[0001]The present invention relates to a laminate halogen-containing rubber heterogeneous excellent adhesion is formed by bonding.
BACKGROUND
[0002]Fluorinated rubber heat resistance, oil resistance, chemical resistance, excellent weather resistance, useful industrial materials, in other fields. However fluorinated rubber is expensive, and it is not possible to ignore the economic efficiency when used generically in these areas, expected to drastically usage while having excellent performance is increased not of the can under the present circumstances.
[0003]
　On the other hand, halogen-containing rubbers such as acrylic rubber is a copolymer of homopolymer or acrylic acid ester and 2-chloroethyl vinyl ether acrylate (ACM), epichlorohydrin rubber (ECO) is oil resistance, heat resistance, because of its excellent weather resistance, various sealing materials around the automobile, gaskets, packings, oil hoses, are widely used in functional parts of the heat-resistant, oil hoses, such as air hose.
[0004]
　Recently, more and more the temperature in the engine room has been heated to a high temperature, improved material more resistant performance conventional heat-resistant, oil hose is required for the purpose of performance improvement and fuel efficiency in automobiles.
[0005]
　Industrial hoses, etc. Such heat-resistant, oil hose, strength, flexibility, heat resistance, flex resistance, since various physical properties such as solvent resistance is required, to satisfy all the required properties in one rubber It is difficult. Thus, rubber, for example be used by laminating the fluorine-based rubber and a halogen-containing rubber has been tried with different properties.
[0006]
　However, since poor adhesion between the fluorine-based rubber and a halogen-containing rubber, for example, peroxide acrylic elastomer, quaternary ammonium bromide, a method of blending the epoxidized fatty acid esters and the like (Patent Document 1), fluorine silica filler and an organic peroxide into the system rubber, silica filler in an acrylic rubber, a method of blending an organic peroxide and a silane coupling agent (Patent Document 2), either fluorinated rubber, halogen-containing rubber a method of blending the metal oxide (Patent Document 3), etc., various methods have been proposed.
[0007]
　However, employing any method, the used heat-resistant, oil hose, still, there is insufficient adhesive strength between the fluorine-based rubber and a halogen-containing rubber.
CITATION
Patent Document
[0008]
Patent Document 1: JP 61-189934 Patent Publication
Patent Document 2: JP-A 1-152060 Patent Publication
Patent Document 3: WO 2003/039858
Summary of the Invention
Problems that the Invention is to Solve
[0009]
　The present invention aims to obtain a laminate of the halogen-containing rubber heterogeneous excellent bonding strength (polymer).
Means for Solving the Problems
[0010]
　The present invention has the following layer (1), according to the laminate following layer (2) and is directly joined.
[0011]
　Layer (1): a halogen-based rubber (A) [excluding the fluorine-based rubber]: at least one element selected from the 100 parts by mass of group 2 element and Group 13 element-containing inorganic compounds and oxygen (B): a layer comprising a composition comprising 10 to 30 parts by weight.
[0012]
　Layer (2) except for halogen-containing rubber halogen-containing polymer (C) was prepared in which the layer (1). Layer consisting].
The invention's effect
[0013]
　Conventionally, it is joined epichlorohydrin rubber (ECO) and halogen-containing polymer, such as a layer and a fluorine-based rubber containing halogenated rubbers such as acrylic rubber (ACM) (A) a layer containing (C) directly, firm Although it was not possible to obtain a laminate having an adhesive strength (peel strength), the laminate of the present invention, a layer containing epichlorohydrin rubber (ECO) and halogen-containing rubbers such as acrylic rubber (ACM) (a) because halogen-containing polymers such as fluorine-based rubber and a layer containing (C) are firmly bonded, it can be suitably used for applications such as heat and oil hoses.
DESCRIPTION OF THE INVENTION
[0014]
　
　layer (1) constituting the laminate of the present invention, halogen-containing rubbers and halogenated rubbers (A) (A): with respect to 100 parts by weight, selected from the Group 2 elements and Group 13 elements and at least one element, inorganic compounds containing oxygen (B) [hereinafter, sometimes abbreviated as "inorganic compound (B)". ] Which is a layer made of a composition comprising 10 to 30 parts by weight.
[0015]
　
　halogen-based rubber to form a layer of the laminate of the present invention (1) (A), the rubber containing a halogen atom in the molecule [excluding the fluorine-based rubber] is preferably is a rubber having a constitutional unit derived from a halogen-containing monomer.
[0016]
　The halogen atom, a chlorine atom, a bromine atom, but an iodine atom, the halogen-based rubber, rubber preferably containing chlorine atoms.
