JPH0379621A - Resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain a resin composition for laminate, having excellent heat resistance, toughness, adhesiveness, etc., by blending a specific polyfunctional epoxy resin with phenol resin to give a composition and mixing the composition with specific straightchain polymer. CONSTITUTION:100 pts.wt. composition which is prepared by blending a polyfunctional epoxy resin shown by the formula (R is H, CH3, etc.; X is H or Br; m is 0-5) with a phenol resin (preferably polycondensate of bisphenol A and formaldehyde having 1,000-10,000 molecular weight) in the ratio of 0.7-1.2 equivalent hydroxyl group of the phenol resin based on 1 equivalent end epoxy group of the polyfunctional epoxy group is mixed with 1-100 pts.wt. straight- chain polymer (preferably polyparabanic acid) having 5,000-100,000 molecular weight to give a resin composition for laminate. In order to further improve heat resistance and mechanical strength of the composition, the composition may be incorporated with a bismaleimidotriamine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of application above 1i] The present invention relates to a resin composition with IV% resistance for use in pile-up plates.

[Conventional technology]

The elongation of 11N for laminates, especially W4-clad laminates, is large, and by combining the base material and thermosetting resin, copper-clad laminates that meet various purposes can be obtained. Paper-based phenolic resin steel-clad laminates are the main packaging materials for consumer electronic devices such as color televisions and audio equipment, as well as computers and manipulators.

In the field of industrial electronic equipment such as measuring instruments, Ganis base material poxy resin steel laminate is mainly used.

However, as high-density wiring and multilayering progress, conventional glass-based epoxy resin copper-clad laminated sheets cannot meet the required specifications in terms of dimensional stability and heat resistance. The development of copper-clad laminates with excellent properties has been attempted.

An example of a copper-clad laminate with excellent heat resistance is 1, for example, Tokko Sho IQ.
As shown in Publication No.-21i423.

It is known that S? It has characteristics such as a high glass transition temperature and poor dimensional stability during heating.

[Problem to be solved by the invention]

However, the polyimide resin has high hygroscopicity.

There is a problem with dimensional stability under moist heat, and polar solvents with high boiling points are used as solvents during prepreg production, so solvents are used during lamination molding! 5! However, there are drawbacks such as tV, which tends to be mixed easily and causes variations in quality, and it has been a challenge to solve these problems.

The present invention has been made to solve this problem, and its value product has excellent #Ik1@ properties as well as crab rice, as well as excellent toughness and adhesive properties. The object of the present invention is to obtain a resin composition for a laminate that exhibits the following characteristics.

Another object of the present invention is to obtain a resin composition for a laminate having excellent toughness and adhesiveness.

In addition to the above-mentioned objects, still another aspect of the present invention can provide a moisture-resistant and mechanically crushed wood B'ft composition for dovetail boards.

[Means to solve Ken S]

The resin composition for laminates of the present invention is a multifunctional epoxy resin (α) represented by the formula (where R is H or C11, X is Br or H, and m is a number from a to 5). To, phenol tree JJ! (β), the above polyfunctional epoxy resin (α)
A composition (1) in which the hydroxyl group of the phenol resin (β) is blended in a ratio of 0.7 to 1.2 equivalents to the epoxy group Sung 1211i11 equivalent of 9 molecular weight s, ooo to 100]i parts Too, ooo linear polymer (A)
t' 1 to 100 weight tS is blended.

A resin composition for a laminate according to another aspect of the present invention includes S? The polycondensate of bisphenol A and formaldehyde (β1) is used as the phenolic resin (β).
) with a molecular weight of 5,000 to 0,000.

A resin composition for a laminate according to still another aspect of the present invention is a polyfunctional epoxy resin represented by the formula (wherein R is H or CJ (51 In the resin (α), the hydroxyl group of the phenol resin (β) is Q, T ~ 1.2 equivalents per 1 equivalent of the epoxy group terminal of the phenol resin (β) t-1 the above polyfunctional epoxy resin (α). For 100 parts of composition (1) blended in the ratio,
Bismaleimidotriazine compounds.

Alternatively, 10 to 2 (to A composition containing 1 to 100,000 OOC1 (1 to 100 parts by weight of @-shaped polymer (A) t) is prepared.

