JPH0149738B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for adhering rubber and resin. In recent years, a wide variety of thermoplastic plastics have appeared, including engineering plastics (polyamide, polyester, polycarbonate,
polyacetal, polysulfone, polysilicon,
Polyphenylene oxide, polyimide, ABS,
Resins called methacrylic (methacrylate, etc.) are manufactured and sold, and many of these resins exhibit excellent mechanical strength, heat resistance, creep resistance, chemical resistance, electrical properties, dimensional stability, etc., and are widely used. Under certain conditions, there are many substitutes for metals such as iron, zinc, and aluminum. Usually, industrial rubber products include products such as rubber and metal, rubber and plastics, and rubber and solid materials, but most of them are composites consisting of rubber and metal. However, recently these products have become lighter, rust-proof,
Due to the requirements for chemical resistance, abrasion resistance, electrical properties, coefficient of friction, etc., there is a tendency to replace rubber and plastic composite products. Naturally, to create these composites, the bond between the rubber and plastic must be strong enough. The conventional method is to apply a chlorine-containing adhesive to the surface of a resin molded article obtained by injection molding, and then vulcanize and bond it to unvulcanized rubber. A disadvantage of the vulcanization bonding method for resin molded products and rubber is that the molded products are subjected to cooling and heating cycles during the vulcanization bonding process, or are thermally aged, resulting in a decrease in adhesive strength or cracks in the resin molded product. Problems in the process, problems such as adhesive strength differing greatly depending on the type of resin, and furthermore, when using a resin with a low melting temperature among thermoplastic resins, the temperature or pressure that the molded product is subjected to during vulcanization The inconvenience of deformation has become a problem. In order to overcome the above-mentioned problems, unlike conventional methods, the vulcanized rubber surface is treated to form a specific rubber surface area, and a pre-fused polyester resin,
As a result of various research on bonding methods of vulcanized rubber and these resins by injection or extrusion of styrene resin or acrylic resin, we have found that vulcanized rubber and resin have strong adhesion and can produce molded products with high dimensional accuracy. The present invention was achieved by discovering an adhesion method. That is, in the present invention, the surface of vulcanized rubber is treated with at least one selected from the group consisting of halogen molecules, halogen generators, and pseudohalogen compounds to form a specific rubber surface region, and the vulcanized rubber surface is heated and melted into the specific rubber surface region. The present invention relates to a method for adhering vulcanized rubber and resin, which is characterized by injecting or extruding a resin selected from polyester resin, styrene resin, and acrylic resin. According to the present invention, vulcanized rubber of any shape is prepared in advance, and the surface to be bonded is treated with at least one of halogen molecules, halogen generators, or pseudohalogen compounds, and then assembled into a mold. By bonding the specific resin heated and melted by a method such as injection or extrusion molding, it is possible to obtain a composite of rubber and plastics whose interfaces are firmly bonded. Further, since the rubber article according to the present invention is treated with a solution or the like without mechanical treatment such as buffing with sandpaper or a grinder on the surface to be adhered, a composite having a precise and complicated shape can be obtained. I can do things. The present invention will be explained in detail below. The rubber component of the vulcanized rubber used in the present invention is natural rubber (NR) and synthetic rubber having a carbon-carbon double bond in its structural formula, either alone or in a blend of two or more. The above synthetic rubbers include polyisoprene rubber (IR), which is a homopolymer of conjugated diene compounds such as isoprene, butadiene, and chloroprene, polybutadiene rubber (BR), and polychloroprene rubber, and the above conjugated diene compounds and styrene, acrylonitrile, and vinylpyridine. , acrylic acid, methacrylic acid, alkyl acrylates,
Styrene-butadiene copolymer rubber (SBR), which is a copolymer with vinyl compounds such as alkyl methacrylates, vinylpyridine-butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic acid-butadiene copolymer rubber, methacrylic acid-butadiene copolymer rubber Rubber, methyl acrylate butadiene copolymer rubber, methyl methacrylate butadiene copolymer rubber, etc., olefins such as ethylene, propylene, isobutylene, and diene compounds, such as isobutylene isoprene butadiene copolymer rubber (IIR), copolymer of olefins and non-conjugated diene. Polymer (EPDM) such as ethylene, propylene, cyclopentadiene terpolymer, ethylene propylene-5-ethylidene-2-norbornene terpolymer, ethylene propylene-1,4
- Hexadiene terpolymer, polyalkenamer obtained by ring-opening polymerization of cycloolefin, such as polypentenamer, rubber obtained by ring-opening polymerization of oxirane rings, such as sulfur-curable polyepichlorohydrin rubber or polypropylene oxide rubber etc. are included. Also included are halogenated products of the various rubbers mentioned above, such as chlorinated isobutylene isoprene copolymer rubber (Cl-IIR), brominated isobutylene isoprene copolymer rubber (Br-IIR), and polynorbornene rubber. The vulcanized rubber of the present invention includes fillers such as carbon black, silica, calcium carbonate, calcium sulfate, clay, diatomaceous earth, and mica, softeners such as mineral oil, vegetable oil, and synthetic plasticizers, and stearin. Vulcanization accelerators such as acids, anti-aging agents, vulcanizing agents, accelerators, etc. are thoroughly kneaded in advance using a kneading machine and vulcanized under appropriate vulcanization conditions. Vulcanized rubber can be produced by thiuram vulcanization, peroxide vulcanization, quinoid vulcanization, resin vulcanization, metal salt vulcanization, metal oxide vulcanization, polyamine vulcanization, in addition to the most common and most important sulfur vulcanization. , radiation vulcanization, hexamethylenetetramine vulcanization, etc. Examples of halogen molecules used for treating the surface of vulcanized rubber include chlorine, bromine, iodine, and aqueous solutions thereof. Examples of halogen generators include hypochlorous acid, hypochlorous oxygen, and aqueous solutions thereof. In addition, pseudohalogen compounds (halogenoids) include halogenated isocyanates, N-monohaloalkylurethanes, N,N-dihaloalkylurethanes,
