JPS59148633A - Manufacture of metal plated plastic sheet reinforced with fire retardant fiber - Google Patents

Abstract

PURPOSE:To obtain a metal plated fire retardant FRP sheet containing no solvent and having high productivity, by a method wherein a fibrous material for reinforcement is impregnated with a fire retardant resin liquid containing an electron beam curing chemical compound and one side of the fibrous material is plated with metal foil, to which an electron beam is irradiated. CONSTITUTION:A fibrous base material for reinforcement is made to impregnate with resin including a fire retardant electron beam curing chemical compound including an element having self-flame-extinction property and an ethylene unsaturated chemical compound in the same molecule or liquid resin consisting of a fireproof agent including the element having the self-flame-extinction property and an electron beam curing chemical compound including the ethylene unsaturated bonding. Then after plating metal foil on one side of the fibrous base material, an electron beam is irradiated from a side opposite to the side where the metal foil is plated. As for the electron beam curing chemical compound including the ethylene unsaturated bonding for use, prepolymer, oligomer and monomer having the ethylene unsaturated bonding in their molecules can be cited.

Description

[Detailed Description of the Invention] This invention relates to a method for manufacturing plastic sheets (hereinafter referred to as "metal-clad flame-retardant FRP sheets"), which is solvent-free and highly productive. be.

The conventional manufacturing method for metal-clad FRP sheets is to first make an FRP sheet, then apply adhesive and metal foil or +'L.
The FRP sheet is coated, the bath agent is removed by heat drying, and then the copper agent is laminated.

In addition, in the case of Evokin resin, which is used in the manufacturing method of FRP sheets used in conventional metal-clad FRP zotes, the resin bath liquid obtained by dissolving it with a resinous bath agent is applied to paper or fibers as a reinforcing base material. This is a method in which the material is impregnated, then heated for preliminary curing, and after the volatile bath agent is removed, the material is heated and pressurized using a dancer to form the material. This method has a complicated process and is low in productivity.

On the other hand, unsaturated polyester resins are the most commonly used resins for FRP, both in terms of their use and in terms of the wide range of fields in which they are used. Unsaturated polyester resins can be cured at room temperature and do not produce by-products during curing, so they do not necessarily require pressurization and can be molded in a variety of ways. It is inferior in terms of physical properties such as physical properties and toughness.

In addition, conventionally, when making metal-clad FRP sheets flame-retardant, it is necessary to add flame retardants to the resin liquid, whether they are compounds containing fluorine, chlorine, bromine, nitrogen, phosphorus, arsenic, antimony, etc. is being carried out.

However, when these flame retardants are added to conventional resin liquids, there are problems with compatibility, thermal stability, etc., and there are also practical problems such as bleeding over time and the resin surface becoming sticky. be.

The present inventors aimed to eliminate the drawbacks of such conventional methods (results of research revealed that a compound containing a self-extinguishing aromatic element and a compound containing an ethylenically unsaturated bond in the resin liquid (these are the same compound) We discovered that the flame retardance, chemical resistance, heat resistance, and mechanical properties of the obtained metal-clad FRP sheets were significantly superior to those of conventional sheets by using It is the birth of an invention.

That is, the present invention provides a resin liquid containing a flame-retardant electronic edge-curing compound containing a self-extinguishing element and an ethylenically unsaturated bond in the same molecule, or a flame-retardant resin containing a self-extinguishing element. 7. from an electron beam curable compound containing an ethylenically unsaturated bond; C stone side 'B' A reinforcing fibrous base material was impregnated with fi liquid, then a reinforcing y impregnated with resin liquid, metal foil was laminated on one side of the fibrous base material, and then metal foil was laminated on one side of the fibrous base material. The main idea is a method for manufacturing a metal-clad flame-retardant fiber-reinforced plastic sheet, which is characterized by irradiating electron beams from the opposite side.

The present invention will be explained in detail below.

In the case of an electron beam curable compound containing an ethylenically unsaturated bond, the compound containing an ethylenically unsaturated bond in the molecule is a polymer or oligomer, such as an unsaturated polyester, Various acrylic Vhs such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate; various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane acrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate. Monomers having ethylenically unsaturated bonds in the molecule, such as styrenic monomers such as styrene and X-methylstyrene; methyl acrylate;
Coethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate,
Acrylic esters such as methoxybutyl acrylate and phenyl acrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxytithyl methacrylate, phenyl methacrylate, and lauryl methacrylate; Unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic acid, 2-(N,N-dimethylamine)ethyl, mono(N1N-dimethylamino)ethyl methacrylate, λ-(N,N-dibenzyl acrylate) Substituted amino alcohol esters of unsaturated acids such as (amino)ethyl, (N,N-dimethylamino)methyl methacrylate, mono(N,N-diethylamino)globil acrylate, ethylene glycol diacrylate, brobylene Glycol diacrylate, neopentyl glycol diacrylate, /, 4-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate! JL'-), diethylene glycol diacrylate, ethylene glycol diacrylate, globylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., or a mixture of two or more thereof can be used.

