JPH06102712B2 - Resin composition for laminated board - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for a laminate, and more specifically, a laminate having high heat resistance, moisture resistance and mechanical properties. The present invention relates to a resin composition for use.

[Conventional technology]

Demand for laminated plates, especially copper-clad laminated plates is growing greatly, and by combining a base material and a thermosetting resin, copper-clad laminated plates that meet various purposes have been obtained. In the field of consumer electronic devices such as color televisions and audio equipment, paper-based phenol resin copper-clad laminates are the main products, and in the field of industrial electronic devices such as computers, controllers and measuring instruments, glass-based epoxy resin copper-clad Laminates are mainly used.

However, with the progress of high-density wiring and multi-layering, conventional glass-based epoxy resin copper-clad laminates cannot meet the required specifications in terms of dimensional stability, heat resistance, etc., and have excellent heat resistance. There was a demand for the development of a copper clad laminate.

As a copper clad laminate excellent in heat resistance, for example, Japanese Patent Publication No. 60-2
As shown in Japanese Patent No. 6423, what is known to be composed of a polyimide resin (for example, polyamino bismaleimide resin) and a glass base material is known to have a high glass transition temperature and have excellent dimensional stability during heating. It has features.

[Problems to be Solved by the Invention]

However, the polyimide resin has a high hygroscopic property, there is a problem in dimensional stability during wet heat, since a polar solvent having a high boiling point is used as a solvent during prepreg production, the solvent tends to remain during lamination molding, and the quality is improved. There are drawbacks such as variations, and it has been a problem to solve these problems.

The present invention has been made to solve the above problems, and is a resin composition for a laminate, which has excellent heat resistance to the same degree as conventional ones, and also has excellent adhesiveness, toughness, flexibility, moisture resistance and mechanical properties. The purpose is to get things.

[Means for Solving the Problems]

The resin composition for laminated boards of the present invention has the general formula (Wherein R is H or CH _3, m is an integer from 0 to 5) a polyfunctional epoxy resin represented by (alpha ₁₎ to the general formula (In the formula, n is an integer of 0 or more, X is bromine or H, a is an integer of 1 to 4), and the weight ratio of the bisphenol A type epoxy resin (α ₂ ) is from 100: 0 to 30:70. Chemical formula of the compounded epoxy resin composition (α) (In the formula, b is an integer of 1 to 4) The brominated bisphenol A (β) is represented by the above-mentioned brominated bisphenol A (β) based on 1 equivalent of the epoxy group terminal of the epoxy resin composition (α). A polyfunctional epoxy resin (A) obtained by reacting a composition in which the hydroxyl group of 0.05 to 0.5 equivalent is mixed until the reaction rate of the epoxy group and the hydroxyl group becomes 80% or more, bisphenol A and formaldehyde. A phenol resin (B) having a molecular weight of 1.000 or more and 10.000 or less, which is a polycondensation product of the above, with respect to 1 equivalent of the epoxy group terminal of the polyfunctional epoxy resin (A), the hydroxyl group of the phenol resin (B) is 0.7 to 1.2. 1 to 60 parts by weight of a linear polymer (II) having a molecular weight of 5.000 or more and 100.000 or less compatible with the composition (I) is added to 100 parts by weight of the composition (I) blended in an equivalent ratio. It is also a straight chain It is to use a phenoxy resin as the polymer.

[Action]

In this invention, the flexibility and crosslink density are increased by reacting the polyfunctional epoxy resin mainly with the phenol resin to improve the heat resistance, while the linear polymer is interposed in the crosslinked network structure. A composition that provides toughness while maintaining heat resistance.

〔Example〕

General formula according to the present invention Examples of the polyfunctional epoxy resin (α ₁ ) represented by the formula (wherein R is H or CH ₃ , m is an integer from 0 to 5) include, for example, TACTIX-742 (manufactured by Dow Chemical Co.) and EPPN502 (Japan). Kayaku Co., Ltd.) and those synthesized by the inventor shown in the examples below are used. Here, m is an integer from 0 to 5, and when m exceeds 5, the viscosity becomes too high and the impregnation of the base material during the production of the laminated plate prepreg becomes insufficient.

