JPH0780996A - Adhesive composite member and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide an adhesive composite member in which nylon resin is rigidly adhered directly to rubber or elastomer and a method for manufacturing the same. CONSTITUTION:An adhesive composite member is formed by laminating a layer of rubber composition formed of raw material rubber selected from a group consisting of fluorine rubber, acrylonitrile-butadiene copolymer rubber, epichlorohydrin rubber or a layer of thermoplastic fluorine resin elastomer on a layer of nylon resin selected from a group consisting of nylon 6, nylon 66, nylon 11, nylon 12, copolymer of them, mixture of them and alloy of them. A method for manufacturing the member comprises the steps of disposing unvulcanized rubber composition or thermoplastic fluorine resin elastomer adjacent to nylon resin and then heating them at a temperature of a melting point or higher of the nylon resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composite of nylon resin and rubber or a thermoplastic fluororesin elastomer and a method for producing the same.

[0002]

2. Description of the Related Art Nylon resins such as nylon 11 and nylon 12 have high strength, high elasticity, high toughness, and are lighter than metals, so they are widely used as general-purpose engineering plastics in mechanical parts. It is used. On the other hand, rubber is excellent in elasticity, shock absorption, flexibility, etc., but has drawbacks such as insufficient rigidity and heavy weight as compared with nylon resin. Therefore, if it is possible to form an adhesive composite in which nylon resin and rubber are adhered, it is possible to obtain a high-performance and lightweight material having the properties of both materials.

However, nylon resins are generally
Adhesion to rubber is poor and it is difficult to firmly bond. Conventionally, as an attempt to bond the both, for example, after the nylon resin is surface-treated in advance by a chemical oxidation treatment or the like, an epoxy adhesive or an isocyanate adhesive is applied to the treated surface to adhere the rubber material. There is a way. However, with this bonding method, the adhesive layer becomes hard and has no toughness, and cracks easily occur due to bending, so that it is not possible to obtain durable adhesiveness.

Therefore, the inventors of the present invention have conducted various studies as to how to bond the nylon resin and the rubber to each other without any adhesive agent, and as a result, the nylon resin and the specific rubber or elastomer can be directly bonded under heating. I found something.

[0005]

The present invention has been made based on this finding, and an object of the present invention is to provide an adhesive composite in which a nylon resin and a rubber or an elastomer are strongly bonded directly and a method for producing the same. And The rubber referred to herein is a rubber composition in which various compounding agents such as a vulcanizing agent are mixed with the raw material rubber.

[0006]

The adhesive composite of the present invention comprises:
A layer of nylon resin selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 12, copolymers thereof, mixtures thereof, and alloys thereof, fluororubber,
It is characterized by laminating a layer of a rubber composition composed of a raw material rubber selected from the group consisting of acrylonitrile-butadiene copolymer rubber and epichlorohydrin rubber or a layer of a thermoplastic fluororesin elastomer.

The method for producing the adhesive composite of the present invention is
Nylon 6, Nylon 66, Nylon 11, Nylon 12, copolymers thereof, mixtures thereof, nylon resins selected from the group consisting of these alloys, fluororubber, acrylonitrile-butadiene copolymer rubber, epichlorohydrin rubber An unvulcanized rubber composition composed of a raw material rubber selected from the group or a thermoplastic fluororesin elastomer is placed adjacent to each other and then heated at a temperature higher than the melting point of the nylon resin, or nylon 6, nylon 66, nylon 11, nylon 12, copolymers of these,
A mixture of these, a nylon resin selected from the group consisting of these alloys, a vulcanized product of a rubber composition composed of fluororubber is adjacently adjoined, and then these are heated at a temperature not lower than the melting point of the nylon resin. Is characterized by.

As described above, according to the present invention, since the specific rubber or elastomer is used for the nylon resin, it is possible to firmly bond them directly to each other. Hereinafter, the configuration of the present invention will be described in detail. (1) The adhesive composite of the present invention is formed by laminating a layer of a rubber composition or a layer of a thermoplastic fluororesin elastomer on a layer of nylon resin.

Nylon resin Nylon resin is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 12, copolymers thereof, mixtures thereof, and alloys thereof. Here, the alloy is
Nylon 6, nylon 66, nylon 11, nylon 12, copolymers thereof, or a mixture thereof is used as a matrix, and another polymer such as ethylene-propylene-diene terpolymer rubber (EPDM) is added to the matrix. It means what is dispersed.

