JPH0940751A - Impact-resistant insulating resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an impact-resistant insulating resin compsn. which can form a highly impact-resistant insulating resin layer allowing no crack to occur even in a cutting process and is advantageously used for forming insulating resin layers for multilayered printed circuit boards. SOLUTION: This compsn. essentially contains fine rubber particles or an epoxy resin contg. fine rubber particles dispersed therein, a photosensitive polymer having a carboxyl group and at least two ethylenically unsatd. bonds in the molecule, a photopolymn. initiator, and a diluent. When this compsn. is of thermosetting type, it further contains an epoxy resin and an epoxy resin curative as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact resistant insulating resin composition, and more particularly to an impact resistant insulating resin composition which can be advantageously used for forming an insulating resin layer for mass production of printed wiring boards having high reliability. The present invention relates to an insulating resin composition.

[0002]

2. Description of the Related Art In recent years, with the increasing functionality of electronic equipment, there has been a demand for higher density printed wiring boards, and multilayer boards have become the mainstream. The method for manufacturing a multilayer printed wiring board is roughly classified into a lamination pressing method and a buildup method. The lamination process of the multilayer printed wiring board by the lamination press method includes a lay-up (superposition) and a multilayer molding press. In the lay-up process, a resin such as a glass cloth is formed on the surface of the inner layer board on which the conductor pattern is formed. A method is adopted in which sheet-like prepregs in a semi-cured state that have been impregnated with varnish and dried are stacked, and then copper foil or a copper clad laminate for outer layer and the like are sequentially stacked. In the multi-layer molding press step, the laid-up material is heated and pressed by a device such as a laminating press device, a vacuum laminating press device, or an autoclave to perform multi-layer molding.

On the other hand, in the manufacture of a multilayer printed wiring board by an example of a build-up method, a printed wiring board consisting of at least one layer of conductor pattern and an insulating substrate is used as an inner layer board, and a conductor is formed on the entire surface of the insulating substrate on which the conductor pattern is formed. An insulating resin composition is applied so as to cover the pattern, after temporary drying, a conductor layer is laminated, and the insulating resin layer is further heat-cured to firmly bond the conductor layer. A conductor pattern is formed by etching the outer conductor layer, and when a multilayer printed wiring board is further manufactured, the above-mentioned lamination is applied to the surface of the conductor pattern of the outer layer of the multilayer printed wiring board manufactured by the above method. By repeating the method, the layers can be stacked in layers.

Known methods for laminating the conductor layers include a method of laminating copper foil with a heating / pressurizing roller, a method of electroless copper plating, a vapor deposition method and a sputtering method. In the build-up method, a photosensitive resin composition is used as the insulating resin composition, and a coating film applied so as to cover the conductor pattern is exposed through a negative film to expose an unexposed portion where a via hole is formed. Known methods are a method of removing via development to form a via hole (photo via), and a method of forming an interlayer conduction hole by a drilling method such as drilling or laser processing using a thermosetting resin.

[0005]

Generally, in the manufacturing process of a printed wiring board, a punching (cutting) process from a working size to a product size is performed. In this case, especially in the case of a multilayer printed wiring board by a build-up method. The phenomenon that fine cracks occur in the insulating resin layer near the punched cut surface is observed. Further, there are methods such as router processing, but they are time-consuming and costly and are not suitable for mass production of multilayer printed wiring boards. When a crack occurs in the multilayer printed wiring board as described above, it causes inconveniences such as disconnection of the conductor circuit, deterioration of insulation, and poor appearance, so cracks are reliably prevented from occurring and the productivity of the multilayer printed wiring board is improved. It is desired to improve it. Therefore, the object of the present invention is to prevent the occurrence of cracks even by cutting, it is possible to form an insulating resin layer without causing the above problems,
In particular, it is to provide an impact resistant insulating resin composition that can be advantageously used for forming an insulating resin layer of a multilayer printed wiring board.

[0006]

In order to achieve the above object, according to one aspect of the present invention, (A) rubber fine particles or an epoxy resin in which rubber fine particles are dispersed, and (B) a carboxyl group in one molecule. Alkali-developable photocuring, containing a photosensitive prepolymer having both a group and at least two ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a diluent as essential components A mold impact resistant insulating resin composition is provided. According to another aspect of the present invention,
A thermosetting impact-resistant insulating resin containing (A) rubber fine particles or an epoxy resin having rubber fine particles dispersed therein, (E) an epoxy resin, and (F) an epoxy resin curing agent as essential components. A composition is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The impact resistant insulating resin composition according to the present invention is obtained by dispersing rubber fine particles in a photocurable or thermosetting resin composition, and curing the composition. In the obtained insulating resin layer, rubber particles are dispersed in a so-called sea-island structure, and these rubber particles alleviate the internal stress generated during heat curing and the external stress applied during cutting processing, and the impact resistance and fracture toughness are improved. improves. Therefore,
For example, even when cutting a multilayer printed wiring board, fine cracks do not occur in the insulating resin layer in the vicinity of the cut surface unlike the conventional case, and there is no problem such as cutting of the conductor circuit, deterioration of insulation, and appearance defect. It is possible to manufacture a high-quality multilayer printed wiring board with high productivity. Here, there is a concern that the heat resistance and the like may decrease due to the influence of rubber. Therefore, by adding, for example, acrylic or butadiene crosslinked rubber fine particles in a dispersed state, the insulating resin composition can sufficiently maintain the required characteristics such as heat resistance.

