JPH08858B2 - Laminated sheet and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate sheet suitably used for a packing for capacitors and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a packing for a capacitor, a laminate in which a proper number of resin-containing sheets in which a paper base material is impregnated with a phenol resin and a vulcanized rubber sheet are laminated is used. ing. The laminated body for a capacitor packing is required to have a resin-containing sheet and a rubber sheet firmly adhered to each other and integrated with each other, to have heat resistance, and to be less deteriorated in characteristics even at a high temperature.

In view of the above points, the laminated body for capacitor packing is usually laminated by subjecting a vulcanized rubber sheet to a surface treatment to activate the surface, then stacking the resin-containing sheets and heating and pressing. For the above-mentioned surface treatment, ultraviolet irradiation, electron beam irradiation (Japanese Patent Laid-Open No. 54-10888
5, Japanese Patent Publication No. 60-17338, Japanese Utility Model Publication No. 54
No. 141356), sulfuric acid treatment and the like are performed.

Further, since the heat resistance is mainly controlled by the kind of the rubber constituting the vulcanized rubber sheet, the kind of the rubber constituting the vulcanized rubber sheet is changed depending on the desired heat resistance. Manufactures laminates. More specifically, for example, when the packing for capacitors has a heat resistance of 85 ° C., styrene-butadiene rubber, 105 ° C.
In the above specification, ethylene-propylene rubber or ethylene-propylene-non-conjugated diene rubber is used.

However, the above-mentioned manufacturing method has a problem that the surface treatment step is required, so that the workability and the productivity are lowered, and the obtained laminate is expensive. Further, in the method by surface treatment, the degree of surface treatment is likely to change depending on the type of the vulcanized rubber sheet as the treatment base and the treatment conditions, so the adhesiveness between the resin-containing sheet and the vulcanized rubber sheet is likely to change, and the adhesiveness Also, it is difficult to efficiently manufacture a laminate having excellent integrity. Furthermore, since it is necessary to adjust the heat resistance of the vulcanized rubber sheet by changing the type of rubber, not only the workability is significantly reduced, but also the heat resistance of the vulcanized rubber sheet at high temperatures is combined with the above surface treatment. There is a limit to improving sex.

An object of the present invention is to provide a rubber sheet for a laminate which is excellent in adhesion, integrity and heat resistance with a resin-containing sheet.

Another object of the present invention is to provide a resin-containing sheet for a laminate, which has excellent adhesion and integrity with the rubber sheet for a laminate.

Still another object of the present invention is to provide a method for producing a laminate sheet, which does not require complicated steps, is excellent in the above properties, and is capable of producing a rubber sheet for a laminate easily and with high productivity. Especially.

[0009]

The first invention is a rubber sheet laminated with a resin-containing sheet containing a synthetic resin, wherein the rubber sheet is a monofunctional compound having a polymerization initiator and one polymerizable unsaturated group. The problems described above are solved by a sheet for a laminate that holds a polymerizable monomer or a polyfunctional compound having a functional group other than a polymerizable unsaturated group in an adhesive form.

A second invention is a resin-containing sheet to be laminated with the laminate sheet of the first invention, wherein the resin-containing sheet contains an uncured thermosetting resin. The above problems are solved.

A third aspect of the present invention is to solve the above-mentioned problems by using the resin-containing sheet as a laminate sheet containing a thermoplastic resin.

Further, the fourth invention, the monofunctional monomer, a method for producing a laminated-body sheet <br/> coated fabric to a rubber sheet containing at least an organic peroxide, solving the above problems To do.

[0013] Further, the fifth invention, the polymerizable composition containing a monofunctional monomer and a polymerization initiator, a method for producing a laminated-body sheet you coated cloth rubber sheet, the above-mentioned problems It is a solution.

In the present invention, various rubbers such as natural rubber, chlorinated rubber, hydrochloric acid rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber can be used as the rubber of the laminated rubber sheet. Examples thereof include chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-non-conjugated diene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, silicone rubber and urethane rubber.
The above rubbers are used alone or in combination of two or more. The rubber sheet may be in an unvulcanized state, but is preferably vulcanized in order to facilitate handling during lamination.
The thickness of the rubber sheet can be appropriately set depending on the application of the laminate, but when used as a packing for a capacitor, it is usually about 0.1 to 5 mm.

