JPH05117478A - Fluororubber composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which, as compared with a mere mixture a fluororesin and/or vinyl chloride resin, a diene rubber, and a fluororubber, is superior in roll processability and easier to mold and which gives a cross-linked product (vulcanizate) excellent in heat resistance, compression set, and resistance to compression load. CONSTITUTION:A fluororubber composition obtained by mixing a polymer component consisting of 5-50wt.% fluororesin and/or vinyl chloride resin, 90-20wt.% fluororubber, and 5-70wt.% nitrile rubber with a cross-linking agent for the nitrile rubber, and reacting the mixture under shear deformation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin (1) selected from either a fluororesin or a vinyl chloride resin, a fluororubber (2) and a nitrile rubber (3).
TECHNICAL FIELD The present invention relates to a fluororubber composition capable of providing a vulcanized product containing as a main component excellent in gasoline permeation resistance and weather resistance.

[0002]

2. Description of the Related 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 rubber, fluororubber is
It has outstanding performance in solvent resistance, heat resistance, chemical resistance, and weather resistance compared with other special rubbers, and its demand is increasing year by year in the fields of industrial goods, automobiles and aircraft. However, the price thereof is extremely expensive as compared with elastomers other than fluororubber, and the specific gravity thereof is high, which causes a marked increase in product price, and thus the field of use has been limited.

Thus, it can be said that it has become difficult to meet the contradictory requirements of high performance and low price with one kind of rubber material. To meet such demands, a method of mixing fluororubber with an elastomer other than fluororubber has been proposed. For example, JP-A-52
No. 60839, Japanese Patent Application Laid-Open No. 55-160037, Japanese Patent Application Laid-Open No. 60-101135, those aiming to improve the co-vulcanizability of a fluororubber and a diene rubber, or As disclosed in Japanese Patent Application Laid-Open No. 57-135843, there has been proposed one in which acrylonitrile-butadiene rubber having a specific nitrile content is used to improve 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 get sex. 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 are disclosed. Although proposed, the degree of improvement in heat resistance is still insufficient. As a method for solving these problems, Japanese Patent Application Laid-Open No. 1-190739 has been proposed. However, it must be said that it is still insufficient in terms of oil resistance, especially gasoline permeation resistance and weather resistance.

[0005]

The present invention has been made against the background of the above-mentioned conventional technical problems, and improves the compatibility of fluororesin and / or vinyl chloride resin with fluororubber and nitrile rubber, An object is to provide a fluororubber composition having excellent oil resistance, particularly gasoline permeation resistance and weather resistance.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, a fluorocarbon resin and / or a vinyl chloride resin (1) 5 to 50% by weight, a fluororubber (2) 90 to 20% by weight, and a nitrile rubber (3).
Nitrile rubber (3) 5 to 50 wt% to 5 to 50 wt%
And a cross-linking agent for the nitrile rubber (3), and reacting while giving shear deformation, to provide a fluororubber composition obtained.

The fluororesin in the present invention includes vinylidene fluoride, tetrafluoroethylene, trifluoroethylene, trifluorochloroethylene, vinyl fluoride homopolymers or copolymers of two or more monomers,
The above-mentioned fluorine-containing monomer and perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether),
One or more copolymers of vinyl acetate, ethylene, propylene, butadiene, styrene, acrylic acid ester and the like, preferably polyvinylidene fluoride, and vinylidene fluoride and hexafluoropropene, pentafluoropropene, trifluoro. ethylene,
One or more of trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), vinyl acetate, ethylene, propylene, butadiene, styrene or acrylic ester. It is a copolymer and has at least a melting point (T
n) is a copolymer having a temperature of 100 ° C. or higher. Further, the vinyl chloride resin is obtained by polymerization of any one of bulk, solution, emulsification and suspension, and is a vinyl chloride polymer or vinyl chloride, vinylidene chloride, acrylic ester, acrylonitrile, propylene, etc. Seed or 2
It is a copolymer with one or more species.

The fluorine-based resin and / or the vinyl chloride resin (1) may be used in the powder form as they are, or may be used in the form of a paste with a commonly used plasticizer. When the resin thus obtained, the nitrile rubber (3) and the fluororubber (2) are mixed, the nitrile rubber (3) or the fluororubber (2) is first melt-mixed and then the fluorine is added. A method of adding the rubber (2) or the nitrile rubber (3) may be used.

