CN111954849A

CN111954849A - Photosensitive resin composition, cured product, insulating material, resin material for solder resist, and resist member

Info

Publication number: CN111954849A
Application number: CN201980025082.6A
Authority: CN
Inventors: 宫本正纪; 山田骏介
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2018-04-10
Filing date: 2019-03-26
Publication date: 2020-11-17
Also published as: JPWO2019198489A1; TW201943706A; WO2019198489A1; TWI805726B; JP7290150B2

Abstract

The invention provides a photosensitive resin composition, a cured product, an insulating material, a resin material for a solder resist, and a resist member, wherein the photosensitive resin composition comprises: a (meth) acrylate resin (A) having an acid group, and a photopolymerization initiator (B) which is a Michael addition reaction product of a compound (B1) having an alpha-aminoacetophenone skeleton represented by the general formula (1) and functioning as a Michael addition donor, and a reactive compound (B2) functioning as a Michael acceptor. The photosensitive resin composition has high sensitivity, and can form a cured product which has excellent heat resistance and is not easy to generate air exhaust.

Description

Photosensitive resin composition, cured product, insulating material, resin material for solder resist, and resist member

Technical Field

The present invention relates to a photosensitive resin composition which is less likely to generate outgas, a cured product, an insulating material formed from the photosensitive resin composition, a resin material for a solder resist, and a resist member.

Background

In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays have been widely used as resin materials for solder resists for printed circuit boards. Examples of the required properties of the resin material for a solder resist include: curing with a small amount of exposure; excellent alkali developability; the cured product has various excellent properties such as heat resistance, strength, and dielectric properties.

As a conventional resin material for a solder resist, a photosensitive resin composition containing an acid group-containing epoxy acrylate resin obtained by: an epoxy acrylate resin containing an acid group is obtained by reacting a cresol novolak type epoxy resin with acrylic acid and phthalic anhydride to obtain an intermediate, and further reacting the obtained intermediate with tetrahydrophthalic anhydride (for example, see patent document 1).

Further, the photosensitive resin composition has a problem that, during photocuring, thermal curing as needed, or soldering at the time of mounting, a content component such as a photopolymerization initiator volatilizes and vaporizes, and the surrounding exhaust gas is contaminated.

Therefore, a photosensitive resin composition which is excellent in sensitivity and heat resistance in a cured product and is less likely to generate outgas has been demanded.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 8-259663

Disclosure of Invention

Problems to be solved by the invention

The problem to be solved by the present invention is to provide: a photosensitive resin composition which has high sensitivity and excellent heat resistance in a cured product and is less likely to generate outgas, a cured product, an insulating material formed from the photosensitive resin composition, a resin material for a solder resist, and a resist member.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the above problems can be solved by using a photosensitive resin composition containing a (meth) acrylate resin having an acid group and a specific photopolymerization initiator, and the present invention has been completed.

That is, the present invention relates to a photosensitive resin composition, a cured product, an insulating material formed from the photosensitive resin composition, a resin material for a solder resist, and a resist member, the photosensitive resin composition comprising: the photopolymerization initiator (B) is a Michael addition reaction product of a compound (B1) containing an alpha-aminoacetophenone skeleton, which functions as a Michael addition donor, represented by the following general formula (1), and a reactive compound (B2) having a function as a Michael acceptor.

(in the general formula (1),

R¹represents an aliphatic group or an aromatic group,

R²and R³Each independently represents an aliphatic group or an aryl group,

and R²And R³Optionally integrated to form a ring,

R⁴～R⁷each independently represents a hydrogen atom, an aliphatic group or an aryl group,

X¹represents a single bond or a straight-chain or branched alkylene group having 1 to 6 carbon atoms,

X²represents a carbonyl group or a thiocarbonyl group,

Y¹a group represented by the following general formula (2), the following general formula (3) or the following general formula (4),

Y²represents a group represented by the following general formula (2) or the following general formula (3). Wherein, Y¹And Y²When all have the structure represented by the following general formula (2), X represents at least one of them⁵is-NH-.

n is 0 or 1.

(in the general formula (2), X³And X⁴Each independently represents a linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, X⁵Represents a single bond, -O-or-NH-. )

(in the general formula (3), X⁶Represents a substituted or unsubstituted linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, R⁸And R⁹Each independently represents an aliphatic group or an aryl group. )

(in the general formula (4), R¹⁰And R¹¹Each independentlyRepresents an aliphatic group or an aryl group. )

ADVANTAGEOUS EFFECTS OF INVENTION

The photosensitive resin composition of the present invention has high sensitivity and excellent heat resistance in a cured product, and is less likely to cause outgassing, and therefore, can be suitably used for an insulating material, a resin material for a solder resist, and a resist member formed from the resin for a solder resist.

Detailed Description

The photosensitive resin composition of the present invention is characterized by containing: a (meth) acrylate resin (A) containing an acid group, and a photopolymerization initiator (B) represented by the following general formula (1).

(in the general formula (1),

R¹represents an aliphatic group or an aromatic group,

R²and R³Each independently represents an aliphatic group or an aryl group,

and R²And R³Optionally integrated to form a ring,

X²represents a carbonyl group or a thiocarbonyl group,

n is 0 or 1. )

(in the general formula (4), R¹⁰And R¹¹Each independently represents an aliphatic group or an aryl group. )

In the present invention, the "(meth) acrylate resin" means a resin having one or both of an acryloyl group and a methacryloyl group in a molecule. Further, "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group, and "(meth) acrylate" means one or both of an acrylate and a methacrylate.

The acid group-containing (meth) acrylate resin (A) will be described.

The acid group-containing (meth) acrylate resin (a) is not particularly limited as long as it has an acid group and a (meth) acryloyl group, and various resins can be used without particular limitation to other specific structures, molecular weights, and the like.

Examples of the acid group contained in the acid group-containing (meth) acrylate resin (a) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among them, a carboxyl group is preferable in terms of exhibiting excellent alkali developability.

Examples of the acid group-containing (meth) acrylate resin (a) include: an acid group-containing (meth) acrylate resin (A-1) which comprises an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2) and a polycarboxylic acid anhydride (a1-3) as essential reaction raw materials; an acid group-containing (meth) acrylate resin (A-2) which is obtained by using a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic anhydride (a2-4) as essential reaction raw materials; an acid group-containing (meth) acrylate resin (A-3) which comprises, as essential reaction raw materials, an acid group-or acid anhydride group-containing amide imide resin (a3-1), a hydroxyl group-containing (meth) acrylate compound (a3-2), a (meth) acryloyl group-containing epoxy compound (a3-3), and a polycarboxylic anhydride (a 3-4); and the like.

The (meth) acrylate resin (A-1) having an acid group will be described.

The acid group-containing (meth) acrylate resin (A-1) is obtained by using an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2) and a polycarboxylic acid anhydride (a1-3) as essential reaction raw materials.

The specific structure of the epoxy resin (a1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.

Examples of the epoxy resin (a1-1) include bisphenol epoxy resins, hydrogenated bisphenol epoxy resins, biphenol epoxy resins, hydrogenated biphenol epoxy resins, phenyl ether epoxy resins, naphthyl ether epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol novolac epoxy resins, naphthol novolac epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene-phenol addition reaction epoxy resins, and the like.

The unsaturated monocarboxylic acid (a1-2) is a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, an esterified product, an acid halide, an acid anhydride or the like of the unsaturated monocarboxylic acid (a1-2) may be used. These unsaturated monocarboxylic acids (a1-2) may be used alone or in combination of 2 or more.

Examples of the esterified compound of the unsaturated monocarboxylic acid (a1-2) include alkyl (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; nitrogen-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; other (meth) acrylate compounds such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate.

Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acryloyl chloride.

Examples of the acid anhydride of the unsaturated monocarboxylic acid (b1-3) include (meth) acrylic anhydride and the like.

The polycarboxylic acid anhydride (a1-3) may be any anhydride of a compound having 2 or more carboxyl groups in one molecule, and any anhydride may be used. Examples of the polycarboxylic anhydride include anhydrides of dicarboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid.

The method for producing the acid group-containing (meth) acrylate resin (A-1) is not particularly limited as long as the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride (a1-3) are essential reaction raw materials, and can be produced by any method. For example, the catalyst may be produced by a method in which all the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, the following method is preferred: first, an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) are reacted, and then a polycarboxylic anhydride (a1-3) is reacted. This reaction can be carried out, for example, by the following method: an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) are reacted at a temperature of 100 to 150 ℃ in the presence of an esterification catalyst, and then a polycarboxylic anhydride (a1-3) is added to the reaction system to react at a temperature of 90 to 120 ℃.

The reaction ratio of the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) is preferably 0.9 to 1.1 mol of the unsaturated monocarboxylic acid (a1-2) relative to 1 mol of the epoxy group in the epoxy resin (a 1-1). The reaction ratio of the polycarboxylic acid anhydride (a1-3) is preferably in the range of 0.2 to 1.0 mol based on 1 mol of epoxy groups in the epoxy resin (a 1-1).

Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine, and imidazole compounds such as 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole. These reaction catalysts may be used alone or in combination of 2 or more.

The amount of the reaction catalyst to be added is preferably in the range of 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the reaction raw materials.

The reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride (a1-3) may be carried out in an organic solvent as required. The organic solvent to be used may be suitably selected depending on the solubility of the reaction raw material and the acid group-containing (meth) acrylate resin as the product and the reaction temperature conditions, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, and dialkylene glycol acetate. These organic solvents may be used alone, or 2 or more of them may be used in combination as a mixed solvent.

