JP2002003711A - Curable resin composition containing thermoplastic polyhydroxypolyether resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition containing a thermoplastic polyhydroxypolyether resin having flame retardance, a copper foil with an adhesive for a printed wiring board, an insulating film, etc., formed from the composition. SOLUTION: This curable composition comprises a component (A) composed of a polyhydroxypolyether resin which is represented by general formula (1) (X is a phosphorus-containing aromatic group; Z is a hydrogen atom or a glycidyl group; n is a value of >=21), has 10,000 to 200,000 number-average molecular weight and has 1 wt.%-6 wt.% phosphorus content, a component (B) composed of an epoxy resin and a component (C) composed of a curing agent in the ratio of the component (A) to the components (A)+(B) of 5 wt.%-95 wt.% The copper foil with an adhesive for a printed wiring board, the insulating film and the resist material are formed from the curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful in the electric and electronic fields, such as laminates for electrical use, magnetic tape binders, insulating varnishes, etc., and as adhesives, insulating paints, films and resist materials, and especially multilayer printed wiring boards The present invention relates to a curable resin composition containing a thermoplastic polyhydroxypolyether resin having flame retardancy without using a halide by containing a phosphorus atom, which is useful for applications.

[0002]

2. Description of the Related Art Conventionally, thermoplastic polyhydroxy polyether resins are generally known as phenoxy resins,
Because of its excellent flexibility, impact resistance, insulation, adhesion, and mechanical properties, in the electrical and electronic fields, magnetic tape binders, insulating varnishes for electric machines such as motors, adhesives for circuit boards, Halogenated phenoxy resins are used in a wide range of applications such as films, especially in fields requiring high safety such as fire prevention and delay, for example, in electric and electronic parts. Of these, brominated products are often used. However, it is known that when a material using a halide is used at a high temperature for a long period of time, the halide is dissociated, and halogen and hydrogen halide are generated to cause corrosion of the wiring. Furthermore, when combusting waste from used electronic components and electrical equipment, hazardous substances such as halogens and halides are generated during the pyrolysis and combustion processes. There has been a growing concern about direct and indirect use, and studies have been conducted on the use of alternative materials to impart flame retardancy. A flame-retardant film using a phenoxy resin is disclosed in JP-A-5-93.
041, JP-A-5-93042 and the copper foil with an adhesive is described in JP-A-11-279260. The flame retardants used in these are all based on halides, and there is no description of flame retardancy using phosphorus. The present invention provides the provision of flame retardancy based on a new technical concept without using a halide.

[0003] Examples of flame-retardant compounds using phosphorus compounds include those described in Synthesis and properties by WANG CS and SHIEH J-Y.
ofepoxy resins containingin
g 2- (6-oxid-6H-dibenz <c,
e><1,2> oxaphosphorin-6-y
l) 1,4-benzendiol "Polymer
(GBR) VOL. 39, NO, 23, PAGE. 58
No. 19-5826 1998, which uses a compound obtained by an addition reaction of a phosphorus-containing compound with benzoquinone as a reactive flame retardant for an epoxy resin which is a thermosetting resin, and includes CHO CS and CHEN. L
-W, CHIU Y-S, "Novel frame
retardant epoxy resins.
I. Synthesis, characterizat
ion, and properties of array
l phosphoepoxy epoxy ether
cured with diamine. "Poly
mer Bulletin VOL. 41, NO. 1,
PAGE. 45-52 1998, a novel epoxy resin is obtained as a thermosetting resin using a phosphorus-containing compound, benzoquinone and epichlorohydrin, but any of them imparts flame retardancy to the epoxy resin as a thermosetting resin. A reactive phosphorus-containing flame retardant, and a flame-retardant phosphorus-containing epoxy resin, wherein a curable resin composition containing a thermoplastic polyhydroxypolyether resin is used for electric / electronic parts, It does not disclose use as a flame-retardant insulating film.

[0004] In the conventional multilayer printed wiring board industry, a prepreg sheet, which is obtained by impregnating glass cloth or nonwoven fabric with an epoxy resin and then B-staged, is overlaid on an inner-layer circuit board on which a circuit is formed, and further thereon. A manufacturing method of stacking copper foils and performing integral molding under pressure and heat is mainly employed. However, in this method, usually, first, a glass cloth or a glass nonwoven fabric is impregnated with an epoxy resin and B-staged to prepare a prepreg, but the equipment required for this is expensive, and the problem of poor prepreg productivity is pointed out. In order to further increase the number of layers, various facilities for stacking copper foils and integrally forming them under pressure and heat are required, and it takes a considerable amount of time to obtain a final product, which poses a problem of process economics. In addition, as a fundamental problem, there is a physical limit to the thickness of the interlayer from the viewpoint of maintaining the shape and strength of these materials in order to minimize the interlayer thickness due to the use of glass cloth or glass nonwoven fabric. This is a rather large value, which is a major obstacle to downsizing. The present invention addresses how to reduce this physical limit and contributes to improved process economy.

