JPS6251439A - Rubber laminate and hose consisting of said laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a rubber laminate and a hose made of the same;
More specifically, the present invention relates to a rubber laminate with excellent sour gasoline resistance and heat resistance, and a rubber hose made of the same suitable for automobile fuel hoses.

b. Conventional technology In recent years, the atmosphere in the engine room of automobiles, where rubber fuel hoses are installed, has tended to become increasingly hot as a result of exhaust gas control measures and engine improvements aimed at improving performance. There is a need for fuel rubber hose materials with excellent heat resistance and ozone resistance. In addition, gasoline is oxidized to produce sour gasoline (gasoline is oxidized at high temperatures and contains peroxide.For details, see A.Nersasian: Rubber an
dPractics News June26 (1
978). ) and circulates inside the rubber hose, causing the problem that this deteriorates the rubber.
The inner tube forming material of this type of rubber hose is now required to have durability under harsh conditions.

BACKGROUND ART Conventionally, an acrylonitrile-butadiene rubber (hereinafter abbreviated as NBR) compound has been widely used as a material for forming the inner tube of a fuel rubber hose, as it is an inexpensive material that has excellent oil resistance and gasoline resistance.

Problems to be Solved by the C0 Invention However, when NBR compounds are exposed to sour gasoline for a long period of time, they gradually harden, eventually losing all elasticity and cracking due to repeated internal pressure inside the hose.
The problem arose of fuel leakage.

Means for Solving the d0 Problem The inventors of the present invention have conducted intensive studies to obtain a rubber hose for fuel that has excellent resistance to sour gasoline and excellent heat resistance.

A small amount selected from β-unsaturated nitrile-conjugated diene copolymer rubber, its hydride, or fluorine-containing rubber.
It was discovered that a blended rubber of seed rubber and vinylidene fluoride resin has excellent sour gasoline resistance, and by laminating this new rubber composition and conventional rubber, the new rubber and conventional rubber can be improved. We have found that a laminate that takes advantage of these characteristics can be obtained, that a hose with this laminate structure maintains good elasticity even when in contact with sour gasoline for a long period of time, and that it also has excellent heat resistance. , arrived at the present invention. That is, the present invention provides at least one rubber (1) selected from acrylic rubber, α, β unsaturated nitrile-conjugated diene copolymer rubber or its hydride, or fluorine-containing rubber, and vinylidene fluoride resin. (
II), and the weight ratio of (1) and (II) is 951.
A rubber layer (A) consisting of a rubber (a) characterized by a ratio of 5 to 40/60, and a rubber other than the rubber (a) (b)
a rubber layer (B) consisting of a
), the inner tube is formed of a rubber hose.

The acrylic rubber used in the present invention includes (a) 30 to 99.9% by weight of an acrylic acid alkyl ester and/or an acrylic acid alkoxy-substituted alkyl ester compound, and (g) 0.1 to 10% by weight of a crosslinkable additive. %, and (C) 0 to 70% by weight of another ethylenically unsaturated compound copolymerizable with the above (a) and (b). Specifically, the patent application 1986-1
The multicomponent copolymer rubber shown in No. 5561 or No. 59-244127 can be used.

As α, β unsaturated nitrile-conjugated diene rubber, α
, tolyl component for β-unsaturation) 10 to 60% by weight
, a conjugated diene (component (e)) 15 to 90% by weight and another ethylenically unsaturated compound (component (f)) copolymerizable with the (dl, (el) components) 0 to 75% by weight. It is.

Specific examples of the above α, β unsaturated nitrile of +d+dl include acrylonitrile, α-chloroacrylonitrile,
α-fluoroacrylonitrile, methacrylonitrile,
Among them, acrylonitrile is particularly preferred.

The above (conjugated diene of el component is butadiene-1
, 3,2-chlorobutadiene-1,3,2-methylbutadiene-1,3, among which butadiene-1,3 is particularly preferred.

As the (fl component), various compounds can be used as required, examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl ( Acrylic acid alkyl (meth)esters such as meth)acrylates,
Fluorine-containing (meth)acrylates such as 1,1.1-trifluoroethyl (meth)acrylate, amino-substituted alkyl (meth)acrylates such as diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate
Hydroxyl-substituted alkyl (meth)acrylates such as acrylates are preferably used.

Specifically, α,β unsaturated nitrile-conjugated diene rubber described in Japanese Patent Application No. 60-67683 is used.

These acrylic rubbers and α,β unsaturated nitrile-conjugated diene copolymer rubbers can be produced by emulsion polymerization using a conventional radical polymerization catalyst.

The hydride is produced by emulsion polymerization or solution polymerization, and multi-component copolymer rubber is produced by a conventional method (for example,
No. 39275, JP-A-50-71681, British Patent 2
The conjugated diene units in the rubber are hydrogenated by the method described in No. 070023, etc.).

The hydrogenated product of the α,β unsaturated nitrile-conjugated diene copolymer has a degree of hydrogenation of the conjugated diene unit in the polymer chain of 10% or more, preferably 30% or more, particularly preferably 50% or more. be.

When such a hydride of α,β unsaturated nitrile-conjugated diene copolymer is used, α,β unsaturated nitrile-
Compared to the case where conjugated diene copolymer rubber is used, it has excellent cold resistance, heat resistance, gasoline resistance, gasohol resistance, sour gasoline resistance, and sour gasohol resistance.

Examples of the fluorine-containing rubber used in the present invention include tetrafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and fluorinated Vinylidene-pentafluoropropene copolymer, tetrafluoroethylene-vinylidene fluoride-propylene copolymer, tetrafluoroethylene-ethylene-isobutylene copolymer, ethylene-hexafluoropropene copolymer, tetrafluoroethylene Examples include -butene-1 type copolymers, tetrafluoroethylene-ethyl vinyl ether type copolymers, and tetrafluoroethylene-fluorovinyl ether type copolymers.