The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass based on 100 parts by mass of the total amount of the reaction raw materials, from the viewpoint of improving the reaction efficiency.

The acid value of the acid group-containing (meth) acrylate resin (A-1) used in the present invention is preferably in the range of 30 to 150mgKOH/g, more preferably in the range of 40 to 100mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the (meth) acrylate resin (A-2) having an acid group will be described.

The acid group-containing (meth) acrylate resin (A-2) is obtained by using a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic anhydride (a2-4) as essential reaction raw materials.

The phenolic hydroxyl group-containing resin (a2-1) is a resin having 2 or more phenolic hydroxyl groups in the molecule, and examples thereof include: an aromatic polyhydroxy compound; a novolak-type phenol resin in which 1 or 2 or more kinds of compounds having 1 phenolic hydroxyl group in the molecule are used as reaction raw materials; and a reaction product obtained by reacting the compound having 1 phenolic hydroxyl group with a compound (x) represented by any one of the following structural formulae (x-1) to (x-5) as an essential reaction raw material.

(wherein h is 0 or 1. R)¹Independently represents any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group and an aralkyl group, and i is 0 or 1 to 4An integer number. Z is any of a vinyl group, a halogenated methyl group, a hydroxymethyl group, and an alkoxymethyl group. Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4. )

Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, and bisphenol, and compounds having 1 or more substituents on their aromatic nucleus. Examples of the substituent on the aromatic nucleus include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; phenyl, naphthyl, anthryl, and aryl groups obtained by substituting the aromatic nucleus thereof with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like; phenoxy group, naphthoxy group, and aryloxy group obtained by substituting the above aliphatic hydrocarbon group, the above alkoxy group, the above halogen atom, and the like on the aromatic nucleus thereof; and an aralkyl group obtained by substituting the above aliphatic hydrocarbon group, the above alkoxy group, the above halogen atom, and the like on the aromatic nucleus thereof. These aromatic polyhydroxy compounds can be used alone or in combination of 2 or more. Among them, a compound containing no halogen is preferable in that an acid group-containing (meth) acrylate resin having high insulation reliability can be obtained.

Examples of the novolak phenol resin include: the compound is obtained by reacting 1 or 2 or more compounds having 1 phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.

The compound having 1 phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having 1 hydroxyl group on the aromatic nucleus, and examples thereof include: phenol or a phenol compound having 1 or more substituents on the aromatic nucleus of phenol, naphthol or a naphthol compound having 1 or more substituents on the aromatic nucleus of naphthol, anthraphenol or an anthraphenol compound having 1 or more substituents on the aromatic nucleus of anthraphenol, and the like. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above. These compounds having 1 phenolic hydroxyl group may be used alone, or 2 or more kinds may be used in combination.

Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and caproaldehyde; hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2, 4-dihydroxybenzaldehyde, and 3, 4-dihydroxybenzaldehyde; benzaldehydes having both a hydroxyl group and an alkoxy group, such as 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3, 5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; halogenated benzaldehydes such as bromobenzaldehyde.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These acidic catalysts may be used alone or in combination of 2 or more.

The reaction product of the compound having 1 phenolic hydroxyl group and the compound (x) as essential reaction raw materials can be obtained, for example, by heating and stirring the compound having 1 phenolic hydroxyl group in the molecule and the compound (x) in an acidic catalyst at a temperature of about 80 to 200 ℃. The reaction ratio of the compound having 1 phenolic hydroxyl group in the molecule to the compound (x) is preferably: the compound having 1 phenolic hydroxyl group in the molecule is in a proportion of 0.5 to 5 moles with respect to 1 mole of the compound (x).

The acidic catalyst is the same as the acidic catalyst described above.

Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used alone or in combination of 2 or more. Among them, ethylene carbonate or propylene carbonate is preferable in that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained.

Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of 2 or more. Among them, ethylene oxide or propylene oxide is preferable in that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained.

As the unsaturated monocarboxylic acid (a2-3a), those similar to the unsaturated monocarboxylic acid (a1-2) can be used.

Examples of the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide. Among them, N-methoxymethyl (meth) acrylamide is preferable in that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained. These N-alkoxyalkyl (meth) acrylamide compounds may be used alone or in combination of 2 or more.

As the polycarboxylic anhydride (a2-4), the same ones as those mentioned above for the polycarboxylic anhydride (a1-3) can be used.

When the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is used, the equivalent ratio [ (a2-3b)/(a2-4)) ] to the polycarboxylic anhydride (a2-4)) is preferably in the range of 0.2 to 7, and more preferably in the range of 0.25 to 6.7, in view of obtaining an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product having excellent heat resistance.

The method for producing the acid group-containing (meth) acrylate resin (a-2) is not particularly limited, and can be produced by any method. For example, the catalyst may be produced by a method in which all the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted in sequence. Among them, from the viewpoint of easy control of the reaction, the following method is preferred: first, a resin containing a phenolic hydroxyl group (a2-1) is reacted with a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), and then, an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b) are reacted, and then, a polycarboxylic anhydride (a2-4) is reacted. This reaction can be carried out, for example, by the following method: the phenolic hydroxyl group-containing resin (a2-1) is reacted with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst at a temperature of 100 to 200 ℃, and then the unsaturated polycarboxylic acid (b2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is reacted at a temperature of 80 to 140 ℃ in the presence of an acidic catalyst, and then the polycarboxylic anhydride (a2-4) is added and the reaction is carried out at a temperature of 80 to 140 ℃.

Examples of the basic catalyst include alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, and imidazole compounds such as 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These basic catalysts may be used alone or in combination of 2 or more.

Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These acid catalysts may be used alone or in combination of 2 or more.

The reaction of the phenolic hydroxyl group-containing resin (a2-1), the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), the unsaturated monocarboxylic acid (a2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and the polycarboxylic anhydride (a2-4) may be carried out in an organic solvent, if necessary. The organic solvent to be used may be suitably selected depending on the solubility of the reaction raw material and the acid group-containing (meth) acrylate resin as the product and the reaction temperature conditions, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, and dialkylene glycol acetate. These organic solvents may be used alone or in combination of 2 or more kinds in the form of a mixed solvent.

The specific structure of the acid group-containing (meth) acrylate resin (A-2) is not particularly limited as long as the resin contains an acid group and a (meth) acryloyl group, and the acid group-containing (meth) acrylate resin (A-2) obtained by using a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic acid anhydride (a2-4) as essential reaction raw materials, and examples of the acid group-containing (meth) acrylate resin (A-2) include: a resin structure having a repeating structural unit of a structural moiety (I) represented by the following structural formula (a-1) and a structural moiety (II) represented by the following structural formula (a-2); having a resin structure comprising a structural moiety (III) represented by the following structural formula (a-3) and a structural moiety (IV) represented by the following structural formula (a-4) as repeating structural units.

[ in the formula, R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R³Each independently represents any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and each n independently represents 1 or 2. R⁴Each independently represents a methylene group or a structural portion represented by any one of the following structural formulae (x '-1) to (x' -5). R⁵、R⁶Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R⁵And R⁶Optionally linked to form a saturated or unsaturated ring. R⁷Is a hydrocarbon group having 1 to 12 carbon atoms. R⁸Is a hydrogen atom or a methyl group. x is the same as R³The structural site shown here, or a structural site (I) shown in the structural formula (a-1) or a structural site (II) shown in the structural formula (a-2) via R which is denoted by the symbol ﹡⁴And the attachment site of the linkage.]

[ in the formula, R²Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R³Each independently represents any of a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom, and each n independently represents 1 or 2. R⁴Each independently represents a methylene group or a structural portion represented by any one of the following structural formulae (x '-1) to (x' -5). R⁵、R⁶Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R⁵And R⁶Optionally linked to form a saturated or unsaturated ring. R⁷Is a hydrocarbon group having 1 to 12 carbon atoms. R⁸Is a hydrogen atom or a methyl group. x is the same as R³The structural site shown by the symbol ﹡ is attached to the structural site (III) shown by the structural formula (a-3) or the structural site (IV) shown by the structural formula (a-4)R of (A) to (B)⁴And the attachment site of the linkage.]

[ wherein h is 0 or 1. R⁹Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group and an aralkyl group, and i is 0 or an integer of 1 to 4. R¹⁰Is a hydrogen atom or a methyl group. W is the following structural formula (W-1) or (W-2). Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4.]

(in the formula, R¹¹Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R¹²、R¹³Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R¹²And R¹³Optionally linked to form a saturated or unsaturated ring. R¹⁴Is a hydrocarbon group having 1 to 12 carbon atoms. R¹⁵Is a hydrogen atom or a methyl group. )

The acid value of the acid group-containing (meth) acrylate resin (A-2) is preferably in the range of 30 to 150mgKOH/g, more preferably in the range of 40 to 100mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method according to JIS K0070 (1992).

Next, the (meth) acrylate resin (A-3) having an acid group will be described.

The acid group-containing (meth) acrylate resin (A-3) is obtained by using an acid group-or acid anhydride group-containing amide imide resin (a3-1), a hydroxyl group-containing (meth) acrylate compound (a3-2), a (meth) acryloyl group-containing epoxy compound (a3-3), and a polycarboxylic anhydride (a3-4) as essential reaction raw materials.

