JP7682134B2 - Unsaturated group-containing polycarboxylic acid resin and its production method, photosensitive resin composition containing unsaturated group-containing polycarboxylic acid resin and cured product thereof - Google Patents

Description

The present invention relates to an unsaturated group-containing polycarboxylic acid resin and its production method, a photosensitive resin composition containing an unsaturated group-containing polycarboxylic acid resin, and a cured product thereof.

In recent years, printed wiring boards have been required to be highly accurate and dense in order to make mobile devices smaller and lighter and to improve communication speeds. As a result, the requirements for the solder resist that covers the circuit itself have become increasingly strict, and there is now a demand for excellent adhesion to the substrate while maintaining even greater heat resistance and thermal stability than was previously required, which has created a demand for film-forming materials with tougher curing properties.

As one of these materials, a carboxylate compound obtained by reacting a general epoxy resin with a carboxylic acid, a compound having a hydroxyl group, and acrylic acid is known as a material that has a low acid value but excellent developability. As examples of these, compositions have been proposed that use a resin 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 (Patent Document 1, Patent Document 2, and Patent Document 3). Although these photosensitive resin compositions have excellent developability, they do not satisfy the ever-increasing demand for heat resistance.

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 is large, generating stress, which may cause cracks.

Special Publication No. 7-67008 Special Publication No. 7-17737 Patent No. 2598346 JP 2020-83968 A

The objective of the present invention is to provide a resin composition and its cured product that has excellent photosensitivity to active energy rays, can form a pattern of fine images by development with a dilute alkaline aqueous solution, and produces a cured film that satisfies the low cure shrinkage, adhesion, and heat resistance required for a solder mask.

The present invention has been made in view of the above-mentioned current situation, and is useful for various applications. The present invention aims to provide a resin composition and its cured product, which is obtained by reacting a polyamide-imide resin (a3) having terminal acid groups or acid anhydride groups obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic anhydride (a2) with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c), and which has excellent photosensitivity to active energy rays, can form a pattern of fine images by development with a dilute alkaline aqueous solution, and the obtained cured film satisfies the low cure shrinkage, adhesion, and heat resistance required for a solder mask.

That is, the present invention relates to the following [1] to [8].
[1] An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamide-imide 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).
[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] The photosensitive resin composition according to claim 4 or 5, which is used 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 polyamideimide resin (a3) having a terminal acid group or an acid anhydride group, and reacted simultaneously.

The present invention provides a resin composition and its cured product that have excellent photosensitivity to active energy rays, can form a pattern of fine images by development with a dilute alkaline aqueous solution, and can form a cured film with low cure shrinkage, excellent adhesion, and heat resistance.

The unsaturated group-containing polycarboxylic acid resin (A) in the present invention is obtained by reacting a polyamide-imide resin (a3) having terminal acid groups or acid anhydride groups, 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).

That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced by two reaction steps. First, a cyclic isocyanurate-type polyisocyanate (a1) is reacted 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.

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.

Diisocyanates containing alicyclic diisocyanate compounds include, for example, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.

The trimerization catalyst is not particularly specified, but 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).

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

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, and cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride. Among these, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which has excellent tackiness and cure shrinkage, is preferred.

In the reaction between the alicyclic isocyanurate type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2), the total of the acid anhydride group and the carboxylic acid is preferably 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and even more preferably 1.4 mol to 2.6 mol per mol of isocyanate group in the alicyclic isocyanurate type polyisocyanate (a1). When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the remaining of the isocyanate group is prevented, the increase in molecular weight is suppressed, and the developability is improved. When the total of the acid anhydride group and the carboxylic acid is less than 3.0 mol, the remaining of the alicyclic tricarboxylic anhydride is prevented, and the development residue can be suppressed.

The amide-imidization process is carried out in a solvent-free or hydroxyl-free organic solvent, specifically, for example, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dialkyl ethers such as ethyl acetate, 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 ethers such as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether, and ethylene glycol monoalkyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and triethylene glycol monobutyl ether acetate; propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and dipropylene glycol Polypropylene glycol monoalkyl ether acetates such as 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) that do not have hydroxyl groups among the crosslinking agents (B) described below, can be reacted alone or in a mixed organic solvent.

The amide-imidization reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate polyisocyanates (a1) with one or more of the alicyclic tricarboxylic anhydrides (a2) in a solvent or without a solvent, and then heating the mixture while stirring.

The reaction temperature for 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 using such a reaction temperature, the reaction rate is increased. In the reaction, the anhydride group and the isocyanate group form an imide group accompanied by decarboxylation, and the carboxylic acid group and the isocyanate form an amide group. During the reaction, an antioxidant, a leveling agent, an antifoaming agent, a surfactant, etc. can be used as necessary.

