WO2020202691A1 - Photosensitive resin composition, dry film, cured object, and electronic component - Google Patents

Abstract

Provided are a photosensitive resin composition, or the like, having excellent optical properties (resolution) and with which can be obtained a cured object having excellent reliability with respect to heat resistance, crack resistance, etc. This photosensitive resin composition comprises (A) a curable copolymer resin having at least a first repeating unit represented by formula (1) and a second repeating unit represented by formula (2), (B1) an epoxy resin, (B2) a maleimide compound having two or more maleimide structures within one molecule, (C) a photopolymerization initiator, and (D) silica, and is characterized in that the amount of the (D) silica blended, converted to solid contents, is 25 to 75 % by mass, and when the photosensitive resin composition is irradiated with a 1,000 mJ/cm² light and heated at 160°C for one hour to obtain a cured object, the difference (H-L), between the mean coefficient of linear thermal expansion (L) calculated in the 0°C to 50°C range and the mean coefficient of linear thermal expansion (H) calculated in the 200°C to 250°C range, for this cured object, is over 20 ppm/°C but lower than or equal to 60 ppm/°C.

Description

Photosensitive resin compositions, dry films, cured products, and electronic components

The present invention relates to a photosensitive resin composition, a dry film, a cured product, and an electronic component.

Conventionally, a photosensitive resin composition containing a carboxyl group-containing resin and a thermosetting resin has been used as a material for forming a permanent coating such as a solder resist of a printed wiring board (for example, Patent Document 1). In recent years, due to the expansion of applications in harsh environments such as in-vehicle applications, there is an increasing demand for high reliability of permanent coatings such as solder resists, such as improved heat resistance and crack resistance.

Japanese Patent Application Laid-Open No. 1-141904

In order to achieve the above-mentioned improvement in heat resistance, it is conceivable to use a resin having a large molecular weight and a rigid skeleton, but such a resin causes an increase in melt viscosity and a decrease in developability. In addition, an increase in melt viscosity leads to poor laminating, and a decrease in developability causes a problem that resolution is deteriorated.

In order to solve these problems, a method of using resins having different skeletons together can be considered. For example, by using a maleimide resin having a rigid skeleton in combination with an epoxy resin or an acrylic resin, it is possible to reduce the melt viscosity and improve the developability while maintaining the physical properties. However, this requires compatibility between the resins used in combination. When the compatibility deteriorates, the melt viscosity becomes less likely to decrease as a result.

In addition, it is important to control the coefficient of thermal expansion in order to improve the crack resistance described above. For example, in the case of solder resist, it is in contact with various members such as copper wiring, solder, and underfill, and it is important that the CTE difference does not increase with any of the materials from the viewpoint of suppressing cracks.

Further, in the above-mentioned photosensitive resin composition, the pattern forming property by photolithography is also important, and the improvement of the optical property (resolution) is also required.

Therefore, an object of the present invention is to obtain a photosensitive resin composition having excellent reliability such as heat resistance and crack resistance, and having excellent light characteristics (resolution), from the composition. It is an object of the present invention to provide a dry film having a resin layer, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.

As a result of diligent studies toward the realization of the above object, the present inventors have cured with a repeating unit derived from a maleimide-based monomer and a repeating unit derived from an unsaturated carboxylic acid ester monomer having a heat-crosslinkable group. Obtained by blending a sex copolymer resin, an epoxy resin, a maleimide compound having two or more maleimide structures in one molecule, a photopolymerization initiator, and a specific amount of silica, and subjecting the mixture to light irradiation and heat treatment at 160 ° C. Difference (HL) between the average linear thermal expansion rate (L) calculated in the range of 0 ° C. to 50 ° C. and the average linear thermal expansion coefficient (H) calculated in the range of 200 ° C. to 250 ° C. It has been found that the above-mentioned problems can be solved by having a specific range, and the present invention has been completed.

That is, the photosensitive resin composition of the present invention has (A) at least a first repeating unit represented by the following formula (1) and a second repeating unit represented by the following formula (2). A photosensitive resin composition containing a polymer resin, (B1) epoxy resin, (B2) a maleimide compound having two or more maleimide structures in one molecule, (C) a photopolymerization initiator, and (D) silica. The amount of the silica (D) blended is 25 to 75% by mass based on the total solid content of the photosensitive resin composition, and the photosensitive resin composition is irradiated with light of 1000 mJ / cm ² and 160 ° C. for 1 hour. The average linear thermal expansion rate (L) calculated in the range of 0 ° C to 50 ° C and the average linear thermal expansion rate (H) calculated in the range of 200 ° C to 250 ° C of the cured product obtained by the above heat treatment. The difference (HL) is more than 20 ppm / ° C. and 60 ppm / ° C. or less.

(In the formula, R ₀ is a monovalent organic group having 1 to 30 carbon atoms, R ₁ is a hydrogen atom or an organic group having 1 to 7 carbon atoms, and R ₂ is a single bond or 1 carbon atom. an alkylene group of ~ 5, R ₃ represents a monovalent group having a heat crosslinking.)

The photosensitive resin composition of the present invention preferably has a weight average molecular weight of the curable copolymer resin (A) of less than 10,000.

The photosensitive resin composition of the present invention contains two or more of the (B1) epoxy resin and the (B2) maleimide structure in one molecule in the total solid content of the photosensitive resin composition excluding the (D) silica. It is preferable to contain 1 to 50% by mass of the maleimide compounds having the same.

In the photosensitive resin composition of the present invention, it is preferable that the (D) silica contains at least one of silica having a (meth) acrylic group and silica having an amino group.

The photosensitive resin composition of the present invention preferably has a glass transition point (Tg) of the cured product of 170 ° C. or higher.

The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to the film and drying it.

The cured product of the present invention is characterized by being obtained by curing the photosensitive resin composition or the resin layer of the dry film.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, a cured product having excellent reliability such as heat resistance and crack resistance can be obtained, and a photosensitive resin composition having excellent light characteristics (resolution) can be obtained from the composition. A dry film having a resin layer, the composition or a cured product of the resin layer of the dry film, and an electronic component having the cured product can be provided.

The photosensitive resin composition of the present invention is a curable copolymer resin having (A) at least a first repeating unit represented by the formula (1) and a second repeating unit represented by the formula (2). (Hereinafter, simply abbreviated as "(A) curable copolymer resin"), (B1) epoxy resin, (B2) maleimide compound having two or more maleimide structures in one molecule (hereinafter, simply "(B2) maleimide" A photosensitive resin composition containing (also abbreviated as "compound"), (C) a photopolymerization initiator, and (D) silica, wherein the blending amount of the (D) silica is the solid content of the photosensitive resin composition. The total amount is 25 to 75% by mass, and the cured product obtained by subjecting the photosensitive resin composition to light irradiation of 1000 mJ / cm ² and heat treatment at 160 ° C. for 1 hour is in the range of 0 ° C. to 50 ° C. Difference (HL) between the average linear thermal expansion rate (L) calculated in 1 and the average linear thermal expansion rate (H) calculated in the range of 200 ° C. to 250 ° C. (hereinafter, simply "of the average linear thermal expansion rate". The difference) (also abbreviated as "difference") is more than 20 ppm / ° C. and 60 ppm / ° C. or less. By subjecting the photosensitive resin composition of the present invention to light irradiation and heat treatment after development to main curing, it is possible to obtain a cured product having excellent reliability even at a low heat treatment temperature. If the difference in the average coefficient of linear thermal expansion is 20 ppm / ° C. or less, the CTE difference from the solder or underfill becomes large, which causes cracks. Further, if the difference in the average coefficient of linear thermal expansion exceeds 60 ppm / ° C., the CTE difference from copper becomes large, which causes cracks.