The amide imide resin (a3-1) may have either one of an acid group and an acid anhydride group, or both of them. From the viewpoint of reactivity with the hydroxyl group-containing (meth) acrylate compound (a3-2) and the (meth) acryloyl group-containing epoxy compound (a3-3), and control of the reaction, the acid anhydride group is preferably contained, and both the acid group and the acid anhydride group are more preferably contained. The acid value of the amide imide resin (a3-1) is preferably in the range of 60 to 350mgKOH/g as measured under neutral conditions, that is, under conditions in which the acid anhydride group is not ring-opened. On the other hand, the measured value under the conditions of ring-opening the acid anhydride group in the presence of water or the like is preferably in the range of 61 to 360 mgKOH/g.

The specific structure and production method of the amide imide resin (a3-1) are not particularly limited, and general amide imide resins and the like can be widely used. Examples thereof include those obtained by using a polyisocyanate compound and a polycarboxylic acid or an anhydride thereof as reaction raw materials.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and 2,4, 4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, and o-tolidine diisocyanate; a polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); and isocyanurate, biuret, allophanate modifications thereof. These polyisocyanate compounds may be used alone or in combination of 2 or more.

[ in the formula, R¹Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R²Each independently is an alkyl group having 1 to 4 carbon atoms or a linking site to which the structural part represented by the structural formula (i-1) is linked via a methylene group denoted by the reference character ﹡. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more.]

In addition, as the polyisocyanate compound, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high solvent solubility, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof are preferable, and an alicyclic diisocyanate or an isocyanurate modified product thereof, and an aliphatic diisocyanate or an isocyanurate modified product thereof are more preferable.

In addition, the ratio of the alicyclic diisocyanate compound or a modified form thereof to the total mass of the aliphatic diisocyanate compound or a modified form thereof in the total mass of the polyisocyanate compounds is preferably 70 mass% or more, and preferably 90 mass% or more.

When the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof are used in combination, the mass ratio of the two is preferably in the range of 30/70 to 70/30.

The polycarboxylic acid or an anhydride thereof is not particularly limited in specific structure as long as it is a compound having a plurality of carboxyl groups in the molecular structure or an anhydride thereof, and various compounds can be used. The amide imide resin (a3-1) has both an amide group and an imide group, and therefore, both a carboxyl group and an acid anhydride group need to be present in the system, but in the present invention, a compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

Examples of the polycarboxylic acid or anhydride thereof include aliphatic polycarboxylic acid compounds or anhydrides thereof, alicyclic polycarboxylic acid compounds or anhydrides thereof, and aromatic polycarboxylic acid compounds or anhydrides thereof.

The aliphatic polycarboxylic acid compound or its anhydride may have an aliphatic hydrocarbon group of any of straight chain type and branched chain type, and may have an unsaturated bond in the structure.

Examples of the aliphatic polycarboxylic acid compound or an acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3, 4-butanetetracarboxylic acid, and acid anhydrides thereof.

In the present invention, the alicyclic polycarboxylic acid compound or its acid anhydride is one in which a carboxyl group or an acid anhydride group is bonded to an alicyclic structure, regardless of the presence or absence of an aromatic ring in the other structural parts. Examples of the alicyclic polycarboxylic acid compound or its anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2, 3-dicarboxylic acid, 4- (2, 5-dioxatetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, and anhydrides thereof.

Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

Among them, the alicyclic polycarboxylic acid compound or an acid anhydride thereof, or the aromatic polycarboxylic acid compound or an acid anhydride thereof is preferable in that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained. In addition, from the viewpoint of efficiently producing the amide imide resin (a3-1), it is preferable to use a tricarboxylic anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and it is particularly preferable to use cyclohexanetricarboxylic anhydride or trimellitic anhydride. Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or anhydride thereof is preferably 70 mass% or more, and more preferably 90 mass% or more.

When the amide imide resin (a3-1) is obtained by using the polyisocyanate compound and the polycarboxylic acid or anhydride thereof as reaction raw materials, reaction raw materials other than these may be used in combination according to desired resin properties and the like. In the above case, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or anhydride thereof to the total mass of the reaction raw materials of the amide imide resin (a3-1) is preferably 90 mass% or more, and more preferably 95 mass% or more, from the viewpoint that the effects exhibited by the present invention can be sufficiently exhibited.

The amide imide resin (a3-1) is not particularly limited when a polyisocyanate compound and a polycarboxylic acid or an anhydride thereof are used as reaction raw materials, and can be produced by any method. For example, the resin can be produced by the same method as that for a general amide imide resin. Specifically, the following methods can be mentioned: the reaction is carried out by stirring and mixing a polycarboxylic acid or an anhydride thereof in an amount of 0.8 to 1.2 mol based on 1 mol of an isocyanate group contained in a polyisocyanate compound at a temperature of about 120 to 180 ℃.

The reaction of the polyisocyanate compound with the polycarboxylic acid or anhydride thereof may be carried out in an organic solvent as required. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, and dialkylene glycol acetate. These organic solvents may be used alone, or 2 or more of them may be used in combination as a mixed solvent.

The hydroxyl group-containing (meth) acrylate compound (a3-2) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in its molecular structure, and various compounds can be used. Examples thereof include hydroxy (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like; (poly) oxyalkylene modified bodies obtained by introducing (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains into the molecular structures of the above-mentioned various hydroxy (meth) acrylate compounds; lactone modifications obtained by introducing a (poly) lactone structure into the molecular structure of the above-mentioned various hydroxy (meth) acrylate compounds, and the like. Among them, the molecular weight is preferably 1000 or less, from the viewpoint that an acid group-containing (meth) acrylate resin composition capable of forming a cured product excellent in heat resistance can be obtained. When the hydroxyl group-containing (meth) acrylate compound (a3-2) is the oxyalkylene-modified product or the lactone-modified product, the weight-average molecular weight (Mw) is preferably 1000 or less. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of 2 or more.

The (meth) acryloyl group-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in its molecular structure, and various compounds can be used. Examples thereof include glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl glycidyl (meth) acrylate, and epoxycyclohexylmethyl (meth) acrylate; and mono (meth) acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Among them, a glycidyl group-containing (meth) acrylate monomer is preferable in that an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance can be obtained. Further, the molecular weight thereof is preferably 500 or less. Further, the proportion of the glycidyl group-containing (meth) acrylate monomer in the total mass of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 70 mass% or more, more preferably 90 mass% or more.

The polycarboxylic anhydride (a3-4) is the same as the polycarboxylic anhydride (a1-3) and the polycarboxylic anhydride (a 2-4).

The acid group-containing (meth) acrylate resin (A-3) may be used in combination with other reaction raw materials in addition to the acid group-or acid anhydride group-containing amide imide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2), the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic anhydride (a3-4) depending on the desired resin properties and the like. In the above case, the ratio of the total mass of the components (a3-1) to (a3-4) in the total mass of the reaction raw materials of the acid group-containing (meth) acrylate resin (A-3) is preferably 80 mass% or more, and more preferably 90 mass% or more.

The method for producing the acid group-containing (meth) acrylate resin (a-3) is not particularly limited, and can be produced by any method. For example, the catalyst may be produced by a method of reacting all the reaction raw materials together, or may be produced by a method of reacting the reaction raw materials sequentially. Among them, the following method is preferably used for production: reacting an amide imide resin (a3-1) with a hydroxyl group-containing (meth) acrylate compound (a3-2) (step 1); reacting the product of step 1 with a (meth) acryloyl group-containing epoxy compound (a3-3) (step 2); the product of step 2 is reacted with the polycarboxylic anhydride (a 3-4).

The step 1 is a step of reacting the amide imide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a 3-2). The reaction is mainly a reaction between an acid group or an acid anhydride group in the amide imide resin (a3-1) and a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a 3-2). The amide imide resin (a3-1) preferably has an acid anhydride group as described above, because the hydroxyl group-containing (meth) acrylate compound (a3-2) is excellent in reactivity with an acid anhydride group. Regarding the reaction ratio between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), it is preferable to use the hydroxyl group-containing (meth) acrylate compound (a3-2) in the range of 0.9 to 1.1 mol based on the total of the acid groups and the acid anhydride groups in the amide imide resin (a3-1), and it is particularly preferable to use the hydroxyl group-containing (meth) acrylate compound (a3-2) in the range of 0.9 to 1.1 mol based on the total of the acid anhydride groups in the amide imide resin (a 3-1). The content of the acid anhydride group in the amide imide resin (a3-1) can be calculated from the difference between the measured values of the 2 types of acid values, that is, the difference between the acid value under the condition in which the acid anhydride group is ring-opened and the acid value under the condition in which the acid anhydride group is not ring-opened.

The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) can be carried out, for example, by heating and stirring at a temperature of about 90 to 140 ℃ in the presence of an esterification catalyst. Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine, and imidazole compounds such as 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole. These reaction catalysts may be used alone or in combination of 2 or more.

The reaction in step 1 may be carried out in an organic solvent as required. The organic solvent to be used may be suitably selected depending on the solubility of the reaction raw material and the acid group-containing (meth) acrylate resin as the product and the reaction temperature conditions, and examples thereof include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, dialkylene glycol monoalkyl ether acetate, and dialkylene glycol acetate. These organic solvents may be used alone, or 2 or more of them may be used in combination as a mixed solvent. When the production of the amide imide resin (a3-1) and the step 1 are continuously carried out, the reaction may be continued in the organic solvent used for the production of the amide imide resin (a3-1) while maintaining this state.

