JPH04272845A - Manufacture of laminated board - Google Patents

Abstract

PURPOSE:To obtain a laminated board, which can be precured in a short time at a low temperature, a volatile substance of which is hardly volatilized also and has excellent surface properties, by precuring a laminate by active energy beams, coating the laminate with a required copper foil and heating and pressure-molding the laminate. CONSTITUTION:A long-sized fibrous base material impregnated with a thermo-setting epoxy resin composition containing an active energy-beam curable resin or a laminate thereof is irradiated with active energy beams and precured, and a metallic foil is superposed and the precured base material or the laminate thereof is heated and cured. The epoxy resin composition comprises a resin component with a polymerizable unsaturated group, an epoxy vinyl ester resin and a thermo-setting epoxy resin and the partial vinyl esterified substance of the epoxy resin, and a resin composition containing an acid anhydride compound is used as a curing agent. A long-sized glass cloth or glass nonwoven fabric is employed as the fibrous base material, and ultraviolet rays are used as active energy source.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminate with excellent surface properties.

0002

[Prior Art] A fibrous base material is impregnated with a resin composition consisting of an acid anhydride-curable liquid epoxy resin and a resin having a polymerizable unsaturated group, precured by heating, and then heated and pressure molded. A method of manufacturing a laminate by using the above method (Japanese Unexamined Patent Publication No. 59-49240) is known.

0003

However, in the above method, after impregnating a fibrous base material with a resin composition, the upper and lower surfaces of the laminate are covered with copper foil or a film, and then heated to substantially impregnate the fibrous base material. Since the preliminary curing is carried out under no pressure, the copper foil thermally expands in this step, and there is a problem in that wrinkles occur on the surface of the resulting laminate even after the subsequent heating and pressure forming step.

0004

[Means for Solving the Problems] As a result of intensive research in view of the above circumstances, the present inventors have developed a method using a thermosetting epoxy resin composition containing an active energy beam-curable resin component. By pre-curing the laminate with an active energy beam, then covering it with the necessary copper foil and molding it under heat and pressure, it is possible to pre-cure at a low temperature and in a short time, with less volatilization of volatile substances. They have discovered that a laminate with excellent surface properties can be obtained, and have completed the present invention.

That is, the present invention involves irradiating active energy rays onto a long fibrous base material or a laminate thereof impregnated with a thermosetting epoxy resin composition containing an active energy ray curable resin. The present invention provides a method for manufacturing a laminate, which is characterized in that the metal foils are pre-cured, and then metal foils are stacked and cured by heating.

[0006] As the active energy beam used in the present invention, ultraviolet rays, gamma rays, electron beams, etc. are used, but ultraviolet rays are preferable from the viewpoints of operability, safety, cost, etc. of the apparatus. As the thermosetting epoxy resin composition (hereinafter abbreviated as epoxy resin composition) containing an active energy beam-curable resin used in the present invention, for example, active energy beam-curable resin
Examples include resin compositions whose main components are a line-curable resin and an epoxy resin, and resin compositions whose main component is a partially vinyl esterified epoxy resin. A resin composition containing an epoxy vinyl ester resin and/or a partial vinyl ester of an epoxy resin as a main component, and a resin composition containing a partial vinyl ester of an epoxy resin as a main component are preferred. Among these, the ratio of the number of vinyl ester groups/epoxy groups is 2/9 because it can be easily precured to the center of the resin-impregnated laminate by irradiation with active energy rays.
A resin composition having a ratio of 8 to 60/40, particularly 5/90 to 40/60 is preferred.

