JP2013028037A - Vulcanized rubber-metal laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vulcanized rubber-metal laminate in which an epichlorohydrin-based rubber layer and a brass-plated metal layer are firmly bonded, while keeping physical properties such as compression set properties which are normally expected for epichlorohydrin-based rubber vulcanizate by direct vulcanization-bonding of the epichlorohydrin-based rubber layer to the brass-plated metal layer without preparing an adhesive layer.SOLUTION: First, an unvulcanized epichlorohydrin-based rubber composition layer containing (a) epichlorohydrin-based rubber, (b) silica and/or (c) sulfur, (d) a vulcanizing agent, and (e) an acid acceptor, and the brass-plated metal layer, are heated and bonded together. Consequently, it is found that the vulcanized rubber laminate with both the layers firmly bonded together, can be obtained.

Description

  The present invention relates to a vulcanized rubber-metal laminate. More specifically, an unvulcanized epichlorohydrin rubber composition layer formed from an unvulcanized epichlorohydrin rubber composition containing silica and / or sulfur, a vulcanizing agent, and an acid acceptor, and a brass-plated metal layer And a vulcanized rubber-metal laminate in which both layers are firmly bonded by vulcanizing and bonding without providing an adhesive layer.

  For high-pressure hoses that use brass-plated wire for the reinforcing layer, when used at temperatures below 100 ° C, acrylonitrile-butadiene copolymer rubber (NBR) is used for the inner layer and chloroprene rubber (CR) is used for the outer layer. It is common to use.

  As a result of recent increases in engine compartment temperature, exhaust gas recycling, and fuel transpiration regulations due to vehicle exhaust gas regulations and energy saving measures, heat aging resistance, weather resistance, and acid fuel resistance as rubber materials used In addition, it has been required to have both alcohol-resistant fuel oil resistance, fuel oil-impermeability and the like, and as the hose, acrylonitrile-butadiene copolymer rubber (NBR) and chloroprene rubber (CR) have the above requirements. It has become difficult to satisfy the performance sufficiently.

  For example, fluorine rubber, acrylic rubber, or the like has been selected as a rubber material excellent in heat resistance and oil resistance according to the use environment. However, these rubbers are very expensive in terms of price and have a problem with cold resistance, and therefore, attempts have been made to use epichlorohydrin rubbers excellent in balance between price and performance.

  However, in general, epichlorohydrin rubber and metal have poor adhesion during heat vulcanization. Therefore, when manufacturing the high-pressure hose using epichlorohydrin rubber and brass-plated metal, it is usually necessary to further provide an adhesive layer.

  The present applicant performs vulcanization adhesion with stainless steel by using the epichlorohydrin rubber composition described in Patent Document 1, but does not describe vulcanization adhesion with brass-plated metal. In addition, in vulcanization adhesion between epichlorohydrin rubber and brass-plated metal, a method of bonding by heat vulcanization without using an adhesive has been desired.

JP2007-98895

  In the present invention, an epichlorohydrin rubber vulcanizate such as compression set is usually expected by directly vulcanizing and bonding an epichlorohydrin rubber layer and a brass-plated metal layer without providing an adhesive layer. An object of the present invention is to provide a vulcanized rubber-metal laminate in which both layers are firmly bonded while maintaining the above.

  The present inventors have provided an unvulcanized epichlorohydrin rubber composition containing (a) epichlorohydrin rubber, (b) silica and / or (c) sulfur, (d) vulcanizing agent, and (e) acid acceptor. It is found that a vulcanized rubber laminate in which both layers are firmly bonded can be obtained by heating and bonding an unvulcanized epichlorohydrin-based rubber composition layer formed from a brass-plated metal layer, The present invention has been completed.