The step 2 is a step of reacting the product obtained in the step 1 with a (meth) acryloyl group-containing epoxy compound (a 3-3). The reaction is mainly a reaction between the (meth) acryloyl group-containing epoxy compound (a3-3) and the carboxyl group in the product of step 1. The reaction ratio is preferably 0.5 to 1.2 mol, more preferably 0.9 to 1.1 mol, based on the carboxyl group in the product of step 1, of the (meth) acryloyl group-containing epoxy compound (a 3-3). The reaction in step 2 can be carried out, for example, by heating and stirring at a temperature of about 90 to 140 ℃ in the presence of an esterification catalyst. When the steps 1 and 2 are continuously performed, the esterification catalyst may not be added, and may be added as appropriate. The reaction may be carried out in an organic solvent as required.

The step 3 is a step of reacting the product obtained in the step 2 with a polycarboxylic anhydride (a 3-4). The reaction is mainly a reaction between the polycarboxylic anhydride (a3-4) and the hydroxyl group in the product of step 2. The reaction ratio is preferably adjusted so that the acid value of the acid group-containing (meth) acrylate resin (A-3) as a final product is about 50 to 100 mgKOH/g. The reaction in the step 3 can be carried out, for example, by heating and stirring at a temperature of about 90 to 140 ℃ in the presence of an esterification catalyst. When the steps 2 and 3 are continuously performed, the esterification catalyst may not be added, and may be added as appropriate. The reaction may be carried out in an organic solvent as required.

The acid value of the acid group-containing (meth) acrylate resin (A-3) is preferably in the range of 30 to 150mgKOH/g, more preferably in the range of 40 to 100mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition having high sensitivity and capable of forming a cured product excellent in heat resistance can be obtained. In the present invention, the acid value of the acid group-containing (meth) acrylate resin (a-3) is a value measured by a neutralization titration method according to JIS K0070 (1992).

The photopolymerization initiator (B) will be described.

As the photopolymerization initiator (B), a michael addition reaction product of a compound (B1) containing an α -aminoacetophenone skeleton, which functions as a michael addition donor, represented by the following general formula (1), and a reactive compound (B2) having a function as a michael acceptor is used.

[ Compound (b1) having alpha-aminoacetophenone skeleton ]

The α -aminoacetophenone skeleton-containing compound (b1) has a functional group having a function of supplying michael addition represented by a secondary amino group such as a piperazinyl group, a methylamino group, an ethylamino group, or a benzylamino group in its molecular structure, and is specifically represented by the following general formula (1).

(in the general formula (1),

R¹represents an aliphatic group or an aromatic group,

R²～R³each independently represents an aliphatic group or an aryl group,

and R²And R³Optionally integrated to form a ring,

R⁴～R⁷each independently represents a hydrogen atom or an aliphatic or aromatic group,

X²represents a carbonyl group or a thiocarbonyl group,

Y¹represents a group represented by the following general formula (2), general formula (3) or general formula (4),

Y²represents a group represented by the following general formula (2) or general formula (3). Wherein, Y¹And Y²When all have the structure represented by the general formula (2), X represents at least one of them⁵is-NH-.

n is 0 or 1. )

Here, R in the general formula (1) is defined as¹～R⁷Examples of the aliphatic group of (2) include an alkyl group, an alkenyl group, and an alkynyl group.

Examples of the alkyl group include any of linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms.

Specific examples thereof include methyl, ethyl, propyl, n-butyl, and tert-butyl; sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isopropyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,3, 3-tetramethylbutyl, 2,4, 4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1, 3-trimethylhexyl, 1,3, 3-tetramethylpentyl, isodecyl, 1-methylundecyl or 1,1,3,3,5, 5-hexamethylhexyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 1,3, 3-tetramethylbutyl, 2,4, Straight or branched alkyl groups such as octadecyl, cycloalkyl groups such as cycloheptyl, cyclohexyl, and cyclopentyl, and the like.

Examples of the alkenyl group include a butenyl group such as a propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group and an isobutenyl group, and an alkenyl group such as an n-2, 4-pentadienyl group.

Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

Among these aliphatic groups, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are particularly preferable.

The aliphatic group may further optionally have a substituent on a carbon atom, and examples of the substituent include a substituent containing a monovalent non-metal atom other than a hydrogen atom.

Specific examples thereof include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino groups, N-dialkylamino groups, N-arylamino groups, N-diarylamino groups, N-alkyl-N-arylamino groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N-dialkylcarbamoyloxy groups, N-diarylcarbamoyloxy groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, acylthio groups, acylamino groups, N-alkylacylamido groups, hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, amino groups, N-arylacylamino, ureido, N ' -alkylureido, N ' -dialkylureido, N ' -arylureido, N ' -diarylureido, N ' -alkyl-N ' -arylureido, N-alkylureido, N-arylureido, N ' -alkyl-N-alkylureido, N ' -alkyl-N-arylureido, N ' -dialkyl-N-alkylureido, N ' -dialkyl-N-arylureido, N ' -aryl-N-alkylureido, N ' -aryl-N-arylureido, N ' -diaryl-N-alkylureido, N ' -diaryl-N-arylureido, N ' -aryl, N '-alkyl-N' -aryl-N-alkylureido, N '-alkyl-N' -aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxyureidoAminocarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N-dialkylcarbamoyl, N-arylcarbamoyl, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, (-sulfo (-SO)₃H) And the conjugated base thereof (known as the sulfonate group), alkoxysulfonyl, aryloxysulfonyl, sulfinyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, sulfamoyl, N-alkylsulfamoyl, N-dialkylsulfamoyl, N-arylsulfamoyl, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, phosphono (-PO) group₃H₂) And its conjugated base group (called phosphoryl group), dialkylphosphono group (-PO)₃(alkyl)₂) "alkyl ═ alkyl group, the same applies hereinafter", diarylphosphono group (-PO)₃(aryl)₂) "aryl ═ aryl, the same applies hereinafter", alkylaryl phosphono (-PO) groups₃(alkyl) (aryl)), monoalkyl phosphono (-PO)₃(alkyl)) and its conjugated base (called alkylphosphoryl), monoarylphosphono (-PO)₃H (aryl)) and its conjugate base (called aryl phosphoryl), phosphonoxy (-OPO)₃H₂) And its conjugated base (called phosphoryloxy), dialkylphosphonoxy (-OPO)₃H(alkyl)₂) Diaryl phosphonyloxy (-OPO)₃(aryl)₂) Alkyl aryl phosphonoxy (-OPO)₃(alkyl) (aryl)), monoalkylphosphonoxy (-OPO)₃H (alkyl) and its conjugate base (called alkylphosphoryloxy), monoarylphosphonoxy (-OPO)₃H (aryl)), and its conjugate base (called aryl phosphoryloxy), cyano, nitro, aryl, alkenyl, alkynyl, heterocyclyl, silyl, and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups. Specific examples of the aryl group among the above substituents include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxyphenyl group, an acetoxyphenyl group, a benzoyloxyphenyl group, a methylthiophenyl group, a phenylthiophenyl group, a methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group, a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonophenyl group, a sulfonatophenyl group, a phosphonophenyl.

Examples of the alkenyl group in the above-mentioned substituents include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-vinyl group and the like.

Examples of the alkynyl group in the above-mentioned substituent include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group and the like.

Then, R in the general formula (1) is defined as¹～R⁷Examples of the aryl group of (2) include those in which 1 to 3 benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include phenyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl, tolyl, xylyl, naphthyl, benzyl, α -methylbenzyl, α -dimethylbenzyl, phenethylnaphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl and fluorenyl. Among them, phenyl and naphthyl are more preferable.

In the aforementioned aryl group, a substituent containing a monovalent non-metallic atomic group other than a hydrogen atom is optionally present as a substituent on a ring-forming carbon atom of the aryl group. Preferred examples of the substituent include the alkyl group and those described as the substituent of the substituted alkyl group.

Preferable specific examples of the aryl group having a substituent include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetoxyphenyl, benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, carbamoylphenyl, N-methylcarbamoylphenyl, cumylphenyl, tolylthiophenyl, tolylthiophen, N, N-dipropylcarbamoylphenyl, N- (methoxyphenyl) carbamoylphenyl, N-methyl-N- (sulfophenyl) carbamoylphenyl, sulfophenyl, sulfonatophenyl, sulfamoylphenyl, N-ethylsulfamoylphenyl, N-dipropylsulfamoylphenyl, N-tolylsulfamoylphenyl, N-methyl-N- (phosphonophenyl) sulfamoylphenyl, phosphonophenyl, phosphorylphenyl, diethylphosphonophenyl, diphenylphosphonylphenyl, methylphosphonylphenyl, tolylphosphonophenyl, tolylphosphorylphenyl, allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2-methallylphenyl, 2-methylpropenylphenyl, N-methyl-N- (sulfophenyl) carbamoylphenyl, sulfophenyl, N-ethylphosphonylphenyl, N-dipropylphenyl, N-tolylsulfamoylphenyl, N-methyl-N, 2-propynylphenyl, 2-butynylphenyl, 3-butynylphenyl, and the like.

In the present invention, for R¹Specifically, from the viewpoint of easiness in obtaining raw materials and controlling reaction in production, a linear alkyl group having 1 to 12 carbon atoms is preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.

In addition, for R²～R³Specifically, a linear alkyl group having 1 to 12 carbon atoms is preferable, and a linear alkyl group having 1 to 6 carbon atoms is preferable.

In addition, R⁴～R⁷Specifically, a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms is preferable.