Any rubber fine particles can be used as long as they do not dissolve in a diluent (solvent) or other components in order to keep them dispersed in the cured insulating resin layer, but especially heat resistance. In consideration of the above, it is preferable to use the above-mentioned acrylic or butadiene-based crosslinked rubber fine particles. In addition, since processing such as cutting is performed at room temperature, it is soft at room temperature, for example, has a glass transition point of 20.
Rubber fine particles having a temperature of not higher than 0 ° C. are preferable, and the crosslinkable functional group of the rubber fine particles is preferably 0.01 to 1.4 mmol / g. Furthermore, in order to obtain a uniformly dispersed state in the insulating resin layer having a film thickness of generally about 20 to 100 μm, 0.01
Rubber fine particles having a particle size of 10 μm are preferable.

The rubber fine particles may be added to the composition by itself, or may be dispersed in an epoxy resin solvent, for example, a rubber fine particle-dispersed epoxy resin varnish or a diluent (solvent). It can also be used in the state of being left. Specific examples of the rubber fine particles include XER-91 manufactured by Japan Synthetic Rubber Co., Ltd., Staphyloid AC-3355 manufactured by Takeda Pharmaceutical Co., Ltd., and epoxy rubber varnish dispersed with rubber particles, Epotote YR-528 manufactured by Toto Kasei Co., Ltd. , YR-591, YR-570, YR-5
16, Epodyne RB-2000 manufactured by Resinus Kasei
RB-2010 etc. are mentioned. Further, as the component of the rubber fine particles, styrene rubber, isoprene rubber, ethylene rubber, propylene rubber, urethane rubber, butyl rubber, silicone rubber, nitrile rubber, fluororubber,
Examples thereof include norbornene rubber and ether rubber.

The impact resistant insulating resin composition according to the present invention is
The photocurable resin composition or the thermosetting resin composition is characterized by containing the above-mentioned (A) rubber fine particles or an epoxy resin having rubber fine particles dispersed therein. The proportion of the fine particles is 1 to 50 parts by weight with respect to 100 parts by weight of the photosensitive prepolymer (B) in the case of the photocurable resin composition, and the epoxy resin (E) also in the case of the thermosetting resin composition. It is desirable to be in the range of 1 to 50 parts by weight with respect to 100 parts by weight. If the proportion of the rubber fine particles is less than 1 part by weight, the desired effect of improving the impact resistance of the insulating resin layer cannot be obtained sufficiently, while if the proportion of the rubber fine particles exceeds the above range, the insulating resin becomes too large. This is not preferable because it adversely affects the physical properties such as heat resistance of the layer, and in the case of a photocurable resin composition, the photocurability is likely to be impaired. Hereinafter, other components of the impact resistant insulating resin composition of the present invention will be described.

First, the photocurable insulating resin composition contains as a main component a photosensitive prepolymer (B) having a carboxyl group and at least two ethylenically unsaturated bonds in one molecule. Examples of such a photosensitive prepolymer (B) include (1) an esterification reaction between an epoxy group of a polyfunctional novolac type epoxy compound and a carboxyl group of an unsaturated monocarboxylic acid, and the generated hydroxyl group is further saturated or unsaturated. A reaction product of polybasic acid anhydride of
(2) A copolymer of alkyl (meth) acrylate and glycidyl (meth) acrylate, which is reacted with (meth) acrylic acid, and then with a saturated or unsaturated polybasic acid anhydride, (3 ) Hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate copolymer (meth)
Glycidyl (meth) acrylate obtained by reacting acrylic acid and then further reacting with a saturated or unsaturated polybasic acid anhydride, a copolymer of (4) alkyl (meth) acrylate and (meth) acrylic acid It is possible to use those obtained by partially reacting with.

Since the photosensitive prepolymer (B) has a large number of free carboxyl groups added to the side chains of the backbone polymer, the composition containing this photosensitive prepolymer is developed with a dilute aqueous alkaline solution. At the same time, after exposure and development, by post-heating the coating film, the polymerization of the photosensitive prepolymer and the epoxy resin is promoted, and heat resistance, solvent resistance, acid resistance, adhesion, electrical characteristics, etc. An insulating resin film excellent in various characteristics can be obtained. The acid value of the photosensitive prepolymer (B) is 40 to 160 mg.
It is desirable to be in the range of KOH / g, and the preferable range is 50 to 140 mg KO in the resin of (1) above.
H / g, 50 to 50 in the resins of (2) and (4) above
150 mg KOH / g, 4 in the resin of (3) above
It is 0 to 120 mg KOH / g. Acid value is 40mgKO
If it is less than H / g, the solubility in an aqueous alkaline solution will be poor, and if it is more than 160 mgKOH / g, on the other hand, it will reduce the alkali resistance and electrical properties of the cured film. .