Further, Japanese Patent Application Laid-Open No. 7-202418 describes a copper foil with an adhesive using a high-molecular epoxy resin, but the multilayer printed wiring board manufactured according to the invention is a multilayer printed wiring board manufactured according to the prior art. Compared to printed wiring boards,
The disadvantage is that the heat resistance is poor. The present invention contributes to the improvement of the heat resistance.

[0006]

SUMMARY OF THE INVENTION The present invention provides a multi-layer printed wiring board with a low cost, which could not be achieved by the prior art.
And an epoxy resin composition which can be extremely thinned, has high heat resistance and storage stability, does not use any halide, has flame retardancy, and a print formed using the epoxy resin composition Copper foil with adhesive for wiring board, and an insulating film formed using the epoxy resin composition,
It is an object of the present invention to provide a resist material such as a solder resist.

[0007]

The present invention provides means for solving the problems of the prior art, wherein the component (A) is represented by the following general formula (1) and the average molecular weight range is 1
000-200,000 (Gel Permeation Chromatography (GPC) uses Sho
dex AD-800P + TSKgel SuperHM
-H + SuperHM-H + SuperH2000,
N, N-dimethylformamide (20 mM
(A product containing lithium bromide) and a weight average molecular weight in terms of standard polyethylene oxide measured at a sample concentration of 0.5%. Hereinafter, the average molecular weight is a phenoxy resin having a weight average molecular weight determined by this measurement method, and the component (B) has an epoxy equivalent of 100 g / eq to 4,
500 g / eq of an aromatic epoxy resin having no halogen substituent and / or an epoxy resin containing a phosphorus atom, wherein the component (C) is a composition comprising a curing agent, and optionally has a viscosity It is a curable resin composition having an ability to form a thermosetting insulating layer containing an organic solvent for adjustment and an organic or inorganic filler, wherein the proportion of the component (A) is based on (A) + (B) 5 to 95% by weight, and the total of the phosphorus content of the component (A) and the phosphorus content of the component (B) is 1 to 5% by weight based on the total weight of (A) + (B). And a copper foil with an adhesive for printed wiring boards obtained by applying the curable resin composition to a copper foil, and an insulating film formed from the curable resin composition. The copper foil with an adhesive or the insulating film is used for a multilayer printed wiring board that requires flame retardancy without using any ultra-thin halide by laminating the inner layer circuit board and then thermosetting. Can be

[0008]

Embedded image In the formula, X is selected from the general formulas (2), (3), (6), and (7), and may be a single compound or a combination of a plurality thereof. Formula (2) and / or formula (3) are essential components. Z is either a hydrogen atom or formula (9), and n is a value of 21 or more.

[0009]

Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₃ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₃
More than one may be the same.

[0010]

Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₄ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₄
More than one may be the same.

[0011]

Embedded image In the formula, R _{1 to} R ₈ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₈
More than one may be the same.

[0012]

Embedded image In the formula, R _{1 to} R ₁₀ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two or more of R _{1 to} R ₁₀ may be the same.

[0013]

Embedded image In the formula, R _{1 to} R ₄ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₄
More than one may be the same.

[0014]

Embedded image In the formula, A is absent or represents —CH ₂ —, —C (C
_{H 3) 2 -, - CHCH} 3 -, - S -, - SO 2 -, - O
—, —CO—, or any divalent group of the general formula (8), wherein R _{1 to} R ₈ are any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group. Or
Two or more of R _{1 to} R ₈ may be the same.

[0015]

Embedded image In the formula, R _{1 to} R ₈ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₈
More than one may be the same.

[0016]

Embedded image

Naturally, the thermosetting resin composition of the present invention satisfies various properties such as heat resistance, flame retardancy, and electrical insulation equivalent to those of a glass epoxy circuit board produced by a conventional technique. In addition, when applied to copper foil, the copper foil does not curl after solvent volatilization and does not fall off during cutting, and when laminated to an inner layer circuit board, has an inner layer circuit embedding property. It is.

The average molecular weight of the component (A) used in the present invention ranges from 10,000 to 200,000.
When the average molecular weight of the component (A) is less than 10,000, the copper foil with an adhesive after the epoxy resin composition is applied to a copper foil and dried, causes copper foil curl, powder dropping during cutting, and the like, resulting in a defective product. Is not preferred. The average molecular weight is 200,
If it exceeds 000, even if it is diluted and dissolved with a solvent, the concentration of the solvent is generally 70% by weight, which is the industrially used concentration of 70 to 30%.
If it is% by weight, the solution viscosity is too high and it is extremely difficult to apply it to a copper foil. In order to obtain a solution viscosity that can be applied to a copper foil, a very undesirable solvent must be added in a large amount, which is uneconomical and also reduces VOC (volatile organic compound) to the environment as much as possible. Under certain circumstances, it is hard to say that it is preferable. Therefore, the average molecular weight of the component (A) is in the range of 10,000 to 200,000, preferably 11,000 to 100,000, and more preferably 15,000 to 65,000.

