JP3261066B2 - Heat resistant rubber alloy composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vulcanizable heat-resistant rubber alloy composition, and more particularly to ethylene-α.
-Olefin copolymer rubber and / or ethylene-α-
The present invention relates to a heat-resistant rubber alloy composition having excellent heat resistance, oil resistance and abrasion resistance obtained by alloying an olefin-non-conjugated diene copolymer rubber with a pre-vulcanized fluororubber and / or a compound thereof.

[0002]

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

[0003] Further, ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-nonconjugated diene copolymer rubber have excellent balance of heat resistance, weather resistance and water resistance. Important as a material. However, ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber have inferior heat resistance and abrasion resistance to fluororubber, and have poor oil resistance to engine oil, grease and the like. Due to the scarcity, its application is restricted depending on the use site.

[0004] In recent industrial applications, especially in the field of automobiles, it has been adopted because the heat resistance of ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber is insufficient. In addition, there is a need for improved oil resistance and wear resistance. That is, ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber and fluorine rubber have intermediate heat resistance and good oil resistance and good abrasion resistance, and There is a need for a rubber material that is less expensive than fluororubber.

On the other hand, an attempt has been made to knead and blend an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-non-conjugated diene copolymer rubber with a fluororubber (see, for example, Japanese Unexamined Patent Publication No. -190241). However, kneading is difficult in processing, or the affinity of fluorine rubber for ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber is poor, so that both components are used. It was difficult to disperse sufficiently uniformly, and phase separation occurred during heat treatment for vulcanization, further reducing the degree of dispersion. Therefore, heat resistance, oil resistance and abrasion resistance are unsatisfactory in practical use, and significant cost reduction has not been achieved.

The present invention has been made in view of these points, and has an intermediate heat resistance between a fluororubber and an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-nonconjugated diene copolymer rubber. Heat-resistant rubber alloy composition having good oil resistance and good abrasion resistance is less expensive than fluororubber, and depending on the method, ethylene-α-olefin copolymer rubber and / or ethylene-
An object of the present invention is to provide a heat-resistant rubber alloy composition that can be produced at a lower cost than an α-olefin-non-conjugated diene copolymer rubber.

[0007]

Means for Solving the Problems and Embodiments of the Invention
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, ethylene-α-olefin copolymer rubber and or ethylene-α-olefin-non-conjugated diene copolymer rubber, vulcanized beforehand A vulcanizable heat-resistant rubber alloy composition containing a fluororubber and / or a compound thereof is a fluororubber and an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-
Non-conjugated diene copolymer rubber has intermediate heat resistance and good oil resistance and good abrasion resistance, and is less expensive than fluororubber. Depending on the method, ethylene-α-olefin copolymer rubber and / or ethylene The present inventors have found that they can be provided at lower cost than -α-olefin-non-conjugated diene copolymer rubber, and have completed the present invention.

That is, the heat-resistant rubber alloy composition of the present invention comprises a pre-vulcanized fluororubber and / or a blend thereof prepared by mixing an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-nonconjugated diene copolymer. It is characterized in that it can be vulcanized by being incorporated into a united rubber.

More specifically, the vulcanizable heat-resistant rubber alloy composition of the present invention comprises a preliminarily vulcanized fluororubber and / or a compound thereof, which is obtained by mixing ethylene-α-olefin copolymer rubber and / or ethylene-α- The olefin-non-conjugated diene copolymer rubber is uniformly dispersed in the vulcanizate, and the vulcanized product is prevented from undergoing phase separation during heat treatment for vulcanization, and is further provided with an ethylene-α-olefin copolymer rubber and / or With the vulcanization of the ethylene-α-olefin-non-conjugated diene copolymer rubber itself, the fluorine rubber and the ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin- Since the non-conjugated diene copolymer rubber is considered to be co-crosslinked, the vulcanizate of the heat-resistant rubber alloy composition of the present invention has the excellent chemistry described above. It has a characteristic that has a physical characteristic.

