JP2003155409A - Rubber composition for vulcanization and its vulcanized rubber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber composition for vulcanization having improved heat resistance, and its vulcanized product. SOLUTION: The rubber composition for vulcanization comprises (a) an epihalohydrin based rubber, (b) an organic tin compound, (c) an acid acceptor composed of a metal compound and/or an inorganic microporous crystal, and (d) a vulcanizing agent, and the vulcanized product is obtained from the composition. A preferred organic tin compound is at least one organic tin compound selected from the group consisting of an organic tin maleate compound, an organic tin carboxylate compound, and an organic tin mercapto compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for vulcanization having an epihalohydrin-based rubber as a base and having improved heat resistance, a vulcanized rubber material obtained by vulcanizing the composition, and a material for the same. It relates to a vulcanized rubber laminate used.

[0002]

2. Description of the Related Art Epichlorohydrin rubber materials are widely used as fuel hoses, air hoses, and tube materials by taking advantage of their heat resistance, oil resistance, ozone resistance and the like. However, with the recent rise in exhaust gas regulations and energy-saving measures, temperature rises in engine rooms due to engine performance improvements and compactness, and maintenance-free automobile parts, demand for improved heat resistance of rubber materials is increasing year by year. It's getting tougher.

Conventionally, polyamines, thioureas, mercaptotriazines, quinoxalines and the like have been known as vulcanizing agents for epichlorohydrin type rubbers.

Polyamines generally have poor heat resistance. Thiourea has relatively good heat resistance when a lead compound is used as the acid acceptor, but there is a problem of toxicity of the lead compound used as the acid acceptor. On the other hand, mercaptotriazines, quinoxalines and the like have a problem that the vulcanizates obtained show excellent heat resistance in the long term, but the strength decrease at the initial stage of heat resistance is relatively large.

Conventionally, regarding the organic tin compound, some inventions have been disclosed in which the organic tin compound is added to the vinyl chloride resin for the purpose of preventing thermal decomposition during the molding process (Japanese Patent Publication No. 45- 39176, Japanese Patent Publication Sho 49-112
58, Japanese Patent Publication No. 53-20060). However, these do not relate to improvement of heat resistance of the epichlorohydrin-based rubber vulcanizing composition as in the present invention.

Japanese Patent Publication No. 50-26571 discloses an invention in which a specific organic tin carboxylic acid is added for the purpose of improving moldability such as roll adhesion of epichlorohydrin type rubber. However, the composition of the present invention is different from the vulcanizing composition of the present invention, and there is no description or suggestion of the improvement of heat resistance which is the effect of the present invention.

Japanese Patent Publication No. 47-8375 discloses an invention for improving roll processability by blending a tin salt of an aliphatic carboxylic acid having 10 to 18 carbon atoms with epichlorohydrin type rubber. However, there is no suggestion on the improvement of heat resistance which is the effect of the present invention.

Further, as a fuel hose which is particularly required to have sour gasoline resistance and gasoline permeation resistance, a layer made of fluororubber or fluororesin material having excellent fuel impermeability is disposed on the innermost layer, and the outer surface thereof is provided. A multilayer hose in which a layer made of an epichlorohydrin-based rubber material is arranged as a layer directly laminated is preferably used. When making a laminated hose as described above, 1,8-diazabicyclo (5,4,0) undecene-7 was added to epichlorohydrin-based rubber material to improve the adhesive strength.
The method of blending such an adhesion-imparting agent is usually used. However, although the addition of the adhesion-imparting agent improves the adhesion, it may adversely affect the heat resistance.

[0009]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide an epihalohydrin rubber composition having improved heat resistance, a vulcanized rubber material and a vulcanized rubber laminate. Is.

[0010]

As a result of various studies, the present inventors have found that the above object can be achieved by compounding a specific organotin compound with epihalohydrin rubber, Is completed.