The resin (1) is a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid as described below, a dibasic acid anhydride such as phthalic anhydride, trimellitic anhydride, or pyromellitic anhydride. It is obtained by reacting with an aromatic polycarboxylic acid anhydride such as an acid. In this case, a resin obtained by reacting 0.15 mol or more of a polybasic acid anhydride per one hydroxyl group contained in the reaction product of the novolac type epoxy compound and the unsaturated monocarboxylic acid is suitable. If the number of ethylenically unsaturated bonds present in one molecule of the resin is low, photocurability will be slow, so it is desirable to use a novolac type epoxy compound as the raw material, but for the purpose of reducing the viscosity of the ink, bisphenol A type It is also possible to use a combination of epoxy compounds.

Typical novolac type epoxy compounds include phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A.
There are novolac type epoxy resin, etc.
A compound obtained by reacting each novolak resin with epichlorohydrin can be used.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, saturated or unsaturated dibasic acid anhydrides and 1
There are reaction products with (meth) acrylates having one hydroxyl group in the molecule, and these can be used alone or in combination of two or more, but from the viewpoint of photocurability, acrylic acid or methacrylic acid, especially Acrylic acid is preferred.

As the polybasic acid anhydride, typical ones are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride,
Dibasic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; trimellitic anhydride , Aromatic polycarboxylic acid anhydrides such as pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride; and other incidental compounds such as 5- (2,5-dioxotetrahydrofuryl) -3
A polyvalent carboxylic acid anhydride derivative such as -methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride can be used.

On the other hand, the copolymer, which is the base polymer of the resins of (2) and (3) above, is an alkyl (meth) acrylate and glycidyl (meth) acrylate as a monomer as described above, or further a hydroxyalkyl (meth). It can be obtained by using an acrylate and copolymerizing them by a known method such as a solution polymerization method. The alkyl (meth) acrylate is an alkyl ester of acrylic acid or methacrylic acid,
Here, the alkyl group is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the alkyl (meth) acrylate include, but are not limited to, esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl.

The hydroxyalkyl (meth) acrylate is a hydroxyalkyl ester of acrylic acid or methacrylic acid, and the hydroxyalkyl group is preferably an aliphatic hydrocarbon group having a primary hydroxyl group and having 1 to 6 carbon atoms. . This is a hydroxyalkyl (meth) acrylate having a primary hydroxyl group in terms of easiness of reaction when further reacting the copolymer with (meth) acrylic acid and then reacting with a polybasic acid anhydride. It is desirable to select and use as one of the monomers of the copolymer. Representative examples of such a hydroxyalkyl (meth) acrylate having a primary hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
It is not limited to these.

In the copolymer (2) as the base of the resin, the molar ratio of alkyl (meth) acrylate and glycidyl (meth) acrylate is 40:60 to.
80:20 is preferred. On the other hand, in the copolymer as the base of the resin of (3), the ratio of hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate is 10 in molar ratio.
-50: 10 to 70: 20-60, preferably 15-3
It is 0:30 to 50:30 to 50. If the proportion of glycidyl (meth) acrylate in the copolymer is lower than the above range, it is not preferable because the photocurability is lowered. On the other hand, if it exceeds the above range, the synthesis reaction of the photosensitive resin becomes smooth. It is not desirable because it is not necessary.

The degree of polymerization of the copolymer obtained by copolymerizing the above-mentioned respective monomers is expressed as the weight average molecular weight,
10,000 to 70,000, preferably 20,000
The range of -60,000 is desirable. Weight average molecular weight is 1
If it is less than 10,000, the dryness to the touch is likely to deteriorate, while
If it exceeds 50,000, the developability tends to be lowered, which is not preferable. In addition, in the present invention, vinyl compounds such as styrene and methylstyrene may be used in addition to the above-mentioned monomers within a range that does not affect the characteristics.

Examples of the photopolymerization initiator or sensitizer (C) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert. -Butyltrichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2
-Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1;
Benzophenone, 2-chlorobenzophenone, p, p-
Benzophenones such as dichlorobenzophenone, p, p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4′-methyldiphenylsulfide; benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin ethers such as benzoin isobutyl ether; ketals such as benzyl dimethyl ketal; thioxanthone, 2
-Thioxanthones such as chlorothioxanthone and 2,4-diethylthioxanthone; Anthraquinones such as 2-ethylanthraquinone and 2,3-diphenylanthraquinone; Organic peroxides such as benzoyl peroxide and cumene peroxide; 2,4,5 -Triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds; 2,4,6-tris-s-triazine, 2,
Organic halogen compounds such as 2,2-tribromoethanol and tribromomethylphenyl sulfone; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These compounds can be used alone or in combination of two or more kinds. The photopolymerization initiator (C) can be used in combination with one or more known photopolymerization accelerators such as benzoic acid-based or tertiary amine-based photopolymerization accelerators.