The above fluorine-containing rubber has a Mooney viscosity (ML,...
. 8100° C.] of 10 to 120, particularly about 20 to 60, is preferably employed.

The rubber used for the rubber (1) is preferably an acrylic rubber, an α,β-unsaturated citrile-conjugated diene copolymer rubber, or a hydrogenated product thereof, and particularly preferably an acrylic rubber or an α,β-unsaturated citri-conjugated diene copolymer rubber. It is a β-β-unsaturated lytrile-conjugated diene copolymer rubber compound.

Next, vinylidene fluoride resin (II
) is polyvinylidene fluoride and vinylidene fluoride with hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether) , vinyl acetate, ethylene, propylene, butadiene, styrene, or a copolymer of two or more of them, and the vinylidene fluoride content is 90 mol% or more, preferably 9
It is 5 mol% or more. In a vinylidene fluoride resin having a vinylidene fluoride content of less than about 90 mol%, the gasoline resistance, gasohol resistance, sour gasoline resistance, and sour gasohol resistance of the rubber composition forming the obtained rubber layer (A) are as follows. Undesirable.

Note that vinylidene fluoride resin is not particularly limited, but preferably one having a degree of polymerization of 100 to 100,000 is used.

As described above, the rubber (A) forming the rubber layer (A) of the present invention is at least one selected from acrylic rubber, α, β unsaturated nitrile-conjugated diene copolymer rubber, hydride, or fluororubber. It contains rubber (I) and vinylidene fluoride resin (II), and the weight ratio of both rubber (1) and vinylidene fluoride resin (II) is 9515 to 40/60. be. In other words, the amount of vinylidene fluoride resin (II) used is the same as that of rubber (1),
It is at least 5 parts by weight in 100 parts by weight of the mixture with vinylidene fluoride resin (II), and if it is less than 5 parts by weight, no effect of improving gasohol resistance, heat resistance, and sour gasoline resistance can be seen, and preferably 10 parts by weight. It is more than 100%. As the amount of vinylidene fluoride resin (II) in the mixture increases, processability deteriorates and costs increase, so the upper limit of the amount used is determined naturally, and is usually 60 parts by weight or less, preferably 50 parts by weight or less. be. Particularly preferably, it is 40 parts by weight or less.

The ratio of rubber (1) and vinylidene fluoride resin (II) in the composition of the present invention can be appropriately determined within the above range depending on the purpose of use and required performance.

Although there are no particular restrictions on the method of mixing the components constituting the rubber (a) of the present invention, for example, the following method can be used.

(i) A method of mixing rubber (1) and vinylidene fluoride resin (II) using a mixer such as a roll, Banbury mixer, or intermixer; (ii) Rubber (1)
and vinylidene fluoride resin (II) in the form of a latex or suspension, followed by coagulation treatment to co-precipitate the mixture, or (iii) a method of using the above (i) and (iii) together. It will be done. Specifically, for example, the following method can be used.

After mixing rubber (I) with carbon black in advance using a mixer such as a roll, Banbury mixer, or intermixer, vinylidene fluoride resin (II) is mixed at a high temperature, specifically, from 150 to 250°C. , preferably a method of mixing at 150 to 200°C.

If the mixing temperature exceeds 250°C, the rubber deteriorates, which is undesirable. If the mixing temperature is less than 150°C, the blended state will be insufficient and the physical properties will deteriorate. The crosslinking agent is added after the blend has cooled.

The rubber (B) forming the rubber layer (B) includes butadiene-acrylonitrile rubber, styrene-butadiene rubber, fluororubber, polychloroprene, acrylic rubber,
Ethylene-propylene-termonomer copolymer (EPT)
), chlorinated polyethylene, chlorosulfonated polyethylene, silicone rubber, butyl rubber, and epichlorohydrin rubber.

Among these, especially epichlorohydrin rubber, fluororubber,
Preferred are chlorosulfonated polyethylene, polychloroprene, and butadiene-acrylonitrile rubber.

Examples of metal oxides or metal hydroxides selected from Groups ■ to ■ of the periodic table to be blended into rubber (a) and/or rubber (b) include magnesium oxide, aluminum oxide,
Zinc oxide, zinc dioxide, calcium oxide, lead oxide (■,
(2), silicon dioxide, etc., and their hydroxides, and their addition improves the adhesion between the rubber layer (a) and the rubber layer (b). Among these, magnesium oxide, calcium hydroxide, aluminum hydroxide,
Lead (II) oxide is preferred, and the metal oxide loading is usually 5 to 30 phr.

For rubber (a) and rubber (b), ordinary reinforcing agents, plasticizers, processing aids, vulcanization accelerators, vulcanizing agents, anti-aging agents, and other additives are used. Among these, plasticizers used in rubber (a) include phthalic acid derivative compounds such as diethyl phthalate and di-n-octyl phthalate, isophthalic acid derivative compounds such as diisooctyl isophthalate, di(2-ethylhexyl)tetrahydrophthalate, etc. Tetrahydrophthalic acid derivative compound, di(2-
Adipic acid derivative compounds such as ethylhexyl) adipate, di(butoxy ethoxy ethyl) adipate, butyl diglycol adipate, azelaic acid derivative compounds such as di(2-ethylhexyl) azelate,
Sepacic acid derivative compounds such as di(2-ethylhexyl)sepacate and di-n-butylsepacate, fatty acid derivative compounds such as diethylene glycol monolaurate, tri(2-ethylhexyl)phosphate, triphenyl phosphate, tributoxyethyl phosphate In addition to phosphoric acid derivative compounds such as, glycol derivative compounds such as dibutyl methylene bis thioglycolate, glycerin derivative compounds, epoxy derivative compounds, etc., polyester compounds, polyether compounds, and polyether ester compounds are used as polymeric plasticizers. Examples include compounds.

