alicyclic structure are preferred from the viewpoint of alkaline aqueous solution developability, heat resistance, hydrolysis resistance, etc. Cyclohexane-1,3,4-tricarboxylic-3,4-anhydride is more preferred. From the viewpoint of developability and storage stability, the molar ratio ((c) / (b)) of the aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c) and the (meth)acrylate having an epoxy group (b) in one molecule is preferably in the range of 0.05 to 1.5, more preferably 0.1 to 1.2.

[0025] In producing the unsaturated group-containing polycarboxylic acid resin (A), the (meth)acrylate having an epoxy group in one molecule (b) and the aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic acid anhydride (c) may be reacted separately or simultaneously.

[0026] In producing the unsaturated group-containing polycarboxylic acid resin (A), it is preferable to simultaneously react the (meth)acrylate (b) having an epoxy group in one molecule with the aliphatic dicarboxylic acid anhydride or the aliphatic tricarboxylic acid anhydride (c). The method for producing the unsaturated group-containing polycarboxylic acid resin (A) includes a step (1) of reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), and a step (2) of reacting the polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group obtained in the step (1) with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c). In the step (2), the (meth)acrylate compound (b) having an epoxy group in one molecule and the aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) are preferably added all at once to the polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group and reacted simultaneously.

[0027] During the reaction, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount of the thermal polymerization inhibitor is 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the reaction product obtained by adding the polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, the aliphatic dicarboxylic anhydride or the aliphatic tricarboxylic anhydride (c), and the solvent. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-p-cresol.

[0028] In addition, it is preferable to use a catalyst during the reaction to promote the reaction, and the amount of the catalyst used is 0.05 to 10 parts by mass relative to 100 parts by mass of the total amount of the reaction product obtained by adding the polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, the aliphatic dicarboxylic anhydride or the aliphatic tricarboxylic anhydride (c), and the solvent. The reaction temperature is 60 to 150°C, and the reaction time is preferably 3 to 60 hours. Examples of the catalyst used in this reaction include dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethylsulfide, and diphenylsulfide.

[0029] The carboxylation step can be carried out without a solvent or by diluting with an organic solvent, for example, the same organic solvents as those exemplified in the amide-imidization step.

[0030] The reaction temperature in the carboxylation step is preferably in the range of 60° C. to 160° C., particularly preferably in the range of 70° C. to 150° C., and the reaction time is preferably 3 to 60 hours.

[0031] The reaction is preferably allowed to proceed until the epoxy equivalent (solid epoxy equivalent) is 10,000 g / eq or more. The solid epoxy equivalent is measured by a normal neutralization titration method in accordance with JIS K 7236. In addition, if the concentration of the resin in the solution is known, the solid epoxy equivalent can also be calculated from the epoxy equivalent of the solution.

[0032] The preferred molecular weight range of the unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) is, in terms of polystyrene, 1,500 to 30,000 in terms of weight average molecular weight measured by GPC, more preferably 2,000 to 20,000, and particularly preferably 2,500 to 15,000.

[0033] The photosensitive resin composition contains the unsaturated group-containing polycarboxylic acid resin (A), a crosslinking agent (B), a photopolymerization initiator (C) and a curing agent (D).

[0034] The content of the unsaturated group-containing polycarboxylic acid resin (A) in the photosensitive resin composition is usually 30 to 70 mass%, preferably 40 to 60 mass%, based on 100 mass% of the solid content of the photosensitive resin composition.

[0035] Examples of the crosslinking agent (B) used in the photosensitive resin composition of the present invention include radical reaction type acrylates, cationic reaction type epoxy compounds, and vinyl compounds and maleimide compounds which react with both of these.

[0036] Examples of radical reaction type acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0037] Examples of the 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.

[0038] Examples of the 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 glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, ) acrylate, di(meth)acrylate of an ε-caprolactone adduct of hydroxypivalic acid neopentyl 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 or an ethylene oxide adduct thereof, pentaerythritol tri(meth)acrylate or an ethylene oxide adduct thereof, pentaerythritol tetra(meth)acrylate or an ethylene oxide adduct thereof, dipentaerythritol hexa(meth)acrylate or an ethylene oxide adduct thereof, and the like.

