JP2001107013A - Vulcanizable adhesion composition and laminated product and laminated hose using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide vulcanized rubber laminated products or laminated hoses which have a layer of a fluororubber or a fluoroplastic and a layer of an epichlorohydrin based rubber which have been firmly bonded to each other. SOLUTION: In an epichlorohydrin based rubber vulcanizable adhesion composition comprising an epichlorohydrin based rubber, at least one acid acceptor selected from metallic compounds and inorganic microporous crystals, a vulcanizing agent, and an adhesion imparting agent, the vulcanizable adhesion composition contains, as the adhesion imparting agent, 0.1-5 pts.wt., based on 100 pts.wt. epichlorohydrin based rubber, compound represented by formula [I] or [II] (wherein R1 and R2 in formula [I] are each H, amino, alkyl, alkylamino, dialkyl- amino, cycloalkylamino, dicycloalkylamino, arylamino or aralkyl; and R3 in formula [II] is amino, alkyl, alkylamino, dialkylamino, cycloalkylamino, dicycloalkylamino, arylamino or aralkyl) or its weak acid salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a layer made of epichlorohydrin rubber excellent in heat resistance, oil resistance, cold resistance, weather resistance, ozone resistance and abrasion resistance and a layer made of fluoro rubber or fluoro resin. Or a laminated hose, such as a fuel oil hose for a vehicle, and an epichlorohydrin-based rubber vulcanizing / bonding composition used for producing such a laminated body or a laminated hose It is about.

[0002]

2. Description of the Related Art Conventionally, in hoses used for fuel oils such as gasoline, especially when sour gasoline resistance and gasoline permeation resistance are required, a fluorine rubber vulcanization excellent in fuel impermeability is formed in the innermost layer. Multilayer hoses in which a layer made of a product is arranged and a layer made of an epichlorohydrin rubber vulcanizate is arranged on a layer directly laminated thereon have been suitably used. However, due to the recent implementation of emission control measures and energy saving measures, the temperature of the engine room has increased,
Exhaust gas recycling, gasoline transpiration regulations, etc. have been implemented, and as a rubber material for fuel oil hoses, it also has heat resistance, weather resistance, cold resistance, resistance to rancidity, resistance to alcohol-containing gasoline, and resistance to gasoline permeation. In order to cope with the tightening of regulations, it has been desired to use a fluororesin which is more excellent in fuel impermeability instead of a fluororubber vulcanizate. In the case of a multi-layer rubber hose, adhesion between different types of rubber layers is the most important issue. It is generally known that fluorocarbon rubber or fluorocarbon resin and epichlorohydrin rubber have poor adhesiveness. For this reason, it is common practice to incorporate certain additives such as 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU) into the epichlorohydrin rubber. (Japanese Patent Laid-Open No. 9-858)
No. 98, JP-A-10-264314), there is a demand for further improvement in adhesiveness.

Japanese Patent Application Laid-Open No. 54-158481 discloses an adhesive in which a nitrogen-containing organic compound such as DBU is added to both a composition for vulcanizing a fluororubber and a composition for vulcanizing an epichlorohydrin rubber. A method has been proposed. However, the invention is not a technique applicable to a fluororesin as in the present invention. In fact, such compounds cannot be added to fluororesins. The adhesive strength of the invention is 7.7 kg / in.
ch, and the fluorocarbon rubber to which the adherend is relatively easily adhered has not yet reached a practical level. JP-A-62-282928 discloses that at least one of a fluororubber layer and an unvulcanized rubber layer such as epichlorohydrin rubber is provided with DBU or DBN (1,5-diazabicyclo (4,3,0)). A bonding method in which nonene-5) is added has been proposed. However, even in this method, even if the adherend is made of fluororubber which is relatively easy to adhere, the adhesive strength is 1.6 kg /.
cm (4 kg / inch), which is not at a practical level. Further, there is no teaching about adhesion to a fluororesin.

[0004]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a vulcanized rubber laminate in which a layer made of fluororubber or a fluororesin and a layer made of epichlorohydrin rubber are firmly bonded. To provide an epichlorohydrin-based rubber vulcanization adhesive composition having improved vulcanization properties, which is used for producing such a laminate or a laminated hose. Is to do.

[0005]

Means for Solving the Problems In order to solve the above-mentioned object, the present inventors have made intensive studies and found that (a) epichlorohydrin rubber, (b) a metal compound or an inorganic microporous crystal. An epichlorohydrin rubber vulcanization adhesive composition comprising at least one acid acceptor selected from the group consisting of (c) a vulcanizing agent and (d) an adhesion-imparting agent; Using a composition prepared by compounding a required amount of a compound, a layer made of the same composition is heated and vulcanized and bonded to a layer made of an unvulcanized fluororubber or a fluororesin, thereby providing excellent fuel impermeability. The present inventors have found that a strong vulcanization adhesive strength of an epichlorohydrin rubber layer to a fluororubber or a fluororesin layer can be obtained, and have completed the present invention.