The progress of the reaction can be tracked by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. In the infrared spectrum, the characteristic absorption of isocyanate groups at 2250 cm ⁻¹ decreases with the reaction, and the acid anhydride groups having characteristic absorptions at 1860 cm ⁻¹ and 850 cm ⁻¹ decrease. Meanwhile, the absorption of imide groups at 1780 cm ⁻¹ and 1720 cm ⁻¹ increases. It is preferable to allow the reaction to proceed until the characteristic absorption of isocyanate groups at 2250 cm ⁻¹ disappears, as this makes it easier to control the reaction.

The preferred molecular weight range of the polyamideimide resin (a3) having terminal acid groups or acid anhydride groups obtained by the reaction of the cyclic isocyanurate polyisocyanate (a1) with the alicyclic tricarboxylic anhydride (a2) is a weight average molecular weight 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.

Next, the carboxylation step will be described in detail.
As the (meth)acrylate (b) having an epoxy group 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. Also, 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.

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 viewpoints 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, it is preferable that 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 in the range of 0.05 to 1.5, and more preferably 0.1 to 1.2.

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

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 polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), and a step (2) of 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 in the step (1). In the step (2), it is preferable to add 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) all at once to the polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group and react them simultaneously.

During the reaction, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount 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 polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, and the aliphatic dicarboxylic anhydride or 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.

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 per 100 parts by mass of the total amount of the reaction mixture of the polyamide-imide 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 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 catalysts 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.

The carboxylation step can be carried out without a solvent or by diluting with an organic solvent. Examples of the organic solvent include the same solvents as those exemplified in the amide-imidization step.

The reaction temperature for 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.

It is preferable to allow the reaction to proceed until the epoxy equivalent (solid epoxy equivalent) is 10,000 g/eq or more. The solid epoxy equivalent is measured by the 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 be calculated from the epoxy equivalent of the solution.

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 a weight average molecular weight in terms of polystyrene measured by GPC of 1,500 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 2,500 to 15,000.

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).

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

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, vinyl compounds that react with both, maleimide compounds, and other compounds.

Radical reaction type acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

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.

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, adipic acid 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 hydroxypivalic acid neopentyl glycol ε-caprolactone adduct, poly(meth)acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, etc.

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), and 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, and the like. oxide (such as "Celloxide 3000" manufactured by Daicel Chemical Industries), 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 (such as "Cyracure UVR-6128" manufactured by Union Carbide), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, etc.

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.

There is no particular limitation on the maleimide compounds, so long as they have one or more maleimide groups in the molecule. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5 -diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 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-diphenylmethanebiscyclo Examples of the maleimide compounds represented by formula (6) include citraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethane maleimide, and polyphenylmethane maleimide; maleimide compounds represented by formula (7); fluorescein-5-maleimide; and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

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.

In formula (1), R ₁ 's each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

In formula (2), _R2 each independently represents a hydrogen atom or a methyl group, and _n2 represents an integer of 1 or more, preferably an integer of 1 to 5.

In formula (3), each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; each l ₂ independently represents an integer of 1 to 3; and n ₃ independently represents an integer of 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.

The crosslinking agent (B) may be used alone or in a mixture of two or more. The content of these in the photosensitive resin composition is usually 2 to 40% by mass, preferably 3 to 30% by mass, when the solid content of the photosensitive resin composition is taken as 100% by mass.

The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention can be used without any particular limitation, and specific examples thereof 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. , anthraquinones such as 2-tertiary butyl anthraquinone, 2-chloro anthraquinone, 2-amyl anthraquinone, etc.; thioxanthones such as 2,4-diethyl thioxanthone (for example, DETX-S described in the examples below), 2-isopropyl thioxanthone, 2-chloro thioxanthone, etc.; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, etc.; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. The photopolymerization initiator (C) can be used alone or in a mixture of two or more kinds. The content ratio of these in the photosensitive resin composition is usually 1 to 30% by mass, preferably 2 to 25% by mass, when the solid content of the photosensitive resin composition is 100% by mass.

These photopolymerization initiators (C) can be used alone or as a mixture of two or more kinds, 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 relative to the photopolymerization initiator (C).

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 and oxazine compounds. The curing agent (D) reacts with the carboxyl groups and hydroxyl groups 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 with stronger chemical resistance.

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, etc.

Examples of the phenol novolac type epoxy resin include Epiclon N-770 (manufactured by DIC Corporation), D.E.N438 (manufactured by The 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.).

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).

