JPH03230948A - Laminated sheet and production thereof - Google Patents

Abstract

PURPOSE:To enhance bonding strength of a metallic foil by interposing the layer of the cured material of resin composition contg. epoxy resin and a latent curing agent between layer of the cured material of resin composition contg. epoxy resin and polybasic acid anhydride and a metallic foil. CONSTITUTION:Base material impregnated with resin is obtained by impregnating fibrous base material with resin composition I1 contg. epoxy resin A1 and polybasic acid anhydride B2. A laminated body of base material impregnated with resin is obtained by laminating a plurality of sheets of the said base material impregnated with resin. A constitutional body is formed by utilizing the above-mentioned laminated body, a metallic foil stuck on one face or both faces of the laminated body and resin composition I2 which bonds the metallic foil to the laminated body and contains epoxy resin A2 and a latent curing agent B2. A laminated sheet is formed of the cured material of this constitutional body. In this case, it is preferable that resin having a polymerizable unsaturated group is simultaneously utilized for the resin composition I1 and that a dicyandiamide-based latent curing agent is utilized for the resin composition I2.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminate useful for printed circuit boards and the like, and particularly to a laminate with improved adhesive strength of metal foil, and a method for manufacturing the same.

[Prior art] Laminated boards used as printed circuit boards are produced by impregnating a fibrous base material with a resin composition containing an epoxy resin, polybasic acid anhydride, etc. to obtain a resin-impregnated base material. A laminate is produced by stacking a predetermined number of sheets and pasting metal foil on both sides or one side of the stack, and when pasting metal foil only on one side, pasting a cover film on the other side as necessary. This is manufactured by heating and curing it, for example, as disclosed in Japanese Patent Application No. 1-184994.
It is stated in the No.

[Problems to be solved by the present invention]

However, the adhesive strength of the metal foil of the laminate obtained by the above method is 1.1 when measured according to JIS C-6481 when a 35 μM thick copper foil is used as the metal foil.
The adhesive strength is 2.20 Kg/cm, which is 90 to 2.10 Kg/c+n, which is required to obtain a wiring circuit pattern with a line width of 100 to 150 μl, which is currently in demand.
It has been desired to improve the adhesive strength.

[Means to solve the problem]

As a result of intensive research in view of this situation, the present inventors have found that an epoxy resin and a latent curing agent are placed between a cured layer of a resin composition containing an epoxy resin and a polybasic acid anhydride, and a metal foil. It was discovered that by interposing a cured product layer of a resin composition containing a metal foil, the adhesive strength of the metal foil exceeds 2.20 Kg/cm, and at the same time, the methylene chloride resistance was improved, and the present invention was completed. This is what I came to do.

That is, in the present invention, epoxy resin (A1
) and a polybasic acid anhydride (B1).
A resin-impregnated base material laminate obtained by laminating a plurality of resin-impregnated base materials impregnated with 1), a metal foil affixed to one or both sides of the laminate, and bonding the laminate and the metal foil. A laminate comprising a cured product of a structure using a resin composition (I2) containing an epoxy resin (A2) and a latent curing agent (B2) is provided.

In this case, it is also preferable to use a resin system having a polymerizable unsaturated group in the resin composition (I1), and to use a dicyandiamide-based latent curing agent in the resin composition (I2).

In addition, the present invention provides a method for manufacturing a laminate in which a metal foil is attached using an impregnated prepreg in which a fibrous base material is impregnated with the resin composition (I2), and a metal foil The present invention provides a method for producing a laminate in which a resin composition (I2) is applied to a B-staged laminate and the laminate is adhered to a resin-impregnated base material laminate.

The present invention will be explained in detail below.

