JP2013210405A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in photosensitivity to active energy rays, enabling formation of a fine pattern, giving a cured film having excellent developability, insulating property, heat resistance, folding resistance or the like, and suitably used for a photosolder resist.SOLUTION: The photosensitive resin composition comprises: a photosensitive resin (A); at least one kind of curing agent (B) selected from an epoxy group-containing compound, a non-blocked isocyanate compound and a blocked isocyanate compound; a photopolymerization initiator (C); and a carboxybenzotriazole derivative (D). The photosensitive resin (A) is a hydroxyl group-containing photosensitive resin (A-1) obtained through steps of reacting an epoxy compound (a) having at least two epoxy groups in one molecule with a phenolic curing agent (B) having at least two phenolic hydroxyl groups in one molecule to produce a side-chain hydroxyl group-containing resin (c), reacting the side-chain hydroxyl group-containing resin (c) with a polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e), and reacting the carboxyl group-containing resin (e) with an epoxy group or an oxetane group in a compound (f) having an epoxy group or an oxetane group and having an ethylenically unsaturated group; or a carboxyl group-containing photosensitive resin (A-2) produced by reacting the hydroxyl group in the above hydroxyl group-containing resin (A-1) with an acid anhydride group of the polybasic acid anhydride (d).

Description

  The present invention relates to a photosensitive resin composition containing a photosensitive resin useful for printed wiring boards and the like, a cured product thereof, and a method for producing the photosensitive resin. More specifically, it is useful as a solder resist for flexible printed wiring boards and an interlayer electrical insulating material for multilayer printed wiring boards, and has excellent developability, and its cured film has adhesiveness, flexibility (flexibility), and solder heat resistance. The present invention relates to a photosensitive resin composition containing a specific photosensitive resin that gives a cured product excellent in electrical insulation and the like, a cured product thereof, and a method for producing the photosensitive resin.

  In the soldering process that is performed when protecting the wiring (circuit) pattern formed on the board from the external environment or when mounting electronic components on the printed wiring board, solder does not adhere to unnecessary parts. In order to protect the printed wiring board, a protective layer called a coverlay or a solder mask is coated on the printed wiring board. Until now, since hard printed wiring boards have been the mainstream, the resist coating after curing mainly requires adhesion to the substrate and heat resistance in addition to pattern accuracy. However, in recent years, the use of flexible printed wiring boards has greatly increased, and the protective layer used for the wiring pattern formed on the polyimide film has adhesiveness with polyimide, flexibility, folding resistance, flame resistance, etc. Is required.

Conventionally, as a protective layer for flexible printed wiring boards, a polyimide film called a coverlay film is made by punching a mold that matches the pattern and then pasted using an adhesive, or by thermosetting applied by screen printing There are various types of inks, but for high density and high definition accompanying recent advances in electronics, UV curable photoresist type solder resist ink or dry film type solder resist that can be patterned with higher precision is available. It is being considered.

  In general, in the photo solder resist for flexible printed wiring boards, the photo solder resist conventionally used for rigid substrates can provide pattern accuracy, but the cured coating film is hard and has good adhesion to polyimide. Unfortunately, there was a problem that sufficient flexibility, flexibility and folding resistance could not be obtained.

In recent years, many proposals have been made as flexible photo solder resists. For example, a resist ink composition is disclosed that includes a resin obtained by reacting succinic anhydride with an addition product of an epoxy resin having a bisphenol A skeleton in the main chain and an unsaturated group-containing monocarboxylic acid (Patent Document 1). ). Although this is excellent in developability, photosensitivity, adhesion, heat resistance, etc., there is a problem that flexibility and folding resistance are still insufficient. In addition, as a photosensitive thermosetting composition, a reaction product of a secondary hydroxyl group generated by an esterification reaction of a cresol novolak type epoxy compound and an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic acid anhydride, A reaction product of the secondary hydroxyl group and an unsaturated group-containing isocyanate compound has been proposed (Patent Document 2). Although these are very excellent in adhesion, solder heat resistance, and coating film resistance, there is a problem that flexibility and folding resistance are still insufficient.

There has also been proposed a photosensitive element containing a polymer obtained by copolymerizing a monomer containing (meth) acrylic acid and (meth) acrylic acid ester as a binder component (Patent Document 3). These are excellent in developability and resolution, but when used in flexible printed wiring board applications, sufficient adhesion, flexibility and folding resistance cannot be obtained.

In addition, a polymer obtained by reacting a polyol compound, a polybasic acid anhydride having two acid anhydride groups in the molecule, and a polyisocyanate compound further has one epoxy group in the molecule (meta ) A photosensitive resin composition containing a carboxyl group-containing urethane oligomer obtained by reacting an acrylate has been proposed (Patent Document 4). Although these have sufficient flexibility, they have an ester bond derived from half-esterification with a dibasic acid anhydride in the main chain, so that dehydration occurs at high temperatures and the main chain is easily cleaved. In addition, because the carboxyl group is directly linked to the main chain, the mobility of the carboxyl group is suppressed, so that the developability, various coating film resistance, and solder heat resistance It was not enough.

Moreover, the photosensitive resin composition which added the phosphorus type flame retardant is disclosed (patent document 5). In order to reduce the burden on the environment, these are made flame retardant by using a non-halogen flame retardant. However, in order to impart sufficient flame retardancy with a non-halogen flame retardant, it is necessary to add a large amount of flame retardant. In terms of coating film resistance and solder heat resistance, it was not sufficient. In other words, physical properties other than the flame retardancy required for the resist are deteriorated, so that it is not sufficient to achieve both the flame retardancy and other physical properties.

Further, as with the photosensitive resin of the present invention, a resin whose main chain is synthesized from an epoxy compound and a phenol compound is also disclosed. For example, after adding an alkylene oxide to a hydroxyl group in a polyhydroxy ether resin synthesized from a bisphenol type epoxy compound and a bisphenol compound, an acid anhydride and a (meth) acrylate having one epoxy group in the molecule are added. A carboxyl group-containing unsaturated polyhydroxy ether compound obtained by reaction is disclosed (Patent Document 6). This is due to the addition of alkylene oxide, which develops good developability and resolution with an alkaline aqueous solution and has excellent flexibility and flexibility, but tends to decrease solder heat resistance and chemical resistance. there were.

In addition, acid-modified vinyl obtained by acid-modifying vinyl ester synthesized from bisphenol-type epoxy compound, bisphenol compound and unsaturated carboxylic acid or (meth) acrylate having one epoxy group in the molecule with polybasic acid anhydride Esters are disclosed. (Patent Document 7). This is because the double bond is introduced at the end of the main chain, so the distance between the double bonds is large, and the flexibility and folding resistance of the cured coating film are excellent, but the solubility in an alkaline developer is poor and the developability is high. There was a problem that the resolution was still insufficient. As a similar example, an acid-modified vinyl ester synthesized from a phenol compound, an epoxy compound, an unsaturated carboxylic acid, and a polybasic acid anhydride has also been reported (Patent Document 8). This also has a large distance between double bonds, so it can give flexibility to the cured coating film and has excellent flexibility and cold cycle crack resistance, but has conflicting properties such as tack-free properties, developability, and resolution. I was not satisfied with the balance.

It contains a photopolymerizable unsaturated compound obtained by reacting a compound having a phenolic hydroxyl group, a (meth) acrylate having one epoxy group in the molecule and an acid anhydride, and a polyfunctional dihydroxybenzoxazine. A photosensitive resin composition is disclosed (Patent Document 9). This is because the main chain is composed of a compound having a phenolic hydroxyl group, and the cured coating film has a benzoxazine skeleton. Due to the lack of properties, cracks due to thermal shock are likely to occur.

  There is an example of a photosensitive resist containing a carboxybenzotriazole derivative in a photosensitive resin composition containing a binder polymer containing butyl acrylate as a copolymerization component. However, carboxybenzotriazole is already known in the field of photosensitive resist. Although there is a description regarding heat resistance and developability as in the present invention, there is no mention of improvement in folding resistance (Patent Documents 10 and 11).

As described above, the conventional technology has both sufficient flexibility and folding resistance required as a protective layer for a flexible printed wiring board and developability and solder heat resistance capable of realizing high-precision patterning, and A resin composition that can satisfy all physical properties such as electrical insulation, chemical resistance, and flame retardancy necessary as a protective layer for a circuit and a cured product thereof have not been obtained.

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Flexible printed wiring used mainly in the bent and connected areas of devices. The trend is the same for boards. Against this background, demands for protective layers for flexible printed wiring boards are becoming more and more advanced, and developability that can achieve higher definition of resist patterns and higher flexibility than conventional requirements. Performance that satisfies solder heat resistance, substrate adhesion, high insulation, coating film resistance, flame retardancy, etc. is required while maintaining the properties and folding resistance. Currently, commercially available photo solder resists cannot sufficiently meet these requirements.
Japanese Patent No. 3281473 Japanese Patent No. 2707495 JP 2004-279479 A JP 2001-159815 A JP 2006-251715 A Japanese Patent No. 3125424 JP 2003-73450 A Japanese Patent No. 4376290 JP 2006-343384 A JP 2009-180795 A JP H11-024263

  The present invention improves the developability with a dilute alkaline aqueous solution without impairing the photosensitivity to active energy rays, can form a finer pattern, and the cured coating obtained through a post-curing (post-cure) step is flexible. Providing a photosensitive resin composition suitably used for a photo solder resist having excellent properties, insulating properties, adhesion, solder heat resistance, coating film resistance, and the like, and a cured product thereof, as well as a method for producing a photosensitive resin. Objective.