Next, the fluororubber (2) in the present invention
The following combinations of fluorine-containing monomers can be mentioned.
As the fluorine-containing monomer, vinylidene fluoride,
Monomers that can be copolymerized with hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinylidene), etc. As examples, mention may be made of a rubbery copolymer which is amorphous at room temperature 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 and iodine. You can

Specific examples of the fluororubber (2) include vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and tetrafluoroethylene-propylene copolymer. Examples thereof include a combination and a tetrafluoroethylene-vinylidene fluoride-propylene terpolymer. These fluororubbers (2)
Can be classified into a type (2-a) that can be crosslinked by a combination of an organic peroxide and a crosslinking aid, and a type (2-b) that can be crosslinked with a polyol or an amine without being crosslinked with an organic peroxide. Specific examples of the fluororubber (2-a) include Aflas series (manufactured by Japan Synthetic Rubber Co., Ltd.), Viton GF (manufactured by DuPont, USA), Daier G902 (manufactured by Daikin Industries, Ltd.), and the like. Rubber (2-b)
Viton A, B, E60C (Dupont, USA), Technofron (Monte Edison, Italy)
And so on. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the fluororubber (2) is not particularly limited,
It is preferably 30 to 150.

As the nitrile rubber (3) constituting the composition,
For example, (a) 1,3-butadiene, 2-methyl-1,3
15-70% by weight of at least one aliphatic conjugated diene such as butadiene, (b) acrylonitrile 10-5
0% by weight (c) 0 to 75% by weight of acrylic acid ester and / or methacrylic acid ester, and (d) divinylbenzene, diallyl having a plurality of double bonds in the molecule for containing a gel in nitrile rubber. Phthalate,
1 to 5% by weight of diallylmaleate and trimethylolpropane triallylate (however, (a) + (b) + (c) +
(D) = 100% by weight) copolymerized intermolecular crosslinked products can be mentioned. Examples of the (meth) acrylic acid ester here include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 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, methacrylic acid Dodecyl, n-amyl acrylate, isoamyl acrylate, methyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc. be able to.

Further, the nitrile rubber (3) 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, or an aliphatic conjugated diene. It may be hydrogenated in part or in whole. The Mooney viscosity of these nitrile rubbers (ML _{1 + 4} , 100
(° C) is not particularly limited, but is preferably 2
Those of 0 to 150 are used. The above nitrile rubbers (3) may be used alone or in combination of two or more.

Fluorine resin and / or vinyl chloride resin (1) and fluororubber (2) in the rubber composition of the present invention
The weight ratio of the nitrile rubber (3) to the fluorinated resin and / or the vinyl chloride resin (1) is 5 to 50% by weight, preferably 10 to 30% by weight, and the fluororubber (2) is 90 to 20% by weight, preferably 80 to 30% by weight, nitrile rubber (3) to 5 to 70% by weight, preferably 10 to 50% by weight, fluororesin and / or vinyl chloride resin (1)
If it is less than 5% by weight, the weather resistance and gasoline permeation resistance will be significantly inferior, while if it exceeds 50% by weight, the compression set resistance will be inferior.

In the present invention, the crosslinking agent for the nitrile rubber (3) mixed with the fluorine resin and / or the vinyl chloride resin (1) and the fluororubber (2) and the nitrile rubber (3) is, for example, Examples thereof include organic peroxides, sulfur-based vulcanizing agents, resin vulcanizing agents, and quinoid-based vulcanizing agents. In the rubber composition of the present invention, a fluorinated resin and / or a nitrile rubber (3) other than vinyl chloride (1), a fluororubber (2-a), (2-b), and a nitrile rubber (3) Examples of the combination include the following. Nitrile rubber (3) / fluorine rubber (2-a) / organic peroxide Nitrile rubber (3) / fluorine rubber (2-b) / organic peroxide Nitrile rubber (3) / fluorine rubber (2-a) / Fluorine rubber (2-b) / organic peroxide Nitrile rubber (3) / Fluorine rubber (2-a) / Sulfur-based vulcanizing agent Nitrile rubber (3) / Fluorine rubber (2-b) / Sulfur-based vulcanizing agent Nitrile rubber (3) / fluorine rubber (2-a) / quinoid type vulcanizing agent Nitrile rubber (3) / fluorine rubber (2-b) resin vulcanizing agent Of these combinations, preferably nitrile rubber (3) / Fluorine rubber (2-a) / organic peroxide, and nitrile rubber (3) / fluorine rubber (2-a) / fluorine rubber (2-b) / organic peroxide. In the case of the above combination, fluororubber (2-a)
Is required to be 5% by weight or more based on the total amount of fluororubber as 100% by weight. Further, in the case of this combination, a crosslinking aid may be added if necessary.