[0039] The cationic reaction type epoxy compounds are not particularly limited as long as they are compounds having an epoxy group, including the epoxy compound (i). Examples of the epoxy compounds 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 diamine, and the like. oxide (Daicel Chemical Industries, Ltd.'s "Celloxide 3000", etc.), allylcyclohexene dioxide, 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 (Union Carbide Corporation's "Cyracure UVR-6128", etc.), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, and the like.

[0040] Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

[0041] The maleimide compounds are not particularly limited as long as they are compounds having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidehexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 1,5-bismaleimidopentane, 1,5-bismaleimido-2-methylpentane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,8-bismaleimido-3,6-dioxaoctane, 1,11-bismaleimido-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,Examples of the maleimide compounds include those represented by formula (6) such as 5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, and polyphenylmethanemaleimide, maleimide compounds represented by formula (7), fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

[0042] As the maleimide compound represented by the following formula (1), a commercially available product may be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. As the maleimide compound represented by the following formula (2), a commercially available product may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the maleimide compound represented by the following formula (3), a commercially available product may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0043] [ka]

[0044] In formula (1), R 1 Each independently represents a hydrogen atom or a methyl group. 1 represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0045] [ka]

[0046] In formula (2), R 2 Each independently represents a hydrogen atom or a methyl group. 2 represents an integer of 1 or more, and preferably an integer of 1 to 5.

[0047] [ka]

[0048] In formula (3), R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; 2 each independently represents an integer of 1 to 3; 3 represents an integer from 1 to 10. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a neopentyl group.

[0049] The crosslinking agent (B) may be used alone or in combination of two or more kinds. The content of these in the photosensitive resin composition is usually 2 to 40% by mass, preferably 3 to 30% by mass, based on 100% by mass of the solid content of the photosensitive resin composition.

[0050] The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention can be used without any particular limitation. Specific examples of the photopolymerization initiator (C) 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-morpholinopropan-1-one (for example, Omnirad-907 described in the Examples below); and 2-ethylanthraquinone. Examples of the photopolymerization initiator (C) include anthraquinones such as 2-tertiary butyl anthraquinone, 2-chloro anthraquinone, and 2-amyl anthraquinone; thioxanthones such as 2,4-diethyl thioxanthone (for example, DETX-S described in the examples below), 2-isopropyl thioxanthone, and 2-chloro thioxanthone; 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. The photopolymerization initiator (C) may be used alone or in a mixture of two or more. The content of these in the photosensitive resin composition is usually 1 to 30% by mass, and preferably 2 to 25% by mass, when the solid content of the photosensitive resin composition is taken as 100% by mass.

[0051] These photopolymerization initiators (C) can be used alone or as a mixture of two or more, and can be used in combination with accelerators such as tertiary amines such as triethanolamine and methyldiethanolamine, and benzoic acid derivatives such as N,N-dimethylaminobenzoic acid ethyl ester and N,N-dimethylaminobenzoic acid isoamyl ester. The amount of these accelerators added is preferably 100% by mass or less based on the photopolymerization initiator (C).

[0052] The curing agent (D) used in the photosensitive resin composition of the present invention can be used. Examples of the curing agent (D) include epoxy compounds, oxazine compounds, etc. The curing agent (D) reacts with the carboxyl group or hydroxyl group remaining in the resin coating film after photocuring by heating, and is particularly preferably used when it is desired to obtain a cured coating film having stronger chemical resistance.

[0053] Specific examples of epoxy compounds as the curing agent (D) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, glyoxal type epoxy resins, naphthalene skeleton-containing epoxy resins, heterocyclic epoxy resins, and the like.

[0054] Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by DIC Corporation), DEN438 (manufactured by Dow Chemical Company), jER154 (manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201, and RE-306 (all manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

[0055] Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by The Dow Chemical Company), jER E1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by The Dow Chemical Company).

[0056] Examples of the bisphenol type epoxy resin include bisphenol-A type epoxy resins such as jER828, jER1001 (both manufactured by Japan Epoxy Resins Co., Ltd.), UVR-6410 (manufactured by Union Carbide Corporation), DER-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.), and bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (all manufactured by Nippon Kayaku Co., Ltd.).

[0057] Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), bixylenol type epoxy resins such as YX-4000 (manufactured by Japan Epoxy Resins Co., Ltd.), and YL-6121 (manufactured by Japan Epoxy Resins Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resins Co., Ltd.).