In the general formula (1), X¹Represents a single bond or an alkylene group such as a linear or branched methylene group, ethylene group or propylene group having 1 to 6 carbon atoms. The substituent here may be exemplified by those optionally having the aforementioned substituentThe substituents specified in the aliphatic group of the radical.

Then, X in the general formula (1)²Represents a carbonyl group or a thiocarbonyl group.

In the general formula (1), Y¹And Y²Each independently represents a group represented by the general formula (2) or the general formula (3).

Here constitutes Y¹And Y²The general formula (2) is represented by the following structural formula.

In the above general formula (2), X³And X⁴Each independently represents a linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, X⁵Represents a single bond, -O-or-NH-. X³And X⁴Specific examples thereof include a linear or branched methylene group, an ethylene group, a propylene group, a butylene group, an oxymethylene group, an oxypropylene group, and an oxybutylene group.

Specific examples of the structural site represented by the general formula (2) described in detail above include the following structures.

Then, form Y¹And Y²The general formula (3) is represented by the following structural formula.

In the general formula (3), X⁶Represents a substituted or unsubstituted linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, R⁸And R⁹Each independently represents an aliphatic group or an aryl group. Here, X⁶Specific examples of the substituent in (b) include a linear or branched methylene group, propylene group, butylene group, oxymethylene group, oxypropylene group, oxybutylene group and the like.

R⁸And R⁹Each independently represents an aliphatic group or an aryl group. Here, the aliphatic group and the aryl group may be those constituting the above-mentioned R¹～R⁷Thereby, the number of the parts can be reduced.

Then, form Y¹The general formula (4) is represented by the following structural formula.

R in the above general formula (4)¹⁰And R¹¹Each independently being an aliphatic group or an aryl group. Examples of the aliphatic group or the aryl group include those constituting the above-mentioned R¹～R⁷The aliphatic group or the aryl group of (1) is exemplified.

Here, in the present invention, Y in the general formula (1)¹And Y²When all have the structure represented by the general formula (2), X represents at least one of them⁵is-NH-. Thus, the compound (b1) having an α -aminoacetophenone skeleton can exhibit a Michael addition supplying function.

Next, n in the general formula (1) is 0 or 1.

Among the above general formula (1), the following compounds are particularly preferred: r¹Is ethyl, R²Is methyl, R³Is methyl, R⁴Is hydrogen, R⁵Is hydrogen, R⁶Is hydrogen, R⁷Is hydrogen, X¹Is a short bond, X²Is carbonyl, Y¹Is piperazinyl, and Y²A compound that is a piperazinyl group; r¹Is ethyl, R²Is methyl, R³Is methyl, R⁴Is hydrogen, R⁵Is hydrogen, R⁶Is hydrogen, R⁷Is hydrogen, X¹is-CH (CH)³)-、X²Is carbonyl, Y¹Is piperazinyl, and Y²A compound that is a piperazinyl group; r¹Is ethyl, R²Is 1-hexyl, R³Is methyl, R⁴Is hydrogen, R⁵Is hydrogen, R⁶Is hydrogen, R⁷Is hydrogen, X¹Is a short bond, X²Is carbonyl, Y¹Is a piperazinyl radicalAnd Y is²A compound that is a piperazinyl group; r¹Is ethyl, R²Is methyl, R³Is methyl, R⁴Is hydrogen, R⁵Is hydrogen, R⁶Is hydrogen, R⁷Is hydrogen, X¹Is a short bond, X²Is carbonyl, Y¹Is morpholinyl, Y²A compound that is a piperazinyl group; r¹Is ethyl, R²Is methyl, R³Is methyl, R⁴Is hydrogen, R⁵Is hydrogen, R⁶Is hydrogen, R⁷Is hydrogen, X¹Is a short bond, X²Is carbonyl, Y¹Is piperazinyl, Y²Is a morpholinyl compound.

Specific examples of the compounds represented by the general formula (1) include compounds represented by the structural formulae (5) to (28). Among them, from the viewpoint of high curability, an aminostyrone-based compound having 1 cyclic secondary amino group such as a piperazinyl group, that is, the structural formula (5), the structural formula (6), the structural formula (16), the structural formula (17), the structural formula (19), the structural formula (20), the structural formula (22), the structural formula (23), the structural formula (25), the structural formula (26), and the structural formula (27) are preferable, and the structural formula (5), the structural formula (6), the structural formula (16), the structural formula (17), the structural formula (25), and the structural formula (26) are particularly preferable.

Y in the above general formula (1)¹Among these compounds having only the cyclic secondary amino group, the compound having only the cyclic secondary amino group is very high in curability and preferable. Such compounds are represented by the structural formula (5), the structural formula (6), the structural formula (25), the structural formula (26) and the structural formula (27).

Further, it is considered that Y in the above general formula (1)²Among these, compounds having only the cyclic secondary amino group are particularly preferable because they have extremely high curability and the incorporation of a cleavage product generated by the absorption of active energy rays into a polymer matrix is also promoted. Such compounds are represented by the structural formula (16), the structural formula (17), the structural formula (19), the structural formula (20), the structural formula (22) and the structural formula (23).

These compounds containing an alpha-aminoacetophenone skeleton (b1) are based on Y in the general formula (1)¹-and Y²The difference in the introduction method of (4) can be produced by any of the following methods 1 to 3.

(method 1)

The method 1 comprises the following steps: alkyl acetophenone having a halogen atom on the aromatic nucleus and a compound (Y) containing a secondary amino group¹-H), followed by introduction of a bromine atom to the alpha position of the carbonyl group, followed by reaction of a secondary monoamine compound (HN (R)²)(R³) Followed by reaction with a substituent (-X)¹-X²-OR) benzyl bromide with n as a substituent on the aromatic nucleus. Here, R is an alkyl group, and n is 0 or 1. Then, the compound is treated with a base to produce a compound (P) which is an intermediate having a hydroxyl group (or a mercapto group) at the terminal. Further, the reaction product is reacted with a compound (Y) containing a secondary amino group²-H) reaction to produce the objective compound (b1) containing an α -aminoacetophenone skeleton. In this case, the compound (P) as an intermediate and the compound (Y) containing a secondary amino group²In the reaction of (E) to (E), the compound (Y) containing a secondary amino group²In the case where-H) is a diamine compound having an active hydrogen, the following method can be employed: a compound in which one amino group of the compound is protected with oxycarbonyl or the like is used, and then the compound is treated with an acid to remove the protecting group.

[ reactive Compound (b2) having function as Michael acceptor ]

The reactive compound (b2) having a function as a michael acceptor is preferably a compound having a reactive group which is favorably cured by light irradiation (hereinafter, simply referred to as "photocurable group"), and the photocurable function of the polyfunctional reactive compound having a plurality of the photocurable groups is particularly favorable.

Examples of the polyfunctional reactive compound having a plurality of photocurable groups include α, β -unsaturated carbonyl compounds such as maleimide compounds, maleate compounds, fumarate compounds, and (meth) acrylate compounds. Among them, the (meth) acrylate compound is particularly preferable in that the control of the michael addition reaction during synthesis is easy, the reactivity during photocuring is high, and a photosensitive resin composition in which outgassing is less likely to occur can be obtained.

Examples of the (meth) acrylate compound include: diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and other difunctional acrylates, trimethylolpropane tri (meth) acrylate, its ethylene oxide-modified product such as ethylene oxide and propylene oxide, pentaerythritol tri (meth) acrylate, its ethylene oxide-modified product such as ethylene oxide and propylene oxide, ditrimethylolpropane tetra (meth) acrylate, its ethylene oxide-modified product such as ethylene oxide and propylene oxide, dipentaerythritol tetra-or penta-or hexa (meth) acrylate, and other polyfunctional (meth) acrylates such as bisphenol A diglycidyl ether, and mixtures thereof, Epoxy (meth) acrylates obtained by the reaction of a polyglycidyl ether such as trimethylolpropane triglycidyl ether with (meth) acrylic acid, urethane (meth) acrylates obtained by the reaction of a polyisocyanate compound such as isophorone diisocyanate or hexamethylene diisocyanate trimer with an acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate or pentaerythritol tri (meth) acrylate, polyester (meth) acrylates obtained by the reaction of a polybasic acid such as trimellitic acid or succinic acid with a polyhydric alcohol such as ethylene glycol or neopentyl glycol with a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate or pentaerythritol tri (meth) acrylate, high molecular weight type poly (meth) acrylates obtained by the reaction of a polymer of glycidyl (meth) acrylate and a monofunctional (meth) acrylate with (meth) acrylic acid, and the like, but is not limited thereto. These reactive compounds may be used alone or in combination of two or more.

Among these, the reactive compound is most preferably a 3-functional or higher (meth) acrylate compound because the high molecular weight material obtained after curing can be firmly immobilized by the cured film. When a 3-or more-functional (meth) acrylate having 3 or more (meth) acryloyl groups is selected as the reactive compound having a function as a michael acceptor, the michael addition reaction product of the present invention preferably has 2 or more photocurable groups.

(Michael addition reaction)

In the present invention, the michael addition reaction between the α -aminoacetophenone skeleton-containing compound (b1) and the reactive compound (b2) having a function as a michael acceptor is not particularly limited, and can be carried out under well-known and commonly used reaction conditions. The following methods can be mentioned as a general method: mixing the alpha-aminoacetophenone skeleton-containing compound (b1) and the reactive compound (b2) having a function as a Michael acceptor in a reaction vessel at 0 to 150 ℃. In this case, a catalyst or an organic solvent may be used.