The polymerization initiator may be, for example, a polymerization initiator such as azobisisobutyronitrile,
Organic peroxides are preferred. This organic peroxide functions not only as a polymerization initiator for the monofunctional monomer but also as a vulcanizing agent for the rubber. Therefore, the rubber sheet in which at least the organic peroxide is retained may not retain other polymerization initiators or other vulcanizing agents such as sulfur.

Examples of the organic peroxide include lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and 1,1-bis (t-butylperoxy)-
3,3,5-Trimethylcyclohexane, ethyl methyl ketone peroxide, n-butyl-4,4-bis (t-
Butyl peroxy) barrel, dicumyl peroxide, t
-Butyl cumyl peroxide, di-t-butyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexane, 2,5-dimethyl-2,
Examples include various organic peroxides such as 5-di (t-butylperoxy) hexene-3 and t-butylperoxycumene. These organic peroxides are used alone or in combination of two or more.

The polymerizable unsaturated group of the monofunctional monomer may be any group which is polymerized by the action of a polymerization initiator,
It may be a vinyl group or an allyl group, but is preferably an acryloyl group or a methacryloyl group.

Examples of the monofunctional monomer having a vinyl group include vinyl chloride, vinyl acetate, vinyl propionate, styrene, α-methylstyrene and crotonic acid.

Examples of monofunctional monomers having an allyl group include allyl alcohol, allyl ethyl ether, allyl phenyl ether and allyl benzene.

The monofunctional monomer having one acryloyl group is a monofunctional monomer having an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent; a monofunctional monomer having a hydroxy group. Functional monomer; a monofunctional monomer having an alkoxy group or a phenoxy group; a monofunctional monomer having an acidic group; and other monofunctional monomers.

Examples of the monofunctional monomer having an alkyl group which may have a substituent, a cycloalkyl group, an aryl group and an aralkyl group include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, Isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, isostearyl acrylate, Behenyl acrylate, trifluoroethyl acrylate, 2,2,3
3-tetrafluoropropyl acrylate, 2,2
3,4,4,4-hexafluorobutyl acrylate,
Examples include perfluorooctylethyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, and 2-acryloyloxymethyl-2-benzoylmethylpropane.

As the monofunctional monomer having a hydroxy group, for example, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycerin monoacrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-
Examples thereof include acryloyloxyethyl-2-hydroxypropyl phthalate, 2-acryloyloxypropyl-2-hydroxypropyl phthalate, and 2-acryloyloxypropyl-2-hydroxyethyl phthalate.

As the monofunctional monomer having an alkoxy group or a phenoxy group, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, Examples include methoxy polyethylene glycol acrylate, 2-phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate, nonylphenoxyethyl acrylate, nonylphenoxy polyethylene glycol acrylate, and the like.

Examples of the monofunctional monomer having an acidic group include 2-acryloyloxyethyl succinic acid,
2-acryloyloxypropyl succinic acid, 2-acryloyloxyethyl adipic acid, 2-acryloyloxypropyl adipic acid, 2-acryloyloxyethyl maleic acid, 2-acryloyloxypropyl maleic acid, 2-acryloyloxyethyl phthalic acid, 2- Acryloyloxypropyl phthalic acid, 2-acryloyloxyethyl terephthalic acid, 2-acryloyloxypropyl terephthalic acid, 2-acryloyloxyethyl isophthalic acid, 2-acryloyloxypropyl isophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2- Examples include monoacryl ester of dicarboxylic acid such as acryloyloxypropylhexahydrophthalic acid, acrylic acid, and 2-acryloyloxy acid phosphate. .

Examples of other monofunctional monomers include metal salts of acrylic acid, glycidyl acrylate, acrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrolein, acrylonitrile and the like.

Examples of the monofunctional monomer having a methacryloyl group include monomers corresponding to the above monofunctional monomers having an acryloyl group.

These monofunctional monomers are preferably liquid or solid at room temperature and atmospheric pressure. These monofunctional monomers are used alone or in combination of two or more.

The functional group of the polyfunctional compound may be a functional group excluding a polymerizable unsaturated group, as long as it can ensure the adhesion to the resin-containing sheet. The polyfunctional compound preferably has two or more functional groups. Examples of the polyfunctional compound include an epoxy resin having an epoxy group, a polyisocyanate compound having an isocyanate group, and a silane coupling agent. These polyfunctional compounds can also be used alone or in combination of two or more. In addition, the polyfunctional compound may be used in combination with the monofunctional monomer.

