JPH073077A - Rubber composition - Google Patents

Abstract

(57) [Abstract] [Purpose] Gasoline permeation resistance and weather resistance consisting of vinylidene fluoride resin (I), nitrile rubber (II), vinyl chloride resin (III) and / or polymethyl methacrylate resin (IV) Provided is a vulcanizable rubber composition having excellent cold resistance, compression set, and processability. Composition: 100 parts by weight of a composition containing 10 to 70% by weight of vinylidene fluoride resin (I) and 90 to 30% by weight of nitrile rubber (II), vinyl chloride resin (III) and / or polymethacrylic acid Methyl resin (IV) 5-50
A rubber composition containing 1 part by weight, wherein the rubber composition and the vinylidene fluoride resin (I) are 5 μm or less in which (I) is crosslinked while giving shear deformation during blending of (I) and (II). The rubber composition having the above particle size dispersed therein.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to gasoline permeation resistance containing vinylidene fluoride resin (I), nitrile rubber (II), vinyl chloride resin (III) and / or polymethyl methacrylate resin (IV). The present invention relates to a vulcanizable rubber composition having excellent weather resistance, cold resistance, compression set, and processability.

[0002]

2. Description of the Related Art In recent years, the atmosphere in which products made of gasoline permeable rubber are used in automobiles has become higher and higher as a result of exhaust emission control measures and engine improvements aimed at improving performance. Therefore, a gasoline resistant rubber having excellent heat resistance is required. For example, JP-A-6
JP-A 1-225227 describes a blend of vinylidene fluoride resin and nitrile rubber, but since vinylidene fluoride resin and nitrile rubber have poor compatibility,
There is a problem that the vinylidene fluoride resin aggregates at high temperature. Further, Japanese Patent Application Laid-Open No. 1-245042 describes a blend of a vinylidene fluoride resin and a partially crosslinked nitrile rubber, but it is problematic as a rubber composition in terms of hardness, strength, elongation, cold resistance and compression set. There is.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves problems such as agglomeration of vinylidene fluoride resin at high temperature in a blend of vinylidene fluoride resin and nitrile rubber, and improves oil resistance, particularly gasoline permeation resistance and An object of the present invention is to provide a rubber composition having excellent weather resistance, cold resistance, compression set, and workability.

[0004]

The present invention provides a composition comprising vinylidene fluoride resin (I), nitrile rubber (II), vinyl chloride resin and / or methyl methacrylate resin (I), (I) It is preferably obtained by blending the crosslinking agent of (I) at the time of blending of II) and reacting while giving shear deformation. Here, the vinylidene fluoride resin (I) after the reaction was dispersed and fixed in a particle size of 5 μm or less, whereby the vinylidene fluoride resin (I) at high temperature could be prevented from aggregating. Further, the vinyl chloride resin (III) and / or the polymethylmethacrylate resin (IV) is effective for imparting weather resistance. With these means, they have found that they have excellent gasoline permeation resistance, weather resistance, cold resistance, compression set, and workability, and have reached the present invention.

The weight ratio of the vinylidene fluoride resin (I) to the nitrile rubber (II) in the rubber composition of the present invention is 10 to 70% by weight of the vinylidene fluoride resin (I), preferably 3
The amount is 0 to 60% by weight, the nitrile rubber (II) is 30 to 90% by weight, and preferably 40 to 70% by weight. (I) + (I
I) = 100 parts by weight, the vinyl chloride resin (III) and / or the polymethylmethacrylate resin (IV) is
5 to 50 parts by weight, preferably vinyl chloride resin (II
In the case of I), 20 to 50 parts by weight, particularly preferably 25 to 4
0 parts by weight, 5 to 30 parts by weight in the case of polymethylmethacrylate resin (IV), and particularly preferably 7 to 20 parts by weight. Here, if the vinylidene fluoride resin (I) is less than 10% by weight, the gasoline permeation resistance becomes significantly poor. If it is less than 5 parts by weight of the vinyl chloride resin (III) and / or the polymethylmethacrylate resin (IV), the weather resistance will be significantly inferior. If it exceeds 70% by weight of the vinylidene fluoride resin (I), the hardness becomes too high, which causes a problem as a rubber composition. If the vinyl chloride resin (III) and / or the polymethylmethacrylate resin (IV) exceeds 50 parts by weight, the hardness becomes high, which poses a problem as a rubber composition.