Examples of the epoxy resin used together with the active energy beam-curable resin include epoxy resins obtained from epichlorohydrin or β-methylepichlorohydrin and bisphenol A, bisphenol F, or bisphenol S; polyphenol or alkylphenol novolac resins; Glycidyl ethers; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, or adducts of bisphenol A with ethylene oxide or propylene oxide. Polyglycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or dimer acid; Cyclohexene-based epoxy obtained by epoxidizing cyclohexene or its derivatives with peracetic acid etc. Compounds (3,4-epoxy-6-
Methyl-cyclohexyl-3,4-epoxy-6-methyl-cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.); cyclopentadiene or cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclopentadiene oxide, 2,3-epoxycyclopentyl ether, etc.) obtained by epoxidizing dicyclopentadiene or derivatives thereof with peracetic acid, etc.; limonene dioxide and glycidyl ether ester of hydroxybenzoic acid, which can be used alone or in combination of two or more. Among the above epoxy resins, those which are liquid at room temperature, for example, those having an average epoxy equivalent of 100 to 400,
liquid epoxy resins are preferred.

In addition to the above-mentioned epoxy vinyl ester resins and partially vinyl esterified epoxy resins, active energy beam-curable resins include, for example, polyether acrylate resins, polyester acrylate resins, and polyurethane acrylate resins. Examples include acrylic resins such as carbonate resins, unsaturated polyester resins, spiran resins, and diallyl phthalate resins.

As the epoxy vinyl ester resin and the partially vinyl esterified product of the epoxy resin, for example, the epoxy resin as described above and the unsaturated monobasic acid as shown below are combined into a complete or partial vinyl ester in the presence of an esterification catalyst. Examples include resins obtained by chemical reaction.

Examples of the unsaturated monobasic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutyl maleate, sorbic acid, and mono(2-ethylhexyl) maleate. These can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred.

[0011] Also, as the esterification catalyst, commonly known ones are used, among which phosphine derivatives, 4
Phosphorus compounds such as phosphonium salts are preferred, and phosphine derivatives such as triphenylphosphine, tri-n-butylphosphine and the like are particularly preferred. These esterification catalysts may be added in a catalytic amount, for example, 1 to the total of the raw material epoxy resin and unsaturated monobasic acid.
It is sufficient to add about 00 to 10,000 ppm.

[0012] To obtain the epoxy vinyl ester resin,
It is recommended to use a polymerization inhibitor for the purpose of preventing gelation during the reaction and adjusting the storage stability or curability of the product.

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; p-benzoquinone; , naphthoquinone, p
- quinones such as tolquinone; or copper salts such as copper naphthenate.

The above-mentioned epoxy vinyl ester resin and partially vinyl esterified epoxy resin may be used by being dissolved in a solvent such as ketones or esters, or may be used by being dissolved at the same time as other raw materials such as epoxy resin. is also good, but
Preferably, only polymerizable vinyl monomers are used.

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-
Low boiling ester monomers of (meth)acrylic acid such as hydroxypropyl (meth)acrylate; or trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate or 1 (meth)acrylates of polyhydric alcohols such as , 6-hexanediol di(meth)acrylate, etc. Among them, low-boiling ester monomers of styrene, vinyltoluene, and (meth)acrylic acid are particularly preferred because of their low viscosity. preferable.

[0016] The epoxy resin composition used in the present invention includes:
If necessary, a photopolymerization initiator, a photosensitizer, a reactive monomer, a curing agent for thermosetting epoxy resin, a curing accelerator for thermosetting epoxy resin, and other fillers can be added. In addition, a thermal polymerization initiator is used in combination with a photopolymerization initiator,
It is also possible to thermally harden the unhardened portions during the active energy ray irradiation in the next heating step.

[0017] The photopolymerization initiator used at this time is as follows:
For example, benzoin ether compounds such as benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 1-hydroxycyclohexylphenyl ketone, benzophenone, 4-chlorobenzophenone, methyl orthobenzoylbenzoate, Benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone and 4-benzoyl-4'-methyldiphenylsulfide dibenzyl; ketal compounds such as benzyl dimethyl ketal and benzyl diethyl ketal; 2 , 2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, acetophenone compounds such as pt-butyltrichloroacetophenone, thioxanthone 2 Examples include thioxanthone compounds such as -chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2-ethylanthraquinone, and 2-propylanthraquinone.

