JPH0971664A - Method for bonding resin with rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for bonding a resin with a rubber capable of resolving problems in the health control of workers, preventing an environment from disruption and aiming at the labor saving and the working cost reduction in a production process by bonding the resin and the rubber without using any adhesive for reducing the variations in the adhesive strength and improving the reliability of the adhesion. SOLUTION: This method for bonding a resin with a rubber is to treat a formed body 1 of the resin with a metal plating 2 containing Ni or Cu and cross-link the rubber 4 containing a triazinethiol derivative in the state of contacting with the metal plating 2 for directly bonding the metal plating 2 with the rubber 4 by the cross-linking to bond the formed body of the resin 1 with the rubber 4 through the metal plating 2. The triazinethiol derivative acts as a binder for connecting the metal plating 2 with the rubber 4.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin and a rubber,
The present invention relates to a method for adhering a resin and rubber, which adheres without using an adhesive.

[0002]

2. Description of the Related Art Since it is difficult to directly cross-link and bond resin and rubber, conventionally, when bonding resin and rubber, generally, a reactive adhesive such as a silicone-based, isocyanate-based or epoxy-based adhesive is used. Were used to bond the two. Further, in order to obtain a strong adhesive to a chemically stable resin, glass fiber or a filler is added inside the resin to obtain adhesive strength.

[0003]

However, in the conventional method of bonding resin and rubber using the above-mentioned adhesive, the dispersion of the bonding strength tends to be large, and sometimes the bonding failure may occur. There was a problem that sufficient reliability was not always obtained.

In addition, the use of an adhesive agent using an organic solvent has a problem in the health management of workers and may cause environmental pollution.

Further, there is a problem that the step of applying the adhesive takes time and labor and the working cost becomes high.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for adhering a resin and rubber which can reduce variations in the adhesive strength and can obtain high reliability. To do.

Another object of the present invention is to bond a resin and a rubber without using an adhesive, and therefore, it is possible to solve the problem of health management of workers and prevent environmental damage.
Another object of the present invention is to provide a method of bonding resin and rubber, which does not require a step of applying an adhesive and can save labor in a production process and reduce working cost.

Further objects of the present invention will be apparent from the following description.

[0009]

According to the method for adhering a resin and a rubber according to the present invention, a resin molding is plated with a metal containing Ni or Cu, such as Ni plating, brass plating or copper plating. A rubber containing a triazine thiol derivative is cross-linked in a state of being in contact with plating, and the metal plating and the rubber are directly cross-linked and adhered to each other, whereby a molded body of the resin and the rubber through the metal plating. It is to bond and. If necessary, the surface of the metal plating is surface-treated with a triazine thiol derivative, and then the rubber is crosslinked.

The triazine thiol derivative contained in the rubber is, for example, 1,3,5-triazine-2,4,6-trithiol or 1,3,5-triazine-2,4 which has good compatibility with metal plating. , 6-trithiol metal salt and the like can be used (the metal salt is sodium salt, potassium salt, magnesium salt, calcium salt, lithium salt or the like).

As the triazinethiol derivative used for the surface treatment of the plated surface, for example, 1,3,5-triazine-2,4,6-trithiol monosodium salt or the like can be used.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a rubber containing a triazine thiol derivative is crosslinked in a state of being in contact with a metal plating applied to a resin (preferably in a pressurized state). By directly cross-linking and bonding the rubber and the metal plating, the resin and the rubber are bonded via the metal plating. Therefore, the molding of the rubber and the adhesion of the resin and the rubber are simultaneously performed. At this time, triazine thiol functions as a binder that bonds the metal plating and the rubber. Although the specific mechanism by which triazine thiol serves as a binder between resin and rubber in this way has not been fully clarified yet, it is generally estimated to be as follows.

FIG. 1 is a sectional view schematically showing the vicinity of a bonding surface between a resin and rubber in the present invention. The oxide layer 3 is formed on the surface of the metal plating layer 2 applied to the surface of the resin 1. In the vicinity of the interface with the oxide layer 3 of the rubber 4 (this portion becomes the reinforcing layer 5), Ni or Cu diffused from the metal plating layer 2 and the oxide layer 3 has triazinethiol. It reacts with some of a plurality of SH groups to become NiS or Cu ₂ S, whereby the triazine thiol and the metal plating layer 2 join together. And
When the other SH group of triazine thiol is bound to the rubber, the metal plating layer 2 and the rubber 4 are bonded via the triazine thiol.