As the vinylidene fluoride resin (I) in the present invention, polyvinylidene fluoride, vinylidene fluoride and hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, It is a copolymer of one or more of perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), vinyl acetate, ethylene, propylene, butadiene, styrene or acrylic acid ester.

As the nitrile rubber (II), for example, (a) at least one aliphatic conjugated diene such as 1,3-butadiene and 2-methyl-1,3-butadiene is used.
To 70% by weight, (b) acrylonitrile 10 to 50% by weight, preferably 30 to 50% by weight, (c) acrylic acid ester and / or methacrylic acid ester 0 to 7% by weight, and the nitrile rubber contains a gel component. Therefore, 1 to 5% by weight of (d) divinylbenzene, diallyl phthalate, diallyl malate, trimethylolpropane triallylate having a plurality of double bonds in the molecule (however, (a) + (b) + (c) + An intermolecular crosslinked product obtained by copolymerizing (d) = 100% by weight can be mentioned.

Examples of the (meth) acrylic acid ester 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-acrylate
Nonyl, isononyl acrylate, n-nonyl methacrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, dodecyl methacrylate, n-amyl acrylate, isoamyl acrylate, methyl methacrylate, n-methacrylate Examples thereof include amyl, isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate.

Further, the nitrile rubber (II) is a copolymer of a small amount of an unsaturated carboxylic acid compound such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or allyl glycidyl ether, and a part of the aliphatic conjugated diene. Alternatively, the whole may be hydrogenated. Further, a nitrile rubber grafted with methyl methacrylate may be used.

The Mooney viscosity (M
L _{1 + 4} , 100 ° C.) is not particularly limited, but preferably 20 to 150 is used. The above nitrile rubbers (II) can be used alone or in combination of two or more.

The vinyl chloride resin (III) is a vinyl chloride polymer obtained by any one of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization. As the polymethylmethacrylate-based resin (IV), a homopolymer of methylmethacrylate or a copolymer with another vinyl monomer copolymerizable therewith is used. These copolymers include, for example, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-acrylic acid copolymer, methyl methacrylate-styrene copolymer, methyl methacrylate. -Acrylonitrile copolymer, methyl methacrylate-styrene-acrylonitrile copolymer, methyl methacrylate-methyl acrylate-methacrylic acid copolymer and the like.

Next, as a cross-linking agent for vinylidene fluoride resin (I), various alkylamines such as hexamethylenediamine, tetraethylenepentamine and triethylenetetramine, and various aromatic amines such as aniline, pyridine and diaminobenzene. Also, 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 usually about 0.1 to 5 parts by weight, preferably about 0.3 to 2 parts by weight, per 100 parts by weight of the composition. Further, vulcanization is carried out by using a polyol as a vulcanizing agent and a vulcanization accelerator and a divalent metal oxide or a divalent metal hydroxide in combination. Here, as the polyol vulcanizing agent, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane (bisphenol AF), resorcin, 1, 3,5-trihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxystilbene, 2,6-dihydroxy Anthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (bisphenol B), 4,4-bis (4-
Hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ', 5,5'-tetrabromobisphenol A and the like can be mentioned. Among these polyhydroxy aromatic compounds, bisphenol A, bisphenol AF and hydroquinone are particularly preferable. Further, such a polyhydroxy aromatic compound is
These alkali metal salts or alkaline earth metal salts may be used. The amount of the vulcanizing agent added is 100
It is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per part by weight. As the vulcanization accelerator, a salt of a compound (a) and / or (b) represented by the following general formula and an aromatic sulfonic acid compound, or a compound (a) and / or (b) represented by the following general formula And a mixture of aromatic sulfonic acid compounds.

[Chemical 1] Here, the compound represented by the general formula (a) means 1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter, referred to as
Simply referred to as “DBU”), and the compound may be a ring in which a hydrogen atom is replaced with another atom or molecule. Further, the compound represented by the general formula (b) is 1,5-diaza-bicyclo (4,3,
0) nonene-5 (hereinafter, may be simply referred to as “DBN”), and such a compound may be a compound in which a hydrogen atom in a cyclic ring is replaced by another atom or molecule, as in the above compound. Further, as the aromatic sulfonic acid compound, benzenesulfonic acid, dodecylbenzenesulfonic acid, o, m, p-toluenesulfonic acid, 2,4-toluenedisulfonic acid, sulfanilic acid, naphthalenesulfonic acid, naphthoic acid, p-sulfobenzoic acid Acids and the like can be mentioned, and these compounds may have hydrogen atoms in the cyclic ring substituted by other atoms or molecules.
The amount of the vulcanization accelerator added is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of the composition. Examples of the divalent metal oxide and / or the divalent metal hydroxide include magnesium, calcium,
Examples thereof include oxides or hydroxides of lead, zinc and the like, a mixture of the oxide and the hydroxide, or a mixture of the oxide and / or the hydroxide and a metal salt of a weak acid. Here, as the weak acid metal salt, stearic acid such as barium, sodium, potassium, lead or calcium,
Preferred examples include salts of benzoic acid, carbonic acid, oxalic acid, phosphorous acid and the like. The amount of such metal oxide and / or metal hydroxide added is 2 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the composition.