That is, the rubber composition for vulcanization according to the present invention comprises (a) an epihalohydrin rubber, (b) an organic tin compound, (c) an acid acceptor comprising a metal compound and / or an inorganic microporous crystal, and (D) It contains a vulcanizing agent.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the composition of the present invention, the epihalohydrin-based rubber (a) is a homopolymer of epihalohydrin or another epoxide copolymerizable with epihalohydrin such as ethylene oxide, propylene oxide or allyl glycidyl ether. A polymer.
Illustrating these, epichlorohydrin homopolymer,
Epibromhydrin homopolymer, epichlorohydrin-
Ethylene oxide copolymer, epibromhydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epibromhydrin-propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, Epibromhydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer, epibromhydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary Examples thereof include copolymers. Preferably, epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and more preferably epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether. It is a terpolymer.

In the case of a copolymer, the copolymerization ratio is, for example, 5 mol% to 95 mol% of epichlorohydrin, preferably 10 mol% to 75 mol%, more preferably 10 to 65 mol%, and 5 mol% of ethylene oxide.
~ 95 mol%, preferably 25 mol% to 90 mol
%, More preferably 35 mol% to 90 mol%, allyl glycidyl ether 0 mol% to 10 mol%, preferably 1 mol% to 8 mol%, more preferably 1
mol% to 7 mol%. The molecular weight of these homopolymers or copolymers is not particularly limited, but is usually about ML _{1 + 4} (100 ° C.) = 30 to 150 in terms of Mooney viscosity.

The organotin compound (b) referred to in the present invention may be one generally used as a stabilizer for vinyl chloride resins. As an example, for example, the following general formula (1)
Examples of the organic tin maleate-based compounds, organic tin carboxylate-based compounds, and organic tin mercapto-based compounds represented by (3) to (3).

[0015]

[Chemical 1] [In the formula, R represents a linear or branched alkyl group having 1 to 18 carbon atoms or an alkoxycarbonyl lower alkyl group. R'represents a linear or branched alkyl group having 1 to 36 carbon atoms, an alkenyl group, an aralkyl group, a cycloalkyl group or an alkoxy lower alkyl group. m is 1
The integer of 3 and x represent the integer of 1-10. ]

[0016]

[Chemical 2] [In the formula, R represents a linear or branched alkyl group having 1 to 18 carbon atoms or an alkoxycarbonyl lower alkyl group. R'represents a linear or branched alkyl group having 1 to 36 carbon atoms, an alkenyl group, an aralkyl group, a cycloalkyl group or an alkoxy lower alkyl group. m is 1
Represents an integer of 3. ]

[0017]

[Chemical 3] [In the formula, R represents a sulfur atom, a linear or branched alkyl group having 1 to 18 carbon atoms or an alkoxycarbonyl lower alkyl group having 1 to 20 carbon atoms. R'has 1 to 3 carbon atoms
6 straight chain or branched alkyl groups, alkenyl groups,
It represents an aralkyl group, a cycloalkyl group or an alkoxy lower alkyl group. M represents an integer of 1 to 3, y represents an integer of 1 to 4, and x represents an integer of 1 to 10. ]

The R group is, for example, a methyl group, a butyl group, an octyl group, a dodecyl group, a methoxycarbonylethyl group, an ethoxycarbonylethyl group or a butoxycarbonylethyl group, and the R'group is, for example, an ethyl group,
Butyl group, heptyl group, octyl group, isooctyl group,
Examples thereof include 2-ethylhexyl group, nonyl group, lauryl group, stearyl group, myristyl group, cetyl group, behenyl group, oleyl group, benzyl group, cyclohexyl group and methoxybutyl group.

Examples of the organotin maleate compound represented by the general formula (1) include monooctyltin tris (2-ethylhexylmalate), dioctyltin bis (2-ethylhexylmalate), trioctyltin 2-ethylhexylmalate. , Monooctyltin tris (ethylmalate), dioctyltin bis (ethylmalate), trioctyltin ethylmalate, monooctyltin tris (butylmalate), dioctyltin bis (butylmalate), trioctyltin butylmalate, monooctyltin tris (benzylmaleate), dioctyl Tin bis (benzyl malate), trioctyl tin benzyl malate, monooctyl tin tris (methyl malate), dioctyl tin bis (methyl malate), trioctyl tin methyl malate,
Examples thereof include monooctyl tin tris (cyclohexyl maleate), dioctyl tin bis (cyclohexyl maleate), trioctyl tin cyclohexyl maleate, dioctyl tin malate polymer, dibutyl tin malate polymer, dimethyl tin malate polymer. Examples of the organic tin carboxylate compound represented by the general formula (2) include dibutyltin dilaurate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin distearate,
Dimethyltin distearate, dimethyltin dilaurate,
Examples thereof include didodecyl tin dilaurate and didodecyl tin distearate.