Further general formula (In the formula, n is an integer of 0 or more, X is bromine or H, and a is an integer of 1 to 4). As the bisphenol A type epoxy resin (α ₂ ), for example, trade name Epicoat 828, Epicoat 1001, Epicoat 1004 (both made by Yuka Shell),
Product name YD-115, YD-124 (both manufactured by Tohto Kasei), Product name GY-2
60 (manufactured by Ciba Geigy), trade name DR-331 (manufactured by Dow Chemical), etc. are used.

The above polyfunctional epoxy resin (α ₁ ) and bisphenol A for obtaining the epoxy resin composition (α) according to the present invention
The compounding ratio of epoxy resin (α ₂ ) is 100: 0 to 3 by weight.
It is 0:70, and if the bisphenol A type epoxy resin (α ₂ ) is blended beyond this range, the heat resistance becomes poor.

Further, in order to obtain the polyfunctional epoxy resin (A), the hydroxyl group of the brominated bisphenol A (β) is mixed in a ratio of 0.05 to 0.5 equivalent to 1 equivalent of the epoxy group terminal of the epoxy resin composition (α). , The reaction rate of the epoxy group and the hydroxyl group must be 80% or more.

If the equivalent ratio of reaction is less than 0.05, the above-mentioned uniform polyfunctional epoxy resin (A) cannot be obtained, and if it exceeds 0.5 equivalent, unreacted hydroxyl groups remain and the reactivity deteriorates. Further, when the reaction rate is less than 80%, the reactivity is similarly deteriorated.

Here, the reaction for obtaining the polyfunctional epoxy resin (A) uses no catalyst or a catalyst.

When a catalyst is used, examples thereof include amines such as triethylamine and benzyldimethylamine, imidazoles, phosphorus-based compounds such as tolphenylphosphine, but are not limited thereto.

Examples of the phenol resin (B) according to the present invention include trade name KP-756P (manufactured by Arakawa Chemical Industry Co., Ltd.) and trade name YLH-129.
(Manufactured by Yuka Shell Co., Ltd.) and those synthesized by the inventor shown in Examples below are used.

Here, the molecular weight of the above-mentioned phenol resin (B) is 1.00-10.
If it is 000 and less than 1.000, the toughness is inferior, and if it exceeds 10.000, the viscosity becomes too high and the impregnation of the base material during the production of the prepreg for laminated plate becomes insufficient.

The compounding amount of the polyfunctional epoxy resin (A) and the phenol resin (B) for obtaining the composition (I) according to the present invention is such that 1 equivalent of the epoxy group terminal of the polyfunctional epoxy resin is equivalent to that of the phenol resin. Hydroxyl group is 0.7 to 1.2,
If the amount is less than 0.7 equivalent, unreacted epoxy groups remain, resulting in poor heat resistance. If the amount exceeds 1.2 equivalents, a phenol resin that does not participate in the reaction remains, resulting in poor moisture resistance and heat resistance.

As the linear polymer (II) according to the present invention, polyparabanic acid, polyether sulfone, polysulfone, polyetherimide, polyphenylene sulfide, phenoxy resin, and liquid crystal polymer such as wholly aromatic polyester are suitable. Used. Usually, the molecular weight is preferably 5.000 or more. If it is less than 5.000, the effect of imparting flexibility by the polymer cannot be obtained, and if it exceeds 100.000, the viscosity becomes too high and impregnation becomes insufficient. Further, the compounding amount is 1 to 60 parts by weight with respect to the composition (I), and when the compounding amount is less than 1 part by weight, the effect of imparting flexibility is not sufficient, and the compounding amount is 60 parts by weight. When it exceeds the above range, the resin viscosity increases too much, and the impregnation of the base material during the production of the prepreg for laminated plate is insufficient.