That is, the present invention provides (a) an epichlorohydrin rubber, (b) at least one acid acceptor selected from a metal compound or an inorganic microporous crystal, (c) a vulcanizing agent and (d) An epichlorohydrin rubber vulcanization adhesive composition comprising an adhesion promoter,
(D) As the adhesion promoter, the following general formula [I] or [I
A vulcanizing adhesive composition comprising the compound represented by formula (I) or a weak acid salt thereof in an amount of 0.1 to 5 parts by weight per 100 parts by weight of epichlorohydrin rubber.

[0007]

Embedded image

Embedded image (In the formula [I], R ₁ and R ₂ may be the same or different from each other and represent a hydrogen atom, an amino group, an alkyl group, an alkylamino group, a dialkylamino group, a cycloalkylamino group, And a group selected from the group consisting of an alkylamino group, an arylamino group and an aralkyl group, and in the formula [II], R ₃ represents an amino group,
Alkyl group, alkylamino group, dialkylamino group,
Cycloalkylamino group, dicycloalkylamino group,
It is a group selected from the group consisting of an arylamino group and an aralkyl group. The epichlorohydrin-based rubber which constitutes the main constituent of the vulcanized adhesive composition according to the present invention is an epichlorohydrin homopolymer or another epoxide copolymerizable with epichlorohydrin, for example, ethylene oxide, propylene oxide, It is a copolymer with allyl glycidyl ether and the like. Examples of these copolymers include an epichlorohydrin-ethylene oxide binary copolymer, an epichlorohydrin-propylene oxide binary copolymer, and an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. And terpolymers of epichlorohydrin-propylene oxide-allyl glycidyl ether and quaternary copolymers of epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether.
In these copolymers, at least 10 epichlorohydrin components are required from the viewpoint of securing a practical vulcanization rate.
Preferably, it is contained in a mole%.

The preferred molecular weight of these homopolymers or copolymers is usually ML _{1 + 4 in} terms of Mooney viscosity.
(100 ° C.) = About 30 to 150.

The general formula [I] used as an adhesion promoter
Examples of the compound represented by are: 1,5-diazabicyclo [4,3,0] nonene-5 7,8,8-trimethyl-1,5-diazabicyclo [4,3,0] nonene-5 and the like. No. Preferably, 1,5-diazabicyclo [4,3,0] nonene-5 or a weak acid salt thereof is used.

Examples of the compound represented by the general formula [II] include 6-methylbutylamino-1,8-diazabicyclo [5,4,0] undecene-7 6-methyloctylamino-1,8-diazabicyclo [5,4,0] undecene-7 6-dibutylamino-1,8-diazabicyclo [5,
4,0] undecene-7 6-butylbenzylamino-1,8-diazabicyclo [5,4,0] undecene-7 6-dihexylamino-1,8-diazabicyclo [5,0
4,0] undecene-7 9-methyl-1,8-diazabicyclo [5,4,0] undecene-7 and the like.

Preferably, 6-dibutylamino-1,8-
Diazabicyclo [5,4,0] undecene-7 is used.

The compound represented by the above general formula [I] or [II] may be used per se, but from the viewpoint of handling, can be used as the following weak acid salts. Examples of these weak acid salts include carbonate, stearate, 2-ethylhexylate, benzoate, carboxylate, sorbate, salicylate, naphthoate, and 3-hydroxy-2.
-A weak acid salt selected from the group consisting of naphthoic acid salts, phenolic resin salts, 2-mercaptobenzothiazole salts and 2-mercaptobenzimidazole salts.

Further, the compound represented by the general formula [I] or [II] can be used by mixing it with an inorganic powder such as calcium carbonate, clay and silica.

The ratio of the compound represented by the general formula [I] or [II] to the above weak acid is not particularly limited.

The amount of the adhesion promoter is based on 100 parts by weight of the epichlorohydrin rubber and is represented by the general formula [I] or [I].
It is usually 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on the compound represented by formula [I]. If the amount of the adhesive agent is too small, the vulcanization rate of the epichlorohydrin rubber decreases, and it becomes difficult to obtain a strong adhesive force.If the amount is too large, the scorch of the epichlorohydrin rubber layer becomes fast. Further, there is a tendency that the epichlorohydrin-based rubber layer becomes too rigid so that expected physical properties cannot be obtained.

