JPS606238B2 - rubber laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber laminate characterized in that a rubber compound made of a blend of fluororubber and an NBR polymer and an shrimp chlorohydrin rubber compound are laminated and vulcanized and bonded.

More specifically, the present invention combines a fluororubber rubber compound 'a' consisting of a terpolymer of vinylidene fluoride, propylene hexafluoride and tetrafluoroethylene with an NBR polymer {b} in a capacitive manner. The ratio is
A layer of a rubber compound blended at a ratio of NBR/fluororubber + NBR = 0.05 to 0.3 and a layer of epichlorohydrin, allyl glycidyl ether copolymer, or epichlorohydrin, ethylene oxide, allyl glycidyl ether di-base A rubber laminate characterized in that layers of a shrimp chlorohydrin rubber compound made of a copolymer are laminated and bonded together, and a fluororubber made of vinylidene fluoride and propylene hexafluoride copolymer. Blends and NBR polymer {b)
The capacitance ratio between NBR and fluorocarbon rubber is 0.1~
A layer of rubber compound blended at a ratio of 0.5 and (B
1 A layer of an epichlorohydrin rubber compound consisting of epichlorohydrin and allyl glycidyl ether copolymer or epichlorohydrin and ethylene oxide allyl glycidyl ether niphro copolymer was layered and vulcanized and bonded. The present invention provides a rubber laminate having the following characteristics.

Fluororubber has extremely excellent heat resistance, chemical resistance, gasoline resistance, and sour gasoline resistance, so it has been used in products that are used at high temperatures or in environments where they come into contact with chemicals. It has been heavily used in products used under harsh conditions.

Particularly in the automobile industry, the use of fluororubber is extremely important as a component material used under the above-mentioned harsh conditions. That is, in recent years, automobiles equipped with electronic fuel injection devices are being used to improve fuel efficiency, and the gasoline flowing through the fuel circuit of this device becomes high in temperature due to the heat of the engine, and is also subject to pressure, so that it tends to deteriorate. For this reason, any parts used in the fuel circuit system, such as rubber hoses, must be durable against degraded gasoline. On the other hand, alcohol-added gasoline has come to be used as a vehicle fuel from the point of view of resource conservation, and it has already been put into practical use in the United States, Brazil, and other countries, and is being used in other countries as well. , related parts will be required to be resistant to alcohol-added gasoline.

Furthermore, improved gasoline permeability is also required to prevent air pollution.

From these points, the use of fluororubber as a component material is absolutely essential.

However, fluororubber is much more expensive than other NBR, ebichlorohydrin rubber, etc., and it cannot be said to be satisfactory in terms of cold resistance and bending fatigue resistance.

For this reason, shrimp chlorohydrin rubber, which is cheaper than fluororubber and has excellent cold resistance, bending fatigue resistance, weather resistance, and heat resistance, is layered on fluororubber to combine the characteristics of both fluororubber and shrimp chlorohydrin rubber. It is conceivable to use a laminate prepared with this material, but fluororubber has very weak adhesive strength with other rubbers such as shrimp chlorohydrin rubber, and therefore the adhesive strength between the fluororubber layer and the shrimp chlorohydrin rubber layer is weak. In the case of peeling, stress concentration tends to occur in the peeled part, and generally the durability and fatigue properties of the laminate are significantly reduced.

For this reason, it is possible to use an adhesive to improve the adhesive strength between the fluororubber layer and the epichlorohydrin layer, but this would complicate the manufacturing process of the product, and this is not possible in the case of a cylindrical hose, for example. For example, it becomes impossible to coextrude two rubber layers. As a result of various studies on the adhesion between the fluororubber layer and the shrimp chlorohydrin rubber layer, the present inventors found that a layer of a rubber compound blending fluororubber with NBR in a certain proportion and a layer of a rubber compound blending the shrimp chlorohydrin rubber layer. It has been found that by layering and vulcanizing the two layers, the two layers can be strongly bonded without using an adhesive.