The present invention also discloses a rubber sheet carrying a monomer in which a monofunctional monomer and a polyfunctional monomer are combined. That is, the monofunctional monomer may be used in combination with a polyfunctional monomer having two or more polymerizable unsaturated groups. In this case, the monofunctional monomer preferably contains at least a polymerizable monomer having a hydroxy group or a carboxy group. The monofunctional monomer having a hydroxy group or a carboxy group is a (meth) acrylic ester having a phthalic acid skeleton, for example, 2-
(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, mono (meth) acrylic ester of phthalic acid and the like are preferable.

The polyfunctional monomer used in combination with the monofunctional monomer having a hydroxy group or a carboxy group is 2 or more, preferably 3 or more polymerizable unsaturated groups in one molecule, such as vinyl. Group, an allyl group, an acryloyl group or a methacryloyl group.

The polyfunctional monomer having a vinyl group includes
For example, divinylbenzene and the like are included, and the polyfunctional monomer having an allyl group includes, for example, diallyl itaconate, diallyl phthalate, triallyl phosphate,
Examples include triallyl cyanurate and triallyl isocyanurate. Examples of the polyfunctional monomer having two or more acryloyl groups include ethylene glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate,
Tripropylene glycol diacrylate, polypropylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, dibromo neopentyl glycol diacrylate, 1,10-decanediol diacrylate, phenylene diacrylate, glycerin diacrylate , Glycerin triacrylate, diglycerin tetraacrylate, trimethylolpropane diacrylate, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2,
2-bis (4-acryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxy-3,3-dibromophenyl) propane, 2,
2-bis (4-acryloyloxypropoxyphenyl) propane, 2,2-bis (4-acryloyloxydipropoxyphenyl) propane, 2,2-bis (4-
Acryloyloxypolypropoxyphenyl) propane, trimethylolpropane triacrylate, di- or triacrylate of an adduct of trimethylolpropane with ethylene oxide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
Examples include N, N'-methylenebisacrylamide, hydrogenated dicyclopentadienyl diacrylate, 1,1-bis (acryloyloxymethyl) -1- (benzoylmethyl) propane and the like. The polyfunctional monomer also includes, for example, epoxy acrylate, polyester acrylate, urethane acrylate, melamine acrylate, and the like.

Examples of the polyfunctional monomer having two or more methacryloyl groups include monomers corresponding to the above polyfunctional monomers having an acryloyl group.

The polyfunctional monomer is a monomer having an acryloyl group and a methacryloyl group in the molecule, for example,
It may be 3-acryloyloxyglycerin monomethacrylate or 2-hydroxy-3-acryloyloxypropyl methacrylate.

Among the polyfunctional monomers, monomers having two or more, preferably three or more acryloyl groups or methacryloyl groups in the molecule, such as trimethylolpropane triacrylate and trimethylolpropane trimethacrylate are preferable.

When the monofunctional monomer and the polyfunctional monomer are used in combination, the vulcanized rubber sheet and the resin-containing sheet are stacked in multiple layers and heated under pressure, as compared with the case where they are used alone, When laminating and adhering, strong adhesion can be obtained in a wide adhesion temperature range. That is, when the monomer is used alone, when the laminated plate in which the vulcanized rubber sheet and the resin-containing sheet are laminated in multiple layers is pressurized and heated, the temperature around the laminated plate becomes lower than that in the central part, The adhesion in the peripheral area of the plate is reduced. On the other hand, when the monofunctional monomer and the polyfunctional monomer are used in combination, the adhesiveness is excellent even in the peripheral region of the laminate, probably because the polymerization is performed even at a low temperature.

When the monofunctional monomer and the polyfunctional monomer are used in combination, the content of the monofunctional monomer is
Usually 30 to 90% by weight, preferably 50 to 80% by weight
Is.

The unvulcanized or vulcanized rubber sheet holds the polymerization initiator and the monofunctional monomer or the polyfunctional compound in a form capable of adhering. Examples of the form that can be adhered include a form such as a monomer and a low polymerized product of the monomer, and the polymerization initiator and the monofunctional monomer in the form that can be adhered, as long as they are held on at least the surface of the rubber sheet. Of course, it may be held over the entire rubber sheet including the surface.

