JPH04329130A - Preparation of laminated sheet and precuring method - Google Patents

Abstract

PURPOSE:To obtain a laminated sheet capable of being subjected to uniform precuring in efficient energy consumption by covering the single surface of a fibrous base material impregnated with an epoxy resin composition containing an energy ray curable component with a metal foil and irradiating the same with active energy rays from the surface opposite to the metal foil of said base material. CONSTITUTION:An active energy ray permeable impregnated fibrous base material impregnated with a resin composition consisting of a resin containing a polymerizable unsaturated group as a component curable by active energy rays being ultraviolet rays and an acid anhydride curable type epoxy resin is composed of long glass cloth and/or glass paper. The single surface of this base material or an active energy ray permeable impregnated fibrous laminate composed of a plurality of the base materials is covered with metal foil and the base material or laminate is irradiated with active energy rays from the surface opposite to the metal foil to be precured and subsequently cured under heating and pressure. In an arbitrary stage before precuring, the surface opposite to the metal foil of the base material or the laminate is covered with an active energy ray permeable film.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a laminate, which consumes energy efficiently and can uniformly pre-cure.

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 Patent Laid-Open 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 pre-curing is performed by heating under no pressure, it is possible to pre-cure the entire laminate uniformly and sufficiently without any deviation, but there is a problem that fine wrinkles occur in the copper foil and the pre-curing process is difficult. There is a problem that more energy is required for curing.

On the other hand, in the pre-curing method using active energy rays, the amount of energy can be reduced compared to pre-curing using heat, and the laminate can be uniformly distributed over the entire laminate without any deviation, and can be cured to the necessary extent. can be precured, but a device that can irradiate active energy rays from above and below is required.

[0005]

[Means for Solving the Problem] As a result of intensive research in view of the above situation, the present inventors have devised the following method: one side of a fibrous base material impregnated with an epoxy resin composition containing an energy beam curable component. Covering the laminate with metal foil and irradiating active energy rays from the opposite side of the metal foil will suffice with a device that irradiates active energy rays from only one side, and even if the amount of irradiation energy is further reduced, it will not affect the entire laminate. The present inventors have discovered that it is possible to precure uniformly and to the necessary extent without any deviation over the entire area, and have completed the present invention.

That is, the present invention provides an active energy ray transparent impregnated fibrous base material impregnated with an epoxy resin composition containing an active energy ray curable component, or an active energy ray transparent impregnated fibrous base material formed by laminating a plurality of sheets thereof. One side of the impregnated fibrous laminate is covered with metal foil (1), then the base material or laminate is irradiated with active energy rays from the opposite side of the metal foil (1) to precure, and then cured by heating and pressure. A method for producing a metal foil-clad laminate, and an active energy ray-transparent impregnated fibrous base material impregnated with an epoxy resin composition containing an active energy ray-curable component, or a plurality of sheets thereof laminated. One side of the active energy ray-transparent impregnated fibrous laminate is covered with a metal foil (1), and then the base material or the laminate is irradiated with active energy rays from the opposite side of the metal foil (1). A method for pre-curing an impregnated fibrous laminate is provided.

First, an epoxy resin composition containing an active energy beam-curable component will be explained. Examples of the active energy beam-curable component according to the present invention include acrylic resins such as polyether acrylate, polyester acrylate, polyurethane acrylate, and epoxy vinyl ester, unsaturated polyester resins,
Spirane resin, diallyl phthalate resin, etc. are used, but acrylic resins are preferred from the viewpoint of adhesion to metal foil, and epoxy vinyl ester resins are particularly preferred.

Furthermore, as the epoxy vinyl ester resin, a resin in which the esterification rate of the epoxy groups in the epoxy resin is usually greater than 20%, preferably 30% or more is used. Epoxy vinyl ester resin may be produced by any method, but for example, it may be produced by esterifying an epoxy resin and an unsaturated monobasic acid in the presence of an esterification catalyst if necessary. Examples include the resins obtained.

