JPH09255815A - Oil resistant rubber alloy composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil resistant rubber alloy composition for packing, etc., at a low cost, excellent in fuel oil resistance, resistance to a fuel oil mixed with alcohol and heat resistance by containing a vulcanized fluorine rubber and/or its blended compound. SOLUTION: In this oil resistant rubber alloy composition, (A) 10-90 pts.wt. of a highly saturated polymerized rubber containing nitrile groups is blended with (B) 90-10 pts.wt. of a vulcanized fluorine rubber and/or its compound. The component B is preferably flashes or fragment materials produced in a primary vulcanization processing, especially a vinylidene fluoride- hexafluoropropylene copolymer, a vinylidene fluoride-hexafluoropropylenen- tetrafluoroethylene terpolymer, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vulcanizable oil-resistant rubber alloy composition, and more specifically to an alloy of a pre-vulcanized fluororubber and / or a blend thereof with a nitrile group-containing highly saturated polymer rubber. The present invention relates to an oil resistant rubber alloy composition which is excellent in fuel oil resistance, alcohol mixed fuel oil resistance and heat resistance obtained by chemical conversion.

[0002]

2. Description of the Related Art At present, fluororubber is a rubber material having the best oil resistance and heat resistance, but it has a problem that it is very expensive.

Further, the nitrile group-containing highly saturated polymer rubber has an excellent balance of oil resistance, heat resistance and strength characteristics, and is therefore important as an oil resistance and heat resistance rubber material.
However, the nitrile group-containing highly saturated polymer rubber has an oil resistance,
Since its heat resistance is inferior to that of fluororubber, its application is limited depending on the part to be used.

In recent industrial applications, particularly in the field of automobiles, the oil resistance of nitrile group-containing highly saturated polymer rubbers, particularly fuel oil resistance, alcohol fuel oil resistance and heat resistance, is not sufficient and is intermediate with that of fluororubber. There is a need for a rubber material having the performance of. That is, a rubber material having excellent oil resistance closer to that of fluororubber and heat resistance intermediate between that of the nitrile group-containing highly saturated polymer rubber and the fluororubber and being cheaper than the fluororubber is desired.

On the other hand, an attempt to knead and blend a nitrile group-containing highly saturated polymer rubber and a fluororubber (for example, JP-A-60-101135 and JP-A-61-161).
No. 62538). However, it is difficult to knead in processing, or because the fluororubber has a poor affinity for the nitrile group-containing highly saturated polymer rubber, it is difficult to uniformly disperse both components, and heat treatment is performed for vulcanization. At that time, phase separation occurred, and the degree of dispersion was further lowered. Therefore, the oil resistance and the heat resistance are not practically satisfactory, and a significant cost reduction cannot be achieved.

The present invention has been made in view of these points, and has excellent fuel oil resistance, alcohol fuel oil resistance, and fluorine rubber which are superior to the additive properties of fluororubber and nitrile group-containing highly saturated polymer rubber. Oil-resistant rubber alloy composition capable of producing a rubber alloy composition having heat resistance in the middle of a nitrile group-containing highly saturated polymer rubber at a lower cost than fluororubber and, depending on a method, cheaper than a nitrile group-containing highly saturated polymer rubber. The purpose is to provide.

[0007]

Means for Solving the Problems and Embodiments of the Invention
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, a vulcanizable oil-resistant rubber alloy composition containing a pre-vulcanized fluororubber and / or a blend thereof is a fluororubber. And excellent fuel oil resistance above the additivity of nitrile group-containing highly saturated polymer, alcohol-mixed fuel oil resistance, heat resistance intermediate between that of fluororubber and nitrile group-containing highly saturated polymer rubber, and fluororubber Cheaper,
It has been found that, depending on the method, it can be provided at a lower cost than the nitrile group-containing highly saturated polymer rubber, and has completed the present invention.

That is, the oil-resistant rubber alloy composition of the present invention is characterized in that it is made vulcanizable by containing a vulcanized fluororubber and / or its mixture in a nitrile group-containing highly saturated polymer rubber in advance. To do.