[Effect]

In the present invention, by reacting the polyfunctional epoxy resin mainly with the phenol resin, the degree of n and smm is increased and the heat resistance is improved, while the fruit network #II! By interposing a linear polymer as a flexible component,
II! The composition can be made to have toughness and one-piece wearability.

According to another invention of the present invention, polycondensation q! of phenol 1M fat, sinabisphenol A, and formaldehyde is performed. 1I
By using T-, toughness and adhesiveness can be further improved.

Furthermore, in another invention of the present invention, by adding a bismaleimide triazine compound or a pre-reaction composition of a bismaleimide compound and an aromatic diamine compound,
In addition to the above effects, heat resistance and machining strength can be further improved.

〔Example〕

The polyfunctional epoxy resin represented by the general formula according to the present invention (wherein RFi■ or 03. (Dow Chemical Il, trade name 5PPM502 (Nippon Kayaku Jl)
, and those synthesized by the inventor of the present invention as shown in the Examples below are used.

Here, 1m is an integer from O to 5 (If), m is 5
If it exceeds this, the viscosity will increase and impregnation into the base material during the production of prepreg for laminates will be insufficient.

The phenol resin according to the present invention is not particularly limited, but phenol novolak resin (for example, the product name PS
F4281 (Gunei Chemical IM), YLH-129 (
Yuka-7xh), pz-600o (Hitachi Chemical all
)), cresol novolak resin, alkyl-modified phenol novolak am, bisphenol A type phenol novolak Jugetsuji, etc.

These may be used alone or in combination of two or more. In particular, the phenol resin used for preliminary reaction with the epoxy group of the silicone compound having the epoxy group f: is preferably one having a softening point of 60 to ttot. Also 2
The phenol content related to another invention of the present invention is 1
%, polycondensate (β1) of bisphenol A and formaldehyde 1, for example, KP-rssp (trade name: Arayo Kagaku Kogyo) YLH-128 (@product name: Yuka Shell Co., Ltd.) and as shown in the examples below. The one synthesized by the inventor is used.

Here, top f! The molecular weight of phenolic resin is 1.000~
If it is less than 1,000, the toughness will be poor, and if it exceeds IILOOO, the viscosity will be too high, resulting in insufficient impregnation into the base material during the production of prepreg for laminates.

Examples of linear polymers according to the present invention include polyparabanic acid, polyethernulphone, and polysulfone.

Polyetherimide, polyphenylene sulfide.

As the phenoxy resin, liquid crystal polymers such as wholly aromatic borie ether are preferably used. Molecular weight is usually s, oo
O or above 10G, ODD or below is 1 better” @ s, 000
If the amount is less than 10, the effect of imparting flexibility by the polymer cannot be obtained, and if it exceeds 10 (LOOO), the viscosity increases and impregnation becomes insufficient. (1) 1 to 100 weight i11 for 10031 children
However, if the amount of the mixture is not the same.

The effect of adding flexibility is not sufficient! Total IC amount is 10
If it exceeds 0'J11111fll, the resin viscosity will increase to D.
In the past, the impregnation of the base material during the production of prepreg for skin absorption was insufficient.

What is the blending amount of the polyfunctional epoxy resin and phenol resin to obtain composition 0) according to the present invention?

For 1 equivalent of the epoxy basic end of the above polyfunctional epoxy resin, the hydroxyl group of the phenol resin is Q, T ~ 1.2 equivalents υ
, o, and y equivalents, unreacted epoxy groups remain, resulting in poor heat resistance.If it exceeds 11.2 equivalents, phenol resin that does not participate in the two reactions remains, resulting in poor moisture resistance and heat resistance.

As the bismaleimide triazine compound according to still another invention of the present invention, BT-2070, BT-20TT
, BT-21Go, BT-2108, BT-21To.

BT-2116, BT-2177, BT-2400, B
T-2401, BT-2600, BT-2806, B
T-2J100° BT-3104, BT-3404 (all manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc. were melted, and as a bismaleimide compound, 4. ．． 4'-bismaleimidodiphenyl/ / 4,4'-bismaleimidodiphenyl ether, 4.4'-bismaleimidodiphenyl sulfone, 3.3'-pinemaleimidodiphenylmethane.

3.3'-bismaleimide diphenyl ether j 31
Examples include 3'-bismaleimide diphenyl sulfone.