As a result of intensive studies, the present inventors have found that a specific photosensitive resin composition can solve the above problems, and have completed the present invention.
1st invention is photosensitive resin (A), the hardening | curing agent (B) which is at least 1 type chosen from an epoxy-group containing compound, a non-blocked isocyanate compound, and a blocked isocyanate compound, and a photoinitiator (C). A photosensitive resin composition comprising a carboxybenzotriazole derivative (D),
The photosensitive resin (A) is
Resin (c) containing a side chain hydroxyl group by reacting an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. Produces
Reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e);
Hydroxyl group-containing photosensitive resin (A) obtained by reacting the carboxyl group-containing resin (e) with an epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group -1) or
It is a carboxyl group-containing photosensitive resin (A-2) obtained by reacting a hydroxyl group in the hydroxyl group-containing resin (A-1) with an acid anhydride group in the polybasic acid anhydride (d).
The present invention relates to a photosensitive resin composition.
The second invention relates to the photosensitive resin composition, wherein the carboxybenzotriazole derivative (D) is a benzotriazole derivative having a carboxyl group on a benzene ring.
3rd invention is related with the said photosensitive resin composition whose content of a carboxy benzotriazole derivative (D) is 1-20 weight part with respect to 100 weight part of solid content of the photosensitive resin (A).
4th invention is related with the said photosensitive resin composition whose acid value of photosensitive resin (A) is 10-200 mgKOH / g.
5th invention is related with the said photosensitive resin composition whose ethylenically unsaturated group equivalent of the photosensitive resin (A) is 200-5000 g / eq.
6th invention is related with the said photosensitive resin composition whose weight average molecular weights of the photosensitive resin (A) are 1000-100,000.
The seventh invention relates to a cured product obtained by curing the photosensitive resin composition.
The eighth invention relates to a photosensitive solder resist ink comprising the photosensitive resin composition and a flame retardant.
A ninth invention relates to a dry film type photosensitive solder resist containing the photosensitive resin composition and a flame retardant.

  According to the present invention, it has excellent photosensitivity to active energy rays, and can form a fine pattern by development with a dilute alkaline aqueous solution, and a cured coating film obtained through a post-curing (post-cure) process is flexible, insulating, and adhesive. It is excellent in solder heat resistance, coating film resistance, etc., and can now provide a photosensitive resin composition suitably used for a photo solder resist and its cured product, and further a method for producing a photosensitive resin. It was. The photosensitive resin composition of the present invention includes a solder resist for flexible printed wiring boards, a photosensitive coverlay film, a plating resist, an interlayer electrical insulating material for wiring boards, a photosensitive optical waveguide, and a silver paste on a polyethylene terephthalate film. It can be suitably used as a coverlay resist for a flexible printed circuit board formed with a circuit by printing a conductive ink such as carbon paste.

Since the photosensitive resin (A) does not have an ester bond derived from half esterification with a dibasic acid anhydride or a urethane bond derived from the reaction of an isocyanate group and a hydroxyl group in the main chain, the main chain is chemically stable. Therefore, the resulting cured coating film has excellent resistance to various coating films, exhibits excellent heat resistance even when exposed to high temperature conditions such as a solder bath, and exhibits excellent electrical insulation even under high temperature and high humidity. It is further preferable to do this. Furthermore, since the following photosensitive resin (A) has a photosensitive group and a carboxyl group in the side chain, even if the amount of the photosensitive group and carboxyl group contained is small, very excellent resolution And developability. The functional groups introduced into these side chains are more reactive than when directly connected to the main chain, and the amount of introduction can be adjusted arbitrarily compared to the case where they are introduced only at the ends of the main chain. Curability, developability, resolution and coating film resistance can be exhibited. Hereinafter, the photosensitive resin (A) and the photosensitive resin composition of the present invention will be described.

As shown below, the photosensitive resin (A) of the present invention is a hydroxyl group-containing photosensitive resin (A-1) or a carboxyl group-containing photosensitive resin (A-2). The hydroxyl group-containing photosensitive resin (A-1) of the present invention comprises, as a first step, an epoxy compound (a) having at least two epoxy groups in one molecule and at least two phenolic compounds in one molecule. A side chain hydroxyl group-containing resin (c) is prepared by reacting with a phenol compound (b) having a hydroxyl group. Next, as a second step, the side chain hydroxyl group-containing resin (c) and the polybasic acid anhydride (d) are reacted to produce a carboxyl group-containing resin (e). Furthermore, as a third step, the carboxyl group-containing resin (e) is obtained by reacting the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. be able to. Furthermore, the carboxyl group-containing photosensitive resin (A-2) of the present invention comprises, as the fourth step, an acid anhydride in the hydroxyl group polybasic acid anhydride (d) in the hydroxyl group-containing resin (A-1). It can be obtained by the group. Hereinafter, the manufacturing method of photosensitive resin (A) is demonstrated in detail.

First, the side chain hydroxyl group-containing resin (c) obtained in the first step of the present invention will be described. The side chain hydroxyl group-containing resin (c) reacts an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. In the epoxy compound (a) having at least two epoxy groups in one molecule and in the phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. It is preferable to prepare a phenolic hydroxyl group by reacting with a molar ratio of epoxy group / phenolic hydroxyl group = 1/1 to 1 / 2.5. If the phenolic hydroxyl group is less than the above molar ratio range, the remaining excess epoxy group may react and gel in the subsequent synthesis step. Moreover, when there are more phenolic hydroxyl groups than the range of the said molar ratio, the molecular weight of the photosensitive resin (A) finally obtained becomes low, and it becomes difficult to obtain desired coating-film resistance and film formability. Furthermore, the phenol compound (b) having at least two phenolic hydroxyl groups in one excess molecule may adversely affect physical properties such as solder heat resistance and electrical insulation.

In addition, the molar ratio as used in the field of this invention is a molar ratio with which functional groups actually react, and various starting materials use the quantity which enables reaction by the said molar ratio. Therefore, for example, in the reaction of “epoxy compound (a) having at least two epoxy groups in one molecule” and “phenol compound (b) having at least two phenolic hydroxyl groups in one molecule”, When the starting material is charged, “having at least two phenolic hydroxyl groups in one molecule” with respect to 1.0 mol of epoxy groups in “epoxy compound (a) having at least two epoxy groups in one molecule”. The phenolic hydroxyl group in the “phenolic compound (b)” may be charged in an amount exceeding 2.5 mol (preferably charged at an upper limit of 2.7 mol).

The epoxy compound (a) having at least two epoxy groups in one molecule used in the present invention is not particularly limited as long as it is preferably a compound containing two epoxy groups in the molecule. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct , Resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneope Tyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone Diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane N, N-diglycidylaniline, N, N-dig Ricidyl toluidine, an epoxy compound having excellent flexibility disclosed in JP-A No. 2004-156024, JP-A No. 2004-315595, and JP-A No. 2004-323777, and the following formulas (1) to (3) An epoxy compound having a structure represented by:

Formula (1)

Formula (2)

Formula (3)

Among them, polyethylene glycol diglycidyl ether is preferable in the case where the finally obtained hydroxyl group-containing photosensitive resin (A-1) is provided with flexibility and solubility in an alkaline developer, and is preferably a bisphenol A / epichlorohydrin type. The epoxy resin is preferable in the case where heat resistance is imparted to the finally obtained carboxyl group-containing modified ester resin (A). Thus, in the present invention, the epoxy compound (d) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or in combination. Use in combination is also preferred.

