JPH0732547A - Heat resistant laminate - Google Patents

Abstract

PURPOSE:To provide a laminate which is superior in solder heat resistance and adhesion with a glass cloth by applying a resin composition of which the major component is a polymaleimide compound, and for which a silane compound with a maleimido group represented by a specified formula or other specified formula is blended. CONSTITUTION:A resin composition is obtained by blending a silane compound with a maleimide group represented by a formula I and/or a silane compound with a maleimide group represented by a formula II to a thermosetting resin composition of which the major component is a polymaleimide compound. A prepreg is made by impregnating the obtained resin composition on a glass cloth. A plurality of the prepregs are laminated, pressurized and heat-molded to obtain a heat resistant laminate. R1 in the formula I and formula II shows 1-4C alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having excellent heat resistance and adhesiveness with glass cloth.

[0002]

2. Description of the Related Art Laminates used as printed wiring boards for industrial equipment, electronic equipment and the like have a base material such as glass cloth or paper in which a thermosetting resin such as epoxy resin or polyimide resin is dissolved in an appropriate solvent. The varnish is impregnated and dried to volatilize the solvent to make a prepreg. Further, a predetermined number of the prepregs are stacked, a metal foil such as a copper foil is stacked on one side or both sides, and integrally cured and formed under heating and pressurization. 2. Description of the Related Art In recent years, printed wiring boards have been required to have higher wiring density and higher number of layers, and the heat resistance of laminated boards has been increasing. A large number of resin compositions mainly composed of a polymaleimide resin have been proposed as a resin for a laminated plate which requires such high heat resistance. Examples thereof include French Patent No. 1455514, Japanese Patent Publication No. 46-23250, and Japanese Patent Application Laid-Open No. 61-200149. Further, in order to improve the brittleness and processability of the polymaleimide compound, it has been proposed to use a polyepoxy compound in combination with the polymaleimide compound (Japanese Patent Publication No. Sho 4).
7-42160).

[0003]

It is considered that the laminated plate produced from the resin composition containing these polymaleimide resins as the main component has a high glass transition point and is apparently excellent in heat resistance. However, the laminated plate is a composite material of glass cloth and resin, and a silane coupling agent is generally used to enhance the adhesiveness between the glass cloth and the resin. Specifically, the glass cloth is preliminarily treated with a silane coupling agent such as epoxysilane or aminosilane and impregnated with a resin to produce a prepreg. However, since these silane coupling agents are poor in water resistance and heat resistance, the adhesiveness at high temperature is remarkably deteriorated, and especially when exposed to high temperature in a hygroscopic state, the interface between the glass cloth and the resin peels off and the laminated There is a problem that blisters occur on the surface of the plate. The present invention has been made in view of the above circumstances, and provides a heat-resistant laminate having improved adhesiveness between glass cloth and resin and excellent solder heat resistance.

[0004]

In order to solve the above-mentioned problems, the present inventors have studied a coupling agent having excellent water resistance and heat resistance, and as a result, by using a silane compound having a maleimide group, The present invention has been completed by completing a heat resistant laminate having excellent solder heat resistance. That is, the present invention provides a thermosetting resin composition mainly composed of a polymaleimide compound, a silane compound having a maleimide group represented by the following general formula (1) [Chemical Formula 3], and / or a general formula (2) below. Heat resistance characterized by being formed by laminating a plurality of prepregs obtained by impregnating a glass cloth with a resin composition containing a silane compound having a maleimide group represented by [Chemical Formula 4] Laminated plate. Alternatively, a thermosetting resin composition containing a polymaleimide compound as a main component is prepared by preliminarily preparing a silane compound having a maleimide group represented by the following general formula (1) [Chemical formula 3] and / or a general formula (2) [Chemical formula (2) 4]
The heat-resistant laminated plate is characterized in that a plurality of prepregs impregnated with a glass cloth surface-treated with a silane compound having a maleimide group are laminated and pressure-heated.

[0005]

[Chemical 3] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms)

[0006]

[Chemical 4] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms.) The thermosetting resin composition mainly comprising the polymaleimide compound according to the present invention is a thermosetting resin composition comprising a polymaleimide compound and a polyamino compound. Or a thermosetting resin composition composed of a polymaleimide compound and a polyepoxy compound, or a polymaleimide compound, a thermosetting resin composition composed of a polyamino compound and a polyepoxy compound, preferably in a thermosetting resin. It contains 30% by weight or more of a maleimide compound. If the polymaleimide compound is less than 30% by weight, the glass transition temperature is low and good solder heat resistance cannot be obtained. As the polymaleimide compound, any compound having two or more maleimide groups in one molecule can be used. For example, the general formula (3)
[Chemical 5];