More specifically, in the vulcanizable oil-resistant rubber alloy composition of the present invention, a pre-vulcanized fluororubber and / or a blend thereof is uniformly dispersed in a nitrile group-containing highly saturated polymer rubber, The vulcanized product prevents phase separation during heat treatment for vulcanization, and vulcanizes the nitrile group-containing highly saturated polymer rubber itself, as well as the fluororubber inside the phase centering on the interface of the fluororubber phase. Since it is considered that the nitrile group-containing highly saturated polymer rubber is co-crosslinked, the vulcanized product of the oil-resistant rubber alloy composition of the present invention is characterized by having the above-mentioned excellent chemical and physical properties. .

[0010] Furthermore, a compound of vulcanized fluororubber which has been previously vulcanized includes so-called industrial products such as vulcanized burrs produced by compression molding, vulcanized end materials produced by injection molding, transfer molding, and extrusion molding. Since waste can also be used, resources are reused and it can be provided as an extremely inexpensive material.

As the pre-vulcanized fluororubber and / or the blend thereof in the present invention, the fluororubber simple substance and / or the blend thereof may be vulcanized with a vulcanizing agent. There is no particular limitation on the type and amount of the vulcanizing agent for vulcanization, and any vulcanizing agent may be used as long as it can vulcanize the fluororubber and / or its compound. As the vulcanizing agent, a polyol vulcanizing system, an amine vulcanizing system, a peroxide vulcanizing system, an ion vulcanizing system or the like which is generally used for vulcanizing fluororubber can be used.

Fluorine rubber is generally molded by primary vulcanization and then secondary vulcanized to complete vulcanization. The pre-vulcanized fluororubber and / or the blend thereof in the present invention may be primary vulcanized or secondary vulcanized, but primary vulcanized is preferable. The composition is not particularly limited, and if necessary, a reinforcing filler, an expanding filler, a vulcanization stabilizer, an acid acceptor, a processing aid, a coupling agent, a plasticizer, a pigment, etc. may be added. Good.

It is particularly desirable to use burrs and scraps generated in molding the rubber product by primary vulcanization in the fluororubber compound from the viewpoint of resource reuse and cost reduction.

In the present invention, the primary vulcanization conditions of the pre-vulcanized fluororubber and / or the compound thereof are 10
0 to 300 ° C for several seconds to 48 hours, preferably 100 to
The temperature may be within a range of one hour at 250 ° C. The secondary vulcanization conditions may be 100 to 300 ° C. for 30 minutes to 48 hours, preferably 150 to 250 ° C. for 2 to 24 hours. This is because if the vulcanization time is too short, the degree of cross-linking becomes insufficient, and if it is 24 hours or more, it is not economical and the fluororubber deteriorates depending on the temperature conditions.

The mixing ratio of the pre-vulcanized fluororubber and the nitrile group-containing highly saturated polymer rubber is not particularly limited, but is preferably a pre-vulcanized fluororubber because of the characteristics of the vulcanized rubber alloy composition. The weight ratio of the rubber to the nitrile group-containing highly saturated polymer rubber is 1
It is a range with a mixing ratio of 0/90 to 90/10. If the amount of fluororubber is 10% by weight or less, the effect of improving oil resistance and heat resistance is small, and if it is 90% by weight or more,
Processing is difficult, and physical properties such as tensile strength are reduced, and practical restrictions occur.

The form in which the prevulcanized fluororubber and / or the blend thereof is mixed with the nitrile group-containing highly saturated polymer rubber is not particularly limited. However, for smooth mixing and homogenization with the nitrile group-containing highly saturated polymer rubber, it is more desirable to use a compounded powder having an average particle diameter of 5 mm or less.

The fluororubber in the present invention is a copolymer of a fluorine-containing monomer having 2 to 8 carbon atoms, specifically, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, tetrafluoroethylene, At least one compound selected from the group consisting of chlorofluoroethylene and perfluoro (alkyl vinyl ether) having 1 to 5 carbon atoms in the alkyl group as an essential component, and at least one of tetrafluoroethylene and vinylidene fluoride It may be a copolymer with another olefin copolymerizable therewith, and may be a copolymer obtained by copolymerizing an active halogen group-containing monomer or an epoxy group-containing monomer which becomes a crosslinking point, if necessary.

Among these pre-vulcanized fluororubbers, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-perpolymer A fluoro (methyl vinyl ether) copolymer, a tetrafluoroethylene-propylene copolymer, and a tetrafluoroethylene-vinylidene fluoride-propylene copolymer are particularly preferable, and a commercially available fluororubber can be used. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of these fluororubbers is preferably 20 to 150.

