JPH01294754A - Fluororubber composition and crosslinkable fluororubber composition - Google Patents

Abstract

PURPOSE:To obtain an easily moldable crosslinkable fluororubber composition by adding a crosslinking agent for the following elastomer in mixing a fluororubber with a halogenated polyethylene elastomer and crosslinking this component only. CONSTITUTION:A fluororubber composition is obtained by adding a crosslinking agent for the following component B to a mixture comprising 35-95 pts.wt. fluororubber (A) unreactive with a crosslinking agent for a halogenated polyethylene elastomer (B), 5-65 pts.wt. component B and 5-45 pts.wt. another elastomer (C) crosslinkable with components A and B (provided that the total of components A, B and C is 100 pts.wt., and the A/B ratio (by weight) is 95/5-50/50) and reacting them under applied shearing deformation. According to the above, the particle diameter of dispersed component B can be reduced, the interintrusion between molecules of components A and B can be increased, the interfacial peeling can be prevented, and therefore the obtained composition is excellent in processability and can give a crosslinked product excellent in properties in normal state, heat resistance, oil resistance, compression set resistance and compressive load resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluororubber composition, and more specifically, the present invention relates to a fluororubber composition containing fluororubber and a halogenated polyethylene elastomer as main components, which have good processability, heat resistance, oil resistance, The present invention relates to a fluororubber composition capable of providing a crosslinked product (crosslinked product) with excellent weather resistance, compression set resistance, and compression load resistance.

[Conventional technology]

In recent years, requirements for the performance of rubber materials have become stricter year by year, and the types of rubber materials used are also changing. Among rubbers, fluororubber has outstanding performance compared to other special rubbers in terms of solvent resistance, heat resistance, chemical resistance, and weather resistance, and is in high demand in the industrial goods, automobile, and aircraft fields. is increasing year by year.

However, it is very expensive compared to elastomers other than fluororubber, and its high specific gravity causes a significant increase in product price, so the fields in which it is used have been limited.

In this way, it has become difficult to satisfy the conflicting demands of high performance and low cost at the same time using a single type of rubber material.

In response to these demands, methods have been proposed for mixing fluororubber with elastomers other than fluororubber. (Unexamined Japanese Patent Publication No. 54-93040
(Japanese Unexamined Patent Publication No. 1983-63470), fluororubber and acrylic elastomer (Japanese Patent Application Laid-open No. 58-63470), etc.
Simply mixing them together cannot be said to be sufficiently effective in preventing a decrease in physical properties.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned conventional technical problem, and when mixing fluororubber and a halogenated polyethylene elastomer, by substantially crosslinking only the halogenated polyethylene elastomer component, halogen By reducing the dispersed particle size of the polyethylene elastomer and increasing the interpenetration of molecules between both rubbers, interfacial peeling is prevented. As a result, the crosslinked product (crosslinked product) has excellent processability. The purpose of the present invention is to provide a fluororubber composition that has excellent normal physical properties, heat resistance, oil resistance, compression set resistance, and compression load resistance.

[Means to solve the problem]

The present invention is a halogenated polyethylene elastomer (I
t) Fluororubber (1) that does not react with the crosslinking agent (hereinafter referred to as “(
35 to 95 parts by weight of component I) and halogenated polyethylene elastomer (II) (hereinafter referred to as "component")
(II) 5 to 65 parts by weight (sometimes referred to as "component"),
(1) and other elastomers (m) that can be co-crosslinked with (TI) (hereinafter sometimes referred to as "(■) component") 5-4
5 parts by weight [here, (1) + (■) + (1) = 10
0 parts by weight, and (1) / (III) (weight ratio)
= 9515 to 50150) with the crosslinking agent (II) (hereinafter sometimes referred to as "crosslinking agent (II)") and reacting while applying shear deformation (hereinafter simply referred to as fluororubber composition). (referred to as a "fluororubber composition").