  That is, the present invention provides (a) epichlorohydrin rubber, (b) silica (provided that the content of (b) silica is 15 to 35 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber) and / or. (C) sulfur (provided that (a) the sulfur content is 0.05 to 1 part by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber), (d) vulcanizing agent and (e) acid acceptor. (A) an unvulcanized epichlorohydrin rubber composition layer formed from an unvulcanized epichlorohydrin rubber composition containing silane, and (B) a vulcanized adhesive without providing an adhesive layer. This is a vulcanized rubber-metal laminate.

  In the present invention, it is preferable that (b) silica is a wet process silica.

  In the present invention, (A) the unvulcanized epichlorohydrin rubber composition for forming the unvulcanized epichlorohydrin rubber composition layer is (a) epichlorohydrin rubber, (b) silica (provided that (a) epichlorohydrin rubber 100 parts by weight. (B) The content of silica is 15 to 35 parts by weight.), (C) Sulfur (provided that the content of (c) sulfur relative to 100 parts by weight of (a) epichlorohydrin rubber is 0.1 to 0. 5 parts by weight), (d) a vulcanizing agent, and (e) an acid acceptor.

（式中、３個のＲ^１は互いに同一でも異なっていてもよく、炭素数１〜５の炭化水素基であり、Ｒ^２は炭素数１〜９の２価の炭化水素基であり、Ｘはハロゲン原子である。） The unvulcanized epichlorohydrin rubber composition preferably further contains 0.3 to 15 parts by weight of the halogenoalkoxysilane represented by the general formula (I) with respect to 100 parts by weight of (b) silica.

(In the formula, three R ^{1 s} may be the same or different from each other, and are each a hydrocarbon group having 1 to 5 carbon atoms; R ² is a divalent hydrocarbon group having 1 to 9 carbon atoms; Is a halogen atom.)

  In the present invention, (d) the vulcanizing agent is preferably selected from a quinoxaline vulcanizing agent, a thiourea vulcanizing agent and a bisphenol vulcanizing agent, and 2,3-dimercaptoquinoxaline, quinoxaline-2,3- Dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, quinoxaline vulcanizing agent consisting of 5,8-dimethylquinoxaline-2,3-dithiocarbonate, 2-mercaptoimidazoline (ethylenethiourea), 1,3-diethyl More preferably, it is selected from thiourea vulcanizing agents composed of thiourea, 1,3-dibutylthiourea, trimethylthiourea, bisphenol vulcanizing agents composed of bisphenol AF and bisphenol S. (A) It is preferable to contain 0.1-10 weight part of (d) vulcanizing agents with respect to 100 weight part of epichlorohydrin rubber.

  In the present invention, (e) the acid acceptor is preferably a metal compound and / or an inorganic microporous crystal, more preferably a synthetic hydrotalcite which is a kind of inorganic microporous crystal. (A) It is preferable to contain 0.2-50 weight part of (e) acid acceptor with respect to 100 weight part of epichlorohydrin rubber.

  A vulcanized rubber-metal laminate in which (A) an unvulcanized epichlorohydrin rubber composition layer of the present invention and (B) a brass-plated metal layer are vulcanized and bonded without providing an adhesive layer is a vulcanized rubber-metal laminate. Used as a rubber rubber-metal laminated hose.

  The vulcanized rubber-metal laminate obtained according to the present invention has excellent adhesion between the two layers while maintaining the compression set as a vulcanized rubber, and the adhesive surface is strong. Very useful for high pressure hoses that use wires plated in layers.

  The present invention is described in detail below.

  First, the (A) unvulcanized epichlorohydrin rubber composition layer of the present invention will be described in detail. (A) The unvulcanized epichlorohydrin rubber composition layer comprises (a) epichlorohydrin rubber, (b) silica and / or (c) sulfur, (d) a vulcanizing agent, and (e) an acid acceptor. It is a layer formed from a vulcanized epichlorohydrin rubber composition.

The (a) epichlorohydrin rubber in the unvulcanized epichlorohydrin rubber composition is an epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether ternary copolymer. Examples thereof include a polymer, epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer, and the like. Preferred are epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and more preferred epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether. A terpolymer. 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.