[0017]
　The halogen-based rubber (A) according to the present invention, specifically, epichlorohydrin rubber (ECO), acrylic rubber (ACM), chlorinated polyethylene, chloroprene rubber (CR), chlorinated butyl rubber (CIIR), brominated butyl rubber (BIIR), and the like.
[0018]
　Among these halogen-containing rubbers (A), since the laminate epichlorohydrin rubber (ECO) and acrylic rubber (ACM) is excellent in heat resistance and oil resistance can be obtained preferably.
[0019]
　
　inorganic compound mixed in the halogen-containing rubber (A) to form a layer (1) of the laminate of the present invention (B) is at least 1 selected from the Group 2 elements and Group 13 elements an inorganic compound containing the species of elements, and oxygen.
[0020]
　Inorganic compound (B) according to the present invention includes at least one element selected from the Group 2 elements and Group 13 elements, as long as it is an inorganic compound that contains oxygen is not particularly limited, for example, 2 oxides containing at least one element selected from the group elements and group 13 elements, hydroxides, carbonates, hydrotalcites compound.
[0021]
　The at least one element selected from the Group 2 elements and Group 13 elements such as Mg, Ca, Ba, and at least one element and the like is selected from Al.
[0022]
　As the inorganic compound (B) according to the present invention, a commercially available product may be used, for example, "Mag 150" (manufactured by Kyowa Chemical Industry Co., Ltd., magnesium oxide), "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd. , hydrotalcite compound: Mg 4.3 Al 2 (OH) 12.6 CO 3 · mH 2 O) and the like.
[0023]
　Inorganic compound (B) according to the present invention, the halogen-containing rubber (A): 1 to 30 parts by weight per 100 parts by weight, preferably 2 to 30 parts by weight, more preferably from 5 to 30 parts by weight included.
[0024]
　Layer halogen-based rubber (A) to form a (1), by including inorganic compound (B) in the above range can laminate obtained which is excellent in adhesive strength (peel strength) between the layers (2).
[0025]
　Further, halogen-containing rubber (A) is more inorganic compound (B) 10 to 30 parts by weight to form a layer (1), more preferably it is contained in an amount of 15-30 parts by weight. The inorganic compound (B) preferably in terms of thermal stability when containing more than 10 parts by weight, also preferred from the viewpoint of the contains 15 parts by mass or more thermal stability and processability.
[0026]
　
　The halogenated rubber forming the layer (1) according to the present invention (A), in addition to the above inorganic compound (B), usually, it is possible to add various additives to be blended in the rubber .
[0027]
　Other additives, for example, can be exemplified the following additives.
[0028]
　More specifically, organic peroxides, carbon black, anti-aging agents, softeners, metal oxides, crosslinking aid, etc. onium salts.
[0029]
　"Organic peroxides"
　Specific examples of the organic peroxide according to the present invention, dicumyl peroxide, di -tert- butyl peroxide, 2,5-di - (tert-butylperoxy) hexane, 2,5 dimethyl-2,5-di - (tert- butylperoxy) hexane, 2,5-dimethyl-2,5-di - (tert- butylperoxy) hexyne-3,1,3-bis (tert- butylperoxy-isopropyl) benzene, 1,1-bis (tert- butylperoxy) -3,3,5-trimethylcyclohexane, n- butyl-4,4-bis (tert- butylperoxy) valerate, benzoyl peroxide, p- chlorobenzoyl peroxide, 2 , 4-dichlorobenzoyl peroxide, tert- butyl peroxybenzoate, tert- butylperoxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and the like tert- butyl cumyl peroxide .
[0030]
　Organic peroxides according to the present invention, can either be used alone, it may be used in combination of two or more thereof.
[0031]
　When blending the organic peroxide according to the present invention the halogen-containing rubber (A) is usually against a halogen-based rubber (A) 100 parts by mass of 0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, more preferably desirably used in an amount of 0.5-4 parts by weight. When the amount of the organic peroxide is within the above range, Bloom less to the surface of the laminate, preferred to indicate the crosslinking properties superior the layer (1).
[0032]
　"Carbon black"
　Carbon black according to the present invention, specifically, SRF, GPF, FEF, MAF , HAF, ISAF, SAF, FT, various carbon blacks such as MT; these carbon blacks with a silane coupling agent and the like surface-treated surface-treated carbon black or the like.
[0033]
　When blending the carbon black according to the present invention the halogen-containing rubber (A), the mixing amount of carbon black is usually against a halogen-based rubber (A) 100 parts by mass of 10 to 300 parts by mass, preferably 10 to 200 parts by weight, more preferably from 10 to 100 parts by weight approximately.