Furthermore, the present invention provides a crosslinkable fluororubber composition (hereinafter referred to as "crosslinkable fluororubber composition).

The fluororubber (1'') in the present invention includes the following combinations of fluorine-containing monomers.

Examples of fluorine-containing monomers include vinylidene fluoride,
Hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinylidene), etc. are used, and seven compounds that can be copolymerized with these are used. Examples of the rubber include rubbers copolymerized with vinyl compounds such as acrylic esters, olefin compounds such as propylene, diene compounds, or halogen-containing vinyl compounds containing chlorine, bromine, or iodine atoms.

The fluororubber (1) must not react with the crosslinking agent of the halogenated polyethylene elastomer ([+), and such fluororubber (1) may include vinylidene fluoride-propylene hexafluoride copolymer. Examples include vinylidene fluoride-propylene hexafluoride-ethylene tetrafluoride terpolymer, ethylene tetrafluoride-propylene copolymer, and ethylene tetrafluoride-vinylidene difluoride-propylene terpolymer.

Specific examples of this fluororubber (I) include types that are crosslinked with a combination of an organic peroxide and a crosslinking aid, but not with a polyol or amine, such as JSR Aflas 150.
P (manufactured by Japan Synthetic Rubber ■), types that are difficult to crosslink with organic peroxides and are crosslinked with polyols or amines, such as Paiton A1 B5 260C (manufactured by DuPont), Tecnoflon (manufactured by Monte Edison), etc. It will be done.

Mooney viscosity of fluororubber (1) (MLI+4.100
°C) is not particularly limited, but preferably 30 to 150
are used.

Next, the halogenated polyethylene elastomer (II) used in the present invention is, for example, chlorosulfonated polyethylene having a chlorine content of 20 to 50% by weight and a sulfur content of 0.5 to 1.5% by weight; Content is 20-50
Examples include, but are not limited to, chlorinated polyethylene in weight percent.

The halogenated polyethylene elastomer (n) preferably has a Mooney viscosity (ML, 4, ioo°C) of 20 to 150, from the viewpoint of kneading workability, uniform dispersibility with the fluororubber (1), etc. More preferably 30 to 120
By using a halogenated polyethylene elastomer (■) having such a viscosity, a fluororubber composition having stable quality and properties can be obtained. If the Mooney viscosity of the halogenated polyethylene elastomer (II) is outside the above range, kneading workability and dispersibility will be poor, making it difficult to maintain quality characteristics.

Next, the other elastomer (I[[) is an elastomer that can be co-crosslinked with the component (I) and component (n),
For example, fluororubbers other than the component (1) (hereinafter referred to as "other fluororubbers") that can be co-crosslinked with component (I[) can be mentioned.

Other fluororubbers include vinyl compounds such as acrylic esters, olefin compounds such as propylene,
Fluororubbers copolymerized with diene compounds or halogen-containing compounds containing chlorine, bromine, or iodine atoms, and/or fluororubbers having functional groups such as epoxy, hydroxyl, or carboxyl groups can be used. It is selected depending on the type of crosslinking agent in component (I[).

Specific examples of other fluororubbers include types that can be crosslinked with a crosslinking agent (0) such as a combination of an organic peroxide and a crosslinking aid, such as JSR Aflas 200 (manufactured by Japan Synthetic Rubber)
, Paiton GF (manufactured by DuPont), Daiel G902 (
(manufactured by Daikin Industries, Ltd.).

In addition, other elastomers (II) include styrene-butadiene rubber (SBR) and isoprene rubber (I).
R) and other diene rubbers, ethylene-α-olefin =
(Diene) rubber (BP, (D)M), rubber modified with a halogen atom, hydroxyl group, or carboxyl group on butyl rubber, acrylic rubber having an unsaturated group as a crosslinking point along with an epoxy group or a halogen atom, epichlorohydrin rubber, etc. can be mentioned.

