JPS59148632A - Manufacture of metal plated plastic sheet reinforced with fiber - Google Patents

Abstract

PURPOSE:To obtain metal plated FRP containing no solvent and simplified in its molding process, by a method wherein a fibrous material for reinforcement is impregnated with an electron beam curing chemical compound including organic solvent, plated with metal foil and is made to set completely by the electron beam after mirror face pressing. CONSTITUTION:A fibrous base material for reinforcement is made to impregnate with a composite consisting of an electron beam setting chemical cmpound including ethylene unsaturated bond and an organic solvent. Then, after the foregoing fibrous material has been dried by making the organic solvent in the composite evaporate by hot air, mirror surface pressing is applied to the whole of the fibrous material and the electron beam setting chemical compound is made to set completely by irradiating the electron beam. As for the electron beam setting chemical compound including ethylene unsaturated bond to be used, prepolymar, oligomer and monomer having the ethylene unsaturated bond within their molecules can be cited. As for the organic solvent used for adjustment of adhesiveness, any of chemicals which can dissolve the foregoing electron beam curing chemical compound is pref. for use.

Description

Detailed Description of the Invention The present invention relates to a method for producing an improved metal-clad fiber reinforced plastic sheet (hereinafter referred to as "metal-clad FRP sheet"), which is a method for producing a metal-clad FRP sheet that is solvent-free and has a simplified molding process. It concerns the manufacturing method.

For example, when using an epoxy resin, the conventional manufacturing method for FRP sheets involves impregnating a reinforcing fibrous base material such as paper or fibers with a resin solution prepared by dissolving the resin in a volatile solvent, heating it, and pre-curing it. This is a method in which volatile solvents are removed and then heated and pressed using a hot press to form the product. In this method, the steps are complicated, and the loss of thermal energy and time required for heating is large, resulting in poor productivity.

On the other hand, unsaturated polyester resins are the most commonly used resins for FRP, both in terms of quantity and the wide range of fields in which they are used. Unsaturated polyester resin can be cured at room temperature and does not necessarily require pressure as there are no by-products during curing.
Although it has advantages such as being able to perform multi-layer molding, the resulting product is inferior in physical properties such as chemical resistance, heat resistance, electrical properties, and toughness.

As a result of research in order to solve the drawbacks of the conventional technology, the inventors of wood and others have injected electrons into a reinforcing fibrous base material impregnated with a resin liquid whose main component is an electron beam-curable compound that eats away at ethylenically unsaturated bonds. It was discovered that when irradiated with radiation, the resin liquid hardens and the time required to manufacture FRP sheets can be greatly shortened (Japanese Patent Application No. 111299/1982).

However, since the above method uses a solvent-free resin liquid, the impregnating suitability is insufficient unless the resin liquid is heated to lower the viscosity during impregnation. From the standpoint of impregnation suitability alone, it is better to use a low molecular weight compound, but even if such a low molecular weight compound is cured after impregnation, the resulting product will have poor strength, heat resistance, chemical resistance, etc. Furthermore, even if the physical properties of the obtained product are good, if the composition is solid at room temperature, it is necessary to set the heating temperature conditions high.

As a result of research in order to eliminate the drawbacks of the prior art, the present inventor has developed a composition for reinforcing fibers containing one or more types of ethylenically unsaturated bonds and one or more types of organic solvents. After the organic solvent is dried with hot air, a mirror press is applied, and then an electron beam is irradiated to completely cure the electron beam curable compound. This completes the present invention.

That is, the present invention involves impregnating a reinforcing fibrous base material with a composition comprising one or more electron beam curable compounds containing an ethylenically unsaturated bond and one or more organic solvents. After that, the organic solvent in the composition is evaporated with hot air and the composition is dried, and then the whole is subjected to a mirror press, and then irradiated with an electron beam. It is something.

The present invention will be explained in detail below.

Examples of the electron beam curable compound containing an ethylenically unsaturated bond used in the present invention include prepolymers or oligomers having an ethylenically unsaturated bond in the molecule, such as unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyesters, etc. Various types of acrylates such as ether acrylate, polyol acrylate, and melamine acrylate.