Examples of the organic peroxide as a cross-linking agent for fluororubber (2-a) include 2,5-dimethyl-2,5
-(T-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy) -p-diisopropylbenzene, dicumylper Oxide, di-t-butyl peroxide, t-butyl benzoate,
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 Is. These organic peroxides may be used alone or in combination of 2
More than one species can be used in combination.

The blending amount of the organic peroxide which is a cross-linking agent for the nitrile rubber (3) is such that the fluororesin and / or the vinyl chloride resin (1) and the fluororubber (2) the nitrile rubber (3) and the fluororubber. (2) It is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight. If the amount is less than 0.01 parts by weight, crosslinking of the nitrile rubber (3) is sufficient. In addition, the processability of the rubber composition, the compression set of the vulcanizate, the resistance to compression load, etc. are not sufficient, and when it exceeds 5 parts by weight, the processability tends to deteriorate, and the machine of the obtained composition is high. The vulcanized physical properties such as dynamic strength and elongation are also inferior. As the cross-linking aid, magnesium methacrylate, calcium methacrylate, aluminum methacrylate, allyl compound, metacrylates,
A wide range of functional monomers such as divinyl compounds, reactive unsaturated compounds such as polybutadiene, functional polymers such as polybutadiene, oxime compounds, sulfur compounds, etc. can be used, but they are crosslinkable or kneadable during compounding. From the viewpoint of the above, reactive unsaturated compounds are preferable, and polyallyl compounds such as polyallyl compounds and 1,2-polybutadiene can be preferably adopted from the viewpoint of properties of vulcanizates such as compression set and heat resistance. is there.

As the polyallyl compound which can be preferably used in the present invention, an allyl group (—CH ₂ CH═CH ₂ ) is 2
Various compounds having more than one 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 carboxylic acids such as diallyl phthalate, diallyl melamine, triallyl cyanurate, triallyl isocyanurate and the like. These may be used alone or in combination of two or more. A preferred specific example is 2 mmHg
Triallyl cyanurate (162 ° C / 2 mmHg) having a boiling point of 30 ° C or more under reduced pressure, triallyl phosphate (15
7 ° C./44 mmHg), triallyl isocyanurate, diallyl phthalate (161 ° C./4 mmHg), diallyl melamine and the like. The addition amount of the crosslinking aid is 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the fluororesin and / or the vinyl chloride resin (1), the nitrile rubber (3) and the fluororubber (2). 7 parts by weight.

In the present invention, the method for adding the crosslinking agent to the fluororesin and / or the vinyl chloride resin (1), the nitrile rubber (3) and the fluororubber (2) is to add these and the crosslinking agent at the same time and mix them. It is possible to knead, or after mixing the nitrile rubber (3) and the fluororubber (2) in advance, a crosslinking agent can be added. Mixing is carried out with various extruders, Banbury mixers, kneaders, rolls, etc. The temperature varies depending on the type of the cross-linking agent, but the temperature at which the cross-linking agent usually reacts; ie, 50 to 250 ° C., preferably 1
00 to 200 ° C., time; 2 minutes to 1 hour, preferably 3 minutes to 45 minutes
A preferable kneading method is a method using an internal mixer such as a Banbury mixer or a kneader. At this time, if the kneading temperature is less than 50 ° C., it is difficult to control the reaction, while if it exceeds 250 ° C. And 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 to 200 ° C., preferably 20 to 150 ° C.
Therefore, in the case of an organic peroxide, it is preferable 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, shearing force is applied to the elastomer, so that the dispersed particles of the nitrile rubber (3) or the fluororubber (2) are kept in a smaller state, and the entanglement of molecules at the interface is larger. This is because it has occurred. In this case, if you stop applying the shearing force,
The disperse particles of the nitrile rubber (3) or the fluororubber (2) are associated with each other to increase the particle size and reduce the entanglement of molecules. Thus, by crosslinking the nitrile rubber (3) simultaneously with mixing, the system can be fixed in a good dispersed state.