As the crosslinking agent for the rubber (I) forming the rubber (A), for example, when the rubber forming the rubber (1) is an acrylic rubber, the type of functional group used for crosslinking introduced into the acrylic rubber is used. A suitable compound can be selected depending on the conditions.

For example, by copolymerizing a diene compound or a (meth)acrylic acid ester containing a dihydrodicyclopentadienyl group,
When a carbon-carbon double bond is introduced, so-called vulcanizing agents such as sulfur and thiuram-based vulcanizing agents, and general diene-based rubbers such as organic peroxides (styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber, etc.) may be used. ) can be suitably used.

In addition, when an epoxy group is introduced into the acrylic rubber by copolymerizing an epoxy group-containing ethylenically unsaturated compound, polyamine carbamates, ammonium organic carboxylates, dithiocarbamine M salts, alkali metal salts of organic carboxylic acids, etc. A combination of sulfur compounds can be used.

Furthermore, when active halogen groups are introduced by copolymerizing active halogen-containing ethylenically unsaturated compounds into acrylic rubber, combinations of polyamine carbamates, ammonium organic carboxylates, alkali metal salts of organic carboxylic acids, and sulfur compounds can be used. It is possible to suitably use the following materials.

In addition, when crosslinking α, β unsaturated nitrile-conjugated diene copolymer rubber, use so-called vulcanizing agents such as sulfur and thiuram, and crosslinking agents used for general diene rubber such as organic peroxides. It can be suitably used.

As a crosslinking agent for the rubber (B) constituting the rubber layer (B),
Vulcanizing agents commonly used for each type of rubber can be suitably used.

According to the present invention, rubber (a) and/or rubber (b)
By blending an epoxy resin, a curing agent, and a basic substance into the resin, both layers (A) and (B) can be firmly vulcanized and bonded. Examples of the curing agent include combinations of maleic anhydride, phthalic anhydride, paraaminodiphenylamine, 2-methylimidazole, and the like. Examples of the basic substance include triethylamine and tetrabutylammonium chloride. The rubber laminate of the present invention can also be obtained by bonding vulcanized layers together.

By using the rubber composition of the present invention, the inner tube layer is made of rubber F! (A)
A rubber hose whose outer tube layer is made of the rubber layer (B) can be manufactured by a conventional method. For example, FIG. 1 shows a perspective view of a rubber hose formed of the rubber laminate of the present invention, in which 1 indicates an inner tube layer formed of a rubber layer (A);
2 is a braided reinforcing layer, and 3 is an outer tube layer made of a rubber layer (B).

The outer diameter, inner diameter, wall thickness of the inner tube layer and outer tube layer, etc. of the rubber hose can be appropriately determined depending on the properties of the fluid flowing inside, the usage conditions, etc.

e. Examples The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples as long as they do not go beyond the gist thereof.

Examples 1-9, Comparative Examples 1-4 The test method in the following examples is as follows.

Preparation of dough: Knead the unvulcanized rubber compound on a rubber test kneading roll machine (6 inch and 14 inch rolls),
This is made into a sheet-like kneaded dough with a smooth surface of 8 fi thickness x 50 width x 80 length.

Vulcanization adhesion: Rubber layer (A) and chlorohydrin rubber (CHC) sheet-like dough other than rubber (A) are layered and inserted into a compression mold, and a surface pressure of 2 kg is applied using an electric press.
Vulcanization is performed at 170° C. for 15 minutes at /c1) to obtain a sheet-like laminate.

Measurement of Adhesive Strength 2 The above laminate is cut into tanzak-shaped pieces with a width of 2.5 fl, and the adhesive strength is measured by a peeling test at 90° C. according to the peeling test method specified in JIS K 6801 Section 7.

[Sour gasoline resistance]

Add 2.5 g of lauroyl peroxide to Fuel C (mixed solvent of isooctane:toluene = 1:1 (volume ratio))
The test piece was brought into contact with the solution dissolved in 97.5 g (rubber layer (A) was in contact) and immersed, and then heated at 100°C for 15 hours.
It was vacuum dried and a test piece was prepared.

Note that, unless otherwise specified, each composition ratio is based on weight.

[Sour gasohol resistance]

Evaluation was performed in the same manner as the evaluation method for sour gasoline resistance, except that a mixed solvent of Fuel C and ethanol (in volume ratio, Fuel C: ff-tanol = EfO: 20) was used instead of Fuel C.

The evaluation results are shown in Table-2.

From the results in Table 2, the rubber layer (A) forming the inner tube layer of the rubber hose made of the laminate of the present invention has good gasoline resistance, sour gasoline resistance, gasohol resistance, sour gasohol resistance, and heat resistance. It can be seen that it has an excellent balance between tensile strength, elongation, gasoline resistance and cold resistance.

Moreover, as seen in Examples 5 to 9 shown in Table 3, the laminates of the rubber layer (A) and the rubber layer (B) were all firmly vulcanized and bonded. Therefore, it can be seen that the laminate of the present invention and the hose made of the same are suitable for a fuel rubber hose having an oil-resistant inner tube layer with excellent gasoline resistance, sour gasoline resistance, and sour gasohol resistance. .

