JPH11288087A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. capable of forming a hardened film excellent in heat resistance, wet heat resistance, adhesion and mechanical characteristics and suitable for use in the production of a printed circuit board, a high density multilayered sheet, a semiconductor package, etc. 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 elastomer (C), an epoxy hardening agent (D) and a photopolymn. initiator (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.

[0003] Further, as the mounting method changes from insertion mounting to surface mounting, the temperature during mounting tends to increase. Specifically, in the case of surface mounting, cream solder is printed in advance on necessary parts, the whole is heated with infrared rays, and the solder is reflowed and fixed.
The temperature rises significantly to 240 ° C., and in the conventional liquid photosensitive resist, there is a problem of so-called reflow resistance reduction, in which a crack is generated in the coating film by thermal shock or the coating film is peeled off from the substrate or the sealing material. Improvements are required.

[0004]

SUMMARY OF THE INVENTION The present invention solves these problems, and provides heat resistance, wet heat resistance, adhesion, and the like.
It is an object of the present invention to provide a photosensitive resin composition which can provide a cured film having excellent mechanical properties and is suitably used for manufacturing a printed wiring board, a high-density multilayer board, a semiconductor package, and the like.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a photosensitive compound having a carboxyl group obtained by reacting an esterified product of an epoxy compound (a) and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic anhydride. At least one photosensitive resin (B), an elastomer (C), an epoxy curing agent (D) selected from a photosensitive resin (A), a photosensitive polyamide resin having a carboxyl group, and a photosensitive polyamideimide resin having a carboxyl group; It is intended to provide a photosensitive resin composition containing a photopolymerization initiator (E).

[0006]

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, as a naphthol-modified novolak epoxy compound, NC
7000 (manufactured by Nippon Kayaku), ESN 170, 185 (manufactured by Nippon Steel Chemical) EX # 4700 (manufactured by Dainippon Ink and Chemicals), and the like.

In addition to the novolak type epoxy compound, for example, a salicylaldehyde type epoxy compound obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and phenol or cresol (EPPN502H, FAE2500, etc., manufactured by Nippon Kayaku Co., Ltd.) is preferred. Used. Further, for example, Epicoat 82 manufactured by Yuka Shell Co., Ltd.
8, 1007, 807, Epiklon 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, TETRA manufactured by Mitsubishi Gas Chemical Company
DX, C, Nippon Soda's EPB-13, 27, Ciba
Bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, brominated bisphenol A type, amino group-containing type, alicyclic glycidyl ether type etc. epoxy compounds such as GY-260, 255, XB-2615 manufactured by Geigy Corporation Is also used.

Further, dicyclopentadiene type epoxy compound ZX1329 (manufactured by Toto Kasei Co., Ltd.), HP7200
(Nippon Oil Co., Ltd.), TMH574 (Nippon Kayaku), Techmore VG3101 (Nippon Kayaku), E1031S
(Manufactured by Yuka Shell) and ZX1063 (manufactured by Toto Kasei) can also be used.

Among these, novolak type, salicylaldehyde type, bisphenol Α type and bisphenol F type epoxy compounds are preferably used.

The unsaturated monocarboxylic acid includes (meth) acrylic acid, crotonic acid, cinnamic acid and 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.

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 polycarboxylic acids such as carboxylic acid and benzophenonetetracarboxylic acid, and acid 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 can be used alone or 2
Used in combination of more than one type. 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 (KOH mg / g) of the photosensitive polyamide (imide) resin (B) is from 40 to 250, preferably from 50 to 250, in view of the balance between alkali developability and other characteristics such as electric characteristics.
１５０150.

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.

The photosensitive resin composition of the present invention has a carboxyl group and a (meth) acrylate group.
-92603 or JP-A-63-205649.
Acrylic and styrene-based photosensitive resins containing a carboxyl group as disclosed in JP-A-2003-157, may be blended.

The elastomer (C) used in the present invention includes styrene elastomer, olefin elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer and silicone elastomer.