The rubber composition of the present invention contains vinylidene fluoride resin and / or vinyl chloride resin, nitrile rubber (3) and fluororubber (2) as main components.
Other diene rubbers such as styrene-butadiene rubber (SBR) and isoprene rubber (IR) other than the above rubber components; ethylene-α-olefin- (diene) rubber [EP (D) M], butyl rubber, acrylic rubber Ordinary elastomers such as saturated rubber such as chlorosulfonated polyethylene can be added in an amount of about 10% by weight or less, and various compounding agents which are usually used 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, titanium dioxide, talc, mica powder, aluminum sulfate, calcium sulfate,
Barium sulfate, asbestos, glass fiber, organic reinforcing agent,
Mention may be made of organic fillers.

Examples of dispersion aids include higher fatty acids and metal amine salts thereof; examples of plasticizers include phthalic acid derivatives and adipic acid derivatives; examples of softeners include lubricating oils, process oils, coal tar, castor oil, and steer. Calcium phosphate; Antiaging agents such as phenylenediamines, phosphates, quinolines, cresols, phenols, dithiocarbamate metal salts; Heat-resistant agents such as iron oxide, cerium oxide, potassium hydroxide, iron naphthenate, Potassium naphthenate; In addition, colorants, ultraviolet absorbers, flame retardants, oil resistance improvers, foaming agents, scorch inhibitors, tackifiers, lubricants and the like can be optionally mixed. These compounded rubber compositions (fluororubber compositions) can be added to a crosslinking agent for the fluororubber (2), for example, the above-mentioned organic peroxide and a crosslinking aid, and a polyol by a conventional 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 a crosslinking agent for the fluororubber (2-b), a polyhydroxy aromatic compound such as hydroquinone, bisphenol A,
Bisphenol AF and salts thereof are preferably used. Further, a fluorine-containing aliphatic diol can also be used. The addition amount of these polyol vulcanizing agents is usually 0.1 to 20 per 100 parts by weight of the fluororubber composition.
Parts by weight, preferably about 1 to 10 parts by weight. Also,
Examples of the polyol vulcanization accelerator used in combination with the polyol vulcanizing agent include quaternary ammonium compounds such as methyltrioctylammonium chloride, benzyltriethylammonium chloride and tetrahexylammonium tetrafluoroborate; 8-methyl-1,8-diazacyclo (5. 4,0) -7-Undecenyl chloride, such as 4
Quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride, m-trifluoromethylbenzyltrioctylphosphonium chloride and benzyltrioctylphosphonium bromide are preferred. The amount of the vulcanization accelerator added is usually about 0.2 to 10 parts by weight per 100 parts by weight of the fluororubber composition.

Further, as the amine vulcanizing agent for the fluororubber (2-b), various alkylamines such as hexamethylenediamine, tetraethylenepentamine and toluethylenetetramine, various aromatics such as aniline, pyridine and diaminobenzene. Amines and salts of fatty acids such as carbamic acid and cinnamylidenic acid of these amines can be used. The amount of the amine vulcanizing agent added is
It is usually 0.1 to 100 parts by weight of the fluororubber composition.
It is about 10 parts by weight, preferably about 0.5 to 5 parts by weight.
To vulcanize the vulcanizable fluororubber composition, it is usually at a temperature of 80 to 200 ° C. for a few minutes to 3 hours and 20 to 200K.
Primary vulcanization under pressure of g / cm ² , and if necessary 8
Secondary vulcanization is performed at 0 to 200 ° C. for 1 to 48 hours to obtain a fluororubber crosslinked product. As described above, the fluororubber composition of the present invention has a Banbury mixer, a kneader, and
It can be kneaded uniformly with a kneading machine such as a two-roll mill. In addition, when adding vulcanizing agents, vulcanization accelerators, etc. by means of rolls, if a mixture with diene rubber (including those containing additives such as fillers) is used, it takes a lot of time to wind the rolls. However, the rubber composition of the present invention can be instantly wound by 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.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, various measurements are based on the following test method 1. Gasoline penetration rate

[0025]

[Figure 1]

Gasohol (Fuel C / ethanol = 85/15) was filled using an aluminum cup as shown in FIG. 1, and the upper portion was sealed with a vulcanized sheet (test piece). 40
The sample was placed in a constant temperature bath at ℃, the change with time of the permeation amount was measured, and the permeation rate was calculated. 2. Ozone Deterioration Test Using an apparatus conforming to JIS K6301, ozone concentration is 100ppm and JIS temperature is 40 ° C.
The No. 1 dumbbell test piece was allowed to stand for 40 hours in a stretched state of 40% and the deteriorated state was observed.

