JPH0667608B2 - Elastomer laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly durable elastomer laminate used as a material for automobile hoses and diaphragms, and a raw material composition thereof.

[Conventional technology]

Conventionally, a laminated body of nitrile rubber (hereinafter referred to as NBR) and chloroprene rubber (hereinafter referred to as CR) has been used in fields where oil resistance and durability are required. Various technological innovations in the automobile industry
Higher durability is required for NBR and CR laminates. The NBR layer is made of acrylic elastomer (hereinafter referred to as ACM), which is oil-resistant rubber with higher heat resistance, and the CR layer is more heat resistant. It has become necessary to use chlorosulfonated polyethylene (hereinafter referred to as CSM), which has high ozone resistance.

[Problems to be Solved by the Invention]

However, when NBR and CR compositions are laminated and vulcanized and bonded to form a laminate, both NBR and CR can share the vulcanizing agent by having a double bond in the main chain. , A strong laminate could be obtained relatively easily, but AC
In the case of M and CSM, both do not contain double bonds in the main chain,
Since vulcanization is performed by using different vulcanizing agents, it is difficult to obtain a truly durable laminate because the adhesive strength at the laminate interface is low.

An object of the present invention is to provide an elastomer laminate containing ACM and CSM, which is truly durable, and a raw material composition thereof.

[Means for Solving the Problems]

Briefly describing the present invention, the present invention is an invention relating to an elastomer laminate, a compounding material containing ACM and a peroxide, and a compounding material containing a CSM elastomer, a polyfunctional monomer and a vulcanizing agent. Is laminated and vulcanized and adhered.

The ACM in the present invention means an elastomer of either a homopolymer or a polymer of an acrylic monomer or a copolymer of an acrylic monomer as a main component and an ethylenically unsaturated compound.

Examples of acrylic monomers include acrylic acid alkyl esters and acrylic acid alkoxy-substituted alkyl esters.

Examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate,
n-pentyl acrylate, isoamyl acrylate, n-
Hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate and the like can be mentioned.

As the acrylic acid alkoxy-substituted alkyl ester,
For example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2- (n- Propoxy) propyl acrylate, 2- (n-
Butoxy) propyl acrylate and the like can be mentioned.

As the ethylenically unsaturated compound, various compounds can be used if necessary, and of these, acrylonitrile, ethylene and vinyl acetate are preferable.

Normal ACM is methyl acrylate, ethyl acrylate,
A polymer or copolymer mainly composed of at least one monomer selected from n-butyl acrylate and methoxyethyl acrylate, or selected from these monomers and ethylene, vinyl acetate or acrylonitrile. It is also a copolymer of at least one ethylenic monomer.

As the peroxide to be contained in the ACM-containing compounding material in the present invention, those generally used for crosslinking rubber can be used, but not particularly limited, for example, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl. Peroxide, m-di (α-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butyl peroxy)
Hexin-3,1,1-bis (t-butylperoxy) -3,3,
5-trimethylcyclohexane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, etc. Is mentioned.

Needless to say, the amount of peroxide is the amount necessary for vulcanization of ACM, but the amount is usually 1 part by weight or more per 100 parts by weight of ACM, preferably 2 parts by weight. The amount is 6 parts by weight or more and the addition of more than 6 parts by weight may impair the mechanical properties of the vulcanizate.

CSM elastomers have --SO ₂ Cl groups in the polyethylene skeleton.
This refers to an elastomer having a Cl group substituted, and as commercially available CSM, there are Denka CSM (manufactured by Denki Kagaku), Tosoh CSM (manufactured by Tosoh), and Hypalon (manufactured by Deyupon).

Trimethylolpropane trimethacrylate and trimethylolpropane triacrylate are the most effective as the polyfunctional monomer contained in the CSM elastomer-containing compounding material in the present invention, but triallyl isocyanurate, triallyl cyanurate, and triallyl cyanurate. Allyl trimellitate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, diallyl phthalate and the like are also applicable.

The amount of these polyfunctional monomers is preferably 1 part by weight or more based on 100 parts by weight of the CSM elastomer. If it is less than 1 part by weight, the adhesive strength at the interface of the laminate will gradually decrease. More desirable is 2 to 10 parts by weight.

As a method for adding the polyfunctional monomer to the CSM elastomer, a kneading method performed in the rubber industry is generally used, but a method of drying the polymer solution after adding it to the polymer solution and directly adding it to the polymer. A method may be adopted.

Most of the polyfunctional monomers have a melting point of 80 ° C. or lower, and therefore, when the rubber kneading method is used, it is most effective to add them together with other powdery compounding agents.

The vulcanizing agent used in the CSM elastomer-containing compounded material in the present invention may be a commonly used one, for example,
In addition to the peroxides used in the ACM-containing compound materials described above,
Metal oxides such as magnesia, litharge, tribasic lead maleate, or dibasic lead phosphate, bisphenol epoxy resins, pentaerythritol, maleimides such as N, N'-m-phenylenedimaleimide, mercaptotriazine There are compounds.