The resin composition for laminated boards of the examples of the present invention may contain aromatic amines, phosphorus compounds, imidazoles, and imidazolines for the purpose of promoting the curing reaction. Typical examples thereof include benzyldimethylamine, triphenylphosphine, 2-methylimidazole, and 2-methylimidazole.
Ethyl-4-methylimidazole, 1-benzyl-2-
Methylimidazole, 2-ethyl-4-methylimidazoline, 2-methylimidazoline and the like. Further, the addition amount thereof is preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the composition (I). If it is less than 0.01, the reaction rate is slow and it becomes difficult to control the fluidity of the resin in the case of a prepreg for a laminated plate. If it exceeds 0.5, the pot life of the prepreg for lamination becomes short.

The resin composition for laminates thus obtained is usually dissolved in a solvent shown below and applied as a resin liquid having a predetermined concentration to the production of prepreg.

Examples of the solvent used here include alcohols such as ethyl alcohol, propyl alcohol and butyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ethylene. Solvents such as glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate and the like ethylene glycol, diethylene glycol ethers and acetic acid esters thereof are preferably used, N, N-dimethylformamide, N Amides such as N-dimethylacetamide and polar solvents such as N-methylpyrrolidone and dimethyl sulfoxide can also be used. Furthermore, these solvents may be used alone,
You may use 2 or more types together.

Further, the copper-clad laminate, as described above, the resin composition for laminates is applied to a predetermined substrate, impregnated and dried to produce a prepreg, and a copper foil is superposed on the prepreg and heated. It is obtained by pressurizing.

The base material that can be used here is generally glass fiber, but it is also possible to use aromatic polyamide fiber, or mat-shaped glass, polyester, or aromatic polyamide.

The resin for laminates is usually applied to the substrate at room temperature and the temperature is 80-200 ℃.
It is dried for 1 to 20 minutes and used as a prepreg. A predetermined number of the obtained prepregs are piled up, and copper foil is piled up on at least one side, usually at 80 ° C to 250 ° C, pressure 5 to 100 kg / cm ² .
Heat and press for 10 to 300 minutes to make a copper clad laminate. The conditions shown here are desirable values, but are not limited to these.

The laminate obtained from the resin composition of the present invention is excellent in heat resistance, solder heat resistance, electrical characteristics, and mechanical characteristics, and is suitably used, for example, for high-density multilayers. Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 The following formula Polyfunctional epoxy resin 100g (trade name TACTIX-742
Dow Chemical's) bisphenol A type epoxy resin 10
g (trade name Epicote 1001 manufactured by Yuka Shell Co., Ltd.), tetrabrombisphenol A (25 g) and triethylamine (0.01 g) were mixed and heated at 130 ° C for 1 hour, and the reaction rate of the epoxy group and the hydroxyl group of the composition became 85%. A functional epoxy resin (A) was obtained.

To this, 100 g of composition (I) in which 25 g of bisphenol A novolak type phenolic resin (trade name KP-756P manufactured by Arakawa Chemical Industry Co., Ltd.) is mixed with 15 g of phenolic resin (II) having a molecular weight of 30.000 (trade name PKHH Union Carbide). ) And 2
-Ethyl-4-methyl imidazole 0.1g was mixed, dissolved in ethylene glycol monomethyl ether 80g, 59
A resin composition for laminates of one example of the present invention having a concentration of% was obtained.

This was impregnated into a glass woven cloth having a thickness of 0.18 mm and dried to obtain a prepreg having a resin content of 50% by weight. Four of these prepregs were stacked and press-molded with copper foil of 35 μm on both sides. Molding conditions are press temperature 180 ℃, press pressure 40kg / cm
^2. Press time was 90 minutes. The evaluation results of the physical and electrical properties of the copper clad laminate are shown in the table.

Example 2 100 g of polyfunctional epoxy resin (trade name EPPN-502 manufactured by Nippon Kayaku) and 100 g of bisphenol A type epoxy resin (trade name YD-115 Toto Kasei) and tetrabromobisphenol
Combined with A85g and 0.01g triphenylphosphine, 1
The mixture was heated at 30 ° C. for 1 hour to obtain a polyfunctional epoxy resin (A) in which the reaction rate of the epoxy groups and hydroxyl groups in the composition was 80%.

In addition to this, 29 g of bisphenol A novolak type phenolic resin (trade name YLH-129 manufactured by Yuka Shell Co., Ltd.) was added to 100 g of a composition (I) of phenoxy resin (II) having a molecular weight of 30.000.
10 g, and 2-ethyl-4-methylimidazole 0.1 g
80 g of ethylene glycol monomethyl ether
To obtain a 58% concentration resin composition for laminated plates of another example of the present invention.