In the present invention, since the (A) curable copolymer resin has a specific skeleton, the crosslink density due to thermosetting increases, the Tg increases, and the CTE can be decreased. Although the conventional composition does not satisfy the CTE difference, H becomes smaller and it becomes easier to satisfy the CTE difference. Further, by increasing the crosslink density in this way, the heat shrinkage can be reduced as compared with the case where the ethylenically unsaturated double bond equivalent of the photocurable component is reduced and the crosslink density is increased. Further, in the present invention, 25 to 75% by mass of (D) silica is further blended as a filler. If the amount of silica (D) blended exceeds 75% by mass, the average coefficient of linear thermal expansion L will drop too much, making it difficult to satisfy the difference (HL) in the average coefficient of linear thermal expansion. , Alkali solubility deteriorates. In the present invention, by blending the above components, the difference in average linear thermal expansion coefficient (HL) can be satisfied, and a highly reliable cured product can be obtained.

The difference (HL) in the average coefficient of linear thermal expansion is preferably 30 to 55 ppm / ° C., more preferably 35 to 55 ppm / ° C.

The average coefficient of linear thermal expansion L is preferably 10 to 50 ppm / ° C.

The average coefficient of linear thermal expansion H is preferably 40 to 100 ppm / ° C.

The glass transition point (Tg) of the cured product obtained under the above-mentioned production conditions is preferably 170 ° C. or higher, more preferably 180 ° C. or higher.

The components of the photosensitive resin composition of the present invention will be described below.

((A) Curable copolymer resin)
The photosensitive resin composition of the present invention is a curable copolymer resin having (A) at least a first repeating unit represented by the following formula (1) and a second repeating unit represented by the following formula (2). Contains.

(In the formula (1), R ₀ is a monovalent organic group having 1 to 30 carbon atoms, and in the formula (2), R ₁ is a hydrogen atom or an organic group having 1 to 7 carbon atoms, and R Reference numeral ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₃ is a monovalent group having a thermocrosslinkability.) The monovalent organic group is a monovalent group having a carbon atom. Means the basis of.

In the above formula (1), the monovalent organic group having 1 to 30 carbon atoms that R ₀ can take is an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a lauryl group; a phenyl group. Hydroxyphenyl group; alkylaryl group having 7 to 30 carbon atoms such as 2-methylphenyl group and 2,6-diethylphenyl group; alkoxyaryl group having 7 to 30 carbon atoms such as 2-methoxyphenyl group; benzyl group and the like Aralkyl group having 7 to 30 carbon atoms; cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group; 2-chlorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl An aryl halide group having 1 to 30 carbon atoms such as a group; an alkoxysilylalkyl group having 1 to 30 carbon atoms such as an N- [3- (triethoxysilyl) propyl] group; and 1 carbon number such as a dodecenyl group and an octadecenyl group. Examples thereof include up to 30 alkenyl groups and carboxyl groups. The monovalent organic group having 1 to 30 carbon atoms that can be taken by R ₀ can have 20 or less carbon atoms, 15 or less carbon atoms, 10 or less carbon atoms, or 7 or less carbon atoms.

In the formula (1), R ₀ is preferably an organic group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkylaryl group having 7 to 30 carbon atoms, and 3 carbon atoms. It is preferably a cycloalkyl group of about 30 or an aralkyl group having 7 to 30 carbon atoms.

In the formula (2), R ₁ is preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group, an alkenyl group having 1 to 7 carbon atoms, or a carboxyl group, and is preferably a hydrogen atom or a carboxyl group. It is more preferably an alkyl group having 1 to 5 carbon atoms.

In the formula (2), the alkylene group having 1 to 5 carbon atoms that can be taken by R ₂ may have a substituent. Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, an n-propylene group, a trimethylene group and a butylene group. Examples of the substituent include a hydroxyl group and the like.

In the formula (2), examples of the monovalent group having thermal crosslinkability represented by R ₃ include a hydroxyl group, a carboxyl group, an amino group, and a thiol group. R ₃ is preferably a hydroxyl group.

The curable copolymer resin (A) requires a structural unit derived from the maleimide-based monomer represented by the formula (1) and a structural unit derived from the unsaturated carboxylic acid ester monomer represented by the formula (2) as essential units. It has as. The curable copolymer resin (A) may have a structural unit derived from an unsaturated carboxylic acid monomer or the like, if necessary, and may contain a monomer having a functional group capable of reacting with a carboxyl group. It may have a structure formed by reacting. The first repeating unit represented by the formula (1) is a maleimide-based monomer, that is, a repeating unit derived from a maleimide or a maleimide derivative.

Examples of the maleimide or maleimide derivative (hereinafter, also referred to as “maleimide-based monomer”) include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, and N- (2). , 6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenyl Methylmaleimide, N- (2,4,6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- N-substituted maleimides such as (2-methoxyphenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (1-hydroxyphenyl) maleimide, and unsubstituted. Maleimide can be mentioned, and one or a combination of two or more of these can be used. Among these, N-phenylmaleimide, N- (2-methylphenyl) maleimide, and N- (2,6-diethylphenyl) have a large effect of improving heat resistance, good copolymerizability, and are easily available. Maleimide, N-lauryl maleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are more preferable, and N-phenylmaleimide and N-benzylmaleimide are most preferable. ..
It is also preferable to use N-phenylmaleimide and N-benzylmaleimide in combination. The preferable ratio of N-phenylmaleimide and N-benzylmaleimide when used in combination is 99: 1 to 1:99 by mass ratio.

The maleimide-based monomer (maleimide-based monomer unit) comprises all the monomer components (constituting the base polymer) constituting the polymer (base polymer) in (A) 100% by mass of the curable copolymer resin. It is preferably 10 to 60% by mass based on 100% by mass of all the monomer units.
The curable copolymer resin (A) preferably has 10 to 60% by mass of a constituent unit derived from the maleimide-based monomer represented by the formula (1) in 100% by mass of the main chain and an unsaturated carboxylic acid represented by the formula (2). It may contain 10 to 40% by mass of a structural unit derived from an acid ester monomer, and may contain 10 to 40% by mass of a structural unit derived from an unsaturated carboxylic acid monomer, if necessary, and a radically polymerizable carbon-carbon in the side chain. It may have a double bond (ethylenically unsaturated group).
In the following, the description of the monomer unit indicates a structural unit derived from the monomer, and the polymerizable carbon-carbon double bond (C = C) in the monomer is a single bond (C-). It means the structural unit that became C). For example, the maleimide-based monomer unit means a structural unit derived from the maleimide-based monomer when the maleimide-based monomer is copolymerized or graft-polymerized.
The (A) curable copolymer resin of the present invention may have at least a thermosetting reaction with the (B1) epoxy resin, but the components (A) may have ethylenically unsaturated groups capable of photocuring with each other. preferable.