Next, the mixing method will be described. The vinylidene fluoride resin and nitrile rubber are kneaded with various extruders, Banbury mixers, kneaders, etc. at 100 ° C to 200 ° C, preferably 150 ° C to 180 ° C for 20 minutes to 1 hour, preferably 30 minutes to 50 minutes. Here, if the kneading temperature is less than 100 ° C., there arises a problem that the vinylidene fluoride resin and the nitrile rubber are not uniformly mixed.
Further, when the kneading temperature exceeds 200 ° C., there arises a problem that the rubber deteriorates.

After the vinylidene fluoride resin is completely melted, a crosslinking agent is added. The temperature for adding the crosslinking agent for the vinylidene fluoride resin is 150 ° C to 200 ° C, preferably 16 ° C.
It is 0 ° C to 180 ° C. Here, the crosslinking agent addition temperature is 15
If the temperature is lower than 0 ° C, the vinylidene fluoride resin will be crosslinked in a state where it is not melted, so that the particle size of the dispersed vinylidene fluoride resin will not be uniform and the physical properties will be deteriorated. Further, when the temperature exceeds 200 ° C., there arises a problem that the rubber deteriorates. Next, a vinyl chloride resin and / or a polymethyl methacrylate resin is added and the temperature is 140 ° C. to 180 ° C., preferably 150 ° C. to 170 ° C., for 5 minutes to 30 minutes, preferably 10 minutes.
Knead for 20 minutes. Here, if the kneading temperature is less than 140 ° C., the vinyl chloride resin and / or the polymethylmethacrylate-based resin will not be melted, and the values of tensile strength and elongation will be insufficient, causing a problem as a rubber composition. Further, when the kneading temperature exceeds 180 ° C., there is a problem that vinyl chloride deteriorates. Here, the polymethyl methacrylate resin may be added when kneading the vinylidene fluoride resin and the nitrile rubber.

The plasticizer may be added by impregnating the vinylidene fluoride resin and the nitrile rubber with the vinylidene fluoride resin or by kneading the vinyl chloride resin and / or the polymethyl methacrylate resin. At this time, it may be impregnated with a vinyl chloride resin and / or a polymethyl methacrylate resin. Alternatively, the vinylidene fluoride resin and the vinyl chloride resin and / or the polymethyl methacrylate resin may be added separately and impregnated.

As described above, the crosslinking in the present invention must be carried out during mixing. The reason is that, during mixing, shearing force is applied to the elastomer, so that the dispersed particles of vinylidene fluoride resin (I) or nitrile rubber (II) maintain a smaller state, and the molecular weight at the interface is reduced. This is because more entanglement occurs.

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

Thus, by crosslinking the vinylidene fluoride resin (I) at the same time as mixing, the system can be fixed in a good dispersed state. If the particle size of the vinylidene fluoride resin dispersed here exceeds 5 μm, the values of tensile strength and elongation decrease, so 5 μm or less is preferable.

The rubber composition of the present invention contains vinylidene fluoride resin (I), nitrile rubber (II) and vinyl chloride resin (III) and / or polymethyl methacrylate resin (IV) as a main component. However, other than this, other diene rubbers such as styrene-butadiene rubber (SBR) and isoprene rubber (IR) other than the above rubber component; ethylene-α
-Olefin- (diene) type rubber [EP (D) M], butyl rubber, acrylic rubber, saturated rubber such as chlorosulfonated polyethylene, and the like, about 10% by weight or less of a normal elastomer, and various kinds of compounds usually used. Agents can be added.

If desired, these compounding agents may be added in the process of producing the rubber composition of the present invention, 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, fine quartz powder, diatomaceous earth, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate,
Titanium dioxide, talc, mica powder, aluminum sulfate,
Calcium sulphate, barium sulphate, asbestos, glass fibers, organic reinforcing agents, organic fillers can be mentioned.