[0034]
　If the carbon black within the above range, the tensile strength and can be mechanical properties such as wear resistance to obtain a laminated body that is enhanced, increasing the hardness without deteriorating other properties of the laminate preferably possible to.
[0035]
　"Antioxidant"
　halogen-based rubber to form a layer (1) according to the present invention (A) is to contain an antioxidant, it is possible to prolong the product life of the resulting laminate. As anti-aging agent according to the present invention, conventional antioxidants, such as amine-based antiaging agent, a phenol-based antioxidant, it can be used sulfur-based anti-aging agents.
[0036]
　The anti-aging agent according to the present invention, specifically, a phenyl butyl amine, N, N-di-2-naphthyl -p- phenylenediamine, 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine (aka : 4,4'-dicumyl-diphenylamine) aromatic secondary amine-based anti-aging agents such as amine anti-aging agents such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer, dibutylhydroxytoluene , tetrakis [methylene (3,5-di -t- butyl-4-hydroxy) hydro-cinnamate] phenol antioxidant such as methane, bis [2-methyl-4- (3-n-alkylthio propionyloxy) - 5-t-butylphenyl] thioether antioxidants such as sulfides; dibutyldithiocarbamate nickel dithiocarbamates of Salt-based anti-aging agents; 2-mercapto-benzoyl imidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, sulfur-based antioxidant such as distearyl thiodipropionate and the like.
[0037]
　These anti-aging agents can either be used alone, it may be used in combination of two or more thereof.
[0038]
　When blending the halogenated rubber anti-aging agent (A) according to the present invention, the amount of the antioxidant is usually, relative to 100 parts by weight of halogen-containing rubber (A), 0.5 ~ 5. 0 parts by weight, preferably 0.5 to 4.5 mass parts, more preferably 0.5 to 4.0 mass parts. Within the above range, the obtained laminate is preferable because it is excellent in heat aging resistance.
[0039]
　"Softeners"
　as the softening agent according to the present invention, it is possible to use conventional rubber softener is blended in, widely components known as processing aids and the like.
[0040]
　Specifically, paraffinic process oil, naphthenic process oil, petroleum-based softening agent such as aromatic process oils; synthetic oil-based softening agent, ethylene and α- olefin co-oligomer; paraffin waxes; liquid paraffin; white oil (white oil); petrolatum; coal tar, coal tar-based softeners such as coal tar pitch; castor oil, Nishikimiyu, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, peanut oil, Japan wax, rosin, pine oil, dipentene, pine tar, vegetable oil softening agents tall oil; black sub, white sub, sub candy sub etc. (factice); beeswax, carnauba wax, wax and lanolin; ricinoleic acid, palmitic acid , stearic acid, linoleic acid, lauric acid, myristic acid, barium stearate, calcium stearate Arm, magnesium stearate, zinc stearate, fatty acids such as zinc laurate, fatty acid salts and esters; dioctyl phthalate, dioctyl adipate, ester plasticizers such as dioctyl sebacate; coumarone-indene resin; phenol-formaldehyde resins; terpene phenolic resins; polyterpene resins; synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic-alicyclic petroleum resins, aliphatic-aromatic petroleum resins, hydrogenated modified alicyclic hydrocarbon resins, hydrogenated hydrocarbon resins, liquid polybutene, liquid polybutadiene, and petroleum hydrocarbon resins such as atactic polypropylene.
[0041]
　Fatty Among them, petroleum softeners, phenol-formaldehyde resins, are preferred petroleum hydrocarbon resins, fatty acids, petroleum-based softening agent, more preferably petroleum hydrocarbon resins, fatty acids, petroleum-based softening agent is particularly preferred.
[0042]
　Among the petroleum softening agent is preferably petroleum process oil, paraffinic process oil Among them, naphthenic process oil, aromatic process oils and the like are more preferred, paraffinic process oils are particularly preferable. Also in the petroleum hydrocarbon resin, aliphatic cyclic hydrocarbon resins are preferred. Paraffinic process oil Among these softening agents is particularly preferred.
[0043]
　These softeners can either be used alone, it may be used in combination of two or more thereof.
[0044]
　When blending the softening agent according to the present invention the halogen-containing rubber (A) is usually, relative to 100 parts by weight of halogen-containing rubber (A), an amount less than 200 parts by weight, preferably from 0 to 100 parts by mass parts, more preferably 0 to 80 parts by weight, more preferably from 0 to 70 parts by weight, particularly preferably from 0 to 60 parts by weight.
