JPH0428223B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an elastomer laminate with excellent durability. More specifically, it relates to a laminate of an acrylic elastomer and a fluorine elastomer. (Prior art) Conventionally, regarding rubber parts that come into contact with fuel oil,
A rubber material that does not lose its durability even when it comes into contact with the fluid has been selected and used. For example, fuel oil hoses are made of nitrile rubber (hereinafter referred to as nitrile rubber), which has excellent oil resistance.
The inner tube is made of chlorosulfonated polyethylene (hereinafter referred to as CSM), which has excellent heat resistance.
However, due to various technological innovations in recent years, the temperature in the engine compartment of automobiles has been on the rise, causing fuel oil to deteriorate and, as a result, rubber to deteriorate more easily. MBR has insufficient oil resistance as a material for the inner tube of a fuel oil hose, and CSM for the outer tube may also have insufficient heat resistance, so a material with even higher durability is desired. (Problems to be Solved by the Invention) The present invention provides a material that requires high durability, such as fuel oil hoses for automobiles. (Means for Solving the Problems) That is, the present invention provides a composition layer containing an acrylic elastomer, a peroxide, a quaternary ammonium bromide, and an epoxidized fatty acid ester, and a composition layer containing a fluorine-based elastomer. It is a laminate made by vulcanization bonding, and this laminate is a material that is highly durable and suitable for various applications that are used under various harsh conditions. The acrylic elastomer used in the laminate of the present invention is a polymer of acrylic ester and/or methacrylic ester (hereinafter referred to as (meth)acrylic ester), or a polymer of (meth)acrylic ester and α-oefin, halogenated olefin ( (including vinyl halides), acrylonitrile, fatty acid vinyl, aromatic vinyl, diene compounds, etc., and modified products thereof. In the laminate of the present invention, since the acrylic elastomer is vulcanized with peroxide, special crosslinking monomers such as glycidyl methacrylate, allyl glycidyl ether, vinyl chloroacetate, 2-chloroethyl vinyl ether, ethylidene norbornene, etc. There is no special need for polymerized materials, but
It is also possible to use an acrylic elastomer copolymerized with such a crosslinking monomer in advance. Examples of (meth)acrylic esters for producing acrylic elastomers include (meth)
Methyl acrylate, ethyl (meth)acrylate,
Propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-(meth)acrylate
Octadecyl, 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, (meth) ) Methoxyethyl acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and the like. Examples of the fatty acid vinyl copolymerized with the acrylic acid ester include vinyl acetate and vinyl propionate. As peroxides, those used for cross-linking rubber can be used, including but not limited to, for example, G-t-
Butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane , 2,5-dimethyl-2,
5-di(t-butylperoxy)hexyne-3,
1,1-bis(t-butylperoxy)-3,3,
5-trimethylcyclohesacin, n-butyl-
Examples include 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, and 2,2-bis(t-butylperoxy)octane. The amount of peroxide is not limited, but it is usually 1 part by weight per 100 parts by weight of acrylic elastomer.
~10 parts by weight is used. Examples of the quaternary ammonium bromide include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, octadecyltrimethylammonium bromide, cetyltrimethylammonium bromide, and dodecyltrimethylammonium bromide. The quaternary ammonium bromide is used in an amount of 0.3 parts by weight or more per 100 parts by weight of the acrylic elastomer. If it is less than 0.3 parts by weight, sufficient adhesive strength of the laminated portion of the laminate cannot be obtained. Using a large amount becomes uneconomical. Typical examples of the epoxidized fatty acid ester include materials commonly used as stabilizers for polyvinyl chloride, such as epoxidized soybean oil, epoxidized linseed oil, and triglycerides of epoxidized fatty acids. The amount added must be 0.5 parts by weight or more per 100 parts by weight of the acrylic elastomer.
