JPH10246958A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition superior in adhesion of a resist film to copper and other substrate materials and resistance to hot moisture and suitable as a solder resist composition, by incorporating at least a photosensitive resin, an epoxy resin, and a photopolymerization initiator as essential components. SOLUTION: This photosensitive resin composition contains (A) at least one kind of photosensitive resin selected from among a photosensitive polyamide resin having carboxylic groups and a photosensitive polyamideimide resin having carboxylic group; (B) an epoxy resin, and (C) a photopolymerization initiator as essential components. The photosensitive polyamide resin having carboxylic groups (A) is embodied, preferably, by a polyamide resin with a terminal carboxylic acid synthesizable by condensation reaction of a polyvalent carboxylic acid component, such as dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid dianhydride, and an organic diisocyanate or a diamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitably used as a solder resist composition used for manufacturing rigid and flexible printed wiring boards or LSI packages such as BGA (ball grid array) and CSP (chip size package). The photosensitive resin composition to be obtained.

[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 resistance), which can be referred to as resistance to moisture and heat, but under such severe conditions, they have only a few hours to several tens of hours. Is the current situation.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves these problems, and provides a photosensitive composition suitable as a solder resist composition having excellent adhesion to a resist film and copper and other substrates and excellent wet heat resistance. The present invention provides a resin composition.

[0004]

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, have obtained a photosensitive polyamide resin having a carboxyl or a photosensitive polyamideimide resin, an epoxy resin and a photopolymerization initiator. The present inventors have found that a photosensitive resin composition containing the same has excellent adhesion and durability to copper and other base materials, and have completed the present invention based on this finding.

That is, the present invention provides at least one photosensitive resin (A) selected from a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group, an epoxy resin (B), and a photopolymerization initiator. It is intended to provide a photosensitive resin composition comprising (C) as an essential component.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive polyamide resin having a carboxyl group or the photosensitive polyamideimide resin having a carboxyl group (hereinafter, may be referred to as a carboxyl group-containing photosensitive polyamide (imide) resin (A)) used in the present invention. ) Is a carboxyl-terminated polyamide resin (a1) or a carboxyl-terminated polyamideimide resin which can be synthesized from a polycarboxylic acid component such as dicarboxylic acid, tricarboxylic acid, and tetracarboxylic dianhydride and an organic diisocyanate or diamine by a condensation reaction. (A2) (hereinafter sometimes referred to as a carboxyl group-terminated polyamide (imide) resin (a)) and an epoxy resin (b) at an epoxy group / carboxyl group molar ratio of 1
The epoxy group-containing polyamide resin (c1) or the epoxy group-containing polyamide-imide resin (c2) (hereinafter, sometimes referred to as epoxy group-containing polyamide (imide) resin (c)) obtained by making the reaction larger. A resin obtained by reacting an ethylenically unsaturated monocarboxylic acid (d) and then reacting with a polybasic acid anhydride (e) is preferably used.

The polyvalent carboxylic acid component used for producing the carboxyl group-terminated polyamide (imide) resin (a) 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 Aromatic carboxylic anhydrides such as carboxylic dianhydride and benzophenone tetracarboxylic dianhydride are exemplified. These can be used alone or in combination of two or more.

The organic diisocyanate used for producing the carboxyl group-terminated polyamide (imide) resin (a) includes 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 4,4-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, 3,3-
Bis (3-aminophenoxyphenyl) sulfone, 4,
4-bis (3-aminophenoxyphenyl) sulfone,
3,3-bis (4-aminophenoxyphenyl) sulfone, 4,4-bis (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.

The photosensitive resin (A) used in the present invention, that is, the photosensitive polyamide (imide) resin (A) has at least one polymer unit selected from a polyalkylene oxide unit and a polycarbonate unit in its molecular structure. A photosensitive polyamide (imide) resin having a carboxyl group is preferably used.