Flame retardants include tributyl phosphate, tricresyl phosphate, tributoxyethyl phosphate, tri(α-bromoethyl) phosphate, tris(β-chloroethyl) phosphate, trif, (dichloroglovir) phosphate, tris(chloropromoglovir). )phos7-r--t,)ls(2,j-dibromoglovir)
Phosphate, halogenated polyphosphonate, chlorinated paraffin, brominated polyphenyl, chlorinated polyphenyl,
Organic phosphorus compound caps such as perchloropentacyclodecane, dechlorane plus, tetrabromobutane, /, 2-dibromo-3-chloropropane, /1.2.3-)ribromopropane, tetrabromobenzene, hexabromobenzene, etc. Alternatively, one or more of organic halogen compounds or inorganic compounds such as antimony oxide, aluminum hydroxide, aluminum phosphate, and ammonium polyphosphate are mixed with the electron beam curable compound containing an ethylenically unsaturated bond. It can be used as a resin liquid.

The ratio of adding the above flame retardant is 7 to 6 parts by weight per 700 parts by weight of the electron beam curable compound containing an ethylenically unsaturated bond.
0 parts by weight, preferably 3 to 30 parts by weight. Addition of less than 7 parts by weight of flame retardant does not improve flame retardancy, and addition of more than 10 parts by weight of flame retardant results in poor crosslinking density due to electron beam irradiation (even if improved, heat resistance is poor). , which may bleed over time.

On the other hand, in the present invention, as the resin liquid, a flame-retardant ray-curing compound containing a self-extinguishing element and an ethylenically unsaturated bond in the same molecule may be used, specifically, α
-chloroacrylate, pentachlorophenyl acrylate, tribromophenyl acrylate, -acryloxyethyl phosphate, -monoacryloxyethyl phosphate, and also tetrabromopisph: c) -/l
/ A /-logenated epoxy resin such as diglycidyl ether is acrylated with acrylic acid, λ'-bis(
3-acryloquine-no-hydroxy cloviroxy-3,
One or more of phosphorus-containing acrylates such as S-dibromophenyl)propane, rhodan acrylates or corresponding methacrylates, and rhodanized vinyls such as vinyl chloride and vinyl bromide are used in the mixture. be able to.

In the case of the above compounds containing self-extinguishing elements and ethylenically unsaturated bonds, the reactivity of the ethylenically unsaturated bonds is high;
In particular, flame retardants with long molecular chains, such as acrylated epoxy resins, can be used alone as a resin liquid, but the above-mentioned compounds include electron beam curable compounds containing ethylenically unsaturated bonds. 1 to 100 parts by weight
It can also be used in addition to the go heavy lid.

The resin liquid mentioned above may contain surfactants, plasticizers,
A coloring agent is added and kneaded using a propeller stirrer, kneader, sand mill, triple roll, etc. to obtain a resin liquid.

The reinforcing fibrous base material is impregnated with the above resin liquid. As the reinforcing fibrous base material, paper, nonwoven fabrics and woven fabrics made of organic fibers such as polyester, acrylic, and polyamide, and inorganic fibers such as glass fiber, carbon fiber, and boron nitride fiber can be used. . The above-mentioned reinforcing fibrous base material is impregnated with the above-mentioned resin liquid by a known method.
To give an example of the method, for example, an impregnating device equipped with an impregnating head and a sifting roller or doctor for regulating the amount of impregnated can be used, and a roll coater, hot melt coater, etc. can also be used. .

Assuming that the coating material containing the base material is 700%, the coating amount can be 70% to 90% depending on the porosity of the base material and the required physical properties, and is preferably 1IO% to 60%.

After impregnating as described above, metal foil is pasted on one side of the reinforcing fibrous base material impregnated with resin liquid, and then an electron beam is irradiated from the side opposite to the side where the metal foil was pasted. .