Examples of the organotin mercapto compound represented by the general formula (3) include dimethyltin bis (isooctyl mercaptoacetate), dimethyltin bis (2-ethylhexyl mercaptoacetate), monomethyltin tris (isooctyl mercaptoacetate). , Monomethyltin tris (2-ethylhexyl mercaptoacetate),
Dioctyl tin bis (isooctyl mercaptoacetate), dioctyl tin bis (2-ethylhexyl mercapto acetate), monooctyl tin tris (isooctyl mercapto acetate), monooctyl tin tris (2-
Ethylhexyl mercaptoacetate), dioctyltin bis (C ₁₀ -C ₁₆ alkyl mercaptoacetate), monooctyltintris C ₁₀ -C ₁₆ alkyl mercaptoacetate), dilauryl tin bis (isooctyl mercaptoacetate), dilauryl tin bis (2-ethylhexyl Mercaptoacetate), monolauryltin tris (isooctylmercaptoacetate), monolauryltin tris (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptoacetate), monobutyltin tris (isooctylmercaptoacetate), monobutyltin tris (2-ethylhexyl mercaptoacetate), dibutyltin bis (C ₁₀ -C ₁₆
Alkyl mercaptoacetate), monobutyltin tris C ₁₀ -C ₁₆ alkyl mercaptoacetate), dioctyltin acetate polymers, dioctyltin propionate polymers, and the like.

The amount of the organotin compound used in the present invention is 0. 100 parts by weight based on 100 parts by weight of the epihalohydrin rubber.
The amount is 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight. If the amount is less than this range, the heat resistance improving effect is small, and if it exceeds this range, bleeding or blooming of the organotin compound may occur.

The metal compound used in the present invention and /
Alternatively, as the acid acceptor (c) consisting of an inorganic microporous crystal, there are group II of the periodic table (groups 2 and 12).
Metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, Group IV (groups 4 and 14) metal oxides, basic carbonates , Basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates and the like.

Specific examples of the acid acceptor include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quick lime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate and phthalic acid. Calcium, calcium phosphite, zinc white, tin oxide, litharge, red lead, white lead, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, Examples thereof include basic lead sulfite and tribasic lead sulfate.

Inorganic microporous crystals are preferred as acid acceptors. The inorganic microporous crystal is a crystalline porous material, which can be clearly distinguished from an amorphous porous material such as silica gel or alumina. Examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like. A synthetic hydrotalcite is mentioned as a particularly preferable acid acceptor.

Zeolites include natural zeolites, A
-Type, X-type and Y-type synthetic zeolites, sodalites, natural or synthetic mordenite, various zeolites such as ZSM-5 and metal substitution products thereof, and these may be used alone or in combination of two or more kinds. May be. The metal of the metal substitute is often sodium. As the zeolites, those having a large acid accepting capacity are preferable,
Type A zeolite is particularly preferred.

The synthetic hydrotalcite has the following general formula (4)

[Chemical 4] [Where x and y are real numbers from 0 to 10, and x + y is from 1 to 1]
0 and z are real numbers of 1 to 5, and w is a real number of 0 to 10]. As an example of the hydrotalcites represented by the general formula (4), Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3.5H ₂ O Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O Mg ₅ Al ₂ (OH) ₁₄ CO ₃ · 4H ₂ O Mg ₃ Al ₂ (OH) ₁₀ CO _{3 · 1.7H 2 O Mg 3 ZnAl} 2 (OH) 12 CO 3 · wH 2 O Mg 3 ZnAl 2 (OH) may be mentioned 12 CO ₃ and the like.

