JPH11288090A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. forming a resist film excellent in wet heat resistance and adhesion to copper and other base material and suitable for use as a soldering resist compsn. excellent in flame resistance and mechanical characteristics such as suitability to bending and curving. SOLUTION: A photosensitive resin compsn. contains a photosensitive resin (A) having carboxyl groups obtd. by allowing the esterification product of an epoxy compd. and an unsatd. monocarboxylic acid to react with a satd. or unsatd. polybasic acid anhydride, at least one photosensitive resin (B) selected from a photosensitive polyamide resin having carboxyl groups and a photosensitive polyamidoimide resin having carboxyl groups, an epoxy hardening agent (C) and a photopolymn. initiator (D) and a flame retardant (E).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solder used for manufacturing rigid and flexible printed wiring boards, or LSI packages such as BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package). The present invention relates to a resist composition or a photosensitive resin composition suitably used as a photosensitive interlayer insulating material of a multilayer wiring board.

[0002]

2. Description of the Related Art Solder resist is used in the manufacture of printed wiring boards, but has recently been used in new LSI packages such as BGA and CSP. Solder resist is an indispensable material as a protective film for preventing solder from adhering to unnecessary parts in a soldering process and as a permanent mask. As a solder resist, there is a method of printing and applying a thermosetting type by a screen printing method. The present invention can also be applied to such a method, but in recent years, with the increase in wiring density, there is a limit in terms of resolution in the screen printing method, and a photo solder resist for forming a pattern by a photographic method has been actively used. ing. Among them, an alkali developing type, which can be developed with a weak alkali solution such as sodium carbonate solution, has become mainstream from the viewpoint of working environment conservation and global environment conservation. Japanese Patent Application Laid-Open Nos. 61-243869 and 1-14
What is shown by 1904 gazette is known. However, alkali development type photo solder resist still has a problem in durability. That is, the conventional thermosetting type,
Chemical resistance, water resistance, heat resistance, etc. are inferior to those of the solvent development type. This is because the alkali-developable photosolder resist has a hydrophilic group as the main component so that it can be alkali-developed, and chemicals, water, water vapor, etc. easily penetrate, and these adhere to the resist film and copper. This is to reduce the property. In particular, semiconductor packages such as BGA and CSP require PCT resistance (pressure cooker test resistance), which can be referred to as moisture resistance, but under such severe conditions, they have only several hours to several tens of hours. Is the current situation.

Further, flexible printed wiring boards, CS
The substrate used for the P and TCP packages is a film of polyimide or the like, and a resist suitable for the film is required to have a small amount of warpage and excellent flexibility. If the flame retardancy is also sufficient, the range of use is widened.

[0004]

SUMMARY OF THE INVENTION The present invention solves these problems, and has excellent adhesiveness to a resist film and copper and other substrates and excellent heat and humidity resistance, as well as mechanical properties such as flexibility and warpage. Another object of the present invention is to provide a photosensitive resin composition suitable as a solder resist composition having excellent flame retardancy.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, an epoxy curing agent, a photopolymerization initiator and a flame retardant have been blended with a specific combination of photosensitive resins. It has been found that the resulting photosensitive resin composition is excellent in adhesiveness and wet heat resistance, and excellent in mechanical properties and flame retardancy. Based on this finding, the present invention has been completed.

That is, the present invention relates to an epoxy compound (a)
A photosensitive resin having a carboxyl group (A), a photosensitive polyamide resin having a carboxyl group, and a carboxyl group obtained by reacting a saturated or unsaturated polybasic anhydride with an esterified product of a carboxyl group and an unsaturated monocarboxylic acid. Provided is a photosensitive resin composition containing at least one photosensitive resin (B) selected from photosensitive polyamideimide resins, an epoxy curing agent (C), a photopolymerization initiator (D), and a flame retardant (E). Is what you do.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as the photosensitive resin (A) having a carboxyl group, a saturated or unsaturated polybasic anhydride is reacted with an esterified product of an epoxy compound (a) and an unsaturated monocarboxylic acid. The reaction product obtained by the reaction is used.

The epoxy compound (a) is, for example, a novolak type epoxy compound obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenol or alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin. YDCN-701, 704, YDP manufactured by Toto Kasei Co., Ltd.
N-638, 602, DEN-43 manufactured by Dow Chemical Company
1,439, EPN-1299 manufactured by Ciba Geigy Corporation, N-730, 770, 865, 6 manufactured by Dainippon Ink and Chemicals, Inc.
65, 673, VH-4150, 4240, Nippon Kayaku Co., Ltd. EOCN-120, BREN and the like. In addition to the novolak-type epoxy compounds, for example, epoxy compounds obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and phenol or cresol (EPPN502H, FAE2500, etc., manufactured by Nippon Kayaku Co., Ltd.)
Is preferably used. In addition, for example, Epicoat 828, 1007, 807 manufactured by Yuka Shell Co., Ltd., Epicron 840, 860, 3050 manufactured by Dainippon Ink and Chemicals, DER-330, 337, 361 manufactured by Dow Chemical Company, Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd. Mitsubishi Gas Chemical's TETRAD-X, C, Nippon Soda's EPB-13,2
7. GY-260, 255, XB-2 manufactured by Ciba Geigy
615, such as bisphenol A type, bisphenol F type,
Hydrogenated bisphenol A type, brominated bisphenol A type,
Epoxy compounds such as an amino group-containing type and an alicyclic glycidyl ether type are also used. Rubber-modified epoxy compounds such as epoxidized polybutadiene PB3600, P
B4700 (manufactured by Daicel Chemical Industries, Ltd.), epoxidized butadiene-styrene epoblend @ T014 (manufactured by Daicel Chemical Industries, Ltd.), or epoxy compound X22-163B of polydimethylsiloxane, KF100T (manufactured by Shin-Etsu Silicon Co., Ltd.), and the like. Also, an epoxy compound obtained by reacting the above-mentioned epoxy compound with α, ω-polybutadiene dicarboxylic acid, and an acrylonitrile-butadiene rubber having carboxylic acid at both terminals with one of the above-mentioned bisphenol F type epoxy resin and bisphenol Α type epoxy resin. Epoxy compounds obtained by reacting parts are also used. Among these, a rubber-modified epoxy resin or a bisphenol F type epoxy resin is preferred from the viewpoint of mechanical properties such as flexibility and warpage.