The phenol compound (b) having at least two phenolic hydroxyl groups in one molecule used in the present invention is not particularly limited as long as it is a compound containing two phenolic hydroxyl groups in the molecule. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example, and other examples include bis (4-hydroxyphenol) methane, 1,1-bis (4-hydroxyphenyl). ) Ethane, 1,1-bis (4-hydroxyphenyl) -n-propane, 1,1-bis (4-hydroxyphenyl) -n-butane, 1,1-bis (4-hydroxyphenyl) -n- Pentane, 1,1-bis (4-hydroxyphenyl) -n-hexane, 1,1-bis (4-hydroxyphenyl) -n-heptane, 1,1-bis (4-hydroxyphenyl) -n-octane, 1,1-bis (4-hydroxyphenyl) -n-nonane, 1,1-bis (4-hydroxyphenyl) -n-decane, bis (4-hydroxyphenyl) phenylmethane Bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) toluylmethane, bis (4-hydroxyphenyl)-(4-ethylphenyl) methane, bis (4-hydroxyphenyl)-(4-n- Propylphenyl) methane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-butylphenyl) methane, bis (4-hydroxyphenyl)-(4 -Pentylphenyl) methane, bis (4-hydroxyphenyl)-(4-hexylphenyl) methane, bis (4-hydroxyphenyl)-(4-fluorophenyl) methane, bis (4-hydroxyphenyl)-(4-chlorophenyl) ) Methane, bis (4-hydroxyphenyl)-(2-fluoropheny) ) Methane, bis (4-hydroxyphenyl)-(2-chlorophenyl) methane, bis (4-hydroxyphenyl) tetrafluorophenylmethane, bis (4-hydroxyphenyl) tetrachlorophenylmethane, bis (3-methyl-4-) Hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-ethyl-4-hydroxyphenyl) methane, bis (3-isobutyl-4-hydroxyphenyl) methane, bis (3 -T-butyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (3 , 5-Difluoro-4-hydroxyphenyl) methane, bis (3-chloro- -Hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5- Dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-ethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) ethane, 1,1-bis ( 3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-chloro-4-hydroxyphenyl) ethane, 1, Bisphenols in which a hydrogen atom is bonded to a central carbon such as 1-bis (3,5-dichloro-4-hydroxyphenyl) ethane;
2,2-bis (4-hydroxyphenyl) -n-butane, 2,2-bis (4-hydroxyphenyl) -n-pentane, 2,2-bis (4-hydroxyphenyl) -n-hexane, 2 , 2-bis (4-hydroxyphenyl) -n-heptane, 2,2-bis (4-hydroxyphenyl) -n-octane, 2,2-bis (4-hydroxyphenyl) -n-nonane, 2,2 -Bis (4-hydroxyphenyl) -n-decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (commonly called bisphenol P), 1,1-bis (4-hydroxyphenyl) -1-naphthyl Ethane, 1,1-bis (4-hydroxyphenyl) -1-toluyl ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-ethylphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) -1- (4-n-propylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-isopropylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) L) -1- (4-n-butylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-pentylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1 -(4-hexylphenyl) ethane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-chlorophene) L) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-chlorophenyl) ethane, Bisphenols in which one methyl group is bonded to the central carbon such as 1-bis (4-hydroxyphenyl) -1-tetrafluorophenylethane and 1,1-bis (4-hydroxyphenyl) -1-tetrachlorophenylethane ;
2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propan, 2,2-bis (3- Ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-isobutyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 , 5-Difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, etc. Bisphenols with two methyl groups attached to the carbon;
Bis (4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-methyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-t-butyl-4-hydroxyphenyl) -1,1 -Bisphenols that are diphenylmethane derivatives such as diphenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-chloro-4-hydroxyphenyl) -1,1-diphenylmethane;
1,1-bis (4-hydroxyphenyl) cyclohexane (commonly known as bisphenol Z), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-) Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5 -Bis, which is a cyclohexane derivative such as -dichloro-4-hydroxyphenyl) cyclohexane Phenols;
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, -3,3,5-trimethyl such as 1,1-bis (3,5-difluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane Bisphenols which are cyclohexane derivatives;
9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9 , 9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-isobutyl-4-hydroxyphenyl) fluorene, 1,1-bis (3-fluoro-4-hydroxyphenyl) fluorene, Bisphenols which are fluorene derivatives such as 9,9-bis (3,5-difluoro-4-hydroxyphenyl) fluorene;
1,1-bis (4-hydroxyphenyl) -cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis ( Bisphenols which are cycloalkane derivatives such as 4-hydroxyphenyl) cyclononane and 1,1-bis (4-hydroxyphenyl) cyclodecane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone Bisphenols which are sulfone derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfone, bis (3-fluoro-4-hydroxyphenyl) sulfone, bis (3,5-difluoro-4-hydroxyphenyl) sulfone;
Bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3-ethyl-4-hydroxyphenyl) ether Bisphenols having an ether bond such as bis (3-isobutyl-4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (3,5-difluoro-4-hydroxyphenyl) ether;
Bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, Bisphenols having a sulfide bond such as bis (3-isobutyl-4-hydroxyphenyl) sulfide, bis (3-fluoro-4-hydroxyphenyl) sulfide, bis (3,5-difluoro-4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3-ethyl-4-hydroxyphenyl) sulfoxide Bisphenols which are sulfoxide derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfoxide, bis (3-fluoro-4-hydroxyphenyl) sulfoxide, bis (3,5-difluoro-4-hydroxyphenyl) sulfoxide ;
Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) difluoromethane, 1,1-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoroethane, 2, Examples thereof include bisphenols having no carbon-hydrogen bond such as 2-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoropropane.

And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples thereof include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

In the present invention, the conditions for synthesizing the side chain hydroxyl group-containing resin (c) are not particularly limited, and can be performed under known conditions. For example, an epoxy compound (a) having at least two epoxy groups in one molecule, a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule, and a solvent are charged into a flask while stirring. The side chain hydroxyl group-containing resin (c) can be obtained by heating at 100 to 150 ° C. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

Next, the carboxyl group-containing resin (e) obtained in the second step of the present invention will be described. The carboxyl group-containing resin (e) can be obtained by reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d), and the hydroxyl group in the side chain hydroxyl group-containing resin (c). And an acid anhydride group in the polybasic acid anhydride (d) are preferably reacted at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.1 to 1/1. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. In addition, when there are more acid anhydride groups than the above molar ratio range, excess polybasic acid anhydride (d) generates a by-product in a later synthesis step, so the flexibility and solder heat resistance of the final coating film, Insulation reliability tends to decrease.

The polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. For example, phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydro Examples thereof include compounds containing an acid anhydride group having an alicyclic structure such as phthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, tetrabromophthalic anhydride, or an aromatic ring structure. Other compounds include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic acid Anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride Products, dodecylglutamic acid anhydride, and the like. In the present invention, the polybasic acid anhydride (d) may be used alone or in combination.

Of these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable in the present invention because of their excellent developability, pattern formability, and coating film resistance.

In the present invention, the synthesis conditions of the carboxyl group-containing resin (e) are not particularly limited, and can be performed under known conditions. For example, a side chain hydroxyl group-containing resin (c) is prepared by charging a flask with a side chain hydroxyl group-containing resin (c), a polybasic acid anhydride (d), and a solvent, and heating at 25 to 150 ° C. with stirring. Can be obtained. This reaction proceeds even in the absence of a catalyst, but a catalyst such as a tertiary amino group-containing compound may be used if necessary.

Next, the hydroxyl group-containing resin (A-1) obtained in the third step of the present invention will be described. The hydroxyl group-containing resin (A-1) of the present invention can be obtained by reacting the carboxyl group-containing resin (e) with a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. The carboxyl group in the carboxyl group-containing resin (e) and the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group are converted into a carboxyl group / epoxy group or oxetane group. It is preferable to prepare it by reacting at a molar ratio of 1 / 0.1 to 1/1. When the epoxy group or oxetane group is less than the above molar ratio range, the double bond equivalent functioning as a photo-crosslinking point in the finally obtained photosensitive resin (A) becomes high. It becomes difficult to obtain resistance. Moreover, when there are more epoxy groups or oxetane groups than the range of the said molar ratio, it exists in the tendency for the flexibility of a final coating film to fall with the compound (f) which has an excess epoxy group or oxetane group, and an ethylenically unsaturated group. .

  The compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group used in the present invention may be any compound containing at least one epoxy group or oxetane group and an ethylenically unsaturated group in the molecule. There is no particular limitation. For example, glycidyl (meth) acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) Many hydroxyl-containing groups such as methyl (meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, 1,3-butadiene monoepoxide, oxetanyl (meth) acrylate, oxetanylcinnamic acid, and pentaerythritol triacrylate Modification of most epoxide groups of polyfunctional acrylate groups by reacting epichlorohydrin with hydroxyl groups of functional acrylic monomers, and phenol novolac epoxy resins to acrylate groups with acrylic acid, etc. Epoxy of the compound which has two or more epoxy groups in the molecule to the carboxyl group of the polyfunctional acrylate group-containing monoepoxide and carboxyl group-containing polyfunctional acrylic monomer, in which one epoxy group remains in one molecule on average Polyfunctional acrylate group-containing monoepoxide obtained by reacting a part of the group, and the like. By reacting these epoxy group or oxetane group with the carboxyl group in the carboxyl group-containing resin (e), hydroxyl group is obtained. A group-containing resin (A-1) is obtained. In the present invention, the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group may be used alone or in combination.

Among them, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like are particularly preferable in the present invention because they are highly reactive with carboxyl groups and are very excellent in photosensitivity.

In the present invention, a compound having no ethylenically unsaturated group and having an epoxy group or oxetane group is used in combination with the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group. You can also. In this case, it is possible to control the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention more broadly. Examples of the compound having no ethylenically unsaturated group and having an epoxy group or oxetane group of the present invention include styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamon. Mate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (Daicel Chemical Industries) And oxetane alcohol).