In the nitrile group-containing highly saturated polymer rubber of the present invention, the content of the nitrile group-containing monomer unit is usually 5
５０50% by weight. The iodine value of the polymer rubber is preferably 80 or less, more preferably 0 to 60.
Here, the iodine value of the nitrile group-containing highly saturated polymer rubber is a value determined according to JIS K0070.

The nitrile group-containing highly saturated polymer rubber in the present invention is a conjugated diene-unsaturated nitrile copolymer rubber obtained by hydrogenating the conjugated diene portion, conjugated diene-ethylenically unsaturated monomer-unsaturated nitrile. Examples thereof include those obtained by hydrogenating the conjugated diene portion of the copolymer rubber.

Specifically, butadiene-acrylonitrile copolymer, isoprene-butadiene-acrylonitrile copolymer, butadiene-butyl acrylate-acrylonitrile copolymer, butadiene-cyanoethyl acrylate-acrylonitrile copolymer, butadiene-2-
Ethylhexyl acrylate-acrylonitrile copolymer, butadiene-diethyl itaconic acid-acrylonitrile copolymer, butadiene-di-n-butyl itaconate-
Acrylonitrile copolymer, butadiene-diethylaminoethyl methacrylate-acrylonitrile copolymer,
Examples include hydrogenated rubbers such as a butadiene-trifluoroethyl acrylate-acrylonitrile copolymer, a butadiene-tetrafluoropropyl acrylate-acrylonitrile copolymer, and a butadiene-octafluoropentyl acrylate-acrylonitrile copolymer.

The molecular weight of these nitrile group-containing highly saturated polymer rubbers is required to be at least large enough for the nitrile group-containing highly saturated polymer rubber itself to be self-vulcanized. On the other hand, since an extremely high molecular weight may impair the compatibility with the pre-vulcanized fluororubber and / or the blend thereof, the number average molecular weight is 3,000 to 500,000.
Is desirable. More preferably, the Mooney viscosity (ML
_It is preferable to use one having a temperature of _{1 + 4} , 100 ° C.) of 10 to 150. Generally, commercially available hydrogenated nitrile rubber and HNBR can be used.

For alloying the composition of the present invention, a vulcanizing agent generally used for vulcanizing a nitrile group-containing highly saturated rubber can be used. However, a nitrile group-containing highly saturated polymer rubber and a fluororubber are used. By using a vulcanizing agent capable of co-vulcanization with, more preferable physical properties can be given. For example, an organic peroxide is preferable as a vulcanizing agent, and in that case, it is more preferable to use a crosslinking assistant together.

As the organic peroxide to be used, an organic peroxide usually used in the rubber industry and the plastics industry can be used, and it is not particularly limited.

Specifically, dicumyl peroxide, di-
t-butyl peroxide, t-butyl cumyl peroxide, cumene hydroperoxide, benzoyl peroxide, 2,4-dichlorodibenzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, 2,5-dimethyl-2,
Examples thereof include 5-di (benzoylperoxy) hexane and 1,3-di (t-butylperoxyisopropyl) benzene. The amount of these organic peroxides used is not particularly limited in the present invention, but the alloy rubber 1 is usually used.
It is in the range of 0.5 to 15 parts by weight per 00 parts by weight.

The crosslinking aid to be used may be one used in ordinary organic peroxide vulcanization, for example, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, ethylene dimethacrylate, magnesium dimethacrylate. , Divinylbenzene, diallyl phthalate, toluylene bismaleimide,
Polyfunctional monomers such as metaphenylene bismaleimide, liquid polybutadiene, p-quinone dioxime, p,
Examples thereof include oxime compounds such as p′-dibenzoylquinone dioxime. The amount of these crosslinking aids used is
Usually, it is 0.1 to 15 parts by weight, preferably 1 to 8 parts by weight, per 100 parts by weight of the alloy rubber.

There is no particular limitation on the method for preparing the oil resistant rubber alloy composition of the present invention.
It is easily adjusted by uniformly mixing with a usual rubber kneader such as a pressure kneader, a Banbury mixer, and an internal mixer. At this time, it is preferable that the preliminarily vulcanized fluororubber and / or the compound thereof be used in the form of a sheet using a conventional rubber kneader or powdered using a pulverizer.