The compounding amount of the acid acceptor is 0.2 to 50 parts by weight, for example 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight, relative to 100 parts by weight of the epihalohydrin rubber. If the blending amount is less than this range, the crosslinking will be insufficient. On the other hand, if the blending amount exceeds this range, the vulcanized product becomes too rigid and the physical properties normally expected as an epihalohydrin rubber vulcanized product cannot be obtained.

The vulcanizing agent (d) used in the present invention is not particularly limited as long as it can crosslink the epihalohydrin type rubber, but known vulcanizing agents utilizing the reactivity of chlorine atom, that is, polyamines, Thioureas, thiadiazoles, mercaptotriazines, quinoxalines and the like, and known vulcanizing agents utilizing the reactivity of the side chain double bond, for example, organic oxides, sulfur, morpholine polysulfides, thiuram polysulfides and the like. Are used as appropriate.

Examples of the vulcanizing agent include polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N'-dicinnamylidene-1,6. -Hexanediamine, ethylenediaminecarbamate, hexamethylenediaminecarbamate and the like, thioureas, 2-mercaptoimidazoline, 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea and the like, as thiadiazoles. Is 2,5-dimercapto-1,3,4-thiadiazole-5,2-mercapto-1,3,4-thiadiazole-5.
-Thiobenzoate and the like, and examples of mercaptotriazines include 2,4,6-trimercapto-1,3.
5-triazine, 1-hexylamino-3,5-dimercaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,
5-dimercaptotriazine, 1-dibutylamino-
3,5-dimercaptotriazine, 2-anilino-4,
6-dimercaptotriazine, 1-phenylamino-
3,5-dimercaptotriazine and the like can be mentioned. Examples of the quinoxalines include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-
Methylquinoxaline-2,3-dithiocarbonate,
5,8-dimethylquinoxaline-2,3-dithiocarbonate and the like can be mentioned, and as the organic peroxide, tert-
Butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, tert-butyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
Examples thereof include benzoyl peroxide and tert-butyl peroxybenzoate, examples of morpholine polysulfides include morpholine disulfide, examples of thiuram polysulfides include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide,
Tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide and the like can be mentioned.

The compounding amount of the vulcanizing agent is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the epihalohydrin rubber. If the blending amount is less than this range, the crosslinking will be insufficient. On the other hand, if the blending amount exceeds this range, the vulcanized product becomes too rigid and the physical properties normally expected as an epihalohydrin rubber vulcanized product cannot be obtained. Particularly preferable vulcanizing agents include 2-mercaptoimidazoline and 6-methylquinoxaline-2,3-dithiocarbonate. The vulcanizing agents may be used alone or in combination of two or more.

DB used as an adhesion promoter in the present invention
U salt means DBU-carbonate, DBU-stearate,
DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-
2-naphthoate, DBU-phenol resin salt, DBU
2-mercaptobenzothiazole salt, DBU-2-mercaptobenzimidazole salt and the like.

DB used as an adhesion promoter in the present invention
N salt means DBN-carbonate, DBN-stearate,
DBN-2-ethylhexylate, DBN-benzoate, DBN-salicylate, DBN-3-hydroxy-
2-naphthoate, DBN-phenol resin salt, DBN
2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like.

The organic phosphonium salt used as an adhesion promoter in the present invention is a quaternary phosphonium salt containing an alkyl group having 1 to 20 carbon atoms or a quaternary phosphonium salt containing an aromatic substituent. Specific examples include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tributyl (methoxypropyl) phosphonium chloride, benzyltriphenylphosphonium chloride, benzyltrioctylphosphonium chloride, triphenylbenzylphosphonium chloride,
Examples thereof include tetraalkylphosphonium benzotriazole.

The compounding amount of the adhesion-imparting agent is 0 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the epihalohydrin rubber. When the amount is in this range, a strong adhesive force can be obtained. If the compounding amount exceeds this range, the scorch of the epihalohydrin rubber will be accelerated, which may cause problems in processability and the like.