The above other elastomers (I[[) have good kneading workability,
From the viewpoint of uniform dispersibility with the fluororubber (1), the Mooney viscosity (MLl, 4.100°C) is 10-2001, preferably 20-150, more preferably 30-1)0
By using another elastomer (III) having such a viscosity, it is possible to obtain a fluororubber composition having stable quality and properties. If the Mooney viscosity of the other elastomer (I[[) is outside the above range, kneading workability and dispersibility will be poor, making it difficult to maintain quality characteristics.

In the fluororubber composition of the present invention, the weight ratio of the fluororubber (N), the halogenated polyethylene elastomer (II>), and the other elastomer (III) is as follows:
) 35 to 95 parts by weight, preferably 65 to 95 parts by weight, 5 to 65 parts by weight of halogenated polyethylene elastomer (II)
parts by weight, preferably 5 to 35 parts by weight, and 5 to 45 parts by weight, preferably 5 to 30 parts by weight of other elastomers [herein,
(1) component + (II) component + (III) component = 100 parts by weight], and if component (I) is less than 35 parts by weight or component (II) exceeds 65 parts by weight, the fluororubber The heat resistance, which is a characteristic property, becomes significantly inferior, and the mixture becomes powdered, while the content of component (1) exceeds 95 parts by weight,
If component (II) is less than 5 parts by weight, the compressive load resistance will be poor.

Furthermore, fluororubber (I)/other elastomers (■)
(weight ratio) is 9515 to 50150, preferably 95
15 to 70/30 and other elastomers (TRI)
If it is less than 5% by weight, interfacial peeling phenomenon between component (1) and component (I[) may occur, resulting in a decrease in physical properties and insufficient compression set resistance;
If the amount is exceeded, the formulation will turn into powder.

In the present invention, fluororubber (I), halogenated polyethylene elastomer (n) and other elastomers (
As the crosslinking agent (II) for the halogenated polyethylene elastomer (II) to be mixed in III), any crosslinking agent used for the elastomer (n) can be used.

Examples of the crosslinking agent (II) include organic peroxides, thiourea-based crosslinking agents, diamine-based crosslinking agents, metal oxides, organic lead compounds, polyol-based crosslinking agents, guanidine-based crosslinking agents,
Examples include nitroso compound-based crosslinking agents.

As the organic peroxide, for example, 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-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2゜4 −
Dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzyl peroxide, etc., preferably 2,5-dimethyl-2,5-di(t-
butylperoxy)hexyne-3,2,5-dimethyl-
2,5-di(1-butylperoxy)hexane, α, α
'-bis(t-butylperoxy)-p-diisopropylbenzene. These organic peroxides can be used alone or in combination of two or more.

In the organic peroxide crosslinking, a difunctional vinyl monomer or the like can be used as a crosslinking aid.

Examples of such crosslinking aids include the following compounds.

That is, ethylene glycol dimethacrylate, 1
．． 3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1.6-hexanediol diacrylate, 2
゜2'-bis(4-methacryloyljethoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, divinylbenzene, N,N'-methylenebisacrylamide, p-quinonedioxime , p.

These include p'-dibenzoylquinone dioxime, triazinedithiol, triallylcyanurate, triallylisocyanurate, bismaleimide, and the like.

The amount of this crosslinking aid added is usually 0.1 to 20 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of the rubber component.
Parts by weight.

Examples of the thiourea-based crosslinking agent include 2-mercaptoimidapurine, trimethylthiourea, dilaurylthiourea, dibutylthiourea, and N.

N'-diethylthiourea, thiocarbanilide, N, N
'-Diorthotolylthiourea, dimethylethylthiourea, and the like.

Examples of the diamine crosslinking agent include triethylenediamine, m-phenylenediamine, cumenediamine, alicyclic amine salt, 4,4'-methylene-bis-(2-chloroaniline), ethylenediamine carbamate, N,N
'-dicinnamylidene-1,6-hexamethylenediamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine carbamate, and the like.