The metal compound used as the acid acceptor includes oxides, hydroxides, silicates, phosphites, borates, carboxylates, and metals belonging to Group IVa of the Periodic Table. , A basic phosphite, a basic carbonate, a basic carboxylate, a basic sulfate, a tribasic sulfate, or the like. Specific examples of the metal compound include magnesium oxide,
Magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, barium carbonate, calcium silicate, calcium stearate, zinc stearate, tin stearate, calcium phthalate,
Calcium phosphite, sub-glazing, tin oxide, litharge, lead red,
Lead white, dibasic lead phthalate, dibasic lead carbonate, basic lead phosphite, basic tin carbonate, basic lead sulfite, tribasic lead sulfate and the like, especially magnesium oxide, magnesium hydroxide, Aluminum hydroxide, calcium carbonate, barium carbonate, basic silica and the like are preferred.

The inorganic microporous crystal used as the acid acceptor refers to 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 synthetic zeolites, aluminophosphate-type molecular sieves, layered silicates, hydrotalcite, alkali metal titanates, and the like. Among the inorganic microporous crystals, those having a high ability to adsorb acidic substances generated during vulcanization are preferable.

The zeolite compound is not only natural zeolite but also various types of zeolites such as A-type, X-type and Y-type synthetic zeolites, sodalites, natural or synthetic mordenite, ZSM-5, and metal-substituted products thereof. These may be used alone or in combination of two or more. Further, the metal of the metal substitute is often sodium. As the zeolite-based compound, those having a large acid-accepting ability are preferable, and A-type zeolite is particularly preferable.

The hydrotalcites have the following general formula (III):

Embedded image (Where x and y are real numbers from 0 to 10, where 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).

[0020] To exemplify the hydrotalcites represented by the following general formula _{(III), 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) can be exemplified _{10 CO 3 · 1.7H 2 O Mg} 3 ZnAl 2 (OH) 12 CO 3 · wH 2 O Mg 3 ZnAl 2 (OH) 12 CO 3 and the like.

The amount of the acid acceptor is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the epichlorohydrin rubber.

These acid acceptors may be used alone,
You may use it in combination of 2 or more types.

The vulcanizing agent used in the present invention is not particularly limited. Generally, the vulcanizing agent for the epichlorohydrin rubber includes 2,3-dimercaptoquinoxaline derivatives, thiadiazoles, mercaptotriazines and the like. Polythiol (including polythiol derivatives) vulcanizing agents and thioureas are preferred.

Examples of 2,3-dimercaptoquinoxaline derivatives include quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 6-isopropylquinoxaline-2,3-dithiocarbonate, , 8-Dimethylquinoxaline-2,
3-dithiocarbonate and the like. These vulcanizing agents may be used alone or in combination of two or more.

Examples of thioureas include 2-mercaptoimidazoline, 1,3-diethylenethiourea,
Examples include 3-dibutylthiourea and trimethylthiourea. These vulcanizing agents may be used alone or in combination of two or more.

Examples of thiadiazoles include 2,5-
Dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and the like can be mentioned. These vulcanizing agents may be used alone or in combination of two or more.

Examples of mercaptotriazines include:
2,4,6-trimercapto-1,3,5-triazine, 1-methoxy-3,5-dimercaptotriazine,
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. These vulcanizing agents may be used alone or in combination of two or more.

The amount of the vulcanizing agent is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the epichlorohydrin rubber. If the amount is too small, the vulcanization rate will be reduced, and it will be difficult to obtain strong adhesion between the layers and excellent compression set of the laminate or laminated hose. There is a tendency that the rubber layer becomes too rigid and the physical properties expected as a laminate cannot be obtained.

In the present invention, in order to obtain a sufficient adhesive strength, a polythiol-based (including polythiol derivative) vulcanizing agent such as the above 2,3-dimercaptoquinoxaline derivative, thiadiazole derivative, mercaptotriazine derivative and the above-mentioned general formula By combining with the adhesion-imparting agent represented by [I] or [II], a composition exhibiting excellent results in vulcanization adhesion with a fluororubber or fluororesin layer can be obtained.

The above-mentioned polythiol-based (including polythiol derivative) vulcanizing agents are better than thioureas in terms of compression set of the obtained vulcanized rubber.

The vulcanized adhesive composition according to the present invention also comprises
In addition to the epichlorohydrin rubber (a), the acid acceptor (b), the vulcanizing agent (c) and the adhesion promoter (d),
It may contain carbon black (e) for reinforcement of up to 500 nm.