[0045]
　"Metal oxide"
　as the metal oxide of the present invention may be selected appropriately according to the application of the laminate, it can be used as a mixture of two or more kinds in combination. Zinc white (for example, META-Z102) Specific examples of the metal oxide (trade name: zinc oxide, such as Inoue Lime Industry Co., Ltd.), and magnesium oxide.
[0046]
　When blending the metal oxide according to the present invention the halogen-containing rubber (A) is usually against a halogen-based rubber (A) 100 parts by mass of 0.5 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.
[0047]
　"Coagent"
　The crosslinking assistant of the present invention, sulfur; p-quinone quinone dioxime compounds such as dioxime; polyfunctional monomers such as trimethylolpropane triacrylate, and polyethylene glycol dimethacrylate (meth ) acrylate compound; diallyl phthalate, allyl compounds such as triallyl cyanurate; m-maleimide compound of the phenylene bismaleimide; and divinylbenzene. Coagent according to the present invention may be used alone, it may be used in combination of two or more.
[0048]
　When blending a crosslinking assistant according to the present invention the halogen-containing rubber (A) is usually against a halogen-based rubber (A) 100 parts by mass of from 0 to 4.0 mass parts, preferably 0-3. 5 parts by weight, more preferably 0 to 3.0 parts by mass, more preferably 0.1 to 3.0 parts by. The amount of the crosslinking aid is preferably from 0.5 to 2 moles with respect to the organic peroxide to 1 mole, it is also desirable more preferably in an amount approximately equimolar.
[0049]
　"Onium salt"
　As the onium salt according to the present invention, for example, quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, may be mentioned such as monofunctional amine compound, the Among these quaternary ammonium salts, quaternary phosphonium salts are preferable.
[0050]
　Onium salts according to the present invention may be used alone, it may be used in combination of two or more.
[0051]
　As the quaternary ammonium salt is not particularly limited, for example, dialkyl chloride (C14-18) dimethyl ammonium, 1,8-diazabicyclo [5,4,0] -7-Undeseniumu salt, 8-methyl-1,8 - diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium iodide, 8-methyl-1,8 diazabicyclo [5,4,0] -7-undecenium hydroxide key side, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium methyl sulfate, 8-ethyl-1, 8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-de Sill diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide key side, 8- eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-benzyl - 1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8- benzyl-1,8-diazabicyclo [5,4,0] -7-undec pyridinium hydroxide key side, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropyl) -1,8-diazabicyclo [5,4, ] -7-such as undecenium chloride, and the like. Among these, dialkyl chloride (C14-18) dimethyl ammonium are preferred.
[0052]
　Further, no particular limitation is imposed on the quaternary phosphonium salt, for example, tetrabutylphosphonium chloride, benzyl triphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyl trimethyl phosphonium chloride, benzyl tributyl phosphonium chloride, tributyl allyl phosphonium chloride, tributyl 2-methoxypropyl phosphonium chloride, etc. can be mentioned benzyl phenyl (dimethylamino) phosphonium chloride, among them, vulcanizable, in terms of vulcanizate properties, benzyl triphenyl phosphonium chloride (BTPPC) is preferable .
[0053]
　Further, it quaternary ammonium salts, solid solutions of quaternary phosphonium salts and bisphenol AF, also be used compounds disclosed in JP-A-11-147891.
[0054]
　As the amine compound, for example, hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6-hexamethylenediamine, 4,4'-bis (aminocyclohexyl) methane carbamate and the like. Among these, N, N'-dicinnamylidene-1,6-hexamethylenediamine is preferred.
[0055]
　The onium salts according to the present invention, a commercially available product may be used, for example, "lipo card 2HT flakes" (Lion Specialty Lee Chemicals Co., dialkyl chloride (C14-18) dimethyl ammonium) be used it can.
[0056]
　When blending the onium salt according to the present invention the halogen-containing rubber (A) is usually against a halogen-based rubber (A) 100 parts by mass of, preferably not less than 0.2 part by weight, 0.2 parts by mass or more , more preferably 10 parts by mass, 0.5 parts by mass or more, more preferably 8 parts by mass or less. Using an onium salt of the present invention in the range, when used in combination with the inorganic compound (B), the adhesive strength between the higher layer (2) is improved.
[0057]
　"Other components"
　Halogen rubber to form a layer (1) according to the present invention (A), in addition to the above additives may be blended with the following additives.
[0058]
　Examples of the other components according to the present invention, fillers, foaming agents, antioxidants, processing aids, surfactants, and weather agents usually include various additive components to be added to the rubber composition. It may also optionally contain a resin or rubber component other than halogen-containing rubber (A).