In Table 1, 1) High abrasion furnace black 2) Fast excluding furnace black 3) Semi-reinforced swing furnace black 4) Polyether ester plasticizer: manufactured by Adeka Argus Chemical 5) Trypoxyethyl phosphate 6 ) Di(butoxyethoxyethyl)adipate 7) Shell Ebicor) 182B8) Tetramethylthiuram disulfide 9) N-cyclohexylbenzothiazylsulfenamide 10) Tetraethylthiuram disulfide 1)) Tetramethylthiuram 25 12) DuPont Vulcanization accelerator polycyclic quaternary phosphorus salt 13
) Vulcanization accelerator Aromatic salt manufactured by DuPont 14) Mibuam Thermal Furnace Black 15) E45 manufactured by DuPont 16) Spichromer H manufactured by Osaka Soda ■ [Adhesive strength of laminate] Table 3 Effects of f1 invention According to the present invention With the rubber layer (A) having excellent sour gasoline resistance and sour gasohol resistance, it is possible to obtain a vulcanized rubber that maintains sour gasoline resistance and sour gasohol resistance. From this point of view, the industrially advantageous effects of the present invention are remarkable, and the present invention can be used for rolls, hoses, diaphragms, and the like. In particular, it can be suitably used as a rubber hose for automobile fuel. In addition to the above-mentioned fuel hoses, hoses that are used in control circuits such as carburetors that utilize the negative pressure generated in the engine intake manifold, and through which gasoline paper flows, can also be used to store engine oil as the engine heats up. Because it is resistant to products caused by oxidative deterioration, it can also be applied to pressure transmission circuit hoses in which mineral oil-based oil flows, such as power steering oil, torque converter, and air brake piping hoses.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing an example of a rubber hose of the present invention. l...inner tube layer, 2...braided reinforcement layer,
3... Outer canal layer. Procedural amendment stamp button December 20, 1985 Mr. Michibu Uga, Commissioner of the Patent Office Pi offense 1, Indication of the case 1985 Patent Application No. 191295 2, Title of invention Rubber laminate and hose made from the same 3, Amendment Relationship with the case of a person who does
〒107 (2 idiots) 5. Subject of amendment: “Detailed Description of the Invention” column of the specification. Contents of the amendment (1) The following is added next to page 16, line 7 of the specification. In addition to carbon black, ordinary white fillers can also be used as reinforcing agents and fillers, such as aluminum silicates such as calcium carbonate, magnesium carbonate, kaolin clay, and pyrophyllite clay; Magnesium acid, calcium silicate, aluminum hydroxide, barium silicate, barium sulfate, etc. can be used. (2) Add the following after the third line of page 19 of the same book. Of course, it is not limited to the three-layer structure consisting of the rubber layer (inner tube layer 1 formed by A-te, braided reinforcing layer 2, and outer tube layer 3 made of rubber layer (B)) as exemplified above. The present invention is applicable to various rubber hoses consisting of two layers in which the innermost tube layer is the rubber layer (A) consisting of (A). Display of the matter Patent Application No. 191295 of 1985 2, Name of the invention Rubber laminate and a hose made from the same 3, Intercrop with the person making the amendment Name of patent applicant (417) Japan Synthetic Rubber Co., Ltd. 4, Agent 107 and the full text of the specification. 6. Contents of the amendment As shown in the attached sheet, the following is added below the title of Book i. Add the following between the columns: Note 2. Number of inventions stated in the claims 2 (3)
) Correct the entire specification as shown in the attached sheet. Description 1) Name of the invention Rubber laminate and hose made from the same 2, Claims fl) Made from acrylic rubber, α, β unsaturated nitrile-conjugated diene copolymer rubber or its hydrogenated product, or fluorine-containing rubber Contains at least one selected rubber (N) and vinylidene fluoride resin (II), (1) and (II)
) A rubber layer (A) consisting of rubber (A) characterized in that the weight ratio of
A rubber laminate formed by firmly adhering a rubber layer (B) made of a rubber other than (a) (b). (2) The above rubber (1) is acrylic rubber or α,
The rubber laminate according to claim (1), which is a β-unsaturated nitrile-conjugated diene copolymer rubber or a hydride thereof. (3) The rubber (B) forming the rubber layer (B) is a rubber selected from epichlorohydrin rubber, chlorosulfonated polyethylene, polychloroprene, fluororubber, and butadiene-acrylonitrile rubber. ) The rubber laminate described in item 2. (4) The rubber (A) forming the rubber layer (8) is made of acrylic rubber and vinylidene fluoride resin, and the rubber layer (8) is made of acrylic rubber and vinylidene fluoride resin.
The rubber laminate according to claim 1, wherein the rubber (b) forming B) is epichlorohydrin rubber. (5) A patent claim characterized in that the rubber (a) and/or the rubber (b) contains an oxide or metal hydroxide of a metal selected from Groups II to IV of the Periodic Table. The rubber laminate described in scope (1). (6) The rubber laminate according to claim (4), wherein the rubber (a) and/or the rubber (b) contain an epoxy resin and a curing agent or a basic compound. (7) The above rubber (I) is (a) an acrylic acid alkyl ester and/or an acrylic acid alkoxy-substituted alkyl ester compound 30-9
9.9% by weight, (b) 0.1 to 10% by weight of crosslinking monomer, and (C
) The rubber according to claim (1), which is an acrylic rubber having a polymerization composition of 0 to 69.9% by weight of another ethylenically unsaturated compound copolymerizable with the above (a) and (b). laminate. (8) At least one rubber (I) selected from acrylic rubber, α, β unsaturated nitrile-conjugated diene copolymer rubber or its hydride, or fluorine-containing rubber (I) and vinylidene fluoride resin (II) (I) and (I
A rubber layer (A) consisting of a rubber (A) characterized in that the weight ratio of I) is 9515 to 40/60, and a rubber layer (B) consisting of a rubber (B) other than the rubber (A). A hose having a strongly bonded rubber laminate structure, characterized in that an inner tube layer is formed of the rubber layer (8). 3. Detailed Description of the Invention a. Field of Industrial Application The present invention relates to a rubber laminate and a hose made of the same;
More specifically, the present invention relates to a rubber laminate with excellent sour gasoline resistance and heat resistance, and a rubber hose made of the same suitable for automobile fuel hoses. b. Conventional technology In recent years, the atmosphere in the engine room of automobiles, where rubber fuel hoses are installed, has tended to become increasingly hot as a result of exhaust gas control measures and engine improvements aimed at improving performance. There is a need for fuel rubber hose materials with excellent heat resistance and ozone resistance. In addition, gasoline is oxidized to produce sour gasoline (gasoline is oxidized at high temperatures and contains peroxide.For details, see A.Nersasian: Rubber and