In the present invention, the synthesis conditions of the hydroxyl group-containing resin (A-1) are not particularly limited, and can be performed under known conditions. For example, in the presence of oxygen, the flask is charged with the carboxyl group-containing resin (e), the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group, and a solvent at 25 to 150 ° C. with stirring. The hydroxyl group-containing resin (A-1) can be obtained by heating. At this time, an ethylenically unsaturated group may be added so as not to add a reaction catalyst such as a tertiary amino group-containing compound or the like to promote the reaction, or to cause gelation due to polymerization reaction or progress of polymerization. It is also possible to use a polymerization inhibitor or molecular oxygen.

As the polymerization inhibitor, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, p-benzoquinone, 2,5- Di-t-butylbenzoquinone, naphthoquinone, phenothiazine, N-oxyl compound and the like can be used. Further, even if molecular oxygen is present in the reaction vessel, there is an effect of inhibiting polymerization. For example, air or a mixed gas of air and an inert gas such as nitrogen may be blown into the reaction vessel so-called bubbling. In order to enhance the polymerization inhibition effect, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

  Next, the carboxyl group-containing photosensitive resin (A-2) obtained in the fourth step of the present invention will be described. The carboxyl group-containing photosensitive resin (A-2) of the present invention can be obtained by reacting the hydroxyl group-containing resin (A-1) with the polybasic acid anhydride (d). Prepared by reacting the hydroxyl group in A-1) with the acid anhydride group in the polybasic acid anhydride (d) at a molar ratio of hydroxyl group / acid anhydride group = 1 / 0.01 to 1/1. It is preferable to do. If there are less acid anhydride groups than the above molar ratio range, the concentration of carboxyl groups that function as crosslinking points in the finally obtained photosensitive resin (A) will decrease, so the desired heat resistance and solubility in alkaline developer Is difficult to obtain. Moreover, when there are more acid anhydride groups than the said molar ratio range, it exists in the tendency for the flexibility of a final coating film, solder heat resistance, and insulation reliability to fall with an excess polybasic acid anhydride (d).

As described above, the polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. You may use and you may use multiple together. Of these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable in the present invention because of their excellent developability, pattern formability, and coating film resistance.

In the present invention, the synthesis condition of the carboxyl group-containing photosensitive resin (A-2) is not particularly limited, and the hydroxyl group-containing resin (A-1) is added to the flask in the presence of oxygen in the same manner as in the third step. ), A polybasic acid anhydride (d), and a solvent are charged, and the reaction is preferably performed by heating and stirring at 25 to 150 ° C., and if necessary, a suitable reaction catalyst and an ethylenically unsaturated group A polymerization inhibitor can be newly added.

  It is preferable that the acid value of the photosensitive resin (A) of this invention obtained by the above process is 10-200 mgKOH / g, More preferably, it is 30-150 mgKOH / g. When the acid value is less than 10 mg KOH / g, sufficient developability may be difficult to obtain. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. On the other hand, when the acid value exceeds 200 mgKOH / g, the solubility of the coating film in the developer increases, and even the portion that is desired to be photocured and left as a pattern is dissolved, and the shape of the pattern may deteriorate.

It is preferable that the ethylenically unsaturated group equivalent of the photosensitive resin (A) of this invention is 200-5000 g / eq, More preferably, it is 300-3000 g / eq. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity may be too high, and even the part to be removed by dissolving the film during development is cured by light, and a good pattern shape is obtained. There may not be. When the ethylenically unsaturated group equivalent exceeds 5000 g / eq, the photosensitivity may be too low, the portion to be photocured may not be sufficiently cured, and the pattern dissolves during development, thereby obtaining a good pattern shape. There may not be. The “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of raw materials used during the synthesis of the resin, and the weight of the resin is the ethylenically unsaturated group present in the resin. It is divided by the number of groups and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, ie, the reciprocal of the ethylenically unsaturated group concentration.

It is preferable that the weight average molecular weights of the photosensitive resin (A) of this invention are 1000-100000, More preferably, it is 3000-60000. If the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. On the other hand, when the weight average molecular weight exceeds 100,000, the solder heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling at the time of coating may be problems.

The solvent used for the synthesis of the photosensitive resin (A) can be appropriately selected according to the end use and the solubility of the reactant. For example, when a dry film type photosensitive solder resist is used as the final application, it is preferable to use a low-boiling solvent because the solvent needs to be quickly dried in the dry film preparation step. Examples of the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol and the like. In addition, when liquid solder resist ink is used as the final application, it is necessary to suppress the volatilization of the solvent as much as possible in consideration of the process of kneading fillers and pigments with rolls in the ink preparation process and the storage stability as ink. Therefore, it is preferable to use a high boiling point solvent. Examples of the high boiling point solvent in this case include carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone and the like.

In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

The photosensitive resin composition of the present invention is a curing agent (B) selected from the group consisting of the photosensitive resin (A), an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound. ) And a photopolymerization initiator (C). Here, the curing agent (B) that is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound [hereinafter also simply referred to as “curing agent (B)”. ] Will be described. The photosensitive resin composition of the present invention is characterized by using a curing agent (B) as a curing agent for the above-described photosensitive resin (A).

The epoxy group-containing compound in the present invention is not particularly limited as long as it is a compound containing an epoxy group in the molecule. For example, examples of the compound having one epoxy group in the molecule include compounds such as N-glycidylphthalimide, glycidol, and glycidyl (meth) acrylate. These can be suitably used for the purpose of controlling the crosslink density of the cured product by using together with a compound having two or more epoxy groups in the molecule exemplified below as needed. Examples of the compound containing two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, Bisphenol F / epichlorohydrin type epoxy resin, bisphenol S / epichlorohydrin type epoxy resin, bisphenol AD / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, ethylene oxide adduct of bisphenol A or Propylene oxide adduct epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, naphthalenediol diglycidyl ether, resorcino Rudiglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl Ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full orange glycidyl ether, biscresol full orange glycidyl ether, bisphenoxyethanol full orange glycidyl ether, 1,3-bis ( N, N-diglycidyl Minomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, Japanese Patent Application Laid-Open Nos. 2004-156024, 2004-315595, and 2004-323777. And an epoxy compound having a structure represented by the following formulas (4) to (6).

Formula (4)

Formula (5)

Formula (6)

Further, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, “Epicoat 630” manufactured by Mitsubishi Chemical Corporation, phenol novolac epoxy resin, cresol Novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol / epichlorohydrin adduct, pentaerythritol polyglycidyl ether, trimethylol propane poly, disclosed in JP-A-2001-240654 Examples thereof include glycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

In particular, isocyanurate ring-containing epoxy compounds such as trishydroxyethyl isocyanurate triglycidyl ether and triglycidyl isocyanurate are preferred because they tend to improve the adhesion strength to polyimide and copper when used in the present invention. Also, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, and “Epicoat 630” manufactured by Mitsubishi Chemical Corporation are highly functional in the present invention because they are multifunctional and have excellent heat resistance. Aliphatic epoxy compounds and epoxy compounds described in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777 are preferable because they are excellent in flexibility of a cured coating film. In addition, the dicyclopentadiene type epoxy compound, the phenol novolak type epoxy resin, the cresol novolak type epoxy resin, the biphenol / epichlorohydrin type epoxy resin, etc. described in JP-A No. 2001-240654 are thermally cured in the present invention. It is excellent in terms of durability of a cured coating film including properties, hygroscopicity and heat resistance, and is preferable.

The isocyanate group-containing compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

Specific examples of the isocyanate group-containing compound having one or more isocyanate groups in the molecule include (meth) acryloyloxyethyl isocyanate, monofunctional isocyanate having one isocyanate group in one molecule, , 1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include trimethylolpropane adducts of diisocyanate described above, burettes reacted with water, and trimers having an isocyanurate ring.

The blocked isocyanate group-containing compound is not particularly limited as long as the isocyanate group is an isocyanate group-containing compound protected with ε-caprolactam, MEK oxime, or the like. Specific examples include those obtained by blocking the isocyanate group of the isocyanate group-containing compound with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like.

In this invention, a hardening | curing agent (B) may be used individually by 1 type, and may use multiple together. The amount of the curing agent (B) used may be determined in consideration of the use of the curable resin composition of the present invention, and is not particularly limited, but is 100 parts by weight of the photosensitive resin (A). Thus, it is preferably added at a ratio of 0.5 to 100 parts by weight, more preferably 1 to 80 parts by weight. Since the crosslinking density of the photosensitive resin composition of the present invention can be adjusted to an appropriate value by using the curing agent (B), various physical properties of the cured coating film can be further improved. . If the amount of the curing agent (B) used is less than 0.5 parts by weight, the crosslinking density of the coating after heat curing becomes too low, and the desired adhesive strength and heat resistance may be insufficient. Further, if the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film may be lowered, and the adhesive strength may be significantly deteriorated. is there.

  Next, the photopolymerization initiator (C) will be described. The photopolymerization initiator (C) is added when the photosensitive compound is cured by ultraviolet rays. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

  Specific examples of monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone. 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3′4,4′-tetra ( t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2 (1-Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1, 2-d) thiazoline and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is extremely low but the cost is very low. This is particularly preferable.

