JPH06340773A - Thermoplastic fluororesin/plastics bonded composite material and its production - Google Patents

Abstract

PURPOSE:To provide a fluororesin/plastics bonded composite material produced by strongly bonding a general-purpose resin to a fluororesin and excellent in dynamic adhesion and to provide its production method. CONSTITUTION:A thermoplastic fluororesin and polyethylene or polyvinyl chloride are bonded through an adhesive layer composed of a rubber composition prepared by blending a hydrogenated acrylonitrile-butadiene copolymer rubber with a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide.

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 a thermoplastic fluororesin and a general-purpose plastic and a method for producing the same.

[0002]

2. Description of the Related Art Thermoplastic fluororesin (hereinafter abbreviated as fluororesin) is a flexible and easy-to-process thermoplastic resin having many excellent physical properties such as chemical resistance, weather resistance and food safety. Applications are being developed in the fields, building materials, food / sanitation, electricity / electric wires, etc. On the other hand, polyethylene (hereinafter abbreviated as PE) and polyvinyl chloride (hereinafter abbreviated as PVC) are both typical and inexpensive general-purpose plastics. Moreover, PE is lighter in weight than fluororesin, and PVC has the feature that it can be made into a hard PVC or a soft or semi-hard PVC by adjusting the presence or absence of the plasticizer or adjusting the amount.

Therefore, fluororesin and these PE or P
If VCs can be joined to form an adhesive composite, it is possible to use a material having industrial merits that has the respective characteristics of fluororesin and PE or PVC. For example, if a fluororesin can be adhered to the inner surface of a soft PVC pipe, it can be made excellent in chemical resistance and food safety. If a fluororesin can be adhered to the surface of the polyethylene container, weather resistance and heat resistance can be improved.

However, fluororesin and PE or PVC
Was poor in adhesiveness and could not be firmly bonded. Conventionally, PE or PVC can be bonded to a fluororesin by chemically treating the surface and using a thermosetting epoxy adhesive. However, in this case, not only a complicated chemical treatment is required, but also the adhesive layer becomes hard and has no toughness, so that bending or bending deformation causes damage or peeling of the adhesive layer such as cracks. Easy,
It did not provide a durable adhesive force.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to firmly bond general-purpose plastics to a fluororesin and to have excellent dynamic adhesiveness, and to provide a fluororesin / plastics composite and a method for producing the same. To provide.

[0006]

A fluororesin / plastics adhesive composite of the present invention which achieves the above object is a hydrogenated acrylonitrile-butadiene copolymer comprising a fluororesin and PE or PVC as an adhesive layer. A rubber composition (hereinafter referred to as a modified NBR rubber composition) in which a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide is mixed with rubber (hereinafter referred to as hydrogenated NBR).
It is characterized by being bonded and integrated through.

The method for producing a fluororesin / plastics adhesive composite of the present invention comprises a hydrogenated acrylonitrile-butadiene copolymer rubber, methacrylic acid and zinc oxide between a thermoplastic fluororesin and polyethylene or polyvinyl chloride. And an unvulcanized rubber composition containing a mixture of zinc methacrylate and an organic peroxide are interposed to vulcanize the unvulcanized rubber composition and at the same time, to bond and integrate the unvulcanized rubber composition. .

As described above, the modified NBR rubber composition has not only excellent adhesion to fluororesin but also excellent adhesion to PE or PVC. Therefore, the modified NBR rubber composition is adhered to the modified NBR rubber composition. By forming a layer, the fluororesin and PE or PVC can be bonded to form a composite. In the present invention, the thermoplastic fluororesin means a resin obtained by graft-copolymerizing a trunk polymer made of fluororubber of the flexible segment with a branch polymer made of crystalline fluororesin. Preferred is a polymer obtained by graft-copolymerizing polyvinylidene fluoride on fluororubber. Specifically, "Sefraral Soft G150" (trade name) manufactured and sold by Central Glass Co., Ltd. can be exemplified.

The composite partner P of the fluororesin used in the present invention
The E is not particularly limited, and any of known low density polyethylene, medium density polyethylene and high density polyethylene can be used. The PVC is not particularly limited, and hard PVC containing no plasticizer or soft or semi-hard P containing plasticizer is used.
It may be any of VC. The shape of this PVC may be a single body such as a sheet, a plate or a pipe, or may be a composite sheet-like material obtained by impregnating or coating PVC on a base fabric such as knitted fabric, non-woven fabric or paper.