The polyalkylene oxide unit and the polycarbonate unit introduced into the molecular structure of the photosensitive polyamide (imide) resin (A) are used in the production of the carboxyl-terminated polyamide (imide) resin (a). A glycol or a dicarboxylic acid such as a carboxylic acid compound at both ends of a polycarbonate diol is used as a polyvalent carboxylic acid component, and is reacted with diisocyanate to be introduced into a polyamide (imide) skeleton. Examples of the polyalkylene glycols include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, a reaction product of bisphenol A or hydrogenated bisphenol A with these polyalkylene glycols, and these alkylene oxide units are two kinds in one molecule. The above may be present. 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 having a 1,9-nonanediol residue and a 2-methyl-1,8-octanediol residue and being liquid at ordinary temperature are preferably used.

In order to convert polyalkylene glycols and polycarbonate diols into carboxylic acids at both ends, the same polyvalent carboxylic acids as those described above, preferably dicarboxylic acids, are reacted with polyalkylene glycols and polycarbonate diols. I just need.

[0015] In addition, no matter whether the terminal amine polyalkylene glycol diamine or polycarbonate diamine is used as a diamine component, or if an imidodicarboxylic acid obtained by reacting them with trimellitic acid is used as a polyvalent carboxylic acid component, the carboxyl group is not changed. Terminal polyamide (imide)
It can be introduced into the resin (a).

The total content of the polyalkylene oxide unit or the polycarbonate unit is at least 10% by weight in the carboxyl group-terminated polyamide (imide) resin (a) from the viewpoint of adhesiveness and 90% by weight from the viewpoint of heat resistance.
It is preferable to use the following. In addition, it is preferable to introduce polytetramethylene ether glycol, polypropylene glycol and a reaction product thereof with (hydrogenated) bisphenol A from the viewpoints of adhesion and water absorption resistance. 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 (a), 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 (b) to be reacted with the carboxyl group-terminated polyamide (imide) resin (a), 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.), ESLD-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 (b) are reacted with the carboxyl group-terminated polyamide (imide) resin (a) at a molar ratio of epoxy group / carboxyl group of more than 1, preferably 1.1 to 2.5. . The epoxy group / carboxyl group molar ratio is 1
In the following, a terminal epoxy resin cannot be obtained. The epoxy equivalent of the epoxy group-containing polyamide (imide) resin (c) thus obtained preferably has an epoxy equivalent of 500 to 40,000. If it is smaller than 500, the molecular weight is low and the adhesiveness is poor, and if it exceeds 40,000, the molecular weight is too high and the developability is poor.

Subsequently, the ethylenically unsaturated carboxylic acid (d) to be reacted with the epoxy group-containing polyamide (imide) resin (c) includes (meth) acrylic acid, crotonic acid, cinnamic acid and saturated or unsaturated dicarboxylic acid. Basic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule or half-ester compounds of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound, such as phthalic acid, tetrahydrophthalic acid, hexa Hydrophthalic acid, maleic acid, succinic acid and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate or glycidyl (meth) acrylate in equimolar ratio by a conventional method. Are used alone or as a mixture. The reaction ratio of the ethylenically unsaturated carboxylic acid (d) to the epoxy group-containing polyamide (imide) resin (c) is preferably 0.5 to 2 in a carboxyl group / epoxy group molar ratio.

Further, in consideration of the photosensitivity and the like, the 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)
As the polybasic acid anhydride (e) to be reacted after the reaction of the resin (c) with the ethylenically unsaturated monocarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
Anhydrides such as maleic acid, succinic acid and trimellitic acid are used. If it is desired to further increase the acid value, glycidol may be reacted and then a polybasic acid anhydride may be further reacted.

The acid value of the photosensitive polyamide (imide) resin (A) 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.