These are not limited to the above compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but is preferably added in the range of 1 to 20 parts by weight with respect to 100 parts by weight as the total dry weight of the photosensitive resin (A). . Moreover, a well-known organic amine can also be added as a sensitizer.

一般式（７）中、Ｒ_１水素または炭素数１〜２０のアルキル基であり、Ｒ_２は水素、炭素数１〜２０のアルキル基、又はアミノアルキル基である。一般式（７）で表されるカルボキシルベンゾトリアゾール誘導体（Ｄ）は特に限定されないが、好ましい具体例としては、Ｎ（Ｎ，Ｎ−ジ−２−エチルヘキシル）アミノメチレンカルボキシベンゾトリアゾール、Ｎ（Ｎ，Ｎ−ジ−２ −ヒドロキシエチル）アミノメチレンカルボキシベンゾトリアゾール、Ｎ（Ｎ，Ｎ−ジ− ２−エチルヘキシル）アミノエチレンカルボキシベンゾトリアゾール、５−カルボキシベンゾトリアゾール、３−メチル−５−カルボキシベンゾトリアゾール、３−エチル−５−カルボキシベンゾトリアゾール、及び３−へキシル−５−カルボキシベンゾトリアゾール、５-カルボキシベンゾトリアゾール、５−カルボキシベンゾトリアゾールメチルエステル、５−カルボキシベンゾトリアゾールフェニルエステルなどが挙げられ、好ましくは５-カルボキシベンゾトリアゾール、５−カルボキシベンゾトリアゾールメチルエステル、５−カルボキシベンゾトリアゾールフェニルエステルである。より好ましくは分子内に酸性基と塩基性基を有し分子内塩を形成する５-カルボキシベンゾトリアゾールであり、特に耐熱性、現像性、折り曲げ性に対する効果が高い。
また、添加量は樹脂１００重量部に対して１〜３０重量部が好ましい。１重量部未満では耐熱性、現像性、折り曲げ性の改善が不十分であり、また３０重量部以上になると回路への密着性の低下や耐熱性が低下するため望ましくない。 Next, the carboxybenzotriazole derivative (D) added for the purpose of improving heat resistance, developability and bendability in the present invention will be described. The carboxyl benzotriazole derivative (D) of the present invention refers to a substituted or unsubstituted carboxyl benzotriazole, and includes those in which a carboxyl group is esterified. The carboxyl benzotriazole derivative (D) is not particularly limited, but is preferably a carboxybenzotriazole derivative represented by the general formula (7).
General formula (7)

In General Formula (7), R _{1 is} hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ₂ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aminoalkyl group. The carboxyl benzotriazole derivative (D) represented by the general formula (7) is not particularly limited, but preferred specific examples include N (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, 5-carboxybenzotriazole, 3-methyl-5-carboxybenzotriazole, 3 -Ethyl-5-carboxybenzotriazole, and 3-hexyl-5-carboxybenzotriazole, 5-carboxybenzotriazole, 5-carboxybenzotriazole methyl ester, 5-carboxybenzotriazole phenyl ester, etc. Gerare, preferably 5-carboxy benzotriazole, 5-carboxy benzotriazole methyl ester, 5-carboxy benzotriazole phenyl ester. More preferred is 5-carboxybenzotriazole which has an acidic group and a basic group in the molecule and forms an inner salt, and has particularly high effects on heat resistance, developability and bendability.
Moreover, the addition amount is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin. If the amount is less than 1 part by weight, the heat resistance, developability and bendability are insufficiently improved. If the amount is more than 30 parts by weight, the adhesion to the circuit is deteriorated and the heat resistance is not desirable.

The photosensitive resin composition of the present invention may further contain a thermosetting aid. The thermosetting aid represents a compound that contributes directly or catalytically to the curing reaction during thermosetting.

  Examples of the compound that directly contributes to the curing reaction during thermosetting include amino resins, phenol resins, polyfunctional polycarboxylic acid anhydrides, polyfunctional vinyl ether compounds, high molecular weight polycarbodiimides, and aziridine compounds.

Examples of amino resins and phenol resins include addition compounds of urea, melamine, benzoguanamine, phenol, cresols, bisphenols, and the like with formaldehyde, or partial condensates thereof.

The polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride And polyvalent carboxylic acid anhydrides such as maleic anhydride copolymer resins. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are “compounds having two or more carboxylic acid anhydride groups” in the present invention. "include.

More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”, and the like.

   Examples of maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resin such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride modified maleic anhydride (“Aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

  Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexanedivinyl ether, Hyde Quinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol Examples include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether.

Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

Other compounds that directly contribute to the curing reaction during thermal curing include benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allyl nadiimide compounds, melamine compounds, and guanamine compounds, which are cured by heating. Any of them can be used effectively. These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. be able to.

Examples of compounds that contribute catalytically to the curing reaction during heat curing include tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and N-methylpiperazine. And salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] -Imidazoles such as ethyl-S-triazine and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, etc. Diazabicyclo compounds;
Phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate;
In addition, dicyandiamide, carboxylic acid hydrazide, and the like can be cited as compounds that are catalytic and that directly contribute to the curing reaction. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

Only one type of these thermosetting aids may be used, or two or more types may be used in combination. The amount of the thermosetting aid used may be determined in consideration of the application of the photosensitive resin composition and the like, and is not particularly limited. The range of 1 to 100 parts by weight is more preferable, and the range of 0.5 to 80 parts by weight is still more preferable. Thereby, since the crosslinking density of the photosensitive resin composition can be adjusted to an appropriate value, various physical properties of the photosensitive resin composition can be further improved. If the amount of the thermosetting aid used is less than 0.1 parts by weight, the cross-linking density of the coating film after heat curing becomes too low, and the cohesive strength and durability may be insufficient. Also, if the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film are lowered and the warpage of the substrate is remarkably deteriorated. There is.

The photosensitive resin composition of this invention may contain resin other than the above-mentioned (A) as needed. Examples of resins other than (A) include acrylic resins, polyester resins, urethane resins, urea resins, urethane urea resins, epoxy resins, polyamide resins, and polyimide resins. Those containing a carboxyl group are preferable from the viewpoint of developability, and those having excellent compatibility with (A) are preferable. In this invention, when it contains resin other than (A), it can be used individually or in combination.

  In addition to the above, the photosensitive resin composition of the present invention may further include solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, leveling agents, humectants, viscosity modifiers as optional components within a range not to impair the purpose. Preservatives, antibacterial agents, antistatic agents, anti-blocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic shielding agents, fillers, and the like can be added. Especially used for insulating materials (such as circuit protection films, coverlay layers, interlayer insulating materials, etc.) that are in direct contact with the circuit for electronic materials, and for members that can become high heat around the circuit (printed wiring board adhesive, support substrate, etc.) When doing so, it is preferable to use a flame retardant together.

 Examples of the flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. Phosphate compounds and polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, Phosphinic acid compounds such as aluminum methylbutylphosphinate and aluminum aluminum phosphinate, phosphine oxide compounds, phosphorane compounds, phosphoramidation Phosphorus flame retardants such as products, triazine compounds such as melamine, melam, melem, melon and melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea and other nitrogen flame retardants , Silicon flame retardants such as silicone compounds and silane compounds, halogenated bisphenol A, halogenated epoxy compounds, halogenated flame retardants such as halogenated oligomers and polymers, halogenated flame retardants such as halogenated phenoxy compounds, water Metal hydroxides such as aluminum oxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Nickel, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and inorganic flame retardants such as hydrated glass. In the present invention, taking into consideration the influence on the environment, which has been recently taken into consideration, it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant or a nitrogen flame retardant, and in particular, the thermosetting resin composition of the present invention. It is preferable to use a phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, or the like that is more effective in flame retardancy when used in combination. In the present invention, these flame retardants can be used alone or in combination.

  Since the photosensitive resin composition of the present invention and its cured product are characterized by excellent alkali developability, they can be suitably used for applications in which a film forming process including photocuring, alkali development, and post-cure is used. . Furthermore, since it is excellent in solder heat resistance and coating film resistance, and is also excellent in flexibility and flexibility, it is particularly suitable for use in solder resist inks for flexible printed wiring boards and photosensitive coverlay films. it can.

  The photosensitive resin composition of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

The photosensitive resin composition of the present invention can be cured by a known radiation curing method to obtain a cured product, and as active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  When used as a photo solder resist, the photosensitive resin composition of the present invention can be used as a liquid resist ink dissolved in a solvent or a dry film type resist obtained by previously drying the solvent.