The unsaturated monocarboxylic acid includes (meth) acrylic acid, crotonic acid, cinnamic acid, a saturated or unsaturated polybasic acid anhydride and a (meth) acrylate having one hydroxyl group in one molecule or Reaction products of half-ester compounds of saturated or unsaturated dibasic acids with unsaturated monoglycidyl compounds, such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and hydroxyethyl (meth) acrylate, A reaction product obtained by reacting hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, and glycidyl (meth) acrylate in an equimolar ratio by a conventional method is exemplified. These unsaturated monocarboxylic acids can be used alone or in combination.
Of these, acrylic acid is preferred.

As the above-mentioned saturated or unsaturated polybasic acid anhydride, anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and trimellitic acid are used.

The above-mentioned photosensitive resin having a carboxyl group is further provided with isocyanate ethyl (meth) acrylate,
Or (meth) acrylates having at least one hydroxyl group in one molecule with tolylene diisocyanate or isophorone diisocyanate, for example, hydroxyethyl (meth)
A compound obtained by reacting an equimolar reactant with an acrylate to introduce an unsaturated bond via a urethane bond is also used as the photosensitive resin (A) having a carboxyl group.

Photosensitive resin having carboxyl group (A)
The acid value of KOH (KOH mg / g) is 40 to 250, preferably 5 in view of the balance between alkali developability and electric characteristics and other characteristics.
0 to 150.

The photosensitive resin composition of the present invention contains, in addition to the photosensitive resin (A) having a carboxyl group, a carboxyl group and a (meth) acrylate group.
An acrylic resin or a styrene resin described in JP-A-2603 or JP-A-63-205649 may be blended.

As the photosensitive resin (A) having a carboxyl group shown above, ZFER1179 from Nippon Kayaku Co., Ltd.
Are commercially available.

In the present invention, as the photosensitive resin (B), at least one resin selected from a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group is used. Such a resin is obtained by further reacting an esterified product of an epoxy group-containing polyamide resin and / or an epoxy group-containing polyamideimide resin (b) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic anhydride. Resins are preferably used. The epoxy group-containing polyamide resin and / or epoxy group-containing polyamideimide resin (b) can be synthesized by a condensation reaction from a polycarboxylic acid component such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic dianhydride and an organic diisocyanate or diamine. A carboxyl group-terminated polyamide resin or a carboxyl group-terminated polyamide-imide resin (c) (hereinafter sometimes referred to as a carboxyl group-terminated polyamide (imide) resin (c)) and an epoxy resin (d) are combined with an epoxy group of (d). The epoxy group-containing polyamide resin or the epoxy group-containing polyamide imide resin (hereinafter, sometimes referred to as an epoxy group-containing polyamide (imide) resin) obtained by causing the reaction by making the molar ratio of the carboxyl group of / (c) greater than 1. Is preferably used.

The polycarboxylic acid component used in the production of the carboxyl group-terminated polyamide (imide) resin (c) includes succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decandioic acid, dodecane diacid. Acids, aliphatic dicarboxylic acids such as dimer acid, isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as diphenylsulfonedicarboxylic acid, oxydibenzoic acid, trimellitic acid, pyromellitic acid, diphenylsulfonetetra Examples thereof include aromatic carboxylic acids such as carboxylic acid and benzophenonetetracarboxylic acid, and anhydrides thereof. These can be used alone or in combination of two or more.

The organic diisocyanate used in the production of the carboxyl-terminated polyamide (imide) resin (c) is 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Aromatic diisocyanates such as 2,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-xylene diisocyanate, m-tetramethyl xylene diisocyanate, hexamethylene diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-
Examples thereof include aliphatic isocyanates such as diisocyanate, hydrogenated m-xylene diisocyanate, and lysine diisocyanate. Of these, aromatic diisocyanates are preferred from the viewpoint of heat resistance, and 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate are particularly preferred. These may be used alone, but it is preferable to use two or more kinds in combination because the crystallinity is increased.

Diamines can be used in place of the above organic diisocyanates. Examples of the diamine include phenylenediamine, diaminodiphenylpropane, diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide,
And diaminodiphenyl ether. To improve the solubility in organic solvents, 2,2-bis (3-
Aminophenoxyphenyl) propane, 2,2-bis (4-aminophenoxyphenyl) propane, bis [3
-(3-aminophenoxyphenyl)] sulfone, bis [4- (3-aminophenoxyphenyl)] sulfone,
Bis [3- (4-aminophenoxyphenyl)] sulfone, bis [4- (4-aminophenoxyphenyl)] sulfone, 2,2-bis (3-aminophenoxyphenyl) hexafluoropropane, 2,2-bis ( 4-aminophenoxyphenyl) hexafluoropropane, 1,
4-bis (4-aminophenoxy) benzene, 1,3-
Bis (4-aminophenoxy) benzene, 4,4- (p
-Phenylenediisopropylidene) bisaniline, 4,
It is preferable to use a diamine such as 4- (m-phenylenediisopropylidene) bisaniline.