The oil-resistant rubber alloy composition of the present invention contains, if necessary, a reinforcing filler, a bulking filler, an antioxidant, a vulcanization stabilizer, in order to impart more desirable physical properties and processability balance. Processing aids, coupling agents, compatibilizers, plasticizers, pigments and the like may be added.

The oil-resistant rubber alloy composition of the present invention thus obtained is used in compression molding generally used in the rubber industry.
It is molded by injection molding, transfer molding, extrusion molding, coating dissolved in a solvent, or the like.

[0030]

The vulcanizate obtained by vulcanizing the rubber alloy composition of the present invention has excellent fuel oil resistance and alcohol fuel oil resistance superior to the additivity of fluororubber and nitrile group-containing highly saturated rubber. It has heat resistance intermediate between that of fluororubber and nitrile group-containing highly saturated polymer rubber. Further, it can be produced at a lower cost than fluororubber and, depending on the method, at a lower cost than a nitrile group-containing highly saturated polymer rubber. Therefore, packing, gasket, oil seal, O-ring,
It can be widely used for various applications requiring oil resistance and heat resistance such as valves, diaphragms, tubes, hoses, belts, rolls, roll blades, anti-vibration rubbers, coating materials and coating materials.

[0031]

The present invention will be described below in detail with reference to examples. The present invention is not limited by this.

In the following description, “part” means “part by weight”.
The physical properties of the vulcanized rubber were evaluated according to JIS K6301. Heat resistance is 168 vulcanizates in a gear oven at 175 ° C.
It was evaluated by measuring the rate of change of each physical property value after heat aging for a period of time. The compression set resistance of vulcanized rubber is 2
The compression set of the sample after 168 hours at 175 ° C. after 5 (%) compression was measured. The swelling degree volume change rate showing the oil resistance is as follows: the vulcanized rubber is JIS # 3 oil at 150 ° C. for 70 hours, and JIS fuel oil C and JIS fuel oil C containing 20 volume (%) of methanol are used. 40 ° C in oil
It was obtained by measuring the rate of change after immersion for 70 hours in.

The oil resistant rubber alloy composition in this example was obtained as follows. That is, according to the formulation shown in Table 1, the components were uniformly mixed with a two-roll mill to prepare fluororubber formulations FKM1 to FKM5.

Next, according to the formulation shown in Table 2 and the vulcanization conditions shown in the footnotes, primary vulcanization (press vulcanization) was performed, and then secondary vulcanization was performed to obtain a vulcanized rubber alloy composition. The vulcanization conditions of the rubber alloy composition to be vulcanized are the same from Table 3 to Table 5 below.

Example 1 1 of HNBR1 which is a nitrile group-containing highly saturated polymer rubber
43.3 parts of propylene-containing ternary fluororubber compound FKM3-C1 preliminarily vulcanized in advance with respect to 00 parts.
Parts (rubber content weight ratio of fluororubber to HNBR 25 (%)), 1 part of stearic acid, 2 parts of substituted diphenylamine, 5 parts of zinc oxide, 50 parts of FEF carbon.
Part, 2. a triallyl isocyanurate which is a cross-linking aid.
3 parts and 4.5 parts of Perhexa 25B which is an organic peroxide.

Example 2 86.7 parts of propylene-containing ternary fluororubber compound FKM3-C1 preliminarily primary vulcanized (rubber content weight ratio of fluororubber to HNBR 40%) was used as a crosslinking aid. 3.2 parts of a triallyl isocyanurate,
The mixing ratio was the same as that of Example 1 except that the organic peroxide, Perhexa 25B, was changed to 6.3 parts.

Example 3 241.1 parts of propylene-containing ternary fluororubber compound FKM3-C1 preliminarily primary-vulcanized (rubber content weight composition ratio of fluororubber to HNBR: 65 (%)),
Triallyl isocyanurate, which is a crosslinking aid, was added to 5.3.
And 10.5 parts of Perhexa25B, which is an organic peroxide, were used in the same mixing ratio as in Example 1.

Comparative Example 1 For comparison, only HNBR1 was used as the rubber, and each of them was mixed so that the compounding ratio of the vulcanizing system of triallyl isocyanurate and Perhexa 25B was the same as that of all the rubber components of Example 1. The mixing ratio was the same as in Example 1 except that the mixing ratio was 0.6 parts and 3.2 parts.

COMPARATIVE EXAMPLE 2 For comparison, the rubber was unvulcanized fluororubber compound FKM3.
-C0 was only 130 parts.