The phenoxy resin of the component (A) contains a dihydric phenol represented by the general formula (10) and / or the general formula (11) as an essential component and has a phosphorus content of 1% in the polyhydroxy polyether resin. A mixture containing two or more dihydric phenols alone or in combination with two or more diglycidyl ethers of dihydric phenols in an amine-based,
In the presence of a known catalyst such as imidazole, triphenylphosphonium, and phosphonium salt, in some cases, a non-reactive solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, isopropyl alcohol, butyl alcohol , Methyl cellosolve, ethyl cellosolve, cyclohexanone, etc., alone or in combination of two or more.
9: 1 to 1.1: 1, preferably 0.94: 1 to 1.0
It is prepared by reacting in an amount that provides a phenolic hydroxyl: epoxy group ratio of 6: 1, most preferably 0.97: 1 to 1.03: 1. Examples of dihydric phenols include hydroquinone, 2,5-di-t-
Butyl hydroquinone, bisphenol A, bisphenol F, 4,4'-bishydroxybiphenyl, 9,
9'-bis (4-hydroxyphenyl) fluorene,
Examples thereof include 1,4-naphthalene diol and the like. In the case of bisphenol F, the binuclear substance content is more preferably 96% or more, but is not particularly limited thereto. Examples of diglycidyl ethers of dihydric phenols include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, and bisphenol S
Type diglycidyl ether, hydroquinone type diglycidyl ether, 2,5-di-t-butyl hydroquinone type diglycidyl ether, 1,4-naphthalenediol type diglycidyl ether, 4,4′-bishydroxybiphenyl type diglycidyl ether, 9,9'-bis (4-
(Hydroxyphenyl) fluorene-type diglycidyl ether; and in the case of bisphenol A-type diglycidyl ether, those obtained by molecular distillation of the binuclear component content having a polymerization degree (n) of 0 to 96% or more are more preferable. In the case of bisphenol F-type diglycidyl ether, those obtained from bisphenol F having a binuclear content of 96% or more are preferable, and the binuclear component content at a polymerization degree (n) of 0 is 96%.
As described above, those obtained by molecular distillation are more preferable, but are not particularly limited thereto. Reaction temperature is 60 ° C to 200
C is preferable, and particularly preferably 90C to 180C. The reaction pressure is usually normal pressure, and when it is necessary to remove the reaction heat, the reaction is carried out by flash evaporation / condensation reflux of the solvent used, indirect cooling, or a combination thereof.

[0020]

Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₃ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₃
More than one may be the same.

[0021]

Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₄ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₄
More than one may be the same.

[0022]

Embedded image In the formula, R _{1 to} R ₈ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₈
More than one may be the same.

[0023]

Embedded image In the formula, R _{1 to} R ₁₀ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two or more of R _{1 to} R ₁₀ may be the same.

In the general formula (10), Y is the general formula (4)
As a specific example of 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, a specific example of Y represented by the general formula (5) is diphenyl Examples include phosphinyl hydroquinone, but are not particularly limited thereto.

In the general formula (11), Y is the general formula (4)
Are 1,4-naphthoquinone and 9,10-
Examples of the reaction product with dihydro-9-oxa-10-phosphaphenanthrene-10-oxide include Y, and specific examples of the general formula (5) include diphenylphosphinylnaphthohydroquinone. It is not limited to.

The phenoxy resin (component (A)) thus synthesized has a phosphorus content of 1% by weight to 6% by weight, preferably 1.5% by weight to 5% by weight, more preferably 2% by weight. 4% by weight. If the phosphorus content is less than 1% by weight, sufficient years of life cannot be imparted. If the phosphorus content is 1% by weight or more, flame retardancy is imparted at any concentration. No improvement in flammability is observed. In addition, the component (A) alone is a substance having a low resin flow during molding and having flexibility and flame retardancy. However, in order to impart a circuit embedding property, an epoxy resin is added and heated. It becomes very useful to cure.

Next, the applicable concentration range of the phosphorus content of the components (A) and (B) will be described. It is essential that the phenoxy resin of the component (A) contains phosphorus,
The component (B) may contain phosphorus in the epoxy resin. In this case, if the phosphorus content of the component (A) + (B) is less than 1% by weight, sufficient flame retardancy cannot be imparted to the epoxy resin composition of the present invention. At 1% by weight or more, flame retardancy can be imparted at any concentration. However, even at a concentration of 5% by weight or more, no improvement in flame retardancy according to the added concentration is observed. It is practical to control the weight in the range of 1% to 5% by weight, preferably 1.5% to 4.5% by weight, more preferably 2% to 4% by weight.

Next, the mixing ratio of the components (A) and (B) of the curable resin composition of the present invention will be described. (A) +
When the proportion of the component (A) in the component (B) exceeds 95% by weight, the embedding property of the inner layer circuit when laminated on the inner layer circuit board is not obtained, and the solvent concentration generally used industrially is used. At a certain 70% by weight to 30% by weight, the solution viscosity is too high, and it is extremely difficult to apply to the copper foil,
A large amount of solvent must be added in order to obtain a solution viscosity that can be applied to copper foil, which is uneconomical. Furthermore, it is difficult to say that it is preferable to use the component (A) in an amount exceeding 95% by weight under the current situation in which VOCs (volatile organic compounds) are reduced as much as possible with respect to the environment. If the amount is less than 5% by weight, the coating properties of the copper foil with an adhesive are deteriorated, and phenomena such as curling of the copper foil and powder dropping during cutting are unfavorably observed. For these reasons, the proportion of the component (A) in the component (A) + (B) of the curable resin composition is preferably from 10% by weight to 91% by weight, more preferably from 40% by weight to 80% by weight. .