The rubber laminate obtained by the present invention is extremely excellent in interlayer adhesion and overall properties of the laminate. The present invention will be explained in detail below.

The first rubber laminate provided by the present invention is a fluororubber rubber compound consisting of a terpolymer of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride [
a} and NBR polymer (b} in a volume ratio of NBR rubber + NBR = 0.05 to 0.3; [B; epichlorohydrin;
Laminated with a layer of an allyl glycidyl ether copolymer or an shrimp chlorohydrin rubber compound consisting of an epichlorohydrin, ethylene oxide, and allyl glycidyl ether terpolymer and vulcanized and bonded. It is.

The above blend ratio of NBR/fluororubber ten NBR is:
If this value is smaller than 0.05, the adhesive strength of the vulcanized adhesive will be weak, and if this value is larger than 0.3, the properties of the fluororubber will be lost and the practicality of the product will be lost.

Other conventional formulation ingredients are of course also included in these rubber formulations.

The vulcanizing agent for the shrimp chlorohydrin rubber formulation is not specified, but a commonly used bulking agent is blended. In the first rubber laminate of the present invention, fluororubber can be vulcanized and N
As a vulcanizing agent that does not inhibit vulcanization of BR polymer,
Peroxide-based flow agents are used. Any method may be used to compound the above-mentioned rubber compound, but first, the fluororubber and NBR polymers are blended, and then the compounding components for fluororubber and NBR are simultaneously added to the compound and rolled. It is preferable to knead with Lamination and vulcanization of the layer of the rubber compound described above and the layer of the shrimp chlorohydrin rubber compound of {B' are carried out by a conventional method.

The second rubber laminate provided by the present invention comprises a fluororubber blend {a} consisting of a vinylidene fluoride and propylene hexafluoride copolymer and an NBR polymer [b-] in a volume ratio of NBR/ Fluororubber + NBR = 0.1 to 0.5
A layer of a rubber compound blended in a ratio of [
B} layers of shrimp chlorohydrin rubber compound were laminated and vulcanized and bonded.

If the above blend ratio is less than 0.1, the adhesive force between the two layers of the laminate will be weak, and if this value is larger than 0.5, the properties of fluororubber will be lost and the product will lose its practicality. It's for a reason.

Of course, other commonly used compounding components are also used in these rubber compounds.
** As a vulcanizing agent for the above-mentioned bad vinylidene fluoride and propylene hexafluoride copolymers,
A common polyolefin vulcanizing agent, polyamine vulcanizing agent or peroxide vulcanizing agent is arbitrarily selected and used. A peroxide-based vulcanizing agent is used as the vulcanizing agent for NBR. The method of blending the ingredients is the same as that described for the first rubber laminate, and any suitable method can be selected, but after blending the fluororubber and NBR polymer, other necessary compounding agents are mixed. , it is preferable to cross-wire. The lamination and vulcanization methods are conventional methods. Examples and experimental examples are listed below.

Examples 1 to 5 Fluororubber and NBR consisting of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride terpolymer
Rubber compound with polymer A rubber compound is prepared according to the compounding recipe shown in Tables 1 and 2.

Table 1 (Blend ratio) vol% * 'Mydon GH (manufactured by Jinipon) Table 2 Base composition Rubber/polymer 100 (parts by weight) Highly active Mgo 33-
SRF carbon black 10 Triallyl isocyanurate 32,5-somethyl-2,5-di(t-bunalberoxy) 3 Xane-3 3 Tsukuda Shrimp chlorohydrin rubber compound Rubber compound according to the following formulation (parts by weight) Prepare.