When used as a liquid resist ink, the photosensitive resin composition of the present invention may be subjected to radiation curing after the solvent is volatilized by natural or forced drying after coating on the base material. Although natural or forced drying may be performed after the radiation curing, it is preferable that the radiation curing is performed after natural or forced drying. In the case of a liquid resist ink, it is preferable that the solvent does not evaporate during handling until the application to the substrate is completed, such as the storage step and the coating step. As the dilution solvent at the time of ink preparation, those having a high boiling point are preferable. For example, it is particularly preferable to use carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone or the like. In addition, in the case of liquid resist inks, there are also two-component types that are stored in advance separately from the curing agent in consideration of storage stability and handling, and mixed with a curing agent as necessary before coating. is there. Also in the case of this invention, the hardening | curing agent (B) which is at least 1 type chosen from the group which consists of an epoxy group containing compound, an isocyanate group containing compound, and a blocked isocyanate group containing compound, a photoinitiator (C), ethylene The polymerizable unsaturated group-containing compound (D) and the thermosetting auxiliary agent can be used as a two-component type, for example, by storing separately from the others as necessary.

On the other hand, when using as a dry film type resist, first, a dry film type is obtained by applying a photosensitive composition dissolved in a solvent to a film substrate having good releasability such as a separate film and then drying the solvent. Create a resist. In this case, unlike the above-described liquid resist ink, it is necessary to dry the solvent completely in a short time, and therefore a solvent having a low boiling point is preferable. For example, it is particularly preferable to use methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol, or the like. The dry film formed on the separate film is laminated on a copper circuit or the like formed on polyimide, and thereafter, bubbles and the like are removed and adhered to the circuit by lamination or vacuum lamination. After this pasting step, there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing. When radiation curing is performed by bringing a development pattern into contact, if the dry film has a tack, the development pattern may be contaminated. Therefore, a dry film type resist is required to have a low dry film tack. Since the photosensitive resin composition of this invention can reduce a tack as needed, it can be usefully used also as a dry film resist.

Furthermore, the photosensitive resin composition of the present invention forms a pattern by developing after radiation curing, and forms a film having excellent resistance by thermosetting as post-cure. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Further, in order to further improve the resistance of the coating film, an active energy ray can be irradiated as necessary after post-curing. By irradiating the active energy ray after the post cure, the solder heat resistance and the like can be further improved.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

  The measurement conditions for GPC are as follows.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. In the measurement of the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, and the column temperature is 40. It carried out on the conditions of (degreeC) and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.

<Molecular weight distribution (Mw / Mn)>
The degree of dispersion of the molecular weight is expressed. In the present invention, the weight average molecular weight (Mw) / number average molecular weight (Mn) was determined from the molecular weight measurement result.

[Production Example 1]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 64.8 parts of bisphenol A, 57.1 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 128.1 parts, 1.25 parts triphenylphosphine as catalyst, 1.25 parts N, N-dimethylbenzylamine, 250 parts toluene as solvent The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours to obtain a hydroxyl group-containing resin. Next, 54.6 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 26.0 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.165 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, methyl ethyl ketone was added to this solution to adjust the solid content to 50.0%. The hydroxyl group-containing photosensitive resin (A-1) according to the present design has an ethylenically unsaturated group equivalent of 1803 g / eq, a polystyrene-equivalent weight average molecular weight of 23500, and an actually measured acid value of resin solids of 63 mgKOH / g. there were.

[Production Example 2]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 60.8 parts of bisphenol A, 43.4 parts of YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound) , EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether) 145.8 parts, 1.25 parts of triphenylphosphine as a catalyst, 1.25 parts of DMBA, 250 parts of toluene as a solvent, and stirred under a nitrogen stream However, the temperature was raised to 110 ° C. and the reaction was performed for 8 hours to obtain a hydroxyl group-containing resin. Next, 49.8 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride and reacted at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air, while stirring, 41.1 parts of GMA (manufactured by NOF Corporation: glycidyl methacrylate), hydroquinone 0.17 as a polymerization inhibitor. Part was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, 26.0 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd .: succinic anhydride) was added as an acid anhydride to a flask in which dry air was introduced, and reacted at 80 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Methyl ethyl ketone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive resin (A-2) according to this design is 1269 g / eq, the polystyrene-equivalent weight average molecular weight is 20200, and the acid value of the resin solid content measured is 73 mgKOH / g. there were.

[Production Examples 3 to 4]
By performing the same operations as in Production Example 7 using the raw materials shown in Table 2, the carboxyl group-containing photosensitive resin (A-2) of Production Examples 3 to 4 was obtained.

Table 1 shows the specifications of the photosensitive resins obtained in Production Examples 1 to 4.

ＢｉｓＡ：ビスフェノールＡ
ＹＤ８１２５：新日鐵化学株式会社製、ビスフェノールＡ型エポキシ化合物
ＥＸ８６１：ナガセケムテックス株式会社製、ポリエチレングリコールジグリシジルエーテル
ＳＡ：新日本理化株式会社製、無水コハク酸
ＧＭＡ：日油株式会社製、グリシジルメタクリレート
ＥＸ８３０：ナガセケムテックス株式会社製、ポリエチレングリコールジグリシジルエーテル
ＹＬ７４１０：三菱化学株式会社製、ゴム弾性型エポキシ樹脂

BisA: Bisphenol A
YD8125: manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound EX861: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether SA: manufactured by Nippon Nippon Chemical Co., Ltd., succinic anhydride GMA: manufactured by NOF Corporation, glycidyl Methacrylate EX830: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether YL7410: manufactured by Mitsubishi Chemical Corporation, rubber elastic epoxy resin

[Production Example 5]
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C, and a melt viscosity (150 ° C) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin, and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% aqueous sodium hydroxide solution was added at 70 ° C. over 100 minutes with stirring. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% aqueous sodium hydroxide solution. And reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone is recovered by distillation from the oil layer, and an epoxy resin having an epoxy equivalent of 287, a hydrolyzable chlorine content of 0.07%, a softening point of 64.2 ° C., and a melt viscosity (150 ° C.) of 7.1 poise. 340 parts were obtained.

287 parts of this epoxy resin was put into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, cyclohexanone 194 The reaction mixture was dissolved by heating and stirring at 90 ° C. Subsequently, the reaction liquid was cooled to 60 ° C., 1.7 parts of triphenylphosphine was added, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an actually measured acid value of 1 mgKOH / g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added thereto and reacted at 95 ° C. for about 6 hours to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a bisphenol A type epoxy resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 450 eq / g, the weight average molecular weight in terms of polystyrene is 7400, the molecular weight distribution is 2.23, and the acid value of the resin solid content by actual measurement is 100 mgKOH / g. It was.

[Production Example 6]
To a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 330 parts of a cresol novolac epoxy resin having an epoxy equivalent of 218 g / eq (manufactured by Toto Kasei Co., Ltd .: YDCN-702). The mixture was melted by heating at 90 to 100 ° C. and stirred. Next, 120 parts of acrylic acid, 0.6 part of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours. Next, 400 parts of cyclohexanone was added to this flask and dissolved by heating to 70 ° C. Next, 81 parts of succinic anhydride was added, the temperature was raised to 95 ° C., and the mixture was stirred and reacted for 8 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a cresol novolak skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 319 g / eq, the weight average molecular weight in terms of polystyrene is 11000, the molecular weight distribution is 2.90, and the acid value of the resin solid content by measurement is 85 mgKOH / g. It was.

[Production Example 7]
A dropping funnel was placed in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, and 400 parts of cyclohexanone was charged into the flask, and the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere. did. In a separate container, 15 parts of methacrylic acid, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 25 parts of benzyl methacrylate, 20 parts of azobisisobutyronitrile as a polymerization initiator and 100 parts of cyclohexanone are stirred and dissolved uniformly. did. The monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Stirring was continued at 90 ° C. even after completion of the dropping, and 0.5 part of azobisisobutyronitrile was charged into the flask after 2 hours from the end of the dropping. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700, a molecular weight distribution of 2.58, and an acid value of resin solid content of 98 mgKOH / g.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. , Reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 19,900, a molecular weight distribution of 2.72, and an actually measured acid value of resin solids of 5 mgKOH / g.

Next, 63 parts of succinic anhydride was added to the flask and reacted for 6 hours with stirring at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was an acrylic resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 863 g / eq, the weight average molecular weight in terms of polystyrene is 22000, the molecular weight distribution is 2.81, and the acid value of the resin solid content by measurement is 70 mgKOH / g. It was.

[Production Example 8]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 212 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Part, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 15,200, a molecular weight distribution of 2.87, and an actually measured acid value of 170 mgKOH / g of resin solids.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 110 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed to obtain a carboxyl group-containing photosensitive urethane resin whose main skeleton is an acid anhydride-modified urethane skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design was 896 g / eq, the weight average molecular weight in terms of polystyrene was 18,800, the molecular weight distribution was 3.12, and the acid value of the resin solid content was 72 mgKOH / g as measured.

[Production Example 9]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 218 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 47 Part, 125 parts of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of cyclohexanone as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 111 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 17000, a molecular weight distribution of 2.60, and an actually measured acid value of 110 mgKOH / g of resin solids.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 131 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 19,200, a molecular weight distribution of 3.00, and an actually measured resin solid acid value of 4 mgKOH / g.

Next, 74 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing urethane resin whose main skeleton was an acid anhydride-modified urethane resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design is 765 g / eq, the weight average molecular weight in terms of polystyrene is 21400, the molecular weight distribution is 3.20, and the acid value of the resin solid content by measurement is 67 mgKOH / g. It was.