(Example 1) Polyvinylidene fluoride resin JSR KYNAR731 (manufactured by Pen Walt) was used as the fluorine-based resin and / or vinyl chloride resin (1), and TECHNOFLON TN 80 (manufactured by Monte Edison, Italy) was used as the fluorinated rubber. JSR N as system rubber
When 220S (manufactured by Nippon Synthetic Rubber Co., Ltd.) is used, stearic acid is sequentially added to these components as a processing aid in a rubber mixer (50 to 100 ° C., 60 rpm), and the mixture is kneaded to a uniform state. Then, organic peroxide Perkadox # 14 (manufactured by Kayaku Akzo Co., Ltd.) as a crosslinking agent for nitrile rubber, and Barnock PM (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) as a crosslinking auxiliary agent were mixed and kneaded again. After the state, the temperature was raised to 170 ° C to 180 ° C, and after the kneading torque and the rubber temperature became almost constant (about 20 to 3
After 0 minutes) it was discharged. Next, the sheet thus obtained was again wound around a two-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-vulcanized (100 to 150 kg / cm ² , 17
The mixture was heated and pressed at 0 ° C. for 20 minutes), and the vulcanized physical properties were measured. The results are also shown in Table 1.

[0028]

[Table 1]

Example 2 A crosslinked rubber was prepared in the same manner as in Example 1 except that a vinylidene fluoride (90 mol%) / hexafluoropropylene (10 mol%) copolymer resin was used as the fluororesin. Created and evaluated. (Example 3) Vinyl chloride 3000 as vinyl chloride resin
A vulcanized rubber was prepared and evaluated in the same manner as in Example 1 except that M (manufactured by Mitsui Toatsu Chemical Co., Inc.) was used, and the plasticizer DOP was added and preblended with a Henschel mixer. (Example 4) A vulcanized rubber was prepared and evaluated in the same manner as in Example 1 except that TECHNOFLON P2 (manufactured by Asahi Mondo Co., Ltd.) was used as the fluororubber.

(Example 5) Vinylidene fluoride (91 mol%) / hexafluoropropylene (4 mol%) / tetrafluoroethylene (5 mol%) copolymer resin as vinylidene fluoride resin, Technoflon TH as fluororubber
A vulcanized rubber was prepared and evaluated in the same manner as in Example 1 except that 340 (manufactured by Monte Edison, Italy) and JSR N210S (manufactured by Japan Synthetic Rubber Co., Ltd.) were used as the nitrile rubber. (Example 6) JSR N21 as nitrile rubber (3)
5SL (manufactured by Nippon Synthetic Rubber Co., Ltd.), magnesium methacrylate as a crosslinking aid for nitrile rubber (manufactured by Asada Chemical Co., Ltd.)
A rubber composition was prepared in the same manner as in Example 1 except that TECHNOFLON M2 was used as a crosslinking aid for the fluororubber (2), and a Banbury mixer (50 ° C., 6
(1) at 0 rpm) and kneaded by adding a compounding chemical such as a crosslinking agent and a crosslinking aid shown in Table 1 to the mixture, which was press-vulcanized (1
^{00~150Kg / cm 2) 170 ℃ ×} 20 minutes heat and pressure), and to measure the vulcanized physical properties. The results are also shown in Table 1.

(Comparative Example 1) JSR as nitrile rubber
N220S (manufactured by Nippon Synthetic Rubber Co., Ltd.) and TECHNOFLON TN80 (manufactured by Monte Edison, Italy) as fluororubber are used, and stearic acid is sequentially added to these components as a processing aid in a rubber mixer (50 to 100 ° C., 60 rp).
m) and kneaded to obtain a uniform state, organic peroxide Perkadox # 14 (manufactured by Kayaku Akzo Co., Ltd.) as a nitrile rubber cross-linking agent, and Barnock PM ( Ouchi Shinko Kagaku Kogyo Co., Ltd.) was added and kneaded to make a uniform state again, and then the temperature was 170 ° C to 180 ° C.
The temperature was raised to 0 ° C., and after the kneading torque and the rubber temperature became almost constant (about 20 to 30 minutes), they were discharged. Then, the sheet thus obtained is wound again on a two-roll roll.
The compound obtained by adding other compounding chemicals such as the crosslinking agent and the crosslinking auxiliary agent shown in Fig. 3 and kneading the mixture is press-vulcanized (100 to 150K).
gf / cm ² , 170 ° C. × 20 minutes, heating and pressurization), and vulcanized physical properties were measured. The results are also shown in Table 1. Comparative Example 2 A vulcanized rubber was prepared and evaluated in the same manner as in Example 1 except that 3 parts by weight of vinylidene fluoride resin, 47 parts by weight of fluororubber, and 50 parts by weight of nitrile rubber were used.