The photosensitive resin composition of the present invention may contain another photosensitive resin (D) containing a carboxyl group in combination with the photosensitive resin (A). As the photosensitive resin (D) having a carboxyl group, an addition product obtained by adding a saturated or unsaturated polybasic acid anhydride to an esterified product of an epoxy compound and an unsaturated monocarboxylic acid, and the like are preferably used.

For example, novolak type epoxy compounds obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenols and alkylphenols with formaldehyde in the presence of an acidic catalyst, and epichlorohydrin are suitable. YDCN-
701, 704, YDPN-638, 602, DEN-431, 439 manufactured by Dow Chemical Company, E manufactured by Ciba Geigy Corporation
PN-1299, N-73 manufactured by Dainippon Ink and Chemicals, Inc.
0, 770, 865, 665, 673, VH-415
0,4240, Nippon Kayaku Co., Ltd. EOCN-120, BRP
N and the like. In addition to the novolak type epoxy compound, for example, a salicylaldehyde-phenol type epoxy compound (EPPN502H manufactured by Nippon Kayaku Co., Ltd.) is preferably 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, alicyclic or polybutadiene modified glycidyl ether type such as GY-260, 255 and XB-2615 manufactured by Geigy Corporation The epoxy compound is also preferably used.

Examples of the unsaturated monocarboxylic acid include (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 And hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, and glycidyl (meth) acrylate in a conventional manner in an equimolar ratio. 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 photosensitive resin (D) containing a carboxyl group further comprises isocyanate ethyl (meth) acrylate, or tolylene diisocyanate or isophorone diisocyanate, and (meth) acrylates having at least one hydroxyl group in one molecule; For example, an equimolar reactant with hydroxyethyl (meth) acrylate may be reacted to introduce an unsaturated bond via a urethane bond.

As the photosensitive resin (D) containing a carboxyl group, acrylic resins having a carboxyl group and a (meth) acrylate group described in JP-B-7-92603 or JP-A-63-205649 are also available. Alternatively, a styrene resin may be used.

The preferred compounding ratio of the photosensitive resin (D) containing a carboxyl group is 20 to 80 parts by weight based on 100 parts by weight of the total amount of the resin (A) and the photosensitive resin (D) containing a carboxyl group. is there.

In the photosensitive resin composition of the present invention, the preferred proportion of the photosensitive resin (A) is 10 to 90% by weight.

Further, the photosensitive resin composition of the present invention contains an epoxy resin (B) for improving heat resistance. This epoxy resin (B) may or may not have a photosensitive group. The epoxy resin having a photosensitive group is preferably an epoxy acrylate compound which is an esterified product of a novolak type epoxy compound and an unsaturated monocarboxylic acid, which is not reacted with an acid anhydride in a stage before obtaining a photosensitive resin (D) having a carboxyl group. Used. Further, a urethane compound into which an epoxy acrylate compound isocyanate ethyl methacrylate or the like is introduced via a urethane bond is preferably used.

As the epoxy resin having no photosensitive group, an epoxy resin having two or more epoxy groups in a molecule is preferable. Specifically, bisphenol A type, F type,
S-type epoxy resin and its derivatives such as bromide, phenol or cresol novolak-type epoxy resin, biphenyl-type epoxy resin such as "YX4000" (manufactured by Yuka Shell Epoxy), special glycidyl ether-based epoxy resin such as "YDC-1312" ”(Toto Kasei),“ TACTIX742 ”(Dow Chemical),
"ZX1257" (Toto Kasei), ESLD-80X
Glycidyl ether-based epoxy resins such as Y, -90CR, -120TE, and -80DE (trade name of Nippon Steel Chemical Co., Ltd.); For example, "YH434" (manufactured by Toto Kasei), naphthalene type epoxy resin such as "Epiclon HP-4032" (manufactured by Dainippon Ink and Chemicals, Inc.), dicyclo type epoxy resin such as "Epiclon H"
P7200H "(manufactured by Dainippon Ink and Chemicals, Inc.), special aliphatic resins such as cycloaliphatic epoxy resins, heterocyclic epoxy resins, hydantoin type epoxy resins, and triglycidyl isocyanurate.