The curable copolymer resin (A) can be obtained by radically polymerizing an unsaturated carboxylic acid monomer or the like as necessary, using a maleimide-based monomer and an unsaturated carboxylic acid ester monomer as essential components. preferable.

The unsaturated carboxylic acid ester monomer will be described. Since the unsaturated carboxylic acid ester monomer has a thermally crosslinkable group such as a hydroxyl group, it reacts with the (B1) epoxy resin to improve the cured product properties. Examples of the unsaturated carboxylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , (Di) hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 2-hydroxymethyl ( Meta) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5- Examples thereof include (meth) acrylicoyl-based monomers such as hydroxyalkyl (meth) acrylamide such as hydroxypentyl (meth) acrylamide and 6-hydroxyhexyl (meth) acrylamide, and one or more of these can be used. .. Of these, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable from the viewpoint of copolymerizability.
Further, the unsaturated carboxylic acid ester monomer may be one in which the hydroxyl group (hydroxy group) of the above-exemplified monomer is changed to at least one of a carboxyl group, an amino group and a thiol group. That is, carboxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, and thioalkyl (meth) acrylate may be used.

Next, the unsaturated carboxylic acid (monomer) will be described. It is preferable to use an unsaturated carboxylic acid as a monomer in order to introduce a carboxyl group as an alkali-soluble group necessary for alkaline development and to improve the characteristics of the cured product. Specific examples include (meth) acrylic acid, crotonic acid, silicic acid, sorbic acid, fumaric acid, maleic acid and the like, and among them, (meth) acrylic acid is preferable because it has excellent properties of a cured product. Moreover, as another embodiment, another acid group may be introduced together with the carboxyl group or in place of the carboxyl group. Examples of other acid groups include functional groups that neutralize with alkaline water, such as phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, and sulfonic acid groups, and have only one of these groups. However, it may have two or more kinds. In the following description, the description for the carboxyl group also applies to the other acid groups described above.

Other copolymerizable monomer components may be used in obtaining the polymer (base polymer) as long as the properties are not adversely affected.
Specific examples of such monomer components include aromatic monomers; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like. (Meta) acrylic monomers; alkylvinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and the corresponding alkyl vinyl (thio). Ether; an acid anhydride group-containing monomer such as maleic anhydride, a monomer obtained by ring-opening the acid anhydride group with alcohols, or an unsaturated basic acid other than those described above; N-vinylpyrrolidone, Examples thereof include N-vinyl-based monomers such as N-vinyloxazolidone; cyano group-containing monomers such as acrylonitrile and methacrylonitrile.

Among these, aromatic monomers are preferable because they have good copolymerizability with maleimide-based monomers and also have excellent properties of cured products. Specific examples thereof include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene and the like, and styrene is most preferable because it has excellent electrical characteristics and is inexpensive.

(A) When introducing a polymerizable carbon-carbon double bond into a curable copolymer resin, for example, a functional group capable of reacting with the carboxyl group and ethylene with respect to the carboxyl group of the polymer (base polymer). A monomer having a sex unsaturated group is reacted to impart radical polymerizable property to obtain a radically polymerizable polymer.
The functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of a glycidyl group, an oxazolinyl group, an isocyanate group and an oxetanyl group. The radically polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group. As specific monomers, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

(A) When the curable copolymer resin has an ethylenically unsaturated group, the double bond equivalent is 600 to 4000 g / eq. It is preferable to carry out a radically polymerizable carbon-carbon double bond introduction reaction so as to be. The double bond equivalent is related to the photocurability and the physical properties of the cured product, and by setting the double bond equivalent within the above range, a cured product having excellent physical properties such as heat resistance, strength and flexibility can be provided. In addition, a well-balanced photosensitive resin having both photocurability and alkali developability can be obtained. A more preferred range of double bond equivalents is 700-3000 g / eq. And more preferably 800-2500 g / eq. Is.

When the curable copolymer resin (A) has a carboxyl group, its acid value is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and preferably 160 mgKOH / g or less. , 155 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is further preferable. When the acid value of the curable copolymer resin (A) is 30 mgKOH / g or more, good alkali developability can be easily exhibited. (A) When the acid value of the curable copolymer resin is 160 mgKOH / g or less, the exposed portion is less likely to be eroded by the alkaline developer, and the water resistance and moisture resistance of the cured product are improved.

The preferable range of the weight average molecular weight Mw of the curable copolymer resin (A) is determined by gel permeation chromatography (hereinafter, also referred to as “GPC”) in consideration of alkali developability, physical properties of the cured coating film, heat resistance and the like. The measured value is preferably 1,000 to 100,000 in terms of polystyrene. Further, considering that the physical properties such as sensitivity and crack resistance are both better, it is more preferable that the weight average molecular weight of the (A) curable copolymer resin is less than 10,000.

The blending amount of the (A) curable copolymer resin is, for example, 10 to 80% by mass in the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.

(Alkali-soluble resin)
The photosensitive resin composition of the present invention may further contain an alkali-soluble resin different from the component (A). The alkali-soluble resin may be any resin having an alkali-soluble group, and the alkali-soluble group is, for example, any one of a phenolic hydroxyl group, a thiol group and a carboxyl group. Examples of the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups, and among them, excellent developability. Therefore, a carboxyl group-containing resin is preferable. The carboxyl group-containing resin does not have to have an ethylenically unsaturated group, but a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group is preferable from the viewpoint of photocurability and development resistance. .. As the ethylenically unsaturated group, a (meth) acryloyl group is preferable. As used herein, the term (meth) acryloyl group is a general term for acryloyl groups, methacryloyl groups, and mixtures thereof, and the same applies to other similar expressions. The alkali-soluble resin may be used alone or in combination of two or more.

Specific examples of the carboxyl group-containing resin include the following compounds (either oligomer or polymer).

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing photosensitive urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) During the synthesis of the resin according to (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (4). Meta) Acryloylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin according to (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are formed in the molecule, such as an isophorone diisocyanate and a pentaerythritol triacrylate isomorphic reaction product. A carboxyl group-containing photosensitive urethane resin that is terminally (meth) acrylicized by adding a compound to it.

(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group existing in a side chain.

(7) Carboxylic acid obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups. Group-containing photosensitive resin.

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and the generated primary hydroxyl group is subjected to two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. A carboxyl group-containing polyester resin to which an acid anhydride is added.

(9) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin obtained by reacting a polybasic anhydride such as an acid.

(10) Reaction production obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxide such as ethylene oxide and propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a substance with a polybasic acid anhydride.

(11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (11).

The alkali-soluble resin is preferably an alkali-soluble resin having an aromatic ring. As the alkali-soluble resin having an aromatic ring, a known and commonly used alkali-soluble resin may be used, and when synthesizing the alkali-soluble resin, a raw material having an aromatic ring may be used for synthesis. Examples of the alkali-soluble resin having an aromatic ring include the resin (10), the resin (11), and the corresponding resin (12). Further, the resins (1) to (9) obtained by using a raw material having an aromatic ring and the corresponding resins (12) can also be mentioned.