Examples of aromatic diamine compounds to be pre-reacted with these bismaleimide compounds include diaminodi7-dyl ether, diaminodiphenylmethane, diaminodiphenylnurphone, and diaminobenzani! j)', p-phenylenethiane, 1m-phenylenediamine, dibromdiaminodiphenylmethane.

Dichlordiaminodiphenylmethane, diaminobenzoguanamine, nato-2bromodiminodiphenylmethane, 4
-7 Minobenzoic acid hydrazide etc. are rejected.

The amount of the aromatic diamine compound preliminarily reacted with the bismaleimide compound to prepare the imide composition is 0.3 to 1.0% per mole of the bismaleimide compound. (1 mole is 1
l-1<, 11 If the amount is less than 3 moles, unreacted bismaleimide compounds remain and are not dissolved in general-purpose low-boiling bath additives. Also, if it exceeds 11 moles.

If the aromatic diamine compound is unreacted and used as a curing agent for an ab or polyfunctional epoxy compound, the pot life will be shortened, which is undesirable.

The imide composition, which is one of the imide compositions used in yet another aspect of the present invention, is produced by preliminarily reacting a bismaleimide compound and an aromatic diamine compound. After putting it in a low-boiling bath with a temperature of 5, it is heated to 80C under a nitrogen atmosphere.
11011: by reacting for 2 to 4 hours and precipitating the bath solution in water or the like. The amount of the imide composition or bismaleimide triazine compound thus obtained is 18 to 200 parts by weight per 100 weight and 111 flll of composition (1) containing a polyfunctional epoxy compound and a 7-enol resin. , WIL, 10: * * * The same as above for heat resistance is not recognized, 20011
When the amount St'' is exceeded, heat resistance improves, but moisture resistance improves.

Mechanical properties, especially adhesive strength, are reduced.

One of them is a resin composition for a laminate according to an example of the present invention.

An imidazole compound may be contained for the purpose of accelerating the curing reaction. The imidazoles used as a curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-7dynylimidazole, 2-undecylimidazole, and 2-heptadecyl. Examples include imidazole. or.

The self-load of imidazoles is determined by two compositions (1) and (1).
Seal) 0.00 for 100JIJiffll. (N ~ (L
The range is preferably 3fiJ1 part 0. If ao1@ is less than 1, the reaction rate will be slow and it will be difficult to control the fIt dynamics of the resin when preparing prepreg ε for a laminate. Also.

If it exceeds 0.3 parts, the pot life will be shortened when used as a laminated pulley preg.

The resin m-acid for laminates thus obtained is as follows.

It is commonly used in prepreg production as a resin liquid at a predetermined concentration by dissolving it in a bath agent as shown in the conventional method.

The bath agents used here include alcohols such as ethyl alcohol, flobyl alcohol, and methyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate nato ethylene glycol, ethers of diethylene glycol and their tDeI! Solvents such as esters are preferably used, but amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and polar solvents such as N-methylpyrrolidone and dimethylsulfoxide can also be used. Furthermore, these solvents may be used alone or in combination of two or more.

In addition, as mentioned above, steel clad laminates have the upper IIC! A resin composition for laminates is applied to a predetermined base material, impregnated and dried to form a Gripreg, and a steel foil is superimposed on the Gripreg, heated and pressed.

The base material that can be used here is generally glass fiber, but aromatic polyamide II fiber can also be used.
Also matte glass, polyester.

Aromatic boria curves can also be used.

Laminate resins are usually applied to the substrate at room temperature and have a
01: for 1 to 20 minutes to obtain a prepreg. A predetermined number of prepreg sheets are stacked together.

2 usually 80r~2 with steel foil layered on at least one side
50 t', a pressure of 5 to 100 kx/d, and 10 to 300 minutes of force n to form a steel clad laminate. The conditions shown here are one example, but the conditions are not limited to this.

The laminates obtained from the m-lipid compositions of Examples of the present invention have excellent heat resistance, soldering heat resistance, electrical properties, and mechanical properties.2 They are suitable for use, for example, in high-density multilayer applications. Hereinafter, the present invention will be explained in detail with reference to two examples.

implementation? 111゜Multifunctional epoxy resin represented by the following formula (trade name: TACTIX-
Composition containing 142 Dow Chemical Ifri ssp and 7 enol citrus oil (trade name PSF-4261% manufactured by Sakae Chemical Co., Ltd.) asp (y enol hydroxyl group/epoxy group equivalent ratio: O, T) @ (1) 100 # , polyparabanic acid 15g
(Product name XT-4) [manufactured by Natural Oil Co., Ltd.] and 2-ethyl-4
-Methylimidazole (Llft-formulated).