These organic diisocyanates and diamines may be used alone or in combination of two or more. However, when organic diisocyanate and diamine are used at the same time, they react with each other to form a urea bond having poor heat resistance, which is not preferable.

As the carboxyl group-terminated polyamide (imide) resin (c), a resin having at least one polymer unit selected from a polyalkylene oxide unit and a polycarbonate unit in its molecular structure is preferably used.

The polyalkylene oxide unit and the polycarbonate unit to be introduced into the molecular structure have carboxyl groups at both ends of the polyalkylene glycol or the polycarbonate diol when the carboxyl group-terminated polyamide (imide) resin (c) is produced. The introduced dicarboxylic acid is used as a polyvalent carboxylic acid component, and is reacted with diisocyanate or diamine to be introduced into a polyamide (imide) skeleton. Examples of the polyalkylene glycol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, bisphenol A or a reaction product of hydrogenated bisphenol A with these polyalkylene glycols, and the polyalkylene oxide unit introduced by these is one molecule. Two or more kinds may be present therein. Examples of the polycarbonate diol include straight-chain aliphatic polycarbonate diols, such as Placcel CD series (manufactured by Daicel Chemical Industries, Ltd.), Nipporan 980, 981 (manufactured by Nippon Polyurethane Industry). The chemical structure of the polycarbonate diol includes, for example, those represented by the following formula.

HO (ROCOO) _n R-OH (wherein R represents a dihydric alcohol residue, and n represents 1 to 10)
Is an integer. In particular, when the dihydric alcohol residue has 1 to 100 carbon atoms, for example, a 1,5-pentanediol residue, a methylpentanediol residue, a cyclohexanone dimethanol residue, a 1,6-hexanediol residue, Those which have a 1,9-nonanediol residue and a 2-methyl-1,8-octanediol residue and are liquid at room temperature are preferably used.

In order to obtain a carboxylic acid having carboxyl groups at both ends of a polyalkylene glycol or polycarbonate diol, a polycarboxylic acid similar to the above-mentioned polycarboxylic acid component, preferably a dicarboxylic acid, is used.
The reaction may be carried out with polyalkylene glycol, polycarbonate diol, or polyalkylene glycol diamine or polycarbonate diamine having an amino group introduced into a terminal.

Further, polyalkylene glycol diamine or polycarbonate diamine having an amino group introduced into the terminal may be used as the diamine component, or imidodicarboxylic acid obtained by reacting them with trimellitic acid may be used as the polyvalent carboxylic acid component. It can also be introduced into the carboxyl group-terminated polyamide (imide) resin (c).

The total content of the polyalkylene oxide units or polycarbonate units is at least 10% by weight in the carboxyl group-terminated polyamide (imide) resin (c) from the viewpoint of adhesiveness, and 90% by weight from the viewpoint of heat resistance.
It is preferable to use the following. Further, from the viewpoints of adhesiveness and water absorption resistance, it is preferable to introduce polytetramethylene ether glycol, polypropylene glycol and a reaction product thereof with (hydrogenated) bisphenol A. The molecular weight (calculated from the hydroxyl value) of these diols that can be used is preferably from 200 to 4,000.

Carboxyl-terminated polyamide (imide)
In the production of the resin (c), the polycarboxylic acid component has a molar ratio of 1 or more, preferably 1 to 3, more preferably 1.1 to 1 based on the total of the diisocyanate component and the diamine component.
It mixes so that it may become 2.2, and is made to react.

The above reaction is carried out using lactones such as γ-butyrolactone, amide solvents such as N-methylpyrrolidone (NMP) and dimethylformamide (DMF), sulfones such as tetramethylene sulfone, and ethers such as diethylene glycol dimethyl ether. 50 ° C using solvent
React at ~ 250 ° C. Considering the reaction yield, solubility, and volatility in the subsequent steps, it is preferable to use γ-butyrolactone as the main component of the solvent.

Next, as the epoxy resin (d) to be reacted with the carboxyl group-terminated polyamide (imide) resin (c), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin and its modified products, bixylenyl diglycidyl ether, YD
C1312 (trade name, manufactured by Toto Kasei), Techmore VG31
01 (trade name of Mitsui Petrochemical Co., Ltd.), TMH574 (trade name of Sumitomo Chemical Co., Ltd.), ESLV-80XY, -90CR,
-120TE, -80DE (brand name by Nippon Steel Chemical Co., Ltd.),
Aromatic epoxy resins such as Epicoat 1031S (trade name of Yuka Shell Co., Ltd.), aliphatic epoxy resins such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl tetrahydrophthalate, and triglycidyl isocyanurate And the like.
Of these, bifunctional epoxy resins are preferred from the viewpoint of reaction control, and aromatic or heterocyclic epoxy resins are preferred from the viewpoint of heat resistance. A brominated epoxy resin is useful for imparting flame retardancy. These are used alone or in combination of two or more. These epoxy resins (d) have a carboxyl group-terminated polyamide (imide) resin (c) with a molar ratio of epoxy group of (d) / carboxyl group of (c) of more than 1, preferably 1.1. React at ~ 2.5. When the molar ratio of epoxy group / carboxyl group is 1 or less, a terminal epoxy resin cannot be obtained. The epoxy equivalent of the epoxy group-containing polyamide (imide) resin (c) thus obtained has an epoxy equivalent of 500 to 4
Preferably it is 000. If it is less than 500, the molecular weight is low and the adhesion is poor. If it exceeds 40,000, the molecular weight is too high and the developability tends to be poor.

