JPH0819265B2 - Method for manufacturing fluororubber crosslinked products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is mainly composed of nitrile rubber and / or chloroprene rubber and fluororubber, and has heat resistance, oil resistance, compression set resistance, and compression set resistance. The present invention relates to a method for producing a fluororubber product obtained by crosslinking a fluororubber composition capable of providing a vulcanized product having excellent compressive load properties.

[Prior Art] In recent years, the demands on the performance of rubber materials have become stricter year by year, and the types of rubber materials used have changed. Among rubbers, fluororubber has outstanding performance compared with other special rubbers in solvent resistance, heat resistance, chemical resistance, and weather resistance, and its demand in the field of industrial products, automobiles and aircrafts. Is increasing year by year.

However, the price is extremely high compared to elastomers other than fluororubber, and the specific gravity is high, so that the product price is significantly increased.

In this way, it can be said that it has become difficult to deal with one kind of rubber material in order to simultaneously satisfy the contradictory requirements of high performance and low price.

In response to such demands, a method has been proposed in which an elastomer other than fluororubber is mixed with fluororubber. For example, as shown in JP-A-52-60839, JP-A-55-160037 and JP-A-60-101135, the co-vulcanizability of fluororubber and diene rubber is improved. Japanese Patent Application Laid-Open No. 57-135843 discloses an acrylonitrile-butadiene rubber having a specific nitrile content for improving the compatibility with fluororubber.

However, sufficient mechanical strength and heat resistance can be obtained only by improving the co-vulcanizability of the above-mentioned fluororubber and diene rubber, or by improving the compatibility with fluororubber by limiting the type of acrylonitrile-butadiene rubber. It's hard to say that you can be.

As an example of using hydrogenated acrylonitrile-butadiene rubber instead of ordinary acrylonitrile-butadiene rubber as a means for improving heat resistance, JP-A-60-141737 and JP-A-61-62538 disclose. Although it has been proposed, it must be said that the degree of improvement in heat resistance is still insufficient.

[Problems to be solved by the invention]

The present invention has been made against the background of the above-mentioned conventional technical problems, and significantly improves the compatibility between nitrile rubber and / or chloroprene rubber and fluororubber, and heat resistance,
An object is to provide a fluororubber composition having excellent oil resistance, compression set resistance and compression load resistance.

[Means for solving problems]

The present invention comprises 5 to 70 parts by weight of a nitrile rubber and / or chloroprene rubber (I) (hereinafter simply referred to as “diene rubber (I)), 95 to 30 parts by weight of a fluororubber (II), and a diene rubber. Provided is a method for producing a fluororubber crosslinked product, which comprises blending a crosslinking agent for rubber (I) and reacting the resulting mixture while applying shear deformation to the fluororubber composition (II) for crosslinking. It is a thing.

Examples of the nitrile rubber that constitutes one of the diene rubbers (I) in the present invention include (a) at least one aliphatic conjugated diene such as 1,3-butadiene and 2-methyl-1,3-butadiene. 15-70% by weight, (b) acrylonitrile 10-50% by weight, acrylic acid ester and / or methacrylic acid ester 0-75% by weight (however,
(A) + (b) + (c) = 100% by weight).

Here, as the (meth) acrylic acid ester, for example, methyl acrylate, ethyl acrylate, acrylic acid n
-Propyl, isopropyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, Octyl methacrylate, n-nonyl acrylate, isononyl acrylate, n-nonyl methacrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, dodecyl methacrylate,
Examples include n-amyl acrylate, isoamyl acrylate, methyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate. be able to.

Further, the nitrile rubber (I) is obtained by copolymerizing a small amount of an unsaturated carboxylic acid compound such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or allyl glycidyl ether, or a part or all of the aliphatic conjugated diene. May be hydrogenated.

Examples of the chloroprene rubber constituting the other of the diene rubber (I) include 2-chloro-1,3-butadiene homopolymer, 2-chloro-1,3-butadiene, the acrylonitrile, and acryl. Mention may be made of copolymers with acid esters and / or methacrylic acid esters.