The metal oxides include metal oxides of na, nb, and IV of the periodic table.
Metal oxides of group a or IVb, such as magnesium oxide, litharge, zinc oxide, calcium oxide, and the like.

Examples of the organic lead compound include tribasic lead maleate.

Examples of the polyol crosslinking agent include hydroquinone, bisphenol A, bisphenol AF, and salts thereof.

Examples of the guanidine-based crosslinking agent include diphenylguanidine, di-0-tolylguanidine, 0-)lyrubiguanidine, and di-o-tolylguanidine salt of dicatecolporate.

As the nitroso compound crosslinking agent, for example, poly-p
-Dinitrosobenzene, N-(2-methyl-2-nitropropyl)-4-nitrosoaniline, bistoroso 4
-phenyl)-1,4-piperazine and the like.

The amount of the crosslinking agent (n) mentioned above is usually 0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the rubber components (1) component, (■) component, and (Ilr) component. is 0.1 to 15 parts by weight, more preferably 0.1 to 5 parts by weight.

If the amount of crosslinking agent (II) used is too small, the crosslinking density of the rubber component will be low, resulting in insufficient mechanical strength, oil resistance, and creep resistance, while if it is too large, the crosslinking density of the rubber component will be too high, resulting in poor gains The elongation of the crosslinked product of the crosslinkable rubber composition is reduced.

The selection of these crosslinking agents (It) depends on the type of elastomer used, and specifically, halogenated polyethylene elastomer (n) and other elastomers (I[
Select a system that crosslinks [) and is difficult to crosslink fluororubber (I).

In the present invention, specific examples of the crosslinking agent (n) include the following combinations.

■When the fluororubber (1) is a fluororubber that can be crosslinked by diamine crosslinking, polyol crosslinking, and/or organic peroxide and a crosslinking aid, the crosslinking agent (n) is (I-organic peroxide, (2) Thiourea-based crosslinking agents, (3) Metal oxides, and the like.

■When the fluororubber (1) is a fluororubber capable of diamine crosslinking and/or polyol crosslinking, the crosslinking agent (n) is +1>organic peroxide and/or organic peroxide and crosslinking aid, (2 ) thiourea-based crosslinking agents, (3) metal oxides, and the like.

■If the fluororubber (T) is a fluororubber that can be crosslinked only with an organic peroxide and a crosslinking aid, the crosslinking agent (II) is (1) an organic peroxide, (2) a thiourea-based crosslinking agent. , (3) diamine crosslinking agents, and (4) metal oxides.

In the present invention, fluororubber (1), halogenated polyethylene elastomer (II) and other elastomer (I)
Alternatively, as a method for adding the crosslinking agent (II) of the component (II), the components (1) to (DI) and the crosslinking agent (II) can be added at the same time and kneaded, or the (DI) components can be added in advance.
1) After mixing the components (1), the crosslinking agent (II) can be added, or the components (1) and (II) can be added in advance.
It is also possible to add the crosslinking agent (II) to component ) or component (III), and then add the remaining components.

Mixing is carried out using various extruders, Banbury mixers, kneaders, rolls, etc. at a temperature of 50 to 250°C, preferably 1
It can be carried out by kneading at 00 to 200°C, time: 2 minutes to 1 hour, preferably 3 minutes to 45 minutes,
A preferred kneading method is a method using an internal mixer such as a Banbury mixer or a kneader.

At this time, if crosslinking occurs at a kneading temperature of less than 50°C, it will be difficult to control the reaction, while if the kneading temperature exceeds 250'C, the rubber will tend to deteriorate.

Furthermore, if the kneading time is shorter than 2 minutes, it will be difficult to control the reaction and it will be difficult to obtain a uniform composition, while if it exceeds 1 hour, the kneading cost will increase, which is not preferable.

In addition, the kneading temperature when adding the crosslinking agent (n) is usually 10 to 200°C, preferably 20 to 150°C,
In the case of organic peroxides, it is preferred that their half-life is below 1 minute temperature.