The epoxy resin as the component (B) is an essential component for securing and maintaining the circuit embedding property without deteriorating physical properties such as flexibility, heat resistance and flame retardancy after curing. System and the epoxy equivalent is from 100 g / eq to 4,50
A thing of 0 g / eq is good. Epoxy equivalent is 4,500g
/ Eq, sufficient circuit embedding property cannot be obtained.
In addition, the crosslink density is low, and a cured film having desirable heat resistance cannot be obtained, which is not preferable. Further, in the case of an aliphatic epoxy resin, even if circuit embedding properties can be obtained, flame retardancy does not appear. On the other hand, if the epoxy equivalent is less than 100 g / eq, the crosslinked density of the cured product becomes high, and the cured product becomes hard and brittle, and it is difficult to maintain flexibility. Thus, the epoxy equivalent of the component (B) is from 100 g / eq to 4,500 g /
eq, preferably 130 g / eq to 3,000 g / e
q, more preferably 150 g / eq to 2,000 g / e
q. Examples of the epoxy resin suitable for the composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, co-condensation type epoxy resin of bisphenol A and bisphenol F, novolak type epoxy resin, biphenyl type epoxy resin, A pentadiene-phenol-based co-condensation type epoxy resin is exemplified, and an epoxy resin containing a phosphorus atom is exemplified by 9, 10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and quinone compounds reacted with epichlorohydrin or epoxy resin, epoxy resin FX containing phosphorus atom in resin skeleton
-279BEK75 (manufactured by Toto Kasei, epoxy equivalent 306)
g / eq, phosphorus content 2.0%, NV. 75.0%, viscosity 2,790 mPa · s / 25 ° C.) and the like, but are not particularly limited thereto. These epoxy resins may be used alone or in combination of two or more.

Various substances can be used as the curing agent of the component (C). For example, dicyandiamide and its derivatives. 2-
Imidazoles such as methylimidazole and 2-ethyl-4-methylimidazole and derivatives thereof. Condensation of divalent phenol compounds such as bisphenol A, bisphenol F, brominated bisphenol A, naphthalene diol and dihydroxybiphenyl, phenols such as phenol, cresol, bisphenol A, naphthol and naphthalene diol with aldehydes and ketones such as formaldehyde Novolak type phenolic resins obtained by the reaction, and phenolic compounds such as aralkyl type phenolic resins obtained by a condensation reaction of phenols such as phenol, cresol, bisphenol A, naphthol and naphthalene diol with xylylene glycol.
Acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride and hexahydrophthalic anhydride. Amine compounds such as polyamideamines obtained by a condensation reaction of acids such as diaminodiphenylmethane, triethylenetetramine, isophoronediamine, dimer acid and polyamines. Adipic acid dihydrazide, a curing agent for epoxy resins such as hydrazides such as isophthalic acid dihydrazide, which are commonly used,
It is not particularly limited to these. These curing agents may be used alone or in combination of two or more.

A solvent may be used in the curable resin composition of the present invention in order to maintain an appropriate viscosity when applied to a copper foil. As a solvent for adjusting viscosity, 100 ° C. to 16
It does not remain in the curable resin composition when the solvent is dried at 0 ° C. Specifically, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, cyclohexanone, N , N-dimethylformamide and the like, but are not particularly limited thereto. These solvents may be used alone or in combination of two or more.

The curable resin composition of the present invention has heat resistance,
Silica, calcium carbonate, talc, aluminum hydroxide, alumina, mica, etc. for imparting flame retardancy and low coefficient of linear expansion, and epoxy silane coupling agent and rubber component for improving adhesive strength May be added to such an extent that the physical properties of the cured product of the curable resin composition are not deteriorated.

The curable resin composition of the present invention may optionally contain a curing accelerator. For example, various known curing accelerators such as amine-based, imidazole-based, triphenylphosphonium, and phosphonium salt-based compounds can be used, but are not particularly limited thereto. When using a curing accelerator, 0.01% by weight of epoxy resin
A range of from 10 to 10% by weight is preferred. If it is more than 10% by weight,
This is a problem that storage stability as a copper foil with an adhesive is deteriorated, which is not preferable.

The curable resin composition of the present invention is dissolved in the above-mentioned solvent at 15,000 mPa · s / 25 ° C. or less,
It is adjusted to a viscosity of not more than 000 mPa · s / 25 ° C., and an appropriate amount of a curing agent is added so as to have a certain curing time.
The solvent is volatilized at 0 ° C to 160 ° C to obtain a copper foil with an adhesive. By laminating the obtained copper foil with adhesive on the inner layer circuit board with a dry laminator or the like and curing by heating, a multilayer printed wiring board having an outer layer copper foil can be produced.