The acid value of the alkali-soluble resin is appropriately in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkaline development becomes easy, while drawing a normal cured product pattern of 200 mgKOH / g or less becomes easy, which is preferable.

The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,000 to 10,000, more preferably 1,000 to 9,000. When the weight average molecular weight is 1,000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and deterioration in resolution can be suppressed. On the other hand, when the weight average molecular weight is 10,000 or less, the compatibility is excellent and the increase in melt viscosity can be suppressed. In addition, the developability is good and the storage stability is also excellent.

The blending amount of the alkali-soluble resin is, for example, 0 to 70% by mass in the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.

[(B1) Epoxy resin]
The photosensitive resin composition of the present invention contains (B1) epoxy resin. The (B1) epoxy resin is preferably a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 850 manufactured by DIC Corporation, EPICLON 1050, EPICLON 2055, and Epototo YD-011 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -013, YD-127, YD-128, D.D., manufactured by Dow Chemical Corporation. E. R. 317, D.I. E. R. 331, D. E. R. 661, D.I. E. R. 664, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, etc. (all trade names) bisphenol A type epoxy resin; Mitsubishi Chemical Co., Ltd. jERYL903, DIC Corporation EPICLON 152, EPICLON 165, Epototo YDB-400, YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., D.D. E. R. 542, Sumitomo Chemical's Sumi-Epoxy ESB-400, ESB-700, etc. (all trade names) brominated epoxy resins; Mitsubishi Chemical's jER152, jER154, Dow Chemical's D.D. E. N. 431, D.I. E. N. 438, EPICLON N-730A manufactured by DIC, EPICLON N-770, EPICLON N-865, N-870, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPPN-201 manufactured by Nippon Steel & Sumikin Co., Ltd. Novolak type epoxy resins such as EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Industry Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, etc. (all trade names); EPICLON manufactured by DIC Co., Ltd. 830, Mitsubishi Chemical's jER807, Nippon Steel & Sumikin Chemical's Epototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Nippon Steel & Sumikin Chemical's Epototo ST-2004 , ST-2007, ST-3000 (trade name), etc. Hydrogenated bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Sumi-epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. Glysidylamine type epoxy resin of -120 etc. (both trade names); alicyclic epoxy resin of Celoxide 2021P etc. (trade name) manufactured by Daicel Co., Ltd .; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.K. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resins; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 (all trade names), etc. Mold or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayakusha, EPX-30 manufactured by ADEKA, EXA-1514 (trade name) manufactured by DIC; manufactured by Mitsubishi Chemical Co., Ltd. Bisphenol A novolac type epoxy resin such as jER157S (trade name); Tetraphenylol ethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd .; TEPIC manufactured by Nissan Chemical Co., Ltd. (both trade names) Diglycidyl phthalate resin such as Blemmer DGT manufactured by Nichiyu Co., Ltd .; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Nittetsu Sumikin Chemical Co., Ltd .; ESN-190 and ESN-360 manufactured by Nittetsu Sumikin Chemical Co., Ltd. , DIC HP-4032, EXA-4750, EXA-4700 and other naphthalene group-containing epoxy resins; DIC HP-7200, HP-7200H and other epoxy resins having a dicyclopentadiene skeleton; Nichiyu CP-50S , CP-50M and other glycidyl methacrylate copolymer epoxy resins; further, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, Daicel's Epolide PB-3600, etc.), CTBN-modified epoxy resins (For example, YR-102, YR-450, etc. manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc., but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a novolak type epoxy resin, a modified novolak type epoxy resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin, or a mixture thereof is particularly preferable.

The blending amount of the (B1) epoxy resin is preferably 20 to 90% by mass based on the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.

[(B2) Maleimide compound having two or more maleimide structures in one molecule]
The photosensitive resin composition of the present invention contains a maleimide compound having (B2) two or more maleimide structures in one molecule. The maleimide compound (B2) is not particularly limited, and a known and commonly used compound may be used.

In the present invention, examples of the (B2) maleimide compound include polyfunctional aliphatic or alicyclic maleimides and polyfunctional aromatic maleimides. Among the maleimide compounds (B2), in the present invention, a polyfunctional aromatic maleimide is preferable, and a maleimide compound represented by the following general formula (I) is particularly preferable. In general, bismaleimide compounds have poor light transmittance, and when used in a photosensitive resin composition, resolution and sensitivity are lowered. However, in the present invention, by blending the maleimide compound represented by the following general formula (I) and the epoxy resin (B1), the heat resistance can be improved without impairing the optical characteristics such as resolution and sensitivity. It has become possible. Examples of the maleimide compound represented by the following general formula (I) include MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd.

(In the formula (I), R ₄ may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or the like, and n is an integer of 1 <n ≦ 5. Represents.)

Other polyfunctional aromatic maleimides include, for example, N, N'-(4,4'-diphenylmethane) bismaleimide (commercially available as BMI (manufactured by Keiai Kasei Co., Ltd.)) and bis- (3-ethyl-5). -Methyl-4-maleimidephenyl) methane (commercially available as BMI-70 (manufactured by KAI Kasei Co., Ltd.)), 2,2'-bis- (4- (4-maleimidephenoxy) propane (BMI-70 (Kai)) Commercially available as (manufactured by Kasei)), N, N'-(4,4'-diphenyloxy) bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N '-2,4-Tolylenbismaleimide, N, N'-2,6-Tolylenbismaleimide, maleimide carboxylic acid and various aromatic polyols are dehydrated esterified, or maleimide carboxylic acid ester and various aromatic polyols Aromatic polymaleimide ester compounds obtained by ester exchange reaction, aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of maleimide carboxylic acid and various aromatic polyepoxides, maleimide alcohol and various aromatic polyisocyanates. Examples thereof include aromatic polymaleimide urethane compounds obtained by subjecting and to a urethanization reaction.

Examples of the polyfunctional aliphatic or alicyclic maleimide include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimidecarboxylic acid. Isocyanulate skeleton such as a maleimide ester compound having an isocyanurate skeleton obtained by dehydration esterification of and tris (carbamatehexyl) isocyanurate and a maleimide urethane compound having an isocyanurate skeleton obtained by urethaneizing an aliphatic / alicyclic maleimide alcohol. Polymaleimides, isophoronbis urethanebis (N-ethylmaleimide), triethylene glycolbis (maleimideethyl carbonate), aliphatic / alicyclic maleimidecarboxylic acids and various aliphatic / alicyclic polyols are dehydrated and esterified, or Adipose / alicyclic polymaleimide ester compounds and aliphatic / alicyclic maleimide carboxylic acids obtained by ester exchange reaction between an aliphatic / alicyclic maleimide carboxylic acid ester and various aliphatic / alicyclic polyols. Adipose / alicyclic polymaleimide ester compounds, aliphatic / alicyclic maleimide alcohols, and various aliphatic / alicyclic polyisocyanates obtained by ether ring-opening reaction of various aliphatic / alicyclic polyepoxides. Examples thereof include aliphatic / alicyclic polymaleimide urethane compounds obtained by a urethanization reaction.