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

That is, during mixing, shearing force is applied to the engineered elastomer, so the dispersed particles of fluororubber (I), halogenated polyethylene elastomer (II), or other elastomer ([1)] become smaller. This is because more molecular entanglement occurs at the interface.

In this case, when you stop applying shearing force, the fluororubber (
I), halogenated polyethylene elastomer (II)
Alternatively, the dispersed particles of other elastomer (III) will associate with each other, increasing the particle size and reducing molecular entanglement.

In this way, by co-crosslinking the halogenated polyethylene elastomer (n) and the other elastomer (nu) at the same time as mixing, the system can be fixed in a well-dispersed state.

The rubber composition of the present invention mainly contains fluororubber (I), halogenated polyethylene elastomer (■), and other elastomer (Ill), but may also contain various commonly used compounding agents. Can be added.

These compounding agents may be added during the process of manufacturing the rubber composition of the present invention, or may be added after the composition is manufactured, as necessary.

That is, examples of reinforcing fillers and extenders include carbon black, fumed silica, wet silica, fine quartz powder, diatomaceous earth, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, Mention may be made of talc, mica powder, aluminum sulfate, calcium sulfate, barium sulfate, asbestos, graphite, wollastonite, molybdenum disulfide, carbon fibers, aramid fibers, various whiskers, glass fibers, organic reinforcing agents, and organic fillers. .

Dispersion aids include higher fatty acids and their metal amine salts; plasticizers include, for example, phthalic acid derivatives, adipic acid derivatives, and sebacic acid derivatives; softeners include, for example, lubricating oil, process oil, coal tar, castor oil, Calcium stearate; anti-aging agents such as phenylene diamines, phosphates, quinolines, cresols, phenols, dithiocarbamate metal salts; other colorants, ultraviolet absorbers, flame retardants, oil resistance improvers, blowing agents , a scorch inhibitor, a tackifier, a lubricant, etc. can be optionally added.

These fluororubber compositions are mixed into fluororubber (1) using a conventional kneading machine such as a roll or a Banbury mixer.
A crosslinking agent (■), for example, the organic peroxide and a crosslinking aid,
A polyol crosslinking agent and a polyol crosslinking accelerator or an amine crosslinking agent are added and kneaded to form a crosslinkable fluororubber composition, which is then molded and crosslinked under normal crosslinked rubber manufacturing conditions to produce a fluororubber crosslinked product. can be done.

Here, as the polyol crosslinking agent, polyhydroxy aromatic compounds such as hydroquinone, bisphenol A
1-bisphenol AF and salts thereof are preferably used. Further, fluorine-containing aliphatic diols can also be used.

The amount of these polyol crosslinking agents added is usually 0.1 to 20 parts by weight per 100 parts by weight of the fluororubber composition.
Preferably it is about 1 to 10 parts by weight.

In addition, as polyol crosslinking accelerators used in combination with polyol crosslinking agents, quaternary ammonium compounds such as methyltrioctylammonium chloride, benzyltriethylammonium chloride, and tetrahexylammonium tetrafluoroborate; 8-methyl-1,8-diaza -Quaternary ammonium compounds such as -cyclo(5°4.0)-7-unzocenyl chloride; such as benzyltriphenylphosphonium chloride, m-trifluoromethylbenzyltrioctylphosphonium chloride, and benzyltrioctylphosphonium bromide 4 Class phosphonium compounds are preferred.

The amount of the crosslinking accelerator added is 100% of the fluororubber composition.
It is usually about 0.2 to 10 parts by weight per part by weight.

Furthermore, examples of amine crosslinking agents include various alkyl amines such as hexamethylene diamine, tetraethylene pentamine, and triethylene tetramine, various aromatic amines such as aniline, pyridine, and diaminobenzene, and the carbamic acids of these amines. Salts of fatty acids such as cinnamylidenic acid can be used.