In addition, the so-called industrial waste such as vulcanized burrs generated by compression molding and vulcanized offcuts generated by injection molding, transfer molding and extrusion molding are added to the pre-vulcanized fluoro rubber compound. Since a product can be used, resources are reused, and it can be provided as an extremely inexpensive material.

In the present invention, the pre-vulcanized fluororubber and / or the compound thereof may be obtained by vulcanizing the fluororubber and / or the compound using 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. In addition, the fluororubber referred to here is a compound obtained by compounding only a vulcanizing agent and vulcanizing fluororubber, which is generally referred to as pure rubber compounding, or only a vulcanizing agent and a vulcanizing aid. And vulcanized. As the vulcanizing agent, a polyol vulcanizing system, an amine vulcanizing system, a peroxide vulcanizing system, a sulfur vulcanizing system, etc. which are generally used for vulcanizing fluororubber can be used. Further, the composition of the pre-vulcanized fluoro rubber compound 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, and the like. Furthermore, fluororubber is generally formed by primary vulcanization and then secondary vulcanization to complete vulcanization.

In the present invention, the pre-vulcanized fluororubber and / or its compound may be those after primary vulcanization or those after secondary vulcanization, but those after primary vulcanization are preferred.

As the fluororubber compound in the present invention, it is particularly desirable to use burrs or scraps generated when a rubber product is formed and processed by primary vulcanization from the viewpoint of resource recycling 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 of the pre-vulcanized fluororubber and / or its blend in the present invention is carried out at 100 to 300 ° C. for 30 minutes to 48 hours, preferably at 150 to 250 ° C. for 2 to 24 hours. Should be within the range.
If the vulcanization time is too short, the degree of crosslinking is insufficient,
If the time is longer than 4 hours, not only is it not economical, but also the fluoro rubber deteriorates depending on the temperature conditions.

In the present invention, the mixing ratio of the pre-vulcanized fluororubber and / or its blend with the ethylene-α-olefin copolymer rubber and / or the ethylene-α-olefin-nonconjugated diene copolymer rubber is particularly Although not limited, from the characteristics of the vulcanized heat-resistant rubber alloy composition, desirably, the fluororubber contained in the prevulcanized fluororubber and / or the compound thereof is converted into an ethylene-α-olefin copolymer rubber and / or ethylene. It is in the range of about 10% by weight to 90% by weight based on the rubber content of the -α-olefin-non-conjugated diene copolymer rubber. When the fluorine rubber content is 10% by weight or less, heat resistance,
If the effect of improving oil resistance and wear resistance is small, and if the content is 90% by weight or more, there is a tendency that processing is difficult, physical properties such as tensile strength are reduced, and practical restrictions are generated.

The form of mixing the pre-vulcanized fluororubber and / or its blend with the ethylene-α-olefin copolymer rubber and / or the ethylene-α-olefin-nonconjugated diene copolymer rubber in the present invention is as follows. ,
There is no particular limitation. However, ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-
For smooth mixing and homogenization with the non-conjugated diene copolymer rubber, powder having an average particle diameter of 5 mm or less is more desirable.

In the present invention, the pre-vulcanized fluoro rubber and / or the fluoro rubber used for the compound thereof are:
It is a copolymer of a fluorine-containing monomer having 2 to 8 carbon atoms, specifically, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, tetrafluoroethylene, chlorofluoroethylene, and carbon atoms of an alkyl group. Having at least one compound selected from the group consisting of perfluoro (alkyl vinyl ether) having 1 to 5 as an essential component and at least one of tetrafluoroethylene and vinylidene fluoride and another olefin copolymerizable therewith. The copolymer may be a copolymer obtained by copolymerizing an active halogen group-containing monomer or an epoxy group-containing monomer which becomes a cross-linking point, if necessary.

Among these fluororubbers, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-vinylidene Particularly preferred are a fluoride-propylene copolymer and a vinylidene fluoride-tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer.
In general, commercially available fluorine rubber can be used. Mooney viscosity (ML1 + 4, 1
(00 ° C.) is preferably 20 to 150.

The ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-
As the α-olefin in the non-conjugated diene copolymer rubber, for example, propylene, 1-butene, 1-pentene,
Examples thereof include 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and among them, propylene is preferred. Examples of the non-conjugated diene include 1,4-hexadiene, 1,6-octadiene,
Methyl-1,5-hexadiene, 6-methyl-1,5-
Chain non-conjugated dienes such as heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-
Methylene-2-norbornene, 5-isopropylidene-
Cyclic non-conjugated dienes such as 2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene;
-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norobornene, 2-
Propenyl-2,2-noborobornadiene, 1,3,7-
Trienes such as octatriene and 1,4,9-decatriene are exemplified, and among them, 1,4-hexadiene, dicyclopentadiene and 5-ethylidene-2 are preferable.
-Norbornene.

The molecular weight of the ethylene-α-olefin copolymer rubber and / or the ethylene-α-olefin-nonconjugated diene copolymer rubber is at least ethylene-α-olefin-non-conjugated diene copolymer rubber.
α-olefin copolymer rubber and / or ethylene-α
-The olefin-non-conjugated diene copolymer rubber itself needs to be larger than the size capable of self-vulcanization. On the other hand, the extremely high molecular weight is likely to impair the compatibility with the pre-vulcanized fluororubber and / or its compound, so that the number average molecular weight is desirably 3,000 to 500,000. More preferably, the Mooney viscosity (ML1 + 4, 100 ° C.) is 1
It is good to use the thing of 0-150. These are generally
Commercially available EPM and EPDM can be used.

The heat-resistant rubber alloy composition of the present invention is generally used for vulcanizing an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-non-conjugated diene copolymer rubber. A vulcanizing agent can be used, but a vulcanizing agent capable of co-vulcanizing an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-non-conjugated diene copolymer rubber and a fluororubber is used. By using it, 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, organic peroxides commonly used in the rubber and plastic industries can be used, and are not particularly limited. Specifically, dicumyl peroxide, di-t-butyl peroxide, t
-Butylcumyl 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-2,5-di (benzoylperoxy) hexane, 1,3-di (t-butylperoxyisopropyl) benzene, and the like. The use amount of these organic peroxides is not particularly limited in the present invention, but is usually in the range of 0.5 to 15 parts by weight per 100 parts by weight of the heat-resistant rubber alloy composition.

The crosslinking assistant may be one used in ordinary organic peroxide vulcanization, such as triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, ethylene dimethacrylate,
Polyfunctional monomers such as magnesium dimethacrylate, divinylbenzene, diallyl phthalate, toluylene bismaleimide, and metaphenylene bismaleimide; oxime compounds such as liquid polybutadiene, p-quinone dioxime, and p, p'-dibenzoylquinone dioxime; Is mentioned. The amount of these crosslinking aids to be used is generally 0.1 to 15 parts by weight, preferably 1 to 8 parts by weight, per 100 parts by weight of the heat-resistant rubber alloy composition.

The method for preparing the heat-resistant rubber alloy composition of the present invention is not particularly limited.
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 heat-resistant rubber alloy composition of the present invention may further comprise a reinforcing filler, a bulking filler, an antioxidant, a vulcanization stabilizer, Processing aids, coupling agents, compatibilizers, plasticizers, pigments and the like may be blended.

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

[0028]

The vulcanizate obtained by vulcanizing the heat-resistant rubber alloy composition of the present invention is obtained by copolymerizing a fluororubber with an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-non-conjugated diene. It has intermediate heat resistance and good oil resistance as well as good abrasion resistance with polymer rubber. Further, it can be produced at a lower cost than fluororubber and, depending on the method, at lower cost than ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin-non-conjugated diene copolymer rubber. Therefore, heat resistance, oil resistance, and wear resistance of packings, gaskets, oil seals, O-rings, valves, diaphragms, tubes, hoses, belts, rolls, roll blades, anti-vibration rubber, coating materials, coating materials, etc. are required. Can be widely used for various applications.