If it is less than 0.5 part by weight, the adhesive strength of the laminated portion of the laminate will not be sufficient, and if it is added in a large amount, the acrylic elastomer composition will tend to gradually lose its mechanical strength. The preferred amount added is 2 parts by weight or less and 10 parts by weight or less. The acrylic elastomer composition can be produced by kneading the above-mentioned materials using a method commonly used in the rubber industry, such as an open roll or internal mixer. The composition of the fluorine-based elastomer includes a copolymer of chlorotrifluoroethylene and vinylidene fluoride, a copolymer of 1,2,3,3,3-pentafluoropropene and vinylidene fluoride, and a copolymer of hexafluoropropene and vinylidene fluoride. The product names include 3M's Keruf Elastomer, Monte Edison's Tecnoflon, 3M's Florel, Dupont's Viton, and Daikin Industries' Daiel. The fluorine-containing elastomer composition is a fluorine-containing elastomer to which reinforcing agents, fillers, vulcanizing agents, and other commonly used compounding agents are added. In order to obtain a laminate, there is a method in which an acrylic elastomer composition and a fluorine elastomer composition are bonded together or coated using an extruder, and the composite is heated and vulcanized. Vulcanization of the composite requires a time and temperature to achieve sufficient crosslinking, depending on the half-life of the peroxide used. A preferred method for obtaining a stable vulcanizate is to heat-treat the primary vulcanizate again in an air oven if necessary and then perform vulcanization. In the laminate of the present invention, the fluorine-based elastomer layer has fuel oil resistance and heat resistance, and the acrylic elastomer layer has heat resistance, oil resistance, and cold resistance, and these layers are firmly bonded by vulcanization adhesive. It is extremely durable. This laminate can be used for hoses or tubes such as air hoses, fuel oil hoses, various control hoses, radiator hoses, covering electric wires, diaphragms, etc. Based on the requirements, an acrylic elastomer layer is applied to the outside, and fluorine It is used by laminating the elastomer layer on the inside or vice versa. Further, three or more layers of these two types of elastomer layers may be laminated. In particular, for automobile fuel oil hoses or tubes that require fuel oil resistance, a laminate using a fluorine-based elastomer for the inner layer and an acrylic elastomer for the outer layer is most preferable. (Example) The effectiveness of the present invention will be explained below using examples. Examples 1 to 5 Comparative Examples 1 to 3 Daiel 701G (manufactured by Daikin Industries, Ltd.) was used as the fluorine-based elastomer and the following acrylic ester copolymer was used as the acrylic elastomer.
Compounds were prepared using an 8-inch roll according to the formulations shown in 1 and 2, sheeted, and both unvulcanized rubber sheets were laminated together, followed by press vulcanization at 170° C. for 20 minutes. Post-vulcanization was performed at 150°C for 8 hours in an air open environment to produce a vulcanized product. The adhesive strength of the composite and the physical properties of each elastomer were measured in accordance with JIS/K6301. The acrylic ester copolymer (1) used was produced as follows. That is, in an autoclave, 43 kg of water, 8 kg of vinyl acetate, 32 kg of methoxyethyl acrylate, 700 g each of electrified Poval B-05 and B-17 as polyvinyl alcohol, 60 g of sodium acetate, 2 g of ferrous sulfate, 4 g of ethylenediaminetetraacetic acid, and 90 g of cocatalyst. Add and stir to mix.
The internal temperature of the autoclave was set to 45°C. The air in the upper part of the autoclave was replaced with nitrogen, and then ethylene was introduced under pressure to make the ethylene pressure 50 kg/cm ³ . A polymerization initiator aqueous solution was separately injected through an injection port to allow polymerization to proceed, and the injection was completed in 12 hours. Add a sodium sulfate aqueous solution to the generated polymer emulsion to solidify the polymer,
This was washed with water, dehydrated and dried, and the resulting polymer was tested as an acrylic ester copolymer. As shown in Table 2, peroxide and epoxidized fatty acid ester and quaternary
The system using quaternary ammonium bromide exhibits sufficient adhesive strength compared to the system not using epoxidized fatty acid ester or quaternary ammonium bromide. Table-1 Formula of fluorine elastomer composition Daiel G-701 ⁽¹⁾ 100 parts (weight) MT carbon black 20 parts Magnesium oxide (high activity) 3 parts Calcium hydroxide 6 parts

【table】

[Table] Example 6 Comparative Example 4 Acrylic ester copolymer (2) was produced in the same manner as acrylic ester copolymer (1) used in Examples 1 to 5. However, the amount of vinyl acetate was 16 kg, and 16 kg of ethyl acrylate and 8 kg of n-butyl acrylate were used instead of 32 kg of methoxyethyl acrylate. The obtained acrylic ester copolymer (2) is shown in Table 3.
Adhesion to the fluorine-containing elastomer composition shown in Table 1 was tested using the formulation shown in Table 1 in the same manner as in Examples 1 to 5.

【table】

[Table] Plasticizer Example 7 Comparative Example 5 Using acrylic rubber AR-31 (polyethyl acrylate) manufactured by Nippon Zeon Co., Ltd., and using the compounding recipe shown in Table 4, the table was prepared in the same manner as in Examples 1 to 5.
Adhesion with the fluorine-based elastomer composition of No. 1 was tested.

【table】

【table】

Claims (1)

[Claims] 1. A laminate formed by vulcanizing and adhering a composition layer containing an acrylic elastomer, peroxide, quaternary ammonium bromide, and epoxidized fatty acid ester and a composition layer containing a fluorine-based elastomer.