  In the case of epichlorohydrin-ethylene oxide copolymer, the copolymerization ratio of epichlorohydrin is preferably 5 mol to 95 mol%, more preferably 10 mol% to 75 mol%, and particularly preferably 10 to 65 mol%. . Ethylene oxide is preferably 5 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and particularly preferably 35 mol% to 90 mol%.

  In the case of an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, the copolymerization ratio thereof is, for example, preferably 4 mol to 94 mol%, more preferably 9 mol% to 74 mol%, and more preferably 9 mol% to 9 mol%. It is especially preferable that it is 64 mol%. Ethylene oxide is preferably 5 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and particularly preferably 35 mol% to 90 mol%. The allyl glycidyl ether is preferably 1 mol% to 10 mol%, more preferably 1 mol% to 8 mol%, and particularly preferably 1 mol% to 7 mol%.

  As the (b) silica in the unvulcanized epichlorohydrin rubber composition of the present invention, either wet method silica or dry method silica can be used, but wet method silica is preferably used. Wet process silica is hydrous silicic acid fine particles produced by acid decomposition of aqueous sodium silicate solution or alkaline earth metal silicate, and is a rubber filler mainly composed of silicon dioxide. Depending on the method, it is classified into precipitated silica, gel silica and the like, but it can be used without any particular limitation. Specific examples of commercially available wet-process silica include carplex, toxeal, nip seal, and shilton. By using wet method silica, compared with the case where dry method silica such as Aerosil having a small apparent specific gravity is used, the mixing operation of the rubber composition is easy, the compound viscosity is good, and the processability is excellent. . Furthermore, the wet process silica is preferable in that the compression set of the vulcanizate is superior to the case where the dry process silica is blended.

  The content of (b) silica is preferably 15 to 35 parts by weight and more preferably 15 to 30 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber. Within these ranges, sufficient vulcanization adhesion between (A) the unvulcanized epichlorohydrin rubber composition layer and (B) the brass-plated metal can be obtained sufficiently.

（式中、３個のＲ^１は互いに同一でも異なっていてもよく、炭素数１〜５の炭化水素基であり、直鎖状ないしは分枝状の炭化水素基であれば特に限定されず、特に−ＣＨ_３基、−ＣＨ_２−ＣＨ_３基、又はこれらの組み合わせが好ましい。Ｒ^２は炭素数１〜９の炭化水素基であり、直鎖状ないしは分枝状の２価の炭化水素基であれば特に限定されず、−ＣＨ_２−基、−ＣＨ_２ＣＨ_２−基、−ＣＨ_２ＣＨ_２ＣＨ_２−基、−ＣＨ_２ＣＨ_２−Ｐｈ−ＣＨ_２−基（Ｐｈはフェニレン基）であることが好ましい。Ｘはハロゲン原子であり、塩素、臭素、ヨウ素などが例示される。） When the unvulcanized epichlorohydrin rubber composition contains (b) silica, it preferably contains a halogenoalkoxysilane represented by the general formula (I).

(In the formula, three R ^{1 s} may be the same or different from each other, and are hydrocarbon groups having 1 to 5 carbon atoms, not particularly limited as long as they are linear or branched hydrocarbon groups, In particular, —CH ₃ group, —CH ₂ —CH ₃ group, or a combination thereof is preferable, and R ² is a hydrocarbon group having 1 to 9 carbon atoms, and is a linear or branched divalent hydrocarbon group. is not particularly limited as long as, -CH ₂ - group, _{-CH 2} CH 2 - _group, -CH 2 _CH 2 CH ₂ - _{group, -CH 2 CH 2 -Ph-CH} 2 - group (Ph is a phenylene group) X is a halogen atom, and examples thereof include chlorine, bromine and iodine.

  Specific examples of the halogenoalkoxysilane represented by the general formula (I) include chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloropropyldimethoxymonoethoxysilane, chloropropyldiethoxymonomethoxysilane and the like. These are preferred.