Further, known accelerators (that is, vulcanization accelerators), retarders and the like which are usually used together with these vulcanizing agents can be used as they are in the rubber composition for vulcanization of the present invention. Examples of these vulcanization accelerators include sulfur, thiuram sulfides, morpholine sulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts,
Examples thereof include quaternary phosphonium salts, polyfunctional vinyl compounds, mercaptobenzothiazoles, sulfenamides, and dimethiocarbamates. Examples of the retarder include N-cyclohexanethiophthalimide and the like. The amount of the accelerator or retarder compounded is 0 to 10 parts by weight, for example 0.1 to 5 parts by weight, based on 100 parts by weight of the epihalohydrin rubber.

The composition and cross-linked product of the present invention may be added to the compounding agents other than the above, for example, as long as the effects of the present invention are not impaired.
A lubricant, an antioxidant, an antioxidant, a filler, a reinforcing agent, a plasticizer, a processing aid, a flame retardant, a foaming aid, a conductive agent, an antistatic agent, etc. can be optionally blended. Further, it is also possible to carry out blending of rubber, resin and the like which are usually carried out in the technical field within a range in which the characteristics of the present invention are not lost.

To produce the rubber composition for vulcanization according to the present invention, any means conventionally used in the field of polymer processing such as mixing rolls, Banbury mixers and various kneaders can be used. The vulcanized rubber material of the present invention is usually obtained by adding the vulcanized rubber composition of the present invention to 1
It is obtained by heating to 00 to 200 ° C. The vulcanization time varies depending on the temperature, but is usually 0.5 to 300 minutes. As the vulcanization molding method, any method such as compression molding with a mold, injection molding, steam can, air bath, heating with infrared rays or microwaves can be used.

The present invention also provides a vulcanized rubber laminate in which a layer made of the epihalohydrin rubber vulcanizing rubber composition and a layer made of unvulcanized fluororubber or fluororesin are vulcanized and adhered. It is a thing.

The unvulcanized fluororubber used in the laminate of the present invention is preferably a highly fluorinated elastic copolymer such as vinylidene fluoride and another copolymerizable fluorine-containing olefin. You can list coalescence. Examples of the fluorine-containing olefin include hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and the like. At least one species is used as the copolymerization component.

Examples of preferable unvulcanized fluororubber include
Vinylidene fluoride-hexafluoropropene binary copolymer, vinylidene fluoride-hexafluoropropene-tetrafluoroethylene ternary copolymer, vinylidene fluoride-trifluorochloroethylene binary copolymer, vinylidene fluoride-perfluoro Examples thereof include vinyl ether-tetrafluoroethylene terpolymer, tetrafluoroethylene-propylene binary copolymer, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer and the like.

The fluororesin used in the laminate of the present invention includes vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer, ethylene-tetrafluoroethylene binary copolymer and hexafluoropropene-tetrafluoro. Ethylene binary copolymer, polyvinylidene fluoride, polytetrafluoroethylene and the like can be mentioned, preferably vinylidene fluoride-
Hexafluoropropene-tetrafluoroethylene terpolymer (THV) is exemplified.

The unvulcanized fluororubber includes various known compounding agents such as vulcanizing agents, vulcanization accelerators and acid acceptors selected from polyols, polyamines, organic peroxides, etc. depending on the purpose of use. A metal compound as an agent, a filler, a reinforcing agent, a plasticizer, a stabilizer, a flame retardant, a coloring agent, a processing aid and the like may be blended. The compounding ratio of the compounding agent is not limited, and an unvulcanized fluororubber composition containing the compounding agent in an arbitrary ratio is prepared according to the purpose of use.