A resin composition for a laminate according to an embodiment of the present invention containing ethylene glycol monomethyl ether 5Of tocyclohexanone 5oyKttxs and a 59# concentration li! 21t'' was obtained.

This was impregnated and dry woven into a 0.18 m thick glass woven fabric to form an I
IJJ! Gripreg with a content of 50 Jlfi* was obtained. Four sheets of this Gripreg were stacked and press-molded with 35 μm copper foil interposed on both sides. The molding conditions are press temperature 111
Or, the press pressure was 40 to 40, and the press time was 90 minutes. The evaluation results for the q15 physical and 1 mm temperamental properties of steel clad laminates are shown in the table.

Example 2 Multifunctional epoxy resin (ffl=1) shown by the following formula (trade name EPPN502 Nippon Kayaku! 1it) 57# and phenol resin (trade name pz-sooo Hitachi Kaoru) 4ap()i
Nordic hydroxyl group/epoxy group equivalent ratio: 0.95)
Composition (1) containing 100 IF and 2 molecules fi3
0.0o.

A mixture of phenoxy resin 1 (trade name: PKI (manufactured by H Union Carbide) and 0.1 jlt of 2-ethyl-4-methylimidazole, dissolved in ethylene glycol monomethyl ether 80 I, and a 58# concentration Another example of the present invention was obtained.

This is glass with a thickness of 0.181111 #! A resin-containing prepreg with a weight of 1,150 kg was obtained by impregnating and converting the resin.

This prepreg T-4 material was then press-molded with 35 μm copper foil interposed on both sides. The molding conditions are press temperature 1
80'c, press pressure a Okg/d, press LI
It was assumed that X hours were sO minutes. The evaluation results for the physical and electrical properties of the steel clad laminate are shown in Table 1.

Examples & The following formula is shown (m=33 polyfunctional epoxy shelf fat T111 and 7
Enol resin (product name YL) I-129 manufactured by Yuka Shell)
Composition (1) 1001 containing 29g of polyether sulfone 157 (trade name Victoretsukunu 1.C,
I Japan) and 2-ethyl-4-methylimidazole 0.1 f't-, ethylene glycol monomethyl ether 50# and N,N-dimethylformamide 3 (
A phenol for a laminate according to another example of the present invention was obtained with a temperature of 511,411 degrees.

The method for producing a polyfunctional epoxy resin represented by the above formula involves mixing 384 parts of parabromophenol and 61 parts of salicylaldehyde with 1 ml of a-salt. Q, in the presence of 3 parts, 30 at 100
After reacting for a minute, 0.5 part of p-toluene sulfonic acid was added and reacted with 111017 for 2 hours to form the following formula.

(m=3) A polyphenol represented by the following is obtained. It is obtained by reacting 110 parts of this polyphenol with epichlorohydrin 740fiftSk according to a conventional method.

The above resin composition was impregnated into a glass woven fabric having a thickness of a and 18 mm and dried to obtain a Gripreg having a resin content of 50 weights and 1 m.

Four sheets of this prepreg were stacked and press-molded with 35 μm steel foil interposed on both sides. What are the molding conditions?

Press temperature treat', press pressure 4 (1 kg/d,
The pressing time was 90 minutes. The table shows the evaluation results regarding the physical and electrical properties of the steel clad laminate.

Polyfunctional epoxy resin (trade name: EP
PN502 Nippon Kayaku 1! f) Bisphenol A in 6ny
Composition containing 5 syt of novolac type 7 enol resin (1) 1 molecule in 1001 [3000G phenoxy resin (product name: PKHH Union Carbide) 1 (1
, $- and 2-ethyl-4-methylimidazole 0.1
ft blended with ethylene glycol monomethyl ether 8
A resin composition for a laminate according to another embodiment of the present invention having a flaw density of 58 was obtained.

The above bisphenol A novolac type 7 enol resin was prepared by putting 100 parts of bisphenol A, 22 parts of 37g6 formaldehyde, and 1 part of shu into a flask with a cooling tube and stirring am, refluxing for 2 hours to react, and then dehydrating and concentrating. I got it good.