  The content of the halogenoalkoxysilane used in the present invention is preferably 0.3 to 15 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of (b) silica. Within these ranges, when (b) silica is contained in the unvulcanized epichlorohydrin rubber composition, the vulcanized product is preferable in terms of compression set and the like.

  Examples of the sulfur (c) in the unvulcanized epichlorohydrin rubber composition of the present invention include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

  (C) The sulfur content is preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of (a) epichlorohydrin rubber. Within these ranges, sufficient vulcanization adhesion between (A) the unvulcanized epichlorohydrin rubber composition layer and (B) the brass-plated metal is obtained, and the vulcanizate becomes too rigid. In addition, the physical properties normally expected as an epichlorohydrin rubber vulcanizate can be obtained, which is preferable.

  In the unvulcanized epichlorohydrin-based rubber composition, (b) silica and (c) sulfur may be used alone, but (b) containing silica and (c) sulfur together may be compression set and It is preferable in terms of adhesiveness. Specifically, the content of (b) silica (preferably wet process silica) is 15 to 35 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber in the unvulcanized epichlorohydrin rubber composition, and (c) sulfur It is preferable to contain (b) silica and (c) sulfur together with a content of 0.1 to 0.5 parts by weight. More preferably, the content of (b) silica is 15 to 30 parts by weight, and the content of (c) sulfur is 0.1 to 0.3 parts by weight.

  The (d) vulcanizing agent in the unvulcanized epichlorohydrin rubber composition of the present invention is at least one selected from the group consisting of a quinoxaline vulcanizing agent, a thiourea vulcanizing agent and a bisphenol vulcanizing agent. It is preferably a quinoxaline vulcanizing agent and / or a bisphenol vulcanizing agent, particularly preferably a quinoxaline vulcanizing agent.

  Examples of the quinoxaline vulcanizing agent include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithio. And carbonate.

  Examples of the thiourea vulcanizing agent include 2-mercaptoimidazoline (ethylene thiourea), 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea and the like.

  Examples of the bisphenol vulcanizing agent include bisphenol AF and bisphenol S.

  Practically preferred vulcanizing agents include 2-mercaptoimidazoline (ethylene thiourea), 6-methylquinoxaline-2,3-dithiocarbonate, bisphenol AF, bisphenol S, and particularly preferred vulcanizing agents include 6-methylquinoxaline. -2,3-dithiocarbonate is mentioned. These vulcanizing agents may be used in combination of two or more unless the effects of the present invention are impaired.

  The content of the (d) vulcanizing agent is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber. . Within these ranges, it is preferable because the physical properties normally expected as an epichlorohydrin rubber vulcanizate can be obtained without sufficiently crosslinking and the vulcanizate becoming too rigid.

  In the present invention, known vulcanization accelerators, vulcanization retarders and the like which are usually used together with these vulcanizing agents can be used.

  Examples of the vulcanization accelerator include morpholine sulfides, amines, weak acid salts of amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal salts of fatty acids, thiuramsphides, polyfunctional vinyl compounds, mercaptobenzoic compounds. Examples include thiazoles, sulfenamides, dimethylthiocarbamates, and polyhydric alcohols. As a particularly preferred accelerator when a quinoxaline vulcanizing agent is applied to the composition of the present invention, a 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU) salt, 1,5-diazabicyclo ( 4, 3, 0) Nonene-5 (hereinafter abbreviated as DBN) salt and alkali metal salt of fatty acid.

  Examples of the DBU salt include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-2-naphthoate, DBU- Examples thereof include phenol resin salts, DBU-2-mercaptobenzothiazole salts, DBU-2-mercaptobenzimidazole salts, and the like. Examples of the DBN salt include DBN-carbonate, DBN-stearate, DBN-2-ethylhexylate, DBN-benzoate, DBN-salicylate, DBN-3-hydroxy-2-naphthoate, Examples thereof include DBN-phenol resin salt, DBN-2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like. When these DBU salts and / or DBN salts are used as vulcanization accelerators, the content is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber, 0.5 More preferably, it is ˜3 parts by weight.