Typical examples of the above epoxy resin include epichlorohydrin or β-methylepichlorohydrin, bisphenol A, and brominated bisphenol A.
, bisphenol F or bisphenol S; phenol or alkylphenol.
Polyglycidyl ethers of novolac resins; 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 ethers; adipic acid,
Polyglycidyl esters of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or dimer acid; cyclohexene-based epoxy compounds obtained by epoxidizing cyclohexene or its derivatives with peracetic acid etc. (3, 4-Epoxy-6-
Methyl-cyclohexyl-3,4-epoxy-6-methyl-cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate, 1-epoxyethyl-3,4-
cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclopentadiene oxide, 2,3
-epoxycyclopentyl ether, etc.); limonene dioxide; and glycidyl ether ester of hydroxybenzoic acid, which can be used alone or in combination of two or more.

Typical unsaturated monobasic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutyl maleate, sorbic acid, and mono(2- ethylhexyl) malate, etc., and these may be used alone or in combination of two or more.

[0011] Furthermore, as an esterification catalyst to be used as necessary when producing an epoxy vinyl ester resin,
Generally known compounds are used, but phosphorus compounds such as phosphine derivatives and quaternary phosphonium salts are preferred, and phosphine derivatives such as triphenylphosphine and tri-n-butylphosphine are particularly preferred. These esterification catalysts may be added in catalytic amounts;
For example, about 100 to 10,000 ppm may be added to the epoxy resin and unsaturated monobasic acid as raw materials.

[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.

Representative examples of such polymerization inhibitors include hydroquinone, pt-butylcatechol,
Hydroquinones such as mono-t-butylhydroquinone; hydroquinone monomethyl ether, di-t-p-
Examples include phenols such as cresol; quinones such as p-benzoquinone, naphthoquinone, and p-torquinone; and copper salts such as copper naphthenate.

These epoxy vinyl ester resins may be used by being dissolved in a solvent such as ketones or esters, or may be used by being dissolved together with other raw materials such as epoxy resin, but polymerizable vinyl monomers may be used. It is preferable to use only Examples of the polymerizable vinyl monomer in this case include styrene, vinyltoluene, t-butylstyrene,
Styrene and its derivatives such as chlorstyrene or divinylbenzene; ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate
low boiling ester monomers of (meth)acrylic acid such as acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; or trimethylolpropane tri(meth)acrylate, diethylene glycol Examples include (meth)acrylates of polyhydric alcohols such as di(meth)acrylate, 1,4-butanediol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate, among which viscosity is low. Styrene, vinyltoluene, (meth)
Low boiling ester monomers of acrylic acid are preferred.

The active energy rays used in the present invention include ultraviolet rays, gamma rays, and electron beams, but ultraviolet rays are preferred from the viewpoints of operability, safety, cost, etc. of the apparatus. When an electron beam curable component is selected as the active energy ray curable component, it is not particularly necessary to use a photoinitiator in combination, but when an ultraviolet ray curable component is selected, it is preferable to use a photoinitiator in combination. .

Examples of the photopolymerization initiator used as necessary when curing the active energy ray-curable component include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin ether compounds such as 1-hydroxycyclohexylphenyl ketone, benzophenone,
Benzophenone compounds such as 4-chlorobenzophenone, methyl orthobenzoylbenzoate, 3,3'-dimethyl-4-methoxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide dibenzyl, benzyl dimethyl ketal, benzyl diethyl ketal ketal compounds such as -al, 2,2'-diethoxyacetophenone,
2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone Acetophenone compounds such as pt-butyltrichloroacetophenone, thioxanthone 2-chlorothioxanthone, 2-methylthioxanthone , 2,4-dimethylthioxanthone, 2-ethylanthraquinone, 2-propylanthraquinone, and other thioxanthone compounds.

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

In the present invention, an epoxy resin composition is prepared by mixing the active energy beam-curable component and a thermosetting epoxy resin composition. Next, the components of the thermosetting epoxy resin composition will be explained.

As the epoxy resin that can be used in preparing the composition used in the present invention, for example, the epoxy resin that can be used for producing the above-mentioned epoxy vinyl ester resin can be used as is. The epoxy resin used in this case is preferably one that is liquid at room temperature, for example, a liquid epoxy resin having an average epoxy equivalent of 100 to 400.