Here, the oxide layer 3 usually occurs on the surface of the metal plating layer 2 without any special treatment, but its presence is due to the following reasons. It is considered that the adhesive strength between the rubber and the rubber 4 is further improved. Without the oxide layer 3, the number of bonds between the triazine thiol and the metal would be too large compared to the number of bonds between the triazine thiol and the rubber, and the number of bonds between the triazine thiol and the metal would be greater than the number of bonds between the triazine thiol and the metal. However, the bonding strength between the metal plating layer 2 and the rubber 4 is reduced as a whole, but the presence of the oxide layer 3 moderately suppresses the bonding between the metal and the triazine thiol. The balance between the bond strength between the triazine thiol and the rubber and the bond strength between the triazine thiol and the metal is improved, and the adhesive strength between the metal plating layer 2 and the rubber 4 is increased.

In the present invention, usual vulcanization agents and vulcanization accelerators for rubber can be used.

A wide variety of resins can be adhered by the present invention, for example, polyethylene, polypropylene, polystyrene, ABS resin (acrylonitrile butadiene styrene copolymer), acrylic resin, nylon resin, polycarbonate resin, PBT (polybutylene terephthalate) resin, PPE (polyphenylene). Ether), PPO
(Polyphenylene oxide), PPS (Polyphenylene sulfide), Phenolic resin, Epoxy resin, EV
A (ethylene vinyl acetate copolymer), TPEA
(Polyamide Thermoplastic Elastomer), TP
It has been confirmed that U (thermoplastic polyurethane elastomer) and TPS (polystyrene thermoplastic elastomer) can be bonded.

Further, according to the present invention, it is considered that almost all rubbers can be adhered. For example, CR (chloropyrene rubber), NBR (acrylonitrile butadiene rubber),
It has been confirmed that natural rubber, isoprene rubber, ethylene propylene terpolymer, hydrogenated acrylonitrile butadiene rubber and the like can be bonded.

[0018]

Embodiments of the present invention will be described below.

Example 1 30 mm × 50 mm × 1 mm
Electrolytic Ni plating was applied to the polyphenylene sulfide resin plate (hereinafter referred to as PPS plate). Plating thickness is 0.5
It was set to μ or more. The PPS plate was placed in a mold having a depth of 3 mm, and the rubber kneading material shown in the rubber composition 1 in Table 1 was placed thereon.
A pressure of 150 kgf / cm ² was applied at 0 ° C. for 20 minutes to perform compression molding to directly cross-link and bond the PPS plate and the rubber via Ni plating. In addition,
The numerical values of the formulations in Table 1 indicate parts by weight.

(Example 2) The PPS plate and the rubber were directly cross-linked and bonded via Ni plating in the same manner as in Example 1 except that the Ni plating on the PPS plate was performed by electroless Ni plating.

(Example 3) Ni was used in the same manner as in Example 1 except that the rubber kneaded material shown in the rubber composition 2 in Table 1 was used in place of the rubber kneaded material shown in the rubber composition 1 in Table 1.
The PPS plate and rubber were directly cross-linked and bonded via plating.

Example 4 A PPS plate having the same shape and size as in Example 1 was electrolytically Ni-plated, and then 1, 3, 5
-Triazine-2,4,6-trithiol monosodium salt was dipped in a 0.6% by weight aqueous solution at 50 ° C for 5 minutes, so that the plated surface was 1,3,5-triazine-2,
The surface was treated with 4,6-trithiol monosodium salt. Thereafter, the PPS plate was charged in the same mold as in the case of Example 1, the rubber kneading material shown in the rubber composition 1 of Table 1 was placed, and 150 kgf / cm ² at 160 ° C. for 20 minutes.
The PPS plate and the rubber were directly cross-linked and bonded via Ni plating by applying a pressure of 1. to the compression molding.

(Example 5) Except for using the kneading material shown in the rubber composition 2 of Table 1 instead of the kneading material shown in the rubber composition 1 of Table 1, Ni plating was performed in the same manner as in the above Example 4. Then, the PPS plate and the rubber were directly cross-linked and bonded.

(Embodiment 6) An electroless Ni plating having a plating thickness of 0.5 μ or more is applied to a PPS plate having the same shape and size as in the case of the first embodiment, and the PPS plate is the same as the case of the first embodiment. By charging in the same mold, placing the rubber kneading material shown in the rubber composition 3 in Table 1, applying a pressure of 150 kgf / cm ² at 160 ° C. for 20 minutes, and performing compression molding,
The PPS plate and rubber were directly cross-linked and bonded via Ni plating. In addition, 1,3,5-triazine-2 in the rubber compound,
The 4,6-trithiol metal salt was separately adhered as a potassium salt, a magnesium salt, a calcium salt, and a lithium salt.

