JPH02106338A - rubber laminate - Google Patents

Abstract

PURPOSE:To improve adhesion of rubber laminate by vulcanizing a specific copolymer rubber mixture consisting of or trithiol-s-triazine compound and a vulcanizer, and nickel-plated metal, and then joining them. CONSTITUTION:Rubber mixture mixed with di- or trithiol-s-triazine compound, vulcanizer in unsaturated nitrile.conjugated diene copolymer rubber is prepared. The rubber mixture and nickel-plated metal are vulcanized to be applied to mold a rubber laminate. The example of the copolymer rubber includes, for example, acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene- butadiene copolymer rubber, etc. The mixing quantity of the triazine compound is desirably 0.5 - 10 pts.wt. to 100 pts.wt. of copolymer. The rubber laminate thus obtained is useful particularly for diaphragms, valves, necessary for oil resistance, fuel oil resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rubber laminate made by vulcanizing and adhering an unsaturated nitrile-conjugated diene copolymer rubber compound and a nickel-plated metal.

(Prior Art) Conventionally, some rubber products have been composites of metal and rubber, and in order to satisfy the functions of these products, adhesion between metal and rubber is important. - On the other hand, nickel-plated metals have begun to be widely used mainly in automobile parts because they have excellent chemical and mechanical properties such as corrosion resistance and wear resistance (Automotive Technology Vol. 7).
? 41. /167.738.1987) o For this reason, adhesion between rubber and nickel-plated metal has become a technical issue.

Traditionally, acrylonitrile-butadiene copolymer rubber (NBR) has been used as an oil-resistant rubber as a rubber material for automobiles.
Although widely used, this bonding of NBR to nickel-plated metal is usually accomplished using adhesives. however.

In the adhesive method, the adhesive applied to the metal
When molding rubber, there is a disadvantage that the rubber flows due to pressure and heat, which causes problems such as poor vulcanization adhesion and contamination of the molding die. For this reason.

Before vulcanizing and bonding the metal coated with adhesive, there are methods such as baking the adhesive onto the metal using heat opening or pressing, allowing a certain degree of chemical reaction to proceed, and then vulcanizing and bonding the metal with rubber. Although it has been.

The above problem has not been completely resolved.

(Problems to be Solved by the Invention) The object of the present invention has been made in view of the above-mentioned technical problems, and it is an object of the present invention to solve the problems of unsaturated nitrile without using an adhesive.
An object of the present invention is to provide a rubber laminate in which a conjugated diene copolymer rubber compound and a nickel-plated metal are vulcanized and bonded. When obtaining a rubber laminate in which a conjugated diene yarn copolymer rubber compound and a nickel-plated metal are vulcanized and bonded.

It has been discovered that a rubber laminate with improved adhesion to nickel-plated metal can be obtained by using a rubber compound containing the rubber, a di- or trithiol-8-triazine compound, and a vulcanizing agent. Unsaturated 2) IJ sil-functional diene copolymer rubbers of the invention include unsaturated nitrile-conjugated diene copolymer rubbers and copolymer rubbers in which part of the conjugated diene of this copolymer rubber is replaced with ethylenically unsaturated monomers. The monomers used for producing the copolymer rubber of the present invention are illustrated below.

Acrylonitrile is an unsaturated nitrile.

Examples of conjugated dienes include methacrylonitrile.

1,3-butadiene, 2,5-dimethylbutadiene.

Examples include isoprene and 1,3-pentadiene.

Examples of ethylenically unsaturated monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic #1, itaconic acid, and maleic acid, and their salts methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, etc. Alkoxyalkyl esters of unsaturated carboxylic acids such as methoxy acrylate, ethoxyethyl acrylate, methoxyethoxyethyl acrylate, etc. β-hydroxyethyl acrylate, β
-Hydroxyglobil acrylate.

hydroxyalkyl esters of the unsaturated carboxylic acids 1-acrylamide, such as β-hydroxyethyl methacrylate, β-hydroxyglobil methacrylate, β-hydroxyisobutyl acrylate, β-hydroxy n-butyl acrylate, γ-hydroquine n-butyl acrylate; Methacrylamide IN-methylol (meth)acrylamide, N,N'-dimethylol (meth)acrylamide, N-i-substituted (meth)acrylamide such as N-ethoxymethyl (meth)acrylamide, and the like are included.

In the present invention, the amount of the above-mentioned nitrile used is not particularly limited, but the amount of unsaturated nitrile is usually 10 to 6 in all monomers.
The amount of conjugated diene used in the present invention is 40 to 90%, and the ethylenically unsaturated monomer is used in a range of 20% or more of the amount of conjugated diene used, if necessary. Specifically, the copolymer rubber is an acrylonitrile-butadiene copolymer rubber or an acrylonitrile-inoprene-butadiene copolymer rubber.