[0020] Further, as a curing agent for curing the epoxy resin in the epoxy resin composition according to the present invention,
Examples include aromatic polyamines and their salts, polybasic acid anhydrides, boron trifluoride-amine complexes, dicyandiamide, dibasic acid hydrazides, diaminomaleonitrile, melamine, imides, etc. Among them, polybasic acids that are liquid at room temperature Anhydrides are 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)
Examples include -3-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 these, preferred are liquid forms such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic anhydride. Also, 5-(2,5
-dioxotetrahydrofuryl)-3-methyl-3-
A solution obtained by dissolving a solid acid anhydride such as cyclohexene-1,2-dicarboxylic acid with a liquid acid anhydride is also preferably used.

[0021] Examples of the curing accelerator used as necessary during curing of the epoxy resin composition include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, and diethylaminopropylamine; Contains aromatic rings such as menthene diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, alicyclic amines such as N-aminoethylpiperazine, metaxylene diamine, tetrachloro-p-xylene diamine, etc. Aliphatic amine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
Aromatic amines such as bisaminomethyldiphenylmethane,
2-Methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-
imidazole compounds such as 2-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole;
Further examples include latent curing accelerators, but it is particularly desirable to use latent curing accelerators in view of not reducing the storage stability of the epoxy resin composition of the present invention.

[0022] Examples of the latent curing accelerator include:
■Frozen type latent curing accelerator made by mixing epoxy resin and amine compound and immediately freezing to stop the reaction, ■Microcapsule type latent curing accelerator made by microcapsulating amine compound, ■Monocular sieve. Monocular sieve type latent curing accelerator with compound adsorbed,■
Latent curing accelerators are made by surface-treating adducts of amine compounds and compounds with epoxy groups with compounds having isocyanate groups. The latent curing accelerator (2) above is particularly preferred since it has an appropriate curing accelerating effect and does not cause deterioration in physical properties.

The above adduct of an amine compound and an epoxy compound can be produced, for example, by a conventionally known general method. The reaction ratio between the amine compound and the epoxy compound is such that the number of epoxy groups is 1.0 to 1.5, preferably 1.2 to 1.4 per active hydrogen of the amine compound. It is. Although the addition reaction may be carried out without a solvent, a method is usually used in which the amine compound is dissolved in a suitable solvent and the epoxy compound is added dropwise or in portions. The solvent used in this case is preferably an aromatic solvent or a ketone solvent, such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and the like. When the above addition reaction is carried out in a solvent-free system, it is preferable to use the resulting adduct after pulverizing it to a desired particle size. Further, when the above addition reaction is carried out in a solvent, after the reaction is completed, a method of spray drying using a spray drying method, a method of removing the solvent and pulverizing, etc. can be adopted. The particle size of the adduct is usually 30 μm or less, preferably 0.1 to 10 μm, particularly 1 to 6 μm. The particle size of the adduct is 3
If it exceeds 0 μm, the dispersibility tends to be poor.

[0024] Examples of amine compounds that can be used in the production of the adduct (2) above include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine,
Aliphatic amines such as diethylaminopropylamine, menzendiamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, alicyclic amines such as N-aminoethylpiperazine, metaxylene diamine, tetrachloro-p - Aliphatic amines containing aromatic rings such as xylene diamine, aromatic amines such as metaphenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, bisaminomethyldiphenylmethane, 2
-Methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2
Examples include imidazole compounds such as -methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

Further, as the compound having an epoxy group that can be used in producing the adduct, any compound having one or more epoxy groups can be used, such as aliphatic glycidyl ether, aromatic glycidyl ether,
Examples include monoepoxy compounds such as glycidyl alkylate, epoxy resins that can be used in producing the epoxy vinyl ester resin, and solvent-free liquid or solid epoxy resins are particularly preferred.