This was impregnated into a glass woven cloth having a thickness of 0.18 mm and dried to obtain a prepreg having a resin content of 50% by weight.

Four of these prepregs were stacked and press-molded with copper foil of 35 μm on both sides. Molding condition is press temperature 180
° C., pressing pressure 40 kg / cm ^2, and the pressing time 90 minutes. The evaluation results of the physical and electrical properties of the copper clad laminate are shown in the table.

Example 3 The following formula Bisphenol A to 100 g of polyfunctional epoxy resin
-Type epoxy resin 250g (trade name DR-331 made by Dow Chemical), dibromobisphenol A 53g and triphenylphosphine 0.01g were mixed and heated at 130 ° C for 1 hour, and the reaction rate of epoxy group and hydroxyl group of the composition A polyfunctional epoxy resin (A) having a ratio of 85% was obtained.

To this, 100 g of a composition (I) in which 29 g of a bisphenol A novolak type phenolic resin was mixed, 10 g of polyparabanic acid (II) (trade name: XT-4 TOKYO HOT Sekiyu) and 2-
Ethyl-4-methylimidazole 0.1g was mixed, dissolved in ethylene glycol monomethyl ether 80g, 58%
A resin composition for a laminated board of another example of the present invention having a concentration was obtained.

The polyfunctional epoxy resin represented by the above formula is prepared by reacting 234 parts of paracresol and 211 parts of salicylaldehyde in the presence of 0.3 part of concentrated hydrochloric acid at 100 ° C. for 30 minutes, and then reacting with P
-Toluenesulfonic acid (0.5 parts) was added, and the mixture was reacted at 180 ° C for 2 hours to obtain the following formula, To obtain the polyphenol. It can be obtained by reacting 110 parts of the polyphenol with 150 parts of epichlorohydrin according to a conventional method.

A glass woven cloth having a thickness of 0.18 mm was impregnated with the above resin composition and dried to obtain a prepreg having a resin content of 50% by weight.

Four of these prepregs were stacked and press-molded with copper foil of 35 μm on both sides. Molding condition is press temperature 180
° C., pressing pressure 40 kg / cm ^2, and the pressing time 90 minutes. The evaluation results of the physical and electrical properties of the copper clad laminate are shown in the table.

The phenol resin used in Example 3 was bisphenol A1.
00 parts, 22 parts of 37% formaldehyde, and 1 part of oxalic acid were placed in a flask equipped with a cooling tube and a stirring device, refluxed for 2 hours to react, and then dehydrated and concentrated.

Comparative Example 1 To 125 g of an epoxy resin (trade name Epikote 5046B-80 manufactured by Yuka Shell Co., Ltd.), 2 g of dicyandiamide and 0.15 g of 2-ethyl-4-methylimidazole were added, dissolved in 65 g of ethylene glycol monomethyl ether, and laminated at a concentration of 53% by weight. A board resin composition was obtained.

This was impregnated and dried in a 0.18 mm-thick glass woven fabric to obtain a prepreg having a resin content of 47% by weight.

Four of these prepregs were stacked and press-molded with copper foil of 35 μm on both sides. Molding condition is press temperature 170
° C., pressing pressure 40 kg / cm ^2, and the pressing time 60 minutes.

The evaluation results of the physical and electrical properties of the obtained copper clad laminate are shown in the table.

Comparative Example 2 100 g of a polyimide resin (trade name: Kelimide 601 manufactured by Nippon Polyimide) was dissolved in 100 g of N-methylpyrrolidone to obtain a resin composition for a laminate having a concentration of 50% by weight.

This was impregnated with a glass woven cloth having a thickness of 0.18 mm and dried at 150 ° C. for 30 minutes to obtain a prepreg having a resin amount of 45% by weight. 4 layers of this prepreg are placed on each side with 35μm copper foil at 220 ℃
It was heated and pressed at 0 kg / cm ² for 90 minutes to obtain a copper clad laminate. The evaluation results of the obtained copper clad laminate are shown in the table.