Comparative Example 3 For comparison, unvulcanized fluororubber compound FKM3-C0
Was used instead of FKM3-C1 in the same proportion as in Example 1.

Evaluation Normal state physical properties, heat aging resistance, compression set resistance, oil resistance, fuel oil resistance, and methanol resistance mixture of the secondary vulcanizates of Examples 1 to 3 and Comparative Examples 1 to 3 The evaluation results of fuel oil properties are shown in Table 2 together with the compounding and vulcanization conditions.

As shown in Table 2, the change rate of tensile strength showing the heat aging resistance of the oil resistant rubber alloy composition of Example 1 is the same as that of Comparative Examples 1 and 2 which are the secondary vulcanizates of the respective single rubbers. Compared to Comparative Example 2, the elongation change rate and the hardness change rate are in the middle of those of Comparative Example 1 and Comparative Example 2, and are excellent in heat aging resistance. The compression set is similarly excellent. Further, the oil resistant rubber alloy composition of Example 1 was HNBR.
Compared with (Comparative Example 1), the oil resistance, the fuel oil resistance, and the methanol-mixed fuel oil resistance are small and excellent in volume change. Furthermore, a mixture with an unvulcanized fluororubber compound (Comparative Example 3)
It was found that the composition was superior in heat aging resistance, oil resistance, fuel oil resistance, and methanol-mixed fuel oil resistance to the above.

The heat resistance of the oil resistant rubber alloy compositions of Examples 2 and 3 was also superior to that of Comparative Example 1, and oil resistance,
It was found that the fuel oil resistance and the methanol mixed fuel oil resistance were further improved as compared with Example 1, and the same effects as described above were exhibited.

Regarding the volume change rate showing fuel oil resistance and methanol mixed fuel oil resistance, Comparative Example 1 which is a single blend of HNBR1 and Comparative Example 2 which is a single blend of fluororubber.
The result of plotting the values of Examples 1, 2, and 3 with respect to is shown in FIG.

As is clear from FIG. 1, the fuel oil resistance and the methanol mixed fuel oil resistance of Examples 1 to 3 are H
It can be seen that it is superior to the additivity of NBR and fluororubber.

Then, in Examples 4 to 7, the fluororubber compound used was evaluated in the same manner as above, except that the preparation conditions and morphology were changed. Table 3 shows the composition and the evaluation results.

Example 4 Fluorine rubber compound FKM3- pre-secondarily vulcanized
The compounding ratio was the same as in Example 1 except that C2 was used instead of FKM3-C1.

Example 5 The same blending ratio as in Example 1 was used, except that the burr-unmilled product FKM3-C1B, which was a fluororubber compound produced by compression molding vulcanization, was used instead of FKM3-C1.

Example 6 Burrs of a fluororubber compound generated by compression molding vulcanization were mechanically crushed and sieved to 3 mm or less FKM3-C1B
Was used in place of FKM3-C1, and the blending ratio was the same as in Example 1 above.

Example 7 Burrs of a fluororubber compound produced by compression molding vulcanization were mechanically pulverized, then jet stream pulverized, and FKM3-C1B sieved to 100 μm or less was used instead of FKM3-C1. The blending ratio was the same as in Example 1.

Evaluation As shown in Table 3, the oil-resistant rubber alloy of the present invention was used for both the fluororubber compound preliminarily secondary vulcanized from Example 4 and the burr generated by compression molding vulcanization from Example 5. The composition exhibits the same excellent characteristics as described above. From Example 6 and Example 7, it was found that the burr-milled products of the fluororubber compound each had slightly improved properties.

Further, in Examples 8 to 11, the fluororubber blends were made into binary fluororubbers such that the rubber weight composition ratio of fluororubber to HNBR was 25 (%). In case of ternary fluororubber, perfluoro (methyl vinyl ether)
Evaluations were made for the case of using a ternary fluororubber containing and the case of using a pure rubber compound. Table 4 shows the composition including the comparative examples and the evaluation results.

Example 8 Binary fluororubber compound FK preliminarily subjected to primary vulcanization
The compounding ratio was the same as in Example 1 except that 44.5 parts of M1-C1 was used instead of FKM3-C1.

Example 9 FK, a ternary fluororubber compound pre-vulcanized in advance
The compounding ratio was the same as in Example 1 except that 44.5 parts of M2-C1 was used instead of FKM3-C1.