The method for surface treating the adduct of the amine compound and epoxy compound with a compound having an isocyanate group is not particularly limited, but for example, a solvent that does not dissolve the adduct in powder form, such as toluene, xylene, acetone, etc. Examples include a method of first dissolving a predetermined amount of a compound having an isocyanate group in methyl ethyl ketone or the like, then dispersing the powdered adduct therein, subjecting the surface to treatment, scattering the solvent, and drying. The amount of the compound having an isocyanate group used is usually 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight, per 100 parts by weight of the above adduct.
Parts by weight.

Examples of compounds having isocyanate groups that can be used to treat the surface of the adduct include aromatic or aliphatic monoisocyanates, aromatic or aliphatic polyisocyanates, and polysaccharides which are adducts of polyols and polyisocyanates. Examples include isocyanate, biuret type polyisocyanate obtained by reaction of polyisocyanate and water, cyclopolymerization type polyisocyanate, etc.
Specifically, monoisocyanate compounds such as phenyl isocyanate and tolyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isopropylidenecyclohexyl isocyanate, lysine isocyanate, tolylene diisocyanate and trimethylolpropane. Polyisocyanate compounds such as adducts, adducts of tolylene diisocyanate and pentaerythritol, adducts of tolylene diisocyanate and polyethylene glycol, adducts of tolylene diisocyanate and polypropylene glycol, prepolymers of hexamethylene diisocyanate and polyethylene adipate, etc. It will be done. Among these, aromatic or aliphatic polyisocyanates and polyisocyanates which are adducts of polyols and polyisocyanates are preferred.

[0028] The composition according to the present invention may optionally contain:
Fillers can be added. Examples of fillers used in this case include aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, calcium sulfate, mica, talc, titanium dioxide, quartz powder, zirconium silicate, glass powder, asbestos powder, diatomaceous earth. , antimony trioxide, etc.

The composition used in the present invention comprises an active energy ray-curable component, a photoinitiator used as necessary to cure the component, an epoxy resin, a curing agent thereof, and a curing agent used as necessary. The content of the active energy ray curable component in the total weight of the active energy ray curable component, the epoxy resin component, and the epoxy resin curing agent component, which are essential components, is usually 2. ~
80% by weight, and has excellent adhesive strength with metal foil.
It is preferable that it is 50%.

[0030] 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.

Next, a fibrous base material is impregnated with the above epoxy resin composition to prepare an impregnated fibrous base material. The impregnated fibrous base material needs to transmit active energy rays. The fibrous base material used in the present invention is preferably one that transmits active energy rays after being impregnated with the epoxy resin composition according to the present invention. Typical examples of such fibrous base materials include glass fibers, carbon fibers, and aromatic polyamide fibers, of which glass fibers are preferred. Among these, glass fibers include E-glass, C-glass, A-glass, and S-glass in terms of their raw materials.
- Although there are glasses, any type can be applied in the present invention. These fibrous base materials are
Depending on the shape, there are rovings, chopped strand mats, continuous mats, cloths, non-woven fabrics, roving cloths, surfacing mats, and chopped strands, but the types and shapes listed above are selected as appropriate depending on the intended use and performance of the molded product. If necessary, two or more types or shapes may be used in combination. Among them, cloth and nonwoven fabric are preferred.

The precuring method of the present invention is to precure the active energy ray-curable component in the impregnated fibrous base material by irradiation with active energy rays. One side of the laminate was covered with metal foil (1
) and then pre-cure by irradiating active energy rays from the opposite side of this metal foil.

Metal foil (1) that can be used in this case
Examples include metal foils such as gold foil, silver foil, copper foil, and aluminum foil. When preliminary curing is performed by irradiating active energy rays from the opposite side of the metal foil (1) in this way, not only the active energy ray irradiated surface (i.e. the surface of the impregnated fibrous base material or its laminate) but also the active energy The wire penetrates into the interior of the impregnated fibrous base material or the laminate thereof, near the bonding area between the metal foil and the impregnated fibrous base material or the laminate thereof, and surprisingly, further penetrates into the impregnated fibrous base material or the laminate thereof. Precuring can be performed evenly and uniformly throughout the entire thickness, even at the center of the thickness.