Examples of the styrene-based elastomer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer. In addition to styrene, which is a part of the styrene elastomer, α-methylstyrene, 3-methylstyrene, 4-propylstyrene,
-Styrene derivatives such as cyclohexylstyrene can be used. Specifically, Tufprene, Solprene T, Asaprene T, Tuftec (all made by Asahi Kasei Kogyo Co., Ltd.), Elastomer @ R (Aron Kasei), Clayton G, Califlex (all made by Shell Japan), JSR-TR, TSR-SIS, Dynalon (above, manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku), Quintac (manufactured by Zeon Corporation), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, High Blur (Kuraray), Sumiflex (Sumitomo Bakelite Co., Ltd.),
Rheostomer, actimer (all, manufactured by Riken Vinyl Industry Co., Ltd.) and the like.

The olefin elastomer is ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
It is a copolymer of an α-olefin having 2 to 20 carbon atoms such as 1-pentene, for example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), and the like. A non-conjugated diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene and α
-Olefin copolymers. Further, a carboxyl group-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer is exemplified. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. No. More specifically, Mirastoma (manufactured by Mitsui Petrochemical), EX @ CT (manufactured by Exxon Chemical), ENG @ GE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber "DYNABON HSB"
R "(manufactured by Nippon Synthetic Rubber), butadiene-acrylonitrile copolymer" NBR series "(manufactured by Japan Synthetic Rubber), or" XER series "of a modified butadiene-acrylonitrile copolymer having a crosslinking point (manufactured by Nippon Synthetic Rubber) Is mentioned.

The urethane elastomer comprises structural units of a hard segment composed of low molecular weight ethylene glycol and diisocyanate, and a soft segment composed of high molecular weight (long chain) diol and diisocyanate. ,
Polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), poly (1,6-hexylene neoate) Pentylene adipate) and the like. The number average molecular weight of the high molecular (long chain) diol is 500 to 10,000.
Is preferred. In addition to ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol
And the like, and the number average molecular weight of the short chain diol is preferably from 48 to 500. As a specific example of urethane elastomer, P @ NDEX T-218
5, T-2983N (manufactured by Dainippon Ink), Sylactolan E790, and the like.

The polyester elastomer is obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof. Specific examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atoms of these aromatic nuclei are substituted with a methyl group, an ethyl group, a phenyl group, etc., and adipine Examples thereof include an aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid. Two or more of these compounds can be used. Specific examples of the diol compound include ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,6-hexanediol,
1,10-decanediol, aliphatic diols such as 1,4-cyclohexanediol and alicyclic diols, or
Specific examples thereof include bisphenolΑ, bis- (4-hydroxyphenyl) methane, and bis- (4-hydroxy-
3-methylphenyl) propane, resorcin and the like. Two or more of these compounds can be used.
Further, an aromatic polyester (for example, polytetramethylene glycol) is used as a hard segment component with an aromatic polyester (for example, polybutylene terephthalate) as a hard segment component.
A multi-block copolymer in which a part is a soft segment component can be used. There are various grades depending on the type, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by DuPont-Toray), Perprene (manufactured by Toyobo), Espel (manufactured by Hitachi Chemical), and the like.

Polyamide-based elastomers are roughly classified into two types: a polyether block amide type using a hard phase of polyamide and a polyether or polyester as a soft phase, and a polyether ester block amide type. 6, 11, 12 and the like are used, and as polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol and the like are used. Specifically, UBE polyamide elastomer (made by Ube Industries), Daiamide (made by Daicel Huls), PEBΑX (made by Toray), Grillon ELY (made by Ms Japan), Novamid (made by Mitsubishi Chemical), Glair (made by Dai Nippon Ink) ) And the like.

The acrylic elastomer is mainly composed of an acrylate ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like are used, and glycidyl methacrylate, allyl glycidyl ether and the like are used as a crosslinking point monomer. Can be Further, acrylonitrile or ethylene can be copolymerized. Specific examples include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

The silicone-based elastomer contains an organopolysiloxane as a main component, and is classified into a polydimethylsiloxane-based, a polymethylphenylsiloxane-based, and a polydiphenylsiloxane-based elastomer. Some of them are modified with a vinyl group or an alkoxy group. Specific examples include the SY series (manufactured by Wacker), the KE series (manufactured by Shin-Etsu Chemical), the SE series, the CY series, and the SH series (above, manufactured by Dow Corning Toray Silicone).