N,N-dihaloallylsulfonamide, sulfur halide sulfenyl halide, halomethyl ether, thiocyanogen, azide iodide, azide bromide,
Iodine chloride, iodine bromide, trichloroacetate iodide, acetate iodide, iodine nitrate, alkyl hypohalide, alkylthionyl chloride, allylthionyl chloride, nitrosyl chloride, nitrosyl bromide, halogenated isocyanuric acid, halogenated Examples include methylhydantoin. Among the above-mentioned processing agents, pseudohalogen compounds, especially halogenated isocyanates, N,N-dihaloalkyl urethanes, N,N-dihaloallylsulfonamides, alkylhypohalites, The use of halogenated isocyanuric acids, halogenated methylhydantoins, etc. are suitable for the purposes of the present invention. Specifically, iodized isocyanate, N,N-dichloroethyl urethane, N,N-dibromoethyl urethane, N,N-dichloropropylurethane,
N,N-dibromopropyl urethane, N,N-dichlorobenzyl urethane, N,N-dibromobenzyl urethane, N,N-dichloro-p-toluenesulfonamide, N,N-dibromotoluenesulfonamide, N,N-dichlorobenzyl urethane Compounds such as chlorobenzenesulfonamide, N,N-dibromobenzenesulfonamide, tertiary butyl hypohalide, trichloroisocyanuric acid, dichloroisocyanuric acid, dibromomethylhydantoin, dichlorodimethylhydantoin, dichloromethylisobutylhydantoin, dichloromethylhexylhydantoin, etc. . During actual processing, pseudohalogen compounds (halogenoids) are dissolved in an appropriate solvent to a concentration of 0.1 to 20%.
It is used in concentrations of 1 to 15% by weight, preferably 1 to 15% by weight. Specific examples of solvents include carbon tetrachloride, halogenated hydrocarbons such as chloroform and dichloromethane, aromatic hydrocarbons such as benzene, nitrobenzene, halogenated benzene, toluene and xylene, dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane. Chain or cyclic ethers, esters such as ethyl acetate, pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as cyclohexane, acetone, cyclohexanone, ketones such as methyl ethyl ketone, ethanol, ethylene glycol,
Examples include alcohols such as tertiary butyl alcohol, among which tetrahydrofuran,
Dioxane, acetone, benzene, toluene, carbon tetrachloride, chloroform, methyl ethyl ketone,
Ethyl acetate is preferably used. The method of treating the rubber surface with the treatment agent to form a specific rubber surface area includes application with a brush,
Any industrial means capable of contacting the rubber surface with the treatment solution can be employed, such as spraying, dipping, etc. In the present invention, the resin that adheres to the vulcanized rubber is selected from polyester resins, styrene resins, and acrylic resins. As the polyester resin, polyethylene terephthalate, polybutylene terephthalate, copolymers and blends thereof, or partially modified functional groups of these polyesters are preferably used, but of course other polyester resins may also be used. Styrene resins include polystyrene resin, ethylene propylene non-conjugated diene-styrene-acrylonitrile copolymer resin (EPSAN resin), acrylonitrile-acrylo-styrene copolymer resin (AAS resin), acrylonitrile-styrene copolymer resin (AS resin), and acrylonitrile. - Copolymers such as butadiene-styrene copolymer resin (ABS resin), butadiene-styrene-methyl methacrylate copolymer resin (MBS resin), or blends thereof are used. Alternatively, copolymer resins in which functional groups or carbon-carbon double bonds are partially modified are also included. As acrylic resins, polyacrylic acid resins, methacrylic acid resins, polyacrylamide resins, polyacrylonitrile resins, copolymers and blends thereof, etc. are used, and acrylic resins with partially modified functional groups are also used. used. Added to these resins are glass fibers, inorganic fillers such as calcium carbonate and talc, colorants, ultraviolet absorbers, and other substances normally filled in plastics. Furthermore, it is also possible to mix other thermoplastic resins in order to improve processability and adhesion. The invention will be illustrated with reference to the following examples. Example 1 From a rubber composition with the formulation shown in Table 1,
ASTM: D429, Method B, for 90° peeling shown in b and ASTM: D429 shown in Figure 2 a, b,
A vulcanized rubber was prepared to obtain a conical tensile test specimen according to Method C (dimensions of the specimen in the drawings are in millimeters). On the other hand, pseudohalogen compounds are used as surface treatment solutions.
Prepare an acetone solution containing DCTS (N,N-dichloro-p-toluenesulfonamide) and TCCA (trichloroisocyanuric acid) at a concentration of 2, 5, 10, and 20% by weight, respectively, and brush it on the surface of the part of the vulcanized rubber to be adhered. Painted and treated. As polyester resins, polyethylene terephthalate (FR-PET, manufactured by Teijin Co., Ltd. B-3030) and polybutylene terephthalate (manufactured by Mitsubishi Rayon Co., Ltd.) were used.
Tuffpet N1000), Hytrel 7246 manufactured by DuPont (USA), and Pelprene 150B manufactured by Toyobo were prepared and each was heated to
Dry for an hour. Then use an injection molding machine at 265℃ for FR-PET.
260℃ for polybutylene terephthalate, 250℃ for Hytrel 7246, and 250℃ for Pelprene 150B.
Under injection conditions of 240°C, the vulcanized rubber pieces shown above were assembled into a mold, and each polyester resin was injected to form a composite test piece of rubber and plastic as shown in Figures 1 and 2. was created. After that, ASTM: D429 Method B and
Table 2 shows the results of an adhesion test conducted according to Method C. These results show that vulcanized rubber and polyester resin do not adhere to each other in the case of no treatment, but when adhesion is performed by the method of the present invention, they are strongly adhered to each other.