Examples of the thermal polymerization initiator used in combination with the photopolymerization initiator include cyclohexanone peroxide, 3,
3,5-trimethylcyclohexanone peroxide,
Methylonexanone peroxide, 1,1-bis(t-
butyl peroxide) 3,3,5-trimethylcyclohexane, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, benzoyl peroxide, di-myristyl peroxydicarbonate , t-butylperoxy (2-ethylhexanoate)
, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxybenzoate, cumylperoxyoctoate, and other organic peroxides.

As the reactive monomer, for example, the above-mentioned polymerizable vinyl monomer can be used. Examples of fillers include aluminum hydroxide, aluminum silicate,
Colloidal silica, calcium carbonate, calcium sulfate,
Examples include mica, talc, titanium dioxide, quartz powder, zirconium silicate, glass powder, asbestos powder, diatomaceous earth, and antimony trioxide.

[0020] Examples of curing agents for thermosetting epoxy resins include aromatic polyamines and their salts, polybasic acid anhydrides, boron trifluoride-amine complexes, dicyandiamide, dibasic acid hydrazides, diaminomaleonitrile,
Examples include melamine, imide, etc., but polybasic acid anhydrides which are liquid at room temperature are particularly preferred. Typical polybasic acid anhydrides include 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, dodecenylsuccinic anhydride, chlorendic anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, ethylene glycol bistrimelitate anhydride, glycerin trimellitate anhydride, etc.
These may be used alone or in combination of two or more. Among these, preferred are liquid forms such as methylhexahydrophthalic anhydride and methylnadic anhydride. Also preferably used is a solid acid anhydride such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dissolved in a liquid acid anhydride. .

Examples of curing accelerators for thermosetting epoxy resins include ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
Aliphatic amines such as dipropylene diamine and diethylaminopropylamine, alicyclic amines such as menzendiamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, N-aminoethylpiperazine, metaxylene diamine, Aliphatic amines containing aromatic rings such as tetrachloro-p-xylene diamine, aromatic amines such as metaphenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, bisaminomethyldiphenylmethane, 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc. imidazole compounds, as well as latent curing accelerators, among others, it is particularly desirable to use latent curing accelerators in terms of not reducing the storage stability of the epoxy resin composition used in the present invention.

[0022] Examples of the latent curing accelerator include (i)
A frozen type latent curing accelerator made by mixing an epoxy resin and an amine compound and immediately freezing it to stop the reaction. ■ A microcapsule type latent curing accelerator made by microcapsulating an amine compound. ■ A compound in a monocular sieve. monocular sieve-type latent curing accelerators adsorbed with However, the latent curing accelerator mentioned above is particularly preferable because it is easy to handle, has high workability, has an appropriate curing accelerating effect during heating, and does not deteriorate physical properties.

[0023] The method and order of blending each component to obtain an epoxy resin composition are not particularly limited, but after mixing the liquid components, solid components are added in powder form and decomposed. Alternatively, a method of dissolving is preferred.

On the other hand, 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, glass fibers include E-glass, C-glass, A-glass, and S-glass from the viewpoint of their raw materials, but any of these types can be used in the present invention.

These fibrous base materials are classified into rovings, chopped strand mats, continuous mats, cloths, nonwoven fabrics, roving cloths, surfacing mats, and chopped strands depending on their shape.
The above-mentioned types and shapes are appropriately selected depending on the intended use and performance of the molded product, and two or more types or shapes may be used in combination if necessary. Among them, glass cloth and glass nonwoven fabric are preferred.