Epichlorohydrin, ethylene oxide, allyl glycidyl ether terpolymer *(1) 100 stearic acid 1Mg0
3CaC03
5MAF carbon black 40 di(butoxyethoxyethyl)adibate *2) 1○nickel dibutylthiocarbamate 1 triazine
1 *1) Zekron #3100 (manufactured by Nippon Zeon ■) *21
Thiokol TP-95 (manufactured by Thiokol Chemical Co.) Each of the above-mentioned wind and field rubber compounds was formed into a sheet with a thickness of 2 according to the method described in JIS K6301, and
Laminate these sheet materials, apply pressure of 20k9/carp, put in a vulcanization can, and press vulcanize with steam pressure of 1.4k9/ground.
145-150°C, 60 minutes).

For each laminate obtained in Examples and Comparative Examples, J
ISK6301No. Table 3 shows the results of the adhesive strength test conducted using the 7 peel test. Table 3 Next, tests were conducted for cold resistance, heat aging resistance, sour gasoline resistance, and alcohol-added gasoline resistance.

The results are shown in Table 4. Table 4 *1) Cold resistance JISK 6301-Ship]-4 Based on low temperature impact stiffening test.

*2) A heat aging resistant piece was punched into a size 3 dumbbell shape and subjected to a tensile test after aging at 120°C for 288 days (placed in a heated air oven) to determine the elongation at cutting before aging and the cutting after aging. Calculate the rate of elongation in time.

The tensile test is based on JISK 6301 1-2 tensile test.
*3) Add K, a liquid (gasoline forcibly oxidized) made by adding rhoyl haoxide IWt to gasoline-based gasoline, and crush at 80°C for 144 hours.

Replace the liquid every 24 hours. After that, perform a tensile test in the same manner as *2). *4) Mix 80 ÷ 20 K of gasoline-based gasoline and methanol with 7 anti-corrosion additives; soak in this at 40°C for 288 hours.

Measure the change in volume during that time. Measurement method is JISK
6301, according to pig'2 immersion test.

Examples 6 to 10 3 Vinylidene fluoride "Rubber compound of fluororubber consisting of hexafluoropropylene copolymer and NBR polymer Table 5,
A rubber compound is prepared according to the compounding recipe shown in Table 6.

4 Table 5 (Blend ratio) VO Co* Beitone B430 (manufactured by Jupon) 'B) Shrimp chlorohydrin rubber formulation table 6 Base formulation: Rubber/polymer 100 (parts by weight)
Highly active Mgo 30a(oH)2
6SRF carbon black 10 Same as described in Examples 1 to 5 above.

A laminate was prepared using each of the above-mentioned rubber compounds [B} in the same manner as in Examples 1 to 5.

Regarding the rubber laminates obtained in each example, Examples 1 to 1
Tables 7 and 8 show the results of measuring the physical properties using the same machine as the physical property tests described in Section 5.

Table 7 *1 to *4) are the same as Table 4 above. However, ethanol is used as the alcohol in *4).

Claims (1)

[Scope of Claims] 1 (A) A fluororubber consisting of a terpolymer of vinylidene fluoride, propylene hexafluoride, and ethylene tetrafluoride and an NBR polymer are combined in a volume ratio of NBR/fluororubber+NBR. a layer of a rubber compound blended in a ratio of =0.05 to 0.3; and (B) an epichlorohydrin rubber consisting of an epichlorohydrin, allyl glycidyl ether copolymer or an epichlorohydrin, ethylene oxide, allyl glycidyl ether terpolymer. A rubber laminate characterized in that layers of a compound are laminated and vulcanized and bonded. 2 (A) A rubber obtained by blending fluororubber consisting of vinylidene fluoride and propylene hexafluoride copolymer with NBR polymer at a volume ratio of NBR/fluororubber + NBR = 0.1 to 0.5. A layer of the compound and (B) a layer of an epichlorohydrin rubber compound consisting of an epichlorohydrin and allyl glycidyl ether copolymer or an epichlorohydrin and ethylene oxide allyl glycidyl ether terpolymer are laminated and vulcanized and bonded. Characteristic rubber laminate.