The resin composition (I1) in the present invention is an epoxy resin (
A1) and a polybasic acid anhydride (B1). Typical epoxy resins (A1) include epichlorohydrin or β-methylepichlorohydrin and bisphenol A, bisphenol F, or bisphenol S.
Epoxy resins obtained from; polyglycidyl ethers of phenol or alkylphenol novolac resins; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or ethylene oxide of bisphenol A or polyglycidyl ethers of polyhydric alcohols such as adducts of propylene oxide;
Polyglycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or dimer acid; cyclohexene-based epoxy compounds obtained by epoxidizing cyclohexene or its derivatives with peracetic acid etc. If (3,4
epoxy-6-methyl-cyclohexyl-3,4-epoxy-6-methyl-cyclohexanecarboxylate,
34-epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate, 1-epoxyethyl-3,
Cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclopentadiene oxide, Site, 2
．． (3-epoxycyclopentyl ether, etc.); limonene dioxide; and glycidyl ether ester of hydroxybenzoic acid, which may be used alone or in combination of two or more.

The above epoxy resin (A1) is liquid at room temperature,
For example, a liquid epoxy resin having an average epoxy equivalent of 100 to 400 is preferred.

To name a few: phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trimellitic anhydride, pyromellitic anhydride. , maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, chlorendeic anhydride, hensiphenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, 5-(2,5- dioxotetrahydrofuryl) 3
Examples include -methyl-3-cyclohexene-1,2-dicarboxylic acid, ethylene glycol bistrimelitate anhydride, and glycerin trimellitate anhydride, and these may be used alone or in combination of two or more. Among them, preferred are liquid ones, such as liquid acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, and methylnadic anhydride. Also preferably used is a solid acid anhydride such as 5-(25-dioxotetrahydrofuryl)-3=methyl-3-hexene-1,2-dicarboxylic acid dissolved in a liquid acid anhydride.

The above resin composition (1) contains a resin (C) having a polymerizable unsaturated group, a polymerization initiator (D), and a polymerizable vinyl nitrate.
(E) is added to form a resin composition that is liquid at room temperature and does not contain any welding agent other than polymerizable vinyl heptamer, which improves moldability and is more preferable. A resin having this polymerizable unsaturated group (
(hereinafter referred to as unsaturated resin) (C) refers to a resin that has a radically polymerizable carbon-carbon double bond and that hardens this double bond by a radical polymerization reaction. Examples include ester resins, urethane acrylate-1-resins, unsaturated polyester resins, diallyl phthalate resins, spiran resins, and addition-polymerized polyimides. Epoxy vinyl ester resins and/or unsaturated polyester resins are particularly preferred.

As the epoxy vinyl ester resin, various epoxy resins such as those mentioned above as the epoxy resin, preferably bisphenol type or novolac type epoxy resins, or a mixture thereof, are esterified with the following unsaturated basic acids. Examples include resins obtained by reaction in the presence of a catalyst. Typical unsaturated basic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, motubuvir maleate, monobutyl maleate, sorbic acid, and mono(2-ethylhexyl) maleate. However, these may be used alone or in combination of two or more.

These resins may be used by being dissolved in a welding agent of ketones or esters, or may be used by being dissolved at the same time as other raw materials such as epoxy resin, but polymerizable vinyl monomer (E)
It is preferable to use only

Examples of the polymerizable vinyl monomer in this case include styrene and its derivatives such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene, or divinylbenzene: ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate , n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. ) low-boiling ester monomers of acrylic acid; or trimethylolpropane tri(meth)acrylate, diprolene glycol di(meth)acrylate, 14-butanediol di(meth)acrylate or 1,6-hexanethiol di(
Examples include (meth)acrylates of polyhydric alcohols such as meth)acrylate, and among them, low-boiling ester monomers of styrene, vinyltoluene, and (meth)acrylic acid are preferred because of their excellent volatility.

Further, examples of the unsaturated polyester resin include those obtained by reacting a dicarboxylic acid containing an unsaturated dibasic acid with a polyhydric alkone. For melting the unsaturated polyester resin, the polymerizable vinyl monomer (E) and melting agent used for the above-mentioned epoxy vinyl ester resin can be used, and these can be optionally added alone or in a mixture of two or more. However, it is preferable to use only polymerizable vinyl hexamer (E).