[0059]
　
　The filler according to the present invention, silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine powder talc, talc, fine powder silicic acid, and inorganic fillers such as clay. These fillers are usually 0-300 parts by weight with respect to the halogen-based rubber (A) 100 parts by mass of, preferably to 0 to 200 parts by weight approximately. By using fillers, the tensile strength, it is possible to obtain a laminate mechanical properties are improved, such as tear strength and abrasion resistance, it is possible to increase the hardness without deteriorating other properties of the laminate .
[0060]
　
　The antioxidant according to the present invention, specifically,
　a phenyl naphthylamine, 4,4 '- (α, α- dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl -p - aromatic secondary amine-based stabilizers such as phenylenediamine;
　2,6-di -t- butyl-4-methylphenol, tetrakis - [methylene-3- (3 ', 5'-di -t- butyl-4 '- hydroxyphenyl) propionate] phenolic stabilizers such as methane;
　bis [2-methyl -4- (3-n- alkylthio propionyloxy) -5-t-butylphenyl] thioether stabilizers such as sulfides; 2- benzimidazole type stabilizers, such as mercaptobenzimidazole;
　dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate;
　quinoline type stabilizers of the polymer, such as 2,2,4-trimethyl-1,2-dihydroquinoline can be mentioned It is. These may be used alone or in combination of two or more.
[0061]
　When blending an antioxidant according to the present invention the halogen-containing rubber (A) is usually against a halogen-based rubber (A) 100 parts by mass of, for example, 5 parts by mass or less, preferably in an amount of less than 3 parts by weight it can be used in.
[0062]
　
　As the surfactant according to the present invention, specifically, di -n- butylamine, dicyclohexylamine, mono- gills alkanolamine, triethanolamine, "Akuchingu B (Yoshitomi Pharmaceutical Co., Ltd.)," Akuchingu amines such as SL (Yoshitomi Pharmaceutical Co., Ltd.), polyethylene glycol, diethylene glycol, polyethylene glycol, lecithin, thoria reroute trimellitate, aliphatic and zinc compound of an aromatic carboxylic acid (eg, "Struktol Activator 73", "Struktol IB 531 ", manufactured by" Struktol FA541 "Schill & Seilacher Co., Ltd.)," ZEONET ZP "(manufactured by Nippon Zeon Co., Ltd.), octadecyl trimethyl ammonium bromide, synthetic hydrotalcite, special quaternary Anne Moniumu compounds (e.g.,. "Lipoic Card 2HTF" (Lion Specialty Lee Chemicals Co., dialkyl chloride (C14-18) As the surfactant dimethyl ammonium) and the like, lipoic card 2HTF is most preferred.
[0063]
　When a surfactant is added in accordance with the present invention the halogen-containing rubber (A) is usually a halogen-based rubber (A) with respect to 100 parts by weight, for example 0.2 to 10 parts by weight, preferably 0.3 8 parts by mass to, and more preferably 0.3 to 7 parts by mass, particularly preferably from 0.5 to 7 parts by weight, and most preferably 1 to 6 parts by mass. Surfactants can be appropriately selected according to the application, it can be used as a mixture of two or more kinds in combination.
[0064]
　
　The pseudo gel inhibitor according to the present invention, for example, "NHM-007" (manufactured by Mitsui Chemicals, Inc.).
[0065]
　When blending a pseudo anti-gelling agent according to the present invention the halogen-containing rubber (A) is usually, relative to 100 parts by weight of halogen-containing rubber (A), 0.1 ~ 15 parts by weight, preferably 0. 5-12 parts by weight, more preferably 1.0 to 10 parts by weight.
[0066]
　Halogen-based rubber (A) to form a layer (1) according to the present invention, further other additives if necessary may be blended. Other additives, heat stabilizers, weathering stabilizers, antistatic agents, coloring agents, lubricants and a thickener.
[0067]
　
　halogen-containing polymer to form a layer of the laminate of the present invention (2) (C) is a polymer other than halogen-based rubber (A) for forming the layer (1) is there.
[0068]
　Halogen-containing polymer according to the present invention (C) is a polymer containing a halogen atom in the molecule, preferably a polymer having a constitutional unit derived from a halogen-containing monomer.
[0069]
　The halogen-containing polymer according to the present invention (C), preferably a fluorine atom-containing polymer, more preferably a fluorine-based rubber.
[0070]
　Halogen-containing polymer to form a layer (2) as (C), the use of fluorine-based rubber, the laminate having excellent heat and oil resistance may be obtained preferably.