[0026] Using the epoxy resin composition of the present invention,
As a method for obtaining a laminate, for example, (1) a fibrous base material is impregnated with an epoxy resin composition, a predetermined number of sheets are stacked, and active energy rays such as ultraviolet rays are irradiated in air or an inert gas such as nitrogen. A method of pre-curing by irradiation, further covering with metal foil, and then heating and curing; (2) impregnating a fibrous base material with an epoxy resin composition and applying it one by one in air or in an inert gas such as nitrogen; (3) A method of pre-curing by irradiating active energy rays such as ultraviolet rays with active energy rays such as ultraviolet rays, stacking a predetermined number of sheets, further covering with metal foil, and then curing by heating. is impregnated with an epoxy resin composition, and after stacking a predetermined number of sheets, they are covered with an active energy ray-transparent film, and then precured by irradiation with active energy rays such as ultraviolet rays, and then the required surfaces of the metal foil are coated with an epoxy resin composition. Examples include a method in which the film is peeled off, a metal foil is pasted on the surface, and then the film is heated and cured.

The heat curing in (1), (2), and (3) above may be carried out under no pressure in a continuous heating furnace, or may be carried out continuously under heat and pressure using a continuous double belt press or the like. However, from the viewpoint of surface smoothness of the laminate, heat-pressing molding is preferable. Alternatively, the preheated laminate may be cut and subjected to batchwise heating and pressure molding. Heat curing is usually
It is carried out at 130-190°C. In the case of hot pressure molding, it is usually carried out under a pressure of 5 to 40 kg/cm2.

[0028]

[Example] Next, the present invention will be explained in more detail with reference to production examples, working examples, and comparative examples. In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Example 1 Epoxy resin 18.2 with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin
1 part, 22.8 parts of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, 2 parts of methylhexahydrophthalic anhydride
5.2 parts, 28.0 parts of an epoxy vinyl ester resin solution consisting of methacrylate (60%) of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (40%). , 0.3 parts of 1-hydroxycyclohexyl phenyl ketone, 0.56 parts of benzoyl peroxide, 4.8 parts of styrene and 0.28 parts of 2-ethyl-4-methylimidazole were mixed to prepare a liquid epoxy resin composition. (
I-1) was prepared.

Next, this epoxy resin composition (I-1) was immediately applied to a long glass cloth with a thickness of 0.18 mm and a width of 1050 mm so that the content of the epoxy resin composition was 43%. 4 sheets were stacked and exposed to 500 ml of heat from the top and bottom using a mercury lamp in an air atmosphere.
0 millijoule/cm2 (hereinafter referred to as mJ/cm2)
The laminate was pre-cured by being transported while being irradiated with ultraviolet rays. Furthermore, 35μm thick copper foil was layered on top and bottom of the copper foil, and then 20K was applied using a double belt press heated to 170℃.
After heating and pressure molding for 10 minutes at a pressure of g/cm2, 1
A laminate (II-
20 pieces of 1) were obtained.

Using the obtained 20 laminates (II-1), the surface smoothness of the laminate, the amount of resin flowing out during molding, the water absorption rate, and the solder heat resistance were measured as follows. Smoothness: Good, resin flow rate during molding: 2.8
%, water absorption rate: 0.14%, and solder heat resistance: Good results were obtained. In addition, there was little variation in the results.

-Surface smoothness: The occurrence of fine waviness on the surface of the laminate was visually determined.・Resin flow rate (%) = (W
0 - W1)/W0 x 100 and shown as an average value (where W0 is the weight of a resin-impregnated base material with an epoxy resin composition content of 43% and dimensions of 1000 mm x 1000 mm, and W1 is the weight of a resin-impregnated base material with a size of 1000 mm x 1000 mm. Dimensions obtained by molding: 1000
This is the weight obtained by subtracting the copper foil weight from the mm x 1000 mm laminate. ).

・Water absorption rate (%): After removing the copper foil on one side of the laminated board cut into 25 mm x 25 mm by etching,
A pressure cooker test was conducted for 4 hours at 120°C and 2 atm, and the water absorption rate was calculated using (W'-W)/W x 100, and the average value is shown (where W is the weight of the laminate before the test). , W' is the laminate weight after the test).