Various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, etc., which have an ethylenically unsaturated bond in the molecule, such as styrene 5α-methylstyrene Styrenic monomers such as methyl acrylate, acrylic acid 2-
Ethylhexyltoxyethyl, butoxyethyl acrylate, butyl acrylate, methacrylic acid esters such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Methoxyethinope methacrylate Methacrylic acid esters such as ethoxytityl methacrylate, phenyl methacrylate, and lauryl methacrylate; Unsaturated carboxylic acid amides such as acrylamide and acrylamide; Acrylic acid 2. -(N
, N-dimethylamino)ethyl, methacrylic acid 2-(N
, N-9methynoneamino)ethyl, acrylic acid 2-(N
．． N-dibenzylamino)ethyl, methacrylic acid (N.
N-dimethylamino)methyl, acrylic acid 2-(N.N
Substituted amino alcohol esters of unsaturated acids such as -diethylamino)propyl; ethylene glycol diacrylate), 4-opentyl glycol diacrylate), 1
．． 6-Hexanediol diacrylate.

Use one type or a mixture of two or more of polyfunctional compounds such as diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate. be able to.

To the electron beam curable compound containing an ethylenically unsaturated bond as described above, a thermoplastic resin may be added as an optional component up to 30 parts based on the total amount as long as it does not interfere with curing by electron beam irradiation. Examples of such thermoplastic resins include cellulose derivatives such as ethyl cellulose cellulose acetate bromine, cellulose acetate, styrene resins such as polystyrene and polyα-methylstyrene, and styrene copolymer resins.
Single or copolymer resins of acrylic or methacrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, polymerized rosin, etc. Rosin ester resins, polyvinyl acetate resins, coumaron resins, vinyltoluene resins, vinyl chloride resins, polyester resins, polyurethane resins, butyral resins, and mixtures of several of these resins can be used.

Further, the organic solvent used for adhesion adjustment may be any solvent as long as it dissolves the above-mentioned electron beam curable compound, such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene, etc. Examples include aromatic systems, alcohol systems such as methyl alcohol and ethyl alcohol, ester systems such as ethyl acetate and butyl acetate, and cellosolve systems such as methyl cellosolve and butyl cellonorb. 5 One or more of these can be used.

The above organic solvent is the electron beam curable compound 100 described above.
It can be used in an amount of usually 10 to 500 parts by weight.

The above-mentioned electron beam curable compound containing an ethylenically unsaturated bond is mixed with a thermoplastic resin and other appropriate components such as a surfactant, a plasticizer, a colorant, etc. in a propeller stirrer or a kneader. - A resin liquid is prepared using a sand mill, three rolls, etc., and is impregnated into a reinforcing fibrous base material by a known coating or impregnation method.

Paper, woven fabric, non-woven fabric, etc. can be used as the reinforcing fibrous base material, and polyester, acrylic, i+? Nonwoven fabrics made of organic fibers such as lyamide fibers and inorganic fibers such as glass fibers, carbon fibers, and boron nitride fibers can be used.

For impregnation, for example, an impregnating device equipped with a sifting roller or a doctor for regulating the amount of impregnation can be used, and in addition, a roll coater, a hot melt coater, etc. can also be used. When the coated material including the base material is 100 inches, the coating amount can be 10% to 90% depending on the porosity of the base material and the necessary physical properties, and is preferably 4.
0% to 60cm is appropriate.

After impregnating as described above, metal foil is laminated on one side of the reinforcing fibrous base material impregnated with resin liquid, dried with hot air, and then the other side of the reinforcing fiber base material is laminated with hot air. irradiate with an electron beam.

As the metal foil, single metal foils such as iron, copper, lead, aluminum, zinc, tin, gold, silver, platinum, etc., or composite metal foils such as plated steel sheets such as galvanized iron or tin plate can be used. It can be done by method.