The preferred proportion of the epoxy resin (B) 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 (C) 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,
-(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,
5-diphenylimidazole dimer, 2,4-di (p-
2,4,5-triarylimidazole dimer such as methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenyl Acridine,
Examples include acridine derivatives such as 1,7-bis (9,9'-acridinyl) heptane, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These may be used alone or in combination of two or more. it can. A preferred blending ratio of the photopolymerization initiator (C) is 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the photosensitive resin composition.

Further, as a photoinitiating aid, there are ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, dimethylethanolamine, triethylamine, triethanolamine and the like. There are tertiary amines. These can be used alone or as a mixture in the range of 0.1 to 20% by weight in the photosensitive resin composition.

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

Further, if necessary, other curing agents and heat curing accelerators can be used. Examples of the curing agent include boron trifluoride-amine complex, dicyandiamide, acetoguanamine, guanamines such as benzoguanamine, organic acid hydrazide, diaminomaleonitrile, urea, melamine, amine imide, and alkylated melamine such as hexamethoxymethylated melamine. Resins, polyamine salts, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylmethane, metaxylenediamine, diaminodiphenylsulfone, “Hardener HT9
72 "(manufactured by Ciba Geigy), triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; Aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), benzophenonetetracarboxylic anhydride, maleic anhydride, tetrahydroanhydride Examples include aliphatic acid anhydrides such as phthalic acid, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, and alkylphenol novolak. As a thermosetting accelerator, metal salts of acetylacetone such as acetylacetonate Zn, enamine,
Tertiary phosphines such as tin octylate, quaternary phosphonium salts and triphenylphosphine; tri-n-
Phosphonium salts such as butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; diphenyliodonium tetrafluoroporoate; triphenylsulfonium hexane Poloates such as fluoroantimonates, antimonates, dimethylbenzylamine, 1,
Tertiary amines such as 8-diazabicyclo [5,4,0] undecene, m-aminophenol, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, 2-ethyl-4-methylimidazole, Examples thereof include imidazoles such as 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-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 range of 0.01% by weight to 10% by weight of the photosensitive resin composition.

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 60% by weight. If necessary, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black can be used. Hydroquinone, hydroquinone monomethyl ether, te
polymerization inhibitors such as rt-butylcatechol, pyrogallol, and phenothiazine; thixotropic agents such as bentone, montmorillonite, aerosil, and amide wax; silicone-based, fluorine-based, and polymer-based antifoaming agents;
And imidazole, thiazole, triazole,
Additives such as an adhesion-imparting agent such as a silane coupling agent can be used.

The photosensitive resin composition of the present invention can be obtained by uniformly mixing the compounding raw materials compounded in the above ratio by a roll mill, a bead mill or the like, and curing the mixture as follows, for example, to obtain a cured product. 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)
(0.5 ° C. for 0.5 to 1.0 hours) to obtain a cured film.

The photosensitive resin composition of the present invention is particularly useful as a solder resist composition for printed wiring boards and packages such as BGA and CSP.
It can also be used for coating materials such as glass, ceramic, plastic and paper.

[0043]

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

[Example of Production of Carboxylic Acid Compound (A-1) at Both Terminals of Polytetramethylene Ether Glycol (PTG)]
PTG (average molecular weight: 1,000) in a flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer;
1,000 g, sebacic acid; 405 g were charged, the temperature was raised to 200 ° C. over 2 hours, and the reaction was further performed for 3 hours. After cooling, the carboxylic acid compound at both ends of PTG having an acid value of 81.9 and a molecular weight of 1,370 was obtained. Obtained.

Similarly, a carboxylic acid compound (A-2) at both ends of polypropylene glycol diamine at both ends (PPG-NH ₂ : average molecular weight: 900) was obtained in the proportions shown in Table 1.