Soldering heat resistance: After thoroughly wiping off moisture on the surface of the laminate after the pressure cooker test,
It was measured according to JIS C-6481 and evaluated based on the following criteria. ○: No samples with poor solder heat resistance. △: Less than 1/4 of the samples had poor solder heat resistance. ×: More than 1/4 of the samples had poor solder heat resistance.

Example 2 An epoxy resin composition (I-
1) was applied to a long glass cloth with a thickness of 0.18 mm and a width of 1050 mm, and the content of the epoxy resin composition was 43%.
After stacking 4 sheets, the upper and lower sides were covered with a 25 μm thick polyethylene terephthalate film, and then the top and bottom were soaked with a mercury lamp for 5
After pre-curing by irradiating ultraviolet rays of 000 mJ/cm2, the film was peeled off and a 0.8 mm thick laminate (
20 pieces of II-2) were obtained.

Using the obtained 20 laminates (II-2), the surface smoothness of the laminate, amount of resin flowing out during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 2.8%, water absorption rate: 0.12%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 3 Methacrylate (60%) and styrene (40%) of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin
Instead of 28.0 parts of an epoxy vinyl ester resin solution consisting of Using 28.0 parts of an epoxy vinyl ester resin solution consisting of methyl methacrylate (30%) and 4.8 parts of methyl methacrylate, 1500 mJ/cm2 was applied from the top and bottom using a mercury lamp under a nitrogen atmosphere.
Twenty laminate plates (II-3) having a thickness of 0.8 mm were obtained in the same manner as in Example 1 except that the ultraviolet rays were irradiated.

Using the obtained 20 laminates (II-3), the surface smoothness of the laminate, amount of resin flowing out during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 2.9%, water absorption rate: 0.13%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 4 A 0.8 mm thick laminate (II-4
) was obtained.

Using the obtained 20 laminates (II-4), the surface smoothness of the laminate, the amount of resin flowing out during molding, the water absorption rate, and the solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 3.1%, water absorption rate: 0.15%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 5 Twenty laminates (II-5) having a thickness of 0.8 mm were obtained in the same manner as in Example 1 except that 8 glass cloths were used instead of 4 glass cloths.

Using the obtained 20 laminates (II-5), the surface smoothness of the laminate, amount of resin flowing out during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 3.0%, water absorption rate: 0.14%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 6 100 parts of the epoxy resin composition (I-1) obtained in the same manner as in Example 1 and water with an average particle size of 8 μm were placed on two glass nonwoven fabrics each having a width of 1050 mm and a weight of 50 g/m2. The epoxy resin composition (I-6) mixed with 70 parts of aluminum oxide is impregnated and adhered, and after stacking, the epoxy resin composition is applied to glass cloth with a thickness of 0.18 mm and a weight of 210 g/m2 on both upper and lower surfaces. The impregnated glass cloth substrates impregnated with the substance (I-1) were laminated one by one, and the content of the epoxy resin compositions (I-1) and (I-6) in the entire impregnated substrate laminate was determined. The impregnation amount was adjusted to 72% using the rolls, and then both the upper and lower surfaces of the laminate were covered with 25 μm thick polyester films, and pre-cured by irradiating ultraviolet rays of 4000 mJ/cm2 from the top and bottom with a mercury lamp. The thickness was 1.
Twenty 6 mm laminates (II-6) were obtained.

Using the obtained 20 laminates (II-6), the surface smoothness of the laminate, amount of resin flowing out during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 2.9%, water absorption rate: 0.13%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 7 Epoxy resin 18.2 with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin
1 part, 22.8 parts of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, 2 parts of methylhexahydrophthalic anhydride
5.2 parts, 16.6 parts of an epoxy vinyl ester resin solution consisting of methacrylate (60%) of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (40%). , 0.18 parts of 1-hydroxycyclohexyl phenyl ketone, 0.33 parts of benzoyl peroxide,
A liquid epoxy resin composition (I-7) was prepared by mixing 2.8 parts of styrene and 0.28 parts of 2-ethyl-4-methylimidazole.
7) in the same manner as in Example 1 except that the thickness was 0.8
Twenty mm laminate plates (II-7) were obtained.