The method for producing a laminate in the present invention is a coextrusion molding method or a sequential extrusion molding method, which comprises a layer made of an epichlorohydrin-based rubber vulcanizing composition and a layer made of an unvulcanized fluororubber or a fluororesin. A method of heat-vulcanizing or heat-curing the obtained laminate,
There is a method in which a layer made of an epichlorohydrin-based rubber vulcanizing composition and a layer made of unvulcanized fluororubber or a fluororesin are laminated at the same time by heat vulcanization molding using a mold.
Alternatively, a method in which one layer of the rubber composition for vulcanization is heated and vulcanized weakly so as not to lose its shape, and then the other layer is laminated to sufficiently heat vulcanize and mold both of them can be employed. As a method of heat-vulcanizing and molding the laminate obtained by the above-mentioned extrusion molding, there is molding with a die, and as the method of heat-vulcanizing, a steam can, an air bath, an infrared ray, a microwave, and a lead-containing material are used. A known method using vulcanization or the like can be appropriately adopted. The vulcanization temperature is usually 100 to 200 ° C., and the heating time is selected in the range of 0.5 to 300 minutes, although it depends on the temperature.

In the case where the laminate of the present invention is applied to a fuel oil type hose, a layer made of fluororubber or a fluororesin is arranged as an inner layer and a layer made of epichlorohydrin rubber is arranged as an outer layer. A two-layer hose consisting of two layers, a three-layer hose consisting of a braid material and a braid reinforcement layer outside the two-layer hose, and a four-layer hose consisting of an outermost layer of rubber outside the three-layer hose. It can be mentioned as a representative. As the braid material used for the above three-layer hose or four-layer hose, polyester fiber, polyamide fiber,
Examples include braided glass fibers, vinylon fibers, cotton and the like. The material of the outermost layer of the four-layer hose is
In addition to epichlorohydrin rubber, synthetic rubbers such as acrylic rubber, ethylene-acrylic rubber, chloroprene rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, etc. that have aging resistance, weather resistance, oil resistance, etc. are usually used. . Further, when the inner layer is a fluororesin layer alone and the flexibility is poor and the adhesiveness with the joining vip is weak, an innermost layer made of rubber having rubber elasticity and excellent fuel oil property may be disposed inside thereof. As the rubber of the innermost layer, epichlorohydrin rubber, acrylonitrile-butadiene rubber,
Examples thereof include blends of acrylonitrile-butadiene rubber and polyvinyl chloride, hydrogenated acrylonitrile-butadiene rubber, and fluororubber.

The vulcanized product of the present invention can be widely applied to the fields where epihalohydrin rubber is usually used.
For example, it is useful as a rubber material for various fuel / air laminated hoses, tubes, belts, diaphragms, seals, etc. for automobiles, etc., and a rubber material for general industrial equipment / devices.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

[Examples] Examples 1 to 10 and Comparative Examples 1 to 4 The materials shown in Tables 1, 3, and 5 below were kneaded with a kneader and an open roll to prepare unvulcanized rubber sheets.
Using the unvulcanized rubber sheet obtained, JIS K6300
The Mooney scorch test specified in 1. was conducted. The unvulcanized rubber sheet obtained in the same manner was press-vulcanized at 170 ° C. for 15 minutes to obtain a primary vulcanized product having a thickness of 2 mm. Furthermore, this
A secondary vulcanizate was obtained by heating in an oven at 150 ° C for 2 hours. Tensile test (initial physical properties) using the obtained secondary vulcanizate
And the heat resistance was evaluated. JIS for each evaluation test
It carried out according to the method described in K6251 and JIS K6257.

The compression set test was conducted as follows. The obtained unvulcanized rubber sheet was press-vulcanized at 170 ° C. for 20 minutes using a mold for producing a test piece to obtain a primary vulcanized cylindrical test piece having a diameter of about 29 mm and a height of about 12.5 mm. It was Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary vulcanized product. Using the same secondary vulcanizate, JI
The test was performed according to the method described in SK 6262.

A test piece for adhesion test was prepared as follows. Each material of the fluororubber composition shown in Table 7 was kneaded with a kneader and an open roll to obtain an unvulcanized fluororubber sheet. The unvulcanized epihalohydrin-based rubber sheet having the composition shown in Table 5 and the unvulcanized fluororubber sheet are overlaid, and a mold having a thickness of 3 mm is used, and the temperature is 160 ° C. and 20 to 25 k.
The pressure was applied at g / cm ² for 30 minutes to obtain a vulcanized rubber laminate having a thickness of about 3 mm. Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary vulcanized rubber laminate. The above laminate was cut into a strip of 2.5 cm × 10 cm to prepare a test piece for adhesion test.