As the metal foil, single metal foils such as iron, copper, lead, aluminum, zinc, tin, gold, silver, platinum, etc., and composite metal foils such as plated steel sheets such as galvanized iron and tin can be used. The bonding is done by a known method, and the electron beams used include various types of electron beam acceleration, such as the Kotsukuro 7 Towarton type, the Papgraph type, the resonant transformer type, the insulated core transformer type, the linear type, the Dynamidron type, and the high frequency type. Released from the aircraft, left θ ~ 100
An electron beam with a high energy in the range of 0 Ke, preferably ioo to 3θ0 KeV is used, and the irradiation dose is preferably 7 to -0 Mrad, and if it is less than /Mrad, curing will be insufficient and stickiness will remain, resulting in AOMrad. If it exceeds the limit, the decomposition reaction due to electron beam irradiation will proceed and physical properties such as chemical resistance and mechanical properties will deteriorate.

According to the above-described method of the present invention, the metal-clad FRP of Jumei can be completely cured in an extremely short period of time by electron beam irradiation.
The heat drying and hot press processes required in the sheet manufacturing process are not required, and the time required for manufacturing can be shortened.

In addition, due to the reaction with electron beams, not only the reaction of unsaturated bonds in the compound molecules that make up the resin liquid progresses, but also the crosslinking of side chains increases, so the crosslinking density increases, and even with the flame retardant addition, the heat resistance is not so high. bleed of the flame retardant is also prevented. If a flame-retardant compound containing unsaturated bonds is used, the self-extinguishing element polymerized by electron beam irradiation can be compressed by chemical bonds to the main chain polymer, reducing various physical properties. Flame retardancy can be significantly improved without

Furthermore, the bonding between the metal foil and the reinforcing fibrous base material is also performed using electron beams. Because it is done at the same time as curing, conventional metal foil and FRP
Compared to the method of pasting sheets together with adhesive, the work time is shorter and productivity is higher.

The present invention will be explained in more detail below with reference to Examples.

Example/ Amount s of co,-'-bis(lI-acryloxydietoxyphenyl)furopane and parts by weight of tris(co,3-dibromoglovir) phosphate/S as a sulfurizing agent are heated to GC. After melting and impregnating glass woven fabric (07D manufactured by Nitto Boseki) to an impregnation rate of qo%, copper foil (manufactured by Fukuda Metal Foil & Powder Industries, T-7, thickness 35 μm) was laminated with a laminator. Ray irradiation device (manufactured by ESI,
Electro Curtain CB J o o/s.

/30), acceleration voltage /7 left, irradiation line i, 2
A copper-clad FRP sheet was obtained by irradiating an electron beam from the side opposite to the side to which the copper foil was laminated under the condition of 0 Mrad.

From the obtained copper-clad FRP sheet, the length /
A test piece with a width of 27 m/171 DI from which the copper foil was completely removed was prepared, and the test piece was hung vertically and ignited with a Bunsen burner. The average time for 70 test pieces to extinguish is 20
The maximum time was 27 seconds.

Example 7 A copper-clad flame-retardant FRP was obtained in the same manner as in Example except that 60 parts by weight of 3-dibromopropyl methacrylate was added as a flame retardant.

When the obtained sheet was evaluated for flame retardancy in the same manner as in Example, the average time until flame extinction was 77 seconds, and the maximum time was 75 seconds.

Example 3 Halogenated epoxy 14 resin (Nel Chemical Co., Ltd., Epicoat/04' A-A-70, epoxy equivalent <=7.1
) 7S by weight, 7.2 parts by weight of acrylic acid, and 3 parts by weight of pyridine were heated at goC for 3 hours to react. Example / except that the reaction product obtained by removing the reaction and removing the solvent was used as a resin liquid.
A copper-clad flame-retardant FRP sheet was obtained in the same manner as above.

When the obtained sheet was evaluated for flame retardancy in the same manner as in Example, the average time to extinguish the flame was 7 seconds, and the maximum time was 9 seconds.
It was seconds.

Claims (1)

[Claims] (11) A resin liquid containing a flame-retardant electron-curable compound containing a self-extinguishing element and an ethylenically unsaturated phase bond in the same molecule, or a flame clearing agent containing a self-extinguishing element. A reinforcing fibrous base material is impregnated with an electron beam curable compound containing an ethynic unsaturated bond @ and a karanaro resin solution, and then a reinforcing fiber T impregnated with the resin solution (with gold @ foil on one side of the base material). A method for producing a metal-clad, combustible, fiber-reinforced plastic sheet, which is characterized by pasting the metal scraps together, and then irradiating them with electron beams from a 1L (il) opposite to the side on which the metal scraps are pasted.