【table】

【table】

[Table] Example 2 The adhesion of another polyester resin (polyarylate resin AX1500, manufactured by Unitika and referred to as U-polymer) was evaluated in the same manner as in Example 1. The injection molding temperature was 230°C. The results are shown in Table 3.

【table】

[Table] Example 3 The adhesion of styrenic resin was evaluated in the same manner as in Example 1. The styrene resin used and the injection molding conditions were polystyrene resin (Asahi Dow Styron 683, molding temperature 260℃, acrylonitrile-butadiene-
These are styrene copolymer resin (Seviern SER20 manufactured by Daicel Corporation, molding temperature 200°C), and acrylonitrile-styrene copolymer resin containing glass fiber (Seviern N080FS manufactured by Daicel Corporation). The results are shown in Table 3.

【table】

[Table] Example 4 The adhesiveness of acrylic resin was evaluated in the same manner as in Example 1. The acrylic resin used and the injection molding conditions were methacrylic resin (acrylic resin manufactured by Mitsubishi Rayon Co., Ltd.) and injection molding conditions.
MD, molding temperature: 220°C) and a mixture of methacrylic resin and polycarbonate resin (Metamarble, manufactured by Teijin, molding temperature: 260°C). The results are shown in Table 4.

【table】

【table】 [Brief explanation of drawings]

Figures 1a and b are a plan view and a sectional view of a test piece for evaluating the bonding method of the present invention, Figure 2a is a
and b are a side view and a cross-sectional view of another test piece. 1...Resin, 2...Rubber.

Claims (1)

[Scope of Claims] 1. A vulcanized rubber surface is treated with at least one selected from the group consisting of halogen molecules, halogen generators, and pseudohalogen compounds to form a specific rubber surface area, and the specific rubber surface area is treated with A method for bonding vulcanized rubber and resin, characterized by injecting or extruding a heat-molten resin selected from polyester resin, styrene resin, and acrylic resin. 2. The method of bonding vulcanized rubber and resin according to claim 1, wherein the halogen molecule is at least one selected from chlorine, bromine, and iodine. 3. The method of bonding vulcanized rubber and resin according to claim 1, wherein the halogen generator is hypochlorous acid. 4 The pseudohalogen compound is N,N-dichloro-p-
2. The method of bonding vulcanized rubber and resin according to claim 1, wherein the adhesive is at least one selected from the group consisting of toluenesulfonamide and trichloroisocyanuric acid. 5. The method of bonding vulcanized rubber and resin according to claim 1, wherein the resin is a polyester resin. 6. The method of bonding vulcanized rubber and resin according to claim 5, wherein the polyester resin is a thermoplastic resin mainly composed of polyethylene terephthalate or polybutylene terephthalate. 7. The method of bonding vulcanized rubber and resin according to claim 1, wherein the resin is a styrene resin. 8. The method for bonding vulcanized rubber and resin according to claim 1, wherein the resin is an acrylic resin.