A lath woven fabric having a thickness of 0.111 fl was impregnated with the above resin composition and dried to obtain a prepreg having a resin content of 50% by weight.

Four sheets of this prepreg T- were stacked and press-molded with 35 μm copper foil interposed on both sides. What are the molding conditions?

The press temperature was 18 (1), the press pressure was 40 kg/d, and the press time was 90 minutes. The evaluation results for the physical and temperamental properties of the steel clad laminate are shown in the T-table.

Examples & Multifunctional epoxy resin represented by the following formula (trade name: TACT
4 .Imide composition obtained by reacting 4'-bismaleimide diphenylmethane and diaminodiphenyl ether in a dioxane solvent at a molar ratio of 1:11.70 at 80'C for 3 hours CB) 1oot, molecular mouth so, o o o 7C/Xia fat 35F (A)
, > and 2-ethyl-4-methylimitasole a, 1
ptfit and dissolved in ethylene glycol monomethyl ether 1331 to obtain a resin composition for a laminate according to another embodiment of the present invention having a concentration of 60% by weight.

This was impregnated into a glass fiber cloth with a thickness of 0.18 mm and dried.
A fat-containing J148 heavy prepreg was obtained.

Four sheets of this prepreg T- were stacked and press-molded with 35 μm steel foil interposed on each side. The molding conditions are press temperature R
tsot'', press pressure a O#/de press time 60 minutes.Physical properties of the obtained copper clad laminate.

The evaluation results for electrical properties are shown in the table.

Examples Multifunctional Evo Life Resin (trade name EP) shown in the following formula (m=1)
PN-502PPN-502 Nippon Chemical, phenolic resin (product name PSF-4261n manufactured by Eikagaku Co., Ltd.) se p (
Composition (Summer) 10 (IK, 4°4'-bismaleimide diphenyl ether and diaminodiphenylmethane in a tetrahydrofuran solvent at a 1:Q, 30 molar ratio) containing a phenolic hydroxyl group/epoxy group equivalent ratio: t, o) 1ia1: Imide composition (B) 10F obtained by reacting for 2 hours, polystyrene with a molecular weight of 15.000 (A
) 501. and 0.1f of 2-ethyl-4-methylimidazole, dissolved in ethylene glycol monomethyl ether T3f, and having a concentration of 60 weight 1 iq6, a resin composition for a laminate according to another embodiment of the present invention. I got it.

This was impregnated into a glass woven fabric of thickness (Lllo) and dried to obtain a prepreg with a resin content of 52 double corrosion. Four sheets of this prepreg T-4 were stacked and press molded with 35 μm 041A foil on both sides. Molding conditions The press temperature is 180℃,
The press pressure was aom/da and the press time was 60 minutes. The evaluation results regarding the physical and electrical properties of the obtained copper-clad J-board are shown in the table.

Example 7゜Multifunctional epoxy a! ! 11w (product name TACTIX-7
Composition (1) 1001!42 Dow Chemical Company g) s4p and phenolic resin (trade name YLH-129 Yuka Shell Company 1111) 36F (phenolic hydroxyl group/epoxy group equivalent ratio: O, S) a, 4/-bismaleimide diphenyl ether and diaminodiphenylmethane in a 1:1 molar ratio of 100'r in dioxane solvent.
:, imide composition obtained by reaction for 2 hours (B) tsop
, molecular weight S & OOQ (D 7 x / * resin (A) 100 #, and 2-methylimidazole Q
, 15F, methyl ethyl ketone 150f and N,
Dissolved in N-dimethylacetamide 551,
A resin composition for a laminate according to still another example of the present invention having a weight silver concentration was obtained.

This was impregnated into a lath woven fabric of 18 cm and dried to obtain a prepreg with a resin content of 46 weight. Four sheets of this prepreg were stacked and press-molded with 35 μm copper foil interposed on both sides. The molding conditions were a press temperature of 200° C., a press pressure of goiq/ci#, and a press time of 90 minutes. Physical properties of the resulting **laminates.

The evaluation results for electrical properties are shown in the table.