Subsequently, the ethylenically unsaturated carboxylic acids to be reacted with the epoxy group-containing polyamide (imide) resin include (meth) acrylic acid, crotonic acid, cinnamic acid and a saturated or unsaturated dibasic acid anhydride. (Meth) acrylates having one hydroxyl group in the molecule or half-ester compounds of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound, for example, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid , Obtained by reacting succinic acid with hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate or glycidyl (meth) acrylate in an equimolar ratio by a conventional method. These are used alone or as a mixture. The reaction ratio of the ethylenically unsaturated carboxylic acid to the epoxy group-containing polyamide (imide) resin (c) is determined by the ratio of the carboxyl group of the ethylenically unsaturated carboxylic acid /
The molar ratio of the epoxy group (c) is preferably 0.5 to 2.

Further, in consideration of the photosensitivity and the like, hydroxyl groups remaining in the resin are combined with isocyanate ethyl (meth) acrylate, tolylene diisocyanate or isophorone diisocyanate in one molecule to have at least one hydroxyl group (meth A) Acrylates, for example, an equimolar reactant with hydroxyethyl (meth) acrylate may be reacted to introduce an unsaturated bond via a urethane bond.

The above-mentioned epoxy group-containing polyamide (imide)
Examples of the polybasic acid anhydride to be reacted after the reaction of the resin (c) with the ethylenically unsaturated monocarboxylic acid include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, trimellitic acid and the like. Anhydride is used. When it is desired to further increase the acid value, glycidol may be reacted and then a polybasic anhydride may be further reacted.

The acid value of the photosensitive resin (B) (KOH mg /
g) is from 40 to 250, preferably from 50 to 150, in view of the balance between alkali developability and other characteristics such as electric characteristics.

In the photosensitive resin composition of the present invention, the preferred amount of the total amount of the photosensitive resin (A) and the photosensitive resin (B) is 10 to 90% by weight based on the total amount of the photosensitive resin composition. . The photosensitive resin (A) is the photosensitive resin (A)
And the total amount of (B) is preferably 50 to 95% by weight, and the photosensitive resin (B) is 5 to 50% by weight based on the total amount of the photosensitive resins (A) and (B). Is preferred. If the amount of the photosensitive resin (A) is less than 50% by weight, the developability tends to be poor, and if it exceeds 95% by weight, the warp tends to occur. If the content of the photosensitive resin (B) is less than 5% by weight, it tends to be warped, and if it exceeds 50% by weight, developability tends to be poor.

Epoxy curing agent (C) used in the present invention
May be any compound having an epoxy group, and an epoxy resin having two or more epoxy groups in a molecule is preferable. Specifically, bisphenol F type epoxy resin,
Bisphenol A type epoxy resin, bisphenol S type epoxy resin and derivatives such as bromide thereof, phenol or cresol novolak type epoxy resin, biphenyl type epoxy resin, for example, "YX4000" (manufactured by Yuka Shell Epoxy), special glycidyl ether type Epoxy resin, for example, YDC1312 manufactured by Toto Kasei, ESLV-80XY manufactured by Nippon Steel Chemical Co., Ltd., ESLV-90C
R, "TACTIX742" (manufactured by Dow Chemical Company),
"ZX1257" (manufactured by Toto Kasei), ESLV-120
Glycidyl ether-based epoxy resins such as TE, -80DE (manufactured by Nippon Steel Chemical Co., Ltd.); glycidyl ester-based epoxy resins such as "Denacol EX711" (manufactured by Nagase Kasei Kogyo Co., Ltd.) and glycidylamine-based epoxy resins such as "YH434" (Toto Kasei) ), A naphthalene type epoxy resin such as “Epiclon HP-4032” (manufactured by Dainippon Ink and Chemicals, Inc.), a dicyclo type epoxy resin such as “Epiclon HP7200H” (manufactured by Dainippon Ink and Chemicals, Inc.) Specific examples include epoxy resins, heterocyclic epoxy resins, hydantoin type epoxy resins, and special epoxy resins such as triglycidyl isocyanurate.

When the above epoxy resin is used as the epoxy curing agent (C), a part (50% by weight or less) may be used in place of another epoxy curing agent having a photosensitive group. As the epoxy curing agent having a photosensitive group, an epoxy acrylate compound which is an esterified product of a novolak type epoxy compound and an unsaturated monocarboxylic acid which does not react with an acid anhydride in a stage before obtaining a photosensitive resin (A) having a carboxyl group is preferable. Used for Further, urethane compounds in which isocyanate ethyl methacrylate or the like is introduced into an epoxy acrylate compound via a urethane bond are preferably used.

The preferred proportion of the epoxy curing agent (C) is 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the weight of the photosensitive resin composition.

The photopolymerization initiator (D) used in the present invention includes benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-
Acetophenones such as [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-diethoxyacetophenone, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, -Tert-butylanthraquinone,
Anthraquinones such as 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone;
Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4 '-Dichlorobenzophenone, 4,4'
Benzophenones such as -bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer,
2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7
Acridine derivatives such as -bis (9,9'-acridinyl) heptane; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These can be used alone or in combination of two or more. The preferred mixing ratio of the photopolymerization initiator (D) is 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the photosensitive resin composition.

Furthermore, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, dimethylethanolamine,
There are tertiary amines such as triethylamine and triethanolamine. These can be used alone or as a mixture in the range of 0.1 to 20% by weight in the photosensitive resin composition.

Examples of the flame retardant (E) used in the present invention include those containing at least one triazine compound, brominated compound or phosphorus compound.