The amount of active energy ray irradiation is not particularly limited and may be selected depending on the type of active energy ray used and the time for preliminary curing, but in the case of ultraviolet rays, usually 2000 ~20000mJ/
It is sufficient to perform irradiation with an energy amount of cm.

[0035] This active energy ray irradiation is applied to metal foil (
This may be carried out with the impregnated fibrous base material on the opposite side of 1) exposed, or the impregnated fibrous base material on the opposite side of the metal foil (1) may be coated with active energy ray transparent film (2) in advance. You may also cover the film (2) and perform the process from above.

Examples of the active energy ray transparent film (2) include plastic films such as polyethylene, polypropylene, polyester, polyimide, and polyfluoroethylene films.

[0037] Of the energy ray-curable components, the uncured portions upon irradiation with active energy rays can be thermally cured in the next heating step. The method of heating and curing the precured fibrous base material or laminate after precuring is not particularly limited, and any known and commonly used method can be employed. The heat curing method may be carried out under no pressure in a continuous heating furnace, or may be continuously heated and pressed in a continuous double belt press, but from the viewpoint of surface smoothness of the laminate, heating is Pressure molding is preferred. Alternatively, the pre-cured laminate may be cut and subjected to batchwise heating and pressure molding. Heat curing is usually performed at 130 to 190°C. In the case of hot pressure molding, it is usually carried out under a pressure of 5 to 40 kg/cm2.

[0038] 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, the lower surface of the fibrous base material alone or a predetermined number of laminated sheets is covered with metal foil (1), and the upper surface is exposed to air or air while being transported. Precure by irradiation with active energy rays in an inert gas such as nitrogen, then cover the top surface with a film that may or may not be transparent to active energy rays, then heat cure and peel off the film. Method for producing a single-sided metal foil-clad laminate, ■ Impregnating a fibrous base material with an epoxy resin composition, covering the lower surface of the single or predetermined number of laminated sheets with metal foil (1), and transmitting active energy rays to the upper surface. A method for manufacturing a single-sided metal foil-clad laminate, which comprises covering the sheet with a plastic film (2), pre-curing it by irradiating active energy rays from the top surface while transporting it, then curing it by heating, and then peeling off the top film (2); ■A fibrous base material is impregnated with an epoxy resin composition, and the bottom surface of the material is covered with metal foil (1) either alone or in a predetermined number of layers, and activated energy is applied from the top surface in the air or inert gas such as nitrogen while transporting the material. Pre-cure by irradiating the wire, then cover the top surface with metal foil (
Method for manufacturing a double-sided metal foil-clad laminate, covered with 1) and then heated and cured; Cover the upper surface with an active energy ray-transparent film (2), irradiate active energy rays from the upper surface to pre-cure while transporting, peel off the film (2), and then cover the upper surface with a metal foil (1). For example, a method for manufacturing a double-sided metal foil-clad laminate in which the metal foil is covered with a metal foil and further heat-cured is used.

As shown in (1) and (2) above, when the film, which may or may not be transparent to active energy rays, is peeled off after being heated and cured, the pre-cured fibrous base is peeled off immediately after being pre-cured. This is preferable because it does not cause problems such as distortion of the material or the laminate, a large amount of resin adhering to the peeled film, and a decrease in the amount of resin near the surface of the pre-cured fibrous base material or the laminate.

Compared to the manufacturing method (2), the above manufacturing method (2) may cause distortion in the pre-cured fibrous base material or laminate, or a large amount of resin may adhere to the film to be peeled off, causing the pre-curing to be difficult. This is preferable because there is no problem that the amount of resin near the surface of the fibrous base material or the laminate decreases.

[0041]

[Examples] 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 with an epoxy equivalent of 190 obtained by reaction of bisphenol A and epichlorohydrin 18.2
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 of epoxy resin obtained by the reaction of tetrabromobisphenol A and epichlorohydrin 370 epoxy resin methacrylate (60%) and styrene monomer (40%) to prepare a solution of epoxy vinyl ester resin 28.0% parts, 0.3 parts of 1-hydroxycyclohexylphenyl ketone, 0.3 parts of benzoyl peroxide.
56 parts, 4.8 parts of styrene monomer and 2-ethyl-
A liquid epoxy resin composition (I-1) was prepared by mixing 0.28 part of 4-methylimidazole.