In addition to the above elastomers, rubber-modified epoxy compounds can be used. The following can be used as the rubber-modified epoxy compound. For example, epoxidized polybutadiene PB3600, PB4700
(Daicel Chemical Industry Co., Ltd.), epoxidized butadiene-styrene epoblend @ T014 (Daicel Chemical Industry Co., Ltd.), or epoxy compound X22-163B of polydimethylsiloxane, KF100T (Shin-Etsu Silicon Co., Ltd.). Further, it is obtained by reacting a part of a bisphenol F type epoxy compound or a bisphenol A type epoxy compound with acrylonitrile-butadiene rubber having a carboxylic acid at both terminals. These rubber-modified epoxy compounds can also be used as the epoxy compound (a) of the photosensitive resin (A).

Among these elastomers, a composition using a butadiene-acrylonitrile-based elastomer, a polyester-based elastomer, a silicone-based elastomer, and a rubber-modified epoxy compound in terms of reflow resistance (shear adhesion to a sealing material). Is preferred.

The amount of the elastomer (C) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, in the photosensitive resin composition. If it is less than 1% by weight,
The elastic modulus of the cured film in the high-temperature region does not tend to decrease, and when it exceeds 50 parts by weight, the heat resistance, developability and the like tend to be poor.

The curing shrinkage and flexibility of the cured film are improved by blending the elastomer (C) into a polymer alloy, and the dynamic viscoelasticity in a temperature range of 180 to 260 ° C., which is the temperature at the time of reflow. By measurement, the elastic modulus of the cured film of the composition can be reduced to 0.1 to 10 MPa, and the shear adhesion with the sealing material can be improved. That is, if the elastic modulus is less than 0.1 MPa, the mechanical strength tends to decrease, and if it exceeds 10 MPa, the shear adhesive strength tends to decrease.

In the present invention, not only the photosensitive resin (A) and the elastomer (C) are blended independently, but also the chemical structure of the elastomer (C) can be changed by changing the molecular structure of the photosensitive resin (A) having a carboxyl group. The photosensitive resin (AC) having a carboxyl group can be used as the component (A) and the component (C). Such a photosensitive resin (AC) is, for example, when the photosensitive resin (A) is manufactured, the epoxy resin is α,
A resin produced by using an epoxy resin modified with ω-polybutadiene dicarboxylic acid is exemplified.

The epoxy curing agent (D) 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 can be used. Also, bisphenol A type and S type epoxy resins and derivatives thereof such as bromide, 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, E
SLV-80XY, ESLV-90DR, and "TAC
TIX742 "(manufactured by Dow Chemical Company)," ZX125
7 "(manufactured by Toto Kasei), ESLV-120TE, -80
Glycidyl ether epoxy resins such as DE (trade name of Nippon Steel Chemical Co., Ltd.); glycidyl ester epoxy resins,
For example, "Denacol EX711" (manufactured by Nagase Kasei Kogyo Co., Ltd.), a glycidylamine-based epoxy resin such as "YH
434 "(manufactured by Toto Kasei Co., Ltd.), naphthalene-type epoxy resin such as" Epiclon HP-4032 "(manufactured by Dainippon Ink and Chemicals, Inc.), and dicyclo-type epoxy resin such as" Epiclon HP-4032 "(manufactured by Dainippon Ink and Chemicals, Inc.) Dicyclo-type epoxy resin, for example, "Epiclon HP7200H" (manufactured by Dainippon Ink and Chemicals, Inc.), cycloaliphatic epoxy resin, heterocyclic epoxy resin, hydantoin-type epoxy resin, special epoxy resin such as triglycidyl isocyanurate, etc. Is mentioned. Preferably 2-3
Functional epoxy resins are preferred in terms of wet heat resistance and mechanical properties.

A portion (50% by weight or less) of the above epoxy curing agent (D) used as the epoxy curing agent (D) may be used in place of an epoxy curing agent having another 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 (D) 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 (E) 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 blending ratio of the photopolymerization initiator (E) 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, preferably in the range of 0.1 to 20% by weight in the photosensitive resin composition.