When the monofunctional monomer or polyfunctional compound and the polymerization initiator are held in a form capable of adhering to the surface of the rubber sheet, the laminate laminated with the resin-containing sheet exhibits remarkably large adhesion. Usually, the resin-containing sheet and the rubber sheet are hardly separated from each other, and breakage or cohesive failure occurs in the rubber sheet. When the monofunctional monomer or the like and the polymerization initiator are held in a form capable of adhering to the surface of the rubber sheet, the rubber sheet contains not only organic peroxide but also other vulcanizing agents such as sulfur. It may be an unvulcanized rubber sheet or a vulcanized rubber sheet vulcanized with another vulcanizing agent.

When the monofunctional monomer or the like and the polymerization initiator are held in a form capable of adhering to the entire rubber sheet, the upper limit of the content of the monofunctional monomer in a form capable of adhering is a critical value. Although not desired, the content of the polymerizable monomer or the polyfunctional compound is usually 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the rubber. When the amount of the monofunctional monomer or the polyfunctional compound is less than 1 part by weight, the adhesion between the resin-containing sheet and the vulcanized rubber sheet is insufficient. Even when the amount of the monomer and the like exceeds 30 parts by weight, a large adhesion is exhibited, but it is not economical. When the content of the monofunctional monomer or the like in the above-mentioned form is in the above-mentioned range, a remarkably large adhesive force is exhibited, and usually, the rubber sheet undergoes cohesive failure at the time of peeling, and there is little deterioration in properties even under high temperature conditions, and heat resistance is improved. Are better.

The rubber sheet includes various additives, for example, co-vulcanizing agents such as sulfur and metal oxides other than organic peroxides; guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamine. Vulcanization accelerators such as acid salts and xanthates; vulcanization aids such as zinc white;
Vulcanization retarders such as sulfenamide compounds; antioxidants, antioxidants such as UV absorbers; carbon black, silicic anhydride, calcium silicate, aluminum silicate, clay, rayon, nylon, polyester, fragrance Reinforcing agents such as synthetic fibers such as group polyamide, carbon fibers, glass fibers; fillers or extenders such as calcium carbonate, talc, barium sulfate, alumina sulfate, lithopone, styrene resin, phenol resin, petroleum resin, recycled rubber; linole Softeners such as acids, oleic acid, tall oil;
Plasticizers; tackifiers such as alkylphenol resins, coumarone-indene resins and rosin derivatives; processing aids or lubricants such as stearic acid, metal stearate soaps and waxes; coloring agents and the like.

The content of the above-mentioned additive can be appropriately selected according to the characteristics of the rubber sheet.

The resin-containing sheet to be laminated with the rubber sheet for laminate of the present invention contains an uncured thermosetting resin. As this thermosetting resin, phenol resin,
Silicone resin, urea resin, melamine resin, furan resin, epoxy resin, vinyl ester resin, unsaturated polyester, diallyl phthalate resin, polyurethane, polyimide, etc. are exemplified, and one or more kinds are used. Of the above thermosetting resins, a resol-type phenol resin that is inexpensive and has excellent heat resistance is preferable. Further, since the phenol resin is excellent in reinforcing property, a thin resin-containing sheet can be formed.

The thermosetting resin contained in the resin-containing sheet is preferably a so-called B stage in order to improve handleability and mechanical strength.

The resin-containing sheet for laminate according to another embodiment of the present invention contains a thermoplastic resin. The thermoplastic resin is
It is preferable to have a functional group. Examples of the thermoplastic resin having a functional group include polyester having an ester bond such as polyethylene terephthalate, nylon or polyamide having an amide bond such as nylon 6, polycarbonate having a carbonate bond, polyacetal, polyphenylene oxide, polysulfone, polyether sulfone. , Polyphenylene sulfide, modified polyester having a hydroxyl group or a carboxy group, and the like. Among these thermoplastic resins, a polymer having an ester bond or an amide bond as a functional group is preferable.
The thermoplastic resin may include the oligomer having the functional group.