  Examples of the alkali metal salt of the fatty acid include alkali metal salts such as higher fatty acids, resin acids, and naphthenic acids, and more preferably alkali metal salts of higher fatty acids having 6 or more carbon atoms. More specifically, examples include soda salts such as semi-cured tallow fatty acid, stearic acid, oleic acid, sebacic acid, castor oil, and potassium salts. Preferable salts include semi-cured tallow fatty acid soda salt, stearic soda salt, semi-cured tallow fatty acid potassium salt, and stearic potassium salt, more preferably stearic soda salt and / or stearic potassium salt. In particular, when using a soda salt such as semi-cured beef tallow fatty acid soda salt or stearin soda salt, the storage stability is good, which is preferable. When these alkali metal salts of fatty acids are used as an accelerator, the content thereof is preferably 0.2 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of (a) epichlorohydrin rubber. It is more preferable that

  In the vulcanization accelerator, the content of the vulcanization accelerator other than the DBU salt, DBN salt, and fatty acid alkali metal salt is 0.1 to 5 parts by weight with respect to 100 parts by weight of the epichlorohydrin rubber. Preferably there is.

  Examples of the vulcanization retarder include N-cyclohexylthiophthalimide, phthalic anhydride, and an organic zinc compound. The content of the vulcanization retarder is 0-10 with respect to 100 parts by weight of epichlorohydrin rubber. It is preferable that it is a weight part, and it is more preferable that it is 0.1-5 weight part.

  As the (e) acid acceptor in the unvulcanized epichlorohydrin rubber composition of the present invention, a metal compound and / or an inorganic microporous crystal is used.

  Examples of the metal compound (e) as an acid acceptor include Group II metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, periodic Examples include oxides of group IVA metals, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, and tribasic sulfates.

Specific examples of the metal compound (e) as an acid acceptor include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, sodium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, Zinc stearate, calcium phthalate, calcium phosphite, zinc white, tin oxide, risurge, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, basic lead silicate, tin stearate, basic Examples thereof include lead phosphite, basic tin phosphite, basic lead sulfite, and tribasic lead sulfate.
Particularly preferred acid acceptors include magnesia, calcium carbonate, slaked lime, quicklime and sodium carbonate.

  The inorganic microporous crystal means a crystalline porous body and can be clearly distinguished from amorphous porous bodies such as silica gel and alumina. Examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like. A particularly preferred acid acceptor is synthetic hydrotalcite.

  The zeolites are natural zeolite, A-type, X-type, Y-type synthetic zeolite, sodalite, natural or synthetic mordenite, various zeolites such as ZSM-5, and metal substitutes thereof. It may be used in combination of two or more. Further, the metal of the metal substitution product is often sodium. As the zeolite, those having a large acid-accepting ability are preferable, and A-type zeolite is preferable.

［式中、ｘとy はそれぞれｘ＋ｙ＝１〜１０の関係を有する０〜１０の実数、ｚは１〜５の実数、ｗは０〜１０の実数をそれぞれ示す。］ The synthetic hydrotalcite is represented by the following general formula (II).

[Wherein, x and y are real numbers from 0 to 10 having a relationship of x + y = 1 to 10, z is a real number from 1 to 5, and w is a real number from 0 to 10, respectively. ]

Examples of hydrotalcites represented by the general formula (II) include 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 · 3.5H 2 O, can be cited _{Mg 3 ZnAl 2 (OH) 12} CO 3 and the like.

  The content of the (e) acid acceptor is preferably 0.2 to 50 parts by weight and more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the (a) epichlorohydrin rubber. 1 to 20 parts by weight is particularly preferable. Within these ranges, it is preferable because the physical properties normally expected as an epichlorohydrin rubber vulcanizate can be obtained without sufficiently crosslinking and the vulcanizate becoming too rigid.