[0058] Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation). An example of the glyoxal type epoxy resin is GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation), etc. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc.

[0059] Specific examples of the oxazine compound as the curing agent (D) include Bm-type benzoxazine, Pa-type benzoxazine, and Ba-type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.).

[0060] The curing agent (D) may be used alone or in combination of two or more. The content in the photosensitive resin composition is usually 5 to 50 mass%, preferably 5 to 40 mass%, when the solid content of the photosensitive resin composition is 100 mass%. If the amount is less than this amount, the obtained cured product tends to be weak, and if the amount is too much, the curing property may be adversely affected due to the balance with the epoxy curing agent described below.

[0061] The curing agent (D) may be mixed in advance with the photosensitive resin composition of the present invention, but it can also be mixed before application to a printed wiring board. That is, the method is to mix a base solution mainly made of the component (A) and an epoxy curing accelerator, etc., with a two-liquid curing agent solution mainly made of the curing agent (D), and mix them when in use.

[0062] Furthermore, various additives and resins may be used as necessary, for example, a thermosetting catalyst such as melamine, a thixotropy imparting agent such as Aerosil, a silicone-based or fluorine-based leveling agent or defoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, and a flame retardant for imparting flame retardancy. In particular, when used as a film-forming material for electrical insulation, it is preferable to use it in combination with a flame retardant.Preferred flame retardants include known general flame retardants, such as halogen-based flame retardants such as brominated epoxy resins and bromodiphenyl ether, phosphazene resins, phosphoric acid ester resins such as triphenyl phosphate, organic phosphorus-based flame retardants such as dihydro-9-oxa-phosphaphenanthrene-10-oxide derivatives, metal hydroxide-based flame retardants such as magnesium hydroxide, and inorganic flame retardants such as red phosphorus and antimony trioxide.

[0063] The pigment material that may be contained in the photosensitive resin composition of the present invention includes coloring pigments intended for coloring and extender pigments not intended for coloring. Examples of the color pigment include organic pigments such as phthalocyanine, azo and quinacridone pigments, and inorganic pigments such as carbon black and titanium oxide. Examples of the extender pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay, and the like.

[0064] Furthermore, it may contain resins that are not reactive to active energy rays (so-called inert polymers).These resins may include, for example, epoxy resins other than the epoxy resins used as the curing agent, 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 may be contained in the active energy ray curable resin composition of the present invention.These resins are preferably used in the active energy ray curable resin composition in an amount of up to 40% by mass.

[0065] The photosensitive resin composition of the present invention is easily cured by active energy rays. Examples of active energy rays include ultraviolet rays, visible light rays, infrared rays, electromagnetic waves such as X-rays, gamma rays, and laser beams, and particle rays such as alpha rays, beta rays, and electron beams. In consideration of the preferred applications of the present invention, among these, ultraviolet rays, laser beams, visible light, and electron beams are preferred.

[0066] The present invention also includes the use of the photosensitive resin composition as a film-forming material for coating the surface of a substrate, for example, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink, etc., coating materials such as hard coat, top coat, overprint varnish, clear coat, etc., adhesive materials such as adhesives and pressure sensitive adhesives for lamination and optical disks, etc., resist materials such as solder resist, etching resist, resist for micromachine, etc. Furthermore, a so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film, and then the film is attached to the intended substrate to form a film, also falls under the category of film-forming material.

[0067] The present invention also includes the use of the photosensitive resin composition as a material for forming a film for the purpose of electrical insulation, namely, a solder resist material for a circuit board, an insulating molding material, an interlayer insulating material, a semiconductor protective film material, a wiring coating material, and other materials that require electrical insulation.

[0068] The present invention also includes the use of the active energy ray-curable resin composition as an active energy ray-sensitive resist material for 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 portions to perform drawing. That is, the active energy ray-curable resin composition is used for the purpose of removing the irradiated or unirradiated portions by some method, for example, dissolving the irradiated or unirradiated portions with a solvent or an alkaline solution, and then performing drawing.

[0069] The present invention also includes the photosensitive resin composition used for a permanent resist. A permanent resist is one of the resist materials described above that is not intended to be peeled off after drawing, but rather is one that maintains its purpose and function without being peeled off until the substrate is actually used.