[0007]

[Chemical 5] (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a direct bond, —CH ₂ —, —CO—, —SO ₂ —, —SO—, —S—, —O
-Or represents a cycloalkyl group. n represents 0 or 1. ), Bismaleimide compounds represented by the following, more specifically, N, N'-4,4'-diphenylbismaleimide, N, N '
-(1,3-phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-
Maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfine, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-
Examples thereof include bis (4-maleimidophenyl) cyclohexane. In addition, general formula (4) [Chemical formula 6];

[0008]

[Chemical 6] (In the formula, Y represents a divalent organic group having at least one substituted or unsubstituted aromatic ring.) A more specific example is 1,3-bis (4-maleimidophenoxy). ) Benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [ 4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1, 2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [
4- (4-maleimidophenoxy) phenyl] propane, 2,
2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl]
Butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4
-(4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-maleimidophenoxy) biphenyl, 4,4'-bis (4-maleimide (Phenoxy) biphenyl, bis [4- (3-maleimidophenoxy)
Phenyl] ketone, bis [4- (4-maleimidophenoxy)
Phenyl] ketone, bis [4- (3-maleimidophenoxy)
Phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-
Maleimidophenoxy) phenyl] sulfone, bis [4-
(3-Maleimidophenoxy) phenyl] ether, bis
[4- (4-maleimidophenoxy) phenyl] ether, 1,
4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4- Screw
[4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy)-
α, α-Dimethylbenzyl] benzene, 1,4-bis [4- (4-
Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1 , 4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl- α, α
-Dimethylbenzyl] benzene and the like. Furthermore,
General formula (5) [Chemical formula 7];

[0009]

[Chemical 7] (In the formula, Z represents a methylene group or a p-xylylene group, m represents a number of 0 to 5 not including 0.) More specifically, such a polymaleimide compound is exemplified. The compound is a polymaleimide compound obtained by subjecting a polyamine, which is a reaction product of aniline and formaldehyde, or a reaction product of α, α′-dichloro-p-xylene, and maleic anhydride to a condensation / dehydration reaction under an acidic catalyst. These bismaleimide compounds or polymaleimide compounds may be used alone or in combination of two or more.

As the polyamino compound, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1'-bis (4-
Aminophenyl) ethane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4 -(3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3 -Aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) 1,3-dichloro-1,1,
3,3-Tetrafluoropropane, 4,4'-Diaminodiphenyl ether, 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfoxide, 4,4'-Diaminodiphenyl sulfone, 3,3'-Diamino Diphenyl sulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone and the general formula (6) [Chemical formula 8];

[0011]

[Chemical 8] (In formula, A shows a methylene group or a p-xylylene group. P shows the number of 0-5.) It is a polymaleimide compound represented by these. As the polyepoxy compound, all epoxy compounds having two or more epoxy groups in the molecule can be used. As an example of such an epoxy compound,
Phenols such as phenol, cresol, resorcinol, and naphthol, or phenols obtained by halogenating these, formaldehyde, acetaldehyde,
An epoxy resin obtained by reacting a reaction product obtained by a condensation reaction with an aldehyde such as benzaldehyde, hydroxybenzaldehyde, tolualdehyde, glyoxal, and alkanedial with epichlorohydrin. Epoxy resin obtained by the reaction of the reaction product of the above phenols and aralkyl alcohol derivative with epichlorohydrin, an epoxy resin derived from the compound shown below having two or more active hydrogens in one molecule, for example, bisphenol A , Brominated bisphenol A, bisphenol F, resorcin, bishydroxydiphenyl ether, bishydroxybiphenyl, bishydroxynaphthalene, trihydroxyphenylmethane, and other polyhydric phenols; ethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, Polyhydric alcohols such as diethylene glycol and polypropylene glycol; ethylenediamine,
Examples thereof include amines such as aniline and bis (4-aminophenyl) methane; epoxy resins obtained by reacting polychlorocarboxylic acids such as adipic acid, phthalic acid and isophthalic acid with epichlorohydrin. These epoxy resins are 1
A kind or a mixture of two or more trees can be used. When using a polyepoxy compound, as a curing agent, a polyphenolic compound such as a phenolic compound novolac resin or aralkyl resin, an acid anhydride such as pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, a known curing agent such as dicyandiamide Can be used.