Polyfunctional aliphatic or alicyclic maleimide is preferable because it has high curability and excellent physical properties of the cured film after irradiation with active energy rays. In particular, a maleimide alkylcarboxylic acid or a maleimidealkylcarboxylic acid ester having an alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group, polyethylene glycol having a number average molecular weight of 100 to 1000, and a number average molecular weight of 100 to 1000. The following general formulas (II) and (III) obtained by dehydration esterification reaction or ester exchange reaction with polypropylene glycol and at least one selected from polytetramethylene glycol having a number average molecular weight of 100 to 1000. The represented aliphatic bismaleimide compound is particularly preferable because it has an excellent balance between the curability of the obtained composition and the physical properties of the cured film.

(In formula (II), m is an integer of 1 to 6, n is a value of 2 to 23, and R ₅ is a hydrogen atom or a methyl group.)

(In formula (III), m is an integer of 1 to 6 and p is a value of 2 to 14.)

(B2) The maleimide compound can be used alone or in combination of two or more. The blending amount of the maleimide compound (B2) is preferably 1 to 30% by mass based on the total solid content of the photosensitive resin composition of the present invention excluding (D) silica. When it is 30% by mass or less, the thermal reaction does not become too good and the developability becomes good.

In the photosensitive resin composition of the present invention, the total blending amount of the (B1) epoxy resin and the (B2) maleimide compound is 1 to 50 in the total solid content of the photosensitive resin composition excluding the (D) silica. It is preferably mass%.

Further, the photosensitive resin composition of the present invention may contain a thermosetting resin other than (B1) epoxy resin and (B2) maleimide compound as long as the effects of the present invention are not impaired. Examples of such thermosetting resins include isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, and episulfide resins.

[(C) Photopolymerization Initiator]
The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. Known photopolymerization initiators can be used, and benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone. , 4- (1-t-butyldioxy-1-methylethyl) acetophenone and other acetophenones; 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4 -Thioxanthones such as dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; acetophenone dimethylketal, ketals such as benzyldimethylketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, Benzophenones such as 3,3', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one and 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides, xanthones and the like can be mentioned.

Further, as the photopolymerization initiator, an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator and the like are used. You can also do it.

Examples of the oxime ester-based photopolymerization initiator include commercially available products such as IrgacureOXE01 and IrgacureOXE02 manufactured by BASF Japan, N-1919 and NCI-831 manufactured by ADEKA.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-. 1- (4-morpholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone , N, N-Dimethylaminoacetophenone and the like, and as commercially available products, Omnirad 907, Omnirad 369, Omnirad 379 and the like manufactured by IGM Resins can be used.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6). -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like are mentioned, and as commercially available products, Omnirad TPO manufactured by IGM Resins, Omnirad 819 manufactured by IGM Resins and the like are used. be able to.

Specific examples of the titanosen-based photopolymerization initiator include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl). -Bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrole-1-yl) phenyl) titanium and the like can be mentioned. .. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.

(C) The photopolymerization initiator may be used alone or in combination of two or more. The blending amount of the photopolymerization initiator (C) is preferably 0.005 to 40% by mass based on the total solid content of the photosensitive resin composition of the present invention excluding (D) silica. When the amount of the photopolymerization initiator is 0.005% by mass or more, the light irradiation time may be short and polymerization is likely to occur, so that an appropriate surface hardness can be obtained. Even if the photopolymerization initiator is blended in an amount of more than 40% by mass, there is little merit in using a large amount.

[(D) Silica]
The photosensitive resin composition of the present invention contains (D) silica in an amount of 25 to 75% by mass based on the total solid content of the photosensitive resin composition. More preferably, (D) silica is contained in an amount of 30 to 60% by mass based on the total solid content of the photosensitive resin composition. When silica is contained in the range of 25 to 75% by mass in the total solid content of the photosensitive resin composition, both sensitivity and developability and physical properties such as crack resistance are good.

As the silica, known and commonly used silica particles that can be used as an inorganic filler may be used, and examples thereof include fused silica, spherical silica, amorphous silica, crystalline silica, and solgel silica, but spherical silica is preferable. ..

Further, it is preferable that the silica is subjected to a surface treatment capable of introducing a curable reactive group. Having a curable reactive group on the surface makes it possible to strengthen the bond between silica and the curable resin, and it is also possible to improve the physical properties of the cured product, for example, to reduce the CTE. Here, the curable reactive group may be a group that undergoes a curing reaction with a component (for example, (A) curable copolymer resin, (B1) epoxy resin, or (B2) maleimide compound) to be blended in the photosensitive resin composition. For example, the present invention is not particularly limited, and may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, a styryl group and the like, and examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group and an oxetanyl. Examples thereof include a group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group and the like. The curable reactive group is preferably a photocurable reactive group, more preferably a (meth) acrylic group. When a thermosetting reactive group is introduced as the curable reactive group, an amino group is more preferable. The method for introducing a curable reactive group onto the surface of the coated silica particles is not particularly limited, and the curable reactive group may be introduced using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reaction The surface of the coated silica particles may be treated with a coupling agent or the like having a group as an organic group. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Of these, a silane coupling agent is preferable.

The average particle size of silica is preferably 50 nm to 800 nm. Here, in the present specification, the average particle size of the silica particles is the average particle size (D50) including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates), and is a laser diffraction method. It is a value of D50 measured by. Examples of the measuring device by the laser diffraction method include Microtrac MT3300EXII manufactured by Microtrac Bell.

The average particle size of silica may be adjusted, and it is preferable to pre-disperse silica with, for example, a bead mill or a jet mill. Further, silica is preferably blended in a slurry state, and by blending in a slurry state, high dispersion is facilitated, aggregation is prevented, and handling is facilitated.

(Compound with ethylenically unsaturated group)
The photosensitive resin composition of the present invention may contain a compound having an ethylenically unsaturated group. As the compound having an ethylenically unsaturated group, known and commonly used photosensitive monomers such as a photopolymerizable oligomer and a photopolymerizable vinyl monomer can be used, and a radically polymerizable monomer or a cationically polymerizable monomer may be used.

As the photosensitive monomer, a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in the molecule can be used at room temperature. The photosensitive (meth) acrylate compound, which is liquid at room temperature, has the purpose of increasing the photoreactivity of the composition, adjusting the composition to a viscosity suitable for various coating methods, and assisting in the solubility in an alkaline aqueous solution. Also fulfills.

The double bond equivalent of the photosensitive monomer is preferably 400 g / eq or less.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. Examples of the (meth) acrylate-based oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). ) Acrylic, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate and the like.

As the photopolymerizable vinyl monomer, known and commonly used ones, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- Vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, (Meta) acrylamides such as methacrylicamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylicamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide; triallyl isocyanurate, diallyl phthalate, Allyl compounds such as diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfreel (meth) acrylate, isobolonyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like. (Meta) acrylic acid esters; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl Alkoxyalkylene glycol mono (meth) acrylates such as (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( Alkylene polyol poly (meth) acrylates such as meta) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di Polyoxyalkylene glycol poly (meth) acrylates such as (meth) acrylate, ethoxylated trimetylolpropan triacrylate, propoxylated trimethylol propantri (meth) acrylate Poly (meth) acrylates such as neopentyl glycol ester di (meth) acrylate of hydroxybivariate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate.