As the triazine compound, melamine,
Acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, manufactured by Shikoku Chemicals; 2MZ-
AZINE, 2E4MZ-AZINE, C ₁₁ Z-AZI
NE, 2MΑ-OK and the like. Alternatively, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine are exemplified. These compounds have an effect as a flame retardant, as well as an increase in adhesion to a copper circuit, an improvement in PCT resistance, and an effect in electrolytic corrosion. These are preferably used in an amount of 0.1 to 15% by weight based on the photosensitive resin composition.

Examples of the brominated compound include the above-mentioned brominated epoxy compounds and photosensitive resins other than the components (A) and (B) modified with these compounds. In addition to these, tetrabromobisphenol (TBA) and derivatives thereof such as TBA bromoethyl ether oligomer, TBA bis (2,3-dibromopropyl ether), TBA bis (allyl ether), and TBA bis (2
-Hydroxyethyl ether), TBA-carbonate oligomer and the like, and decabromobiphenyl oxide, octabromobiphenyl oxide, hexabromobiphenyl oxide, polydibromophenylene oxide, bis (pentabromophenoxy) ethane, tetrabromobisphenol S, etc. Is mentioned. Other examples include Pyrogard SR245 having a triazine skeleton (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). These bromine compounds are preferably incorporated in the resin composition in an amount of 1 to 30% by weight.
It is useful to use antimony pentoxide in combination with the brominated compound as a flame retardant aid, and it is preferable to use 10% by weight or less in the resin composition. Further, antimony pentoxide has an effect of suppressing migration in an electrolytic corrosion test as an ion trapping agent.

Examples of the phosphorus compound include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylyl phosphate, tris (chloroethyl) phosphate, Phosphate compounds such as tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl) phosphate, or CR-733S, CR
-751, CR-747, PX-200 (above, manufactured by Daihachi Chemical Co., Ltd.), etc., and an aromatic condensed phosphate ester, CR-50
5, CR-509, CR-530, CR504L, CR
And halogen-containing condensed phosphoric esters such as -570, CR-380, and CR-387 (all manufactured by Daihachi Chemical Co., Ltd.). Alternatively, PPZ (manufactured by Kyoeisha Chemical Co., Ltd.), SP134
(Made by Otsuka Chemical Co., Ltd.). These are preferably incorporated in the resin composition in an amount of 0.5 to 20% by weight.

Further, if necessary, other curing agents and heat curing accelerators can be used. As the curing agent, boron trifluoride-amine complex, dicyandiamide, organic acid hydrazide, diaminomaleonitrile, urea, alkylated melamine resin such as hexamethoxymethylated melamine, polyamine salts, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylmethane , Meta-xylene diamine, diamino diphenyl sulfone,
Aromatic amines such as "Hardner HT972" (manufactured by Ciba Geigy), phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate),
Aromatic anhydrides such as glycerol tris (anhydrotrimellitate) and benzophenonetetracarboxylic anhydride; aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride; polyvinylphenol; polyvinylphenol bromide; and phenol There are polyphenols such as novolak and alkylphenol novolak. As a thermosetting accelerator, metal salts of acetylacetone such as acetylacetonate Zn, enamine, tin octylate,
Quaternary phosphonium salts, tertiary phosphines such as triphenylphosphine, phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, benzyltrimethylammonium chloride, phenyltributyl Quaternary ammonium salts such as ammonium chloride, porates such as diphenyliodonium tetrafluoroporoate, triphenylsulfonium hexafluoroantimonate, antimonates, dimethylbenzylamine, 1,8-diazabicyclo [5,
4,0] undecene, m-aminophenol, 2,4
Tertiary amines such as 6-tris (dimethylaminophenol) and tetramethylguanidine, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2- Examples thereof include imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole, which can be used alone or in a mixed system. The curing agent and the thermosetting accelerator can each be used in the photosensitive resin composition in an amount of preferably 0.01 to 10% by weight.

The photosensitive resin composition of the present invention can be used by adding various photosensitive monomers for the purpose of improving the photosensitivity and various characteristics as required. For example, 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N-dimethyl (meth) acrylate, N-methylol (Meth) acrylamide, urethane (meth) acrylate, or mono- or polyfunctional (meth) acrylates such as polyethylene glycol, polypropylene glycol, a reaction product of bisphenol A with polyethylene glycol or propylene glycol, and tris (2-hydroxyethyl) isocyanuric acid And (meth) acrylates of glycidyl ethers such as triglycidyl isocyanurate and photopolymerizable monomers such as diallyl phthalate. These can be used alone or in a mixed system. Each of the functional monomers is preferably 0.1 to 30 in the photosensitive resin composition.
Used in the range of weight percent.

The photosensitive resin composition of the present invention can be diluted with an organic solvent, if necessary. For example, ethyl methyl ketone, ketones such as cyclohexanone, toluene,
Aromatic hydrocarbons such as xylene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether; ethyl acetate; butyl acetate , Butyl cellosolve acetate, esters such as carbitol acetate, alcohols such as ethanol, propanol, ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. And other petroleum solvents.

The photosensitive resin composition of the present invention may contain, if necessary, barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, or the like for the purpose of improving properties such as adhesion and hardness.
Inorganic fillers such as talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder and the like can be used. Of these, aluminum hydroxide is particularly preferred. The amount used is preferably from 0 to 50% by weight. If it exceeds 50% by weight, the flexibility tends to decrease.

Further, if necessary, phthalocyanine blue,
Colorants such as phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black can be used. Further, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine; thixotropic agents such as bentone, montmorillonite, aerosil, and amide wax; silicone-based, fluorine-based, and polymer-based antifoaming agents , A leveling agent, and additives such as an imidazole compound, a thiazole compound, a triazole compound, and an adhesion imparting agent such as a silane coupling agent.