Examples of the carbon black used in the present invention include SAF, ISAF, HAF, MAF, FE
F, SRF, FT, MT and the like are listed, and use of SRF, FT, MT or the like, which is a carbon black having a particle diameter of 61 to 500 nm, is preferable from the viewpoint of improving the adhesion.

Further, in the vulcanized adhesive composition according to the present invention, it is possible to use a commonly used inorganic filler in addition to carbon black.

Specific examples of the inorganic filler used in the present invention include precipitated calcium carbonate, calcium bicarbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum silicate, and hydrous silicate. Aluminum, magnesium silicate, calcium silicate, hydrous calcium silicate, natural silicic acid,
Synthetic silicic acid, mica, wallaceite, asbestos, sepiolite, slag fiber, zonotolite, potassium titanate, elestadite, gypsum fiber.

As a method for preventing metal corrosion of metal members (clamps and the like) attached to rubber members, it is known that it is effective to reduce the amount of carbon black and increase the volume specific resistance. In the vulcanized adhesive composition according to the present invention, the volume specific resistance can be increased and a decrease in physical properties and workability can be suppressed by reducing the blending amount of carbon black and blending an inorganic filler.

Particularly preferred examples of the inorganic filler include acidic, neutral, basic and other natural and synthetic silicic acids, and talc or aluminum silicate which is a filler mainly composed of ultrafine magnesium silicate. It is a fired clay which is a filler as a main component.

The vulcanized adhesive composition according to the present invention also comprises
In addition to the epichlorohydrin rubber (a), the acid acceptor (b), the vulcanizing agent (c) and the adhesion promoter (d), an adhesion promoter (f) selected from imidazolium salts and pyridinium salts May be included.

The adhesion-providing aid (f) used in the present invention includes an imidazolium salt, a pyridinium salt and a mixture thereof. The same agent (f) is used as the adhesion-providing agent (d).
By using together, the adhesive strength can be further improved. Specific examples of the adhesion-providing aid (f) include 1-
Dodecyl-2-methyl-3-benzylimidazolium chloride, cetylpyridinium chloride and the like.

The amount of the adhesion promoter aid (f) is preferably 0.1 to 3.0 parts by weight based on 100 parts by weight of the epichlorohydrin rubber.

It is effective to mix the vulcanization adhesive composition according to the present invention with a known vulcanization accelerator or vulcanization retarder together with the vulcanizing agent for the purpose of adjusting the vulcanization rate. . Examples of the vulcanization accelerator include sulfur, thiuram sulfides, morpholine polysulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, polyfunctional vinyl compounds, mercaptobenzothiazoles , Sulfenamides, dithiocarbamates and the like. Examples of the vulcanization retarder include N-cyclohexylthiophthalimide. The amounts of the vulcanization accelerator and the vulcanization retarder are preferably from 0 to 10 parts by weight based on 100 parts by weight of the epichlorohydrin rubber.

The vulcanized adhesive composition according to the present invention includes various additives conventionally used in the field of rubber processing, such as fillers, reinforcing agents, plasticizers, acid acceptors, antioxidants, lubricants,
An adhesion promoter, a stabilizer, a viscosity promoter, a pigment, a flame retardant, an ultraviolet absorber, a foaming agent, a defoaming agent, a vulcanization regulator and the like can be appropriately added. Further, short fibers or the like can be added to improve the strength and rigidity.

The vulcanization-adhesive composition of the present invention can be compounded by any means conventionally used in the field of polymer processing, for example, mixin gall, Banbury mixer, various kneaders and the like. The method used can be applied. The rubber vulcanizate using the vulcanized adhesive composition according to the present invention is prepared by subjecting the vulcanized adhesive composition of the present invention to 100 to 200 ° C.
The vulcanization time varies depending on the temperature, but is usually between 0.5 and 300 minutes. As a method of vulcanization molding, compression molding by a mold, injection molding, a steam can,
Any method such as heating by air bath, infrared ray or microwave can be used.

According to the present invention, a layer made of a fluororubber or a fluororesin and a layer made of an epichlorohydrin rubber are firmly adhered to each other by using the above-mentioned vulcanized adhesive composition for epichlorohydrin rubber. Vulcanized rubber laminate or laminated hose.

That is, according to the present invention, a vulcanized rubber laminate in which a layer made of the above vulcanized adhesive composition and a layer made of an unvulcanized fluoro rubber or fluoro resin are heated and vulcanized, and There is provided a vulcanized rubber laminated hose, particularly a fuel oil hose, in which an inner layer made of rubber or a fluororesin and an outer layer and / or an intermediate layer made of the vulcanized adhesive composition are heat-vulcanized and bonded.