[0070] The photosensitive resin composition for resists of the present invention can be applied to various materials requiring patterning, and is particularly useful as a solder resist material, an interlayer insulating material for a build-up method, and can also be used as an optical waveguide in electrical / electronic / optical substrates such as printed wiring boards, optoelectronic boards, and optical boards.

[0071] Particularly suitable applications include a wide range of applications requiring a resin composition, such as 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, and component-embedding resins, taking advantage of the properties of good heat resistance and developability. Among these, it is preferable to use the resin composition as 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), and a resin composition for plating (a multilayer printed wiring board in which plating is formed on a cured product of a photosensitive resin composition). Furthermore, it exhibits good developability even at high pigment concentrations, and can be suitably used as a color resist, a resist material for a color filter, and particularly as a black matrix material.

[0072] Furthermore, taking advantage of the characteristics of good developability and ability to give a cured product having excellent heat resistance and adhesion, the composition can be used in solder resist applications and interlayer insulating layer applications which require insulating reliability, and these applications are suitable because they allow the effects of the present invention to be maximized.

[0073] The method of film formation is not particularly limited, and various coating methods such as gravure printing method like gravure, relief printing method like flexo, stencil printing method like silk screen, lithographic printing method like offset, roll coater, knife coater, die coater, curtain coater, spin coater, etc. can be arbitrarily adopted.

[0074] The present invention also includes a cured product obtained by irradiating the photosensitive resin composition with active energy rays and curing it.

Examples

[0075] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Also, in the examples, parts represent parts by weight unless otherwise specified.

[0076] The epoxy equivalent and acid value were measured under the following conditions. 1) Epoxy equivalent (WPE): Measured by a method according to JIS K 7236:2001. 2) Acid value: Measured by a method according to JIS K 0070:1992. 3) The measurement conditions of gel permeation chromatography (GPC) are as follows. Model: TOSOH HLC-8220GPC Column: TSKGEL Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, temperature 40 °C Detector: Differential refractometer Molecular weight standard: Polystyrene

[0077] Production Example 1 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1 It was confirmed that the absorption of 1,250 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,250, the weight average molecular weight was 4,040, and the solid acid value was 164 mgKOH / g. The solution was cooled to 60°C, and 494.5 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.27 g of dibutylhydroxytoluene were added and stirred, and then 2.27 g of triphenylphosphine was added and heated to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (I) was obtained with a solid acid value of 94.1 mgKOH / g, a (meth)acrylic equivalent of 629, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 5,320. The epoxy equivalent was also measured to be 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0078] Manufacturing Example 2 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 661.2 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 198.0 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,290 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,290, the weight average molecular weight was 3,590, and the solid acid value was 155 mgKOH / g. The solution was cooled to 60°C, and 537.5 g of carbitol acetate, 198.8 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.38 g of dibutylhydroxytoluene were added and stirred, and then 2.38 g of triphenylphosphine was added and heated to 116°C. The reaction was carried out at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin II) was obtained with a solid acid value of 92.2 mgKOH / g, a (meth)acrylic equivalent of 629, a number average molecular weight by GPC of 1,710, and a weight average molecular weight of 4,930. The epoxy equivalent was also measured to be 11,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0079] Production Example 3 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,260 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,260, the weight average molecular weight was 4,120, and the solid acid value was 159 mgKOH / g. The solution was cooled to 60°C, and 448.0 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 123.2 g of hexahydrophthalic anhydride, and 2.17 g of dibutylhydroxytoluene were added and stirred, and then 2.17 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (III) was obtained with a solid acid value of 85.9 mgKOH / g, a (meth)acrylic equivalent of 604, a number average molecular weight by GPC of 1,750, and a weight average molecular weight of 5,500. The epoxy equivalent was also measured to be 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0080] Production Example 4 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,190 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,190, the weight average molecular weight was 3,850, and the solid acid value was 151 mgKOH / g. The solution was cooled to 60°C, and 494.8 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydro-4-methylphthalic anhydride, and 2.44 g of dibutylhydroxytoluene were added and stirred, and then 2.44 g of triphenylphosphine was added and heated to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (IV) was obtained with a solid acid value of 95.8 mgKOH / g, a (meth)acrylic equivalent of 641, a number average molecular weight by GPC of 1,640, and a weight average molecular weight of 4,790. The epoxy equivalent was also measured to be 12,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0081] Production Example 5 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,300 mgKOH / g had disappeared completely. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,300, the weight average molecular weight was 3,690, and the solid acid value was 152 mgKOH / g. The solution was cooled to 60°C, and 491.7 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 152.2 g of 1,2,3,6-tetrahydrophthalic anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued for 20 hours at the same temperature, and an unsaturated group-containing polycarboxylic acid resin (V) was obtained with a solid acid value of 97.9 mgKOH / g, a (meth)acrylic equivalent of 628, a number average molecular weight by GPC of 1,690, and a weight average molecular weight of 4,980. In addition, the epoxy equivalent was measured to be 14,000 g / eq, confirming that the epoxy groups had reacted sufficiently.