Practics News June 26 (1
978). ) and circulates inside the rubber hose, causing the problem that this deteriorates the rubber.
The inner tube forming material of this type of rubber hose is now required to have durability under harsh conditions. BACKGROUND ART Conventionally, an acrylonitrile-butadiene rubber (hereinafter abbreviated as NBR) compound has been widely used as a material for forming the inner tube of a fuel rubber hose, as it is an inexpensive material that has excellent oil resistance and gasoline resistance. Problems to be Solved by the C0 Invention However, when NBR compounds are exposed to sour gasoline for a long period of time, they gradually harden, eventually losing all elasticity and cracking due to repeated internal pressure inside the hose.
The problem arose of fuel leakage. d3 Means for Solving Problems Therefore, the inventors of the present invention have made intensive studies to obtain a fuel rubber hose with excellent sour gasoline resistance and heat resistance. unsaturated nitrile
It has been discovered that a blended rubber of at least one rubber selected from conjugated diene copolymer rubber, its hydrogenated product, or fluorine-containing rubber and vinylidene fluoride resin has excellent sour gasoline resistance, and this new rubber composition has been developed. By laminating the material and conventional rubber, a laminated body that takes advantage of the respective characteristics of the new rubber and conventional rubber can be obtained, and even if a hose with this laminated structure comes into contact with sour gasoline for a long period of time, The present invention was achieved by discovering that it maintains good elasticity and also has excellent heat resistance. That is, the present invention provides acrylic rubber, α. At least one member selected from β-unsaturated nitrile-conjugated diene copolymer rubber, its hydride, or fluorine-containing rubber
Contains seed rubber (I) and vinylidene fluoride resin (II), and the weight ratio of (I) and (II) is 9515 to 40/6.
0 Rubber layer (A) made of a rubber (A) characterized by: 0 and a rubber layer (B) made of a rubber other than the rubber (B) body,
The present invention also provides a rubber hose comprising the rubber laminate and having an inner tube formed of the rubber layer (A). The acrylic rubber used in the present invention includes (a) 30 to 99.9% by weight of an acrylic acid alkyl ester and/or acrylic acid alkoxy-substituted alkyl ester compound, (b) 0.1 to 10% by weight of a crosslinking monomer, and (C) a nacrylic rubber having a polymer composition of 0 to 70% by weight of another ethylenically unsaturated compound copolymerizable with (a) and (b) above can be used. Specifically, the patent application 1986-15
The multi-component copolymer rubber shown in No. 561 or No. 59-244127 can be used. As α, β unsaturated nitrile-conjugated diene rubber, α
, β-unsaturated nitrile (component (d)) 10 to 60% by weight
, 15 to 90% by weight of a conjugated diene (component (e)) and 0 to 75% by weight of other ethylenically unsaturated metals (component (f)) that can be copolymerized with the (d+, component (e)). Specific examples of the α,β unsaturated nitrile of component (d) include acrylonitrile, α-chloroacrylonitrile,
α-fluoroacrylonitrile, methacrylonitrile,
Among them, acrylonitrile is particularly preferred. As the conjugated diene of the component (e), butadiene-1
, 3,2-chlorobutadiene-1,3,2-methylbutadiene-1,3, among which butadiene-1,3 is particularly preferred. As the (fl component), various compounds can be used as necessary, examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl ( Acrylic acid alkyl (meth)esters such as meth)acrylates,
1.1.1-) Fluorine-containing (meth)acrylates such as lifluoroethyl (meth)acrylate, amino-substituted alkyl (meth)acrylates such as diethylaminoethyl (meth)acrylate, and hydroxyethyl (meth)acrylates.
Hydroxyl-substituted alkyl (meth)acrylates such as acrylates are preferably used. Specifically, α,β unsaturated nitrile-conjugated diene rubber described in Japanese Patent Application No. 60-67683 is used. These acrylic rubbers and α,β unsaturated nitrile-conjugated diene copolymer rubbers can be produced by emulsion polymerization using a conventional radical polymerization catalyst. The above-mentioned hydride can be obtained by adding α,β-unsaturated nitrite-conjugated diene rubber produced by emulsion polymerization or solution polymerization using a conventional method (for example, Japanese Patent Publication No. 45-39275, Japanese Patent Application Laid-Open No. 1983-1983).
71681, British Patent No. 2,070,023, etc.), the conjugated diene units in the rubber are hydrogenated. In the hydrogenated product of the α,β unsaturated nitrile-conjugated diene copolymer, the degree of hydrogenation of the conjugated diene unit in the polymer chain is 10% or more, preferably 30% or more, particularly preferably 50% or more. . When such a hydride of α,β unsaturated nitrile-conjugated diene copolymer is used, α,β unsaturated nitrile-
Compared to the case where conjugated diene copolymer rubber is used, it has excellent cold resistance, heat resistance, sour gasoline resistance, and sour gasohol resistance. The fluorine-containing rubber used in the present invention includes a tetrafluoroethylene-propylene copolymer, a vinylidene fluoride-hexafluoropropene copolymer, and a vinylidene fluoride-hexafluoropropene-tetrafluoroethylene copolymer. , vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-pentafluoropropene copolymer, tetrafluoroethylene-vinylidene fluoride-propylene copolymer, tetrafluoroethylene-ethylene-isobutylene copolymer Examples include ethylene-hexafluoropropene copolymers, tetrafluoroethylene-butene-1 copolymers, tetrafluoroethylene-ethyl vinyl ether copolymers, and tetrafluoroethylene-fluorovinyl ether copolymers. The above fluorine-containing rubber has a Mooney viscosity [ML+, +a+
100° C.] is preferably 10 to 120, particularly about 20 to 60. The rubber used for the rubber (1) is preferably an acrylic rubber or a hydrogenated product thereof, particularly preferably an acrylic rubber or an α,β-unsaturated citri-conjugated diene copolymer rubber. - It is an unsaturated unsaturated citrile-conjugated diene copolymerized rubber product. Next, vinylidene fluoride resin (If
) is polyvinylidene fluoride and vinylidene fluoride with hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether) , vinyl acetate, ethylene, propylene, butadiene, styrene, or a copolymer of two or more of them, and the vinylidene fluoride content is 90 mol% or more, preferably 9
It is 5 mol% or more. When the vinylidene fluoride resin has a vinylidene fluoride content of less than 90 mol%, the resulting rubber layer (
The gasoline resistance, gasohol resistance, sour gasoline resistance, and sour gasohol resistance of the rubber composition forming A) are