The fluororubber used in the present invention includes:
Vinylidene fluoride-hexafluoropropene binary copolymer, vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer, vinylidene fluoride-trifluorochloroethylene binary copolymer, vinylidene fluoride-perfluoro Examples include a methyl vinyl ether-tetrafluoroethylene terpolymer, a tetrafluoroethylene-propylene binary copolymer, and a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer.

The fluororesin used in the present invention includes:
Vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer, ethylene-tetrafluoroethylene binary copolymer, hexafluoropropene-tetrafluoroethylene binary copolymer, polyvinylidene fluoride, polytetrafluoroethylene And the like, and preferably a vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer (THV) is exemplified.

According to the purpose of use of the fluororubber, various known compounding agents, for example, vulcanizing agents and vulcanization accelerators selected from polyols, polyamines, organic peroxides and the like,
Metal compounds as fillers, fillers, reinforcing agents, plasticizers,
Stabilizers, colorants, processing aids and the like may be added. The compounding ratio of the compounding agent is not limited, and a vulcanizing fluororubber composition containing an arbitrary ratio of compounding agent is prepared according to the purpose of use.

In the present invention, as a method for producing a laminate, an unvulcanized epichlorohydrin rubber composition and a non-vulcanized fluororubber composition or a fluororesin are laminated by coextrusion or sequential extrusion. Then, a method of heat vulcanization or heat vulcanization molding of the laminate, lamination of an epichlorohydrin-based rubber unvulcanized composition and a fluororubber unvulcanized composition or a fluororesin using a mold, and simultaneously heat vulcanization molding. There is a method to do. A method in which one of the unvulcanized rubber compositions is heated and vulcanized so weakly that it does not lose its shape, and then the two are laminated and sufficiently heated and vulcanized can be employed.
As a method of heating and vulcanizing the laminated body laminated by the above extrusion molding, there is a molding by a mold, and a method of heating and vulcanizing includes a steam can, an air bath, an infrared ray, a microwave, a lead-coated material. A known method such as vulcanization can be arbitrarily adopted.
At the time of vulcanization, the vulcanization temperature is usually 100 to 200 ° C, and the heating time varies depending on the temperature, but is selected in the range of 0.5 to 300 minutes.

As an embodiment in which the laminate of the present invention is applied to a fuel oil hose, as shown in FIG. 1, a layer made of fluororubber or a fluororesin is used as an inner layer (1), and epichlorohydrin rubber is used. A two-layer hose in which a layer made of a braided reinforcing layer made of a braid material is arranged outside the two-layer hose, as shown in FIG. Further, as shown in FIG. 3, a typical example is a four-layer hose in which an outermost layer (4) made of rubber is disposed outside a three-layer hose. 3 layer hose or 4 above
As a braided material used for a layer hose or the like, polyester fiber, polyamide fiber, glass fiber, vinylon fiber,
An example is a braid made of cotton or the like. The material of the outermost layer (4) of the four-layer hose is, for example, aging resistance such as acrylic rubber, ethylene-acryl rubber, chloroprene rubber, chlorinated polyethylene rubber, and chlorosulfonated polyethylene rubber in addition to epichlorohydrin rubber. Synthetic rubber having water resistance, weather resistance, oil resistance and the like is usually used. In addition, as shown in FIG. 4, when the inner layer is only a fluororesin layer, the flexibility is poor and the adhesion to the joint pipe is weak, and further, the innermost layer made of rubber having excellent rubber elasticity and excellent in fuel oiliness (inside thereof) 5) may be arranged. Examples of the rubber of the innermost layer (5) include epichlorohydrin rubber, nitrile butadiene rubber, a blend of nitrile butadiene rubber and polyvinyl chloride, hydrogenated nitrile butadiene rubber, and fluoro rubber.

[0050]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, typical examples will be described as examples, but the present invention is not limited to these examples.

[0051]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 An epichlorohydrin rubber composition having the composition shown in
The mixture was kneaded with an inch roll at 70 to 80 ° C for 15 to 20 minutes to prepare a sheet (A) having a thickness of 2 to 2.5 mm.

A binary fluororubber composition (formulation I) having the composition shown in Table 2 was kneaded under the same conditions as described above to a thickness of 1 to 1.5.
mm sheet (B) was produced. A sheet (B) was produced in the same manner as above except that the binary fluororubber composition (formulation I) was replaced by the ternary fluororubber composition (formulation II).

Pellets of a fluororesin (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer) shown in Table 3 were added at ²⁰ to 25 kg / cm ² for 4 minutes in a mold maintained at 190 ° C. Press
A sheet (C) having a thickness of 0.3 to 0.5 mm was obtained.