[0035]

The present invention will be specifically described below based on Synthesis Examples, Examples and Comparative Examples. In the following Synthesis Examples, Examples and Comparative Examples, "parts" indicates "parts by weight".

Synthesis Example 1 Phosphorus-containing phenol, HCA-HQ (10
-(2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, hydroxyl equivalent 162 g / eq, phosphorus content 9.5%)
162 parts, bifunctional epoxy resin, YD-8125 (manufactured by Toto Kasei: molecular distilled bisphenol A type epoxy resin,
175 parts of epoxy equivalent (171.6 g / eq), 144 parts of cyclohexanone, and 0.13 part of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals, hereinafter abbreviated as 2E4MZ) as a catalyst, a stirrer, a thermometer, A four-necked glass separable flask equipped with a cooling pipe and a nitrogen gas introducing device was charged into a separable flask having a temperature of 150 ° C. to 170 ° C. under normal pressure.
After reacting for an hour, 156 parts of cyclohexanone, N, N
Dimethylformamide (300 parts), epoxy equivalent 17,200 g / eq, phosphorus content 4.6%, solid content 36% (hereinafter abbreviated as NV), solution viscosity 5,900.
937 parts of a mixed varnish of cyclohexanone / N, N-dimethylformamide as a polyhydroxy polyether resin having a mPa · s / 25 ° C and a weight average molecular weight of 62,000 was obtained. This resin was designated as synthetic resin varnish I.

Synthesis Example 2 Phosphorus-containing phenol, HCA-HQ (described above)
Parts, bisphenol A (hydroxyl equivalent 114 g / eq) 52 parts, bifunctional epoxy resin, YD-8125 (described above)
218 parts, 171 parts of cyclohexanone, and 0.16 part of 2E4MZ as a catalyst were charged into a four-necked glass separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device, and then subjected to normal pressure, 150 After reacting for 18 hours at a temperature of
And 198 parts of methyl ethyl ketone, and an epoxy equivalent of 13,300 g / eq, a phosphorus content of 3.0%, and an NV.
A cyclohexanone / methyl ethyl ketone mixed varnish of 40%, a solution viscosity of 5,200 mPa · s / 25 ° C. and a weight average molecular weight of 38,000 was mixed with 99.
0 parts were obtained. This resin was designated as synthetic resin varnish II.

Synthesis Example 3 Phosphorus-containing phenol, HCA-NQ (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
A reaction product of -oxide and 1,4-naphthoquinone, hydroxyl equivalent 187 g / eq, phosphorus content 8.2%)
Parts, bisphenol fluorene (manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl equivalent: 175.2 g / eq) 115 parts, bifunctional epoxy resin, YDF-8170 (manufactured by Toto Kasei: molecular distilled bisphenol F type epoxy resin, epoxy equivalent: 157.5 g /
eq), 162 parts of cyclohexanone, and 0.14 part of 2E4MZ as a catalyst were charged into a four-necked glass separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device. After reacting at a temperature of 150 ° C. to 170 ° C. for 16 hours, cyclohexanone 193 was added.
Parts, 169 parts of methyl ethyl ketone, and an epoxy equivalent of 12,500 g / eq, a phosphorus content of 1.5%, NV.
A mixed varnish of cyclohexanone / methyl ethyl ketone of a polyhydroxy polyether resin having a weight of 33,000 and a solution viscosity of 40%, a solution viscosity of 7,800 mPa · s / 25 ° C. and 84
7 parts were obtained. This resin was designated as synthetic resin varnish III.

Synthesis Example 4 Phosphorus-containing phenol, diphenylphosphinylhydroquinone (hydroxyl equivalent 155 g / eq, phosphorus content 1
0.0%), 195 parts, bifunctional epoxy resin, YDF-
215 parts of 8170 (described above) and 17 parts of cyclohexanone
6 parts and 0.41 part of triphenylphosphine (manufactured by Hokuko Chemical) as a catalyst were charged into a four-necked glass separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device, and then subjected to normal pressure. After reacting at a temperature of 150 ° C. to 170 ° C. for 8 hours, 29 parts of cyclohexanone and 205 parts of methyl ethyl ketone were added, and the epoxy equivalent was 4,600 g.
/ Eq, phosphorus content 4.8%, NV. 50%, solution viscosity 5,000 mPa · s / 25 ° C, weight average molecular weight 20,000
820 parts of a methyl ethyl ketone mixed varnish was obtained. This resin was designated as synthetic resin varnish IV.