The amount of the amine crosslinking agent added is as follows:
It is usually about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight per 00 parts by weight.

The selection of these crosslinking agents (1) depends on the fluororubber (
Determined by the type of 1).

In the present invention, specific examples of the crosslinking agent (1) include the following combinations.

■Fluororubber (I) is converted into vinylidene fluoride-propylene hexafluoride copolymer and/or vinylidene fluoride-propylene hexafluoride-ethylene tetrafluoride terpolymer,
In the case of a fluororubber copolymerized with a diene compound or a halogen-containing compound containing a chlorine atom, a bromine atom, or an iodine atom, and/or a vinylidene fluoride-propylene-tetrafluoroethylene terpolymer, a crosslinking agent (1 )
Examples include (1) diamine crosslinking agents, (2) polyol crosslinking agents, and (3) organic peroxides and crosslinking aids.

■When the fluororubber (1) is a vinylidene fluoride-propylene hexafluoride copolymer and/or a terpolymer of vinylidene fluoride-propylene hexafluoride-ethylene tetrafluoride, the crosslinking agent (1) is! Examples include 1) diamine-based crosslinking agents, (2) polyol-based crosslinking agents, and the like.

(2) When the fluororubber (I) is a tetrafluoroethylene-propylene copolymer, examples of the crosslinking agent <1) include only a combination of an organic peroxide and a crosslinking aid.

In addition, when crosslinking the fluororubber (1), in addition to the crosslinking agent (1) described above, a crosslinking agent (II) of the halogenated polyethylene elastomer (II) can also be used in combination.

To crosslink the crosslinkable fluororubber composition, it is usually carried out at 80 to 200°C for several minutes to 3 hours using 20 to 200 kg.
/- primary crosslinking under pressure of 80 to 2 if necessary.
Secondary crosslinking is performed at 00°C for 1 to 48 hours to obtain a fluororubber crosslinked product.

As described above, the fluororubber composition of the present invention can be uniformly kneaded using a kneading device such as the Banbury mixer or kneader with one or two rolls as described above. In addition, when adding crosslinking agents, crosslinking accelerators, etc. using rolls, if the mixture is simply mixed with halogenated polyethylene elastomer (including mixtures with additives such as fillers), it takes a lot of time to wind the rolls. However, the rubber composition of the present invention can be rolled up instantly, and the workability is significantly improved.

Furthermore, the crosslinked fluororubber products obtained by crosslinking the crosslinkable rubber composition of the present invention have excellent heat resistance, weather resistance, compression set, and compression load resistance, and are suitable for general industrial, electrical, and chemical fields. It can be used for

〔Example〕 Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, various measurements in the examples were based on the following methods.

That is, the initial physical properties, aging test, and compression set test were determined by J.
Evaluation was made in accordance with IS K6301 under the conditions shown in Table 1.

Compressive load resistance (compressive stress) is determined by compression set test sample (
Thickness 12.70mm±0.131m, diameter 29.0mm
(Right cylindrical shape) was used for evaluation using the following method.

Measurement temperature: 150°C Compression speed: Loam/min Compression rate: 0 to 50% Measurement test device 1) s5000 (fi Toyo Seiki manufacture and preparation autograph) Examples 1 to 6 As fluororubber (1), Piton E60 (DuPont) ), Hypalon 30 (manufactured by DuPont) as the halogenated polyethylene elastomer (II) and JSR Aflas 200 (manufactured by Japan Synthetic Rubber ■) as the other elastomer (III), and sodium stearate as a processing aid. Rubber mixer (50-150℃, 60rp
m), kneaded, and when it became homogeneous, barriki dox 1, which is an organic peroxide, was added as a crosslinking agent (II).
4(α.