The photosensitive monomer can be used alone or in combination of two or more. The blending amount of the photosensitive monomer is preferably 0.1 to 40% by mass in the total amount of the photosensitive resin composition of the present invention excluding (D) silica. When it contains 0.1% by mass or more, it becomes more heat resistant, and when it is 40% by mass or less, curing shrinkage can be suppressed.

(Curing accelerator)
The photosensitive resin composition of the present invention can contain a curing accelerator. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1-. Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Examples include amine compounds such as amines, 4-methyl-N, N-dimethylbenzylamine and 4-dimethylaminopyridine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used. Of these, amine compounds are preferable because they improve dispersibility and fluidity. Further, preferably, a compound that also functions as an adhesion imparting agent is used in combination with a thermosetting catalyst. The curing accelerator may be used alone or in combination of two or more.

The blending amount of the curing accelerator is, for example, 0.01 to 30% by mass in the total solid content of the composition.

(Elastomer)
The photosensitive resin composition of the present invention preferably contains an elastomer. Since the elastic modulus can be lowered by containing the elastomer, the stress at the time of curing can be relaxed and the crack resistance can be further improved. As the elastomer, known elastomers can be used, for example, polyester-based elastomers, styrene-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, olefin-based elastomers, and silicones. A system elastomer or the like can be used. Further, a resin obtained by modifying a part or all of the epoxy groups of an epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Further, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, block copolymers and the like can also be used. For example, the product names are R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Co., Ltd.), Denarex R-45EPT (manufactured by Nagase ChemteX), Tough Serene (Sumitomo Chemical Co., Ltd.) , Ricon series (manufactured by Clay Valley), Hytrel (manufactured by Toray DuPont), Perprene (manufactured by Toyobo), Esper 1612, 1620 (manufactured by Hitachi Chemical Co., Ltd.) and the like. These elastomers can be used alone or in combination of two or more.

The blending amount of the elastomer is preferably 0.5 to 10% by mass based on the total solid content of the composition.

(Colorant)
The photosensitive resin composition of the present invention may contain a colorant. As the colorant, known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable that it does not contain halogen from the viewpoint of reducing the environmental load and affecting the human body. As the colorant, one type may be used alone or two or more types may be used in combination.

The blending amount of the colorant is, for example, 0.01 to 10% by mass based on the total solid content of the composition.

(Organic solvent)
The photosensitive resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, γ-butyrolactone; aliphatic hydrocarbons such as octane and decane; petroleum-based such as petroleum ether, petroleum naphtha, solvent naphtha, etc. A known and commonly used organic solvent such as a solvent can be used. These organic solvents may be used alone or in combination of two or more.

(Other optional ingredients)
Further, the photosensitive resin composition of the present invention may contain other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antioxidants, antibacterial / antifungal agents, defoamers, leveling. Agents, thickeners, adhesion imparting agents, thixoness imparting agents, photoinitiator aids, sensitizers, organic fillers, thermoplastic resins, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifications Agents, stabilizers, phosphors and the like can be mentioned.

The photosensitive resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film. When forming a dry film, first, the photosensitive resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. , Reverse coater, transfer coater, gravure coater, spray coater, etc., and apply to a uniform thickness on the carrier film. Then, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but is generally selected as appropriate in the range of 3 to 150 μm, preferably 5 to 60 μm after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After forming the resin layer made of the photosensitive resin composition of the present invention on the carrier film, a peelable cover is further provided on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to laminate the films. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. The cover film may be smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, the photosensitive resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, either a carrier film or a cover film may be used as the film to which the photosensitive resin composition of the present invention is applied when the dry film is produced in the present invention.

As a method for producing a printed wiring board using the photosensitive resin composition of the present invention, for example, the photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above organic solvent, and the substrate is used. After applying by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, etc., the organic solvent contained in the composition is applied at a temperature of 60 to 100 ° C. A tack-free resin layer is formed by volatile drying (temporary drying). Further, in the case of a dry film, a resin layer is formed on the substrate by sticking the resin layer on the substrate with a laminator or the like so as to be in contact with the substrate and then peeling off the carrier film.

The above-mentioned substrates include printed wiring boards and flexible printed wiring boards whose circuits are formed in advance with copper or the like, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc., and all grades (FR-4, etc.) of copper-clad laminates. In addition, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned. The circuit may be pretreated. For example, GliCAP manufactured by Shikoku Chemicals Corporation, New Organic AP (Adhesion promoter) manufactured by MEC, Nova Bond manufactured by Atotech Japan, etc. are used for pretreatment and solder. Adhesion to a cured film such as a resist may be improved, or pretreatment may be performed with a rust preventive.

Volatile drying performed after applying the photosensitive resin composition of the present invention is carried out in a hot air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. (using a steam-based air heating type heat source in the dryer). It can be carried out by using a method of bringing hot air into countercurrent contact and a method of blowing hot air onto a support from a nozzle).

After forming a resin layer on the printed wiring board, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed portion is exposed to a dilute alkaline aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution). ) To form a pattern of the cured product. Further, the cured product is adhered by irradiating the cured product with active energy rays and then heat curing (for example, 100 to 220 ° C.), or by irradiating the cured product with active energy rays after heat curing or by performing final finish curing (main curing) only by heat curing. It forms a cured film with excellent properties such as properties and hardness. In the present invention, the heat curing temperature may be a low temperature, for example, 150 to 200 ° C., preferably 160 to 180 ° C.

As the exposure machine used for the above-mentioned active energy ray irradiation, if it is a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates the active energy ray in the range of 350 to 450 nm. Often, a projection exposure machine using a projection lens or a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser from CAD data from a computer) can also be used as a maskless exposure that does not contact the substrate. .. The lamp light source or the laser light source of the direct drawing machine may have a wavelength in the range of 350 to 450 nm. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally in the range of 10 to 1000 mJ / cm ² , preferably in the range of 800 to 1000 mJ / cm ² .

The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as ammonia and amines can be used.