[0029]

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, parts are parts by weight.
The physical properties of the vulcanized rubber were evaluated according to JIS K6301. Heat resistance is measured by heating the vulcanizate in a gear oven at 150 ° C for 16
It was evaluated by measuring the rate of change of each property value after heat aging for 8 hours. The compression set resistance was measured by measuring the compression set rate of a sample at 150 ° C. for 168 hours after vulcanized rubber was compressed by 25%. The swelling volume change rate showing oil resistance was determined by measuring the change rate after immersing the vulcanized rubber in JIS # 3 oil at 150 ° C. for 70 hours. TR10 showing cold resistance was measured according to the TR test method of ASTM D1329. Abrasion resistance was evaluated according to the Williams abrasion test method described in Rubber Test Method, edited by The Rubber Association of Japan.

The heat-resistant rubber alloy composition in this example was obtained as follows. That is, according to the composition shown in Table 1, the respective components were uniformly mixed with two rolls to prepare fluororubber compounds FKM1 to FKM5 and FKM6.

Next, according to the composition shown in Table 2 and the vulcanization conditions shown in the footnote, primary vulcanization (press vulcanization) is performed, followed by secondary vulcanization to obtain a vulcanized heat-resistant rubber alloy composition. Was. The vulcanization conditions for the vulcanized oil-resistant rubber alloy composition are the same from Table 3 to Table 6 below.

Example 1 Propylene-containing tertiary fluororubber composition as a fluororubber composition previously primary vulcanized with 100 parts of EPDM1 as an ethylene-α-olefin-non-conjugated diene copolymer rubber 57 copies of FKM4-C1 (EP
The mixing ratio of the rubber component of the fluororubber compound to the rubber component of DM is 30% by weight), 1 part of stearic acid, 5 parts of zinc oxide, 70 parts of SRF carbon, and 1 part of a cross-linking aid, triallyl isocyanurate. And 2 parts of Perhexa 25B which is an organic peroxide as a vulcanizing agent.

Example 2 130 parts of a propylene-containing ternary fluororubber compound FKM4-C1 as a preliminarily vulcanized fluororubber compound (the mixing ratio of the fluororubber compound to EPDM was 50% by weight) and crosslinked. Example 1 except that 1.5 parts of triallyl isocyanurate as an auxiliary agent and 3 parts of Perhexa 25B as an organic peroxide as a vulcanizing agent were used.
The same mixing ratio was used.

Example 3 310 parts of a propylene-containing ternary fluororubber compound FKM4-C1 as a preliminarily vulcanized fluororubber compound (the mixing ratio of the fluororubber compound to EPDM was 70% by weight) was crosslinked. The same mixing ratio as in Example 1 was used except that 2 parts of triallyl isocyanurate as an auxiliary agent and 4 parts of Perhexa 25B as an organic peroxide as a vulcanizing agent were used.

Comparative Example 1 For comparison, the same compounding ratio as in Example 1 was used except that only rubber was EPDM1. That is, ethylene-α-
An olefin-nonconjugated diene copolymer rubber compounding.

COMPARATIVE EXAMPLE 2 For comparison, an unvulcanized fluororubber compound FKM4 was used for comparison.
-C0 was only 130 parts. That is, it is a blend of a fluorine rubber compound. Comparative Example 3 For comparison, an unvulcanized fluorine rubber compound FKM4-C0
Was used in place of FKM4-C1, except that FKM4-C1 was blended. That is, the unvulcanized ethylene-α-olefin-nonconjugated diene copolymer rubber is mixed with the unvulcanized fluoro rubber compound.

Evaluation Evaluation of normal physical properties, heat resistance, compression set resistance, oil resistance, cold resistance, and abrasion resistance of the secondary vulcanizates of Examples 1 to 3 and Comparative Examples 1 to 3. The results are shown in Table 2 together with the formulation and vulcanization conditions.

As shown in Table 2, the rate of change in tensile strength and the rate of change in elongation indicating the heat resistance of the heat-resistant rubber alloy composition of Example 1 were as follows: ethylene-α-olefin-non-conjugated diene copolymer rubber Is smaller than that of Comparative Example 1 which is a secondary vulcanizate of Comparative Example 1, and the hardness change rate is intermediate between Comparative Examples 1 and 2, and is excellent in heat resistance. Further, the heat-resistant rubber-rubber alloy composition of Example 1 has a smaller volume change rate in oil resistance than Comparative Example 1 which is a secondary vulcanized product of an ethylene-α-olefin-non-conjugated diene copolymer rubber, and is excellent. ,Also,
The wear resistance is small and the wear resistance is excellent. Furthermore, it turned out that it is excellent in heat resistance, oil resistance, and abrasion resistance compared with the mixture with the unvulcanized fluororubber compound (Comparative Example 3).