Undesirable. Note that vinylidene fluoride resin is not particularly limited, but preferably one having a degree of polymerization of 100 to 100,000 is used. As described above, the rubber (a) forming the rubber N(^) of the present invention is at least one selected from acrylic rubber, α, β unsaturated nitrile-conjugated diene copolymer rubber, its hydride, or fluororubber. It contains a kind of rubber (I) and vinylidene fluoride resin (II), but the proportion of both is rubber (1) and vinylidene fluoride resin (II).
The weight ratio of f) is 9515 to 40/60. In other words, the amount of vinylidene fluoride resin (II) used is the same as that of rubber (I).
and vinylidene fluoride resin (II) in 100 parts by weight, and if it is less than 5 parts by weight, the effect of improving gasohol resistance, heat resistance, and sour gasoline resistance will not be observed, and it is preferable. It is 10 parts by weight or more. As the amount of vinylidene fluoride resin (II) in the mixture increases, processability deteriorates and costs increase, so the upper limit of the amount used is determined naturally, and is usually 60 parts by weight or less, preferably 50 parts by weight or less. be. Particularly preferably 4
It is 0 parts by weight or less. Rubber (I) in the composition of the invention
The proportion of the vinylidene fluoride resin (II) and the vinylidene fluoride resin (II) can be appropriately determined within the above range depending on the purpose of use and required performance. The method of mixing each component constituting the rubber (a) of the present invention is (
Although there is no limit to this, for example, the following method can be used. (i) A method of mixing rubber (I) and vinylidene fluoride resin (II) using a mixer such as a roll, Banbury mixer, or intermixer, (ii) Rubber (I) and vinylidene fluoride resin (II) ) are mixed in the form of latex or suspension, and then subjected to coagulation treatment to form a coprecipitate, or (iii) a method of using the above (i) and (ii) together. Specifically, for example, the following method can be used. After mixing rubber (I) with carbon black in advance using a mixer such as a roll, Banbury mixer, or intermixer, vinylidene fluoride resin (II) is mixed at a high temperature, specifically, from 150 to 250°. C1 Preferably, a method of mixing at 150 to 200°C can be mentioned. If the mixing temperature exceeds 250°C, the rubber deteriorates, which is undesirable. If the mixing temperature is less than 150°C, the blended state will be insufficient and the physical properties will deteriorate. The crosslinking agent is added after the blend has cooled. Rubber (
B) Examples include butadiene-acrylonitrile rubber, styrene-butadiene rubber, fluororubber, polychloroprene, acrylic rubber, ethylene-propylene-termonomer copolymer (BPT), chlorinated polyethylene, chlorosulfonated polyethylene, silicone rubber, butyl rubber. , epichlorohydrin rubber. this house,
Especially epichlorohydrin rubber, fluororubber, chlorosulfonated polyethylene, polychloroprene, butadiene.
Acrylonitrile rubber is preferred. Examples of metal oxides or metal hydroxides selected from Groups ■ to ■ of the periodic table to be blended into rubber (a) and/or rubber (b) include magnesium oxide, aluminum oxide,
Zinc oxide, zinc dioxide, calcium oxide, lead oxide (■,
(2), silicon dioxide, etc., and their hydroxides, and their addition improves the adhesion between the rubber layer (a) and the rubber layer (b). Among these, magnesium oxide, calcium hydroxide, aluminum hydroxide, and lead (U) oxide are particularly preferred. The amount of metal oxides added is usually 5 to 30 phr. For rubber (a) and rubber (b), ordinary reinforcing agents, plasticizers, processing aids, vulcanization accelerators, vulcanizing agents, anti-aging agents, and other additives are used. Among these, plasticizers used in rubber (a) include phthalic acid derivative compounds such as dieur phthalate and di-n-octyl phthalate, isophthalic acid derivative compounds such as diisooctyl isophthalate, and di(2-ethylhexyl)tetrahydrophthalate. Tetrahydrophthalic acid derivative compounds such as di(2-
Adipic acid derivative compounds such as ethylhexyl) adipate, di(butoxy ethoxy ethyl) adipate, butyl diglycol adibate, azelaic acid derivative compounds such as di(2-ethylhexyl) azelate,
Sebacic acid derivative compounds such as di(2-ethylhexyl)sepacate and di-n-butylsepacate, fatty acid derivative compounds such as diethylene glycol monolaurate, tri(2-ethylhexyl)phosphate, triphenyl phosphate, tributoxyethyl phosphate In addition to phosphoric acid derivative compounds such as, glycol derivative compounds such as dibutyl methylene bis thioglycolate, glycerin derivative compounds, epoxy derivative compounds, etc., polyester compounds, polyether compounds, and polyether ester compounds are used as polymeric plasticizers. Examples include compounds. In addition to carbon black, regular white fillers can also be used as reinforcing agents and fillers, such as aluminum silicates such as calcium carbonate, magnesium carbonate, kaolin clay, and pyrophyllite clay, silicic acids such as talc, and mica. Magnesium, calcium silicate, aluminum hydroxide, barium silicate, barium sulfate, etc. can be used. For example, when the rubber constituting the rubber (I) is an acrylic rubber, the crosslinking agent for the rubber (1) forming the rubber (A) may be a functional group introduced into the acrylic rubber and used for crosslinking. A suitable compound can be selected depending on the type. For example, by copolymerizing a diene compound or a (meth)acrylic acid ester containing a dihydrodicyclopentadienyl group,
When a carbon-carbon double bond is introduced, ′
It is preferable to use so-called vulcanizing agents such as sulfur and thiuram-based vulcanizing agents, and cross-linking agents used in general diene-based rubbers (styrene-butadiene rubber, isoprene rubber, butadiene-acrylonitrile rubber, etc.) such as organic peroxides. I can do it. In addition, epoxy groups are introduced into acrylic rubber by copolymerizing epoxy group-containing ethylenically unsaturated compounds.
In such cases, polyamine carbamates, organic ammonium carboxylates, dithiocarbamates, combinations of organic carboxylic acid alkali metal salts and sulfur compounds, etc. can be used.゛Furthermore,
When an active halogen group is introduced by copolymerizing an ethylenically unsaturated compound containing an active halogen into an acrylic rubber, a combination of polyamine carbamates, ammonium organic carboxylic acids, alkali metal salts of organic carboxylic acids, and a sulfur compound can be used. It is possible to suitably use the following materials. In addition, when crosslinking α, β unsaturated nitrile-conjugated diene copolymer rubber or its hydride, so-called vulcanizing agents such as sulfur and thiuram, and organic peroxides are used for general diene rubber. A crosslinking agent can be suitably used. When the rubber constituting rubber (1) is fluorine-containing rubber,
polyamines, polyols or organic peroxides, etc.
It can be suitably used depending on the type of fluororubber. As a crosslinking agent for the rubber (B) constituting the rubber layer (B),
Vulcanizing agents commonly used for each type of rubber can be suitably used. According to the present invention, rubber (a) and/or rubber (b)