The photosensitive resin composition of the present invention is suitably used for forming a cured film on an electronic component, particularly for forming a cured film on a printed wiring board, and more preferably for forming a permanent film. And more preferably used to form solder resists, interlayer insulating layers, and coverlays. Further, it is suitable for forming a permanent coating (particularly solder resist) for a printed wiring board, for example, a package substrate, particularly FC-BGA, which requires a high degree of reliability. Further, it can be suitably used for forming a permanent coating such as a solder resist of a printed wiring board exposed to a high temperature state for in-vehicle use.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

[(A) Synthesis of curable copolymer resin]
(Synthesis Example 1: Curable Copolymer Resin A-1)
82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropanol were charged in a separable flask with a cooling tube as a reaction tank, and the temperature was raised to 100 ° C. after nitrogen substitution. On the other hand, 20 parts of N-phenylmaleimide and 20 parts of N-benzylmaleimide, 128 parts of propylene glycol monomethyl ether acetate and 32 parts of isopropanol were mixed in the dropping tank 1, 13 parts of styrene and methacrylic in the dropping tank 2. A mixture of 20 parts of 2-hydroxyethyl acid, 27 parts of methacrylic acid, and 22.2 parts of isopropanol, perbutyl O (trade name: manufactured by Nippon Oil & Fats Co., Ltd., t-butylperoxy) as a polymerization initiator in the dropping tank 3. -2-Ethylhexanoate) 8 parts were charged respectively. While maintaining the reaction temperature at 100 ° C., the dropping was carried out from the dropping tanks 1 to 3 for 3 hours. After the completion of the dropping, the reaction was continued at 100 ° C. for 30 minutes. Then, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Next, 13.7 parts of Cyclomer M100, 31.2 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.9 part of Antage W-400 as a polymerization inhibitor were added to this polymer solution. Two parts were added, and a mixed gas of nitrogen and oxygen (oxygen concentration 7%) was reacted at 115 ° C. while bubbling to obtain a solution of the curable copolymer resin A-1.
When various physical properties of the obtained solution of the curable copolymer resin A-1 were measured, the weight average molecular weight was 7600, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid. The acid value per minute was 126 mgKOH / g.

(Synthesis Example 2: Curable Copolymer Resin A-2)
81.5 parts of carbitol acetate was placed in a separable flask with a cooling tube as a reaction vessel, replaced with nitrogen, and then the temperature was raised to 80 ° C. On the other hand, 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in the dropping tank 1, 29 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate were mixed in the dropping tank 2, and the dropping tank 3 21 parts of acrylic acid and 10.6 parts of hydrocarbon acetate are mixed, and the dropping tank 4 contains 70% of t-butylperoxypivalate as a polymerization initiator, Luperox 11 (trade name: manufactured by Alchema Yoshitomi Co., Ltd.). A mixture of 10 parts (hydrocarbon solution) and 21.2 parts of carbitol acetate was charged. While maintaining the reaction temperature at 80 ° C., the dropping was carried out from the dropping tanks 1, 2, 4 to 3 hours and from the dropping tank 3 for 2.5 hours. After the completion of the dropping, the reaction was continued at 80 ° C. for 30 minutes. Then, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Next, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate as a reaction catalyst, 0.7 parts of triphenylphosphine as a reaction catalyst, and Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor in this polymer solution. ) Is added and reacted at 115 ° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to prepare a solution of the curable copolymer resin A-2 which is a radical polymerizable polymer. Obtained.
When various physical properties of the obtained solution of the curable copolymer resin A-2 were measured, the weight average molecular weight was 19,800, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid. The acid value per minute was 121 mgKOH / g.

[Synthesis of alkali-soluble resin]
(Synthesis Example 3: Carboxylic Acid Group-Containing Resin R-1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolak type cresol resin (trade name "CRG951", manufactured by Aika Kogyo Co., Ltd., OH equivalent: 119.4) 119.4 parts by mass, water. 1.19 parts by mass of potassium oxide and 119.4 parts by mass of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts by mass of propylene oxide was gradually added dropwise, and the mixture was reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm2 for 16 hours. Then, the mixture was cooled to room temperature, and 1.56 parts by mass of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The non-volatile content was 62.1% and the hydroxyl value was 182.2 mgKOH / g (307). A propylene oxide reaction solution of a novolak-type cresol resin having a weight of .9 g / eq.) Was obtained. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts by mass of the propylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 parts by mass of acrylic acid, 11.53 parts by mass of methanesulfonic acid, 0.18 parts by mass of methylhydroquinone and 252.9 parts by mass of toluene. , Introduced into a reactor equipped with a stirrer, thermometer and air blowing tube, air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 parts by mass of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts by mass of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts by mass of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 parts by mass of the obtained novolak type acrylate resin solution and 1.22 parts by mass of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and 10 ml / min of air was introduced. With stirring, 60.8 parts by mass of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled, and then taken out. In this way, a solution of the photosensitive carboxyl group-containing resin R-1 having a weight average molecular weight of 5000, a solid content of 65%, and an acid value of 87.7 mgKOH / g of the solid content was obtained.

[Preparation of filler]
(Preparation of methacrylic silane treated silica)
50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. , Filtering, washing with water, and vacuum drying to obtain silica treated with methacrylsilane.

(Preparation of aminosilane-treated silica)
50 g of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 400 nm), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having an amino group (KBM-573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) are uniformly dispersed. Silica surface-treated with aminosilane was obtained by filtration, washing with water, and vacuum drying.

[Examples 1 to 11, Comparative Examples 1 to 5]
The various components shown in Tables 1 to 3 below are blended in the proportions (parts by mass) shown in Tables 1 to 3, diluted with an organic solvent to a viscosity that can be dispersed with a bead mill, premixed with a stirrer, and then bead milled. The photosensitive resin composition was dispersed. The obtained dispersion was passed through a filtration filter having an opening of 10 μm to obtain a photosensitive resin composition. The ratio (parts by mass) in the table is the amount of solid content.

<Making dry film>
The photosensitive resin compositions prepared in the above Examples and Comparative Examples are each diluted appropriately with propylene glycol monomethyl ether acetate (PMA) to a viscosity, and then PET is used so that the film thickness after drying becomes 20 μm using an applicator. It was applied to a film (T100: 25 μm manufactured by Mitsubishi Chemical Co., Ltd.) and dried at 80 ° C. for 30 minutes to obtain a dry film.

<Coefficient of linear expansion (CTE)>
The dry film was heat-laminated on a low-profile copper foil using a vacuum laminator. The obtained laminate was completely exposed and the PET film was peeled off, and then a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm ² for 60 seconds. After development, the film was irradiated with light on a UV conveyor at an integrated light intensity of 1000 mJ / cm ² , and heat-cured in a drying oven at 160 ° C. for 60 minutes to obtain a resist film. The obtained cured film was cut out so that a measurement size (size of 3 mm × 10 mm) could be obtained, and CTE was measured with TMA6100 manufactured by Hitachi High-Tech. As the measurement conditions, a test load of 5 g and a temperature rise rate of 10 ° C./min were repeated twice to obtain a coefficient of linear expansion (CTE) of Tg or less in the second time. From the average coefficient of linear thermal expansion (L) calculated in the range of 0 ° C. to 50 ° C. calculated from the following formula and the average coefficient of linear thermal expansion (H) calculated in the range of 200 ° C. to 250 ° C., the CTE difference (HL) ) Was asked.
Average coefficient of linear expansion (L or H) = (1 / d) × (Δd / Δt)
d: Sample length, Δd: Length change, Δt: Temperature change ◎ (HL) is over 20 ppm / ° C and 50 ppm / ° C or less 〇 (HL) is over 50 ppm / ° C and 60 ppm / ° C. Below x (HL) is 20 ppm / ° C or less or more than 60 ppm / ° C.