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 process oil, coal tar, castor oil, calcium stearate; aging. Examples of the inhibitor include phenylenediamines, phosphates, quinolines, cresols,
Phenols, metal salts of dithiocarbamates; heat-resistant agents such as iron oxide, cerium oxide, iron naphthenate, potassium naphthenate; colorants, UV absorbers, flame retardants, oil resistance improvers, foaming agents, scorch inhibitors, Tackifiers, lubricants and the like can be optionally mixed.

Examples of the cross-linking agent for the nitrile rubber (II) include organic peroxides, sulfur-based vulcanizing agents, resin vulcanizing agents, and quinoid-based vulcanizing agents. In addition, the blending amount of the organic peroxide which is a crosslinking agent of the nitrile rubber (II) is
Vinylidene fluoride resin (I) and nitrile rubber (II)
It is preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight. If it is less than 0.01 parts by weight, the crosslinking of the nitrile rubber (II) is insufficient,
The processability of the rubber composition, the compression set of the vulcanizate, the resistance to compressive load, etc. are not sufficient, while when it exceeds 10 parts by weight, the vulcanizate such as the mechanical strength and elongation of the resulting composition are inferior. Will be things.

As the cross-linking aid, reactive unsaturated compounds such as magnesium methacrylate, calcium methacrylate, aluminum methacrylate, allyl compounds, methacrylates, functional monomers such as divinyl compounds, and functional polymers such as polybutadiene. Further, a wide range of compounds such as oxime compounds and sulfur compounds can be adopted. A reactive unsaturated compound is preferable from the viewpoint of cross-linking property or kneading property during compounding. Compression set,
From the viewpoint of vulcanizate properties such as heat resistance, polyallyl compounds and polyfunctional compounds such as 1,2-polybutadiene are particularly preferable.

Polyallyl which can be preferably used in the present invention
As the compound, an allyl group (-CH ₂CH = CH₂)
The compound which has two or more can be illustrated. example
For example, diallyl ether of glycerin, diallylamine,
Alkyl or polyallyl-substituted alkyl such as triallylamine
Represented by aromatic amines, triallyl phosphoric acid, etc.
Phosphoric acid or phosphorous acid substituted with polyallyl groups, diallylsac
Cinate, diallyl adipate, diallyl phthalate
When carvone is a polyallyl substitution product, diallyl melamine,
Reallyl cyanurate, triallyl isocyanurate
Which can be mentioned. These are one kind or more than two kinds.
It can be used as a mixture. As a preferred concrete example, 2 m
Triallyl having a boiling point of 30 ° C or higher under reduced pressure of mHg
Cyanurate (162 ° C / 2mmHg), Triaphosphate
Ril (157 ° C / 44mmHg), triallyl isocyanate
Nulate, diallyl phthalate (161 ° C / 4mmH
g), diallyl melamine and the like. Such a bridge
The amount of the auxiliary agent added is the same as that of vinylidene fluoride resin (I)
Rubber (II) and vinyl chloride resin (III) and / or
To 100 parts by weight of methyl methacrylic acid resin (IV)
0.1 to 10 parts by weight, preferably 1 to 7 parts by weight
It

These compounded rubber compositions are prepared by using a conventional kneading machine such as a roll or a Banbury mixer to crosslink the nitrile rubber (II), for example, the above-mentioned organic peroxide, a crosslinking aid and a sulfur-based vulcanizing agent. After adding a resin vulcanizing agent and a quinoid vulcanizing agent and kneading to make a vulcanizable rubber composition, molding and vulcanization can be performed under ordinary vulcanized rubber production conditions to obtain a rubber crosslinked product. .

The rubber composition of the present invention can be instantly wound by a roll, and the workability is remarkably improved. Furthermore, the vulcanized rubber composition of the present invention (rubber elastic body) has excellent weather resistance, compression set, gasoline permeation resistance, and cold resistance. It can be used in the chemical field.

[0027]

EXAMPLES The present invention will be described in more detail with reference to examples. In addition, in the examples, various measurements were based on the following methods.