The heat resistance, oil resistance and abrasion resistance of the heat resistant rubber alloy compositions of Examples 2 and 3 were also superior to Comparative Example 1, and were further improved from Example 1 to obtain the same effects as described above. It turned out to work.

Next, in Examples 4 to 7, evaluation was made in the same manner as described above, except that the preparation conditions and form of the vulcanized fluororubber compound used for the heat-resistant rubber alloy composition were changed. Table 3 shows the composition and the evaluation results.

Example 4 A pre-vulcanized fluoro rubber compound FKM4-
Except that C2 was used instead of FKM4-C1, the blending ratio was the same as in Example 2 above.

Example 5 The same blending ratio as in Example 2 was used except that FKM4-C1B, a non-burr product of a fluororubber compound produced by compression molding vulcanization, was used instead of FKM4-C1.

Example 6 FKM4-C1B obtained by mechanically pulverizing burrs of a fluororubber compound produced by compression molding vulcanization and sieving to 3 mm or less.
Was used in the same manner as in Example 2 except that was used instead of FKM4-C1.

Example 7 After the burrs of the fluororubber compound produced by compression molding vulcanization were mechanically pulverized, jet stream pulverized and sieved to 100 μm or less, FKM4-C1B was used in place of FKM4-C1. The same mixing ratio as in Example 2 was used.

Evaluation As shown in Table 3, the heat-resistant rubber alloy of the present invention can be used regardless of the fluororubber composition preliminarily vulcanized from Example 4 or the burr generated by compression vulcanization from Example 5. The composition was found to exhibit the same excellent characteristics as described above. Further, from Examples 6 and 7, it was found that each of the pulverized burrs of the fluororubber compound had slightly improved properties.

Further, in Examples 8 to 13, the fluororubber and / or the fluororubber compound was obtained by pre-vulcanizing the fluororubber and / or the rubber component of the ethylene-α-olefin-nonconjugated diene copolymer rubber. The mixing ratio of the rubber component of the fluororubber compound is 50% by weight
When the fluororubber compound is a binary fluororubber, when it is a ternary fluororubber, when it is a propylene-containing binary fluororubber, it contains perfluoro (methyl vinyl ether). In the case of raw fluorine rubber, in the case of pure rubber compounded fluorine rubber, and
The evaluation was made for a mixture of a propylene-containing ternary fluororubber compound and a pure rubber compounded fluororubber. Table 4 shows the composition including the comparative examples and the evaluation results.

Example 8 2 as pre-vulcanized fluororubber compound
The same blending ratio as in Example 2 was used, except that 133.6 parts of the original fluororubber compound FKM1-C1 was used instead of FKM4-C1.

Example 9 3 as a pre-vulcanized fluororubber compound
The same compounding ratio as in Example 2 was used, except that 133.6 parts of the original fluororubber compound FKM2-C1 was used instead of FKM4-C1.

Example 10 A propylene-containing binary fluororubber composition FKM3-C1 as a pre-vulcanized fluororubber composition was used in place of FKM4-C1 in the amount of 130 parts.
The same blending ratio as in Example 2 of the previous term was used.

Example 11 138.2 parts of a tertiary fluororubber compound FMK5-C1 containing perfluoro (methyl vinyl ether) as a prevulcanized fluororubber compound was added to F
Except that KM4-C1 was used instead of KM4-C1, the same blending ratio as in Example 2 was used.

Example 12 105 parts of a pure rubber compound FKM6-C1 of a preliminarily vulcanized fluororubber as a fluororubber was added to FKM
The same blending ratio as in Example 2 was used except that 4-C1 was used instead of 4-C1.