The preferred range of the amount of the photopolymerization initiator (C) used is the above-mentioned photosensitive prepolymer (B) 100.
0.2 to 30 parts by weight, preferably 2 to 2 parts by weight
The ratio is 0 parts by weight. When the compounding ratio of the photopolymerization initiator is less than 0.2 parts by weight, the photocurability is deteriorated, while when it is more than 30 parts by weight, the properties of the cured coating film are deteriorated, and the resin composition It is not preferable because the storage stability becomes poor.

Various organic solvents and / or photopolymerizable monomers can be used as the diluent (D). Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, butyl cellosolve, carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. Glycol ethers such as ethyl acetate, butyl acetate, cellosolve acetate,
Acetates such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, solvent naphtha, etc. Although petroleum-based solvents and the like can be used, glycol ethers, esters, and petroleum-based solvents are preferably used from the viewpoints of toxicity and ink characteristics.

The organic solvent as described above may be used alone or
Used as a mixture of more than one species. And the suitable range of the usage amount is the above-mentioned photosensitive prepolymer (B) 100.
15 to 300 parts by weight, preferably 30 to 300 parts by weight
The ratio is 200 parts by weight. The purpose of using the organic solvent is to adjust the viscosity of the resin composition to a value suitable for the coating method and to temporarily dry the coating film to form a film, thereby enabling contact exposure.

The photocurable insulating resin composition of the present invention serves to serve as the diluent and enhances the photocurability, so that it is added to the photosensitive prepolymer (B) in an amount of 50 parts by weight. The photopolymerizable monomer or oligomer may be contained in a proportion of not more than parts by weight. Typical examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, N. , N-dimethylacrylamide,
N-methyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol di Acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, glycerin diglycidyl ether diacrylate, glycerin triglycidyl ether triacrylate, isoborneolyl acrylate, Cyclopentadiene mono- or di -Acrylate, hexanediol, trimethylolpropane, pentaerythritol,
Ditrimethylolpropane, dipentaerythritol,
Polyhydric alcohols such as tris-hydroxyethyl isocyanurate or polyhydric acrylates of ethylene oxide or propylene oxide adducts thereof, and respective methacrylates corresponding to the above acrylates, monobasic acids and hydroxyalkyl (meth) acrylates -, Di-, tri- or higher polyesters and the like.

The photocurable insulating resin composition of the present invention has been described above in order to form an insulating resin layer having excellent characteristics such as solder heat resistance, electric insulation, adhesion and hardness of a cured coating film. It is desirable to contain an epoxy resin in addition to each component. When an epoxy resin varnish in which rubber particles are dispersed as the component (A) is used, it is not necessary to add the epoxy resin separately, but when only the rubber particles are used, it is preferable to add an epoxy resin as described below. In this case, the compounding amount of the epoxy resin is appropriately 5 to 100 parts by weight, preferably 15 to 60 parts by weight, based on 100 parts by weight of the photosensitive prepolymer (B).

In order to form an interlayer insulating resin layer of a multilayer printed wiring board using the photocurable insulating resin composition of the present invention, the viscosity is adjusted as necessary according to the coating method, and this is adjusted to, for example, It is applied by a known method such as a screen printing method, a curtain coating method, or a spray coating method on the conductor layer of the circuit-formed wiring board, and the organic solvent contained in the composition is volatilized at a temperature of 60 to 100 ° C., for example. By drying, a tack-free coating film can be formed. Then 10
It is exposed by an active ray selectively through a negative film having a black circle of about 0 μm, and the unexposed portion is, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine. By developing with a dilute alkaline aqueous solution such as the like, and further by heating at a temperature of 140 to 180 ° C. to cure, impact resistance, heat resistance, solvent resistance having via holes corresponding to the black circles of the negative film. , Acid resistance,
An interlayer insulating resin layer excellent in various properties such as adhesion and electrical properties can be formed. Further, since it is not necessary to use an organic solvent for cleaning the screen printing plate and the like, the environment is not polluted, the human body is not harmed, and the risk of fire or the like is reduced. A low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable as an irradiation light source for photo-curing.
In addition, a laser beam or the like can also be used as an active light beam for exposure.