The resin-containing sheet may be composed of the above-mentioned thermosetting resin or thermoplastic resin alone, but in the case of a thermosetting resin, it is preferably used by holding it on a substrate.
In particular, impregnated paper obtained by impregnating paper with thermosetting resin, woven cloth, non-woven cloth, for example, impregnated woven cloth obtained by impregnating thermosetting resin with woven cloth or non-woven cloth made of natural or synthetic fiber, glass fiber, carbon fiber. It is preferably composed of Further, it is preferably composed of impregnated paper. The impregnated paper, etc.,
Depending on the desired thickness of the resin-containing sheet, for example, 5 to 2
An appropriate number such as 0 sheets can be used, and when used as a packing for a capacitor, it is usually about 0.5 to 5 mm. Further, when a thermoplastic resin is used, it is not necessary to impregnate the reinforcing base material. In this case, a thermoplastic resin-containing sheet to which a filler such as calcium carbonate or reinforcing fiber is added in order to enhance mechanical strength may be used.

The rubber sheet for a laminate can be produced by using a monofunctional monomer and / or a polyfunctional compound and a polymerizable composition containing the monomer and a polymerization initiator. That is, when a monofunctional monomer and / or a polyfunctional compound is used, the monofunctional monomer or the like may be applied to or kneaded with a rubber sheet containing at least an organic peroxide to form a rubber sheet. When the polymerizable composition is used, the rubber composition may be formed by coating or kneading the polymerizable composition on the rubber sheet. In any of the above cases, the obtained rubber sheet may be unvulcanized or vulcanized. Further, when the polymerizable composition is used, the rubber sheet may be an unvulcanized rubber sheet containing another vulcanizing agent such as sulfur or a vulcanized rubber sheet vulcanized with another vulcanizing agent such as sulfur. Good. More specifically, the following aspects can be mentioned as a method for producing the unvulcanized rubber sheet and the vulcanized rubber sheet.

(A) An unvulcanized rubber and a vulcanizing agent containing at least an organic peroxide are kneaded to form an unvulcanized rubber sheet, and then a monofunctional monomer is formed on the surface of the unvulcanized rubber sheet. Alternatively, a method of applying a polyfunctional compound to form an unvulcanized rubber sheet, (B) vulcanizing the unvulcanized rubber sheet obtained by the method of (A) above,
Method for forming a vulcanized rubber sheet, (C) unvulcanized rubber, a vulcanizing agent containing at least an organic peroxide, a monofunctional monomer or a polyfunctional compound is kneaded to form an unvulcanized rubber sheet (D) vulcanize the unvulcanized rubber sheet obtained by the method of (C) above,
Method of forming a vulcanized rubber sheet, (E) In the method of (A) (B), instead of the monofunctional monomer, a polymerizable composition is applied to the surface of the unvulcanized rubber sheet, and unvulcanized. A method of forming a rubber sheet or a vulcanized rubber sheet, (F) a method of applying a monofunctional monomer or a polymerizable composition to the surface of the vulcanized rubber sheet obtained by the methods (C) and (D), (G) ) Unvulcanized rubber and a vulcanizing agent containing at least an organic peroxide are kneaded, and a monofunctional monomer, a polyfunctional compound or a polymerizable composition is applied to the surface of the vulcanized vulcanized rubber sheet. Method, (H) polymerizable composition on the surface of an unvulcanized rubber sheet containing a vulcanizing agent other than organic peroxide, or on the surface of a vulcanized rubber sheet vulcanized with a vulcanizing agent other than organic peroxide How to apply etc.

Of the various embodiments described above, the methods (B) (D) (F) are particularly preferable. According to the method (B), workability,
It is possible to easily produce a rubber sheet which is excellent in productivity and is excellent in adhesiveness, integrity and heat resistance with a resin-containing sheet even when the coating amount is small. Further, according to the method (D), the vulcanized rubber sheet is cross-linked throughout with the monofunctional monomer and the like, and a rubber sheet excellent in adhesion, integrity and heat resistance can be obtained. Furthermore, according to the method (F), sufficient adhesion can be obtained even with a monofunctional monomer or the like for which it is difficult to obtain sufficient adhesion by the method (D).

The amount of the vulcanizing agent to be kneaded with the unvulcanized rubber can be set appropriately, and usually about 1 to 10 parts by weight of the vulcanizing agent is sufficient with respect to 100 parts by weight of the unvulcanized rubber.

When a monofunctional monomer, a polyfunctional compound or a polymerizable composition is applied to the surface of a rubber sheet, the amount applied to the surface of the rubber sheet is usually not less than 75 g / m ² so that it can be applied uniformly. The following is sufficient.