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), D.E.R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (both 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 (both manufactured by Nippon Kayaku Co., Ltd.).

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.).

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.

Specific examples of the oxazine compound as the curing agent (D) include B-m type benzoxazine, P-a type benzoxazine, and B-a type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.).

The curing agent (D) may be used alone or in a mixture of two or more. The content in the photosensitive resin composition is usually 5 to 50% by mass, preferably 5 to 40% by mass, when the solid content of the photosensitive resin composition is 100% by mass. If the amount is less than this amount, the resulting cured product is likely to be weak, and if the amount is too much, it may have an adverse effect on the curability, etc. due to a problem of balance with the epoxy curing agent described below.

The curing agent (D) may be mixed in advance with the photosensitive resin composition of the present invention, but it can also be mixed and used before application to a printed wiring board. In other words, a base solution mainly made of the component (A) and containing an epoxy curing accelerator, etc., and a curing agent solution mainly made of the curing agent (D) are mixed into a two-liquid type, and these are mixed when used.

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, phosphate ester resins such as phosphazene resins and 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.

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.

Furthermore, resins that do not show reactivity to active energy rays (so-called inert polymers) may be contained. Examples of such resins include epoxy resins other than the epoxy resin 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. These may be contained in the active energy ray curable resin composition of the present invention in an amount of up to 40% by mass in the active energy ray curable resin composition.

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

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.

The present invention also includes the use of the photosensitive resin composition as a material for forming a film for electrical insulation. That is, this includes materials that require electrical insulation, such as solder resist materials for circuit boards, insulating molding materials, interlayer insulating materials, semiconductor protective film materials, and wiring coating materials.

The present invention also includes the use of the active energy ray curable resin composition as an active energy ray sensitive resist material in which a coating layer of the composition is formed on a substrate, and then the substrate is partially irradiated with active energy rays such as ultraviolet rays, and drawing is performed by utilizing the difference in physical properties between the irradiated and unirradiated areas. In other words, the irradiated or unirradiated areas are removed by some method, for example, by dissolving them with a solvent or an alkaline solution, and then the composition is used for the purpose of drawing.

The present invention also includes the photosensitive resin composition used in a permanent resist. A permanent resist is not one of the resist materials described above that is used on the premise that it will be peeled off after drawing, but rather is a material that maintains its purpose and function without being peeled off until the substrate is actually used.

The photosensitive resin composition for resists of the present invention can be applied to various materials that require patterning, and is particularly useful as a solder resist material or an interlayer insulating material for build-up construction methods. It can also be used as an optical waveguide in printed wiring boards, optoelectronic boards, optical boards, and other electrical, electronic, and optical substrates.

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 insulating layers of multilayer printed wiring boards (multilayer printed wiring boards in which a cured product of a photosensitive resin composition is used as an insulating layer), a resin composition for interlayer insulating layers (multilayer printed wiring boards in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer), or a resin composition for plating (multilayer printed wiring boards 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.

In addition, the product has good developability and can produce a cured product with excellent heat resistance and adhesion. Taking advantage of this property, the product is suitable for use in solder resist applications and interlayer insulating layer applications, which require insulating reliability, and can maximize the effects of the present invention.

There are no particular limitations on the method for forming the film, but any of a variety of coating methods can be used, including gravure and other intaglio printing methods, flexography and other letterpress printing methods, silk screen and other screen printing methods, offset and other planographic printing methods, and methods using a roll coater, knife coater, die coater, curtain coater, spin coater, etc.

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

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, parts are by weight unless otherwise specified.

The epoxy equivalent and acid value were measured under the following conditions.
1) Epoxy equivalent (WPE): Measured according to a method in accordance with JIS K 7236:2001.
2) Acid value: Measured according to a method in accordance with JIS K 0070:1992.
3) The measurement conditions for 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