Examples & Multifunctional epoxy resin (trade name: YL) represented by the following formula (m=1)
-8048 Yuka Shell Co., Ltd.) 74F and phenol resin (
Composition (1) containing 26 g of bismaleimide triazine resin BT-2077 (product name: pz-aooa, manufactured by Hitachi Chemical Co., Ltd., equivalent ratio of phenolic hydroxyl group/epoxy group: 20.8) (product name: pz-aooa, manufactured by Hitachi Chemical Co., Ltd.) (produced by Mitsubishi Gas Chemical Co., Ltd.) at 10 m+. (B) 2001. Borinoculanic acid (A)
85 F, > and 2-methylimidacillin 0.21
Contains Yt, methyl ethyl ketone 821. N.

# to N-dimethylformamide 1001! Let me understand.

A resin composition for a laminate according to still another example of the present invention having a weight density of 65% was obtained.

This thickness is α11. A prepreg with a resin content of 53% by weight was obtained by impregnating and drying all of the galanu cloth. Press molding conditions were the same as in Example 3. The results of the characteristic evaluation of the obtained steel clad laminate are shown in the table.

What color polyfunctional epoxy resin (product name EPPN-502PPN-
502 Nipponka Upper 7 Enol Resin (Product Name: Pz-sooo
Composition (1) containing 43N (manufactured by Hitachi Chemical Co., Ltd.) (phenolic hydroxyl group/epoxy group equivalent ratio: QJ5)
For Too f, 3,3'-bismaleimidodiphenylmethane and dibromdiaminodiphenylmethane in tetrahydro7 run solvent? : Sot' at 0.70 molar ratio
, imide composition (B) Sol, which was reacted for 3 hours.
Polyphenylene sulfide (A) 10#, t? and 2-
Ethyl-4-methylimidacylin o, ts If: Blend and dissolve in methyl ethyl ketone 1501, 5Q
A resin composition for a laminate according to another example of the present invention having a fiii* concentration was obtained.

This was impregnated into a 0.18-meter-thick thick fabric and dried to obtain a prepreg with a resin content of 43 weight and corrosion. Four sheets of this prepreg were stacked and press-molded with 35 μm O copper foil interposed on both sides. The molding conditions were a press temperature of 18011:, a press pressure of 401 s/Cjl*, and a press time of 60 minutes. Physical properties of the resulting copper-clad laminates.

The evaluation results for electrical properties are shown in the table.

Example 1G.

Polyfunctional epoxy resin (product name YL-6046 Yuka Shell Co., Ltd. 11j) 71F and phenol resin (product name YLH-1
29 Enolic water H1 group manufactured by Tsukuda Shell Co., Ltd. /
Composition t@(1
) 100 jF, bismaleimide triazine resin BT-3104 (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

Product name) 801. Polyether sulfone (A) 50p
,>yo01-benzy-2-methylimidazole015
N was blended and methyl ethyl ketone 71001° methyl inbutyl ketone 3 (l) was added to ms4 to obtain a resin composition for a laminate according to still another embodiment of the present invention having an excellent concentration of 58 g.

This was impregnated into Saisa Q, 111 Peng glass cloth and dried.
A prepreg with a fat content of 151% by weight was obtained.

Four sheets of this prepreg T- were stacked and press-molded with 35 μm O steel foil interposed on both sides. The molding conditions are press temperature 1
The pressure was 110 r, the press pressure was 40 m/a, and the press time was 9 a minute. Physical properties of the obtained steel clad laminates.

The evaluation results for electrical properties are shown in the t-table.

Comparative example 1゜Epoxy resin (W7JA name Epicor) 5041iB-8
Dicyandiamide 2L2- to 1251
Process ethyl-4-methylimidazole 0.151,
It was dissolved in ethylene glycol monomethyl ether 659 to obtain a resin composition for a laminate having a torsion of 53i11[i*.

This was impregnated into a galanu woven fabric having a thickness of 0.18111 m and dried to obtain a prepreg T having a resin content of 4rllfi.

Four sheets of this prepreg were stacked and press-molded with 35 μmowA foil interposed on both sides. M, shape condition is press 1l
i170t', 2res pressure 40 kv'd, 7
The response time was 60 minutes.

Physical and temperamental properties of the obtained copper-clad laminates are shown in Tables 1 and 2.

Comparative Example 1 Polyimide resin (@product name Kelimide 601 manufactured by Nippon Polyimide) 100 f'iN-methylpyrrolidone 100j
A resin composition for laminates having a concentration of 50 fi x 96 was obtained.