[0071]
　"Fluororubber"
　The fluorine-based rubber of the present invention, for example, vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer, VdF / tetrafluoroethylene (TFE) / HFP copolymer, VdF / TFE / perfluoro (alkyl vinyl ether) (PAVE) copolymer, VdF / VdF / perhalo olefin elastomers such as chlorotrifluoroethylene (CTFE) copolymers; TFE / propylene / VdF copolymer, HFP / ethylene / VdF perfluoro elastomers such as TFE / PAVE copolymer; copolymers such as VdF / non perhalo olefin elastomer TFE / propylene copolymer, a non-perfluoro elastomer such as HFP / ethylene copolymers; and fluorosilicone rubber Agerare .
[0072]
　The fluoro (alkyl vinyl ether) may comprise a plurality of ether bonds. Further molecular weight of the fluorine-based rubber has a number average molecular weight 20,000 to 300,000, preferably 50,000 to 200,000.
[0073]
　Of these, heat resistance, oil resistance, from the viewpoint of chemical resistance, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / TFE / PAVE copolymer, TFE / propylene / VdF copolymer , HFP / ethylene / VdF copolymer, TFE / propylene copolymers, elastomers are preferred for HFP / ethylene copolymer, VdF / HFP copolymer, the elastomer of VdF / TFE / HFP copolymer particularly preferred.
[0074]
　Fluorinated rubber according to the present invention, as the crosslinking group-containing units may be copolymerized polyfunctional monomer or iodine or bromine-containing monomer having a plurality of vinyl groups or allyl groups. Also, it may be generated in the molecule a double bond to a crosslinking point promote dehydrofluorination by performing heat treatment or the like. Particularly crosslinkable units, iodide olefins, using a bromide olefin, fluorine-based rubber having a constitutional unit derived constituent unit or bromide olefins from iodide olefins are preferred.
[0075]
　The crosslinking point content of the fluorine-based rubber (e.g., content of the constitutional unit derived from bromide olefins in the case of using bromide olefin as crosslinking units) is preferably from 0.05 to 5 mol% , more preferably 0.15 to 3 mol%, particularly preferably 0.25 to 2 mol%. Sealability and adhesive strength and the cross-linking point is less than this is insufficient, more than the elongation and flexibility which there is a fear that the rubber elasticity is lost, such as lower.
[0076]
　
　halogen-containing polymer to form a layer (2) according to the present invention (C) preferably contains a polyol crosslinking agent.
[0077]
　The polyol-based crosslinking agent according to the present invention, bisphenols are preferable. Specifically, for example, 2,2'-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) hexafluoropropane [bisphenol AF], bis (4-hydroxyphenyl ) sulfone [bisphenol S], bisphenol a bis (diphenyl phosphate), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl methane, 2,2-bis (4-hydroxyphenyl) butane [bisphenol B] and the like of poly hydroxyaromatic compounds.
[0078]
　The polyol-based crosslinking agent according to the present invention, preferably bisphenol A, bisphenol AF is used. As the polyol crosslinking agent may be an alkali metal salt or alkaline earth metal salts of the polyhydroxy aromatic compound.
[0079]
　Further, as the polyol crosslinking agent may be used a commercially available masterbatch containing a raw rubber and a polyol crosslinking agent. Commercially available masterbatches, for example Curative VC # 30: etc. (Du Pont Dow Elastomer one company manufactured crosslinking agent [bisphenol AF] 50 wt% content) and the like.
[0080]
　Polyol crosslinking agent according to the present invention may be used alone or in combination.
[0081]
　When blending the polyol crosslinking agent to the halogen-containing polymer to form a layer (2) according to the present invention (C), relative to the halogen-containing polymer (C) 100 parts by weight, 0.5 to 10 parts by weight, preferably 1.0 to 8.0 mass parts, more preferably desirably used in an amount of 1.5-6.0 parts by weight.
[0082]
　The halogen-containing polymer (C) is obtained laminate to contain the polyol crosslinking agent to form a layer (2) can laminate excellent in peel strength of more layers (1) is obtained.
[0083]
　Layer (2) according to the present invention, a fluorine-based rubber is a halogen-containing polymer, it may be formed by using a commercially available compositions containing said polyol crosslinking agent. And fluorine-based rubber, a commercially available composition comprising a polyol crosslinking agent, for example, DAI-EL DC-2270F, DAI-EL DC-4070 (both manufactured by Daikin Industries) and the like. DAI-EL DC-2270F is, fluorine-based polyol in addition to rubber-based crosslinking agent, a filler, a composition comprising an acid acceptor, DAI-EL DC-4070, in addition to fluorine-based rubber, an organic peroxide, a filler a composition comprising.