[0082] Production Example 6 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,250 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,250, the weight average molecular weight was 3,680, and the solid acid value was 161 mgKOH / g. The solution was cooled to 60°C, and 261.9 g of carbitol acetate, 170.4 g of glycidyl methacrylate, and 1.90 g of dibutylhydroxytoluene were added and stirred, and then 1.90 g of triphenylphosphine was added and heated to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (I') was obtained with a solid acid value of 19.2 mgKOH / g, a (meth)acrylic equivalent of 527, a number average molecular weight by GPC of 1,740, and a weight average molecular weight of 6,950. The epoxy equivalent was also measured to be 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0083] Production Example 7 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,180 mg KOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,180, the weight average molecular weight was 3,860, and the solid acid value was 154 mg KOH / g. The solution was cooled to 60°C, and 494.5 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 148.1 g of phthalic anhydride, and 1.90 g of dibutylhydroxytoluene were added and stirred, and then 1.90 g of triphenylphosphine was added and heated to 116°C. The reaction was continued for 20 hours at the same temperature to obtain an unsaturated group-containing polycarboxylic acid resin (II') with a solid acid value of 99.5 mg KOH / g, a (meth)acrylic equivalent of 624, a number average molecular weight by GPC of 1,630, and a weight average molecular weight of 4,830. The epoxy equivalent was also measured to be 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0084] Production Example 8 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 100 mg KOH / g had completely disappeared. The mixture was cooled to 60°C, and 97.58 g of a mixture of pentaerythritol (tri / tetra)acrylate (Daicel-Allnex Corporation's "PETRA", hydroxyl value 115 mg KOH / g) was added. The mixture was heated to 116°C and reacted at the same temperature for 10 hours to obtain an amide-imide resin (8) solution with a number average molecular weight of 1,070 and a weight average molecular weight of 3,080 measured by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 135 mg KOH / g. The mixture was cooled to 60°C, and 494.8 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydro-4-methylphthalic anhydride, and 2.44 g of dibutylhydroxytoluene were added and stirred, and then 2.44 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III') having a solid acid value of 82.1 mgKOH / g, a (meth)acrylic equivalent of 395, a number average molecular weight by GPC of 1,370, and a weight average molecular weight of 3,700. The epoxy equivalent was measured to be 15,000 g / eq, confirming that the epoxy groups had reacted sufficiently.

[0085] Production Example 9 In a four-neck flask equipped with a stirrer, thermometer, and condenser, 250.3g of carbitol acetate, 435.7g of cresol novolac epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218g / eq), and 1.75g ​​of dibutylhydroxytoluene were added and stirred at 80℃ to dissolve the epoxy resin. Then, 148.4g of acrylic acid and 1.75g ​​of triphenylphosphine were added and the temperature was raised to 116℃, and the reaction was carried out at the same temperature for 12 hours to obtain a reactive exicarboxylate resin (9) solution with a solid acid value of 2.2mg·KOH / g and an epoxy equivalent of 13kg / eq. The solution was cooled to 60℃, and 48.6g of carbitol acetate and 113.5g of 1,2,3,6-tetrahydrophthalic anhydride were added and the temperature was raised to 100℃. The reaction was continued at the same temperature for 5 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV') with a solid acid value of 61.2 mgKOH / g, a (meth)acrylic equivalent of 349, a number average molecular weight by GPC of 2058, and a weight average molecular weight of 6420. The epoxy equivalent was measured to be 13,000 g / eq, confirming that the epoxy groups had reacted sufficiently.