The electron beams used are emitted from various electron beam accelerators such as Cockroft-Walton type, bumpgraph type, resonant transformer type, insulated core transformer type, linear type, dynamidron type, high frequency type, etc. An electron beam having an energy of Key, preferably in the range of 100 to 300 Key is used. The irradiation dose of electron beam is 5-5 Q
Mrad is preferred; if it is less than 5 Mrad, the curing reaction will be insufficient, and if it exceeds 50 Mrad, there is a risk of deterioration.

The press used for mirror pressing may be either a roll press or a flat press, and the surface in contact with the object to be pressed is preferably made of chrome-plated metal. Further, the surface in contact with the object to be pressed may be subjected to silicone treatment in order to increase the releasability after mirror pressing. For example, the press pressure is 1 to 20 in the case of a roll press.
Y9/Cm, in the case of a flat press, is 2 to 50-.

In addition, the reinforcing fibrous base material impregnated with a resin liquid has a sticky surface, which makes it easy for dust to adhere to it, and often stains the rolls of manufacturing machines. In order to eliminate this problem, it is recommended to impregnate the reinforcing fibrous base material with a resin liquid and attach a peelable film to it using a laminate, etc. Examples of peelable films include polyvinylidene chloride, polyvinyl chloride, ethylene/
Common films such as vinyl acetate copolymer, polytetrafluoroethylene, polystyrene, polyethylene, polypropylene, polymethyl methacrylate, polyethylene terephthalate, polycarbonate, and polyamide can be used, and those having a thickness of 12 to 10 μm are preferable. As described above, even if the film is brought into close contact with a reinforcing base material impregnated with a resin liquid, the effect of electron beam irradiation will not be substantially reduced. This has the advantage that curing is effectively carried out without being inhibited by oxygen in the air during electron beam irradiation.

Since the present invention has the above configuration, it has the following effects L5.

(a) Since an organic solvent is used for dilution, it can be easily impregnated with a compound that itself has good physical properties after curing but has poor impregnating suitability. (Materials in which the curing agent has a high molecular weight and strong intermolecular interactions have good curing properties, but since they are solid or highly viscous liquid at room temperature, they themselves have poor impregnation properties.) (B) Dilution Since an organic solvent is used for this purpose, "wetting" to the reinforcing fibrous base material is improved, and thus the adhesive strength is improved. This tendency is particularly noticeable for glass cloth.

(c) Since an organic solvent is used for dilution, "wetting" to the surface of the metal foil is improved, thereby improving the adhesive strength of the metal foil.

b) The surface smoothness of the product obtained is improved by mirror pressing in the B stage state after hot air drying.

Compared to conventional thermosetting resins, i.e., unsaturated polyester resins, phenolic resins, or diallyl butanate resins, it can be bonded and cured instantly at room temperature, so manufacturing time can be shortened. , the present invention will be explained in more detail.

Example-1 60 parts of epoxy acrylate (Lipoxy VR-60, manufactured by Showa Kobunshi Co., Ltd.), epoxy acrylate (Vinucote 5)
40 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 40 parts of MEK5Q, and 50 parts of toluene was impregnated into a glass woven fabric (manufactured by Nitto Boseki) in a dry state to an impregnation rate of 50%. Wet laminated 35μ copper foil at 100°
After drying with hot air at step C, between the chrome plated shida rolls (
It was then pressed using an electron beam irradiation device (manufactured by E, S, R, USA, Electrocurtain CB 2 ()0150/30) under the conditions of an acceleration voltage of 175 kV and an irradiation beam of 5t 2 Q Mrad. irradiated with electron beam. The obtained copper cladding F, R, P,
has excellent heat resistance and chemical resistance, and its adhesive strength with copper foil is 2.
It was 9/5/5.

Example-2 The same procedure as Example 1 was carried out except for using the above composition,
Obtained similar results.

Claims (1)

[Claims] A reinforcing fibrous base material is impregnated with a composition consisting of one or more electron beam curable compounds containing an ethylenically unsaturated bond and one or more organic solvents, and then a metal foil is impregnated into the reinforcing fibrous base material. A method for producing a reinforced plastic sheet, in which the organic solvent in the composition is evaporated with hot air and dried, and the entire sheet is subjected to a mirror press.