Test method 1. Gasoline permeation rate Gasohol (Fuel C / ethanol = 85/15) was filled using an aluminum cup, and the upper part was sealed with a vulcanized sheet (test piece). The sample was placed in a constant temperature bath at 40 ° C., the change in permeation amount with time was measured, and the permeation rate was calculated. This was used as an index of gasoline permeation resistance. 2. Normal physical property It carried out based on JISK6301. 3. Ozone degradation test Using an apparatus conforming to JIS K6301, under the environment of ozone concentration of 50 pphm and test temperature of 40 ° C, J
The IS1 dumbbell test piece was left for 168 hours in a state of being stretched by 50%, and the deterioration state was observed. This was used as an index of weather resistance. 4. Low temperature impact embrittlement test It was performed according to JIS K6301. This was used as an index of cold resistance. 5. Workability (roll workability) The following was used as an index of workability. Time to wrap around roll 1 minute or more × Time to wrap around roll less than 1 minute ○ 6. Compression set It was performed according to JIS K6301. This was used as an index of compression set. 7. Measurement of particle size of vinylidene fluoride resin (I) in the composition It was carried out by observing with an electron microscope.

Example 1 KYNAR741 as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000M (manufactured by Mitsui Toatsu Chemical Co., Inc.). Plasticizer TP-95 (Thiokol) was added to 57 parts by weight of vinylidene fluoride resin (I).
(Manufactured by the company) 25 parts by weight were added, and this and nitrile rubber (II) 4
When 3 parts by weight were put into a kneader (150 ° C., 40 rpm) and kneaded to be uniform, amine compound V1 (hexamethylenediamine) was used as a crosslinking agent for vinylidene fluoride resin, and Kyowamag 150 (Kyowa) was used as an acid acceptor. (Manufactured by Kagaku Co., Ltd.) was added and kneaded, and the mixture was homogenized again. Then, the temperature was raised to 180 ° C., and after the kneading torque and the rubber temperature became almost constant (30 minutes), the mixture was discharged. Next, 35 parts by weight of vinyl chloride resin (III) and carbon black Thermax MT (manufactured by Cancarb) were added to the above blend.
0 parts by weight was put into a kneader (140 ° C., 40 rpm) and kneaded to raise the temperature when uniform (160 ° C.).
Then, it was discharged after the kneading torque and the rubber temperature became almost constant (10 minutes). Next, the sheet thus obtained was wound around a two-roll and kneaded by adding a crosslinking agent for nitrile rubber (II), and then press-vulcanized (150
It was heated at 180 ° C. for 10 minutes under a pressure of kg / cm ² , and the vulcanized physical properties were measured. The results are also shown in Tables 1 and 2.

[Table 1]

[Table 2]