Production Example 1
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (1) solution was obtained, which had a number average molecular weight of 1,250 and a weight average molecular weight of 4,040 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 164 mgKOH/g. The mixture was cooled to 60°C, and 494.5g of carbitol acetate, 170.4g of glycidyl methacrylate, 154.0g of hexahydrophthalic anhydride, and 2.27g of dibutylhydroxytoluene were added and stirred, and then 2.27g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I) having a solid acid value of 94.1mgKOH/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 measured to be 13,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 2
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (2) solution was obtained, which had a number average molecular weight of 1,290 and a weight average molecular weight of 3,590 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 155 mgKOH/g. The mixture was cooled to 60°C, and 537.5g of carbitol acetate, 198.8g of glycidyl methacrylate, 154.0g of hexahydrophthalic anhydride, and 2.38g of dibutylhydroxytoluene were added and stirred, and then 2.38g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin II) having a solid acid value of 92.2mgKOH/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 11,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 3
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (3) solution was obtained, which had a number average molecular weight of 1,260 and a weight average molecular weight of 4,120 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 159 mgKOH/g. The mixture 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 heated to 116° C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III) having a solid acid value of 85.9 mg KOH/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 measured to be 14,000 g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 4
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (4) solution was obtained, which had a number average molecular weight of 1,190 and a weight average molecular weight of 3,850 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 151 mgKOH/g. The mixture was cooled to 60°C, and 494.8g of carbitol acetate, 170.4g of glycidyl methacrylate, 154.0g of hexahydro-4-methylphthalic anhydride, and 2.44g of dibutylhydroxytoluene were added and stirred, and then 2.44g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV) having a solid acid value of 95.8mgKOH/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 measured to be 12,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 5
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,300 and a weight average molecular weight of 3,690 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 152 mgKOH/g. The mixture was cooled to 60°C, and 491.7g of carbitol acetate, 170.4g of glycidyl methacrylate, 152.2g of 1,2,3,6-tetrahydrophthalic anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (V) having a solid acid value of 97.9mgKOH/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. The epoxy equivalent was measured to be 14,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 6
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (6) solution was obtained, which had a number average molecular weight of 1,250 and a weight average molecular weight of 3,680 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 161 mgKOH/g. The mixture 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. Then, 1.90 g of triphenylphosphine was added and the temperature was raised to 116° C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I′) having a solid acid value of 19.2 mg KOH/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 measured to be 13,000 g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 7
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (7) solution was obtained, which had a number average molecular weight of 1,180 and a weight average molecular weight of 3,860 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 154 mgKOH/g. The mixture 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 mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II') having 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.

Production Example 8
Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line were added 646.3 g of carbitol acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. Cooled to 60 ° C., 97.58 g of pentaerythritol (tri / tetra) acrylate mixture (Daicel Allnex "PETRA", hydroxyl value 115 mg KOH / g) was added, heated to 116 ° C., and reacted at the same temperature for 10 hours to obtain an amide imide resin (8) solution having a number average molecular weight of 1,070, a weight average molecular weight of 3,080, and a solid acid value of 135 mg KOH / g by gel permeation chromatography using polystyrene as a standard. Cooled to 60 ° C., 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 dibutyl hydroxytoluene 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 to obtain an unsaturated group-containing polycarboxylic acid resin (III') having an acid value of 82.1 mgKOH/g solid content, 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, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 9
250.3 g of carbitol acetate, 435.7 g of cresol novolac type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218 g/eq) and 1.75 g of dibutylhydroxytoluene were added to a four-neck flask equipped with a stirrer, a thermometer and a condenser, and the mixture was stirred at 80°C to dissolve the epoxy resin. Then, 148.4 g of acrylic acid and 1.75 g of triphenylphosphine were added, and the mixture was heated to 116°C and reacted at the same temperature for 12 hours to obtain a reactive exicarboxylate resin (9) solution with a solid acid value of 2.2 mg KOH/g and an epoxy equivalent of 13 kg/eq. The mixture was cooled to 60°C, and 48.6 g of carbitol acetate and 113.5 g of 1,2,3,6-tetrahydrophthalic anhydride were added, and the mixture was heated to 100°C. The reaction was continued at the same temperature for 5 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV') having an acid value of 61.2 mgKOH/g of solid content, 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, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 10
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,310 and a weight average molecular weight of 3,810 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 152 mgKOH/g. The mixture was cooled to 60°C, and 338.6g of carbitol acetate, 142.0g of glycidyl methacrylate, 79.2g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VI) having a solid acid value of 87.1mgKOH/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. The epoxy equivalent was measured to be 16,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 11
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 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. 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. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,260 and a weight average molecular weight of 3,600 by gel permeation chromatography using polystyrene as a standard, and a solid acid content of 156 mg KOH/g. The mixture was cooled to 60°C, and 441.4g of carbitol acetate, 170.4g of glycidyl methacrylate, 118.8g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VII) having a solid acid value of 80.6mgKOH/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. The epoxy equivalent was measured to be 14,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Examples 1 to 5, Comparative Examples 1 to 4
The unsaturated group-containing polycarboxylic acid resins obtained in 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.