[0042] Then, immediately this epoxy resin composition (
I-1) was added 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 layering 4 of these sheets and layering a 35 μm thick copper foil on the bottom surface, the top surface was exposed to ultraviolet rays at 6000 m using a mercury lamp (80 W/cm) in an air atmosphere.
The laminate was precured by transporting it while irradiating it at a rate of J/cm.

A part of this pre-cured laminate was cut out as a sample, and then the first layer (the layer in contact with the copper foil) and the fourth layer (the outermost layer, that is, the layer exposed to ultraviolet rays) were peeled off. When the resin was extracted from the glass cloth layer with tetrahydrofuran and analyzed using a liquid chromatograph (LC-08 manufactured by Nippon Analytical Industry Co., Ltd.), the reaction rate of each epoxy vinyl ester resin was 60%.

Next, a 35 μm thick copper foil was superimposed on the upper surface of the pre-cured laminate that remained after the sample was collected, and
20kg/double belt press machine heated to 70℃
After heating and pressure molding for 10 minutes at a pressure of cm2, 1000
mm x 1000 mm, and then post-cured at 170°C for 50 minutes to form a double-sided copper-clad laminate with a thickness of 0.8 mm.
I got one.

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. Good results were obtained with a small amount of The results are shown in Table 1.・Surface smoothness: The occurrence of fine waviness on the surface of the laminate was visually determined.・Resin flow rate (%) = (W0 - W1)/W0 ×10
It was calculated at 0 and shown as an average value. (However, W0 has an epoxy resin composition content of 43%, dimensions of 1000 mm x
The weight of four resin-impregnated substrates of 1000 mm, W1, is the weight obtained by subtracting the weight of the copper foil from a laminate with dimensions of 1000 mm x 1000 mm obtained by heat-pressure molding. ) ・Water absorption rate (%): After removing the copper foil on one side of the laminated board cut into 25 mm x 25 mm by etching, it was heated at 120°C for 2
A pressure cooker test was conducted for 4 hours under atmospheric pressure conditions, and the water absorption rate was calculated based on the following formula, and the average value was shown. W'-W Water absorption rate (%) = ------- x 100 W (W is the weight of the laminate before the test, W' is the weight of the laminate after the test.) Solder heat resistance: Pressure cooker above After thoroughly wiping off moisture on the surface of the laminate after the test, it was measured according to JIS C-6481 and evaluated using 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 Same as Example 1 except that the upper surface of the pre-cured laminate of Example 1 was covered with a 25 μm thick PET film instead of the copper foil laminated on the upper surface, and the 25 μm thick PET film was peeled off after heat curing. 20 single-sided copper-clad laminates each having a thickness of 0.8 mm were obtained.

A sample was taken from the pre-cured laminate before being coated with PET film, and the reaction rate of the epoxy vinyl ester resin was measured for the first and fourth layers of the pre-cured laminate in the same manner as in Example 1. When investigated, the reaction rates were all 60%.

[0047] The remaining pre-cured laminate was heat-cured under the same conditions as in Example 1. The results are shown in Table 1. Example 3 A 25 μm thick PET film was used instead of the copper foil laminated on the top surface of the pre-cured laminate in Example 1, and the top surface was covered with the PET film before irradiation with active energy rays.
Next, pre-cure, and after heat curing the above 25 μm
Twenty single-sided copper-clad laminates each having a thickness of 0.8 mm were obtained in the same manner as in Example 1, except that the thick PET film was peeled off.

After the completion of pre-curing, PE is removed from the pre-cured laminate.
The first layer (the layer in contact with the copper foil) and the fourth layer (the layer in contact with the PET film) of the pre-cured laminate were prepared in the same manner as in Example 1, except that the T film was peeled off and a sample was taken from it. When the reaction rates of the epoxy vinyl ester resins were investigated for the layer containing the epoxy resin, the reaction rates were all 60%. Heat curing was performed under the same conditions as in Example 1 using the remaining pre-cured laminate. The results are shown in Table 1. Example 4 A glass cloth with a thickness of 1.6 mm was prepared in the same manner as in Example 1, except that the glass cloth of Example 1 was impregnated with the epoxy resin composition to a content of 43%, and 6 sheets of this were stacked on top of each other. 20 double-sided copper-clad laminates were obtained.