When the thermosetting resin composition is composed of a polymaleimide compound and a polyepoxy compound, glycidol, glycerin diglycidyl ether, ethylene glycol monoglycidyl ether, resorcinol monocompound are used for the purpose of improving the compatibility of both compounds. A compound containing an alcoholic or phenolic hydroxyl group and an epoxy group in one molecule, such as glycidyl ether and naphthresorcinol monoglycidyl ether, may be blended. The silane compound having a maleimide group used to achieve the object of the present invention is represented by the following general formula (1)

[0013]

[Chemical 9] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms) and / or the following general formula (2)

[0014]

[Chemical 10] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms). Such a silane compound is excellent in water resistance because it is hydrophobic, and also excellent in heat resistance because it has a maleimide group, reacts strongly with the polymaleimide compound, and is excellent between the glass cloth and the resin in the water absorption solder treatment. It retains good adhesiveness. The silane compound is used in a resin composition, that is, a polymaleimide compound and a polyamino compound, or a polymaleimide compound and a polyepoxy compound, or a polymaleimide compound, and a varnish of a polyamino compound and a polyepoxy compound with a solvent. There is a method of mixing them at the same time, or a method of preliminarily surface-treating the glass cloth, that is, a method of immersing the glass cloth in a diluting solution of the silane compound and then heating and drying it. The blending amount of the silane compound is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the thermosetting resin composition containing a polymaleimide compound as a main component. If the amount is less than 0.01 parts by weight, sufficient adhesiveness cannot be obtained and good solder heat resistance cannot be obtained. Further, when it is used in excess of 5 parts by weight, the excess silane compound causes a decrease in heat resistance.

In curing the resin composition in the present invention, a curing accelerator such as an imidazole compound or an organic phosphine compound may be used. To produce a prepreg using the thermosetting resin composition, the prepreg is dissolved in an appropriate solvent and used in the form of a varnish. The concentration of the thermosetting resin composition in the varnish is preferably 40 to 70% by weight. If it is less than 40% by weight or more than 70% by weight, good impregnation property to the glass cloth cannot be obtained. As the solvent used at this time, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, N,
N-dimethylformamide, N, N-dimethylacetamide, dioxane, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like can be used.

The glass cloth used in the production of the prepreg in the present invention is not particularly limited, but it is produced from glass fiber containing 50% or more of SiO ₂ component in the composition, and the thickness of the cloth. Is 40 to 200
μ is preferable. After coating and impregnating the base material with the varnish, a prepreg is manufactured through a drying step, but the coating method, impregnation method, and drying method are not particularly limited. The drying conditions are appropriately determined depending on the boiling point of the solvent used, but the amount of the residual solvent in the prepreg is 0.5
It is desirable to be less than or equal to weight%. The laminated plate is manufactured by heating and pressurizing a plurality of the prepregs which are stacked, and at this time, a metal foil may be stacked on one side or both sides as the outermost layer. Copper, aluminum, stainless steel or the like can be used as the metal foil. The molding conditions for the laminated plate are a temperature of 160 to 210 ° C. and a pressure of 10 to 1.
It can be manufactured by heating / pressurizing integral molding at a pressing time of 1 to 3 hours at 00 kg / cm ² .

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples. Reference Example 1 Bis (4-maleimidophenyl) methane (BMI-S,
Mitsui Toatsu Chemical Co., Ltd. 360 g and 4,4′-diaminodiphenylmethane (MDA-220, Mitsui Toatsu Chemical Co., Ltd.) 40 g were charged in a reactor, and the mixture was charged at 10 ° C. at 10 ° C.
The reaction was carried out for a minute to obtain a resin composition (1).

Reference Example 2 Bis (4-maleimidophenyl) methane (BMI-S,
200 g of Mitsui Toatsu Chemical Co., Ltd., 40 g of glycidol (Epiol OH, manufactured by NOF CORPORATION), 100 g of bisphenol A type epoxy resin (Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) are installed in the reactor. Enter, 13
The reaction was performed at 0 ° C. for 1 hour to obtain a resin composition (2).

Reference Example 3 4.0% by weight of a mixture of 70% by weight of a silane compound in which R ₁ is an ethyl group in the general formula (1) and 30% by weight of a silane compound in which R ₁ is an ethyl group in the general formula (2). To
It was dissolved in a mixed solution of 50% by weight of distilled water containing 50% by weight of acetic acid and 50% by weight of ethanol. 1 thickness for this solution
After immersing 00 μ of glass cloth, it was dried at 110 ° C. for 10 minutes to obtain a treated glass cloth (1). The amount of the silane compound attached to the glass cloth was 0.30% by weight.

Comparative Reference Example 1 3-aminopropyltriethoxysilane 4.0% by weight
Was dissolved in distilled water containing 0.5% by weight of acetic acid. After immersing 100 μm thick glass cloth in this solution,
It was dried at 0 ° C. for 10 minutes to obtain a treated glass cloth (2). The amount of the silane compound attached to the glass cloth was 0.
It was 28% by weight.