Next, in the thermosetting insulating resin composition, the epoxy resin (E) is used as the main component. Specific examples of the epoxy resin include Epicoat 1001 and Epicoat 1004 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron 900 and Epicron 105 manufactured by Dainippon Ink and Chemicals, Inc.
0, Toto Kasei Epotote YD-134, YD-0
11, D.C. manufactured by Dow Chemical Company. E. FIG. R. 661, Arbaldite 6071 manufactured by Ciba Geigy, AER-661 manufactured by Asahi Kasei Kogyo, and Sumi-Epoxy E manufactured by Sumitomo Chemical Co., Ltd.
Phenoxy type epoxy compounds such as LA-134 and ESA-011 (both are trade names); Epicoat YL903 and YL906 manufactured by Yuka Shell Epoxy Co., Epicron 1120 manufactured by Dainippon Ink and Chemicals, and Epotote YDB manufactured by Toto Kasei -400, YDB-500, D.C. manufactured by Dow Chemical Company. E. FIG. R. 511, Ciba Geigy Araldite 8011, Asahi Kasei Kogyo AER-711, AE
R-755, Sumi-epoxy ELB manufactured by Sumitomo Chemical Co., Ltd.
-240, ESB-500 (both are trade names) and the like brominated epoxy compounds; Dainippon Ink and Chemicals, Inc. Epicron TSR-930, TSR-601, Toto Kasei Epotote YR-207, YR-450, YR-102
Rubber modified epoxy compounds such as (both are trade names); Dimer acid modified epoxy compounds such as Epototo YD-172 (trade name) manufactured by Tohto Kasei; Epicoat 807, 828 manufactured by Yuka Shell Epoxy Co., Dainippon Ink and Chemicals Epicron 840 manufactured by Kogyo Co., Ltd., Epototo YD-1 manufactured by Tohto Kasei Co., Ltd.
28, D.C. manufactured by Dow Chemical Company. E. FIG. R. 331, Ciba Geigy's Araldite GY260, Asahi Kasei's AER331, Sumitomo Chemical's Sumi-Epoxy E
Bisphenol A type epoxy compounds such as LA-128 (both are trade names); Epicoat 154, 181, manufactured by Yuka Shell Epoxy Co., Ltd., Epicron N-740, N-865, N-665 manufactured by Dainippon Ink and Chemicals, Inc. N-695,
Toto Kasei Epotote YDPN-638, YDCN
-704, D.C. manufactured by Dow Chemical Company. E. FIG. N. 431,
D. E. FIG. N. 438, Ciba Geigy's Araldite EPN1138, ECN1235, ECN1299, Nippon Kayaku's RE-306, EPPN-201, EOC.
N-1020, EOCN-104S, AER ECN-235, ECN-299 made by Asahi Kasei Corporation, Sumi-epoxy ESCN-195X, ESCN made by Sumitomo Chemical Co., Ltd.
Novolak type epoxy compounds such as -220 (all are trade names); Epichron 830 manufactured by Dainippon Ink and Chemicals,
Bisphenol F type epoxy compounds such as Epotote YDF-170 manufactured by Tohto Kasei Co., Araldite XPY306 (both are trade names) manufactured by Ciba Geigy; YL-933 manufactured by Yuka Shell Epoxy Co., T.I. manufactured by Dow Chemical Co. E. FIG.
N. (All are trade names) trihydroxyphenylmethane type epoxy compounds; YX- manufactured by Yuka Shell Epoxy Co., Ltd.
Biphenyl type or bixylenol type epoxy compounds such as 4000 and YL-6121 (both are trade names); Bisphenol S type epoxy compounds such as EXA-1514 (trade name) manufactured by Dainippon Ink and Chemicals; Hydrogenated bisphenol A type epoxy compounds such as Epotote ST-3000 (trade name); Epicoat E157S (trade name) manufactured by Yuka Shell Epoxy Co., Ltd .; , Tohto Kasei Epotote YH-434, Ciba-Geigy Araldite MY720, Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120 (all are trade names)
Glycidyl amine type epoxy compounds such as; Epicoat YL-931 manufactured by Yuka Shell Epoxy Co., Tetraphenylolethane type epoxy compounds such as Araldite 163 (all are trade names) manufactured by Ciba Geigy; Araldite PT810 manufactured by Ciba Geigy, Nissan TEPIC manufactured by Kagaku
Heterocyclic epoxy compounds such as (all are trade names); Hydantoin type epoxy compounds such as Araldite CY350 (trade name) manufactured by Ciba Geigy; Celoxide 2021 manufactured by Daicel Chemical Industries; Araldite CY175 and CY179 manufactured by Ciba Geigy (all). (Trade name) and the like.

The epoxy resin curing agent (F) used as an essential component together with the epoxy resin (E) in the thermosetting insulating resin composition of the present invention includes amines, acid anhydrides, aminopolyamide resins and polysulfides. Resin, boron trifluoride amine complex, novolac resin, dicyandiamide, acid hydrazide, carboxyl group-containing compound and the like can be mentioned.