Example 13 As a mixture of a pre-vulcanized fluoro rubber and a pre-primarily vulcanized fluoro rubber compound, a propylene-containing ternary fluoro rubber compound as a pre-vulcanized fluoro rubber compound was prepared. FKM4-C1 was replaced by 65 parts of the product FKM4-C1 and 52.5 parts of the pure rubber compound FKM6-C1 of a preliminarily vulcanized fluororubber as a fluororubber were used in place of the FKM4-C1. The blending ratio was the same as in Example 2.

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

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

Evaluation As shown in Table 4, in Examples 8 to 13, the fluororubber contained a binary system, a ternary system, a propylene-containing binary system and a perfluoro (methyl vinyl ether) having different compositions. It has been found that excellent heat resistance, oil resistance and abrasion resistance are exhibited even when a ternary system, a pure rubber compound and a mixture of a fluorine rubber and a fluorine rubber compound are used. Further, from the comparison between Example 8 and Comparative Example 4 and between Example 9 and Comparative Example 5, the heat-resistant rubber alloy composition of the present invention exhibits the above-mentioned excellent characteristics as compared with the case where unvulcanized fluoro rubber is used. You can see that it is doing.

Further, in Examples 14 to 17, the heat-resistant rubber alloy compositions in which various ethylene-α-olefin-nonconjugated diene copolymer rubbers having different compositions and iodine values were used, Evaluation was made in comparison with Comparative Examples 6 to 13 using α-olefin-non-conjugated diene copolymer rubber alone and a mixture with an unvulcanized fluororubber compound. Table 5 shows the formulations and evaluation results.

Example 14 EP having the same propylene content and a high iodine value as an ethylene-α-olefin-nonconjugated diene copolymer rubber
Except that DM2 was used in place of EPDM1, the same blending ratio as in Example 2 was used.

Example 15 EPD having the same tertiary component and a low propylene content as an ethylene-α-olefin-non-conjugated diene copolymer rubber
Except that M3 was used in place of EPDM1, the same blending ratio as in Example 2 was used.

Example 16 The same blending ratio as in Example 2 was used except that EPDM4 having a different third component as the ethylene-α-olefin-nonconjugated diene copolymer rubber was used instead of EPDM1.

Example 17 The same blending ratio as in Example 2 was used except that EPDM5 having a different third component as the ethylene-α-olefin-nonconjugated diene copolymer rubber was used instead of EPDM1.

Comparative Example 6 For comparison, the blending ratio was the same as in Example 14 except that the ethylene-α-olefin-non-conjugated diene copolymer rubber was EPDM2 only.

Comparative Example 7 For comparison, an unvulcanized fluoro rubber compound FKM4-C0
Was used in the same manner as in Example 14 except that was used instead of FKM4-C1.

Comparative Example 8 For comparison, the blending ratio was the same as in Example 15 except that the ethylene-α-olefin-non-conjugated diene copolymer rubber was EPDM3 only.

Comparative Example 9 For comparison, an unvulcanized fluoro rubber compound FKM4-C0
Was used in the same manner as in Example 15 except that was used instead of FKM4-C1.

Comparative Example 10 For comparison, the blending ratio was the same as in Example 16 except that the ethylene-α-olefin-non-conjugated diene copolymer rubber was EPDM4 only.

Comparative Example 11 For comparison, an unvulcanized fluoro rubber compound FKM4-C0
Was used in place of FKM4-C1, except that FKM4-C1 was used.

Comparative Example 12 For comparison, the blending ratio was the same as in Example 17 except that the ethylene-α-olefin-non-conjugated diene copolymer rubber was EPDM5 only.

Comparative Example 13 For comparison, an unvulcanized fluoro rubber compound FKM4-C0
Was used in the same manner as in Example 17 except that was used instead of FKM4-C1.

Evaluation As shown in Table 5, Example 14 and Comparative Examples 6 and 7 and Example 15 and Comparative Examples 8 and 9 and Example 1 were performed.
6 and Comparative Examples 10 and 11, and Example 17 and Comparative Examples 12 and 13 showed that various ethylene-α-olefin-non-conjugated diene copolymers having different iodine values, propylene contents, and third components. It was found that even when rubber was used, the heat-resistant rubber alloy compositions of these examples exhibited the same excellent characteristics as described above.