Further, a vulcanization accelerator may be used in the CSM elastomer-containing compounding material in the present invention, and examples thereof include dipentamethylene thiuram tetrasulfide, tetramethyl thiuram disulfide and dibenzothiazyl disulfide. Can be mentioned.

In the ACM-containing compounding material in the present invention, in addition to peroxides, it is of course possible to add various compounding agents for the purpose of providing the desired performance in each laminate, and in particular the action of peroxides. In order to adjust the above, it is also effective to add the above-mentioned polyfunctional monomer, thiourea derivative, radical polymerization inhibitor and the like used in the CSM elastomer-containing compounding material in the present invention.

For the purpose of further improving the oil resistance of ACM, vinyl chloride resin, vinylidene chloride resin, vinylidene fluoride resin,
You may mix vinyl acetate resin, hydrogenated NBR, fluororubber, etc.

For the CSM elastomer-containing compounding material in the present invention, it is preferable to use an acid acceptor that captures an acidic substance generated from CSM in the same manner as in the conventional method, and as in the other ACM-containing compounding materials, the desired performance of the laminate is obtained. Various compounding agents may be compounded for the purpose of providing.

In order to improve the oil resistance of CSM elastomer, N
BR, hydrogenated NBR, vinyl chloride resin, vinylidene chloride resin, vinylidene fluoride resin, vinyl acetate resin and the like may be blended.

Further, 1,2-polybutadiene and liquid polybutadiene may be blended.

In addition, both of these compounded materials include the commonly used carbon black,
Fillers such as silica, clay, calcium carbonate, talc, fillers and various plasticizers, processing aids, antioxidants,
You may mix | blend an antiblocking agent, a lubricant, a pigment, etc.

As a method for obtaining the laminate, a general method such as a method in which sheet materials are laminated by a calender, or a method in which they are compounded by an extruder is adopted.

Vulcanization adhesion has no limitations other than the time and temperature at which sufficient cross-linking takes place.

The laminate of the present invention is particularly useful for practical use in the form of a hose. A hose having an ACM as an inner pipe and a CSM elastomer as an outer pipe is a particularly effective material for automobile lubricating oil hoses, automatic transmission oil hoses, and fuel oil hoses that require oil resistance and heat resistance.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these examples.

Examples 1 to 12 and Comparative Examples 1 and 2 The following acrylic ester copolymer elastomer (elastomer A or B) was used as ACM, and Denka CSM340 (manufactured by Denki Kagaku) as the CSM elastomer. After making the compound with an 8-inch roll and sheeting it, and pasting both unvulcanized compound materials, 170
A laminate was prepared by performing press vulcanization at 20 ° C. for 20 minutes.

The adhesive strength of the laminate was measured according to JIS K 6301.

(Preparation of Elastomer A) 43 kg of water, 4 kg of acrylonitrile, 36 kg of methoxyethyl acrylate, 700 g of electric Poval B-05 and B-17 as polyvinyl alcohol, 60% of sodium acetate in an autoclave
g, ferric sulfate 2g, ethylenediaminetetraacetic acid 4g, co-catalyst 9
Add 0 g and stir to mix, and set the internal temperature of the autoclave to 45
℃ was made. The air in the upper part of the autoclave was replaced with nitrogen.

A polymerization initiator aqueous solution was separately injected from the injection port to proceed polymerization, and the injection was completed in 12 hours. An aqueous solution of Glauber's salt was added to the produced polymer emulsion to coagulate the polymer, and the polymer was washed with water and dehydrated and dried, and the polymer was tested as an acrylate copolymer.

(Preparation of Elastomer B) 43 kg of water, 40 kg of ethyl acrylate, 700 electrified Poval B-05 and B-17 as polyvinyl alcohol in an autoclave
g, sodium acetate 60 g, ferric sulfate 2 g, ethylenediaminetetraacetic acid 4 g, and cocatalyst 90 g were added and mixed by stirring, and the internal temperature of the autoclave was set to 45 ° C. The air in the upper part of the autoclave was replaced with nitrogen.

A polymerization initiator aqueous solution was separately injected from the injection port to proceed polymerization, and the injection was completed in 12 hours. An aqueous solution of Glauber's salt was added to the produced polymer emulsifier to solidify the polymer, and the polymer was washed with water and dehydrated and dried, and the polymer was tested as an acrylate copolymer.

[Effects of the Invention] As described above, the elastomer laminate of the present invention is
Unlike the conventional products, the adhesive strength is high, and accordingly, the product is truly durable and has a remarkable effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 62-51439 (JP, A) JP 62-156155 (JP, A) JP 62-79247 (JP, A) JP 61- 179735 (JP, A) JP 58-3485 (JP, B2)

Claims (1)

[Claims] 1. A compounding material containing an acrylic elastomer and a peroxide and a compounding material containing a kerolosulfonated polyethylene elastomer, a polyfunctional monomer and a vulcanizing agent are laminated and vulcanized and adhered. And an elastomer laminate.