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 resins such as hexamethoxymethylated melamine, salts of polyamines, aromatic amines such as diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylmethane, metaxylenediamine, diaminodiphenylsulfone, "Hardner HT972" (manufactured by Ciba Geigy) Phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), aromatic acid anhydrides such as benzophenonetetracarboxylic anhydride, maleic anhydride, Examples thereof include aliphatic acid anhydrides such as tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, and alkylphenol novolak. As the thermosetting accelerator, acetylacetonate Z
metal salts of acetylacetone such as n, enamine, tin octylate, quaternary phosphonium salts, tertiary phosphines such as triphenylphosphine, tri-n-butyl (2,5
Phosphonium salts such as -dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; and poroates such as diphenyliodonium tetrafluoroporoate and triphenylsulfonium hexafluoroantimonate. , Antimonates, dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undecene, m-aminophenol,
Tertiary amines such as 2,4,6-tris (dimethylaminophenol) and tetramethylguanidine, 2-ethyl-4-methylimidazole, 2-methylimidazole,
Examples thereof include imidazoles such as 1-benzyl-2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, which can be used alone or in a mixed system. The curing agent and the thermosetting accelerator are each preferably used in the photosensitive resin composition.
It can be used in the range of 1% by weight to 10% by weight.

The photosensitive resin composition of the present invention can be used by adding various photosensitive monomers as needed for the purpose of improving photosensitivity and various characteristics. 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 Mono- or polyfunctional (meth) acrylates such as (meth) acrylamide, urethane (meth) acrylate, polyethylene glycol, polypropylene glycol, polyethylene glycol of bisphenol A or propylene glycol, tris (2-hydroxyethyl) isocyanuric acid, and triglycidyl Photopolymerizable monomers such as glycidyl ether (meth) acrylates such as isocyanurate and diallyl phthalate can be used. These can be used alone or in a mixed system.

The photosensitive resin composition of the present invention may contain
Triazine compound to improve flame retardancy and adhesion
Can be used for As triazine compounds, for example
Melamine, acetoguanamine, benzoguanamine,
Lamin-phenol formalin resin, Shikoku Chemicals
2MZ-AZINE, 2E4MZ-AZINE, C
₁₁Z-AZINE, 2MΑ-OK and the like. is there
Or ethyldiamino-S-triazine, 2,4-diamine
No-S-triazine, 2,4-diamino-6-xylyl
Triazine derivatives such as -S-triazine;
You. These are 0.1 to 15 times the photosensitive resin composition.
It is preferably used in the amount%.

In the photosensitive resin composition of the present invention, if necessary, a brominated compound or a phosphorus compound can be used as a flame retardant. Examples of the brominated compound include the above-mentioned brominated epoxy compounds and photosensitive resins modified with these compounds. Besides these, tetrabromobisphenol Α (TBA) and derivatives thereof such as TBA
Bromoethyl ether oligomer, TBA bis (2,3
Dibromopropyl ether), TBA bis (allyl ether), TBA bis (2-hydroxyethyl ether), TBA-carbonate oligomer, and the like, as well as decabromobiphenyl oxide, octabromobiphenyl oxide, hexabromobiphenyl oxide, and polydibromo. Examples include phenylene oxide, bis (pentabromophenoxy) ethane, and tetrabromobisphenol S. Other examples include Pyrogard SR245 having a triazine skeleton (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Also, antimony pentoxide is useful as a flame retardant aid used in combination with the brominated compound, and is preferably used at 10% by weight or less in the composition. Further, antimony pentoxide has an effect of suppressing migration in an electrolytic corrosion test as an ion trapping agent.

Examples of the phosphorus-based compound as a flame retardant include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylyl phosphate, tris (Chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl)
Phosphate compounds such as phosphate, or CR-
733S, CR-741, CR-747, PX-200
(Above, manufactured by Daihachi Chemical Co., Ltd.), CR-505, CR-509, CR-530, CR
504L, CR-570, CR-380, CR-387
(Above, manufactured by Daihachi Chemical Co., Ltd.). Alternatively, phosphazene compounds such as PPZ (manufactured by Kyoeisha Chemical) and SP134 (manufactured by Otsuka Chemical) can be used.

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. The amount used is preferably from 0 to 70% by weight.