Table 2 summarizes the specifications of the resins obtained in Production Examples 5 to 9.

A photosensitive resin composition was prepared by the following method and evaluated as a photosensitive dry film and a photosensitive resist ink.
<Preparation of photosensitive resin composition>
[Examples 1 to 15]
In accordance with the solid content ratio shown in Table 3 with respect to 100 parts of the solid content of the photosensitive resin solution obtained in the production example, Epicoat 1031S (manufactured by Mitsubishi Chemical Corporation: polyfunctional glycidyl ether type epoxy resin) ), BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd .: isocyanurate type blocked isocyanate), aluminum phosphinate EXOLITOP-935 (manufactured by Clariant Japan) and phosphazene SPB-10 (manufactured by Otsuka Chemical Co., Ltd. and cyano) as flame retardant (E) Phenoxyphosphazene FP-300 (manufactured by Fushimi Pharmaceutical Co., Ltd.), 5-carboxybenzotriazole, 5-carboxybenzotriazole phenyl ester, 5-carboxybenzotriazole methyl ester manufactured by Johoku Chemical Industry as the carboxybenzotriazole derivative (D) Copper phthalocyanine pigment LIONOL BLUE FG7350 (Toyochem Co., Ltd.) as a colorant and Irgacure 907 (Ciba Specialty Chemicals Co., Ltd .: 2-methyl-1- [4- (methylthio) as a photopolymerization initiator (C) ) Phenyl] -2-morpholino-1-propane) and DETX-S (manufactured by Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone) as a photosensitizer are uniformly dissolved and mixed, and a horizontal sand mill DYNO-MILL ( (Manufactured by Shinmaru Enterprise Co., Ltd.) and dispersed with a grind gauge until coarse particles were less than 10 μm to obtain a photosensitive resin composition.

[Comparative Examples 1-14]
Except having changed into the material and usage-amount shown in Table 5, the photosensitive resin composition was produced like the Example.

The types of carboxybenzotriazole derivatives and benzotriazole derivatives used are shown below.

カルボキシベンゾトリアゾール(CBT-1：城北化学工業製)

Carboxybenzotriazole (CBT-1: Johoku Chemical Industry)

５-カルボキシベンゾトリアゾールフェニルエステル（５−ＣＢＴ−ＰＥ：城北化学工業製）

5-Carboxybenzotriazole phenyl ester (5-CBT-PE: manufactured by Johoku Chemical Industries)

５-カルボキシベンゾトリアゾールメチルエステル（５−ＣＢＴ−ＭＥ：城北化学工業製）

5-Carboxybenzotriazole methyl ester (5-CBT-ME: manufactured by Johoku Chemical Industries)

2,6-ヒ゛ス〔(1H-ヘ゛ンソ゛トリアソ゛ール-1-yl）メチル〕4-メチルフ゜ロハ゜ノール（ＢＴ−３７００：城北化学工業製）

2,6-bis [(1H-Benzotriazole-1-yl) methyl] 4-methylfluorophenol (BT-3700: Johoku Chemical Industry)

2,4-シ゛-ter-フ゛チル-6-〔(1H-ヘ゛ンソ゛トリアソ゛ール―1イル)メチル〕フェノール（ＢＴ−３３７：城北化学工業製）

2,4-di-ter-butyl-6-[(1H-benzotriazole-1-yl) methyl] phenol (BT-337: manufactured by Johoku Chemical Industry)

1-〔N，N-ヒ゛ス（2エチルヘキシル）アミノメチル〕ヘ゛ンソ゛トリアソ゛ール（ＢＴ−ＬＸ：城北化学工業製）

1- [N, N-bis (2-ethylhexyl) aminomethyl] benztriazole (BT-LX: Johoku Chemical Co., Ltd.)

<Production and evaluation of photosensitive dry film>
The photosensitive resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 10 were uniformly coated on a 12 μPET film (S-12 manufactured by Toray DuPont Co., Ltd.) so that the dry film thickness was 40 μm. The film was dried at 100 ° C. for 5 minutes, cooled to room temperature, and a biaxially stretched polypropylene film (OPP film) was laminated on the surface of the photosensitive resin composition to obtain a photosensitive dry film. Evaluation is performed by the following method, and the evaluation results are shown in Tables 3 and 4.

(1) A 2 mm copper border is placed on a Nikkan Kogyo 3 layer copper-clad laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) with a substrate warpage of 5 cm × 5 cm, and a pattern: line width 125 μm / between lines A dry film resist was vacuum-laminated on a pattern having a 125 μm pattern. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds.
The vacuum-laminated sample was exposed to 300 mJ with a mercury short arc amplifier (5 kW) over a 120 μm PET Mylar sheet on 12 μPET, and then the 12 μPET film was peeled off, followed by thermosetting (post-cure) for 1 hour with a 150 ° C. hot air dryer. After passing through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds, it was allowed to stand for 12 hours on a flat table at 25 ° C. and a humidity of 50%. For the sample after standing, the height at which the four corners of the square were lifted from the table was measured, the average value was calculated, and evaluated according to the following criteria. The smaller this value, the less the sample warps, indicating better.
◎ ・ ・ ・ 2mm or less ○ ・ ・ ・ 5mm or less △ ・ ・ ・ 6mm or more-10mm or less × ・ ・ ・ 11mm or more

(2) The OPP film was peeled off from the developable photosensitive dry film, and vacuum laminated to a polyamide film (Toray DuPont Co., Ltd .; Kapton 100H). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. The vacuum-laminated sample was exposed to 120 μm PET Mylar sheet / Stouffer step tablet 21 steps on a 12 μPET with a mercury short arc amplifier (5 kW), and then the 12 μPET film was peeled off. % Na2CO3 aqueous solution was developed at a spray pressure of 0.2 MPa for 40 seconds. After development, the film was heat-cured (post-cured) for 1 hour in a hot air dryer at 150 ° C. The obtained cured film was cooled to room temperature, and developability was evaluated.
The number of steps at which the coating film was washed away with the developer was defined as the number of peeling steps, and the exposure amount at which the number of peeling steps was 6 was determined and evaluated. The exposure amount was measured using an integrated exposure meter UV-351 manufactured by Oak Manufacturing Co., Ltd.
◎ ・ ・ ・ less than 200 mJ / cm ² ○ ・ ・ ・ 200 to 400 mJ / cm ²
Δ: 400 to 600 mJ / cm ²
× ・ ・ ・ greater than 600 mJ / cm ²

(3) Resolution The same cured film as used in the evaluation of developability was evaluated. The number of steps where the coating film was swollen by the developer was taken as the number of swelling steps, and the resolution step was determined by the following formula for the number of peeling steps confirmed by evaluation of developability.
[Resolution step] = [Number of peeling steps]-[Number of swelling steps]
It can be said that the smaller the resolution step, the sharper the pattern can be formed in the actual pattern forming process, and the better the resolution. Using this resolution step, the resolution was judged according to the following criteria.
◎ ・ ・ ・ Resolution step ≦ 1
○ ・ ・ ・ Resolution step = 2 ～ 3
△ ・ ・ ・ Resolution step = 4-7
× ・ ・ ・ Resolution step ≧ 8

(4) The OPP film is peeled off from the folding-resistant photosensitive dry film, and the photosensitive dry film is vacuum-laminated on a 2 cm × 9 cm two-layer substrate (Nippon Steel Chemical Co., Ltd .: Espanex MC-18-25-00FRM). . The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. A vacuum-laminated sample was irradiated on a 12μPET with a mercury short arc amplifier (5kW) through a 120μm PET Mylar sheet and irradiated with UV rays with an integrated light quantity of 300mJ / cm ² , and then heat-cured for 1 hour in a 150 ° C hot air dryer. (Post cure).
This sample was bent 180 degrees at a portion of conductor pattern width / space width = 50/50, and a 500 g weight was placed on the bent portion for 5 seconds, and this was performed once.
Whether or not a crack was generated in the dry film provided on the copper side of the two-layer substrate was observed with a microscope “VHX-900” manufactured by Keyence Corporation, and the number of times of bending without cracks was evaluated.
◎ ・ ・ ・ 20 times or more ○ ・ ・ ・ 11 times or more Δ ・ ・ ・ 5-10 times × ・ ・ ・ less than 5 times