[0025]

[Table 1] In each of the above examples, two cuts having a width of 10 mm were made in the longitudinal direction on the rubber side of the PPS plate to which rubber was adhered, and the rubber between the cuts was 50 cm at room temperature in accordance with JIS K6301. The strength when peeled from the PPS plate in the vertical direction at a speed of / min was measured. Table 2 shows the peel strength test results of Examples 1 to 5 by such a test method, and Table 3 shows the peel strength test result of Example 6.

[0026]

[Table 2] As is clear from the test results, the PPS plate and the rubber are firmly bonded to each other in each of the examples. It should be noted that the rubber is C in comparison with Examples 1, 2 and 4 in which the rubber is NBR.
The reason why the peel strength of Examples 3, 5, and 6 which are R is low is due to the difference in the strength of the rubber itself to be bonded (CR is lower in strength than NBR).

Further, as is clear from the fact that a large peeling strength is obtained in both Example 1 in which electrolytic Ni plating is performed and Example 2 in which electroless Ni plating is performed, the Ni plating on the resin is electrolytic Ni. Either plating or electroless Ni plating may be used.

Further, comparing Examples 1 and 4 and Examples 3 and 5, which respectively use the same rubber, 1,3,5-triazine-2,4,6-trithiol monosodium was applied to the plated surface. The peel strength is higher in Examples 4 and 5 in which the surface treatment is performed with salt. Thus, by surface-treating the metal-plated surface with the triazine thiol derivative, the triazine thiol and the metal plating can be easily bonded to each other, and the adhesive strength can be further improved.

Examples 1 to 5 were prepared by incorporating 1 in rubber.
This is an example in which the metal salt of 3,5-triazine-2,4,6-trithiol is a sodium salt (monosodium salt). In Example 6, the metal salt is potassium salt, magnesium salt, calcium salt, lithium salt. It is what As is clear from Table 3, good adhesion results are obtained when the metal salt is potassium salt, magnesium salt, calcium salt or lithium salt.

[0030]

[Table 3] Although the rubber is crosslinked by compression molding in each of the above-described embodiments, the rubber may be crosslinked by molding other than compression molding such as injection molding in the present invention.

[0031]

As described above, according to the present invention, since the resin and the rubber are directly cross-linked and bonded through the metal plating,
(A) The variation in adhesive strength can be reduced and high reliability can be obtained. (B) Since resin and rubber can be bonded without using an adhesive, the problem of health management of workers can be solved and the environment can be improved. It is possible to obtain an excellent effect such that the destruction can be prevented, the step of applying the adhesive is unnecessary, the labor of the production process can be saved, and the working cost can be reduced.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing the vicinity of a bonding surface between a resin and rubber according to the present invention.

[Explanation of symbols]

 1 Resin 2 Metal Plating Layer 3 Oxide Layer 4 Rubber 5 Reinforcement Layer

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Claims (6)

[Claims] 1. A resin molded body is plated with a metal containing Ni or Cu, and in contact with the metal plated,
A rubber containing a triazine thiol derivative is cross-linked, and the metal plating and the rubber are directly cross-linked and bonded, whereby the molded body of the resin and the rubber are bonded via the metal plating. Adhesion method between resin and rubber. 2. A resin molded body is plated with a metal containing Ni or Cu, the surface of the metal plating is surface-treated with a triazine thiol derivative, and then a triazine thiol derivative is contained in contact with the metal plating. A resin and a rubber, wherein the formed rubber of the resin and the rubber are bonded to each other through the metal plating by directly crosslinking and bonding the metal plating and the rubber by cross-linking the rubber. Adhesion method. 3. The method for adhering a resin and rubber according to claim 1, wherein the triazine thiol derivative contained in the rubber is 1,3,5-triazine-2,4,6-trithiol. 4. The method for adhering a resin and rubber according to claim 1, wherein the triazine thiol derivative contained in the rubber is 1,3,5-triazine-2,4,6-trithiol metal salt. 5. The method for adhering a resin and rubber according to claim 4, wherein the metal salt is a sodium salt, a potassium salt, a magnesium salt, a calcium salt or a lithium salt. 6. The triazine thiol derivative used for the surface treatment of the plated surface is 1,3,5-triazine-2,
3. A monosodium salt of 4,6-trithiol.
A method for adhering the described resin and rubber.