[0084]
　Further, the halogen-containing polymer to form a layer (2) according to the present invention (C), similar to the halogen-containing rubber (A), usually, various additives to be blended in the rubber, the described it can be added in an amount.
[0085]
　A halogen-containing polymer to form a layer (2) according to the present invention (C), as a filler, magnesium hydroxide, aluminum hydroxide, metal hydroxides such as calcium hydroxide; magnesium carbonate, aluminum carbonate, carbonate calcium, carbonates such as barium carbonate; magnesium silicate, calcium silicate, sodium silicate, silicates such as aluminum silicate; aluminum sulfate, calcium sulfate, sulfates such as barium sulfate; synthetic hydrotalcite, molybdenum disulfide, iron sulfide, metal sulfides such as copper sulfides; wet silica, dry silica, quartz powder, silicon oxide such as glass fibers; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, fluoride calcium, coke, talc, mica powder, Warasuto Ito, carbon fiber, aramid fiber, other inorganic fillers for various whiskers, etc., organic reinforcing agents may be used such as organic fillers.
[0086]
　Further, the halogen-containing polymer, as other components, acid acceptor, ultraviolet absorbers, flame retardants, oil resistance improvers, scorch retarders, etc. can be arbitrarily blended tackifier.
[0087]
　
　The laminate of the present invention, the layer (1) and said layer (2) is a laminate formed by bonding directly.
[0088]
　The thickness of the layer constituting the laminate of the present invention (1) and the layer (2) is not particularly limited, the layer (1) is usually a 1 ~ 30 mm, there preferably 1 ~ 5 mm , the layer (2) is usually a 1 ~ 30 mm, preferably 1 ~ 5 mm. The thickness of the laminate as a whole is not particularly limited, usually from 5 ~ 31 mm, preferably 5 ~ 20 mm.
[0089]
　The laminate of the present invention so long as it has a layer in which the layer (1) and said layer (2) is directly bonded is not particularly limited to this layer, the outer [layer of the layer (1) (2) the surface not bonded is], or outside [layer (1) surface not joined the] a layer (2), the other layers may be laminated.
[0090]
　
　The production method of the laminate of the present invention is not particularly limited, a method may be mentioned of obtaining a laminate by, for example, the following method (a) ~ (c). Incidentally, the method (a) ~ (c), after obtaining the layered product, may be subjected to cross-linking step, or perform secondary vulcanization process like an oven in the primary vulcanization, the crosslinked polymer, or it may obtain a laminate having a layer containing a rubber.
[0091]
　(A) layer (1) respectively the material constituting and layer material constituting the a (2), a kneader, a roll, a Banbury mixer, kneaded by a mixer such as a inter mixer, layer by extruding simultaneously by an extruder ( method 1) and the layer (2), to obtain a laminate are joined directly.
[0092]
　The material constituting the (b) layer (1), a kneader, a roll, a Banbury mixer, kneaded by a mixer such as a inter mixer, to form a layer (1) by extrusion by an extruder, a layer (2) the material constituting, kneader, roll, Banbury mixer, kneaded by a mixer such as a inter mixer, a method for bonding a layer (1) and the layer (2) directly by extruding on the layer (1) by an extruder.
[0093]
　The material constituting the (c) layer (2), a kneader, a roll, a Banbury mixer, kneaded by a mixer such as a inter mixer, forming a layer (2) by extrusion by an extruder, the layer of (1) the material constituting, kneader, roll, Banbury mixer, kneaded by a mixer such as a inter mixer, a method for bonding a layer (2) and the layer (1) directly by extruding on the layer (2) by an extruder.
[0094]
　Incidentally, the peel strength of in the preparation of the laminate, the layer (1) and the layer (2), the laminate being bonded directly be press-formed and the layer (1) layer and (2) from the viewpoint of enhancing the.
[0095]
　(Cross-linking step, primary curing)
　The crosslinked process or primary vulcanization, the layer (1), advance by blending components necessary for crosslinking, such as pre-cross-linking agent to the material constituting the layer (2), step out the crosslinking by heating (e.g., 150 ~ 240 ℃), electron beam (e.g., electron rays having energy of 0.1 ~ 10 MeV), include the step of performing crosslinking by irradiating the laminate. The irradiation of the electron beam, the absorbed dose of the laminate, is usually 0.5 ~ 36Mrad, preferably 0.5 ~ 20 Mrad, and more preferably carried out so that the 1 ~ 10 Mrad.
[0096]
　Incidentally, in the crosslinking step or the primary vulcanization, when performing crosslinking by heating, applying heat while press molding is preferable from the viewpoint of increasing the peel strength between the layer (1) and the layer (2) .