(5) Insulation reliability The OPP film is peeled off from the photosensitive dry film, and a 65 mm × 65 mm sheet is formed into a comb pattern in which a copper circuit is formed on a polyimide (conductor pattern width / space width = 50 μm / 50 μm). Vacuum laminated to the printed circuit board. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. The vacuum-laminated sample was irradiated with ultraviolet light of 300mJ / cm ^{2 with} a UV exposure device with a mercury short arc amplifier (5kW) over a 120μm PET Mylar sheet on 12μPET, and then heat cured for 1 hour with a 150 ° C hot air dryer. (Post-cure) to prepare a test piece for evaluation. The conductor circuit of this test piece was placed in a pressure cooker (PC-422R8 manufactured by Hiraoka Seisakusho), and a DC voltage of 50 V was continuously applied for 100 hours under an atmosphere of 130 ° C., 85% relative humidity and 2 atm. The insulation resistance value between the conductors was measured. The evaluation criteria are as follows.
○ ・ ・ ・ Insulation resistance value 10 ⁷ or more △ ・ ・ ・ Insulation resistance value 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・ Insulation resistance value less than 10 ⁶ Ω (6) Heat resistance 5 cm × 5 cm Nikkan Kogyo's 3-layer copper 2mm copper edging on the laminated laminate (electrolytic Cu 18μm / adhesive 20μm / PI 25μm), and the pattern: line width 125μm / line spacing 125μm pattern formed on the inside, vacuum photosensitive dry film resist Laminated. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds.
The vacuum-laminated sample was exposed to 300 mJ with a mercury short arc amplifier (5 kW) over a 120 μm PET Mylar sheet on 12 μPET, and then the 12 μPET film was peeled off, followed by thermosetting (post-cure) for 1 hour with a 150 ° C. hot air dryer. Thereafter, it was passed through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds. The degree of discoloration after passing was evaluated.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slight discoloration × ・ ・ ・ Significant discoloration

<Evaluation of photosensitive resist ink>
The photosensitive resin compositions obtained in Examples 9 to 15 and Comparative Examples 11 to 14 were evaluated by the following methods, and the evaluation results are shown in Table 3 and Table 4.

(1) A 2 mm copper border is placed on a Nikkan Kogyo 3 layer copper-clad laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) with a substrate warpage of 5 cm × 5 cm, and a pattern: line width 125 μm / between lines A photosensitive resin composition is uniformly applied on a 125 μm pattern so as to have a dry film thickness of 40 μm, dried at 100 ° C. for 5 minutes, and then a mercury short arc amplifier over a 120 μm PET Mylar sheet on the sample. After 300 mJ exposure at (5 kW), heat curing (post-cure) was performed for 1 hour with a 150 ° C. hot air dryer. After passing through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds, it was allowed to stand for 12 hours on a flat table at 25 ° C. and a humidity of 50%. For the sample after standing, the height at which the four corners of the square were lifted from the table was measured, the average value was calculated, and evaluated according to the following criteria. The smaller this value, the less the sample warps, indicating better.
◎ ・ ・ ・ 2mm or less ○ ・ ・ ・ 5mm or less △ ・ ・ ・ 6mm or more-10mm or less × ・ ・ ・ 11mm or more

(2) The photosensitive resin composition is uniformly coated on a developable polyimide film (Toray DuPont Co., Ltd .; Kapton 100H) so that the dry film thickness is 40 μm and dried at 100 ° C. for 5 minutes, and then on the sample. 120μm PET Mylar sheet / Stouffer step tablet After exposure with 21 steps of mercury short arc amplifier (5kW), the following development conditions with a developing machine (1% Na2CO3 aqueous solution with a liquid temperature of 30 ° C, 0.2 MPa spray pressure) And developed for 40 seconds.
After development, the film was heat-cured (post-cured) for 1 hour in a hot air dryer at 150 ° C. The obtained cured film was cooled to room temperature, and developability was evaluated. The number of steps at which the coating film was washed away with the developer was defined as the number of peeling steps, and the exposure amount at which the number of peeling steps was 6 was determined and evaluated. The exposure amount was measured using an integrated exposure meter UV-351 manufactured by Oak Manufacturing Co., Ltd.

◎ ・ ・ ・ less than 200 mJ / cm ² ○ ・ ・ ・ 200 to 400 mJ / cm ²
Δ: 400 to 600 mJ / cm ²
× ・ ・ ・ greater than 600 mJ / cm ²

(3) The same cured film as that used in the evaluation of resolution developability was evaluated. The number of steps where the coating film was swollen by the developer was taken as the number of swelling steps, and the resolution step was determined by the following formula for the number of peeling steps confirmed by evaluation of developability.
[Resolution step] = [Number of peeling steps]-[Number of swelling steps]
It can be said that the smaller the resolution step, the sharper the pattern can be formed in the actual pattern forming process, and the better the resolution. Using this resolution step, the resolution was judged according to the following criteria.
◎ ・ ・ ・ Resolution step ≦ 1
○ ・ ・ ・ Resolution step = 2 ～ 3
△ ・ ・ ・ Resolution step = 4-7
× ・ ・ ・ Resolution step ≧ 8

(4) Folding resistance
A photosensitive resin composition is uniformly coated on a 2 cm × 9 cm two-layer substrate (Nippon Steel Chemical Co., Ltd .: Espanex MC-18-25-00FRM) to a dry film thickness of 40 μm, and then at 100 ° C. for 5 minutes. After drying, the sample was exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW) and then heat-cured (post-cured) with a hot air dryer at 150 ° C. for 1 hour.
This sample was bent 180 degrees at the portion of conductor pattern width / space width == 50/50, and a 500 g weight was placed on the bent portion for 5 seconds, and this was performed once.
Whether or not a crack was generated in the dry film provided on the copper side of the two-layer substrate was observed with a microscope “VHX-900” manufactured by Keyence Corporation, and the number of times of bending without cracks was evaluated.
◎ ・ ・ ・ 20 times or more ○ ・ ・ ・ 11-19 times Δ ・ ・ ・ 5-10 times × ・ ・ ・ less than 5 times

(5) Insulation reliability A sheet having a size of 65 mm × 65 mm is coated with a photosensitive resin composition on a printed circuit board having a comb pattern (conductor pattern width / space width = 50 μm / 50 μm) in which a copper circuit is formed on polyimide. After coating uniformly to a dry film thickness of 40 μm and drying at 100 ° C. for 5 minutes, the sample is exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW) and then dried with hot air at 150 ° C. It was heat-cured (post-cure) for 1 hour in a vessel. The conductor circuit of this test piece was placed in a pressure cooker (PC-422R8 manufactured by Hiraoka Seisakusho), and a DC voltage of 50 V was continuously applied for 100 hours under an atmosphere of 130 ° C., 85% relative humidity and 2 atm. The insulation resistance value between the conductors was measured. The evaluation criteria are as follows.
○ ・ ・ ・ Insulation resistance value 10 ⁷ or more △ ・ ・ ・ Insulation resistance value 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・ Insulation resistance value less than 10 ⁶ Ω (76) Heat resistance 5 cm × 5 cm Nikkan Kogyo's 3-layer copper A photosensitive resin composition is applied to a laminated laminate (electrolytic Cu 18 μm / adhesive 20 μm / PI 25 μm) with a 2 mm copper border and a pattern with a pattern width of 125 μm / line spacing of 125 μm formed inside. After coating uniformly to a dry film thickness of 40 μm and drying at 100 ° C. for 5 minutes, the sample was exposed to 300 mJ through a 120 μm PET Mylar sheet with a mercury short arc amplifier (5 kW), and then a hot air dryer at 150 ° C. For 1 hour. The sample was passed through a solder reflow furnace at 260 ° C. and a peak temperature of 10 seconds. The degree of discoloration after passing was evaluated.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slight discoloration × ・ ・ ・ Significant discoloration

From the evaluation results of Examples and Comparative Examples, by adding the carboxybenzotriazole derivative (D), developability, resolution, folding resistance, and heat resistance are improved, and the effect is most effective when carboxybenzotriazole is added. I found out that

Claims (9)

Photosensitive resin (A), epoxy group-containing compound, unblocked isocyanate compound, at least one selected from blocked isocyanate compound, curing agent (B), photopolymerization initiator (C), and carboxybenzotriazole derivative A photosensitive resin composition comprising (D),
The photosensitive resin (A) is
Resin (c) containing a side chain hydroxyl group by reacting an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. Produces
Reacting the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e);
Hydroxyl group-containing photosensitive resin (A) obtained by reacting the carboxyl group-containing resin (e) with an epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group -1) or
It is a carboxyl group-containing photosensitive resin (A-2) obtained by reacting a hydroxyl group in the hydroxyl group-containing resin (A-1) with an acid anhydride group in the polybasic acid anhydride (d).
The photosensitive resin composition characterized by the above-mentioned.   The photosensitive resin composition of Claim 1 whose carboxy benzotriazole derivative (D) is a benzotriazole derivative which has a carboxyl group in a benzene ring.   The photosensitive resin composition according to claim 1 or 2, wherein the content of the carboxybenzotriazole derivative (D) is 1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin (A).   The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the photosensitive resin (A) is 10 to 200 mgKOH / g. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive resin (A) has an ethylenically unsaturated group equivalent of 200 to 5000 g / eq. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive resin (A) has a weight average molecular weight of 1,000 to 100,000. Hardened | cured material formed by hardening | curing the photosensitive resin composition in any one of Claims 1-6. The photosensitive soldering resist ink containing the photosensitive resin composition in any one of Claims 1-7, and a flame retardant. A dry film type photosensitive solder resist comprising the photosensitive resin composition according to claim 1 and a flame retardant.