Examples of the catalyst include tetraethylammonium fluoride, tetrabutylammonium hydroxide, potassium hydroxide, tetramethylguanidine, diazabicycloundecene, sodium tert-butoxide, tri-n-octylphosphine, and triphenylphosphine.

Examples of the organic solvent include saturated hydrocarbons such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, isopropanol, 2-butanol, tert-butanol, ethylene glycol and carbitol, ethers such as dimethyl ether, diethyl ether, 1, 4-dioxane and Tetrahydrofuran (THF), amides such as Dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, and dimethyl sulfoxide (DMSO).

The mixing ratio of the α -aminoacetophenone skeleton-containing compound (b1) and the reactive compound (b2) having a function as a michael acceptor is not particularly limited, and the equivalent ratio [ (ii)/(i) ] of the group (ii) having a michael accepting function to the group (i) having a michael addition supplying function is preferably 1/1 to 1/30, more preferably 1/2 to 1/30.

Examples of the michael addition reaction product obtained by subjecting the α -aminoacetophenone skeleton-containing compound (b1) and the reactive compound (b2) having a function as a michael acceptor to a michael addition reaction include the following formulae (M1) to (M18).

The amount of the photopolymerization initiator (B) is preferably in the range of 1 to 20 parts by mass per 100 parts by mass of the acid group-containing (meth) acrylate resin (a).

The photosensitive resin composition of the present invention may contain a photoinitiator such as a photosensitizer and a tertiary amine as necessary to further improve the curing performance. Examples of the photosensitizer include thioxanthone-based photosensitizers such as 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone, benzophenone-based photosensitizers such as 4, 4' -bis (diethylamino) benzophenone, and anthraquinones. On the other hand, examples of the tertiary amine include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N, N-dimethylbenzylamine. In addition, a high molecular weight compound obtained by branching a plurality of photosensitizers or tertiary amines into 1 molecule with a polyhydric alcohol or the like can also be suitably used. The photoinitiator aid is preferably used in an amount of 0.03 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on the total amount of the photosensitive resin composition.

Further, other photopolymerization initiators than the photopolymerization initiator (B) may be used in combination within a range not impairing the effects of the present invention.

Examples of the other photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethan-1-one, diphenyl (2,4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like.

Examples of the other photopolymerization initiators which are commercially available include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "KAYACURE-DETX", "KAYACURE-MBP", "YACURE-DMBI", "KACUYARE-EPA", "KAYACURE-OA" (manufactured by JAPONIC CHEMICAL Co., Ltd), "BiYACURE-10", "TRI-55" (manufactured by Akzo Co., 3. Akik. for example "Sandray 1000" (manufactured by Sandoz Co., Ltd.), "DEAP" (manufactured by APJOHN Co., LTD.), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinson Co., Ltd.), "Runtercure-1104" (manufactured by Runtec Co., Ltd.), and the like.

The photosensitive resin composition of the present invention may contain other resin components than the acid group-containing (meth) acrylate resin (a). Examples of the other resin components include: resins having a carboxyl group and a (meth) acryloyl group in the resin obtained by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, a dicarboxylic anhydride, and, if necessary, an unsaturated monocarboxylic acid anhydride, and various (meth) acrylate monomers.

Examples of the (meth) acrylate monomer include: aliphatic mono (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds including benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: (poly) oxyalkylene-modified mono (meth) acrylate compounds obtained by introducing a polyoxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of each of the above-mentioned mono (meth) acrylate monomers; lactone-modified mono (meth) acrylate compounds obtained by introducing a (poly) lactone structure into the molecular structure of each of the above-mentioned mono (meth) acrylate compounds; aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds obtained by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of each of the above di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds obtained by introducing a (poly) lactone structure into the molecular structure of each of the above di (meth) acrylate compounds; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; a (poly) oxyalkylene-modified tri (meth) acrylate compound obtained by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of the aliphatic tri (meth) acrylate compound; a lactone-modified tri (meth) acrylate compound obtained by introducing a (poly) lactone structure into the molecular structure of the aliphatic tri (meth) acrylate compound; aliphatic poly (meth) acrylate compounds having 4 or more functions such as pentaerythritol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; a (poly) oxyalkylene-modified poly (meth) acrylate compound having 4 or more functional groups, which is obtained by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain into the molecular structure of the aliphatic poly (meth) acrylate compound; and lactone-modified poly (meth) acrylate compounds having 4 or more functions obtained by introducing a (poly) lactone structure into the molecular structure of the aliphatic poly (meth) acrylate compound.

The photosensitive resin composition of the present invention may contain an organic solvent for the purpose of adjusting coating viscosity, and the type and amount of the organic solvent may be appropriately selected and adjusted depending on the desired performance.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents may be used alone or in combination of 2 or more.

The photosensitive resin composition of the present invention may contain various additives such as inorganic fine particles, polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers, as necessary.

The cured product of the present invention can be obtained by irradiating the photosensitive resin composition with active energy rays. Examples of the active energy ray include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the curing reaction by ultraviolet rays can be efficiently performed, and the irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere.

As the ultraviolet light generating source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.

In addition, the cured product obtained by curing the photosensitive resin composition of the present invention has excellent heat resistance and is less likely to outgas, and therefore, can be suitably used as a package adhesive layer for a solder resist, an interlayer insulating material, a packaging material, an underfill material, a circuit element, or the like, or an adhesive layer between an integrated circuit element and a circuit board, for example, in the application to a semiconductor device. Further, the present invention can be suitably used for a protective film of a thin film transistor, a protective film of a liquid crystal color filter, a pigment resist for a color filter, a resist for a black matrix, a spacer, and the like in applications of thin displays represented by LCDs and OELDs.

The resin material for a solder resist of the present invention may contain, as required, various additives such as a curing agent, a curing accelerator, an organic solvent, inorganic fine particles, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer in the photosensitive resin composition.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth) acrylate resin (a), and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resins, phenyl ether type epoxy resins, naphthyl ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, and the like. These epoxy resins may be used alone or in combination of 2 or more. Among them, from the viewpoint of excellent heat resistance in the cured product, novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol-phenol condensed novolac-type epoxy resins, and naphthol-cresol condensed novolac-type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ℃ are particularly preferable.

The curing accelerator is a substance that accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, examples thereof include a phosphorus compound, a tertiary amine, imidazole, an organic acid metal salt, a lewis acid, and an amine complex salt. These curing accelerators may be used alone or in combination of 2 or more. The amount of the curing accelerator added is preferably in the range of 1 to 10 parts by mass per 100 parts by mass of the curing agent.

The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin (a) and the curing agent, and examples thereof include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents may be used alone or in combination of 2 or more.

The resist member of the present invention can be obtained, for example, as follows: the solder resist resin material is coated on a substrate, an organic solvent is evaporated and dried at a temperature of about 60 to 100 ℃, then, the substrate is exposed to active energy rays through a photomask having a desired pattern formed thereon, an unexposed portion is developed with an aqueous alkali solution, and the substrate is further heated and cured at a temperature of about 140 to 180 ℃.

Examples

The present invention will be specifically described below with reference to examples and comparative examples.

Synthesis example 1 Synthesis of (meth) acrylate resin (A-1) containing acid group

In a flask equipped with a thermometer, a stirrer and a reflux condenser, 101 parts by mass of diethylene glycol monomethyl ether acetate was placed to dissolve 428 parts by mass of an o-cresol novolak-type epoxy resin ("EPICLON-680", manufactured by DIC corporation; epoxy equivalent; 214g/eq), 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 part by mass of hydroquinone monomethyl ether (methoquinone) as a thermal polymerization inhibitor were added, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 120 ℃ for 10 hours while blowing air. Then, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added to the mixture, and the mixture was reacted at 110 ℃ for 2.5 hours to obtain an acid group-containing (meth) acrylate resin (A-1). The solid acid value of the acid group-containing (meth) acrylate resin (A-1) was 85 mgKOH/g.

Synthesis example 2 Synthesis of (meth) acrylate resin (A-2) containing acid group

379 parts by mass of diethylene glycol monomethyl ether acetate, 185 parts by mass of a modified isocyanurate of isophorone diisocyanate ("VESTANAT T-1890/100" manufactured by EVONIK, having an isocyanate group content of 17.2% by mass), 146 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene were charged into a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolved therein. The reaction was carried out at 160 ℃ for 5 hours under a nitrogen atmosphere, and it was confirmed that the content of isocyanate groups was 0.1% by mass or less. Next, 0.3 part by mass of hydroquinone monomethyl ether, 112 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toyo Seisaku-Sho, having a pentaerythritol triacrylate content of about 67% and a hydroxyl value of 159.7mgKOH/g), and 3.1 parts by mass of triphenylphosphine were added, and the reaction was carried out at 110 ℃ for 5 hours while blowing air. Then, 125 parts by mass of glycidyl methacrylate was added thereto, and the reaction was carried out at 110 ℃ for 5 hours. Further, 87 parts by mass of succinic anhydride was added thereto, and the reaction was carried out at 110 ℃ for 5 hours to obtain an acid group-containing (meth) acrylate resin (A-2). The solid acid value of the acid group-containing (meth) acrylate resin (A-2) was 80 mgKOH/g.