Typical unsaturated basic acids for obtaining unsaturated polyester resins include maleic acid, maleic anhydride, fumaric acid, halogenated maleic anhydride, etc., and saturated dibasic acids other than these can also be used in combination. Typical examples of these are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, succinic acid, adipic acid, and sebacic acid, while typical polyhydric alcohols include ethylene glycol and diethylene glycol. , propylene glycol, dipropylene glycol, 1,3-phthylene gelicol, ■, 4-butylene glycol, neopentyl glycol, adducts of hydrogenated bisphenol and ethylene oxide or propylene oxide,
Examples include glycerin and trimethylolpropane.

To obtain epoxy vinyl ester resin or unsaturated polyester resin, conventionally known methods can be followed, and polymerization is inhibited for the purpose of preventing gelation during the reaction and adjusting the storage stability or curability of the product. It is recommended to use an agent.

Typical examples of such polymerization inhibitors include hydroquinones such as hydroquinone, p-t-butylcatechol, and mono-t-butylhydroquinone; phenols such as hydroquinone monomethyl ether and di-tp-cresol; -benzoquinone, naphthoquinone,
P-) quinones such as luquinone; or copper salts such as naphthene M copper.

The polymerization initiator (D) used when adding the unsaturated resin to the resin composition (I1) in the present invention is preferably one that decomposes at a temperature lower than the heating and pressure molding temperature, such as cyclohexanone peroxide, 3 .3.5-trimethylcyclohexanone peroxide, methylonexanone peroxide, 1,1-bis(t-butylperoxy)3,3.5-)limethylcyclohexane, cumene hydroperoxide, dicumyl peroxide oxide,
lauroyl peroxide, 3,5.5-)limethylhexanoyl peroxide, benzoyl peroxide, di-myristyl peroxydicarbonate, t-
Butyl peroxy (2-ethylhexanoate), t-
Examples include organic peroxides such as butylperoxy-3,5,5-)limethylhexanoate, t-phthylperoxybenzoate, and cumylperoxyoctoate.

The resin composition (I1) may further contain a curing accelerator, an internal mold release agent, a pigment, a filler, and other additives, if necessary.

Epoxy resin ((C) + (D) + (E)) of the unsaturated resin (C), polymerization initiator (D), and polymerizable vinyl monomer (E) used in the resin composition (I1). A
1) and polybasic acid anhydride (B1) ((A1) +
Weight ratio ((C) + (D) + (E
) ) / ((7h)+(B1)) is usually 2/98
~60/40, preferably 5/95~40/60
It is.

In the present invention, resin composition (I2) is used,
It contains an epoxy resin (A2) and a latent curing agent (B2). As the epoxy resin (A2), those similar to the above-mentioned epoxy resin (A1) can be used, but among them, those having an average epoxy equivalent of 300 to 800 are preferred. The latent curing agent (B2) is an epoxy resin (A2
) does not cause a curing reaction at room temperature,
Preferably, it refers to a substance that causes a curing reaction when heated to 80°C or higher, particularly 120°C or higher, and specifically includes boron acid fluoride-amine complex, dicyandiamide and its derivatives, organic acid hydrazide and its derivatives, and melamine. and its derivatives, diaminomaleonitrile and its derivatives, amine imide', polyamine salts, etc. Among them, dicyandiamide and its derivatives are preferred because they are inexpensive and have excellent prepreg stability.

Examples of dicyandiamide derivatives include 0-tolyl biguanide, α-2,5-dimethyl biguanide, α, ω diphenyl biguanide, 5-hydroxynaphthyl 1-biguanide, α α1-bisguanylguanidinodiphenyl ether, phenyl biguani, and pchlorphenyl biguanide. , α-penzylbiguanide, α,ω-dimethylbiguanide, α,α1-hexamethylenebis[ω-(p-chlorophenyl)]biguanide, and metal salts of the above-mentioned bianide compounds. Among these, dicyandiamide is Particularly preferred.