The photosensitive resin composition of the present invention can be obtained by uniformly mixing the raw materials blended in the above-mentioned ratio by a roll mill, a bead mill or the like, and then curing, for example, as follows. That is, the composition of the present invention is applied to a printed wiring board or the like with a thickness of 10 to 160 μm by a method such as a screen printing method, a spray method, an electrostatic spray method, an airless spray method, a curtain coater method, and a roll coating method, After the coating film is dried at 60 to 110 ° C., a negative film is placed on the coating film, irradiated with radiation such as ultraviolet rays, and then the unexposed portion is diluted with a dilute alkaline aqueous solution (eg, 0.5 to 2% by weight sodium carbonate carbonate). Aqueous solution, etc.), and then usually irradiation with ultraviolet light and / or heating (for example, 100 to 200 ° C.)
For 0.5 to 1.0 hours) to obtain a cured film.

The photosensitive resin composition of the present invention comprises a rigid or flexible printed wiring board, BGA, CSP, TC
It is particularly useful as a solder resist composition for packages such as P or as a build-up material for multilayer materials, but can also be used for coating materials such as paints, glass, ceramics, plastics, and paper.

[0050]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

[Photosensitive resin having carboxyl group (A
-1) Production Example] In a flask equipped with a stirrer, a reflux condenser and a thermometer, add α, ω-polybutadiene dicarboxylic acid N
ISSO-PB C-1000 (Nippon Soda Co., Ltd.) 48
2.6 parts by weight, brominated bisphenol A type epoxy resin Y
400 parts by weight of DB-400 (manufactured by Toto Kasei Co., Ltd.), 183 parts by weight of carbitol acetate, and 110 parts by weight of solvent naphtha (Solvesso 150) were added and heated at 110 ° C. for 8 hours. 36.4 parts by weight of acrylic acid, 0.5 parts by weight of methylhydroquinone, carbitol acetate 6
Parts by weight, and at 70 ° C., triphenylphosphine 3
Parts by weight, 6 parts by weight of solvent naphtha, 100 ° C
And reacted until the acid value of the solid content was 2 (KOH mg / g) or less. Next, the obtained solution was cooled to 50 ° C., and 100 parts by weight of tetrahydrophthalic anhydride, 126 parts by weight of carbitol acetate, and solvent naphtha 6
By weight, the mixture was reacted at 80 ° C. for a predetermined time to obtain an unsaturated group-containing polycarboxylic acid resin (A-1) having a solid content of 70 (KOH mg / g) and a solid content of 70% by weight.

[Photosensitive resin having carboxyl group (A
Production Example of -2)] In a flask equipped with a stirrer, a reflux condenser and a thermometer, 1,052 parts by weight of bisphenol F type epoxy resin (epoxy equivalent 526), acrylic acid 144
Parts by weight, 1 part by weight of methylhydroquinone, 850 parts by weight of carbitol acetate, and 100 parts by weight of solvent naphtha were charged and heated and stirred at 70 ° C. to dissolve the mixture. Next, the solution was cooled to 50 ° C., and 2 parts by weight of triphenylphosphine and 75 parts by weight of solvent naphtha were charged and heated to 100 ° C., and the acid value of the solid content was 1 (KOH mg
/ G) or less. Next, the obtained solution was cooled to 50 ° C., and tetrahydrophthalic anhydride 745 was used.
Parts by weight, 75 parts by weight of carbitol acetate and 75 parts by weight of solvent naphtha were charged and reacted at 80 ° C. for a predetermined time, and the solid content acid value was 80 (KOH mg / g) and the solid content was 6
2% by weight of unsaturated group-containing polycarboxylic acid resin (A-2)
I got

[Photosensitive resin having carboxyl group (A
Production Example of -3)] In a flask equipped with a stirrer, a reflux condenser and a thermometer, 200 parts by weight of a cresol novolak type epoxy resin (epoxy equivalent: 200), acrylic acid 7
0 parts by weight, 0.4 parts by weight of methylhydroquinone, 80 parts by weight of carbitol acetate and 20 parts of solvent naphtha
A part by weight was charged, and the mixture was heated and stirred at 70 ° C. to dissolve the mixture. Next, the solution was cooled to 50 ° C., 1 part by weight of triphenylphosphine was charged and heated to 100 ° C., and reacted until the acid value of the solid content became 1 (KOH mg / g) or less. Next, the obtained solution was cooled to 50 ° C., charged with 51 parts by weight of maleic anhydride, 48 parts by weight of carbitol acetate and 10 parts by weight of solvent naphtha, and reacted at 80 ° C. for a predetermined time to obtain a solid acid value of 67 ( KOH mg /
g), an unsaturated group-containing polycarboxylic acid resin (A-3) having a solid content of 67% by weight was obtained.

[Example of Production of Carboxylic Acid Compound (B-1) at Both Terminals of PEGPΑ (α, ω-bis- (3-aminopropyl) polyethylene glycol ether)] Stirrer, reflux condenser, inert gas inlet and temperature In a flask equipped with a meter,
PEGg II-1000 (manufactured by Hiroei Chemical Industry Co., Ltd .: average molecular weight: 1,000); 1,000 g, sebacic acid; 405 g were charged, the temperature was raised to 220 ° C. over 2 hours, and the reaction was further continued for 4 hours, followed by cooling, followed by acidification. 81.9, P with a molecular weight of 1,370
A carboxylic acid compound at both ends of EGPΑ was obtained.

Similarly, diamines of both ends of polypropylene glycol having amino groups introduced at both ends of polypropylene glycol (PPG-NH ₂ : average molecular weight 900)
(B-2) was obtained with the composition shown in Table 1.