Further, this chloroprene rubber is a copolymer of a small amount of an unsaturated carboxylic acid compound such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, allyl glycidyl ether, etc., as well as the above-mentioned chloroprene rubber. It may be modified and / or mercaptan modified.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of these nitrile rubbers or chloroprene rubbers is not particularly limited, but 20 to 150 is preferably used.

The above nitrile rubber and chloroprene rubber constituting the diene rubber (I) can be used alone or in combination of two or more.

Next, the fluororubber (II) in the present invention includes the following combinations of fluorine-containing monomers.

Examples of the fluorinated monomer include vinylidene fluoride, hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), and perfluoro (propylvinylidene). Use, further, as a monomer copolymerizable therewith, a rubber obtained by copolymerizing a vinyl compound such as an acrylate ester, an olefin compound such as propylene or a diene compound, a halogen-containing vinyl compound containing chlorine, bromine, or iodine. Can be.

Specific examples of the fluororubber (II) include vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-
Hexafluoropropylene-tetrafluoroethylene terpolymer,
Examples include ethylene tetrafluoride-propylene copolymer, ethylene tetrafluoride, and vinylidene fluoride-propylene terpolymer.

These fluororubbers (II) include a type (II-a) which is crosslinkable with a combination of an organic peroxide and a crosslinking aid, and a type (II-b) which is not crosslinked with an organic peroxide and is crosslinked with a polyol or an amine. ) Can be divided into.

Specific examples of fluororubber (II-a) include Afras series (manufactured by Japan Synthetic Rubber Co., Ltd.), Viton GF (manufactured by DuPont, USA), and DAIEL G902 (manufactured by Daikin Industries, Ltd.). Examples of the fluororubber (II-b) include Viton A, B, E60C (manufactured by DuPont, USA) and Technoflon (manufactured by Monte Edison, Italy).

The Mooney viscosity of fluororubber (II) (ML _{1 + 4} , 100
C) is not particularly limited, but a temperature of 30 to 150 is preferably used.

The weight ratio of the diene rubber (I) to the fluororubber (II) in the rubber composition of the present invention is 5 to 50% by weight of the diene rubber (I).
70 parts by weight, preferably 10 to 50 parts by weight, fluororubber (II)
95 to 30 parts by weight, preferably 90 to 50 parts by weight [wherein diene rubber (I) + fluororubber (II) = 100 parts by weight], and when the fluororubber (II) is less than 30 parts by weight, fluororubber The heat resistance, which is the characteristic of No. 1, becomes significantly inferior, and the compound is powdered. On the other hand, when it exceeds 95 parts by weight, the compressive load resistance is inferior.

Next, in the present invention, as the cross-linking agent for the diene rubber (I) mixed with the diene rubber (I) and the fluororubber (II), for example, an organic peroxide, a sulfur vulcanizing agent, a resin Examples thereof include a vulcanizing agent and a quinoid vulcanizing agent.

A diene rubber (I) in the rubber composition of the present invention;
Examples of combinations of the fluororubbers (II-a) and (II-b) and the diene rubber (I) include the following.

Diene rubber (I) / fluorine rubber (II-a) / organic peroxide, diene rubber (I) / fluorine rubber (II-b) / organic peroxide, diene rubber (I) / fluorine rubber ( II-a) / fluorine rubber (II-b) / organic peroxide, diene rubber (I) / fluorine rubber (II-a) / sulfur vulcanizing agent diene rubber (I) / fluorine rubber (II- b) / Sulfur-based vulcanizing agent Diene-based rubber (I) / Fluorine rubber (II-a) / Quinoid-based vulcanizing agent Diene-based rubber (I) / Fluorine rubber (II-b) / Resin vulcanizing agent Combination of these Among them, diene rubber (I) / fluorine rubber (II-a) / organic peroxide is preferable, and diene rubber (I) / fluorine rubber (II-a) / fluorine rubber (II-b) / organic peroxide is preferable. Oxides.

In the case of the above combination, fluororubber (II-
a) is 5% by weight based on 100% by weight of the total of fluororubber
The above is necessary. In the case of this combination, a crosslinking assistant may be added as necessary.