A part of this pre-cured laminate was cut out as a sample, and then the first layer (the layer in contact with the copper foil) and the sixth layer (the outermost layer, that is, the layer exposed to ultraviolet rays) were peeled off. When the resin was extracted from the glass cloth in the first layer with tetrahydrofuran and analyzed using a liquid chromatograph (LC-08 manufactured by Nippon Analytical Industry Co., Ltd.), the reaction rate of the epoxy vinyl ester resin in the first layer was 60%, and the reaction rate of the epoxy vinyl ester resin in the first layer was 60%. That of the layer was 62%. Comparative Example 1 The epoxy resin composition (I-1) of Example 1 was
A long glass cloth measuring 8 mm and width 1050 mm was impregnated with the epoxy resin composition so that the content was 43%, and four sheets were stacked together, and a copper foil with a thickness of 35 μm was stacked on the bottom surface. The laminate was precured at 110° C. for 4 minutes.

[0050] This pre-cured laminate had fine undulations in the copper foil. Next, a 35 μm thick copper foil was superimposed on the upper surface of the pre-cured laminate that remained after collecting the sample,
20kg in a double belt press heated to 170℃
After heating and pressure molding at a pressure of /cm2 for 10 minutes,
Cut into 0mm x 1000mm, then heat at 170℃ for 50 minutes.
After curing for 2 minutes, the double-sided copper clad laminate with a thickness of 0.8 mm was
I got 0 pieces.

The degree of waviness in the copper foil of the laminate that had covered the laminate before pre-curing became more noticeable than immediately after pre-curing. The results are shown in Table 1.

[0052]

[Table 1]

[0053]

[Effects of the Invention] In the present invention, one side of the impregnated fibrous base material or its laminate is covered with metal foil, and active energy rays are irradiated from the opposite side of the metal foil, so the active energy ray irradiation device is used to irradiate the active energy rays from one side. It has the particularly remarkable effect of being able to be used as an irradiation device, reducing the amount of irradiation energy, and being able to pre-cure the laminate uniformly and sufficiently without any deviation over the entire laminate. play.

Moreover, since the preliminary curing is performed using active energy rays, no waving phenomenon occurs in the metal foil.

Claims (7)

[Claims] Claim 1: An active energy ray permeable impregnated fibrous base material impregnated with an epoxy resin composition containing an active energy ray curable component, or an active energy ray permeable impregnated fibrous material obtained by laminating a plurality of sheets thereof. It is characterized by covering one side of the laminate with metal foil (1), then irradiating the base material or the laminate with active energy rays from the opposite side of the metal foil (1) to pre-cure it, and then heating and curing it. A method for manufacturing metal foil-clad laminates. Claim 2: At any stage before pre-curing, metal foil (
2. The manufacturing method according to claim 1, wherein the base material or the laminate surface opposite to step 1) is covered with an active energy ray-transparent film (2). 3. The manufacturing method according to claim 1 or 2, wherein the active energy rays are ultraviolet rays. 4. The method according to claim 1, wherein the active energy beam-curable component is a resin having a polymerizable unsaturated group. 5. The method according to claim 1, wherein the epoxy resin composition is a resin composition comprising an active energy beam-curable component and an acid anhydride-curable epoxy resin. 6. Claims 1, 2, 3, 4, wherein the fibrous base material is a long glass cloth and/or glass paper.
or the manufacturing method described in 5. 7. An active energy ray permeable impregnated fibrous base material impregnated with an epoxy resin composition containing an active energy ray curable component, or an active energy ray permeable impregnated fibrous material obtained by laminating a plurality of sheets thereof. A method for pre-curing an impregnated fibrous laminate, which comprises covering one side of the laminate with a metal foil (1), and then irradiating the base material or the laminate with active energy rays from the opposite side of the metal foil (1). .