[0086] Manufacturing Example 10 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,310 mgKOH / g had disappeared completely. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,310, the weight average molecular weight was 3,810, and the solid acid value was 152 mgKOH / g. The solution was cooled to 60°C, and 338.6 g of carbitol acetate, 142.0 g of glycidyl methacrylate, 79.2 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued for 20 hours at the same temperature, and an unsaturated group-containing polycarboxylic acid resin (VI) was obtained with a solid acid value of 87.1 mgKOH / g, a (meth)acrylic equivalent of 652, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 6,010. In addition, the epoxy equivalent was measured to be 16,000 g / eq, confirming that the epoxy groups had reacted sufficiently.

[0087] Manufacturing Example 11 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,260 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,260, the weight average molecular weight was 3,600, and the solid acid content was 156 mgKOH / g. The solution was cooled to 60°C, and 441.4 g of carbitol acetate, 170.4 g of glycidyl methacrylate, 118.8 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued for 20 hours at the same temperature, and an unsaturated group-containing polycarboxylic acid resin (VII) was obtained with a solid acid value of 80.6 mgKOH / g, a (meth)acrylic equivalent of 600, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 6,010. In addition, the epoxy equivalent was measured to be 14,000 g / eq, confirming that the epoxy groups had reacted sufficiently.

[0088] Examples 1 to 5, Comparative Examples 1 to 4 The unsaturated group-containing polycarboxylic acid resins obtained in the above Production Examples 1 to 9 were mixed in the proportions shown in Table 1, and then uniformly dispersed in a stirrer to obtain resist resin compositions.

[0089] [Table 1] Note *1 Nippon Kayaku Co., Ltd.: ε-caprolactone modified dipentaerythritol hexaacrylate *2 IGM Resins B.V.: 2-Methyl-(4-(methylthio)phenyl)-2-morpholinopropan-1-one *3 Nippon Kayaku Co., Ltd.: 2,4-diethylthioxanthone *4 Nippon Steel Chemical & Material Co., Ltd.: Bisphenol-A type epoxy resin *5 Triphenylphosphine manufactured by Hokko Chemical Industry Co., Ltd. *6 Shinko Organic Chemical Industry Co., Ltd.: Diethylene glycol monoethyl ether acetate

[0090] Examples 6 to 7 The unsaturated group-containing polycarboxylic acid resins obtained in Production Examples 10 and 11 were mixed in the proportions shown in Table 2, and then uniformly dispersed in a stirrer to obtain resist resin compositions.

[0091] [Table 2]

[0092] Each evaluation item will be described in detail. Photosensitivity evaluation (abbreviation in table: photosensitivity) The resist resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80° C. A step tablet (manufactured by Stouffer: 21 steps) was placed on the dried coating, and the amount of irradiation was adjusted using an ultraviolet irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)) to perform curing. Thereafter, spray development was performed using a 1% aqueous sodium carbonate solution as the developer. The amount of irradiation when the step tablet was used to cure up to the 7th step was used to evaluate the photosensitivity. ○ 150mJ / cm 2 below × 150mJ / cm 2 End

[0093] Developability evaluation (abbreviation in table: developability) The resist resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80° C. Thereafter, spray development was performed using a 1% aqueous sodium carbonate solution as a developer. The time until the coating was completely dissolved, so-called break time, was used to evaluate the developability. ○ 40 seconds or less △ 41 seconds or more × Swelling peeling

[0094] Copper adhesion evaluation (abbreviation in table: copper adhesion) The resist resin composition was applied to a copper-clad laminate ELC-4762 (manufactured by Sumitomo Bakelite) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80°C. After that, it was irradiated with an ultraviolet ray irradiator (GS YUASA: CS 30L-1) at 500 mJ / cm 2 The film was then irradiated with ultraviolet light at an energy of 1000 Hz. It was then cured in an oven at 150°C for 30 minutes to obtain a cured product. The degree of peeling of the cured film was evaluated using a substrate peeling test (JIS K 5400-8.5). Evaluation criteria: The number of stitches on the previous base (100) was used as the denominator and the number of remaining squares was used as the numerator. ◎ 100 squares ○ 81 to 99 squares △ 80 or less squares