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 , Leveling agents, and imidazoles,
Additives such as thiazole-based, triazole-based, and silane coupling agents can be used.

The photosensitive resin composition of the present invention can be obtained by uniformly mixing the compounding raw materials mixed 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.

[0063]

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, 400 parts by weight of brominated bisphenol A type epoxy resin YDB-400 (manufactured by Toto Kasei Co., Ltd.), 183 parts by weight of carbitol acetate, and 110 parts by weight of solvent naphtha (Solvesso 150) are added, and the mixture is heated at 110 ° C. for 8 hours. Heated. Acrylic acid (36.4 parts by weight), methylhydroquinone (0.5 parts by weight), carbitol acetate (6 parts by weight) were charged. At 70 ° C., triphenylphosphine (3 parts by weight) and solvent naphtha (6 parts by weight) were charged.
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 6 parts by weight of solvent naphtha were charged and reacted at 80 ° C. for a predetermined time to obtain a solid acid value of 70%. (KOH mg / g) and an unsaturated group-containing polycarboxylic acid resin (A-1) having a solid content of 70% by weight.

[Production Example of Photosensitive Resin Containing Carboxyl Group (A-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) was added. 144 parts by weight of acrylic acid, 1 part by weight of methylhydroquinone, 850 parts by weight of carbitol acetate and solvent naphtha 1
Then, the mixture was 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 7
45 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 to obtain an unsaturated group-containing poly (acid value 80 (KOH mg / g), solid content 62% by weight). Carboxylic resin (A-
2) was obtained.

[Production Example of Photosensitive Resin (A-3) Containing Carboxyl Group] A salicylaldehyde-phenol type epoxy resin (epoxy equivalent: 168) was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. 7 parts by weight, 24.1 parts by weight of acrylic acid, 0.1 part by weight of methylhydroquinone, 26 parts by weight of carbitol acetate and 17 parts by weight of solvent naphtha (Solvesso 150) were charged and heated and stirred at 70 ° C. to dissolve the mixture. did. Next, the solution was cooled to 50 ° C., 1 part by weight of triphenylphosphine was 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 20.3 parts by weight of tetrahydrophthalic anhydride and carbitol acetate 5 were added.
Parts by weight and 4 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), an unsaturated group-containing polycarboxylic acid resin (A-3) having a solid content of 67% by weight was obtained.

[Production Example of Photosensitive Resin (A-4) Containing Carboxyl Group] A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 200 parts by weight of a cresol novolak type epoxy resin (epoxy equivalent: 200). 70 parts by weight of acrylic acid, 0.4 parts by weight of methylhydroquinone, 80 parts by weight of carbitol acetate and solvent naphtha 2
0 parts by weight were charged and 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-4) having a solid content of 67% by weight was obtained.

[Production Example 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 reaction product of bisphenol A (Bis-PPG: average molecular weight 1,450) was obtained with the composition shown in Table 1.

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

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

[0073]

[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 (B-2) were obtained.

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

[0076]

[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 4 and Comparative Examples 1, 2, and 3 The compositions were blended according to the blending compositions (unit: g) shown in Table 3 and kneaded with a three-roll mill to prepare a photosensitive resin composition. This was applied to a copper-clad laminate by screen printing using a 120-mesh tetron screen to a thickness (after drying) of about 30 μm.
It was dried in a hot air circulation type dryer for minutes. Next, a negative mask film having a predetermined pattern was brought into close contact with the coating film and exposed to 500 mJ / cm ² using an ultraviolet exposure apparatus. Then, 1.8k with 1% sodium carbonate aqueous solution for 60 seconds
Spray development was performed at a pressure of gf / cm ² , and the unexposed portions were developed by dissolution. The developability and the photosensitivity were evaluated using the obtained image, and then heated at 150 ° C. for 1 hour to prepare a test plate.
The test plates were tested for adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, and shear adhesion described below. The dynamic viscoelasticity of the coating film peeled off from the substrate (copper-clad laminate) was measured. Table 4 summarizes the evaluation results. The test method and the evaluation method are as follows. FIG. 1 shows the measurement results of the viscoelasticity of the coating films produced in Example 1 and Comparative Example 1.