This was impregnated into a glass woven cloth with a thickness of 01800, and it was
After drying for 0 minutes, prepreg T- with a resin content of 45% by weight was obtained.

Four sheets of this prepreg were stacked and heated and pressed at 22 Or, lkx/d, for 110 minutes with copper foil of 35 μm on each side interposed, to obtain a 1-board. Table 1 shows the evaluation results of the obtained steel clad laminates.
, 2.

As shown in the examples on the board, the resin composition for a laminate according to an example of the present invention has heat resistance to the same extent as conventional resin compositions, and is excellent in @ properties and adhesive properties. Further, the resin composition for a laminate according to another embodiment of the present invention has excellent toughness p and adhesiveness in addition to the above-mentioned durability.

In addition to the above-mentioned effects, the resin composition for 541-board according to still another embodiment of the present invention has excellent moisture resistance and mechanical strength.

〔Effect of the invention〕

As explained above, the present invention is a polyfunctional epoxy resin (α) represented by the general formula (where R is H or CHI, X is Br or H, and m is !II from O to 5).
phenol resin (β) t-1 per equivalent of the epoxy group terminal of the above polyfunctional epoxy resin (α).

A composition (i) in which the hydroxyl groups of the phenol resin (β) are blended in a ratio of Q, T to 1.2 equivalents, with a molecular weight of 2 to 10 parts by weight L000 to 10Q, 0000 orthogonal polymer (A) l to 100 parts by weight. By using a compound containing 100 parts by weight, the cured product has the same excellent heat resistance as conventional products, as well as excellent toughness and adhesive properties, and has excellent properties when used in copper-clad laminates, for example. It is possible to obtain a resin composition for a laminate having the following properties.

Another invention of the present invention relates to the above invention.

As a phenol resin, a polycondensate of biphenol A and formaldehyde with a molecular weight of 1.0 OO to
By using a resin composition of o o o, it is possible to obtain a resin composition for a laminate having excellent toughness and adhesiveness.

9 Still another invention of the present invention is a polyfunctional epoxy resin (α) represented by the formula (wherein R is H or (:□5*XriH or Br, m is l1ll [) from O to 5) Then, add phenol 4l! fat (β) to the epoxy basic fine 1 of the above polyfunctional epoxy resin Ca).

The hydroxyl group of the phenol resin (β) is 0. Composition (1) blended at a ratio of T ~ 1.2 teeth per 1001 parts to 9 molar ratio of the bismaleimide triazine compound or the bismaleimide compound and the bismaleimide compound!
Aromatic diamine compound f of 0.3 to 1.0: Imide Iia or product (B) made from a pre-reacted composition
t 10-200
2) In addition to the effects of the present invention, by using a monochain polymer (A) containing 1 to 100 parts by weight,
Furthermore, it is possible to obtain a resin composition for a wooden deck which is excellent in moisture resistance and stability.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is H or CH_3, X is Br or H, m is an integer from 0 to 5) polyfunctional epoxy resin (α)
A composition in which the phenolic resin (β) is blended in a ratio such that the hydroxyl group of the phenolic resin (β) is 0.7 to 1.2 equivalents per 1 equivalent of the epoxy group end of the polyfunctional epoxy resin (α). For 100 parts by weight of substance (I), molecular weight 5,
000 to 100,000 linear polymer (A) to 1 to 1
00 parts by weight of a resin composition for laminates. (2) Phenol resin (β) is a polycondensate of bisphenol A and formaldehyde (β_1), with a molecular weight of 1.0
00 to 10,000, the resin composition for a laminate according to claim 1. (3) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or CH_3, X is H or Br, m is an integer from 0 to 5) Polyfunctional epoxy resin (α)
A composition in which the phenolic resin (β) is blended in a ratio such that the hydroxyl group of the phenolic resin (β) is 0.7 to 1.2 equivalents per 1 equivalent of the epoxy group end of the polyfunctional epoxy resin (α). The molar ratio of the bismaleimide triazine compound or the bismaleimide compound and the bismaleimide compound to 100 parts by weight of compound (I) is 0.3 to 1.
A composition (I) containing 10 to 200 parts by weight of an imide composition (B), which is a composition prepared by pre-reacting an aromatic diamine compound having a molecular weight of 5,000 to 100, is added to the composition (I).
,000 linear polymer (A) in an amount of 1 to 100 parts by weight.