Specific examples of the epoxy resin curing agent (F) include diethylenetriamine, triethylenetetramine, isophoronediamine, metaxylylenediamine, metaphenylenediamine, paraphenylenediamine, 4,
Amine such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, aniline-formalin resin; phthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, methyl Nadic acid anhydride, trimellitic acid anhydride,
Acid anhydrides such as pyromellitic acid anhydride and benzophenone tetracarboxylic acid anhydride; aminopolyamide resins that are condensation products of dimer acid and diethylenetriamine, triethylenetetramine; polysulfide resins having mercaptan groups at the ends; boron trifluoride Trifluoride amine complex with aniline, benzylamine, ethylamine, etc .; novolac resin obtained by condensation reaction of phenol, cresol, xylenol, resorcin, etc. with formalin; latent of dicyandiamide, adipic dihydrazide, sebacic hydrazide, melamine, etc. Contains a hardener. In addition, a carboxyl group-containing compound, for example, a (meth) acrylic acid copolymer such as John Cryl-68 manufactured by Johnson Polymer Co., can be used.

In the case of amines, polyamide resins, polysulfide resins, boron trifluoride amine complex, novolac resins, etc., the amount of these epoxy resin curing agents used in the thermosetting insulating resin composition of the present invention is The amount of active hydrogen in these curing agents is 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the amount of epoxy groups in the epoxy resin component. The amount of acid anhydride is 0.5 to 1.0 equivalent, preferably 0.7 to the amount of epoxy group in the epoxy resin component.
0.9 equivalent, and in the case of a latent curing agent, the amount of active hydrogen is 0.2 to 1.2 equivalents, preferably 0.3 to 0.
A ratio of 7 equivalents is desirable.

In the thermosetting insulating resin composition of the present invention, a curing accelerator can be used if necessary.
Specific examples of the curing accelerator include triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4 -Tertiary amines such as methyl-N, N-dimethylbenzylamine; quaternary ammonium salts such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride; phosphines such as triethylphosphine and triphenylphosphine; n
-Phosphonium salts such as butyltriphenylphosphonium bromide; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-
Examples thereof include imidazoles such as cyanoethyl) -2-ethyl-4-methylimidazole or organic acid salts thereof; and guanamines such as guanamine, acetoguanamine and benzoguanamine.

In the thermosetting insulating resin composition of the present invention, when a liquid epoxy resin is used as the epoxy resin (E), a diluent such as an organic solvent is not necessarily used, but a solid epoxy resin is used. When using a resin, it is necessary to use a diluent. As the diluent, various organic solvents and reactive diluents exemplified for the photocurable insulating resin composition are 0 to 200 parts by weight, preferably 0 to 100 parts by weight, relative to 100 parts by weight of the epoxy resin (E). It can be used in a proportion of parts. Examples of the reactive diluent include butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-t-butylphenyl glycidyl ether, glyceryl glycidyl ether, ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 2-methyloctyl glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and the like.

When a thermosetting insulating resin composition containing the above-mentioned components is used to produce, for example, a multilayer printed wiring board, the thermosetting insulating resin composition containing the above-mentioned components is first formed into a circuit. The conductor layer of the formed wiring board is coated with a known method such as a screen printing method, a spray coating method, or a curtain coating method. Depending on the coating method, a coating film having a desired film thickness may not be obtained by one coating, but in that case, coating is performed multiple times. After the insulating resin layer having a desired film thickness is coated, the first heat treatment is performed to obtain a semi-cured state. After that, after performing a predetermined interlayer conduction hole or the like, if necessary, roughening treatment is performed with a roughening agent such as an oxidizing agent, an alkaline aqueous solution, or an organic solvent, and the roughened insulating resin layer surface is formed. After coating the conductor layer by electroless plating, electrolytic plating, or the like, a second heat treatment is performed to increase the crosslink density of the insulating resin layer and relax the stress. Then, the conductor layer on the surface of the insulating resin layer is etched according to a conventional method to form a predetermined circuit pattern, and a conductor layer having a circuit is formed. Further, such an operation can be sequentially repeated as desired, and the insulating resin layer and the conductor layer having a predetermined circuit pattern can be alternately built up to be formed. In the method for manufacturing a multilayer printed wiring board as described above, the temperature T ₁ of the _first heat treatment after coating the insulating resin layer is also affected by the formulation of the insulating resin composition, but generally 1
It is in the range of 10 to 170 ° C., and the temperature T ₂ of the _second heat treatment after the conductor layer plating is higher than the temperature T _{1 of the first} heat treatment, preferably the glass transition temperature Tg of the insulating resin layer. It is preferable to set it higher than.

The thermosetting insulating resin composition of the present invention is used not only as an insulating resin layer in the method for producing a multilayer printed wiring board by the build-up method as described above, but also as a multilayer print by, for example, a copper foil laminating method. It can also be used as an insulating resin composition for the formation of an insulating resin layer in the production of a wiring board or for a prepreg used in a lamination pressing method.