As shown in the above examples, the resin composition for laminated boards of the examples of the present invention, the cured product is as excellent in heat resistance as conventional, moisture resistance, mechanical strength, excellent adhesion. A resin composition for a laminated board is provided.

〔The invention's effect〕

As described above, the present invention has the general formula To polyfunctional epoxy resin (wherein R is an integer from H or CH _3, m is 0 to 5) represented by (alpha _1), the general formula (In the formula, n is an integer of 0 or more, X is bromine or H, a is an integer of 1 to 4), and the weight ratio of the bisphenol A type epoxy resin (α ₂ ) is from 100: 0 to 30:70. Chemical formula in the compounded epoxy resin composition (α) (In the formula, b is an integer of 1 to 4) The brominated bisphenol A (β) is represented by the above-mentioned brominated bisphenol A (β) based on 1 equivalent of the epoxy group terminal of the epoxy resin composition (α). A polyfunctional epoxy resin (A) obtained by reacting a composition in which the hydroxyl groups of 0.05 to 0.5 equivalent are mixed until the reaction rate of the epoxy groups and hydroxyl groups becomes 80% or more, bisphenol A and formaldehyde. The phenol resin (B) having a molecular weight of 1.000 or more and 10.000 or less, which is a polycondensation product, is 0.7 to 1.2 equivalents of the hydroxyl group of the phenol resin (B) to 1 equivalent of the epoxy group terminal of the polyfunctional epoxy resin (A). 1 to 60 parts by weight of a linear polymer (II) having a molecular weight of 5.000 or more and 100.000 or less compatible with the composition (I) is added to 100 parts by weight of the composition (I). And linear polymers By those using phenoxy resin Te, along with the cured product excellent in heat resistance conventional level, flexibility, moisture resistance,
A laminate composition having excellent mechanical strength, toughness and adhesiveness can be obtained.

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H05K 1/03 D 7011-4E (72) Inventor Mitsuhiro Nogaki 8-1-1 Tsukaguchihonmachi, Amagasaki City, Hyogo Prefecture Production Engineering Laboratory, Ryoden Electric Co., Ltd. (72) Takumi Kikuchi, 8-1-1 Tsukaguchi Honcho, Amagasaki City, Hyogo Sanryishi Electric Co., Ltd., Production Technology Laboratory (56) Reference JP-A-2-283717 (JP, JP, A) JP 57-141419 (JP, A) JP 63-264622 (JP, A) JP 60-260627 (JP, A) JP 1-135884 (JP, A) JP 64 -6018 (JP, A) JP-A-63-146918 (JP, A)

Claims (2)

[Claims] 1. A general formula (Wherein R is H or CH ₃ , and m is an integer from 0 to 5), the polyfunctional epoxy resin (α1) is represented by the general formula (In the formula, n is an integer of 0 or more, X is bromine or H, a is an integer of 1 to 4) and a bisphenol A type epoxy resin (α2) is blended at a weight ratio of 100: 0 to 30:70. Chemical formula for epoxy resin composition (α) (In the formula, b is an integer of 1 to 4) brominated bisphenol A (β) is a hydroxyl group of the brominated bisphenol A (β) with respect to 1 equivalent of epoxy group terminal of the epoxy resin composition (α). Polycondensation of bisphenol A and formaldehyde with a polyfunctional epoxy resin (A) obtained by reacting a composition blended in a ratio of 0.05 to 0.5 equivalents until the reaction rate of epoxy groups and hydroxyl groups becomes 80% or more. The ratio of the phenolic resin (B) having a molecular weight of 1.000 or more and 10.000 or less, which is 0.7 to 1.2 equivalents of the hydroxyl group of the phenol resin (B), relative to 1 equivalent of the epoxy group terminal of the polyfunctional epoxy resin (A). 1 to 60 parts by weight of a linear polymer (II) having a molecular weight of 5.000 or more and 100.000 or less compatible with the composition (I) blended with 100 parts by weight of the composition (I) blended in 1. Resin composition. 2. The resin composition for laminates according to claim 1, wherein the linear polymer is a phenoxy resin.