α'-bis(t-butylperoxy)-p-diisopropylbenzene, manufactured by Kayaku Nouri Specialty], and triallyl isocyanurate (manufactured by Nippon Kasei, Example 6) as a crosslinking aid.
(without adding rubber) and kneading, and after becoming uniform again, the temperature was raised to 170-180℃, and after the kneading torque and rubber temperature became almost constant (about 10-180℃)
After 20 minutes), Tsukrac CD (4,4
'-(α,α'-dimethylbenzyl)diphenylamine, manufactured by Ohmukai Shinko Kagaku Kogyo ■] and as a filler Nip Seal LP <manufactured by Nippon Silikani Industry ■, MT carbon (Example 2)
), and silane coupling agent TSL8350
(γ-glycidoxypropyltrimethoxysilane,
(manufactured by Toshiba Silicone ■) was added and further kneaded, and after the mixture became uniform again, it was discharged.

Next, the rubber composition thus obtained was wound around two rolls again, and other compounded chemicals such as crosslinking agent (I) and crosslinking aid shown in Table 1 were added and kneaded. For press crosslinking (50-150 kg/c+J, 1
70°C x 20 minutes, heat and pressure), and open crosslinking (
200° C. for 4 hours), and the crosslinking properties were measured.

The results are also shown in Table 1.

Example 7 Except for changing the halogenated polyethylene elastomer (It) to Daisolac H135 (manufactured by Osaka Soda ■),
A rubber composition was prepared in the same manner as in Example 1, and a crosslinked rubber was prepared and evaluated in the same manner.

The results are shown in Table 1.

Examples 8 to 9 JSR Aflas 150P (manufactured by Japan Synthetic Rubber) as the fluororubber (1), Daisorufuku H135 (manufactured by Osaka Soda) as the halogenated polyethylene elastomer (n)
and other elastomers (1) JSR Afras 2
00 and magnesium oxide # as the crosslinking agent ([[)
150 (manufactured by Kyowa Chemical Industry ■) and DIAC Nal
A rubber composition was prepared in the same manner as in Example 1, except that hexamethylene diamine carbamate (manufactured by DuPont) was used in combination, and a crosslinked rubber was similarly prepared and subjected to evaluation.

The results are shown in Table 1.

Comparative Examples 1 to 5 The same procedure as in Example 1 was carried out, except that the crosslinking agent (n) added for the purpose of crosslinking the halogenated polyethylene elastomer (n) during kneading was not added according to the formulation shown in Table 1. A rubber composition and a crosslinked rubber were prepared and subjected to evaluation.

The results are shown in Table 1.

Comparative Example 6 A rubber composition was prepared in the same manner as in Example 1 except that the weight ratio of the components (1)/(II)/(III) was changed to 20/70/10. The mixture turned into powder in the machine, and although it was repeatedly passed through rolls, it could not be pulverized.

Comparative Example 7 Rubber was produced in the same manner as in Example 1, except that only JSR Aflas 150P, which is fluororubber (1), was used as the rubber component, and halogenated polyethylene elastomer (n) and other elastomer (III) were not blended. A composition and crosslinked rubber were prepared and subjected to evaluation. The results are shown in Table 1.

(The following is a blank space) [Effects of the Invention] The fluororubber composition of the present invention has extremely superior roll processability and moldability compared to a simple mixture of fluororubber and a halogenated polyethylene elastomer. Furthermore, crosslinked products obtained by crosslinking crosslinkable fluororubber compositions also have excellent heat resistance, compression set properties, and compression load resistance.

Because the fluororubber crosslinked products of the present invention have such properties, they can be used as backings, O-rings, hoses, etc. for oil, chemical, heat, steam, and weather resistance in transportation facilities such as automobiles, ships, and aircraft. seals, diaphragms, valves, and similar buffing, O-rings, seals, diaphragms,
Valves, hoses, rolls, tubes, chemical-resistant coatings, linings, and similar backings, O-rings, hoses, seals, belts, diaphragms, valves, rolls, in food plant equipment and food equipment (including household items). Similar backings, O-rings, hoses, seals, diaphragms, valves, tubes, similar backings, O-rings, hoses, seals, diaphragms, valves, similar banking, O-rings, hoses, seals in general industrial parts,
It is suitable for use in diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, roll blades for PPC copying machines, and the like.