(Synthesis example 3 Synthesis of photopolymerization initiator (M17))

In a 1L four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, an alkali trap and a dropping funnel, 121.8g of aluminum chloride (anhydrous) and 300mL of dehydrated dichloromethane were charged, and the mixture was ice-cooled in an ice bath under a nitrogen stream. To this was added 200g of 2-bromobutyryl bromide. A mixed solution of 83.6g of fluorobenzene and 100mL of dehydrated dichloromethane was added dropwise to the flask over 20 minutes using a dropping funnel. After the addition was complete, the ice bath was removed and stirring was continued for 2 hours. After completion of the stirring, the reaction mixture was poured into 1L of ice water, and the stirring was continued for 2 hours. After standing, liquid separation was carried out, and the lower layer was recovered. Washing with 2N hydrochloric acid 2 times, saturated aqueous sodium bicarbonate solution 1 time, and saturated brine 2 times. After drying over magnesium sulfate overnight, methylene chloride was distilled off under reduced pressure to obtain an intermediate (101).

Yield: 214.3g, yield: 100 percent

In a 2L four-necked flask equipped with a stirrer and a thermometer, 789.9g of an 11% dimethylamine/ethanol solution was charged, and the mixture was cooled in ice bath. To this was added dropwise 157.7g of intermediate (101) over 30 minutes from a dropping funnel. After the dropwise addition, the ice bath was removed and the mixture was stirred continuously for a whole day and night. After completion of the stirring, ethanol was distilled off, and toluene was added. After washing with water, the upper layer was adjusted to pH1 using 2N hydrochloric acid, followed by liquid separation and recovery of the lower layer. The lower layer after recovery was adjusted to pH12 using a 10% aqueous solution of sodium hydroxide, and then toluene was added to recover the upper layer. The supernatant was washed with saturated saline 2 times, and the supernatant was collected and dried over magnesium sulfate overnight. The toluene was distilled off under reduced pressure to obtain an intermediate (102).

Yield: 134.6g, yield: 100 percent

In a 500mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 79.5g of intermediate (102), 71.4g of benzyl bromide (103) and 120mL of isopropyl alcohol (hereinafter abbreviated as "IPA") were charged, and the mixture was stirred at 50 ℃ for 2 hours. Then, 104mL of an 8M aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ℃ for 1 hour. After completion of the stirring, the reaction mixture was adjusted to pH6 with hydrochloric acid aqueous solution, and IPA was distilled off to remove precipitated crystals by filtration to obtain intermediate (104).

Yield: 96.7g, yield: 85.0 percent

34.3g of intermediate (104), 105mL of dimethyl sulfoxide (DMSO), 29.6g of anhydrous piperazine, and 7.9g of potassium carbonate were put in a 1L four-necked flask equipped with a stirrer, a thermometer, and a condenser, and heated at 120 ℃ for 24 hours under a nitrogen stream. After the reaction was stopped by adding water, extraction was performed with toluene. After washing with water 2 times, the mixture was dried over magnesium sulfate overnight. The toluene was distilled off under reduced pressure and recrystallized from methanol to obtain intermediate (5) having Michael addition supplying ability.

Yield: 36.9g, yield: 98.0% by mass

In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 45g of ethylene oxide-modified trimethylolpropane triacrylate ("Aronix M-350" manufactured by Toyo Seisaku-sho Co., Ltd.) and 12g of intermediate (5) having Michael addition supplying ability were charged, and the mixture was stirred at 80 ℃ for 6 hours to obtain 57g of a Michael addition reaction product (M17) represented by the following structural formula. The ratio of the group having a michael donating function to the group having a michael accepting function at the time of the reaction introduction is 1: 5.5.

(Synthesis example 4 Synthesis of photopolymerization initiator (M11))

In a 5L flask equipped with a stirrer, a thermometer, a nitrogen inlet, a condenser and an alkali trap, 500g of 4-fluorobenzophenone (105), 250mL of dimethyl sulfoxide (DMSO) and 1000mL of morpholine were charged, and the reaction was carried out while stirring at 95 ℃ for 2 days under nitrogen. The reaction was followed by gas chromatography to confirm conversion. After cooling naturally, 1.4L of toluene and 2.1L of water were added, and after standing still, liquid separation was performed, and then, the organic layer was washed with water 3 times, and toluene was distilled off under reduced pressure. To the obtained residue was added 700mL of isopropyl alcohol while stirring, and crystals precipitated under ice-cooling were collected by filtration and dried under reduced pressure to obtain intermediate (106).

Yield: 597g, yield: 85 percent of

348g of intermediate (106) and 348mL of methylene chloride were put into a 3L flask equipped with a stirrer, a thermometer, a nitrogen inlet, a condenser, a dropping funnel and an alkali trap, and then cooled with ice under nitrogen, and 724g of a 25% hydrogen bromide-acetic acid solution was added dropwise over 1 hour. After completion of the dropwise addition, 238g of bromine was added dropwise over 1 hour to maintain the temperature of 20 ℃ or lower, and the reaction was terminated by stirring at the same temperature for 1 hour. 2L of water was added, followed by neutralization with sodium hydroxide, and then 1.5L of methylene chloride was added to and dissolved in the crystals of the precipitated product. The organic layer was washed with 5% sodium hydrogencarbonate 1 time, water 1 time, and saturated sodium chloride 1 time, and then dichloromethane was distilled off under reduced pressure. 1.5L of hexane was added thereto, and ice-cooling was performed, and the precipitated crystals were collected by filtration and dried to obtain an intermediate (107).

Yield: 438g, yield: 94 percent of

290g of intermediate (107) and 870mL of 2-butanone were put into a 3L flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 251g of a 50% dimethylamine aqueous solution was added dropwise at 5 to 10 ℃ while cooling with ice, and the mixture was stirred at the same temperature for 5 hours to complete the reaction. After the organic layer was washed 4 times with 500mL of water, 2-butanone was distilled off under reduced pressure to obtain a crude product containing intermediate (108). The obtained crude product was used in the next step without purification. A part of the crude product was sampled and recrystallized using hexane, thereby obtaining intermediate (108) as pale yellow crystals.

The intermediate (108) obtained as described above, 256g of methyl 4- (bromomethyl) benzoate (109), and IPA510mL were put into a 3L flask equipped with a stirrer, a thermometer, and a condenser, and stirred at 50 ℃ for 3 hours. Then, 232mL of 8M aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ℃ for 1 hour. After completion of the stirring, pH5.7 was adjusted with hydrochloric acid aqueous solution, and IPA was distilled off. The concentrated residue was extracted with ethyl acetate, washed with water 2 times and saturated brine 1 time. After ethyl acetate was distilled off under reduced pressure, the precipitated crystals were removed by filtration by adding hexane, and dried under reduced pressure to obtain intermediate (110).

Yield: 2900g, yield: 760% of

In a 300mL flask equipped with a stirrer, a thermometer and a dropping funnel, 28.9g of intermediate (110), 1mL of N, N-Dimethylformamide (DMF) and 100mL of methylene chloride were added and dissolved, and 16.8g of thionyl chloride was added dropwise thereto and reacted for 2 hours. The reaction solution was concentrated under reduced pressure, and the concentrated residue was dissolved in 50mL of methylene chloride to prepare a methylene chloride solution of acid chloride. In another 500mL flask equipped with a stirrer, a thermometer and a dropping funnel, 30.3g of piperazine and 200mL of methylene chloride were added and dissolved, and a methylene chloride solution of the acid chloride was added dropwise thereto over 30 minutes. After stirring for 30 minutes, the reaction was terminated, and a 1M aqueous sodium hydroxide solution was added to stop the reaction. The reaction solution was transferred to a separatory funnel, and the organic layer was washed with water 2 times and then dried over magnesium sulfate overnight. Methylene chloride was distilled off under reduced pressure to obtain intermediate (16) having Michael addition supplying ability.

Yield: 33.0g, yield: 98.0 percent

In a 100mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 12.5g of ethylene oxide-modified trimethylolpropane triacrylate ("Aronix M-350" manufactured by Toyo Seisaku-sho.) and 12g of intermediate (16) having Michael addition supplying ability were charged and stirred at 80 ℃ for 6 hours to obtain 24.5g of a Michael addition reaction product (M11) represented by the following structural formula. The ratio of the group having a michael donating function to the group having a michael accepting function at the time of the reaction introduction is 1: 3.5.

(Synthesis example 5 Synthesis of photopolymerization initiator (M3))

Into a 500mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 79.5g of the intermediate (102) prepared in Synthesis example 3, 87.0g of methyl 4- (bromomethyl) benzoate (109) and IPA120mL were charged, and the mixture was stirred at 50 ℃ for one day and night. Then, 105mL of an 8M aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ℃ for 1 hour. After completion of the stirring, pH5.6 was prepared using 6N hydrochloric acid, IPA was distilled off, and the residue was crystallized from ethyl acetate and hexane to obtain intermediate (112).

Yield: 72.5g, yield: 50.2 percent

In a 500mL four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 19.3g of 2-chloro-4.6-dimethoxy-1, 3, 5-triazine and 100mL of dehydrated dichloromethane were charged, and the mixture was ice-cooled in an ice bath. To this was added dropwise 33.3g of N-methylmorpholine over 10 minutes from a dropping funnel. After completion of the dropwise addition, 38.0g of intermediate (112) was added, and the mixture was stirred under ice-cooling for 2 hours. To this, 200mL of dehydrated dichloromethane containing 34.4g of piperazine dissolved therein was added dropwise over 20 minutes using a dropping funnel. The ice bath was removed and stirring continued at room temperature for 2 hours. After completion of the stirring, the mixture was poured into distilled water, and the methylene chloride layer was recovered. Further, the intermediate (113) was obtained by washing the reaction mixture with distilled water 2 times, drying the reaction mixture over magnesium sulfate overnight, and distilling off methylene chloride under reduced pressure. Then, 100mL of dimethyl sulfoxide (DMSO) and 34.4g of piperazine were added, and the mixture was heated at 120 ℃ for 15 hours under a nitrogen stream. After completion, distilled water was added to remove the precipitated crystals by filtration, and the crystals were washed with distilled water and ethanol alternately 2 times and dried to obtain an intermediate (7) having Michael addition supplying ability.