<Heat resistance>
The dry film was heat-laminated on a low-profile copper foil using a vacuum laminator. The obtained laminate was completely exposed and the PET film was peeled off, and then a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm ² for 60 seconds. After development, the film was irradiated with light on a UV conveyor at an integrated light intensity of 1000 mJ / cm ² , and heat-cured in a drying oven at 160 ° C. for 60 minutes to obtain a resist film. The obtained cured film was cut out so as to obtain a measurement size (size of 5 mm × 10 mm), measured by DMA, and the glass transition point was measured from the temperature of the peak top of tan δ. The measurement was carried out at a frequency of 1 Hz under the condition that the temperature was raised in the range of 25 ° C. to 300 ° C. at a rate of 5 ° C./min. The judgment criteria are as follows.
⊚: 180 ° C or higher ○: 170 ° C or higher and lower than 180 ° C ×: less than 170 ° C

<Crack resistance>
The dry film was heat-laminated using a vacuum laminator on an evaluation substrate for FC-BGA having a pad pitch of 200 μm. On the other hand, in the step tablet (Photo 41 step), direct imaging exposure was performed with an exposure amount of 80 μm so as to have 12 steps. Then, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm ² for 60 seconds to obtain a cured film pattern. Further, after irradiating with ultraviolet rays at an integrated exposure amount of 1000 mJ / cm ² , the mixture was heated at 160 ° C. for 1 hour to cure. Then, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.
The evaluation substrate obtained as described above was placed in a thermal cycle machine in which a temperature cycle was performed between −65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film at 500 cycles and 1000 cycles was observed. The judgment criteria are as follows.
⊚: No abnormality in 1000 cycles ○: No abnormality in 500 cycles, cracks in 1000 cycles ×: Cracks in 500 cycles

<Developability>
The dry film was heat-laminated on a CZ-treated copper-plated substrate using a vacuum laminator. Then, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm ² , and the time until the dry coating film was removed without residue was measured with a stopwatch.
⊚ ... The coating film was removed within 10 seconds or more and 50 seconds or less.
◯… The coating film was removed in more than 50 seconds.
× ... Residue remained.

<Resolution>
A dry film having a thickness of 10 to 15 μm prepared by the above method was heat-laminated on a CZ-treated copper-plated substrate using a vacuum laminator. This substrate was exposed to a step tablet (Photo 41 step) using a projection exposure machine, and then a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm ² for 60 seconds. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure of 1000 mJ / cm ² , and then heat-cured at 160 ° C. for 60 minutes. Of the obtained cured films, when the step tablet shows 8 levels of sensitivity, the openings of the mask design are observed by SEM to check for halation and undercuts, and they have a predetermined opening diameter. Those that did not have a good opening diameter were used and evaluated. The judgment criteria are as follows.
⊚: Good opening diameter at 50 μm.
◯: Good opening diameter at 60 μm.
Δ: Good opening diameter at 70 μm.
X: A good opening diameter could not be obtained at 70 μm, or development was not possible.

<Melting viscosity>
(Melted viscosity of resin layer)
The dry film prepared above using CVP-300 manufactured by Nikko Material Co., Ltd. was laminated at a laminating temperature of 30 to 40 ° C. to prepare a resin layer (laminated body of resin layers) having a thickness of about 300 μm and a width of 20 mm. The melt viscosity was measured using RS-6000 manufactured by Scientific Co., Ltd. under the following measurement conditions.
(Measurement conditions for melt viscosity)
Heating rate: 5 ° C / min
Measurement frequency: 1Hz
Measurement pressure: 3Pa
⊚: The melt viscosity at the lowest point on the melt viscosity curve is less than 4000 Pa · s ○: The melt viscosity at the lowest point on the melt viscosity curve is 4000 Pa · s or more and less than 5000 Pa · s ×: The melt viscosity at the lowest point on the melt viscosity curve Is over 5000 Pa · s

* 1: Curable copolymer resin A-1 synthesized above
* 2: Curable copolymer resin A-2 synthesized above
* 3: Carboxylic acid group-containing resin R-1 synthesized above
* 4: Maleimide compound having the skeleton of the following formula

(In the above, R ₄ represents a hydrogen atom, and n represents an average value of 1.5.)
* 5: BMI-70 (bis- (3-ethyl-5-methyl-4-maleimidephenyl) methane) manufactured by KAI Kasei Co., Ltd.
* 6: Mitsubishi Chemical's jER1001 (bisphenol type epoxy resin)
* 7: DEN431 (Novolac type epoxy resin) manufactured by Dow Chemical Co., Ltd.
* 8: EPICLON N-870 manufactured by DIC (modified novolac type epoxy resin)
* 9: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins.
* 10: Omnirad 907 manufactured by IGM Resins (2- [4- (methylthio) benzoyl] -2- (4-morpholinyl) propane * 11: Silica prepared above, which has been treated with methacrylsilane after inorganic treatment * 12: Above. Prepared, aminosilane-treated silica * 13: Denka SFP-20M
* 14: B-30 manufactured by Sakai Chemical Industry Co., Ltd.
* 15: Daicel's Epolide PB3600 (epoxy polybutadiene)
* 16: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
* 17: Phthalocyanine blue * 18: Melamine * 19: DICY (dicyandiamide)

From the results shown in the above table, the photosensitive resin compositions of Examples 1 to 11 of the present invention can obtain a cured product having excellent reliability such as heat resistance and crack resistance, and have optical characteristics (solutions). It can be seen that the image quality is excellent.

Claims (8)

1. (A) A curable copolymer resin having at least a first repeating unit represented by the following formula (1) and a second repeating unit represented by the following formula (2).
   (B1) Epoxy resin,
   (B2) A maleimide compound having two or more maleimide structures in one molecule,
   (C) Photopolymerization initiator and
   (D) A photosensitive resin composition containing silica.
   The blending amount of the silica (D) is 25 to 75% by mass based on the total solid content of the photosensitive resin composition.
   The average coefficient of linear thermal expansion (L) calculated in the range of 0 ° C. to 50 ° C. of the cured product obtained by irradiating the photosensitive resin composition with light at 1000 mJ / cm ² and heat-treating at 160 ° C. for 1 hour. The photosensitive resin composition is characterized in that the difference (HL) between the above and the average coefficient of linear thermal expansion (H) calculated in the range of 200 ° C. to 250 ° C. is more than 20 ppm / ° C. and 60 ppm / ° C. or less.
   

   

   (In the formula, R ₀ is a monovalent organic group having 1 to 30 carbon atoms, R ₁ is a hydrogen atom or an organic group having 1 to 7 carbon atoms, and R ₂ is a single bond or 1 carbon atom. an alkylene group of ~ 5, R ₃ represents a monovalent group having a heat crosslinking.)
2. The photosensitive resin composition according to claim 1, wherein the curable copolymer resin (A) has a weight average molecular weight of less than 10,000.
3. A total of 1 to 50 mass of the (B1) epoxy resin and the maleimide compound having two or more of the (B2) maleimide structures in one molecule in the total solid content of the photosensitive resin composition excluding the (D) silica. The photosensitive resin composition according to claim 1 or 2, which comprises%.
4. The photosensitive resin according to any one of claims 1 to 3, wherein the silica (D) contains at least one of silica having a (meth) acrylic group and silica having an amino group. Composition.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the glass transition point (Tg) of the cured product is 170 ° C. or higher.
6. A dry film having a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 5 to a film and drying the film.
7. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5 or the resin layer of the dry film according to claim 6.
8. An electronic component having the cured product according to claim 7.