Examples of the organic peroxide as a cross-linking agent for fluororubber (II-a) include 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, dicumyl peroxide, di-t-butylperoxide, t-butylbenzoate, 1 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, etc., preferably 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α,
α′-bis (t-butylperoxy) -p-diisopropylbenzene.

These organic peroxides can be used alone or in combination of two or more.

The amount of the organic peroxide which is a cross-linking agent for the diene rubber (I) is preferably 0.01 to 5 parts by weight, and more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the diene rubber (I) and the fluororubber (II). The amount is preferably 0.05 to 2 parts by weight, and if it is less than 0.01 parts by weight, the crosslinking of the diene rubber (I) is not sufficient, and the processability of the rubber composition, the compression set of the vulcanizate, the compression load resistance, etc. On the other hand, if it exceeds 5 parts by weight, the processability tends to be deteriorated, and the vulcanized physical properties such as mechanical strength and elongation of the resulting composition are deteriorated.

As a crosslinking aid, a wide range of reactive monomers such as allyl compounds, methacrylates and divinyl compounds, and reactive unsaturated compounds such as functional polymers such as polybutadiene, as well as oxime compounds and sulfur compounds can be used. However, a reactive unsaturated compound is preferable from the viewpoints of cross-linking property or kneading property at the time of compounding, and particularly, a polyallyl compound and a 1,2- A polyfunctional compound such as polybutadiene can be preferably employed.

As the polyallyl compound that can be suitably employed in the present invention, various compounds having two or more allyl groups (—CH ₂ CH ＝ CH ₂ ) can be exemplified.

For example, polyallyl-substituted alkyl or aromatic amines such as diallyl ether of glycerin, diallylamine, and triallylamine, polyallyl-substituted phosphoric acid or phosphorous acid represented by triallyl phosphoric acid, diallyl succinate, diallyl adipate, etc. , Polyallyl substitution products of carvone such as diallyl phthalate, diallyl melamine, triallyl cyanurate, triallyl isocyanurate and the like. These can be used alone or in combination of two or more. Specific preferred examples include triallyl cyanurate (162 ° C / 2mmHg) having a boiling point of 30 ° C or higher under a reduced pressure of 2mmHg, triallyl phosphate (1
57 ° C./44 mmHg) triallyl isocyanurate, diallyl phthalate (161 ° C./4 mmHg), diallyl melamine and the like.

The amount of the crosslinking aid added is 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the diene rubber (I) and the fluororubber (II).

In the present invention, as a method for adding a cross-linking agent to the diene rubber (I) and the fluororubber (II), the diene rubber (I), the fluororubber (II) and the cross-linking agent are simultaneously added and kneaded. Alternatively, the diene rubber (I) and the fluororubber (II) may be mixed in advance and then the crosslinking agent may be added.

Mixing is carried out with various extruders, Banbury mixers, kneaders, rolls, etc. at a temperature of 50 to 250 ° C., preferably 100 to 2
00 ° C., time; 2 minutes to 1 hour, preferably 3 minutes to 45 minutes, and a preferable kneading method is to use an internal mixer such as a Banbury mixer or a kneader. .

At this time, if the kneading temperature is less than 50 ° C and crosslinking occurs, it is difficult to control the reaction, while if it exceeds 250 ° C, the rubber tends to deteriorate.

If the kneading time is shorter than 2 minutes, it is difficult to control the reaction, and it is difficult to obtain a uniform composition. On the other hand, if the kneading time exceeds 1 hour, the kneading cost increases, which is not preferable.

The kneading temperature at the time of adding the crosslinking agent is usually 10
˜200 ° C., preferably 20˜150 ° C., and in the case of organic peroxide, it is suitable that its half-life is 1 minute or less.

As described above, the crosslinking in the present invention must be performed during mixing.

That is, during mixing, a shearing force is applied to the elastomer, so that the dispersed particles of the diene rubber (I) or the fluororubber (II) are kept in a smaller state, and the entanglement of molecules at the interface is better. This is because many have occurred.