As the nylon resin, a commercially available product can be used. Further, it may be in the form of fiber-reinforced plastics which is reinforced with inorganic fibers such as glass fibers and carbon fibers, and organic fibers such as aramid fibers to increase rigidity.
It may be mixed with a plasticizer in order to improve flexibility. Rubber composition Fluorine rubber (FKM), acrylonitrile-butadiene copolymer rubber (NBR), epichlorohydrin rubber (C
HC) composed of a raw rubber selected from the group consisting of

FKM is a copolymer of vinylidene fluoride and 6-fluorinated propylene. Due to its excellent oil resistance at high temperatures, it is usually used, for example, in resin hoses for fuel piping. This rubber composition contains a compounding agent such as sulfur or carbon black as required.

Thermoplastic fluororesin elastomer A trunk polymer is vinylidene fluoride-based fluororubber, a branch polymer is polyvinylidene fluoride, and both of them are graft-polymerized. As this elastomer, for example, "Cefural Soft G150" manufactured by Central Glass Co., Ltd. is commercially available. Since this elastomer has excellent chemical resistance, gas barrier resistance, and flexibility, it is generally used in the fields of food and corrosion-resistant equipment. (2) To produce this adhesive composite, an unvulcanized product of the rubber composition or the thermoplastic fluororesin elastomer is placed adjacent to the nylon resin, and then these are heated at a temperature equal to or higher than the melting point of the nylon resin. do it. For example,
Nylon 6 has a melting point of 220 ° C, Nylon 66 has a melting point of 240
℃, nylon 11 has a melting point of 175 ℃, nylon 12 has a melting point of 18
Since the temperature is 0 ° C, heating is performed at a temperature higher than this. As a result, mutual adhesion is performed, and in the case of a rubber composition, vulcanization is performed. Thus, for example, nylon 11 or nylon
When manufacturing 12 molded products by injection molding, unvulcanized rubber composition is placed in advance in a mold and the nylon 11 or nylon is kept at a temperature of 180 ° C to 250 ° C.
If 12 is poured into the mold, the rubber composition is vulcanized at the same time as the bonding, and the bonded composite can be obtained. At this time, nylon 11 and nylon 12 may be held in the mold until the temperature in the mold becomes equal to or lower than the melting points of nylon 11 and nylon 12, and then the product (adhesive composite) may be taken out of the mold.

When using a rubber composition composed of fluororubber, a vulcanized product is placed adjacent to the nylon resin instead of the unvulcanized product, and then these are heated at a temperature not lower than the melting point of the nylon resin. However, the mutual adhesion is similarly performed.

[0014]

【Example】

Example 1 Nylon resin commercially available as nylon resin 6 (melting point 220 ° C.),
Nylon 66 (melting point 240 ° C), Nylon 11 (melting point 175
℃), nylon 12 (melting point 180 ℃), alloy (nylon 6)
A resin sheet having a thickness of 2 mm, a length of 80 mm, and a width of 30 mm was prepared for each of (nylon 11-EPDM copolymer, melting point 190 ° C.).

On the other hand, a rubber sheet of an unvulcanized FKM composition (hereinafter referred to as unvulcanized FKM) having the following composition was prepared. Further, this rubber sheet was heated and pressed by a press at 170 ° C. for 10 minutes to obtain a vulcanized FKM composition (hereinafter, vulcanized FK composition).
A rubber sheet of M) was prepared. The size of these rubber sheets is 2 mm thick x 80 mm long x 30 mm wide.
And Formulation content FKM 100 parts by weight MgO 3 parts by weight Ca (OH) ₂ 6 parts by weight MT carbon black 20 parts by weight wax 1 part by weight Next, the above-mentioned unvulcanized FKM rubber sheet and vulcanized FKM are added to the resin sheet. The rubber sheets were laminated to each other so that they were adjacent to each other, and each was vulcanized at 240 ° C. for 10 minutes to produce an adhesive composite.

The adhesiveness of this adhesive composite was evaluated as follows. The results are shown in Table 1. Adhesiveness : A sample with a width of 20 mm was prepared from the above-mentioned adhesive composite and a peeling test was conducted. If interfacial peeling occurred, poor adhesion was evaluated as "x".