Example 10 A ternary fluororubber compound FMK4 containing perfluoro (methyl vinyl ether) which has been pre-vulcanized in advance
The mixing ratio was the same as in Example 1 except that 46.1 parts of -C1 was used instead of FKM3-C1.

Example 11 Pure rubber compound F of fluororubber pre-vulcanized in advance
The mixing ratio was the same as in Example 1 except that 35 parts of KM5-C1 was used instead of FKM3-C1.

Comparative Example 4 For comparison, an unvulcanized binary fluororubber compound FKM1
The mixing ratio was the same as in Example 8 except that -C0 was used.

Comparative Example 5 For comparison, an unvulcanized ternary fluororubber compound FKM2
The mixing ratio was the same as in Example 9 except that -C0 was used.

Evaluation In Examples 8 to 11, excellent heat aging resistance was obtained even when the fluororubbers were compounded with different binary compounds, ternary compounds, ternary compounds containing perfluoro (methyl vinyl ether) and pure rubber. , Oil resistance, fuel oil resistance and methanol mixed fuel oil resistance. Further, from the comparison between Example 8 and Comparative Example 4 and between Example 9 and Comparative Example 5, the oil resistant rubber alloy composition of the present invention exhibits the above-mentioned excellent characteristics as compared with the case where unvulcanized fluororubber is used. You can see that

Further, in Examples 12 to 14, alloy compositions of various HNBRs having different compositions and iodine values were prepared.
Evaluation was made in comparison with Comparative Examples 6 to 11 in which each HNBR alone and a mixture with unvulcanized fluororubber were used. Table 5 shows the formulations and evaluation results.

Example 12 The same blending ratio as in Example 1 was used except that HNBR2 having a small iodine value was used instead of HNBR1.

Example 13 The mixing ratio was the same as in Example 1 except that HNBR3 having a high nitrile content was used instead of HNBR1.

Example 14 Low temperature type H having low nitrile content and slightly low iodine value
The blending ratio was the same as in Example 1 except that NBR4 was used instead of HNBR1.

Comparative Example 6 For comparison, the compounding ratio was the same as in Example 12 except that the rubber was HNBR2 only.

Comparative Example 7 For comparison, unvulcanized fluororubber compound FKM3-C0
Was used in place of FKM3-C1, and the blending ratio was the same as in Example 12.

Comparative Example 8 For comparison, the compounding ratio was the same as in Example 13 except that the rubber was HNBR3 only.

Comparative Example 9 For comparison, unvulcanized fluororubber compound FKM3-C0
Was used in place of FKM3-C1 and the blending ratio was the same as in Example 13 above.

Comparative Example 10 For comparison, the compounding ratio was the same as in Example 14 except that the rubber was HNBR4 only.

Comparative Example 11 For comparison, unvulcanized fluororubber compound FKM3-C0.
Was used instead of FKM3-C1 in the same mixing ratio as in Example 14.

Evaluation From the comparison between Example 12 and Comparative Examples 6 and 7, Example 13 and Comparative Examples 8 and 9, Example 14 and Comparative Examples 10 and 11 and these and Comparative Example 1, the composition and iodine value of Different types of HNB
It was found that even when R is used, the oil resistant rubber alloy compositions of these examples exhibit the same excellent characteristics as described above.

[0071]

[Brief description of drawings]

FIG. 1 is a characteristic diagram showing a relationship between a composition ratio of FKM to HNBR and a volume change rate.

Claims (4)

[Claims] 1. A vulcanizable oil-resistant rubber alloy composition comprising a nitrile group-containing highly saturated polymer rubber and a pre-vulcanized fluororubber and / or a blend thereof. 2. The oil-resistant rubber alloy composition according to claim 1, wherein the compound of the pre-vulcanized fluororubber is burrs or mill ends generated during the primary vulcanization molding process. 3. Pre-vulcanized fluororubber is used in an amount of 10 / by weight based on the nitrile group-containing highly saturated polymer rubber.
The oil resistant rubber alloy composition according to claim 1 or 2, wherein the oil resistant rubber alloy composition is contained in a ratio of 90 to 90/10. 4. The pre-vulcanized fluororubber includes vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-perfluoro. (Methyl vinyl ether) copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-vinylidene fluoride-propylene copolymer, which is one kind or a plurality of kinds, characterized in that The oil resistant rubber alloy composition according to any one of items.