The photocurable or thermosetting insulating resin composition of the present invention contains barium sulfate, depending on desired physical properties.
Known / conventional fillers such as silicon oxide, magnesium oxide, calcium carbonate, zirconium silicate, zirconium oxide, calcium silicate, talc, clay, silica, bentonite, kaolin, glass fiber, carbon fiber, mica, and metal powder, phthalocyanine blue, Phthalocyanine green,
Various additives such as known and commonly used dyes and coloring pigments such as titanium oxide and carbon black, defoaming agents, flame retardants, adhesion promoters or leveling agents may be added.

[0036]

EXAMPLES Examples and comparative examples in which the effects of the present invention are specifically confirmed are shown below. In the following, "parts" means "parts by weight" unless otherwise specified.

Synthesis Example 1 A cresol novolac type epoxy resin (trade name Epicron N-695; manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in carbitol acetate, and then an equivalent amount of acrylic acid was reacted to give a photosensitive group. , Then 2 produced in this reaction
70 mol% of hexahydrophthalic anhydride is reacted with the hydroxyl group of the primary grade to give an alkali-soluble photosensitive resin (B-
A solution (S-1) having a solid content of 70% by weight of 1) was obtained.

Synthesis Example 2 A mixture of 26 parts of hydroxyethyl methacrylate, 40 parts of methyl methacrylate, 57 parts of glycidyl methacrylate, and 2 parts of benzoyl peroxide was added dropwise to 185 parts of carbitol acetate heated to 100 ° C. over 2 hours, The temperature was maintained for 8 hours to obtain an acrylic copolymer having a weight average molecular weight of about 25,000. Next, 29 parts of acrylic acid, 0.2 parts of tetraethylammonium bromide and 0.02 part of hydroquinone were added to the obtained acrylic copolymer, and the mixture was reacted at 95 ° C for 8 hours, after which the liquid temperature was lowered to 70 ° C. , 31 parts of tetrahydrophthalic anhydride and reacted for 8 hours to obtain a solution of a photosensitive resin (B-2) having an acid value of 64 at a solid content of 50% by weight (S-
2) was obtained.

Example 1 Epoxy resin varnish containing rubber fine particles dispersed therein (trade name YR-59)
1 [rubber component 16%]; 35 parts carbitol acetate dissolved product (solid content 10%) of Toto Kasei Co., 45 parts photosensitive resin solution (S-1), dipentaerythritol hexaacrylate (trade name KAYARADO DPHA) ; Nippon Kayaku Co., Ltd.) 8 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (trade name Irgacure 907; Ciba Geigy) 4 parts,
1 part dicyandiamide, 6 parts carbitol acetate,
0.5 part of dimethylpolysiloxane and 0.5 part of phthalocyanine green were blended and premixed, and then the mixture was kneaded and dispersed by a three-roll mill to obtain a photocurable impact-resistant insulating resin composition capable of alkali development. It was

Example 2 Rubber fine particles (trade name: XER-91; manufactured by Japan Synthetic Rubber Co., Ltd.)
3 parts, phenol novolac type epoxy resin (trade name E
PPN-201; Nippon Kayaku Co., Ltd.) carbitol acetate dissolved product (solid content 75%) 15 parts, photosensitive resin solution (S-2) 45 parts, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1 (trade name Irgacure 907) 6 parts, dicyandiamide 1
Parts, carbitol acetate 11 parts, barium sulfate 16
Parts, finely divided silica 2 parts, dimethyl polysiloxane 0.5
And 0.5 part of phthalocyanine green were mixed and premixed, and the mixture was kneaded and dispersed with a three-roll mill to obtain a photocurable impact-resistant insulating resin composition capable of alkali development.

Example 3 8 parts of rubber fine particles (trade name: XER-91), 30 parts of liquid bisphenol A type epoxy resin (trade name: Epicoat 828; manufactured by Yuka Shell Epoxy Co., Ltd.), solid bisphenol A
Type epoxy resin (trade name Epikote 1001; manufactured by Yuka Shell Epoxy Co., Ltd.) 30 parts of carbitol acetate dissolved product (solid content 75%), 5 parts of dicyandiamide, 11 parts of carbitol acetate, 15 parts of barium sulfate, dimethylpolysiloxane 0 0.5 parts, phthalocyanine green 0.
After mixing 5 parts and premixing, the mixture was kneaded and dispersed with a three-roll mill to obtain a thermosetting impact-resistant insulating resin composition.

Example 4 Epoxy resin varnish containing rubber fine particles dispersed therein (trade name YR-52)
8 [rubber component 20%]; manufactured by Tohto Kasei Co., Ltd. 40 parts, novolac type epoxy resin (trade name DEN431, manufactured by Dow Chemical Co.) 20 parts, dicyandiamide 5 parts, carbitol acetate 9 parts, sulfuric acid Barium 25 parts, dimethyl polysiloxane 0.5 parts, phthalocyanine green 0.1.
A thermosetting impact-resistant insulating resin composition was obtained in the same manner as in Example 3 except that 5 parts were blended.