When using dicyandiamide or a derivative thereof as the latent curing agent, the ratio of the epoxy resin (A2) and the latent curing agent (B2) is usually 1 epoxy group in the epoxy resin (A2) to dicyandiamide or a derivative thereof. The number of active hydrogens in the derivative is 0.2 to 1.0.

The resin composition (I2) containing the epoxy resin (A2) and the latent curing agent (B2) is usually dissolved in a melt. Here, ketones such as methyl ethyl ketone and acetone are usually used as the welding agent. However, since dicyandiamide has poor solubility in a melt, it is preferable to uniformly dissolve it in advance in a mixed melt such as dimethylformamide, methyl cellosolve, methyl ethyl ketone, acetone, etc. before use.

A curing accelerator, pigment, filler, and other additives can be added to the resin composition (I2) if necessary.

Typical fibrous base materials used in the present invention include glass fibers, carbon fibers, and aromatic polyamide fibers, with glass fibers being preferred. Among these, first of all, glass fiber is E-
There are glass, C-glass, A-glass, S-glass, etc., and any of these types can be applied in the present invention.

These fibrous base materials are classified into roving, chopped strand mat, continuous cloak, cloth, non-woven fabric, roving cloth, surficing cloak, and chopped strand depending on their shape. The materials may be appropriately selected depending on the intended use and performance of the molded product, and if necessary, a mixture of types or shapes on two sides may be used. Among them, cloth and nonwoven fabrics are preferred.

Further, examples of the metal foil used in the present invention include copper foil, aluminum foil, etc., and examples of the cover film used when no metal foil is used include plastic films such as polyester film and polyimide.

Examples of the method for using the resin composition (I1) include the following method.

■ Add resin composition (I1) to polymerizable vinyl monomer (E)
A predetermined number of resin-impregnated base materials obtained by impregnating the above-mentioned fibrous base material with a room-temperature liquid composition containing no other welding agent are stacked, the amount of the resin composition is adjusted appropriately, and a resin-impregnated base material laminate [hereinafter referred to as , referred to as resin-impregnated base material laminate (I)].

■ Add resin composition (I1) to polymerizable vinyl monomer (E)
A resin composition that is liquid at room temperature without any other welding agent or an impregnable resin composition dissolved in a welding agent is impregnated into the above-mentioned fibrous base material to obtain a resin-impregnated base material, which is then preheated. A method of stacking a predetermined number of sheets from which the polymerizable vinyl monomer (E) has been volatilized to form a resin-impregnated base material laminate (hereinafter referred to as resin-impregnated base material laminate (2)). At this time, it is usually heated at 70 to 180°C, preferably 100 to 170°C in a heating drying oven, on a flat plate at 170°C, 20 kg/a+1
It is preferable to proceed with curing until the proportion of the resin composition flowing out of the fibrous base material (flow rate) when heated and pressurized under the following conditions becomes 1 to 35% by weight.

Moreover, as a method of using the resin composition (I2), there are, for example, the following methods.

■ Impregnating the fibrous base material with the resin composition (I2),
The melt is volatilized in a heating drying oven, B-staged to produce a prepreg, which is stacked on one or both of the upper and lower sides of the resin-impregnated base material laminate (I) or (2), and a metal layer is further placed on top of the prepreg. In addition to overlapping the foil, a cover film is overlaid on one side of the laminate without prepreg, and then heated and cured. The prepreg obtained here was heated at 170°C on a flat plate.
It is preferable to proceed with curing until the proportion of the resin composition flowing out of the fibrous base material (flow rate) is 1 to 35% by weight when heated and pressurized under conditions of 20 kg/-.

■°The above resin composition (I
2) is applied, the melt is volatilized in a heating drying oven, the B-staged product is stacked on one or both sides of the laminate (I) or (2), and then heated and cured.