Furthermore, as specific applications, (a) In the automotive field, ■Sealing applications: *Carburetor needle valve speculation, *Carburetor flange gasket, *Power piston seal, *Automobile gasoline mixing pump O-ring, *Cylinder liner seal, *Pulp stem seal, *Front pump seal of automatic transmission, *Rear axle pinion seal, *Universal joint gasket, Binion seal of this speedometer, *Piston cup of foot brake, *Torque transmission. O-rings, oil seals, *exhaust gas reburning device seals, pairing seals, gasoline pump O-rings, *gasoline hose seals, car air conditioner seals, *Hose applications include *fuel hoses, *EGR tube, this twin carb tube, *Diaphragm applications include: diaphragm for this gasoline pump, *diaphragm for carburetor sensors, *Other uses include: *vibration-proof rubber (engine mount, exhaust section, etc.), *for reburning equipment Hoses, (b) In the chemical industry, ■Sealing applications include: *Chemical pumps, rheometers, piping seals, *Heat exchanger seals, *Glass cooler banking for sulfuric acid production equipment, *M chemical spraying machines. , Seals for pesticide transfer pumps, *Seals for gas pipes, *Seals for liquids, *Packets for high-temperature vacuum dryers, CoroSeals for car paper belts, *Seals for fuel cells, *Joint seals for wind tunnels, ■Rolls Applications include: *Trigrain-resistant rolls (for textile dyeing), ■Lining and coating applications: *Corrosion-resistant lining for alumite processing tanks, *Masking jig coating for plating,
Gasoline tank lining, *Wind tunnel lining, ■Other uses include: acid-resistant hose (for concentrated sulfuric acid), *gas chromatography and pH meter tube joints, chlorine gas transfer hose, *oil-resistant hose, *Rainwater drain hoses for benzene and toluene storage tanks, expansion joints for main flues (asbestos cloth coating), (c) For general machinery, ■ Seal applications include seals for hydraulic and lubricating machines, pairing seals, Seals for dry copying machines, windows and other seals for dry cleaning equipment, seals for uranium fluoride concentrators, seals (vacuum) valves for cyclotrons, *Seals for automatic packaging machines, ■Other uses , the belt of this dry copying machine, the diaphragm of the pump for analyzing sulfur dioxide and chlorine gas in the air (pollution measurement n), the snake bon lining, the rolls and belts of this printing machine, the squeeze roll for pickling, (2) ) Aircraft-related products: *Jet engine valve stem seals, *Fuel supply hoses, gaskets and O-rings, low-cheating shaft seals, *Hydraulic equipment gaskets, *Firewall seals, (e) Ship-related products: Propeller shaft stern seals for screws, intake and exhaust valve stem seals for diesel engines, * Valve seals for butterfly valves, * Shaft seals for butterfly valves, (f) Food and medical related products, * Seals for plate heat exchangers, *Vending machine solenoid valve seals, *Medicine plugs, (g) In the electrical field, *Insulating oil caps for Shinkansen trains, *Penting seals for liquid-sealed transformers, *Oil well cable jackets, etc.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (2)

[Claims] (1) 35 to 95 parts by weight of fluororubber (I) that does not react with the crosslinking agent of halogenated polyethylene elastomer (II) and 5 parts by weight of halogenated polyethylene elastomer (II)
~65 parts by weight and 5 to 45 parts by weight of another elastomer (III) co-crosslinkable with (I) and (II) [here, (
I) + (II) + (III) = 100 parts by weight, and (I)
/(III) (weight ratio) = 95/5 to 50/50], (
A fluororubber composition obtained by blending the crosslinking agent II) and reacting it while applying shear deformation. (2) A crosslinkable fluororubber composition obtained by blending the fluororubber composition according to claim 1 with a crosslinking agent for fluororubber (I).