Example 2 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN220S (manufactured by Nippon Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000H (manufactured by Mitsui Toatsu Chemical Co., Inc.), and polymethylmethacrylate resin (IV), Parapet G (manufactured by Kuraray Co., Ltd.). 25 parts by weight of a plasticizer RS107 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added to 43 parts by weight of vinylidene fluoride resin (I), and 57 parts by weight of this and a nitrile rubber (II) were kneader (160 ° C, 40 rpm).
When the mixture was kneaded and kneaded to homogeneity, the amine compound tetraethylenepentamine was added as a cross-linking agent for vinylidene fluoride resin, and Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) was added as an acid acceptor, kneaded, and homogenized again. After the state, the temperature was raised to 175 ° C., and the kneading torque and the rubber temperature became almost constant (35 minutes) before discharging. Next, to the above blend, 25 parts by weight of vinyl chloride resin (III), 7 parts by weight of polymethylmethacrylate resin (IV) and 5 parts by weight of carbon black Thermax MT (manufactured by Cancarb) were placed in a kneader (140 degrees, 40 rpm). When the mixture was charged, kneaded and heated to a uniform state, the temperature was raised (160 ° C.), and after the kneading torque and the rubber temperature became almost constant (10 minutes), the mixture was discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Example 3 KYNAR741 as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) and Parapet SP100 (manufactured by Kuraray Co., Ltd.) were used as the polymethylmethacrylate resin. When 28 parts by weight of vinylidene fluoride resin (I) and 72 parts by weight of nitrile rubber (II) were put into a kneader (150 degrees, 40 rpm) and kneaded to be uniform, amine was used as a crosslinking agent for the vinylidene fluoride resin. Compound V1 (hexamethylenediamine) and Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) as an acid acceptor were added and kneaded. After the mixture became uniform again, the temperature was raised to 180 ° C., and the kneading torque and rubber temperature were increased. It was discharged after it became almost constant (30 minutes). Next, 10 parts by weight of polymethylmethacrylate resin (IV) and carbon black Thermax MT (manufactured by Cancarb) were added to the above blend.
Parts by weight and plasticizer TP-95 (manufactured by Thiokol) 20
Pour parts by weight into a kneader (140 ° C, 40 rpm),
When the mixture is kneaded and becomes uniform, the temperature is raised (170 ° C),
After the kneading torque and rubber temperature become almost constant (15
Min) discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Example 4 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Nippon Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000H (manufactured by Mitsui Toatsu Chemical Co., Ltd.), and polymethyl methacrylate resin (IV), Parapet G (manufactured by Kuraray Co., Ltd.). . 33 parts by weight of vinylidene fluoride resin (I) and 5 parts by weight of polymethylmethacrylate resin (IV) are added to plasticizer TP-95 (Thio).
(manufactured by Kol) 25 parts by weight, and 67 parts by weight of this and nitrile rubber (II) are kneader (160 ° C., 40 rpm)
When the mixture was kneaded and kneaded to homogeneity, amine compound V1 hexamethylenediamine as a cross-linking agent for vinylidene fluoride resin and Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) as an acid acceptor were added and kneaded, and then homogenized again. After getting into the state
The temperature was raised to 175 ° C., and the kneading torque and the rubber temperature became almost constant (35 minutes) before discharging. Next, 30 parts by weight of vinyl chloride resin (III) was added to the above blend in a kneader (140 ° C., 40 rpm) and kneaded, and when uniform, the temperature was raised (160 ° C.), kneading torque and rubber It was discharged after the temperature became almost constant (10 minutes).
In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Example 5 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
Parapet SP100 (manufactured by Kuraray Co., Ltd.) was used as SRN220S (manufactured by Japan Synthetic Rubber Co., Ltd.) as the polymethylmethacrylate resin. Vinylidene fluoride resin (I)
Plasticizer RS107 (made by Asahi Denka Co., Ltd.) 25 in 37 parts by weight
In addition, 16 parts by weight of polymethyl methacrylate resin (IV), 63 parts by weight of nitrile rubber (II), and carbon black Thermax MT (Cancarb)
10 parts by weight of Banbury mixer (160 ° C, 4
0 rpm), and when kneading and uniforming, amine compound tetraethylenepentamine as a crosslinking agent for vinylidene fluoride resin and Kyowamag 150 as an acid acceptor
(Manufactured by Kyowa Chemical Co., Ltd.) was added and kneaded, and after the mixture became uniform again, the temperature was raised to 175 ° C., and after the kneading torque and the rubber temperature became almost constant (35 minutes), the mixture was discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Example 6 KYNAR500 as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000M (manufactured by Mitsui Toatsu Chemicals, Inc.). To 57 parts by weight of vinylidene fluoride resin (I), 25 parts by weight of a plasticizer TP-95 (manufactured by Thiokol) was added, and 43 parts by weight of this and nitrile rubber (II) were put into a kneader (150 ° C., 40 rpm) and mixed. Knead
When uniform, 2 parts by weight of bisphenol AF as a cross-linking agent for vinylidene fluoride resin and a quaternary ammonium salt of DBU (8benzyl-1,8 diazabicyclo (5,4,0) -7 as a vulcanization accelerator are used. 0.5 parts by weight of undecenium chloride), 3 parts by weight of Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) as a metal oxide, and 6 parts by weight of calcium hydroxide as a metal hydroxide, and the mixture is kneaded to obtain a uniform state again. After that, the temperature was raised to 180 ° C., and after the kneading torque and the temperature became almost constant (25 minutes), the mixture was discharged. Next, vinyl chloride resin (III) 35
Parts by weight and carbon black Thermax MT (Ca
10 parts by weight (manufactured by Ncarb Co.) were put into a kneader and kneaded to raise the temperature (160 ° C.) when a uniform state was obtained, and after the kneading torque and the rubber temperature became almost constant (10 minutes).
Discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Comparative Example 1 KYNAR741 as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
Using SRN220S (manufactured by Japan Synthetic Rubber Co., Ltd.), 47 parts by weight of vinylidene fluoride resin (I) and plasticizer R
20 parts by weight of S107 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added, and 53 parts by weight of this and nitrile rubber (II) and carbon black Th
10 parts by weight of ermax MT (manufactured by Cancarb) was put into a kneader (150 ° C., 40 rpm), and after kneading and homogenizing, the temperature was raised to 180 ° C., and the kneading torque and rubber temperature became almost constant. And then discharged (20 minutes). In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Comparative Example 2 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000M (manufactured by Mitsui Toatsu Chemical Co., Inc.). To 7 parts by weight of vinylidene fluoride resin (I), 25 parts by weight of a plasticizer TP-95 (manufactured by Thiokol) was added, and this and nitrile rubber (II) 93
Pour parts by weight into a kneader (150 ° C, 40 rpm),
At the time of kneading and homogenization, amine compound V1 (hexamethylenediamine) as a cross-linking agent for vinylidene fluoride resin and Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) as an acid acceptor were added and kneaded, and then homogenized again. After that, the temperature was raised to 180 ° C., and after the kneading torque and the rubber temperature became almost constant (30 minutes), the mixture was discharged. Next, 30 parts by weight of vinyl chloride resin (III) and 10 parts of carbon black Thermax MT (manufactured by Cancarb) were added to the above blend.
Pour parts by weight into a kneader (140 ° C, 40 rpm),
When the mixture is kneaded and becomes uniform, the temperature is raised (160 ° C),
After the kneading torque and rubber temperature became almost constant (10
Min) discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Comparative Example 3 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), VINICLON 3000H (manufactured by Mitsui Toatsu Chemical Co., Ltd.), and polymethylmethacrylate resin (IV), Parapet G (manufactured by Kuraray Co., Ltd.). . Plasticizer RS107 is added to 89 parts by weight of vinylidene fluoride resin (I).
(Asahi Denka Kogyo Co., Ltd.) 25 parts by weight was added, and 11 parts by weight of this and nitrile rubber (II) were kneader (160 ° C., 40 rp).
m), and when kneaded to be uniform, an amine compound tetraethylenepentamine as a crosslinking agent for vinylidene fluoride resin and Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) as an acid acceptor are added and kneaded. After the temperature became uniform again, the temperature was raised to 175 ° C., and the kneading torque and the rubber temperature became almost constant (35 minutes) before discharging. Next, 20 parts by weight of vinyl chloride resin (III), 2 parts by weight of polymethylmethacrylate resin (IV) and carbon black Thermax MT (manufactured by Cancarb) were added to the above blend.
0 parts by weight was put into a kneader (140 ° C., 40 rpm) and kneaded to raise the temperature when uniform (160 ° C.).
Then, it was discharged after the kneading torque and the rubber temperature became almost constant (10 minutes). In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Comparative Example 4 JSRN215SL (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as the nitrile rubber (II), and VINICLON 3000H (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used as the vinyl chloride resin (III). Parts, 35 parts by weight of vinyl chloride resin (III), 25 parts by weight of plasticizer TP-95 (manufactured by Thiokol) and carbon black Thermax MT (Canca).
20 parts by weight of kneader (140 ° C., 40 rp)
m), the mixture was kneaded, the temperature was raised (170 ° C.) when it became uniform, and the kneading torque and the rubber temperature were almost constant (15 minutes) before discharging. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