Here, B-staging of a product impregnated or coated with the resin composition (I2) means that the reaction of the impregnated resin composition or the resin composition of the coating progresses to the point where it substantially loses fluidity at room temperature and under no pressure. , the viscosity of the resin composition is high, but at 140°C
This refers to a state in which the reaction can proceed to a state where the resin impregnated base material or coating film is further heated within this range after it shows fluidity again and is cured. Tack-free surface with no sticky residue,
Or, it refers to progressing the reaction to a state close to this.

In addition, in the above ■° and ■°, the melt or B
- The staging temperature is usually 70-180°C, preferably 100-170°C. At temperatures below 70°C, the melt is difficult to volatilize, and at temperatures above 180°C, the flow of the resin during heat molding is too low, which tends to cause voids in the resulting laminate, which is not preferable.

Examples of methods for efficiently volatilizing the welding agent include a method of blowing hot air, a method of performing heating and suction or depressurization simultaneously or separately, a method of using infrared rays or far infrared rays, and a method of using high-frequency heating. These methods may be carried out under an inert gas, preferably nitrogen gas atmosphere.

To manufacture a laminate using the above ■, ■, ■゛, ■'', metal foil, and cover film, the resin-impregnated base material laminate (■)
When using I), (1) Overlay the prepreg of ■゛ on this laminate (I), further overlay metal foil on one or both of the upper and lower sides, and place a cover film on the other side where this metal foil is not overlapped. (I1) B-staged resin-coated metal foils stacked on one or both upper and lower surfaces of the laminate (I) are precured in a heating furnace and then heat cured.

The preliminary curing at this time is such that the flow rate of the resin composition when molded under heat and pressure at 170°C and 20 kg/- is 1 to 15.
It is preferable to carry out the process under conditions such that 1% by weight, especially 1% by weight.
-10% by weight is particularly preferred. Normally 1 at 80-160℃
The heating time is preferably 5 minutes or less, preferably 10 minutes at 90 to 140°C.

Outflow rate of resin composition (%) =W+/Wox, □10
0 (However, No. is the weight of the laminate with a predetermined area excluding the metal foil and cover film, and leg 1 is the weight of the part protruding from the specific predetermined area of molding.) In addition, the above resin-impregnated base material laminate (2) is used. In this case, after layering the corresponding metal foils through the prepreg of ■゛ or layering the corresponding metal foils of ■゛,
If necessary, preliminary curing is performed and then heat curing is performed.

As for heat curing, heat and pressure curing is preferable in terms of removing voids from the object to be treated, and is usually 100 to 240°C,
5-50Kg/nK", preferably 120-200°C
It is carried out under conditions of 110 to 40 kg/-.

The above-mentioned heating and pressure curing is performed by a batch press, an endless double press, etc., but an endless double belt press is preferable from the viewpoint of improving productivity, and roll pressure,
Examples include air pressurization, oil pressurization, etc.

In any of the above cases, after heat curing, post-curing may be performed if necessary.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Example 1 12.8 parts of a melt-free liquid epoxy resin (AI-1) with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin, and 37.2 parts of methyltetrahydrophthalic anhydride (B+-1) , 0.26 parts of benzyldimethylamine, methacrylate of phenol novolak type epoxy resin with an epoxy equivalent of 184 (70%
) and styrene monomer (30%) and 20 parts of epoxy vinyl ester resin (C-1) and 0.42 parts of hensoil peroxide (D-1) were mixed to give a bromine content of 19.9% based on the solid content. 0% resin composition (I-1
) was prepared.

Next, six long pieces of glass cloth with a thickness of 0.18 m and a width of 1020 m were individually impregnated with the resin composition (I-1), and the resulting resin-impregnated base materials were overlapped with a squeeze roll, and the resin composition was simultaneously applied. /Glass cloth weight ratio is 4315
The excess resin composition was squeezed out so as to give a resin impregnated base material laminate (I-1).