By blending an epoxy resin, a curing agent, and a basic substance into the resin, both layers (A) and (B) can be firmly vulcanized and bonded. Examples of the curing agent include combinations of maleic anhydride, phthalic anhydride, para-aminodiphenylamine, 2-methylimidapool, and the like. Examples of the basic substance include triethylamine and tetrabutylammonium chloride. The rubber laminate of the present invention can also be obtained by bonding vulcanized layers together. Using the rubber composition of the present invention, a rubber hose in which the inner tube layer is formed of the rubber layer (A) and the outer tube layer is formed of the rubber layer (B) can be manufactured by a conventional method. For example, FIG. 1 shows a perspective view of a rubber hose formed from the rubber laminate of the present invention, in which 1 is an inner tube layer formed of a rubber layer (A), 2 is a braided reinforcing layer, and 3 is a rubber layer (B). ) is the outer canal layer. The outer diameter, inner diameter, wall thickness of the inner tube layer and outer tube layer, etc. of the rubber hose can be appropriately determined depending on the properties of the fluid flowing inside, the usage conditions, etc. Of course, the structure is not limited to the three-layer structure consisting of the inner tube layer 1 made of the rubber layer (A), the &W reinforcing layer 2, and the outer tube layer 3 made of the rubber layer (B) as exemplified above. (
The present invention is applicable to various rubber hoses consisting of two or more layers in which the rubber layer (A) consisting of (a) forms the innermost tube layer. e. Examples The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples as long as they do not go beyond the gist thereof. Examples 1 to 9, Comparative Examples 1 to 4 Rubber (A) and Rubber (1) of Examples 1 to 4 and Comparative Examples 1 to 4 shown in the upper row of Table 2 were mixed into the formulations shown in Table 1, respectively. According to the following, blending was carried out using a Banbury mixer. The resulting mixture was pre-cured according to the conditions shown in the upper row of Table 1. The properties of the obtained crosslinked rubber were measured according to JIS K2SO3. The laminate was produced by the following method and had sour gasoline resistance,
Sour gasohol resistance and adhesive strength were measured. Preparation of dough: epichlorohydrin rubber, NBR. The fluororubbers were mixed with compounding recipe number e1f in Table 1, respectively.
It was blended according to g. These blends and the unvulcanized rubber blends of the rubbers (a) of Examples 1 to 4 shown in the upper row of Table 2 were tested on rubber test kneading roll machines (6 inch and 1 inch), respectively.
Knead with a 4 inch roll) and mix this into a 8 mm thick x 5 mm
Make a sheet-like kneaded dough with a width x 80 u length and a smooth surface. Vulcanization adhesion: Rubber layer (A) and sheet-like kneaded dough of rubber other than rubber (A) are layered and inserted into a compression mold,
170°C x 1 with a surface pressure of 2kg/ad using an electric heat press
Vulcanization is performed for 5 minutes to obtain a sheet-like laminate. Measurement of Adhesive Strength 2 The above laminate is cut into tanzak-shaped pieces with a width of 2.5 mm, and the adhesive strength is measured by a peeling test at 90° C. according to the peeling test method specified in JIS K 6801 Section 7. [Sour gasoline resistance] 2.5 g of lauroyl peroxide in Fuel C (mixed solvent of isooctane:toluene = 1:1 (volume ratio))
The test piece was brought into contact with a solution dissolved in 97.5 g (rubber layer (
After immersion (contact), vacuum drying was performed at 100° C. for 15 hours to prepare a test piece. Rubber 71 (
It was bent 180 degrees so that A) was on the outside, and the state of crack generation was observed. Note that, unless otherwise specified, each composition ratio is based on weight. [Sour gasohol resistance] Instead of Fuel G, use a mixed solvent of Fuel C and ethanol (in volume ratio, Fuel C: ethanol = 80
: 20) was used, but the evaluation was carried out in the same manner as the evaluation method for sour gasoline resistance. The evaluation results are shown in Table-2 and Table-3. From the results in Table 2, the rubber layer (A) forming the inner tube layer of the rubber hose made of the laminate of the present invention has good gasoline resistance, sour gasoline resistance, gasohol resistance, sour gasohol resistance, and heat resistance. It can be seen that it has an excellent balance between tensile strength, elongation, gasoline resistance and cold resistance. Further, as seen in Examples 5 to 9 shown in Table 3, the laminates of the rubber layer (^) and the rubber layer (B) were all firmly vulcanized and bonded. Therefore, it can be seen that the laminate of the present invention and the hose made of the same are suitable for a fuel rubber hose having an oil-resistant inner tube layer with excellent gasoline resistance, sour gasoline resistance, and sour gasohol resistance. In Table 1, 1) High ablation furnace black 2) Fast excluding furnace blank 3) Semi-reinforced swing furnace black 4) Polyether ester plasticizer: manufactured by Adeka Argus Chemical 5) Tributoxyethyl phosphate 6) Di (Butoxyethoxyethyl)adipate 7) Epicote 1828 manufactured by Shell 8) Tetramethylthiuram disulfide 9) N-cyclohexylbenzothiazyl sulfenamide 10) Tetraethylthiuram disulfide 1)) Tetramethylthiuram 25 12) DuPont Co., Ltd. Sulfur accelerator polycyclic quaternary phosphorus salt 13
) Vulcanization accelerator aromatic salt manufactured by DuPont 14) Mibuam Thermal Furnace Black 15) N45 manufactured by DuPont 16) Epichromer-N manufactured by Osaka Soda 17) JSRN220S manufactured by Japan Synthetic Rubber [Adhesion strength of laminate] Table 3 f1 Effects of the Invention According to the present invention, a vulcanized rubber that maintains sour gasoline resistance and sour gasohol resistance can be obtained by using the rubber layer (A) that has excellent sour gasoline resistance and sour gasohol resistance. From this point of view, the industrially advantageous effects of the present invention are remarkable, and the present invention can be used for rolls, hoses, diaphragms, and the like. In particular, it can be suitably used as a rubber hose for automobile fuel. In addition to the above-mentioned fuel hoses, hoses that are used in control circuits such as carburetors that utilize the negative pressure generated in the engine intake manifold, and through which gasoline paper flows, can also be used to store engine oil as the engine heats up. It has resistance to products caused by oxidative deterioration of
Pressure transmission circuit hose through which mineral oil-based oil flows,
For example, it can be applied to power steering, oil, torque converter, air brake piping hoses, etc. 4. Brief Description of the Drawings FIG. 1 is a perspective view showing an example of the rubber hose of the present invention. l...inner tube layer, 2...braided reinforcement layer,
3... Outer canal layer. Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent
Patent attorney Hisao Okuyama (and 2 others)