When the unvulcanized rubber and the monofunctional monomer or the like are kneaded, the ratio of the monofunctional monomer or the like is 100 to 1 part by weight of the unvulcanized rubber.
It is 0 part by weight, preferably 5 to 20 parts by weight. It should be noted that as the amount of the monofunctional monomer or the like increases, usually, there is a tendency that not the interfacial separation between the resin-containing sheet and the rubber sheet but the cohesive failure in the rubber sheet occurs.

The unvulcanized rubber sheet is vulcanized by, for example, 1
It can be performed by heating at a temperature of about 00 to 200 ° C.

The laminate is obtained by stacking an appropriate number of the resin-containing sheets and an unvulcanized rubber sheet or a vulcanized rubber sheet in the laminating step, and heating and pressurizing the laminate in the heating and pressing step. You can

In the laminating step, for example, the resin-containing sheet and the rubber layer may be simply superposed on each other or pressed by a pressure roller or the like. The heating and pressurizing step is performed under an appropriate condition that does not impair the integrity of the laminate, for example, a pressing pressure of 30 to 150.
30 under the condition of Kg / cm ² and temperature of 100-200 ℃
The pressure may be applied for about 6 minutes to 6 hours. By this heating and pressing,
The rubber sheet can be vulcanized when the rubber sheet is an unvulcanized rubber sheet, and the thermosetting resin can be cured when the thermosetting resin of the resin-containing sheet is in an uncured state, and a monofunctional monomer can be used. Can be polymerized. Therefore, the integrity of the resin-containing sheet and the rubber sheet can be significantly improved.

In the production of the laminate, the above (A)-
In the method (H), a monofunctional monomer, a polyfunctional compound or a polymerizable composition is applied or impregnated on the surface of the resin-containing sheet, not the unvulcanized rubber sheet or the vulcanized rubber sheet, and laminated and heated. You may pressurize. At that time, when a radical polymerizable resin such as vinyl ester resin or unsaturated polyester is used as the thermosetting resin in the resin-containing sheet, the monofunctional monomer or the polymerizable composition is used together with the radical polymerizable resin. It can be polymerized to increase the integrity of the laminate.

Further, when the resin-containing sheet contains a thermoplastic resin, high adhesion and integrity can be obtained, probably because the functional group of the thermoplastic resin contributes to the adhesion with the rubber sheet in the laminating step.

According to the method for producing a rubber sheet for a laminate of the present invention, it is not necessary to surface-treat the rubber sheet, and a laminate having excellent characteristics can be produced easily at low cost with high productivity. Therefore, the laminate sheet and the manufacturing method thereof according to the present invention are not limited to the capacitor packing, and the adhesiveness,
It is also suitable for application to various packings, insulating sheets, protective sheets, etc., which require integrity and heat resistance.

[0058]

As described above, according to the rubber sheet for a laminate of the present invention, the rubber sheet holds the polymerization initiator and the monofunctional monomer or the polyfunctional compound in a form capable of adhering. Excellent in adhesion, integrity and heat resistance with the resin-containing sheet.

Further, according to the resin-containing sheet for a laminate of the present invention, by containing and holding the thermosetting resin in an uncured state, it flows during heating and pressurization and then cures. Excellent adhesion and integration with.

According to the resin-containing sheet for a laminate of the present invention, the use of the thermoplastic resin causes the resin to be melted by heat at the time of heating and pressing, and the functional groups of the thermoplastic resin contribute to the adhesion. Excellent adhesion and integrity with rubber sheet.

Further, according to the production method of the present invention, a monofunctional monomer is applied or kneaded onto a rubber sheet containing at least an organic peroxide, or a polymerizable composition is applied or kneaded onto a rubber sheet. Therefore, a rubber sheet for a laminate, which is excellent in adhesiveness, integrity and heat resistance with a resin-containing sheet, can be easily produced with high productivity without requiring complicated steps.

[0062]

EXAMPLES The present invention will be described in more detail based on the following examples.

Example 1Resin-containing sheet  The paper base is impregnated with a resol-type phenolic resin and dried.
A resin-containing sheet kept in a cured state was produced.

[0064]Unvulcanized rubber composition and unvulcanized rubber sheet  Prepare an unvulcanized rubber composition consisting of the following (1) to (9) components
did.