In the same manner, a carboxylic acid compound (B-3) at both ends of a polypropylene glycol reactant of bisphenol A (Bis-PPG: average molecular weight 1,450) was obtained in the manner shown in Table 1.

Similarly, a carboxylic acid compound (B-4) at both ends of a polycarbonate diol (Placcel CD220: average molecular weight: 2,000; Daicel Chemical Industries, Ltd.) was obtained with the composition shown in Table 1.

Table 1 shows the properties of the obtained carboxylic acid compound at both ends.
It was shown to.

[0059]

[Table 1] [Production Example of Photosensitive Polyamide Resin (C-1)] Stirrer,
In a flask equipped with a reflux condenser, an inert gas inlet and a thermometer, γ-butyrolactone; 100 g, NMP;
7.4.6 g, adipic acid; 3.3 g, sebacic acid; 4.6 g, isophthalic acid; 7.5 g, 4,4'-diphenylmethane diisocyanate (MDI); 8 g, Coronate T80 (tolylene diisocyanate; TDI; manufactured by Nippon Polyurethane Industry Co., Ltd.); 13.4 g, heated to 200 ° C., cooled for 4 hours, cooled, heated residue 40% by weight, acid value (solid content) )
A 58.6 polyamide resin was obtained. Further, 27.6 g of bisphenol A type epoxy resin Epomic R140 (manufactured by Mitsui Petrochemical Industries, Ltd.) was charged, and after keeping the temperature at 140 ° C. for 2 hours, dimethylformamide (DMF) was added to make the heating residue 40% by weight. At 120 ° C., 3.3 g of methacrylic acid was added, and after keeping the temperature for 3 hours, tetrahydrophthalic anhydride (THP) was added.
A); 37.9 g was added and the mixture was kept warm for 1 hour. Then DM
After dilution with F, a photosensitive polyamide resin (C-1) having a heating residue of 55% by weight and an acid value (solid content) of 74 was obtained.

[Photosensitive polyamide-imide resin (C-2)
Production Example] NMP; 50 g was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer.
12.4 g (0.030 mol) of 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter referred to as BAPP), 11.6 g (0.060 mol) of trimellitic anhydride; Incubated for 2.5 hours. 41.0 g (0.033 mol) of the above (B-2), adipic acid; 4.3 g (0.029 mol), sebacic acid;
5.9 g (0.029 mol), isophthalic acid; 4.9 g
(0.029 mol), 4,4'-diphenylmethane diisocyanate (MDI); 18.9 g (0.075 mol), Coronate T80 (tolylene diisocyanate;
TDI; Nippon Polyurethane Industry Co., Ltd.);
050 mol) and 100 g of γ-butyrolactone, the temperature was raised to 200 ° C., the temperature was kept for 4 hours, and the mixture was cooled. A polyamideimide resin having a heating residue of 40% by weight and an acid value (solid content) of 32.8 was obtained. Bisphenol A type epoxy resin so as to have twice the amount of carboxyl groups; Epicoat 1
001; 66.8 g, and kept at 140 ° C. for 2 hours.
DMF was added to make the heating residue 40% by weight.
After adding 5.0 g of acrylic acid and keeping the temperature for 3 hours, THP
A: 42.9 g was added and the mixture was kept warm for 1 hour. Then DM
Diluted with F, heating residue 55% by weight, acid value (solid content conversion)
As a result, 85 photosensitive polyamideimide resins (C-2) were obtained.

Polyamide (imide) resins (C-3 to C-4) were similarly obtained with the composition (unit: g) as shown in Table 2.

[0062]

[Table 2] * Polyamide (imide) compounded: 100 compounded amount ** Made by Mitsui Petrochemical Industries, Ltd .: bisphenol II type epoxy resin [Resin containing acrylate group and epoxy group (D-
Production Example of 1)] (D-1) Production Example A cresol novolak-type epoxy resin (epoxy equivalent: 2) was placed in a flask equipped with a stirrer, a reflux condenser, and a thermometer.
00) 200 parts by weight, acrylic acid 20 parts by weight, methylhydroquinone 0.4 part by weight, carbitol acetate 8
0 parts by weight and 20 parts by weight of solvent naphtha
The mixture was heated and stirred at 0 ° C. to dissolve the mixture. Next, the solution was cooled to 50 ° C., and 0.5 parts by weight of triphenylphosphine was charged and heated to 100 ° C., and the acid value of the solid content was 1 (KO).
H mg / g) or less. 10 parts by weight of solvent naphtha was charged to obtain a resin (D-1) having a solid content of 67% by weight.

Examples 1 to 5, Comparative Examples 1 and 2 According to the compositions shown in Table 3, [I] and [II] were separately kneaded using a three-roll mill and mixed to prepare a resist ink composition. This is screen-printed by 100
Using a mesh polyester screen, apply to a copper polyimide film substrate on which a copper wiring pattern is formed so that the film thickness after drying becomes 25 to 35 μm, and dry the coating film at 80 ° C. for 30 minutes. After the negative mask film having the pattern was brought into close contact with the film, it was irradiated with 600 mJ / cm ² using an ultraviolet exposure apparatus. Next, spray development (spray pressure: 2.0 kg / cm ² ) was performed with a 1% aqueous sodium carbonate solution for 60 seconds to dissolve and remove unexposed portions, and the developability was evaluated.

Next, using a circulating hot air dryer at 150 ° C.
/ 1 hour, and heat cured, and the obtained cured film was evaluated.

In the same manner, in accordance with the composition shown in Table 3, Examples 2, 3, 4, 5 and Comparative Examples 1 and 2 were used, respectively, and subjected to the test in the same manner as in Example 1. The test results are shown in Table 4.