Using the obtained 20 laminates (II-7), the surface smoothness of the laminate, amount of resin flowing out during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 3.2%, water absorption rate: 0.12%, and solder heat resistance: ○. In addition, there was little variation in the results.

Example 8 An epoxy resin with an epoxy equivalent of 190 was obtained by the reaction of bisphenol A and epichlorohydrin.
1 part, 596.9 parts of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, and 37 parts of methyl methacrylate.
．． 2 parts of epoxy A partially vinyl esterified resin was obtained.

68.5 parts of a partially vinyl esterified product of this epoxy resin, 27 parts of methylhexahydrophthalic anhydride.
3 parts, 1-hydroxycyclohexyl phenyl ketone 0
．． 1 part of benzoyl peroxide, 2.0 parts of methyl methacrylate, and 0.6 parts of 2-ethyl-4-methylimidazole to prepare a liquid epoxy resin composition (I-7). did. This epoxy resin composition (
1-8) from the top and bottom using a mercury lamp.
A laminate (II-8) with a thickness of 0.8 mm was prepared in the same manner as in Example 1 except that 500 mJ/cm2 of ultraviolet rays were irradiated.
I got 20 pieces.

Using the obtained 20 laminates (II-8), the surface smoothness of the laminate, resin flow rate during molding, water absorption, and solder heat resistance were measured in the same manner as in Example 1. , Surface smoothness: Good, Resin flow rate during molding:
Good results were obtained: 3.2%, water absorption rate: 0.14%, and solder heat resistance: ○. In addition, there was little variation in the results.

Comparative Example 1 An epoxy resin composition (I-
1) was applied to a long glass cloth with a thickness of 0.18 mm and a width of 1050 mm, and the content of the epoxy resin composition was 43%.
This was impregnated so that 4 sheets were layered, and further, 35 μm thick copper foil was layered on top and bottom of it, and the double belt was heated in a heating furnace at 110℃ for 4 minutes while being conveyed, and then heated to 170℃. After heating and pressure molding for 10 minutes with a press machine at a pressure of 20 kg/cm2,
It was cut to 0 mm and then post-cured at 170°C for 50 minutes to obtain 20 laminates (II'-1) with a thickness of 0.8 mm.

[0051] Using the obtained 20 laminates (II'-1), the surface smoothness of the laminate, the amount of resin flowing out during molding, the water absorption rate, and the solder heat resistance were measured in the same manner as in Example 1. However, fine undulations were observed on the surface of (II'-1).

[0052]

Effects of the Invention: A laminate can be obtained which can be precured at a low temperature and in a short time, has less volatilization of volatile substances, and has excellent surface properties.

Claims (1)

[Scope of Claims] [Claim 1] A long fibrous base material or a laminate thereof impregnated with a thermosetting epoxy resin composition containing an active energy beam-curable resin. A method for manufacturing a laminate, which comprises pre-curing by irradiating with metal foil, and then superimposing metal foils and curing by heating. 2. The method according to claim 1, wherein the epoxy resin composition is a resin composition containing a resin component having a polymerizable unsaturated group. 3. The manufacturing method according to claim 1, wherein the epoxy resin composition is a resin composition containing an epoxy vinyl ester resin and a thermosetting epoxy resin. [
4. The method according to claim 1, wherein the epoxy resin composition is a resin composition containing a partially vinyl esterified epoxy resin. 5. The manufacturing method according to claim 3, wherein the epoxy resin composition is a resin composition containing an acid anhydride compound as a curing agent. 6. The manufacturing method according to claim 1, wherein the fibrous base material is a long glass cloth and/or a glass nonwoven fabric. 7. The manufacturing method according to claim 1, wherein the active energy rays are ultraviolet rays.