In the present invention, fluororesin and PE or PV
The modified NBR rubber composition used as an adhesive layer with C contains 10 to 60 parts by weight of an ethylenically unsaturated nitrile unit and 100 parts by weight of a hydrogenated NBR containing 30 parts by weight or less of a conjugated diene unit. And 20 to 200 parts by weight of zinc methacrylate and 0.5 to 20 parts by weight of organic peroxide. Specifically, ZSC229 manufactured and sold by Nippon Zeon Co., Ltd.
There are 5 (brand name). Zinc methacrylate can be blended with methacrylic acid and zinc oxide as the raw materials so that the molar ratio of methacrylic acid / zinc oxide is in the range of 1 / 0.5 to 1/3. In this case, the hydrogenated NBR100
It is desirable to mix 20 to 60 parts by weight of methacrylic acid and 10 to 60 parts by weight of zinc oxide with respect to parts by weight.

In the adhesive composite of the present invention, the modified NBR
The rubber composition has a function as an adhesive for adhering PE or PVC to the fluororesin. That is, PE or PVC cannot be directly adhered to the fluororesin, but it can be strongly adhered through the modified NBR rubber composition. In the method for producing an adhesive composite of the present invention, the modified NBR rubber composition is subjected to an adhesive treatment in an unvulcanized state. By being unvulcanized, by vulcanizing it under heating,
It diffuses into the fluororesin and PPE or PVC to cause a cross-linking reaction, resulting in strong adhesion between the fluororesin and PE or PVC.

The adhesion conditions are such that the unvulcanized modified NBR rubber composition is vulcanized, preferably 160 to 200.
It is good to heat under press at a temperature of 10 to 30 minutes. This modified NBR rubber composition has a thickness of 10 μm to 1.0 m.
It is desirable to use it in the form of a film of m. The adhesive strength can be increased by setting the thickness to 10 μm or more. However, since the adhesive strength is saturated at a thickness of 1.0 mm or more, it is economical to set the upper limit to 1.0 mm.

[0013]

【Example】

Example A sheet made of a commercially available thermoplastic fluororesin (“Sefraral Soft G150” manufactured by Central Glass Co., Ltd.) was cut to 150
A sheet of mm × 50 mm × 2.5 mm was manufactured.

A rubber composition containing hydrogenated NBR and zinc methacrylate as main components (ZSC-manufactured by Zeon Corporation)
2295) 85% by weight and 15% by weight of hydrogenated NBR (ZETPOL2020 manufactured by Nippon Zeon Co., Ltd.) were kneaded, and then 4,4-bis (α, α-dimethylbenzyl) diphenylamine (aging Inhibitor, Naugard 445) 1.5 parts by weight, 1,
5 parts by weight of 3-Bister Charly butylperoxy-isopropylbenzene (organic peroxide "Perkadox 14/40" manufactured by Kayaku Akzo Co., Ltd.) was added and blended to prepare an unvulcanized modified NBR rubber composition. From this rubber composition, an unvulcanized film of 150 mm × 50 mm × 0.3 mm was prepared.

On the other hand, a commercially available high-density polyethylene sheet,
Soft and hard PVC sheet 150 mm x 50 mm x
It was cut into a 1.0 mm sheet. The above-mentioned fluororesin sheet and high density polyethylene sheet, soft PVC sheet and hard PVC sheet, respectively, are laminated via an unvulcanized film made of a modified NBR rubber composition, and heated at 170 ° C. for 20 minutes to be vulcanized and bonded at the same time. Let As a result of evaluating the adhesiveness of the obtained three kinds of adhesive composites by the following method,
In all cases, the adhesiveness was good (◯).

Adhesiveness Evaluation Method : The adhesiveness of the thermoplastic fluororesin adhesive composite is not accurately evaluated by the magnitude of the adhesive force. Therefore, a sample having a width of about 20 mm was prepared, and a peeling test was performed. When dry noodle peeling occurred, it was evaluated as poor (x) even if the adhesive strength was high. 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 centering on the adhesive interface of the composite,
A peeling test was performed by making a scratch with a razor near the bonding interface, and the case where the sheet was firmly bonded so as to cause cohesive failure inside was evaluated as good adhesion (◯).

[0017]

According to the present invention, fluororesin and PE or P
By using a modified NBR rubber composition as an adhesive layer, VC can be firmly adhered without chemically treating the surface of PE or PVC, and an adhesive composite having excellent dynamic adhesiveness can be obtained. it can.

Claims (2)

[Claims] 1. A thermoplastic fluororesin and polyethylene or polyvinyl chloride are used as an adhesive layer in a hydrogenated acrylonitrile-butadiene copolymer rubber and a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide. A thermoplastic fluororesin / plastics adhesive composite that is integrally bonded through a compounded rubber composition. 2. A hydrogenated acrylonitrile-containing resin between a thermoplastic fluororesin and polyethylene or polyvinyl chloride.
At the same time as vulcanizing the unvulcanized rubber composition by interposing an unvulcanized rubber composition containing a mixture of methacrylic acid and zinc oxide or zinc methacrylate and an organic peroxide in a butadiene copolymer rubber Integral thermoplastic fluororesin /
A method for manufacturing a plastics adhesive composite.