Claims (8)

[Claims] (1) At least one rubber selected from acrylic rubber, α,β unsaturated nitrile-conjugated diene copolymer rubber or its hydride, or fluorine-containing rubber (I) and vinylidene fluoride resin (II) (I) and (II)
A rubber layer (A) made of a rubber (a) characterized in that the weight ratio of Rubber laminate made of strong adhesive. (2) The above rubber (I) is acrylic rubber or α
, a β-unsaturated nitrile-conjugated diene copolymer rubber, or a hydride thereof. (3) The rubber (B) forming the rubber layer (B) is a rubber selected from epichlorohydrin rubber, chlorosulfonated polyethylene, polychloroprene, fluororubber, and butadiene-acrylonitrile rubber. ) The rubber laminate described in item 2. (4) The rubber (A) forming the rubber layer (A) is made of acrylic rubber and vinylidene fluoride resin, and the rubber layer (A) is made of acrylic rubber and vinylidene fluoride resin.
The rubber laminate according to claim 1, wherein the rubber (b) forming B) is epichlorohydrin rubber. (5) A patent claim characterized in that the rubber (a) and/or rubber (b) contains an oxide or metal hydroxide of a metal selected from Groups II to IV of the Periodic Table. The rubber laminate described in scope (1). (6) The rubber laminate according to claim (4), wherein the rubber (a) and/or the rubber (b) contain an epoxy resin and a curing agent or a basic compound. (7) The above rubber (I) is (a) an acrylic acid alkyl ester and/or an acrylic acid alkoxy-substituted alkyl ester compound 30-9
9.9% by weight, (b) 0.1-10% by weight of crosslinking monomer, and (c
) The rubber laminate according to claim (1), which is an arylic rubber having a polymerization composition of 0 to 70% by weight of another ethylenically unsaturated compound copolymerizable with the above (a) and (b). . (8) At least one rubber selected from acrylic rubber, α,β unsaturated nitrile-conjugated diene copolymer rubber or its hydride, or fluorine-containing rubber (I) and vinylidene fluoride resin (II) (I) and (II)
A rubber layer (A) made of a rubber (a) characterized in that the weight ratio of A hose having a strongly adhesive rubber laminate structure, characterized in that an inner tube layer is formed of the rubber layer (A).