Similarly, a carboxylic acid compound (A-3) at both terminals of a propylene glycol reactant of bisphenol A (Bis-PPG: average molecular weight 1,450) was obtained with the composition shown in Table 1.

Similarly, polycarbonate diol (Placcel CD220: average molecular weight: 2,000; Daicel Chemical Industries, Ltd .;
Hexanediol residue / 3-methylpentanediol residue = 7/3, liquid at normal temperature)
4) 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.

[0049]

[Table 1] [Production Example of Polyamide Resin (B-1)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with 100 g of γ-butyrolactone; 1); 55.6 g, adipic acid; 6.1 g, sebacic acid; 8.3 g, isophthalic acid;
13.7 g, 4,4'-diphenylmethane diisocyanate (MDI); 13.8 g, coronate T80 (tolylene diisocyanate; TDI; manufactured by Nippon Polyurethane Industry Co., Ltd.); 14.4 g, heated to 200 ° C., and heated for 4 hours After keeping warm, cool, heating residue 40% by weight, acid value (solid content)
83.5 polyamide resin was obtained. Further, 141.5 g of bisphenol A-type epoxy resin Epicoat 1001 (manufactured by Yuka Shell Epoxy) 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. Acrylic acid at 120 ° C .; 10.7 g
And the mixture is kept warm for 3 hours, and then tetrahydrophthalic anhydride (TH
PA); 90.6 g was added, and the mixture was kept warm for 1 hour. Further, 58.4 g of glycidol was added, and the mixture was kept warm for 2 hours.
A: 240 g was added and kept warm for 2 hours. Subsequently, the resultant was diluted with DMF to obtain a photosensitive polyamide resin (B-1) having a heating residue of 55% by weight and an acid value (solid content) of 145.

[Production Example of Polyamideimide Resin (B-2)] A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with 50 g of NMP;
-Bis (4-aminophenoxyphenyl) propane (hereinafter referred to as BAPP); 12.4 g (0.030 mol),
11.6 g (0.060 mol) of trimellitic anhydride was charged and kept at 200 ° C. for 2.5 hours. 41.0 g (0.033 mol) of the above (A-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;
8.8 g (0.050 mol) and 100 g of γ-butyrolactone were added, and 200 g
The temperature was raised to ° C., and after cooling for 4 hours, 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 be twice the amount of carboxyl groups; Epicoat 1001;
After charging 66.8 g and keeping the mixture at 140 ° C. for 2 hours, DMF was added to make the heating residue 40% by weight. Then, acrylic acid;
9 g was added and the mixture was kept warm for 1 hour. Subsequently, it was diluted with DMF to obtain a photosensitive polyamide-imide resin (B-2) having a heating residue of 55% by weight and an acid value (in terms of solid content) of 85.

Polyamide (imide) resins (# -3 to # -5) were similarly obtained with the composition (unit: g) as shown in Table 2.

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[Table 2] * Polyamide (imide) blend: 100 blended products ** Mitsui Petrochemical Industries, Ltd .; bisphenol II type epoxy resin [Production example of photosensitive resin (C-1) containing carboxyl group] (C-1) Production example Stirring Cresol novolak type epoxy resin (epoxy equivalent: 2) in a flask equipped with a chiller, reflux condenser and thermometer.
00) 200 parts by weight, acrylic acid 70 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., 1 part by weight of triphenylphosphine was charged and heated to 100 ° C., and the acid value of the solid content was 1
(mg / g) or less. Next, the obtained solution was cooled to 50 ° C., and 51 parts by weight of maleic anhydride was added.
48 parts by weight of carbitol acetate and 10 parts by weight of solvent naphtha were charged and reacted at 80 ° C. for a predetermined time, and the solid content acid value was 67 (KOH mg / g), and the solid content was 67% by weight.
(C-1) was obtained.