The sheet (A) and the sheet (B), and the sheet (A) and the sheet (C) are bonded together, and each bonded body is heated at 160 ° C. and 20 to 25 k.
Pressure was applied at g / cm ² for 30 minutes to obtain a rubber-rubber laminate and a rubber-resin laminate having a thickness of 2 to 2.3 mm.

Examples 2 to 6 and Comparative Examples 1 to 3 Rubber-rubber lamination was carried out in the same manner as in Example 1 except that the composition of the epichlorohydrin rubber composition was changed as shown in Table 1. And a rubber-resin laminate.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

The annotation numbers (1) to (16) in Tables 1 to 3
Means the following:

(1) Epichlorohydrin-ethylene oxide binary copolymer (molar ratio 50:50, Mooney viscosity
ML _{1 + 4} (100 ° C.) 65) (2) Trade name “SEAST SO” (particle size 40 to 48 n)
m, manufactured by Tokai Carbon Co., Ltd.) (3) Trade name “SEAST S” (particle size: 61 to 100 n)
m, manufactured by Tokai Carbon Co., Ltd.) (4) Trade name “Asahi Thermal” (particle size 101-20)
(0 nm, manufactured by Asahi Carbon Co., Ltd.) (5) Trade name “ADEKA CYSAAR RS-107” (manufactured by Asahi Denka Kogyo) (6) Trade name “Splendor R-300” (manufactured by Kao Corporation) (7) Trade name “Hydrotalcite DHT-4A "(manufactured by Kyowa Chemical Industry Co., Ltd.) (8) Trade name" Kyomag # 150 "(manufactured by Kyowa Chemical Industry Co., Ltd.) (9) Phenolic resin of 1,5-diazabicyclo (4,3,0) -nonene-5 Salt (composition ratio 1: 9) (10) Phenol resin salt of 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7 (composition ratio 3: 7) (11) 1,8-diazabicyclo (5,4,0) Phenolic resin salt of undecene-7 (composition ratio 1: 2) (12) Trade name “Viton E-430” divinyl aromatic to vinylidene fluoride-hexafluoropropene binary copolymer Compound-based vulcanizing agents and those of the organic phosphonium salt vulcanization accelerator containing (DuPont) (13) trade name "Viton B-50" vinylidene fluoride - hexafluoropropene - tetrafluoroethylene terpolymer. (Manufactured by DuPont) (14) Trade name "Viton Curative No. 20"
(Vulcanization accelerator benzyltriphenylphosphonium chloride, 33% active ingredient, manufactured by DuPont) (15) Trade name “Viton Curative No. 30”
(Vulcanizing agent bisphenol AF, 50% active ingredient, manufactured by DuPont) (16) Trade name "3M THV Fluoroplatic 500"
G "tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (manufactured by Minnesota Mining and Manufacturing Company)

Evaluation Test The unvulcanized epichlorohydrin rubber compositions of Examples 1 to 6 and Comparative Examples 1 to 3, the sheet (A), the rubber-rubber laminate and the rubber-resin laminate were prepared as follows. Items were evaluated.

A) Mooney scorch time The Mooney scorch time refers to the time until the Mooney viscosity of the vulcanizable rubber composition increases by a specified value. According to the method described in JIS-K-6300,
The unvulcanized epichlorohydrin rubber compositions shown in Table 1 were evaluated for initial stability and storage stability. That is, initially and after 3 days of moist heat storage (35 ° C. × 75% RH ×
(72 hours), the minimum Mooney viscosity (Vm) and scorch time (t5) were measured, respectively.

B) Vulcanization Properties The above sheet (A) was placed in a mold of 15 × 15 × 0.2 cm and pressed at 160 ° C. and 100 kg / cm ² with a press machine.
By heating for 0 minutes, a vulcanized rubber test piece for measuring the vulcanized physical properties in the form of a sheet was prepared.

For this test piece, JIS-K-625
1 (tensile test method for vulcanized rubber) and JIS-K-62
Vulcanized physical properties were measured in accordance with the method described in No. 53 (Test method for hardness of vulcanized rubber).

In Table 4, M100 is defined as a tensile test according to JIS-K-6251.
Tensile stress at 100% elongation Tb; Tensile strength defined in JIS-K-6251 tensile test Eb; Elongation defined in JIS-K-6251 tensile test Hs; Defined in JIS-K-6253 hardness test , Hardness (JIS-A hardness).

C) Compression set: The above sheet (A) was subjected to 160 compression molding using a test piece preparation mold.
By heating at 100 ° C. and 100 kg / cm ² for 35 minutes, a vulcanized rubber test piece for measuring compression set was obtained.

For this test piece, JIS-K-626
The compression set was measured according to the method described in 2. However, the compression ratio was 25%, and the heat treatment temperature and time were 12%.
The conditions were 5 ° C. × 70 hours.