注
＊１ 日本化薬（株）製：ε－カプロラクトン変性ジペンタエリスリトールヘキサアクリレート
＊２ ＩＧＭＲｅｓｉｎｓＢ．Ｖ．製：２－メチル－（４－（メチルチオ）フェニル）－２－モルホリノプロパン－１－オン
＊３ 日本化薬（株）製：２，４－ジエチルチオキサントン
＊４ 日鉄ケミカル＆マテリアル（株）製：ビスフェノール－Ａ型エポキシ樹脂
＊５ 北興化学工業（株）製：トリフェニルホスフィン
＊６ 神港有機化学工業（株）製：ジエチレングリコールモノエチルエーテルアセテート

Notes *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 Hokko Chemical Industry Co., Ltd.: triphenylphosphine *6 Shinko Organic Chemical Industry Co., Ltd.: diethylene glycol monoethyl ether acetate

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.

Each evaluation item will be described in detail.
Photosensitivity evaluation (abbreviation in table: photosensitivity)
The resist resin composition was applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) with an applicator to a thickness of 20 μm, and the coating film 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 film, and curing was performed by varying the amount of irradiation using an ultraviolet irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)). Thereafter, spray development was performed using a 1% aqueous sodium carbonate solution as the developer. The amount of irradiation when curing up to the 7th step with the step tablet was used to evaluate the photosensitivity.
○...150mJ/cm2 or ^less ×...150mJ/cm2 or ^more

Developability evaluation (abbreviation in table: developability)
The resist resin composition was applied to a 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. Thereafter, spray development was carried out using a 1% aqueous sodium carbonate solution as a developer. The developability was evaluated based on the time it took for the coating to completely dissolve, the so-called break time.
○: 40 seconds or less △: 41 seconds or more ×: Swelling and peeling

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 film was dried in a hot air dryer at 80° C. for 30 minutes, after which it was irradiated with ultraviolet light at an energy of 500 mJ/cm ² using an ultraviolet irradiator (GS YUASA: CS 30L-1). 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 grain peeling test (JIS K 5400-8.5).
Evaluation criteria: The number of squares on the previous board (100) was used as the denominator, and the number of remaining squares was used as the numerator.
◎ ・・100 squares 〇 ・・81 squares to 99 squares △ ・・80 squares or less

Curl Evaluation (abbreviation in the table: curl)
The resist resin composition was applied to a polyimide film (Toray DuPont: Kapton 100H (thickness 25 μm outer surface)) using a bar coater, and the coating film was dried in a hot air dryer at 80 ° C. for 30 minutes, and then irradiated with ultraviolet light at an energy of 500 mJ / cm ² using an ultraviolet irradiator (GS YUASA: CS 30L-1). Next, it was cured in an oven at 150 ° C. for 30 minutes to obtain a cured film with a film thickness of about 5 μm on the polyimide film. The polyimide film on which the cured film was applied was cut to 5 cm x 5 cm, and the height of each of the four sides that rose on 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. If it is 29 mm or less, it can be said that the curing shrinkage is low.
〇...29mm or less△...30mm or more and 39mm or less×...40mm or more

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 Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried in a hot air dryer at 80 ° C for 30 minutes, and then irradiated with ultraviolet light at an energy of 500 mJ / cm ² using an ultraviolet irradiator (GS YUASA: CS 30L-1). Next, the product was cured in an oven at 150 ° C for 30 minutes to obtain a cured product. The copper foil was removed with iron (III) chloride 45 ° Baume (manufactured by Junsei Chemical Co., Ltd.). The sample from which the cured product was produced was subjected to DMA measurement (TA Instruments: RSA-G2) to determine the temperature at which the storage modulus / loss modulus (= loss tangent) was maximized.

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 Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried in a hot air dryer at 80 ° C for 30 minutes, and then irradiated with ultraviolet light at an energy of 500 mJ / cm ² using an ultraviolet irradiator (GS YUASA: CS 30L-1). Next, the material was cured in an oven at 150 ° C for 30 minutes to obtain a cured product. The copper foil was removed with iron (III) chloride 45 ° Pome (manufactured by Junsei Chemical Co., Ltd.). The temperature at which the weight of the sample produced by preparing the cured product was reduced by 5% was measured using a METTLER TGA / DSC1 in an air flow of 100 ml per minute.

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

The above results confirm 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 also has excellent heat resistance, cure shrinkage, and copper adhesion.

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 (8)

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). The unsaturated group-containing polycarboxylic acid resin (A) according to claim 1, wherein 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. The unsaturated group-containing polycarboxylic acid resin (A) according to claim 1 or 2, wherein the solid content acid value of the unsaturated group-containing polycarboxylic acid resin (A) is 40 to 140 mg KOH/g. 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). The photosensitive resin composition according to claim 4, which is a material for forming a film for insulating purposes. The photosensitive resin composition according to claim 4 for use as a permanent resist. A cured product of the photosensitive resin composition according to claim 4. 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.