Yield: 41.7g, yield: 87.4 percent

28.6g of ethylene oxide-modified trimethylolpropane triacrylate ("Aronix M-350" manufactured by Toyo Seiyaku Co., Ltd.) and 12g of intermediate (7) having Michael addition supplying ability were charged into a 100mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and stirred at 80 ℃ for 6 hours to obtain 40.6g of a Michael addition reaction product (M3) represented by the following structural formula. The ratio of the group having a michael donating function to the group having a michael accepting function at the time of the reaction introduction is 1: 4.0.

(Synthesis example 6 Synthesis of photopolymerization initiator (M18))

The photopolymerization initiator (M18) was synthesized according to the synthesis example of compound 5 described in example 3 of Japanese patent application laid-open No. 2008-519760, to obtain a Michael addition reaction product (M18) represented by the following structural formula.

Example 1 preparation of photosensitive resin composition (1)

100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis example 1, 24.6 parts by mass of an o-cresol novolac type epoxy resin ("EPICLON-680", manufactured by DIC corporation) as a curing agent, 6.3 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of the photopolymerization initiator (M17) obtained in Synthesis example 3, 13.3 parts by mass of diethylene glycol monomethyl ether acetate, 0.5 part by mass of 2-ethyl-4-methylimidazole, and 0.7 part by mass of phthalocyanine green were blended and kneaded by a roll mill to obtain a photosensitive resin composition (1).

(examples 2 to 5 preparation of photosensitive resin compositions (2) to (5))

Photosensitive resin compositions (2) to (5) were obtained in the same manner as in example 1, except that the acid group-containing (meth) acrylate resin (a-1) and the photopolymerization initiator (M17) used in example 1 were changed to the compositions shown in table 1.

Comparative examples 1 and 2 preparation of photosensitive resin compositions (C1) and (C2)

Photosensitive resin compositions (C1) and (C2) were obtained in the same manner as in example 1 except that 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Omnirad 907" by IGM) or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone ("Omnirad 369" by IGM) was used in the compounding amounts shown in table 1 in place of the photopolymerization initiator (M17) used in example 1.

The photosensitive resin compositions (1) to (5) obtained in examples 1 to 5 and the photosensitive resin compositions (C1) and (C2) obtained in comparative examples 1 and 2 were used to perform the following evaluations.

[ method for evaluating sensitivity ]

The photosensitive resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Next, a "stepped Exposure Table No. 2" manufactured by Kodak corporation was placed on the dried coating film "Irradiating with a metal halide lamp at 500mJ/cm²Ultraviolet rays of (1). This was developed in a 1% aqueous solution of sodium carbonate at 30 ℃ for 180 seconds, and evaluated in the number of residual stages of a stepwise exposure table based on the stepwise exposure table method. The larger the number of residual stages, the higher the sensitivity.

[ method for evaluating alkali developability ]

The photosensitive resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and then dried at 80 ℃ for 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, and 100 minutes, respectively, to prepare samples having different drying times. These were developed in a 1% aqueous solution of sodium carbonate at 30 ℃ for 180 seconds, and the drying time at 80 ℃ of the sample with no residue remaining on the substrate was evaluated as the drying control range according to the following evaluation criteria. The longer the drying control width, the more excellent the alkali developability.

O: the drying control range is more than 60 minutes.

X: the drying management amplitude is less than 60 minutes.

The compositions and evaluation results of the photosensitive resin compositions (1) to (5) prepared in examples 1 to 5 and the photosensitive resin compositions (C1) and (C2) prepared in comparative examples 1 and 2 are shown in table 1.

[ Table 1]

Example 6 preparation of photosensitive resin composition (6)

A photosensitive resin composition (6) was obtained by blending 100 parts by mass of the acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis example 1, 24.6 parts by mass of an o-cresol novolak-type epoxy resin ("EPICLON-680", manufactured by DIC corporation) as a curing agent, 8 parts by mass of the photopolymerization initiator (M17) obtained in Synthesis example 3, and 13.3 parts by mass of diethylene glycol monomethyl ether acetate.

Examples 7 to 10 preparation of photosensitive resin compositions (7) to (10)

Photosensitive resin compositions (7) to (10) were obtained in the same manner as in example 6, except that the acid group-containing (meth) acrylate resin (a-1) and the photopolymerization initiator (M17) used in example 6 were changed to the compositions shown in table 2.

Comparative examples 3 and 4 preparation of photosensitive resin compositions (C3) and (C4)

Photosensitive resin compositions (C3) and (C4) were obtained in the same manner as in example 6 except that 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone ("Omnirad 369" manufactured by IGM) was used in the compounding amounts shown in table 2 in place of the photopolymerization initiator (M17) used in example 6.

The following evaluations were carried out using the photosensitive resin compositions (6) to (10) obtained in examples 6 to 10 and the photosensitive resin compositions (C3) and (C4) obtained in comparative examples 3 and 4.

[ method for evaluating Heat resistance ]

The photosensitive resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Subsequently, the mixture was irradiated with a metal halide lamp at 500mJ/cm²After the UV light (2), the cured product was peeled from the glass substrate by heating at 200 ℃ for 1 hour to obtain a cured product. A test piece of 6 mm. times.35 mm was cut out from the cured product, and the glass transition temperature was evaluated using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus "RSAII" manufactured by Rheometrics, Inc., frequency 1Hz, temperature rise rate 3 ℃/min) at a temperature at which the change in elastic modulus became maximum. The higher the glass transition temperature, the more excellent the heat resistance.

[ method of measuring exhaust gas ]

The photosensitive resin compositions obtained in examples and comparative examples were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Then, the mixture was irradiated with 500mJ/cm by a metal halide lamp²After UV irradiation, heating at 200 deg.CAfter 1 hour, the cured product was peeled off from the glass substrate to obtain a cured product. A powder sample was collected from the solidified product and placed in a thermal desorption apparatus (TDU) manufactured by GERSTEL. Then, liquid nitrogen was used to trap (1) the exhaust gas component at a heat extraction temperature of 150 ℃ for 10 minutes and (2) the exhaust gas component at a heat extraction temperature of 260 ℃ for 10 minutes, respectively, at-60 ℃. The trapped exhaust gas components were separated and analyzed by a gas chromatography mass spectrometer (6890N/5973N) manufactured by Agilent Technologies, and quantified in terms of N-dodecane, and evaluated according to the following evaluation standards.

Very good: substantially no exhaust gas components were confirmed.

O: a small amount of exhaust gas components was confirmed.

And (delta): exhaust gas components were confirmed.

X: a large amount of exhaust gas components were confirmed.

The compositions and evaluation results of the photosensitive resin compositions (6) to (10) prepared in examples 6 to 10 and the photosensitive resin compositions (C3) and (C4) prepared in comparative examples 3 and 4 are shown in table 2.

[ Table 2]

The "curing agent" in tables 1 and 2 represents an o-cresol novolac type epoxy resin ("EPICLON-680" manufactured by DIC corporation, epoxy equivalent: 214 g/equivalent).

The "organic solvent" in tables 1 and 2 represents diethylene glycol monomethyl ether acetate.

Claims

1. A photosensitive resin composition, comprising: a (meth) acrylate resin (A) having an acid group and a photopolymerization initiator (B),

the photopolymerization initiator (B) is a Michael addition reaction product of a compound (B1) containing an alpha-aminoacetophenone skeleton, which functions as a Michael addition donor, represented by the following general formula (1), and a reactive compound (B2) having a function as a Michael acceptor,

in the general formula (1) above,

R¹represents an aliphatic group or an aromatic group,

R²and R³Each independently represents an aliphatic group or an aryl group,

and R²And R³Optionally each of which is integrated to form a ring,

X²represents a carbonyl group or a thiocarbonyl group,

Y²represents a group represented by the following general formula (2) or the following general formula (3), wherein Y¹And Y²When all have the structure represented by the following general formula (2), X represents at least one of them⁵is-NH-,

n is a number of 0 or 1,

in the general formula (2), X³And X⁴Each independently represents a linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, X⁵Represents a single bond, -O-or-NH-,

in the general formula (3), X⁶Represents a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms and being substituted or unsubstitutedRadical, R⁸And R⁹Each independently represents an aliphatic group or an aryl group,

in the general formula (4), R¹⁰And R¹¹Each independently represents an aliphatic group or an aryl group.

2. The photosensitive resin composition according to claim 1, wherein the reactive compound (b2) having a function as a Michael acceptor is a polyfunctional (meth) acrylate compound.

3. A cured product of the photosensitive resin composition according to claim 1 or 2.

4. An insulating material comprising the photosensitive resin composition according to claim 1 or 2.

5. A resin material for a solder resist, which is formed from the photosensitive resin composition according to claim 1 or 2.

6. A resist member comprising the resin material for a solder resist according to claim 5.