Acrylonitrile-isoprene copolymer rubber i Acrylonitrile-butadiene-methyl acrylate copolymer rubber,
Examples include acrylonitrile-butadiene-acrylic acid copolymer rubber, acrylonitrile-butadiene-methacrylic acid copolymer rubber, etc. The di- or trithiol-s-triazine compound used in the present invention has the general formula (X and Y are hydrogen, alkali metal PA or alkaline earth metal R is ORI, 8R1, NR1R2s R1 and R
2 is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms which may contain a substituent, and R1 and R2 may be connected at the other end to form a ring. ) is a compound represented by

Here, the hydrocarbon residues constituting R1 and R2 are:
Alkyl groups such as methyl, ethyl, butyl, and ethylhexyl, cycloalkyl groups such as cyclohexyl, aralkyl groups such as benzyl, methylbenzyl, and ethylbenzyl, and aryl groups such as phenyl, naphthyl, phthylphenyl, and hydroxy-di-t-butylphenyl. Examples include substituted aryl groups and alkenyl groups such as allyl and oleyl. Examples of the ring in which R1 and R2 are connected at the other end to form another ring include 1morpholino, piperidyl, and bipecolyl.

Specific examples of the compound include trithiocyanuric acid S2-
Methoxy-2-ethoxy-2-phenoxy-2-butylamino-2-anilino-2-naphthylamino-2-dimethylamino-2-diethylamino-2-dibutylamino-2-diphenylamino-2-dicyclohexylamino-2 -morpholino- or 2-piperidyl-4,6-sithio-8-triazine 1 and the sodium, potassium, calcium, and magnesium salts of these triazines,
Examples include barium salt.

The amount of the triazine compound to be blended is 0.1 to 20 parts by weight, preferably 0.5 to 1 part by weight, per 100 parts by weight of the copolymer rubber.
It is 0 parts by weight. Further, the vulcanizing agent used in the present invention may be either a sulfur-based vulcanizing agent or a peroxide-based vulcanizing agent, but is not particularly limited. Specific examples include sulfur, tetramethylthiuram disulfide, etc. Sulfur-donating compound, zinc white.

Stearic acid, various vulcanization accelerators (guanidine type).

Sulfur-vulcanized dicumyl peroxide consisting of thiazole-based, thiuram-based, dithioate-based, etc.
Examples include organic peroxide vulcanization systems such as dimethyl-2,5-di(t-butylperoxy)hexyne-3.

In addition to the above, there are various compounding agents commonly used in the rubber industry, such as HAF, Pl! Various grades of carbon black such as XA, reinforcing agents such as silica, Merck, calcium carbonate, etc.
Filler 5oTffl agent, process oil.

Processing aids, anti-aging agents, etc. are used. These ingredients are mixed using a conventional mixer to form a rubber compound. The type and amount of compounding agents used are determined according to the intended use (application) of the rubber-gold 11 laminate and are not particularly limited in the present invention.

The metal used in the present invention may be nickel or a metal whose surface to be bonded is nickel-plated. Nickel plating methods include electroplating and nickel ions in a nickel salt aqueous solution are attached to other metal surfaces by a substitution reaction, etc. Chemical plating with precipitation is used. The type and shape of the nickel-plated metal can be appropriately determined depending on the purpose of use (application), and is not particularly limited. The vulcanization is carried out according to the usual vulcanization conditions for the rubber compound.

(Effects of the Invention) The rubber laminate of the present invention is particularly useful for manufacturing diaphragms, valves, seals, packings, etc. that require oil resistance and fuel oil resistance.

(Example) The present invention will be described in more detail with reference to Examples below. In addition, parts and sections in Examples, Comparative Examples, and Reference Examples are based on weight unless otherwise specified.

(Reference Example) A nickel-plated metal plate was created using a chemical nickel plating method that is usually used industrially on iron plates. Iron plate (
0.25X26.5X60) is trichlorethylene and alkaline degreaser 0F-144 [Katsurahara Nishilite ■
After degreasing and washing with water, treatment was carried out with metal activator OV-S45 (manufactured by Katsuragahara Nishilite ■), and after washing with water, nickel plating was performed.

Nickel plating uses hypophosphorous acid as a reducing agent [suMu
uJ [manufactured by Nippon Kanizen ■] was used as a plating bath. After cleaning the plating board with methanol.

It was air-dried and made into a nickel-plated metal plate for adhesion.

(Example) Nickel-plated metal plate created in the reference example and Table 1 1-1
A sheet with a thickness of 2 mm made from the rubber compound shown in No. 0 was placed in a mold and press-cured at a temperature of 160 C for 30 minutes under a pressure of 80 V4/e2 to form a rubber laminate. Measurement was carried out at a tensile speed of 50 m according to J Engineering S-6501.
The test was performed at s+/min. The results are shown in Table 1.

(Comparative Example) Rubber laminates were obtained in the same manner as in the Examples using 2-diameter thick sheets made from the rubber compounds shown in Comparative Examples 1 to 3 in Table 1. Table 1 shows the results of a similar peel test conducted on these.

From the results in Table 1, 1. The rubber laminate of the present invention has excellent adhesion between the rubber compound and the nickel-plated metal plate, but a comparative example using a rubber compound that does not contain a triazine compound has no adhesion at all. I understand O

Claims (1)

[Claims] 1. A rubber laminate made by vulcanizing and adhering a rubber compound containing unsaturated nitrile-conjugated diene copolymer rubber, a di- or trithiol-s-triazine compound, and a vulcanizing agent, and a nickel-plated metal.