D) Adhesion The rubber-rubber laminate and the rubber-resin laminate were each cut into a strip having a width of 2.5 cm × 10 cm to prepare a test piece for an adhesion test.

This test piece was subjected to JIS-K-625
6 (Testing method for adhesion of vulcanized rubber)
The peel test was performed at 25 ° C. at a tensile speed of 50 mm / min.

Table 4 summarizes the results of each test.

[0072]

[Table 4]

In Table 4, indicates the interfacial peeling at the bonding surface, indicates partial rubber breakage at the bonding surface, and indicates rubber breakage, respectively.
FKM is fluororubber, and EPR is epichlorohydrin rubber. FKM and EPR in Table 4 mean that they were destroyed.

As is evident from Table 4, the vulcanized adhesive composition and the vulcanized rubber laminate of the examples showed good results in any of the items.

Thus, according to the present invention, it is possible to provide a vulcanized rubber laminate or a laminated hose in which a layer made of fluororubber or a fluororesin and a layer made of epichlorohydrin rubber are firmly bonded.

Examples 7 to 15 Epichlorohydrin rubber compositions having the compositions shown in Table 5
The mixture was kneaded with an inch roll at 70 to 80 ° C for 15 to 20 minutes to prepare a sheet (D) having a thickness of 2 to 2.5 mm.

With respect to the sheet (D) of Examples 7 to 11, the sheet (D) and the sheet (B), and the sheet (D) and the sheet (C) were respectively bonded, and each bonded body was heated at 151 ° C. and 20 ° C. ~25kg / cm ² in 3
Pressed for 5 minutes to obtain a primary vulcanized rubber-rubber laminate and a rubber-resin laminate having a thickness of 2 to 2.3 mm, and further heated at 150 ° C. for 3 hours in an air oven to obtain a secondary vulcanized product. Obtained.

For the sheets (D) of Examples 12 to 15, the sheets (D) and (B), and the sheets (D) and (C) were bonded together.
Each bonded body is heated at 160 ° C., 20 to 25 kg / cm ²
For 45 minutes to obtain a vulcanized rubber-rubber laminate and a rubber-resin laminate having a thickness of 2 to 2.3 mm.

Evaluation Test The unvulcanized epichlorohydrin rubber compositions of Examples 7 to 15, the sheet (D), and the rubber-rubber laminate and the rubber-resin laminate were evaluated for the following items. Table 6 summarizes the test results.

A) Mooney scorch time The Mooney scorch time of the unvulcanized epichlorohydrin rubber composition was measured by the method described above.

B) Properties of vulcanized sheet (D) of Examples 7 to 11
Put in a mold of × 15 × 0.2cm and press it with a press machine.
At 35 ° C. and 100 kg / cm ² for 35 minutes to prepare a sheet-shaped primary vulcanized rubber test piece, and further heat the obtained primary vulcanized product in an air oven at 150 ° C. for 3 hours to perform secondary vulcanization. A sulphate was obtained.

The sheets (D) of Examples 12 to 15 were placed in a mold of 15 × 15 × 0.2 cm and heated by a press at 160 ° C. and 100 kg / cm ² for 45 minutes to form a sheet. A vulcanized rubber specimen was prepared.

Each test piece was subjected to a vulcanization property evaluation test by the method described above.

C) Compression Set Using the mold for preparing a test piece, the sheet (D) of Examples 7 to 11 was subjected to the same conditions as those in the two-stage vulcanization of the evaluation of the vulcanization properties under the same conditions as in Example 12. Sheets (D) to No. 15 were vulcanized under the same conditions as the one-step vulcanization conditions for the evaluation of vulcanization properties to obtain vulcanized rubber test pieces for measuring compression set. For this test piece, the compression set was measured by the method described above.

D) Adhesion The adhesion of the rubber-rubber laminate and the rubber-resin laminate obtained in Examples 7 to 15 was evaluated by the method described above.

[0086]

[Table 5]

The annotation numbers (17) to (24) in Table 5 mean the following. Other annotation numbers in Table 5 mean those described above.

(17) Tertiary copolymer of epichlorohydrin-ethylene oxide-allyl glycidyl ether (molar ratio 52: 41: 7, Mooney viscosity ML _{1 + 4} (10
(0 ° C) 50) (18) Trade name “Diamond Black H” (particle size 30 to 3)
(19) Trade name "Seast 116" (particle size 25 to 35)
nm, manufactured by Tokai Carbon Co., Ltd.) (20) Brand name “Crown Clay” (manufactured by Shiraishi Calcium Co., Ltd.) (21) Brand name “Nip Seal VN3” (manufactured by Nippon Silica Co., Ltd.) (23) Trade name "Emaster 510P" (manufactured by Riken Vitamin Co.) (24) Phenolic resin salt of 1,5-diazabicyclo (4,3,0) -nonene-5 (composition ratio 1: 2) )

[Table 6]

In Table 6, indicates interface peeling at the bonding surface, indicates partial rubber breakage at the bonding surface, and rubber breakage, respectively.
EPR in Table 6 means epichlorohydrin rubber, which means that EPR was destroyed.