  The unvulcanized epichlorohydrin rubber composition of the present invention includes various compounding agents commonly used in the technical field, such as anti-aging agents, fillers, reinforcing agents, plasticizers, processing aids, pigments, flame retardants and the like. Can be optionally blended.

  In order to produce the unvulcanized epichlorohydrin rubber composition according to the present invention, any mixing means conventionally used in the field of polymer processing, such as a mixing roll, a Banbury mixer, various kneaders and the like can be used.

  Secondly, the (B) brass-plated metal layer of the present invention will be described in detail.

  The (B) brass-plated metal layer is used as a reinforcing material for ordinary rubber products, and includes steel materials, wire materials, pipe materials, plate materials, and the like.

  When the (B) brass-plated metal layer is used in a high-pressure hose, the diameter of the brass-plated wire is appropriately selected according to the pressure applied to the hose. The net structure is not particularly limited, and examples thereof include a braided one.

  The vulcanized rubber-metal laminate of the present invention can be obtained by heat vulcanizing a laminate in which (A) an unvulcanized epichlorohydrin rubber composition layer and (B) a brass-plated metal layer are laminated. . As a method for heat vulcanization, known methods such as steam cans, air baths, infrared rays, microwaves, lead vulcanization and the like can be arbitrarily adopted. In vulcanization, the heating temperature is usually 100 to 200 ° C., and the heating time varies depending on the temperature, but a range of 0.5 to 300 minutes is selected.

  The structure of the vulcanized rubber-metal laminate in the present invention may be a two-layer structure of an epichlorohydrin-based rubber composition layer and a brass-plated wire layer netted together, and the epichlorohydrin-based rubber composition from above the brass-plated wire layer. It is good also as a 3 layer structure which laminated | stacked other polymer layers other than a layer or epichlorohydrin type | system | group rubber. More than four layers in which an epichlorohydrin rubber composition layer, a polymer layer other than epichlorohydrin rubber, a brass-plated metal layer, or another metal layer is further laminated on one side or both sides of the above three-layer structure A multilayer structure may be used. As polymer layers other than epichlorohydrin rubber, acrylonitrile-butadiene rubber (NBR) or its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR) ), Polymer layers containing diene rubber such as isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, acrylic rubber, fluorine rubber, and the like.

  In the following, examples are given as typical examples, but the present invention is not limited thereto. The unit of the compounding amount in Tables 1 and 2 is parts by weight.

(Examples 1-13, Comparative Examples 1-9)
Each material was kneaded at a ratio shown in Table 1 using a 1 L capacity kneader set at 120 ° C., and then kneaded with a 7-inch open roll set at a surface temperature of 70 ° C. to a thickness of 2 to 2.5 mm. An unvulcanized rubber sheet was prepared. After bonding the two unvulcanized rubber sheets (75 mm × 75 mm) so that a 75 mm long brass plating wire (diameter: 0.7 mm) is skewered, at 170 ° C. and 20-25 kg / cm ² . Pressure was applied for 15 minutes to obtain a laminate having a thickness of 4.0 to 4.5 mm. After vulcanization, the test piece was left for 24 hours. At 25 ° C., the skewered brass-plated wire was pulled out at a speed of 50 mm / min, and the adhesion state of rubber on the wire surface after the drawing was observed. The evaluation criteria are shown below, and the evaluation results are shown in Table 3.
<Adhesion evaluation criteria>
(Double-circle): Rubber has adhered to the whole surface of the wire thickly, and rubber and the wire have adhered firmly.
○: Rubber adheres to 50% or more of the surface area of the wire, and the adhesion between the rubber and the wire is relatively good.
(Triangle | delta): Although rubber has adhered to less than 50% of the surface area of a wire, the adhesiveness of rubber | gum and a wire is inadequate.
X: Rubber is hardly adhered to the surface of the wire, and the rubber and the wire are not bonded at all.
In the compression set test, the obtained unvulcanized rubber sheet was press vulcanized at 170 ° C. for 20 minutes using a mold for preparing a test piece, and was cylindrical with a diameter of about 29 mm and a height of about 12.5 mm. A test piece primary vulcanizate was obtained. Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary vulcanizate. Using the obtained secondary vulcanizate, a test was conducted according to the method described in JIS K6262. The evaluation results are shown in Table 4. The lower the compression set (%), the better the rubber elasticity is retained. When it exceeds 80%, the practical physical properties of the rubber vulcanizate are not obtained. 60% or less is preferable.