(1) 100 parts by weight of ethylene-propylene rubber (manufactured by Mitsui Petrochemical Co., Ltd., trade name Mitsui EPT1035), (2) carbon black as a reinforcing agent (manufactured by Asahi Carbon Co., Ltd., trade name Asahi 35) (SRF)) 14 parts by weight, (3) Extended filler (Takehara Chemical Co., Ltd., trade name Sunlite 700) 70 parts by weight, (4) Reinforcing agent (Takehara Chemical Co., Ltd., trade name Hytron A)
20 parts by weight, (5) Vulcanization aid (manufactured by Shodo Chemical Co., Ltd., Zinc Hua No. 1) 5 parts by weight, (6) Processing aid, stearic acid as a dispersant (manufactured by NOF Corporation) 0.5 parts by weight, (7) 0.4 parts by weight of dispersible sulfur (Yab Shoten Co., Ltd.), (8) Organic peroxide (manufactured by NOF CORPORATION, trade name Perhexa 3M-40) 7.5 Parts by weight, (9) 2 parts by weight of trimethylolpropane trimethacrylate (Kyoeisha Oil and Fat Chemical Co., Ltd., trade name Light Ester TMP) as a vulcanization aid, the unvulcanized rubber composition,
An unvulcanized rubber sheet was produced by forming it to a thickness of 1.0 mm.

About 45 g / m ² of 2-hydroxyethyl methacrylate (Kyoeisha Yushi-Kagaku Kogyo KK, trade name Light Ester HO) was applied to an unvulcanized rubber sheet and pressed against a heating drum to be vulcanized. A vulcanized rubber sheet was obtained.

A predetermined number of the obtained vulcanized rubber sheet and the resin-containing sheet are stacked, and the press pressure is 80 kg / cm ² ,
By heating and pressurizing at a temperature of 160 ° C. for 1 hour, and then performing a cooling press for 30 minutes at the same pressure, a thickness of 2.
A 0 mm laminate was prepared.

Example 2 In the same manner as in Example 1 except that dimethylaminoethyl methacrylate (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd., trade name Light Ester DM) was used in place of the 2-hydroxyethyl methacrylate of Example 1. A vulcanized rubber sheet and a laminate were obtained.

Example 3 As the resin-containing sheet, a polyethylene terephthalate sheet containing calcium carbonate as a filler was used, and the unvulcanized rubber sheet used in Example 1 and a pressing pressure of 20 kg / c.
By heating and pressurizing for 45 minutes under the condition of m ² and temperature of 165 ° C., and performing a cooling press for 30 minutes at the same pressure,
A laminate having a thickness of 2.0 mm was produced.

Comparative Example A laminate was prepared in the same manner as in Example 1 without applying 2-hydroxyethyl methacrylate.

Then, the peeled state between the vulcanized rubber sheet and the resin-containing sheet of the laminates obtained in each of the examples and comparative examples was observed, and the results shown in the table were obtained.

[0072]

[Table 1] From the table, it is possible to obtain a laminate having excellent adhesion to the resin-containing sheet by applying the monofunctional monomer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiro Masuda 4-37, Minamitsukaguchi-cho, Amagasaki City, Hyogo Prefecture Risho Kogyo Co., Ltd. Amagasaki Plant (56) References Japanese Patent Publication No. 62-34797 (JP, B1) )

Claims (5)

[Claims] 1. A rubber sheet laminated with a resin-containing sheet containing a synthetic resin, the rubber sheet comprising a polymerization initiator and a monofunctional monomer having one polymerizable unsaturated group, or a polymerizable monomer. A sheet for a laminate, which holds a polyfunctional compound having a functional group except an unsaturated group in an adhesive form. 2. A resin-containing sheet laminated with the laminate sheet according to claim 1, wherein the resin-containing sheet contains an uncured thermosetting resin. . 3. A resin-containing sheet laminated with the laminate sheet according to claim 1, wherein the resin-containing sheet contains a thermoplastic resin. Wherein the monofunctional monomer, method for producing a laminated-body sheet, wherein the coating cloth to Rukoto the rubber sheet containing at least an organic peroxide. 5. A polymerizable composition comprising a monofunctional monomer and a polymerization initiator, method for producing a laminated-body sheet, wherein the coating cloth to Rukoto the rubber sheet.