In this case, when the application of the shearing force is stopped, the disperse particles of the diene rubber (I) or the fluororubber (II) are associated with each other to increase the particle size and reduce the entanglement of molecules.

Thus, by crosslinking the diene rubber (I) simultaneously with mixing, the system can be fixed in a good dispersed state.

The rubber composition of the present invention contains a diene rubber (I) and a fluororubber (II) as main components, but in addition to this, a styrene-butadiene rubber (SBR) other than the rubber component,
Other diene rubbers such as isoprene rubber (IR);
Ethylene-α-olefin- (diene) rubber [EP
(D) M], a butyl rubber, an acrylic rubber, a normal rubber such as a saturated rubber such as chlorosulfonated polyethylene, and the like can be added in an amount of about 10% by weight or less, and various commonly used compounding agents can be added.

These compounding agents may be added in the process of producing the rubber composition of the present invention as needed, or may be added after the production of the composition.

That is, as the reinforcing filler and extender, for example, carbon black, fumed silica, wet silica, quartz fine powder, diatomaceous earth, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, dioxide. Examples thereof include titanium, talc, mica powder, aluminum sulfate, calcium sulfate, barium sulfate, asbestos, glass fiber, organic reinforcing agent, and organic filler.

Dispersion aids include higher fatty acids and metal amine salts thereof; plasticizers such as phthalic acid derivatives and adipic acid derivatives; softeners such as lubricating oil, process oil, coal tar, castor oil, calcium stearate; aging Examples of the inhibitor include phenylenediamines, phosphates, quinolines, cresols, phenols, dithiocarbamate metal salts, and examples of the heat-resistant agent include iron oxide, cerium oxide, potassium hydroxide, iron naphthenate, potassium naphthenate. In addition, a colorant, an ultraviolet absorber, a flame retardant, an oil resistance improver, a foaming agent, an anti-scorch agent, a tackifier, a lubricant and the like may be optionally mixed.

These compounded rubber compositions (fluororubber compositions) can be added to a fluororubber (II) crosslinking agent, for example, the above-mentioned organic peroxide and a crosslinking auxiliary agent, or a polyol addition agent, by an ordinary kneading machine such as a roll or a Banbury mixer. After adding a vulcanizing agent, a vulcanization accelerator for polyol vulcanization, and an amine vulcanizing agent, and kneading to make a vulcanizable fluororubber composition, molding and vulcanization are performed under ordinary vulcanized rubber production conditions, and fluororubber crosslinking is carried out. Can be a product.

Here, as the polyol vulcanizing agent as the crosslinking agent for the fluororubber (II-b), a polyhydroxy aromatic compound,
For example, hydroquinone, bisphenol A, bisphenol AF and salts thereof are preferably used. Further, a fluorine-containing aliphatic diol can also be used. The amount of addition of these polyol vulcanizing agents depends on the fluororubber composition.
Usually, 0.1 to 20 parts by weight, preferably 1 per 100 parts by weight
About 10 parts by weight.

Further, as the polyol vulcanization accelerator used in combination with the polyol vulcanizing agent, quaternary ammonium compounds such as methyltrioctylammonium chloride, benzyltriethylammonium chloride and tetrahexylammonium tetrafluorobollard; 8-methyl-1,8-diaza 4 such as -cyclo (5,4,0) -7-undecenyl chloride
Quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride, m-trifluoromethylbenzyltrioctylphosphonium chloride and benzyltrioctylphosphonium bromide are preferred.

The amount of such a vulcanization accelerator is 100%.
It is usually about 0.2 to 10 parts by weight per part by weight.

Further, as the amine vulcanizing agent for the fluororubber (II-b), various alkylamines such as hexamethylenediamine, tetraethylenepentamine and triethylenetetramine, various aromatic amines such as aniline, pyridine and diaminobenzene, and Carbamate, cinnamylidene, and other fatty acid salts of these amines can be used.

The amount of the amine vulcanizing agent to be added depends on the amount of the fluororubber composition 10
Usually, 0.1 to 10 parts by weight, preferably 0.5
It is about 5 parts by weight.