Further, a heat-resistant rubber alloy composition in which a fluorine rubber and / or a fluorine rubber compound preliminarily vulcanized in Examples 18 to 20 were added to an ethylene-α-olefin copolymer rubber was evaluated. The fluororubber and / or fluororubber blend previously vulcanized in Examples 21 to 23 are contained in an ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-nonconjugated diene copolymer rubber. The heat resistant rubber alloy composition was evaluated.

Example 18 EPM as an ethylene-α-olefin copolymer rubber
Example 2 except that EPDM1 was used in place of EPDM1.
The same mixing ratio was used.

Example 19 FKM6 as Fluororubber Preliminarily Vulcanized
Except that -C1 was used instead of FKM4-C1, the blending ratio was the same as in Example 18 above.

Example 20 F as a pre-vulcanized fluororubber compound
The blending ratio was the same as in Example 18 except that a mixture of KM4-C1 and FKM6-C1 as a preliminarily vulcanized fluorine rubber was used instead of FKM4-C1.

Example 21 The procedure of Example 21 was repeated except that a mixture of EPDM1 as an ethylene-α-olefin-nonconjugated diene copolymer rubber and EPM6 as an ethylene-α-olefin copolymer rubber was used instead of EPDM1. The blending ratio was the same as in Example 2.

Example 22 FKM6 as a fluorinated rubber preliminarily vulcanized
Except that -C1 was used instead of FKM4-C1, the same blending ratio as in Example 21 was used.

Example 23 FKM6 as Fluororubber Preliminarily Vulcanized
The same blending ratio as in Example 21 was used, except that a mixture of -C1 and FKM4-C1 as a preliminarily vulcanized fluororubber compound was used instead of FKM4-C1.

Comparative Example 14 For comparison, the same compounding ratio as in Example 18 was used except that only the rubber was EPM6. That is, ethylene-α-
This is a blend of olefin copolymer (EPM) rubber alone.

Comparative Example 15 For comparison, the blending ratio was the same as in Example 21 except that the rubber was a mixture of EPDM1 and EPM6 only. That is, it is a mixture of an ethylene-α-olefin-non-conjugated diene copolymer rubber and an ethylene-α-olefin copolymer rubber.

Comparative Example 16 For comparison, FKM as an unvulcanized fluoro rubber compound
Except that 4-C0 was used instead of FKM4-C1, the blending ratio was the same as in Example 18 above.

Evaluation As shown in Table 6, as shown in the comparison between Example 18 and Comparative Example 16 and the comparison between Example 18 to Example 20 and Comparative Example 14, ethylene-α-olefin copolymer rubber was used. In the case where is used, even when using Examples 21 to 23 and Comparative Example 1
Even when a mixture of an ethylene-α-olefin copolymer rubber and an ethylene-α-olefin-non-conjugated diene copolymer rubber is used as shown in the comparison with Comparative Example 5, the heat-resistant rubber alloy compositions of these Examples It turned out to exhibit the same excellent characteristics as.

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(56) References JP-A-1-135585 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/16 C08L 27/12-27/20

Claims (3)

(57) [Claims] 1. An ethylene-α-olefin copolymer rubber and / or an ethylene-α-olefin-non-conjugated diene copolymer rubber containing a pre-vulcanized fluororubber and / or a blend thereof. A heat-resistant rubber alloy composition characterized in that it is possible. 2. The heat-resistant rubber alloy composition according to claim 1, wherein the pre-vulcanized fluororubber compound is burrs or scraps generated during primary vulcanization molding. 3. The pre-vulcanized fluororubber and / or the fluororubber used in the compound thereof is a vinylidene fluoride-hexafluoropropylene copolymer,
Vinylidene fluoride-hexafluoropropylene-
Tetrafluoroethylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-
3. One or more of vinylidene fluoride-propylene copolymer and vinylidene fluoride-tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer.
3. The heat-resistant rubber alloy composition according to item 1.