Comparative Example 1 45 parts of photosensitive resin solution (S-1), dipentaerythritol hexaacrylate (trade name KAYARAD O
PHA) 8 parts, 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropanone-1 (trade name I
rgacure 907) 4 parts, a heterocyclic epoxy compound (trade name TEPIC; manufactured by Nissan Chemical Industries, Ltd.) 15 parts, dicyandiamide 1 part, carbitol acetate 11 parts, barium sulfate 15 parts, dimethylpolysiloxane 0.5 part, phthalocyanine green 0.1. By mixing 5 parts by the same method as in Example 1, a photocurable insulating resin composition capable of alkali development was obtained.

Comparative Example 2 35 parts of liquid bisphenol A type epoxy resin (trade name Epikote 828), 35 parts of novolac type epoxy resin (trade name DEN431), 5 parts of dicyandiamide,
9 parts of carbitol acetate, 15 parts of barium sulfate, 0.5 parts of dimethylpolysiloxane, and 0.5 parts of phthalocyanine green were mixed, and a thermosetting insulating resin composition was obtained by the same method as in Example 3.

The insulating resin composition obtained in each of the above Examples and Comparative Examples was applied onto a printed board by screen printing and dried in the case of a photo-curing type: 80 ° C. × 30 minutes, exposure: 1
00 mJ / cm ² , development; 30% with 1 wt% Na ₂ CO ₃
The curing was performed under the conditions of 1 ° C. × 1 minute and 150 ° C. for 60 minutes post cure, and 140 ° C. × 30 minutes for the thermosetting type. The workability of the conductive hole of this insulating resin composition is, for the photo-curing type, the photo-via forming property of φ0.15 mm (presence or absence of undercut), and for the thermosetting type, the drill hole forming property (floating from the underlying copper). Etc.).

Further, the soldering heat resistance of each insulating resin film produced on the substrate was tested according to JIS C6481 and the electrical characteristics were measured by using a comb-shaped electrode of IPC-SM840B B-25 test coupon, insulation resistance before humidification, and Humidification conditions:
85 ° C, 85% R.I. H. The insulation resistance after humidification for 300 hours was measured by applying DC 50V. For impact resistance, punching was performed and the presence or absence of cracks on the cut surface was visually confirmed. Furthermore, the surface of the insulating resin layer of the drilled substrate is roughened with potassium permanganate, the roughened surface is subjected to panel plating, and then punching is performed to determine whether cracks occur on the cut surface and haloing occurs. The presence or absence was visually confirmed. Table 1 shows the results.

[Table 1] As is clear from the results shown in Table 1, when the insulating resin composition of the present invention was used, cracking was not observed near the cut surface even during punching or punching after panel plating, and the impact resistance was excellent. It was

[0047]

INDUSTRIAL APPLICABILITY As described above, the impact resistant insulating resin composition according to the present invention is obtained by dispersing rubber fine particles in a photocurable or thermosetting resin composition. By curing the resin, an insulating resin film excellent in impact resistance and fracture toughness can be obtained. Therefore, when the insulating resin composition of the present invention is used to form an insulating resin layer of a multilayer printed wiring board, for example, even in the case of punching or cutting, fine cracks are generated in the insulating resin layer near the cut surface as in the conventional case. It is possible to manufacture with high productivity a high-quality multilayer printed wiring board that does not occur and has no problems such as disconnection of conductor circuits, deterioration of insulation, and poor appearance. The impact resistant insulating resin composition according to the present invention can be advantageously used for forming an insulating resin layer of a multilayer printed wiring board as described above,
It can also be used for forming solder resists for printed wiring boards and insulating resin films for various electric and electronic devices.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C09D 5/25 C09D 5/25

Claims (5)

[Claims] 1. A rubber fine particle or an epoxy resin in which rubber fine particles are dispersed, (B) a photosensitive prepolymer having both a carboxyl group and at least two ethylenically unsaturated bonds in one molecule, and (C) ) A photopolymerization initiator, and (D)
A high-impact insulating resin composition containing a diluent as an essential component. 2. (A) rubber fine particles or an epoxy resin in which rubber fine particles are dispersed, (E) an epoxy resin, and (F)
An impact-resistant insulating resin composition comprising an epoxy resin curing agent as an essential component. 3. The impact resistant insulating resin composition according to claim 1 or 2, wherein the rubber fine particles are acrylic crosslinked rubber fine particles or butadiene crosslinked rubber fine particles. 4. The rubber fine particles have a glass transition point of 20.
The impact resistant insulating resin composition according to any one of claims 1 to 3, which is a rubber fine particle having a particle diameter of 0.01 to 10 µm at a temperature of not higher than ° C. 5. The rubber fine particles are contained in an amount of 1 to 100 parts by weight of (B) a photosensitive prepolymer having a carboxyl group and at least two ethylenically unsaturated bonds in one molecule or (E) an epoxy resin. The impact resistant insulating resin composition according to any one of claims 1 to 4, wherein the impact resistant insulating resin composition is contained in a proportion of 50 parts by weight.