[0095] Curl Evaluation (abbreviation in the table: curl) The resist resin composition was applied to a polyimide film (Toray DuPont: Kapton 100H (25 μm thick outer surface)) using a bar coater, and the coating was dried for 30 minutes in a hot air dryer at 80°C. After that, it was irradiated with 500 mJ / cm using an ultraviolet irradiator (GS YUASA: CS 30L-1). 2 The substrate was irradiated with ultraviolet light at an energy of 1000 rpm. It was then cured in an oven at 150°C for 30 minutes to obtain a cured film with a thickness of approximately 5 μm on the polyimide film. The polyimide film on which the cured film had been applied was cut to 5 cm x 5 cm, and the height of each of the four sides that rose above a horizontal table was measured, and the sum of the four sides was measured (unit: mm). The curl of the substrate itself was 0 mm. A curl of 29 mm or less can be said to be low cure shrinkage. 〇 29mm or less △ ···30mm or more and 39mm or less × 40mm or more

[0096] Glass transition temperature measurement (abbreviation in table: Tg) The resist resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80°C. After that, it was irradiated with 500 mJ / cm using an ultraviolet irradiator (GS YUASA: CS 30L-1). 2 The cured material was then cured in an oven at 150°C for 30 minutes to obtain a cured product. The copper foil was removed using ferric chloride (III) 45° Baume (Junsei Chemical Co., Ltd.). The cured material was subjected to DMA measurement (TAInstruments: RSA-G2) for the sample to determine the temperature at which the storage modulus / loss modulus (=loss tangent) was maximized.

[0097] Thermal decomposition resistance evaluation (abbreviation in table: thermal decomposition resistance) The resist resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80°C. After that, it was irradiated with 500 mJ / cm using an ultraviolet irradiator (GS YUASA: CS 30L-1). 2 The cured product was then cured in an oven at 150°C for 30 minutes to obtain a cured product. The copper foil was removed using ferric chloride (III) 45° Pomer (Junsei Chemical Co., Ltd.). A 3 mg sample of the cured product was placed in an air flow of 100 ml per minute and the temperature at which the weight decreased by 5% was measured using a METTLER TGA / DSC1.

[0098] The evaluation results for the above evaluation items are shown in Tables 3 and 4.

[0099] [Table 3]

[0100] [Table 4]

[0101] From the above results, it can be confirmed that the coating film obtained from the resin composition containing the unsaturated group-containing polycarboxylic acid compound (A) of the present invention has excellent sensitivity and developability, and the cured product thereof also has excellent heat resistance, cure shrinkage, and copper adhesion.

[0102] From the above, the photosensitive resin composition using the unsaturated group-containing polycarboxylic acid compound (A) of the present invention is suitable for molding materials, film-forming materials, and resist materials. In particular, since it has excellent sensitivity and developability while also having excellent heat resistance, cure shrinkage, and copper adhesion, it is suitable for a photosensitive material composition for printed wiring boards.

Claims

1. The unsaturated group-containing polycarboxylic acid resin (A) is obtained by reacting a polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group, which is obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule, and only an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c).

2. 2. The composition according to claim 1, wherein the molar ratio ((b) / (a2)) of the alicyclic tricarboxylic anhydride (a2) to the epoxy group-containing methacrylate compound (b) is 0.8 to 2.

0. The unsaturated group-containing polycarboxylic acid resin (A).

3. 3. The unsaturated group-containing polycarboxylic acid resin (A) according to claim 1, wherein the acid value of the solid content of the unsaturated group-containing polycarboxylic acid resin (A) is 40 to 140 mg·KOH / g.

4. 3. A photosensitive resin composition comprising the unsaturated group-containing polycarboxylic acid resin (A) according to claim 1 or 2, a crosslinking agent (B), a photopolymerization initiator (C) and a curing agent (D).

5. 5. The photosensitive resin composition according to claim 4, which is a material for forming a film for insulating purposes.

6. The photosensitive resin composition according to claim 4 for use as a permanent resist.

7. A cured product of the photosensitive resin composition according to claim 4.

8. A method for producing an unsaturated group-containing polycarboxylic acid resin (A), comprising the steps of: A step (1) of reacting an alicyclic isocyanurate polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2); The method includes a step (2) of reacting the polyamide-imide resin (a3) ​​having a terminal acid group or an acid anhydride group obtained in the step (1) with only a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c), The step (2) is a method for producing an unsaturated group-containing polycarboxylic acid resin (A), characterized in that a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) are added all at once to a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, and reacted simultaneously.

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