As is evident from Table 6, the vulcanized adhesive composition and the vulcanized rubber laminate of the examples showed good results in any of the items.

Thus, according to the present invention, it is possible to provide a vulcanized rubber laminate or a laminated hose in which a layer made of fluororubber or a fluororesin and a layer made of epichlorohydrin rubber are firmly bonded.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a two-layer hose.

FIG. 2 is a perspective view showing a three-layer hose.

FIG. 3 is a perspective view showing a four-layer hose.

FIG. 4 is a perspective view showing a laminated hose having an innermost layer.

[Explanation of symbols]

 1: inner layer 2: outer layer 3: braided reinforcing layer 4: outermost layer 5: innermost layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08K 3/00 C08K 3/00 5/3432 5/3432 5/3445 5/3445 5/3465 5/3465 5 / 36 5/36 C08L 71/03 C08L 71/03 F16L 11/08 F16L 11/08 A

Claims (10)

[Claims] (1) an epichlorohydrin rubber,
An epichlorohydrin rubber vulcanization / adhesion composition comprising (b) at least one acid acceptor selected from a metal compound or an inorganic microporous crystal, (c) a vulcanizing agent and (d) an adhesion promoter. , (D) a compound represented by the following general formula [I] or [II] or a weak acid salt thereof as an adhesion promoter,
A vulcanizing adhesive composition comprising 0.1 to 5 parts by weight per 0 parts by weight. Embedded image Embedded image (In the formula [I], R ₁ and R ₂ may be the same or different from each other and represent a hydrogen atom, an amino group, an alkyl group, an alkylamino group, a dialkylamino group, a cycloalkylamino group, And a group selected from the group consisting of an alkylamino group, an arylamino group and an aralkyl group, and in the formula [II], R ₃ represents an amino group,
Alkyl group, alkylamino group, dialkylamino group,
Cycloalkylamino group, dicycloalkylamino group,
It is a group selected from the group consisting of an arylamino group and an aralkyl group. ) 2. The method of claim 1, wherein the adhesion promoter is 1,5-diazabicyclo (4,3,0) -nonene-5 or a weak acid salt thereof, or 6-dibutylamino-1,8-diazabicyclo (5,5).
The vulcanized adhesive composition according to claim 1, which is (4,0) undecene-7 or a weak acid salt thereof. 3. The vulcanized adhesive composition according to claim 1, wherein the adhesion promoter is 1,5-diazabicyclo (4,3,0) -nonene-5 or a weak acid salt thereof. object. 4. The vulcanization bonding composition according to claim 1, wherein the inorganic microporous crystal is a hydrotalcite-based compound and / or a synthetic zeolite. 5. The vulcanizing agent according to claim 1, wherein the vulcanizing agent is selected from the group consisting of 2,3-dimercaptoquinoxaline derivatives, thioureas, thiadiazoles and mercaptotriazines. 5. The vulcanized adhesive composition according to item 1. 6. A carbon black (e) having a particle diameter of 61 to 500 nm in addition to the epichlorohydrin rubber (a), the acid acceptor (b), the vulcanizing agent (c) and the adhesion promoter (d).
The vulcanized adhesive composition according to any one of claims 1 to 5, comprising: 7. An adhesive agent selected from an imidazolium salt and a pyridinium salt, in addition to the epichlorohydrin rubber (a), the acid acceptor (b), the vulcanizing agent (c), and the adhesive agent (d). The vulcanized adhesive composition according to any one of claims 1 to 5, further comprising an auxiliary agent (f). 8. A vulcanized rubber obtained by heating and vulcanizing a layer comprising the vulcanizing adhesive composition according to claim 1 and a layer comprising an unvulcanized fluororubber or a fluororesin. Laminate. 9. A vulcanizate obtained by heating and vulcanizing an inner layer comprising a fluororubber or a fluororesin and an outer layer and / or an intermediate layer comprising the vulcanization-adhesive composition according to any one of claims 1 to 7. Vulcanized rubber laminated hose. 10. The vulcanized rubber laminated hose according to claim 9, wherein the hose is a fuel oil hose that flows fuel oil in contact with the inner surface.