Example 1 277.8 parts of synthetic resin varnish I obtained in Synthesis Example 1 and YDF-170 as epoxy resin (manufactured by Toto Kasei, epoxy equivalent 169 g / eq, viscosity 3,300 mPa · s / 25 ° C., bisphenol F) Epoxy resin) 10.0 parts, dicyandiamide (manufactured by Nippon Carbide, hereinafter DIC)
0.62 parts, 2E4MZ as a curing accelerator
(Described above) 0.1 part, methyl cellosolve as a solvent, N,
N-dimethylformamide (26 parts) was added and uniformly stirred and mixed to obtain an epoxy resin composition varnish. This varnish is applied to an anchor surface of a copper foil (manufactured by Mitsui Mining & Smelting) having a thickness of 35 μm using a roller coater so that the resin thickness after solvent drying is 60 μm, and the solvent is applied at 130 ° C. to 150 ° C. for 5 minutes to 15 minutes. Drying was performed to obtain a copper foil with an adhesive. On the other hand, a copper-clad double-sided laminated board (CCL-HL830, manufactured by Mitsubishi Gas Chemical, UL-94V-0, 0.8 mm board) with a 200 μm pitch between lines was used as a simulated inner layer circuit board.
The copper foil with the adhesive was laminated on both sides of the simulated inner layer circuit board with a dry laminator and cured by heating at 180 ° C. for 2 hours to obtain a four-layer printed wiring board having an outer insulating layer thickness of 50 μm.

Example 2 277.8 parts of synthetic resin varnish I obtained in Synthesis Example 1 and YDF-170 (described above) as an epoxy resin, 100.0%
Parts, 6.21 parts of DICY (described above) as a curing agent, 0.2 parts of 2E4MZ (described above) as a curing accelerator, 11 parts of methyl cellosolve and N, N-dimethylformamide as a solvent.
A printed wiring board was obtained in exactly the same manner as in Example 1, except that 6 parts were added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.

Example 3 277.8 parts of the synthetic resin varnish I obtained in Synthesis Example 1 and FX-279BEK75 (manufactured by Toto Kasei, epoxy equivalent 306 g / eq, phosphorus content 2.0) were used as epoxy resin.
%, NV. 75.0%, viscosity 2,790 mPa · s / 25 ° C., phosphorus-containing epoxy resin) 480.0 parts and YDF-200
4 (manufactured by Toto Kasei, epoxy equivalent 969 g / eq, softening point 85 ° C, bisphenol F type epoxy resin) 540.0
Parts, 18.20 parts of DICY (described above) as a curing agent, 1.0 part of 2E4MZ (described above) as a curing accelerator, and 1 part of methylcellosolve and N, N-dimethylformamide as a solvent.
A printed wiring board was obtained in exactly the same manner as in Example 1 except that 18.3 parts were added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.

Example 4 277.8 parts of synthetic resin varnish I obtained in Synthesis Example 1 and 50.0 parts of YDPN-638 (produced by Toto Kasei, epoxy equivalent 177 g / eq, phenol novolak type epoxy resin) as an epoxy resin 2.97 parts of DICY (described above) as a curing agent and 2E4MZ (described above) as a curing accelerator
A printed wiring board was obtained in exactly the same manner as in Example 1, except that 0.1 part of methyl cellosolve and 44 parts of N, N-dimethylformamide as a solvent were added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.

Example 5 250.0 parts of the synthetic resin varnish II obtained in Synthesis Example 2 and YDPN-638 (described above) 25.0 as an epoxy resin.
Parts, 1.48 parts of DICY (described above) as a curing agent, 0.1 part of 2E4MZ (described above) as a curing accelerator, and 36 parts of methylcellosolve and N, N-dimethylformamide as a solvent.
In addition, a printed wiring board was obtained in exactly the same manner as in Example 1 except that an epoxy resin composition varnish was obtained.

Example 6 250.0 parts of the synthetic resin varnish III obtained in Synthesis Example 3 and YDPN-638 (described above) 25.0 as an epoxy resin.
Parts, 1.48 parts of DICY (described above) as a curing agent, 0.1 part of 2E4MZ (described above) as a curing accelerator, and 36 parts of methylcellosolve and N, N-dimethylformamide as a solvent.
In addition, a printed wiring board was obtained in exactly the same manner as in Example 1 except that an epoxy resin composition varnish was obtained.

Example 7 200.0 parts of the synthetic resin varnish IV obtained in Synthesis Example 4 and YDPN-638 (described above) as an epoxy resin were used.
Parts, 2.97 parts of DICY (described above) as a curing agent, 0.1 part of 2E4MZ (described above) as a curing accelerator, and 50 parts of methylcellosolve and N, N-dimethylformamide as a solvent.
The resulting mixture was uniformly stirred and mixed to obtain an epoxy resin composition varnish. This varnish was applied to a release film (PET) using a roller coater so that the resin thickness after solvent drying was 60 μm, and the solvent was dried at 140 ° C. to 160 ° C. for 15 minutes to obtain an insulating film. An insulating film and a copper foil (described above) are laminated in this order on both sides of the simulated inner-layer circuit board (described above), laminated with a dry laminator, and heat-cured at 180 ° C. for 2 hours to form a 4-layer printed wiring having an outer insulating layer thickness of 50 μm. I got a board.