On the other hand, 85 parts of an epoxy resin with an epoxy equivalent of 685 obtained by the reaction of tetrabromohisphenol^tosphenol 8 and epichlorohydrin, and 15 parts of an epoxy resin with an epoxy equivalent of 212 obtained by the reaction of cresol novolac with epichlorohydrin. An epoxy resin mixture (
A2) 133 parts, 43.3 parts of dicyandiamide solution (B2) prepared by dissolving 3.3 parts of dicyandiamide in 10 parts of dimethylformamide, 30 parts of methyl cellosolve, and 21 parts of methyl ethyl ketone, and 0.2 parts of 2-ethyl-4-methylimidazole. A resin composition (I2-1) having a bromine content of 19.5% based on the solid content was prepared.

This resin composition (I2-1) was impregnated into a long glass cloth with a width of 102 On and a thickness of 0.18 mm.
The sample was passed through a vertical hot air drying oven for 3.5 minutes to obtain a tack-free prepreg with a resin composition content of 43%.

This long prepreg was layered one by one on each of the upper and lower surfaces of the above resin-impregnated base material laminate (I--1), and electrolytic copper foil with a thickness of 35 μm was layered on both the upper and lower surfaces.
After passing through a horizontal heating furnace for 4 minutes,
℃, 20 Kg/cnl for 5 minutes using an endless double belt press, trimming and cutting, and then molding into 1000 strips x 100 (l11 x 1.6 t)
A laminate of x was obtained. Furthermore, it was post-cured for 60 minutes in a heating oven at 170°C. The copper foil adhesive strength and methylene chloride resistance of the obtained laminate were measured by the following methods.

The results are shown in Table 1.

[Copper foil adhesive strength]

Measured according to JISC-6481.

[Methylene chloride resistance]

The copper foil on one side of the laminate was removed by etching using an aqueous ferric chloride solution, and the laminate was immersed in methylene chloride at 40° C. for 15 minutes to observe the surface condition. The evaluation is as follows.

○: No change.

△: The texture of the glass cloth stands out.

Example 2 Using the resin composition (I-1) of Example 1 and using 8 sheets of the same glass cloth as in Example 1, a resin was prepared in the same manner as in Example 1 with a resin composition/glass cloth weight ratio of 43157. An impregnated base material laminate (I-2) was obtained.

On the other hand, the resin composition (I2) obtained in Example 1 was applied to the mantle surface of a 35 μm electrolytic copper foil, passed through a heating furnace at 160°C for 3.5 minutes, and formed into 8-stages with a thickness of 50 μm. A copper foil coated with a resin composition was obtained.

This was laminated on both the upper and lower surfaces of the resin-impregnated base material laminate (I-2), and the same procedure as in Example 1 was carried out to obtain a laminate having the same dimensions. This was also measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 To 16.9 parts of a hot liquid epoxy resin having an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin, an epoxy equivalent of 37 was obtained by the reaction of tetrabromobisphenol 8 and epichlorohydrin.
Obtained by the reaction of 43.4 parts of an epoxy resin mixture prepared by melting 26.5 parts of epoxy resin 0, 26.4 parts of methyltetrahydrophthalic anhydride, 0.7 parts of benzyldimethylamine, tetrabromobisphenol A, and epichlorohydrin. An epoxy resin with an epoxy equivalent weight of 370, methacrylate (60%) and a styrene monomer (4
Epoxy vinyl ester resin composition 3 consisting of
0 parts of Baroyl MSP C (polymerization initiator manufactured by Nippon Oil & Fats ■, cimilistyl peroxydicarbonate) and 0.2 parts of Permicle H (polymerization initiator manufactured by Nippon Oil & Fats ■, cumene hydroperoxide). , a uniform resin composition (It-3) was prepared.

This resin composition (ll-3) was made into a long piece with a thickness of 0.18 m,
A glass cloth with a width of 1020 mm was impregnated with the mixture and passed through a vertical hot air drying oven at 120° C. for 6 minutes to obtain a tank-free prepreg with a resin composition content of 43%.