To vulcanize the vulcanizable fluororubber composition, usually, primary vulcanization is carried out at a pressure of ^{20 to} 200 kg / cm ² at 80 to 200 ° C. for a few minutes to 3 hours, and if necessary 80 to 1 to 48 at 200 ° C
Secondary vulcanization is performed for a time to obtain a fluororubber crosslinked product.

As described above, the fluororubber composition of the present invention can be uniformly kneaded with a kneading machine such as the Banbury mixer, the kneader and the two rolls as described above. Also,
When adding vulcanizing agents, vulcanization accelerators, etc. by rolls, it takes a lot of time to wind the rolls with a mixture with a diene rubber (including those containing additives such as fillers), The rubber composition of the present invention can be instantly wound around a roll, and the workability is remarkably improved.

Further, the fluorinated rubber cross-linked product (rubber elastic body) obtained by vulcanizing the vulcanizable rubber composition of the present invention has excellent heat resistance, weather resistance, compression set, and compression load resistance. It can be used in industrial, electrical and chemical fields.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, various measurements were performed according to the following methods.

That is, initial physical properties, aging test, compression set test,
Evaluation was performed under the conditions shown in Table 1 according to JIS K6301.

The compressive load resistance (compressive stress) was evaluated by the following method using a sample for compression set test (thickness 12.70 mm ± 0.13 mm, right cylinder having a diameter of 29.0 mm).

Measurement temperature: 150 ° C. Compression rate: 10 mm / min Compression rate: 0 to 50% Measurement tester: IS5000 [Autograph, manufactured by Toyo Seiki Seisakusho, Ltd.] Examples 1 to 4 JSR N230S as diene rubber (I) (Nippon Synthetic Rubber Co., Ltd., used in Examples 1 and 2), JSR N640H (Nippon Synthetic Rubber Co., Ltd., used in Example 3), Zettopol 10
20 (Nihon Zeon Co., Ltd., nitrile rubber, used in Example 4), and JSR Aflas 150 as fluorine rubber (II)
P (manufactured by Nippon Synthetic Rubber Co., Ltd.) is used for each of these rubber components, sodium stearate as a processing aid, Nippon Silica Industry Co., Ltd. as a silica-based filler, Nipseal LP, and a silane coupling agent. TSL8370 manufactured by Toshiba Silicone Co., Ltd. as a rubber mixer (5
It is put into 0-100 ° C., 60 rpm), kneaded, and when it becomes a uniform state, Perkadox 14 [α, α′-bis, manufactured by Kayaku Nouri Co., Ltd., which is an organic peroxide as a crosslinking agent. (T
-Butylperoxy) -p-diisopropylbenzene]
Add the mixture and knead to make it uniform again.
After raising the temperature to 170 to 180 ° C and the kneading torque and rubber temperature became almost constant (after about 10 to 20 minutes), Ciba-Gaigi Co., Ltd., Irganox 1010 was added as an antioxidant and further kneaded. After it became uniform again, it was discharged.

Next, the sheet thus obtained was rewound on a Japanese roll and kneaded by adding other compounding chemicals such as a cross-linking agent and a cross-linking auxiliary agent shown in Table 1, and press-vulcanizing ( 100-150kg / cm ² , 170 ℃ × 20 minutes, heating and pressurizing)
The vulcanization properties were measured. The results are also shown in Table 1. Example 5 JSR N230 (manufactured by Japan Synthetic Rubber Co., Ltd.) as the diene rubber (I) and Viton GF (manufactured by DuPont, USA) as the fluorine rubber (II). A rubber composition was prepared in the same manner as in Example 1 except that and were used, and a vulcanized rubber was prepared in the same manner and subjected to evaluation.

 The results are shown in Table 1.