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

[0079]

[Table 3] Note) Photosensitive resin, resin: All formulations are shown as solids. * Polyester resin (manufactured by Hitachi Chemical Co., Ltd.) ** Reactive NBR rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.) *** Silicon-core core-shell type silicone rubber (manufactured by Wacker) *** * Epoxy resin (Nippon Steel Chemical Co., Ltd.) Company)

[0080]

[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. × ・ ・ ・ ・ There is abnormality (peeling, blistering) in the appearance of the coating film.
Or those with solder burrs Pressure Cooker Test (PCT): 121 ° C,
After standing in steam at 2 atm for 96 hours, the appearance of the coating film and a grid test were performed. The state of peeling was evaluated by the following criteria.・ ・ ・: No peeling at least 90/100 △: No peeling at least 50/100 to less than 90/100 ×: Peeling at 0/100 to less than 50/100 Shear adhesion: to the test piece A sealing material (CEL9200 manufactured by Hitachi Chemical Co., Ltd.) was molded into a conical shape having a diameter of 3.6 mm and a height of 4 mm, and the adhesion after 85 ° C., 85% RH, and 96 hours of moisture absorption was evaluated. The equipment used is a bond tester (D @ GE
245 ° C, unit: kgf / mm ² Thermal shock resistance: The test piece was subjected to -55 ° C / 30 minutes, 125 ° C /
The heat history was added with 30 minutes as one cycle, and after 1,000 cycles, the test piece was visually observed and observed with a microscope. ○ ・ ・ ・ No crack generation △ ・ ・ ・ ・ Crack generation × ・ ・ ・ ・ Crack generation is remarkable Dynamic viscoelasticity: Solid analyzerΑG-100KNE
(Manufactured by Rheometrics), vibration frequency 1 Hz
The dynamic viscoelasticity was measured at (6.28 rad / sec). The sample size is length 22.6 x width 5.0 x thickness 0.05m
m, measurement temperature 40 to 300 ° C (heating 4 ° C / min)
The viscoelasticity at 220 ° C. was examined. Unit: MP
a

[0082]

Industrial Applicability The photosensitive resin composition of the present invention is excellent in adhesiveness and wet heat resistance, and excellent in mechanical properties such as adhesiveness to a sealing material, and further, thermal shock resistance, and is used for LSI packages. It is suitably used as a solder resist composition or a photosensitive interlayer insulating material for a multilayer wiring board.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 179/08 C09D 179/08 B G03F 7/032 G03F 7/032 7/037 7/037 H05K 3/28 H05K 3/28 D 3/46 3/46 T (72) Inventor Toshihiko Ito Okayama, Kajima-gun, Kashima-gun, Ibaraki Pref., Kashima Plant, Hitachi Chemical Co., Ltd. (72) Inventor Hiroaki Hirakura, Oaza-go, Hasaki-cho, Kashima-gun, Ibaraki, Japan Banichi Hitachi Chemical Co., Ltd. Kashima Plant

Claims (7)

[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 elastomer (C), an epoxy curing agent (D) and a photopolymerization initiator (E) selected from a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group. A photosensitive resin composition. 2. The epoxy compound (a) is at least one epoxy compound selected from the group consisting of a novolak type epoxy compound, a bisphenol Α type epoxy compound, a bisphenol F type epoxy compound and a salicylaldehyde type epoxy compound. 2. The photosensitive resin composition according to item 1. 3. 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 further a saturated or unsaturated polybasic anhydride. The photosensitive resin composition according to claim 1, which is a resin obtained by reacting 4. An epoxy group-containing polyamide resin and / or an epoxy group-containing polyamideimide resin (b), wherein a carboxyl group-terminated polyamide resin and / or a carboxyl group-terminated polyamideimide resin (c) and an epoxy resin (d) are The photosensitive resin according to claim 3, 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 greater than 1. Composition. 5. 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 its molecular structure. 6. The elastomer (C) is at least one elastomer selected from the group consisting of styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers and silicone elastomers. The photosensitive resin composition according to claim 1. 7. A dynamic viscoelasticity measurement in a range of 180 to 260 ° C., wherein the cured film of the composition has an elastic modulus of 0.1 to 10 M.
The photosensitive resin composition according to any one of claims 1 to 6, which is Pa.