Examples 1 to 3 and Comparative Examples 1 to 3 Impregnating varnishes were produced with the compositions (parts by weight) shown in Table 1.
A glass cloth having a thickness of 100 μ was impregnated with this varnish at a resin adhesion amount of 50% by weight and dried to produce a prepreg. Furthermore, 4 pieces of each prepreg are piled up, copper foil is arranged on both sides thereof, and pressure of 40 kg / cm ² is applied to 170 to 200
It was integrally molded under heating conditions of 60 ° C. for 60 minutes to obtain a laminated plate having a thickness of 0.4 mm. The obtained laminated plate was subjected to a solder heat resistance test under a glass transition temperature by dynamic viscoelasticity measurement and under the following conditions. The test results are shown in Table 2. Solder heat resistance test: A laminated plate was cut into 5 cm square pieces, and the copper foil on the surface was removed by etching.
After water absorption treatment for 2 hours, 4 hours, and 6 hours under the condition of 0% RH, it was immersed in a solder bath at 260 ° C. for 30 seconds, and the presence or absence of blisters on the surface was observed.

[0022]

[Table 1] * Α-Naphthol syloc: manufactured by Mitsui Toatsu Chemicals, Inc. Silane compound (1): Silane compound in which R ₁ is an ethyl group in general formula (1) Silane compound (2): R ₁ in general formula (2) A silane compound in which is an ethyl group

[0023]

[Table 2]

Examples 4-6 and Comparative Examples 4-6 Impregnating varnishes were produced with the compositions (parts by weight) shown in Table 3.
This varnish was applied to the treated glass cloths obtained in Reference Example 3 and Comparative Reference Example 1 in the combinations shown in Table 3 and the resin adhesion amount was 5
A prepreg was manufactured by impregnating with 0% by weight and drying. Furthermore, 4 pieces of each prepreg are piled up, copper foil is arranged on both sides thereof, and pressure of 40 kg / cm ² is applied to 170 to 200
It was integrally molded under heating conditions of 60 ° C. for 60 minutes to obtain a laminated plate having a thickness of 0.4 mm. The obtained laminated plate was subjected to a solder heat resistance test under a glass transition temperature by dynamic viscoelasticity measurement and under the following conditions. The test results are shown in Table 4. Solder heat resistance test: A laminated plate was cut into 5 cm square pieces, and the copper foil on the surface was removed by etching.
After water absorption treatment for 2 hours, 4 hours, and 6 hours under the condition of 0% RH, it was immersed in a solder bath at 260 ° C. for 30 seconds, and the presence or absence of blisters on the surface was observed.

[0025]

[Table 3] * Α-Naphthol Zyloc: manufactured by Mitsui Toatsu Chemicals, Inc. ○ indicates the glass cloth used.

[0026]

[Table 4]

[0027]

As described in Examples and Comparative Examples, the heat-resistant laminated sheet according to the present invention uses a silane coupling agent which is excellent in water resistance and heat resistance.
High adhesion between glass cloth and resin, excellent solder heat resistance, and extremely high industrial value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29K 79:00 105: 08 309: 08 B29L 9:00

Claims (6)

[Claims] 1. A thermosetting resin composition mainly composed of a polymaleimide compound is laminated with a plurality of prepregs in which glass cloth is impregnated with a resin composition prepared by blending a silane compound having a maleimide group. -Heat-resistant laminated board characterized by being formed by heating. 2. A thermosetting resin composition containing a polymaleimide compound as a main component is impregnated in a glass cloth which has been surface-treated with a silane compound having a maleimide group in advance, and a plurality of prepregs are laminated, followed by pressure / heat molding. A heat-resistant laminated plate characterized by being formed. 3. A silane compound having a maleimide group is a silane compound represented by the general formula (1) [Chemical formula 1] and / or a silane compound represented by the general formula (2) [Chemical formula 2]. The heat-resistant laminated plate according to claim 1 or 2, which is characterized. [Chemical 1] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms) (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms) 4. The heat resistant laminate according to claim 1 or 2, wherein the thermosetting resin composition containing a polymaleimide compound as a main component is a thermosetting resin composition containing a polymaleimide compound and a polyamino compound. 5. The heat-resistant laminated sheet according to claim 1, wherein the thermosetting resin composition containing a polymaleimide compound as a main component is a thermosetting resin composition containing a polymaleimide compound and a polyepoxy compound. . 6. The heat-resistant resin composition according to claim 1, wherein the thermosetting resin composition mainly containing a polymaleimide compound is a thermosetting resin composition comprising a polymaleimide compound, a polyamino compound and a polyepoxy compound. Laminated board.