Examples 6 to 7 JSR N230S (manufactured by Japan Synthetic Rubber Co., Ltd.) as the diene rubber (I), and Viton E60 as the fluororubber (II).
(Manufactured by DuPont, USA) using Perkadox 14 alone as a cross-linking agent (Example 6), or using Percadox 14 as a cross-linking agent and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) as a cross-linking aid ( A rubber composition was prepared in the same manner as in Example 1 except that Example 7) was performed, and the cross-linking agent curative # 30 (manufactured by DuPont, USA) and the cross-linking accelerator curative # 20 (manufactured by DuPont, USA) were similarly prepared. ) Is added and kneaded, press vulcanization (100-1
After heating at 50 kg / cm ² and 170 ° C. for 20 minutes under heat and pressure), a vulcanized rubber was produced and provided for evaluation. The results are shown in Table 1.

Example 8 The amount of crosslinker Perkadox 14 added was changed to 10
A rubber composition was prepared in the same manner as in Example 1 except that the content was increased to 1.0 part with respect to 0 part, and a vulcanized rubber was prepared in the same manner and subjected to evaluation.

 The results are shown in Table 1.

Example 9 Neoprene W (Showa Neoprene Co., Ltd.) as diene rubber (I) and JSR Aflas 150P as fluororubber (II)
Using (Nippon Synthetic Rubber Co., Ltd.), a rubber composition and a vulcanized rubber were prepared according to the composition shown in Table 1 and provided for evaluation. The results are shown in Table 1.

Examples 10 to 11 JSRN230N (Nippon Synthetic Rubber Co., Ltd.) as a diene (I)
Manufactured by AFLAS 150P (manufactured by Japan Synthetic Rubber Co., Ltd.) as fluororubber (II), sodium stearate is added to these rubber components as a processing aid, and a rubber mixer (50-60 ° C, Kneading at 60 rpm) and at the time when it became uniform, Perkadox 14 was added as a cross-linking agent and kneaded.
The temperature was raised to ~ 180 ° C.

After the kneading torque and rubber temperature became almost constant (after about 10 to 20 minutes), Irganox 10 was used as an anti-aging agent.
10 was added and kneading was further performed, and the mixture was discharged again after it became uniform again.

Next, the rubber composition thus obtained was mixed with Nipseal LP (used in Example 10), MT carbon (used in Example 11) as a filler, and silane coupling agent TSL8370.
And kneading by adding other compounding chemicals such as the cross-linking agent and the cross-linking auxiliary agent shown in Table 1 to each other, press vulcanization (10
0 to 150 kg / cm ² , 170 ° C. × 20 minutes, heating and pressurization), and vulcanized physical properties were measured.

 The results are also shown in Table 1.

Comparative Examples 1 to 4 A rubber composition and a vulcanized rubber were prepared in the same manner as in Example 1 or Example 6 except that a crosslinking agent added for the purpose of crosslinking the diene rubber (I) was not added during kneading. Made,
It provided for evaluation.

 The results are shown in Table 1.

Comparative Example 5 A rubber composition was prepared in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the diene rubber (I) and the fluororubber (II) was changed to JSR N230S / JSR Aflas 150P = 72/28. A vulcanized rubber was prepared and used for evaluation. The results are shown in Table 1.

Comparative Example 6 A rubber composition and a vulcanized rubber were prepared in the same manner as in Example 9 except that a crosslinking agent added for the purpose of crosslinking the diene rubber (I) was not mixed during kneading, and the composition was provided for evaluation. did. The results are shown in Table 1.

Comparative Example 7 A rubber composition was prepared in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the diene rubber (I) and the fluororubber (II) was changed to JSR N230S / JSR Aflas 150P = 0/100. A vulcanized rubber was prepared and used for evaluation. The results are shown in Table 1.

[Effects of the Invention] The fluororubber composition of the present invention has excellent roll processability and easy moldability, as compared with a simple mixture of a diene rubber and a fluororubber. Crosslinked products (vulcanized products) also have excellent heat resistance, compression set and compression load resistance.