The compounding agents used in Examples and Comparative Examples are shown below.
* 1 “Epichromer C” manufactured by Daiso Corporation
* 2 “Epichromer CG” manufactured by Daiso Corporation
* 3 “Nip seal VN-3” manufactured by Nippon Silica Kogyo Co., Ltd.
* 4 “Cabras C” manufactured by Daiso Corporation
* 5 “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd.
* 6 “P-152” manufactured by Daiso Corporation.
* 7 “DynamarRC5251Q” manufactured by 3M
* 8 “Dynamar FC5157” manufactured by 3M
* 9 “Dynamar FC5166” manufactured by 3M

  In Examples 1 to 5, in which a quinoxaline vulcanizing agent was used as a vulcanizing agent and the silica content was included within the scope of the present invention, the adhesion between the epichlorohydrin rubber composition layer and the brass-plated wire was compared. From Table 3, it was shown from Table 3 that the rubber vulcanizate is excellent in compression set. In addition, Example 4 containing the halogenoalkoxysilane represented by the general formula (I) was compared with Example 5 not containing the halogenoalkoxysilane represented by the general formula (I). The compression set was excellent.

  In Examples 6 to 9 in which a quinoxaline vulcanizing agent was used as a vulcanizing agent and a sulfur content was included within the scope of the present invention, Examples 6 to 8 were brass plated with an epichlorohydrin rubber composition layer. Table 3 shows that the adhesion of the wire is relatively good, and Table 4 shows that the compression set of the rubber vulcanizate is excellent. Table 9 shows that Example 9 has excellent adhesion between the epichlorohydrin rubber composition layer and the brass-plated wire, and Table 4 shows that the compression set of the rubber vulcanizate is relatively good. More indicated.

  Examples 10, 11 and 13 in which quinoxaline vulcanizing agent and bisphenol vulcanizing agent were used as the vulcanizing agent and the contents of silica and sulfur were contained within the scope of the present invention were the epichlorohydrin rubber composition layer and Table 3 shows that the adhesion of the brass-plated wire is excellent, and Table 4 shows that the rubber vulcanizate is also excellent in compression set.

  In Example 12, in which a thiourea vulcanizing agent was used as a vulcanizing agent and the contents of silica and sulfur were included within the scope of the present invention, the adhesion between the epichlorohydrin rubber composition layer and the brass-plated wire was adhesive. Is relatively good, and Table 4 shows that the rubber vulcanizate is also excellent in compression set.

  On the other hand, Comparative Examples 1 to 3 in Table 3 are a laminate when a quinoxaline-based vulcanizing agent is used as a vulcanizing agent and the silica content is outside the scope of the present invention. Did not adhere at all.

  Comparative Examples 4 to 6 are laminates when a quinoxaline vulcanizing agent is used as a vulcanizing agent and the content of sulfur or silica and sulfur is less than the range of the present invention. The adhesion of the wire was insufficient.

  Comparative Example 7 using a quinoxaline vulcanizing agent as the vulcanizing agent and containing 2 parts by weight of 100 parts by weight of the epichlorohydrin rubber exceeding the range of the present invention is an epichlorohydrin rubber composition layer. Although it is shown from Table 3 that the adhesion of the brass-plated wire is excellent, the compression set is greatly reduced and the practical physical properties of the rubber vulcanizate are not obtained. It was shown from Table 4.