The adhesion test was carried out in accordance with the method described in JIS K 6256 (adhesion test method for vulcanized rubber), and a peeling test was carried out at 25 ° C. at a tensile speed of 50 mm / min.

Examples and comparisons obtained by each test method
The test results of the examples are shown in Tables 2, 4 and 6. In each table, Vm is the maximum
Low viscosity, t₅Is a JIS K6300 Mooney coach
Mooney scoring time as specified in the exam, M₁₀₀Is JIS
  K6251 tensile test at 100% elongation specified in the test
Tensile stress, M₃₀₀For the JIS K6251 tensile test
Tensile stress at 300% elongation, T_bIs JIS K6
251 Tensile Test Tensile strength specified in the test, E_bIs JIS
  K6251 Tensile test Elongation determined by the test, H _sIs JI
Means the hardness specified in the hardness test of SK6253
To do.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

[Table 6]

[0058]

[Table 7]

In the present invention, good heat resistance means that the tensile strength Tb after the heat resistance test is large. In the above table, it can be seen that the heat resistance is improved in each example as compared with the comparative example in which the organotin compound is not added.

Therefore, according to the present invention, it is possible to provide a vulcanizing rubber composition having improved heat resistance in an epihalohydrin rubber, a vulcanized rubber material thereof and a vulcanized rubber laminate.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C08K 5/3465 C08K 5/405 5/405 5/49 5/49 5/57 5/57 7/24 7 / 24 B60K 15/02 Z (72) Inventor Koichi Hattori 1-10-8 Edobori, Nishi-ku, Osaka City, Osaka Prefecture Daiso Corporation (72) Inventor Yoshizo Misumi 1-10-8 Edobori, Nishi-ku, Osaka City, Osaka Prefecture Daiso Co., Ltd. F-term (reference) 3D038 CA00 CC17 4F100 AA01A AA04A AC10A AH03A AH04A AH08A AK17B AL05A AN02A AN02B BA02 CA03 EJ06A EJ06B GB32 JJ0337 007 DE047 DE047 DE0157 DE087 DE087 DE087 DE087 DE087 DE097 DE097 DE097 DE097 DE097 EN038 EN048 EN098 EU138 EU139 EV048 EV088 EV128 EV168 EV328 EW179 EZ016 EZ046 EZ066 FD148 FD207 FD209 GF00 GJ02 GM00 GM01 GN00

Claims (9)

[Claims] 1. An (a) epihalohydrin rubber, (b)
A vulcanizing rubber composition comprising an organic tin compound, (c) an acid acceptor comprising a metal compound and / or an inorganic microporous crystal, and (d) a vulcanizing agent. 2. The organotin compound is at least one organotin compound selected from the group consisting of organotin maleate compounds, organotin carboxylate compounds and organotin mercapto compounds. The rubber composition for vulcanization according to. 3. The vulcanizing rubber composition according to claim 1, wherein the acid acceptor is an inorganic microporous crystal. 4. The rubber composition for vulcanization according to claim 1, wherein the acid acceptor is synthetic hydrotalcite. 5. The rubber composition for vulcanization according to claim 1, wherein the vulcanizing agent is a thiourea compound. 6. The vulcanizing rubber composition according to claim 1, wherein the vulcanizing agent is a quinoxaline. 7. (e) 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU)
Salt, 1,5-diazabicyclo (4,3,0) nonene-5
7. The vulcanizing rubber material according to claim 1, wherein the rubber material for vulcanization comprises at least one adhesion promoter selected from the group consisting of a salt (hereinafter abbreviated as DBN) and an organic phosphonium salt. 8. A vulcanized rubber material obtained by vulcanizing the rubber composition for vulcanization according to claim 1. 9. A vulcanized rubber laminate obtained by vulcanizing and adhering a layer made of the rubber composition for vulcanization according to any one of claims 1 to 8 and a layer made of unvulcanized fluororubber or fluororesin. body.