B-staged resin-coated copper foil of the resin composition (I2) used in Example 2 was layered on the upper and lower surfaces of the 8 sheets of prepreg stacked together, and heated with an endless double helt breath under the same conditions as Example 1. Pressure molding and post-curing gave laminates of similar dimensions. This was also measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 Electrolytic copper foil with a thickness of 35 μm was overlaid on both the upper and lower surfaces of the resin-impregnated base laminate (I-2) obtained in Example 2, and then precured and heated and pressed in the same manner as in Example 1. Molding and post-curing gave laminates of similar dimensions. This was also measured in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 (margins below this page) [Effects of the invention] According to the present invention, a resin-impregnated resin film laminated using a resin-impregnated base material obtained by impregnating a fibrous base material with an acid anhydride-curable epoxy resin. Since a resin composition containing an epoxy resin and a latent curing agent is interposed between the base material laminate and the metal foil and cured, it is possible to improve the adhesive strength of the metal foil and improve the methylene chloride resistance. can be improved.

February 5, 1990

Claims (7)

[Claims] 1. A resin-impregnated base material laminate obtained by laminating a plurality of resin-impregnated base materials in which a fibrous base material is impregnated with a resin composition (I_1) containing an epoxy resin (A_1) and a polybasic acid anhydride (B_1). , a metal foil attached to one or both sides of the laminate, and an epoxy resin (A_2) for bonding the laminate and the metal foil.
) and a latent curing agent (B_2).
_2) A laminate consisting of a cured product of the construct. 2. The resin composition (I_1) is an epoxy resin that is liquid at room temperature (
A resin composition that is liquid at room temperature and contains a resin (C) having a polymerizable unsaturated group, a polymerization initiator (D), and a polymerizable vinyl monomer (E) in addition to a_1) and a polybasic acid anhydride (B_1). A laminate according to claim 1. 3. The laminate according to claim 1 or 2, wherein the resin composition (I_2) is a resin composition containing an epoxy resin (A_2) and dicyandiamide and/or its derivative (b_2). 4. Resin-impregnated base material laminate obtained by laminating a plurality of resin-impregnated base materials in which a fibrous base material is impregnated with a resin composition (I_1) containing an epoxy resin (A_1) and a polybasic acid anhydride (B_1). In a method for manufacturing a laminate in which a metal foil is attached to one or both sides of the body and cured by heating, an epoxy resin (A_2) and a latent curing agent (B_2) are placed on a fibrous base material between the laminate and the metal foil. ) Resin composition (I_2) containing
A method for manufacturing a laminate, characterized by disposing a prepreg obtained by impregnating and preheating. 5. Resin-impregnated base material laminate obtained by laminating a plurality of resin-impregnated base materials in which a fibrous base material is impregnated with a resin composition (I_1) containing an epoxy resin (A_1) and a polybasic acid anhydride (B_2). In the method of manufacturing a laminate in which metal foil is attached to one or both sides of the body and cured by heating, the surface of the metal foil in contact with the resin-impregnated base material laminate contains an epoxy resin (A_2) and a latent curing agent (B_2). Resin composition (I_2)
A method for producing a laminate, in which a metal foil coated with a resin composition coated film obtained by applying and preheating to B-stage is directly adhered to the resin-impregnated base material laminate. 6. The resin composition (I_1) is an epoxy resin that is liquid at room temperature (
a_1) and a polybasic acid anhydride (B_1), a resin composition that is liquid at room temperature and contains a resin (C) having a polymerizable unsaturated group, a polymerization initiator (D), and a polymerizable vinyl monomer (E). The method for manufacturing a laminate according to claim 4 or 5. 7. The laminate according to claim 4, 5 or 6, wherein the resin composition (I_2) is a room temperature liquid resin composition obtained by dissolving the epoxy resin (A_2) and dicyandiamide and/or its derivative (b_2) in a melt. manufacturing method.