[Production Example of Resin (D-1) Containing Acrylate Group and Epoxy Group] (D-1) Production Example A cresol novolac type epoxy resin (A) was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. Epoxy equivalent: 2
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 Example 1 According to the composition shown in Table 3, A and B were separately kneaded using three rolls, and 75 g of A and 25 g of B were mixed to prepare a resist ink composition. This was applied on a copper-clad laminate by a screen printing method using a 100-mesh polyester screen so that the film thickness after drying was 25 to 35 μm, and the coating film was dried at 80 ° C. for 20 minutes. After the negative mask film having the pattern was brought into close contact with the film, the film was irradiated with ultraviolet light for a predetermined time using an ultraviolet light exposure device. 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, the temperature was set at 150 ° C.
/ 1 hour, and heat cured to evaluate the obtained cured film.

Instead of (Β-1) in the first embodiment, (Β-
2), (Β-3), (Β-4), (Β-5), (C-
Example 1 was replaced with 1), and Examples 2 to 3 and Comparative Example 1 were used. The test results are shown in Table 4.

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[Table 3]

[0058]

[Table 4] * Undeveloped portions of undeveloped portions were observed.

** A cross-cut test (1 × 1 mm square, 100 pieces) according to JIS D0202.

*** According to the test method of JIS C 6481, it was immersed three times in a 260 ° C. solder bath for 10 seconds, and the change in appearance was observed. *** Pressure cooker test: After standing for a predetermined time in steam at 121 ° C. and 2 atm, the appearance of the coating film and a grid test were performed.

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The photosensitive resin composition of the present invention has excellent adhesiveness, heat resistance, PCT resistance and developability, and is suitable as a solder resist composition used for manufacturing LSI packages and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08G 73/14 C08G 73/14 C08L 77/00 C08L 77/00 79/08 79/08 C (72) Inventor Hiroaki Hirakura Ibaraki Kajima Plant, Hasaki-cho, Kashima-gun, Japan Hitachi Kasei Kogyo Co., Ltd. Kashima Plant (72) Inventor Katsushige Tsukada, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Kaichi Plant, Kashima Plant Hitachi Chemical Co., Ltd. Kashima Plant (72) Inventor Yoshino Toshizumi, Kajima-gun, Kashima-gun

Claims (5)

[Claims] 1. A photosensitive polyamide resin having a carboxyl group and at least one photosensitive resin (A) selected from a photosensitive polyamideimide resin having a carboxyl group, an epoxy resin (B), and a photopolymerization initiator (C). A photosensitive resin composition comprising: 2. A photosensitive polyamide resin having a carboxyl group is obtained by reacting a carboxyl group-terminated polyamide resin (a1) with an epoxy resin (b) at a molar ratio of epoxy group / carboxyl group larger than 1. The resin obtained by reacting an ethylenically unsaturated monocarboxylic acid (d) with an epoxy group-containing polyamide resin (c1) and then reacting with a polybasic anhydride (e). Photosensitive resin composition. 3. The photosensitive polyamide resin having a carboxyl group is a resin having at least one polymer unit selected from a polyalkylene oxide unit and a polycarbonate unit in a molecular structure.
Or the photosensitive resin composition according to 2. 4. A photosensitive polyamideimide resin having a carboxyl group is obtained by reacting a carboxyl group-terminated polyamideimide resin (a2) with an epoxy resin (b) at a ratio of epoxy group / carboxyl group of greater than 1. The resulting epoxy group-containing polyamide resin (c1) is reacted with an ethylenically unsaturated monocarboxylic acid (d),
The photosensitive resin composition according to claim 1, which is a resin obtained by further reacting a polybasic acid anhydride (e). 5. The photosensitive resin according to claim 3, wherein the photosensitive polyamideimide resin having a carboxyl group is a resin having at least one polymer unit selected from a polyalkylene oxide unit and a polycarbonate unit in a molecular structure. Composition.