Comparative Example 1 250.0 parts of the synthetic resin varnish III obtained in Synthesis Example 3 and YDPN-638 (described above) as an epoxy resin.
0 parts, 5.93 parts of DICY (described above) as a curing agent, 0.2 parts of 2E4MZ (described above) as a curing accelerator, 1 part of methylcellosolve and N, N-dimethylformamide as a solvent
A printed wiring board was obtained in exactly the same manner as in Example 1, except that 44 parts were added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.

Comparative Example 2 YP-50EK35 (manufactured by Toto Kasei, epoxy equivalent: 10,
300 g / eq, weight average molecular weight 60,000, methyl ethyl ketone varnish, NV. 35%, phenoxy resin)
285.7 parts and FX-279BEK as epoxy resin
75 (as described above) 200.0 parts, DICY (as described above) 5.15 parts as a curing agent, 2E4MZ (as described above) as a curing accelerator
A printed wiring board was obtained in exactly the same manner as in Example 1, except that 0.2 part of methylcellosolve and 134 parts of N, N-dimethylformamide as a solvent were added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.

Comparative Example 3 277.8 parts of synthetic resin varnish I obtained in Synthesis Example 1, 4.0 parts of YDF-170 (described above) as epoxy resin, 0.25 part of DICY (described above) as curing agent, curing accelerator 0.1E of 2E4MZ (described above) and 15 parts of methylcellosolve and N, N-dimethylformamide as solvents were added and uniformly mixed with stirring to obtain an epoxy resin composition varnish. I got a board.

Comparative Example 4 277.8 parts of the synthetic resin varnish I obtained in Synthesis Example 1 and YD-020 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 4,850 g / eq, softening point 143 ° C., bisphenol A type epoxy resin) ) 50.0 parts, DI as curing agent
0.11 part of CY (described above), 2E4MZ as a curing accelerator
(Described above) 0.1 part, methyl cellosolve as a solvent, N,
Example 1 except that 100 parts of N-dimethylformamide was added and uniformly stirred and mixed to obtain an epoxy resin composition varnish.
A printed wiring board was obtained in exactly the same manner as described above.

Comparative Example 5 277.8 parts of synthetic resin varnish I obtained in Synthesis Example 1 and 10.0 parts of YDF-170 (described above) as an epoxy resin,
0.62 parts of DICY (described above) as a curing agent, 0.1 part of 2E4MZ (described above) as a curing accelerator, 79 parts of methylcellosolve and N, N-dimethylformamide as solvents, and uniformly stirred and mixed. I got a varnish. This varnish is impregnated into a glass cloth (manufactured by Nitto Boseki) having a thickness of 180 µm, and is heated at 130 ° C to 150 ° C for 5 minutes to 15 minutes.
The solvent was dried for 5 minutes to obtain a prepreg sheet. on the other hand,
As the simulated inner-layer circuit board, a copper-clad double-sided laminated board (described above) having a 200 μm pitch between lines and having been subjected to copper blackening treatment was used. The prepreg sheet and the copper foil (described above) are stacked on both sides of the simulated inner circuit board in this order, laminated with a dry laminator, and heat-cured at 180 ° C. for 2 hours to form a 4-layer printed wiring having an outer insulating layer thickness of 200 μm. I got a board.

Table 1 shows the characteristic values of the multilayer printed wiring board prepared as described above. In Table 1,
The ratio of the component (A) in [(A) component + (B) component] is as follows:
It is the ratio for each solid content.

[0053]

[Table 1]

(Test Method) Solder heat resistance test: A sample after boiling at 100 ° C. for 2 hours was immersed in a solder bath at 260 ° C. at n = 5, and all samples which did not swell or peel for 20 seconds or more were evaluated as ○. And Circuit embedding: In the inner layer circuit after peeling the outer layer copper foil,
The one in which the resin was embedded was evaluated as ○. Glass transition temperature: heat-cured without laminating copper foil with adhesive, and peeled copper foil for TM
A measurement was performed. In the case of Example 7, the insulating film was cured by heating and the TMA measurement was performed. In the case of Comparative Example 5, the prepreg sheet was cured by heating and TMA measurement was performed.

In Comparative Example 1, [(A) component +
(B) component has a phosphorus content of 0.8% by weight and 1% by weight
Smaller than that, and the flame retardancy (UL-94) is V-1, indicating that the flame retardancy is not sufficient as compared with the examples. In Comparative Example 2, the phenoxy resin of the present invention was not used as the component (A), and the phosphorus content in the component (A) was zero.
The flame retardancy (UL-94) is V-1, indicating that the flame retardancy is not sufficient as compared with the examples. Further, the glass transition point is as low as 103 ° C., the heat resistance is low, and the solder heat resistance is poor. That is, it is shown that the inclusion of phosphorus in the component (A) is extremely useful for flame retardancy and solder heat resistance. In Comparative Example 3, [(A) component + (B) component]
The ratio of the component (A) therein is 96.2% by weight, which exceeds 95% by weight. In this case, the circuit embedding property is poor. That is, to ensure the embedding property of the inner layer circuit when laminated on the inner layer circuit board, it is necessary to use [(A) component + (B)
It is necessary that the proportion of the component (A) in the component] does not exceed 95% by weight. In Comparative Example 4, the epoxy equivalent was 4,850 as the component (B).
g / eq is used. This is because the epoxy equivalent is higher than 4,500 g / eq, and both the solder heat resistance and the circuit embedding property are poor. The epoxy equivalent of the component (B) exceeding 4,500 g / eq indicates that it is not suitable as a resin for printed wiring boards. In Comparative Example 5, a conventionally used glass cloth was used. In this case, the thickness of the obtained printed wiring board is 200 μm. On the other hand, the thickness of the printed wiring board obtained by the present invention is about 50 μm as shown in Embodiment 1, and in the present invention, the thickness of the printed wiring board is made much thinner. You can do things.