Comparative Example 5 KYNAR500W as vinylidene fluoride resin (I)
(Made by Penwalt) as nitrile rubber (II)
SRN220S (manufactured by Japan Synthetic Rubber Co., Ltd.) was used as vinyl chloride resin (III), Vinyklon 3000H (manufactured by Mitsui Toatsu Chemical Co., Inc.). Vinylidene fluoride resin (I)
Plasticizer RS107 (made by Asahi Denka Co., Ltd.) 25 in 40 parts by weight
Parts by weight, and 60 parts by weight of this and nitrile rubber (II),
10 parts by weight of vinyl chloride resin (III), carbon black T
10 parts by weight of hermax MT (manufactured by Cancarb) was put into a kneader (160 ° C., 40 rpm), and when kneading and homogenized, an amine compound tetraethylenepentamine as a crosslinking agent for vinylidene fluoride resin and an acid acceptor Kyowamag 150 (manufactured by Kyowa Chemical Co., Ltd.) was added as an agent and kneaded, and after the mixture became uniform again, the temperature was raised to 175 ° C. and the kneading torque and rubber temperature became almost constant (35 minutes). Discharged. In the following, a vulcanized rubber was prepared and evaluated in the same manner as in Example 1.

[0040]

The rubber composition of the present invention comprises a vinylidene fluoride resin (I), a nitrile rubber (II) and a vinyl chloride resin (I).
II) and / or polymethylmethacrylate resin (I
V), it has excellent roll processability and is easy to mold, and its cross-linked product (vulcanized product) also has excellent weather resistance, compression set resistance, gasoline permeation resistance and cold resistance. It has different characteristics.