[0066]

[Table 3] Note) Photosensitive resin and resin: All formulations are shown as solids. * ZFR1179: Rubber-modified photosensitive resin (Nippon Kayaku Co., Ltd.) ** CR747: Aromatic condensed phosphoric acid ester (Daichaku Chemical Co., Ltd.) ** * SP134: Phosphazene compound (Otsuka Chemical Co., Ltd.) *** ESLV-80XY: Epoxy resin (Nippon Steel Chemical Co., Ltd.)

[0067]

[Table 4] The following test method was used.

Developability: The following evaluation criteria were used.・ ・ ・: After the development, the composition was completely removed and development was completed. Δ: slight residue after development ×: undeveloped part after development Adhesion: 1 mm on test piece according to JIS K5400
Then, 100 peeling test pieces were prepared and subjected to a peeling test using a cellophane tape. The state of peeling was evaluated by the following criteria. ○: No peeling at least 90/100 △: No peeling at 50/100 or more to less than 90/100 ×: Peeling at 0/100 to less than 50/100 Solvent resistance: Test piece 3 in isopropyl alcohol at room temperature
After immersion for 0 minutes and confirming that there was no abnormality in the appearance, a peeling test was performed using a cellophane tape. ○ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no peeling × ・ ・ ・ ・ No abnormality in the appearance of the coating film or peeling off Acid resistance: The test piece was immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After being immersed and confirming that there was no abnormality in the appearance, a peeling test was performed using a cellophane tape. ○ ・ ・ ・ ・ No abnormalities in the appearance of the coating film and no peeling × ・ ・ ・ ・ No abnormalities in the appearance of the coating film or those which peel off Solder heat resistance: Apply rosin flux to the test piece
It was immersed in a solder bath at 60 ° C. for 10 seconds. This was defined as one cycle, and after six cycles were repeated, the appearance of the coating film was visually observed. ○ ・ ・ ・ ・ There is no abnormality (peeling, blistering) in the appearance of the coating film and there is no burring of the solder × ・ ・ ・ ・ Is there any abnormality (peeling, blistering) in the appearance of the coating film?
Or, the one with solder hole Folding resistance: Goby folding (180 °) was performed, and the presence or absence of cracks was observed. When a crack occurred, it was evaluated as x, and when no crack occurred, it was evaluated as ○.

Warpage resistance: The degree of warpage of the coated substrate was visually determined. ○: less warpage △: some warpage ×: significant warpage Pressure cooker test (PCT): 121 ° C,
After standing in steam at 2 atm for 96 hours, the coating film was examined for appearance and graininess. The state of peeling was evaluated by the following criteria.・ ・ ・: No peeling at least 90/100 △: No peeling at 50/100 or more to less than 90/100 ×: Peeling at 0/100 to less than 50/100 Electrolytic: predetermined IPC comb shape 85 ° C, 8
5%, insulation (DC100V) after 1,000 hours, and appearance were evaluated.・ ・ ・: Good appearance, 10 or more extra parrots with insulating property of 10 Δ △: abnormal appearance, 10 or more extra parrots with insulating property 10 ×: abnormal appearance, insulating 10 Flame retardancy: A test piece was prepared and subjected to a combustion test according to the UL94 standard. ○ ・ ・ ・ ・ The flame extinguished within 10 seconds without residual flame until the clamp ×× ・ The flame persisted until the clamp or did not extinguish after more than 10 seconds

[0070]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention is excellent in adhesiveness and heat and humidity resistance, excellent in mechanical properties such as bending resistance and warpage, furthermore excellent in flame retardancy and electrolytic corrosion resistance, and is suitable for production of LSI packages. It is suitable as a solder resist composition to be used.

Claims (10)

[Claims] 1. A photosensitive resin having a carboxyl group (A) obtained by reacting an esterified product of an epoxy compound (a) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic anhydride, a carboxyl group At least one photosensitive resin (B), an epoxy curing agent (C), a photopolymerization initiator (D), and a flame retardant (E) selected from a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group. A photosensitive resin composition containing 2. The photosensitive resin composition according to claim 1, wherein the epoxy compound (a) is a rubber-modified epoxy compound. 3. The photosensitive resin composition according to claim 1, wherein the epoxy compound (a) is a bisphenol F type epoxy compound. 4. The photosensitive resin (B) further comprises an esterified product of an epoxy group-containing polyamide resin and / or an epoxy group-containing polyamideimide resin (b) and an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic anhydride. 4. The photosensitive resin composition according to claim 1, which is a resin obtained by reacting 5. An epoxy group-containing polyamide resin and / or an epoxy group-containing polyamide imide resin (b) comprising: a carboxyl group-terminated polyamide resin and / or a carboxyl group-terminated polyamide imide resin (c); and an epoxy resin (d). The photosensitive resin according to claim 4, wherein the photosensitive resin is an epoxy group-containing polyamide resin and / or an epoxy group-containing polyamideimide resin obtained by reacting at a molar ratio of (d) epoxy group / (c) carboxyl group of greater than 1. Composition. 6. A carboxyl group-terminated polyamide resin and / or a carboxyl group-terminated polyamide imide resin (c)
Is a resin having a polyalkylene oxide unit and / or a polycarbonate unit in a molecular structure. 7. The photosensitive resin composition according to claim 1, wherein the flame retardant (E) is a triazine compound. 8. The photosensitive resin composition according to claim 1, wherein the flame retardant (E) is a phosphorus compound. 9. The photosensitive resin composition according to claim 1, wherein the flame retardant (E) is a mixture of a brominated compound and antimony pentoxide. 10. The photosensitive resin composition according to claim 1, which contains aluminum hydroxide as a filler.