As is clear from the examples and comparative examples, by using the curable resin composition of the present invention,
While ensuring flame retardancy, it has excellent heat resistance, especially solder heat resistance, excellent embedding of the inner layer circuit when laminated to the inner layer circuit board, and can further reduce the thickness of the printed wiring board. is there.

[0057]

By using the curable resin composition according to the present invention, a halide having an outer copper foil can be obtained simply by laminating a copper foil with an adhesive without preparing a prepreg using a glass cloth or a glass nonwoven fabric. And a flame-retardant multilayer printed wiring board containing no. Can be produced, the manufacturing process is simplified, and the process economy is improved accordingly. Further, since a glass cloth or a nonwoven fabric is not used, it is possible to produce an extremely thin and lightweight multilayer printed wiring board without physical limitations based on these materials.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01B 3/40 H01B 3/40 C 5G305 P 5G333 3/42 3/42 G 17/56 17/56 A H05K 3/46 H05K 3/46 T (72) Inventor Hiroshi Sato 3-17-14 Higashikasai, Edogawa-ku, Tokyo F-term (reference) 4F071 AA42 AA51 AC12 AE02 AH12 AH13 BB02 BC01 BC02 4J002 CC03Y CC27Y CD00X CD03X CD04X CD05X CD06X CD15X CH08W CL04Y EJ036 EJ056 EL136 EL146 EN036 EN046 EN076 EQ026 ER026 EU116 FD14Y FD146 FD150 GH01 GJ01 GP03 GQ01 GS01 4J005 AA24 BA00 4J030 DC07 DB07 DC07 DC07 DC07 FB08 FB12 FB13 JA01 JA05 JA06 JA08 JA09 5E346 AA06 AA12 AA16 AA22 CC08 CC09 CC41 CC43 DD03 EE12 EE13 GG19 GG28 HH24 HH31 5G305 AA06 AA07 AA11 AB25 AB36 BA09 BA18 BA26 CA13 CA15 CD08 5G333 AA03 AB13 AB21 CB13 DA04 DA11

Claims (4)

[Claims] 1. A polyolefin wherein the component (A) is represented by the following general formula (1), has an average molecular weight in the range of 10,000 to 200,000, and has a phosphorus content of 1% by weight to 6% by weight. A composition comprising a hydroxypolyether resin, a component (B) being an epoxy resin, and a component (C) comprising a curing agent, wherein the proportion of the component (A) is (A) + (B)
Curable resin composition having a thermosetting insulating layer forming ability of 5% by weight to 95% by weight with respect to Embedded image In the formula, X is selected from the general formulas (2), (3), (6), and (7), and may be a single compound or a combination of a plurality of compounds. Formula (2) and / or formula (3) are essential components. Z is either a hydrogen atom or formula (9), and n is a value of 21 or more. Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₃ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₃
More than one may be the same. Embedded image In the formula, Y is selected from the general formulas (4) and (5), and R _{1 to} R ₄ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; 2 out of _{1 to} R ₄
More than one may be the same. Embedded image In the formula, R _{1 to} R ₈ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₈
More than one may be the same. Embedded image In the formula, R _{1 to} R ₁₀ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two or more of R _{1 to} R ₁₀ may be the same. Embedded image In the formula, R _{1 to} R ₄ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₄
More than one may be the same. Embedded image In the formula, A is absent or represents —CH ₂ —, —C (C
_{H 3) 2 -, - CHCH} 3 -, - S -, - SO 2 -, - O
—, —CO— or any divalent group of the general formula (8), wherein R _{1 to} R ₈ are any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group Or
Two or more of R _{1 to} R ₈ may be the same. Embedded image In the formula, R _{1 to} R ₈ represent any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and two of R _{1 to} R ₈
More than one may be the same. Embedded image 2. An aromatic epoxy resin having no halogen substituent and / or phosphorus, wherein the epoxy resin as the component (B) according to claim 1 has an epoxy equivalent range of 100 g / eq to 4,500 g / eq. An epoxy resin containing atoms, wherein the total of the phosphorus content of the component (A) and the phosphorus content of the component (B) according to claim 1 is (A) + (B)
2. The epoxy resin composition according to claim 1, wherein the amount is from 1% by weight to 5% by weight based on the total weight. 3. A copper foil with an adhesive for printed wiring boards, wherein the epoxy resin composition according to claim 1 or 2 is applied to the copper foil. 4. An insulating film formed from the epoxy resin composition according to claim 1.