  Moreover, since Comparative Examples 8 and 9 are laminated bodies in which thiourea vulcanizing agent and bisphenol vulcanizing agent are used as vulcanizing agents and silica and sulfur are not contained, the rubber and the wire are not bonded at all. There wasn't.

The rubber-metal laminate of the present invention is configured as described above, and the laminate is very excellent in adhesion between both layers and has a strong adhesive surface. Therefore, it is extremely useful for applications such as a high-pressure hose using a wire plated with a brass on a reinforcing layer.
Very useful.

Claims (12)

  (A) epichlorohydrin rubber, (b) silica (provided that the content of (b) silica is 15 to 35 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber) and / or (c) sulfur (provided that (A) The content of sulfur is 0.05 to 1 part by weight with respect to 100 parts by weight of epichlorohydrin rubber.) (D) Unvulcanized containing a vulcanizing agent and (e) an acid acceptor A vulcanized rubber obtained by vulcanizing and bonding an (A) unvulcanized epichlorohydrin rubber composition layer formed from an epichlorohydrin rubber composition and a (B) brass-plated metal layer without providing an adhesive layer A metal laminate.   The vulcanized rubber-metal laminate according to claim 1, wherein (d) the vulcanizing agent is at least one vulcanizing agent selected from a quinoxaline vulcanizing agent, a thiourea vulcanizing agent and a bisphenol vulcanizing agent.   (B) The vulcanized rubber-metal laminate according to claim 1 or 2, wherein the silica is a wet process silica.   The unvulcanized epichlorohydrin rubber composition is (a) epichlorohydrin rubber, (b) silica (provided that the content of (b) silica is 15 to 35 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber). (C) sulfur (provided that (a) the sulfur content is 0.1 to 0.5 parts by weight with respect to 100 parts by weight of (a) epichlorohydrin rubber), (d) vulcanizing agent and (e) The vulcanized rubber-metal laminate according to any one of claims 1 to 3, comprising an acid acceptor. The unvulcanized epichlorohydrin rubber composition further comprises 0.3 to 15 parts by weight of halogenoalkoxysilane represented by the general formula (I) with respect to 100 parts by weight of (b) silica. A vulcanized rubber-metal laminate according to the above.

(In the formula, three R ^{1 s} may be the same or different from each other, and are each a hydrocarbon group having 1 to 5 carbon atoms; R ² is a divalent hydrocarbon group having 1 to 9 carbon atoms; Is a halogen atom.)   (D) The vulcanizing agent is 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate Quinoxaline vulcanizing agent consisting of 2-mercaptoimidazoline (ethylene thiourea), 1,3-diethylthiourea, 1,3-dibutylthiourea, thiourea vulcanizing agent consisting of trimethylthiourea, bisphenol AF consisting of bisphenol AF The vulcanized rubber-metal laminate according to any one of claims 1 to 5, which is at least one vulcanizing agent selected from vulcanizing agents.   (E) Acid acceptor is a metal compound and / or inorganic microporous crystal, The vulcanized rubber-metal laminated body in any one of Claims 1-6.   (E) Acid acceptor is a synthetic hydrotalcite, The vulcanized rubber-metal laminated body in any one of Claims 1-7.   The vulcanized rubber-metal laminate according to any one of claims 1 to 8, comprising 0.1 to 10 parts by weight of (d) a vulcanizing agent with respect to 100 parts by weight of (a) epichlorohydrin rubber.   The vulcanized rubber-metal laminate according to any one of claims 1 to 9, comprising (e) 0.2 to 50 parts by weight of an acid acceptor with respect to 100 parts by weight of (a) epichlorohydrin rubber.   The unvulcanized epichlorohydrin rubber composition further comprises 0.3 to 15 parts by weight of halogenoalkoxysilane represented by the general formula (I) with respect to 100 parts by weight of (b) silica. 10. The vulcanized rubber-metal laminate according to any one of 10 A vulcanized rubber-metal laminated hose using the laminate according to claim 1.