Since the crosslinked product of the rubber composition of the present invention has such characteristics, it is used for oil-, chemical-, heat-, steam-, refrigerant- or weather-proof packing in transportation means such as automobiles, ships and aircraft. O-ring, hose,
For other sealing materials, diaphragms, valves and similar packing, rolling, sealing materials, diaphragms, valves, hoses, rolls, tubes, chemical resistant coatings and linings in chemical plants, food plant equipment and food equipment (household products) Similar packings, O-rings, hoses, seals, belts, diaphragms, valves, rolls, tubes, and similar packings, O-rings, hoses, seals, diaphragms, valves, tubes in nuclear plant equipment. In addition, similar packing in general industrial parts, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, PPC copier rolls. Ruburedo is suitable for application to such.

Further, specific uses include the following. (A) In automobiles, as seal 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-ring, oil seal, exhaust gas re-combustion device seal, bearing seal,
O-rings for gasoline pumps, seals for gasoline hoses,
There are stickers for car air conditioners. Hose applications include fuel hoses, EGR tubes, twin cab tubes, and hoses for refrigerators. Diaphragm applications include gasoline pump diaphragms and carburetor sensor diaphragms. Other uses include anti-vibration rubber (engine mounts,
(Exhaust part, etc.), hoses for reburning equipment, etc. (B) In the chemical industry, sealing applications include chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packing for sulfuric acid production equipment, pesticide sprayers, pesticide transfer pump seals, and gas. There are pipe seals, plating liquid seals, high temperature vacuum dryer packings, papermaking belt roller seals, fuel cell seals, wind tunnel joint seals, and the like. Examples of roll applications include rolls for trichlene resistance (for dyeing fibers). Applications of lining and coating include corrosion-resistant lining of alumite processing tank, coating of masking jig for plating, lining of gasoline tank, lining of wind tunnel, etc. Other uses include acid resistant hoses (for concentrated sulfuric acid), gas coromatography, packing for tube joints of pH meters, chlorine gas transfer hoses, oil resistant hoses, benzene, rainwater drain hoses for toluene storage tanks, expansion joints for flues ( Asbestos cloth coating) etc. (C) In general machinery, as sealing applications, hydraulics, lubrication machinery seals, bearing seals, dry copier seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seals (Vacuum) valve, etc.
There are stickers for automatic packaging machines. Other applications include dry copying machine belts, sulfurous acid gas in air, chlorine gas analysis pump diaphragms (pollution measuring instruments), snake pump linings, printing machine rolls, belts, pickling squeezing rolls, and the like. (D) In the aircraft field, there are jet engine valve stem seals, fuel supply hoses, gaskets and O-rings, rotating shaft seals, gaskets for hydraulic equipment, and fire wall seals. (E) In ship-related fields, there are screw propeller shaft stern seals, intake / exhaust valve stem seals for diesel engines, butterfly valve valve seals, butterfly valve shaft seals, and the like. (F) In food and medical fields, there are seals for plate heat exchangers, solenoid valve seals for vending machines, and drug stoppers. (G) In the electrical field, there are Shinkansen insulating oil caps, liquid sealing transformer venting seals, pickling squeeze rolls, and so on. (H) In the aircraft industry, there are jet engine valve stem seals, fuel supply hoses, gaskets and O-rings, rotating shaft seals, gaskets for hydraulic equipment, and fire wall seals. (I) In ship-related fields, there are screw propeller shaft stern seals, intake / exhaust valve stem seals for diesel engines, butterfly valve valve seals, butterfly valve shaft seals, and the like. (G) In food and medical fields, there are seals for plate heat exchangers, solenoid valve seals for vending machines, and drug stoppers. (E) In the electrical field, it can be used for insulating oil caps for Shinkansen, venting seals for liquid-sealed transformers, and jackets for oil well cables.

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

Claims (2)

[Claims] 1. Vinylidene fluoride resin (I) 10-70
100 parts by weight of a composition containing 90% to 30% by weight of nitrile rubber (II) and vinyl chloride resin (III)
And / or polymethylmethacrylate resin (IV) 5
A rubber composition containing about 50 parts by weight,
A rubber composition, wherein (I) is cross-linked while imparting shear deformation during blending of (I) and (II). 2. The rubber composition according to claim 1, wherein the vinylidene fluoride resin (I) is dispersed in a particle size of 5 μm or less.