Since the fluororubber crosslinked product of the present invention has such characteristics, it is used for oil-, chemical-, heat-, steam-, or weather-proof packing, O-rings, hoses, etc. in transportation means such as automobiles, ships, and aircraft. Sealing material,
Similar to diaphragms, valves, and similar packings, rollings, seals, diaphragms, valves, hoses, rolls, tubes, chemical resistant coatings and linings in chemical plants, food plant equipment and food equipment (including household products) Packing, O
-Rings, hoses, seals, belts, diaphragms,
Valves, rolls, tubes, similar packings in nuclear power plant equipment, O-rings, hoses, sealing materials, diaphragms, valves, tubes, similar packings in general industrial parts, O-rings, hoses, sealing materials, diaphragms, Valve, roll, tube, lining, mandrel, electric wire, flexible joint,
Suitable for belts, rubber plates, weather strips, roll blades for PPC copiers, etc.

Furthermore, as specific applications, (a) In automobile-related applications, as sealing applications, * core valve of carburetor needle valve, * carburetor flange gasket, * power piston packing, * O-ring of automobile gasoline mixing pump, * Cylinder liner seal, * Valve stem seal, * Automatic transmission front pump seal, * Rear axle pinion seal, * Universal joint gasket, * Speedometer pinion seal, * Foot brake piston cup, * Torque transmission O-rings, oil seals, * Exhaust gas re-combustion device seals, * Bearing seals, * Gasoline pump O-rings, * Gasoline hose seals, * Car air-conditioner seals, For hose applications, * Fuel hose, * EGR tube, * For twin cab tubes and diaphragms, * Gasoline pump diaphragms, * Cabrator sensor diaphragms, and other applications * Vibration isolation rubber (engine mounts, exhausts, etc.), * Reburner hoses, (b) Chemical In industrial applications, as seal applications, * chemical pumps, rheometers, piping seals, * heat exchanger seals, * sulfuric acid production equipment glass cooler packing, * pesticide sprayers, pesticide transfer pump seals, * Gas pipe seals, * Plating liquid seals, * High temperature vacuum dryer packing, * Papermaking belt roller seals, * Fuel cell seals, * Wind tunnel joint seals, For roll applications, * Triclene-resistant rolls (fiber dyeing) ), Lining and coating applications. * Corrosion resistant lining of alumite processing tank , * Coating masking jig coating, * gasoline tank lining, * wind tunnel lining, and other applications * acid resistant hose (for concentrated sulfuric acid), * gas coromatography, packing for pH meter tube connection, * Chlorine gas transfer hose, * Oil resistant hose, * Benzene, rainwater drain hose for toluene storage tank, * Expansion joint for flue (coating of asbestos cloth), Seal, * bearing seal, * dry copier seal, * dry cleaning equipment window, other seal, * uranium hexafluoride concentrator seal, * cyclotron seal (vacuum) valve, etc. * automatic packaging machine For seals and other uses, * Dry copying machine belts, * Diaphragm (pollution measuring instrument) for the analysis of sulfurous acid gas and chlorine gas in the air, * Snake pump lining, * Printing machine roll, belt, * Picking roll for pickling, (d) For aircraft related, * Jet engine valve Stem seal, * Fuel supply hose, gasket and O-ring, * Rotating shaft seal, * Hydraulic equipment gasket, * Firewall seal, (e) In ship related, * Screw propeller shaft stern seal, * Diesel engine Air intake / exhaust valve stem seal, * Butterfly valve valve seal, * Butterfly valve shaft seal, (f) Food, medical related * Plate heat exchanger seal, * Vending machine solenoid valve seal, * Medicine For plugs and (g) electrical related products, * Shinkansen insulating oil cap, * Liquid sealed transformer Benching seal, * oil well cable jacket, include the use of the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Takemura 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (56) Reference JP-A-61-62538 (JP, A) JP 55-160037 (JP, A) JP-A-62-156144 (JP, A)

Claims (1)

[Claims] 1. Nitrile rubber and / or chloroprene rubber (I) 5 to 70 parts by weight, and fluororubber (II) 95 to
A fluororubber cross-linked product in which 30 parts by weight of the (I) cross-linking agent is blended, and the fluoro-rubber composition obtained by reacting while giving shear deformation is blended with the fluoro-rubber (II) cross-linking agent to cross-link. Production method.