On the other hand, when the interfacial peeling did not occur, a sheet with a thickness of about 0.5 mm was cut out with a razor around the adhesive interface of the adhesive composite, and a peeling test was performed by making a scratch with a razor near the adhesive interface. Then, the case where the rubber sheet was firmly adhered so as to cause cohesive failure inside was evaluated as “Good” with good adhesiveness. As is clear from Table 1, in the case of FKM (fluorine rubber), the direct adhesion to the nylon resin is good in both unvulcanized and vulcanized.

Example 2 A resin sheet having a thickness of 2 mm, a length of 80 mm and a width of 30 mm was prepared for nylon 11 (melting point: 175 ° C.) which is commercially available as a nylon resin. On the other hand, ethylene-propylene-diene terpolymer rubber (EPDM), styrene-butadiene copolymer rubber (SBR), butyl rubber (IIR), acrylonitrile-butadiene copolymer rubber (NBR), chlorosulfonated polyethylene rubber ( CSM), acrylic rubber (AC
M), fluororubber (FKM), and epichlorohydrin rubber (CHC) were used to prepare rubber sheets of unvulcanized rubber compositions 1 to 8 having the compounding contents (parts by weight) shown in Table 2. The size of this rubber sheet was 2 mm thick × 80 mm long × 30 mm wide.

Next, the above-mentioned rubber sheet was laminated on the above-mentioned resin sheet so that they were adjacent to each other, and vulcanization was carried out at 190 ° C. for 15 minutes to produce an adhesive composite. The adhesiveness of this adhesive composite was evaluated in the same manner as in Example 1. The results are shown in Table 2. All the numerical values in Table 2 are parts by weight.

[0020] * 1: ZEON's fluoro rubber "Technoflon" FOR
65B1 (containing a polyol-based crosslinking agent and an accelerator). * 2: GECHRON 3102 manufactured by Zeon Corporation.

* 3: NIPOL AR 72LS manufactured by Zeon Corporation. * 4: 4,4-bis (α, α-dimethylbenzyl) diphenylamine (antiaging agent 445). * 5: Nickel dibutylthiocarbamate (antiaging agent NBC). * 6: N-phenyl-N'-isopropyl-p-phenylenediamine.

* 7: Fatty acid soda soap (Nonsar SN-1). * 8: Fatty acid potassium soap (Nonsar TK-1). * 9: Ethylenethiourea master (Revital Master # 22). * 10: Nt-butyl-2-benzothiazolesulfenamide. * 11: Tetramethylthiuram disulfide.

* 12: 2-mercaptobenzothiazole. * 13: Dipentamethylene thiuram tetrasulfide. * 14: Benzothiazyl disulfide. From Table 2, rubber composition 1 (NBR), rubber composition 2 (F
It can be seen that KM) and rubber composition 3 (CHC) have excellent direct adhesion to nylon 11.

[0024]

As described above, according to the present invention, it becomes possible to obtain an adhesive composite in which a nylon resin and a rubber or an elastomer are firmly and directly bonded. The adhesive composite can be applied as a container for storing fuel oil such as gasoline, a pipe for fuel oil, and the like.

Claims (3)

[Claims] 1. Nylon 6, nylon 66, nylon 11,
Nylon 12, a copolymer of these, a mixture thereof, a layer of nylon resin selected from the group consisting of these alloys, fluororubber, acrylonitrile-butadiene copolymer rubber, a raw material selected from the group consisting of epichlorohydrin rubber An adhesive composite obtained by laminating a layer of a rubber composition composed of rubber or a layer of a thermoplastic fluororesin elastomer. 2. Nylon 6, nylon 66, nylon 11,
Nylon 12, a copolymer thereof, a mixture thereof, a nylon resin selected from the group consisting of these alloys, a fluororubber, an acrylonitrile-butadiene copolymer rubber, a raw material rubber selected from the group consisting of epichlorohydrin rubber A method for producing an adhesive composite, in which an unvulcanized rubber composition or a thermoplastic fluororesin elastomer to be formed are adjacent to each other, and then these are heated at a temperature not lower than the melting point of the nylon resin. 3. Nylon 6, nylon 66, nylon 11,
Nylon 12, a copolymer thereof, a mixture thereof, a vulcanized product of a rubber composition composed of fluororubber is adjacent to a nylon resin selected from the group consisting of these alloys, and then these are mixed with the above-mentioned nylon resin. A method for producing an adhesive composite, which comprises heating at a temperature equal to or higher than the melting point of.