[0032]

EFFECTS OF THE INVENTION The fluororubber composition of the present invention has extremely excellent roll processability as compared with a simple mixture of a fluororesin and / or a vinyl chloride resin, a diene rubber and a fluororubber, Moldability is easy, and the cross-linked product (vulcanized product) has excellent heat resistance, compression set resistance, and compression load resistance, especially gasoline permeation resistance and weather resistance. ing. Since the fluororubber crosslinked product of the present invention has such characteristics, it can be used for oil-resistant, chemical-resistant, heat-resistant, steam-resistant or weather-resistant packings, O-rings, hoses, and other materials in vehicles such as automobiles, ships, and aircraft. For sealing materials, diaphragms, valves and similar packings, rollings, sealing materials, diaphragms, valves, hoses for chemical plants.
For rolls, tubes, chemical resistant coatings, linings, similar packings, o-rings, hoses in food plant equipment and food equipment (including household items),
Sealing materials, 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 material, diaphragm,
Valve, roll, tube, lining, mandrel,
It is suitable for electric wires, flexible joints, belts, rubber plates, weather strips, roll blades for PPC copiers, etc.

More specific uses are as follows: (a) In automobile-related applications, as seal applications: * carburetor needle valve core valve, * carburetor flange gasket, * power piston packing, * O-ring for automobile gasoline mixing pump , *
Cylinder liner seal, * Valve system seal, * Automatic transmission front pump seal, * Rear axle pinion seal, * Universal joint gasket, * Speedometer pinion seal, *
Foot brake piston cup, * torque transmission O-ring, oil seal, * exhaust gas reburning device seal, *
Bearing seal, * O-ring of gasoline pump,
* Gasoline hose seals, * Car air conditioner seals, for hoses * Fuel hoses, * EGR tubes, * Twin cap tubes, diaphragms * Gasoline pump diaphragms * Carbrator sensor diaphragms, etc. Applications include * anti-vibration rubber (engine mounts, exhaust parts, etc.), hoses for reburning equipment,

(B) In the chemical industry, as seal applications, * chemical pumps, rheometers, pipe seals, * heat exchanger seals, * sulfuric acid production equipment glass cooler packing, * pesticide sprayers, pesticides Transfer pump seal, * Gas pipe seal, * Plating liquid seal, * High temperature vacuum dryer packing, * Papermaking belt roller seal, * Fuel cell seal, * Wind tunnel joint seal, roll application, * proof For trichlene roll (fiber dyeing) lining and coating applications: * Corrosion resistant lining for alumite processing tank, * Masking jig coating for plating, * Gasoline tank lining, * Wind tunnel lining, and other applications * Acid resistant hose ( (For concentrated sulfuric acid), * gas chromatography,
Packing for tube connection part of ph meter, * chlorine gas transfer hose, * oil resistant hose, * benzene, rainwater drain hose for toluene storage tank, * expansion joint of flue (coating of asbestos cloth),

(C) Regarding general machinery, as seal applications, * hydraulic pressure, lubrication machinery seal, * bearing seal, * dry copying machine seal, * dry cleaning equipment window, other seal, * uranium hexafluoride enrichment Equipment seal, *
Cyclotron seal (vacuum) valve, * Automatic packaging machine seal, and other applications * Dry copying machine belt, * Sulfurous acid gas in air, chlorine gas analysis pump diaphragm (pollution measuring instrument), * Snake Pump lining, * Roll of printing press, belt,
* Pickle 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 intake / exhaust valve stem seal, * Butterfly valve valve seal, * Butterfly valve shaft seal, (f) Food, medical related * Plate Type heat exchanger seals, * Vending machine solenoid valve seals, * Medicine taps (g) In the electrical field, * Shinkansen insulating oil caps, * Liquid ring type transformer venting seals, * Oi well cable jackets, etc. To use.

[0036]

[Brief description of drawings]

1 shows an aluminum cup used to measure gasoline permeation rate.

[Explanation of symbols]

 1 Fluoro rubber composition 2 Gasohol

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ken Akiyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A fluororesin and / or a vinyl chloride resin (1) 5 to 50% by weight, and a fluororubber (2) 90 to 20.
A fluororubber composition obtained by blending a cross-linking agent of a nitrile rubber (3) with a polymer component composed of 5% by weight and a nitrile rubber (3) of 5 to 70% by weight, and reacting while giving shear deformation.