[0097]
　(2 vulcanization)
　2 vulcanization is a process performed after the primary vulcanization, by performing heating (e.g. 0.99 ~ 200 ° C.), the step to sufficiently promote vulcanization (crosslinking) is there.
[0098]
　
　The laminate of the present invention can be used in a variety of applications. The laminate of the present invention can be used for example for the automotive, motorcycle, industrial machinery, as a construction machinery or members of agricultural machines. Specific examples of the member, industrial roll, packing (for example, condenser packings), gaskets, belts (e.g., thermal insulation belt, copier belts, conveyor belts), hoses, such as automotive hoses (e.g., turbocharger hose, water hose, brake reservoir hose, radiator hose, air hose), rubber vibration isolators, vibration-proof material or damping material (for example, engine mount, motor mount), muffler hanger, cable (ignition cables, flexible cable, high tension cable) , wire covering material (high-voltage wire covering material, a low-voltage electric wire covering material, marine wire covering material), glass run channels, color skin material, paper feed rolls, roofing sheet, and the like.
[0099]
　Among these, the laminate of the present invention is suitably used in applications requiring the in automotive exterior parts and heat resistance. Applications of the laminate, for example, a laminate of the present invention include a hose having at least as a part. The hose, but not limited to their use for the automotive, motorcycle, industrial machinery, it is preferable to use any of the applications for construction equipment or agricultural machinery. More specifically, turbocharger hoses, brake reservoir hose, etc. radiator hoses and the like, it is particularly preferred for use in turbo-charge hose for automobiles.
[0100]
　Hose of the present invention, the laminate of the present invention may have at least in part, may be a hose which is formed of only the laminate of the present invention.
[0101]
　The laminate of the present invention is suitable as a turbocharger hose.
[0102]
　Method for producing a turbocharger hose of the present invention is not limited in particular, for example, extrusion molding, coextrusion molding, by winding or a combination of these sheet, uncured turbocharger hose having a layered structure ( molding the laminate), by heating with steam or the like, and a method of obtaining a turbocharger hose (laminate). Turbocharger hose uncured without causing contraction or deformation, it preferably has high ability to retain shape.
Example
[0103]
　It will be described in further detail following shows an example for the present invention, but the invention is not limited thereto.
[0104]
　(Measurement and evaluation methods)
　following production examples, examples and comparative examples, measurement and evaluation method of each characteristic is as follows.
[0105]
　(T-peel test)
　The peeling strength of the laminate was measured by the following method.
[0106]
　Example, a laminate obtained in Comparative Example, measurement temperature: 23.0 ° C., test speed: 200.0mm / min, specimen width: performing a T-peel test at 25.0 mm, measured peel strength did.
[0107]
　Halogen-based rubber (A) or the like used in Examples and Comparative Examples of the present invention are shown below.
[0108]
　"Halogen-based rubber (A)"
　 Nipol AR-12: acrylic rubber acrylic acid ester skeleton composed mainly, Nippon Zeon Co. Ltd.
　
　EPICHLOMER H: epichlorohydrin rubber , Osaka soda Ltd.
　"halogen-containing polymer (C)"
　
　DAI-EL DC-2270F: full compounds, 2-way polyol vulcanization system, a specific gravity of 1.85, ML (1 + 10) 100 ℃: about 115, Daikin Industries, Ltd. Co., Ltd.
　In addition, the DAI-EL DC-2270F also referred to as "polyol-based FKM".
[0109]
　[Example 1]
　"Preparation of layer (1) ACM composition forming a"
　as a first step, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), 30 seconds mastication the ACM 100 parts by weight of , and then to this, HAF carbon black 60 parts by weight (Asahi # 70G, manufactured by Asahi carbon Co.), 1 part by weight of stearic acid, and 2 parts by weight of 4,4'-bis (alpha, alpha- dimethylbenzyl) diphenylamine (Nocrac CD, Ouchi Shinko chemical Co., a Ltd.) was added, and the mixture was kneaded for 2 minutes at 140 ° C.. Thereafter, performs cleaning to increase the ram, further, subjected to 1 minute kneading, discharged at about 0.99 ° C., to obtain a first phase of the formulation.
[0110]
　Next, as a second step, the blend obtained in the first stage, 8 Inchiro - Le (Nippon Roll Co., Ltd., before the surface temperature 50 ° C. of the roll, the surface temperature of 50 ° C. of the rear roll, front roll wound rotational speed 16 rpm, the rotational speed 18 rpm) of the rear roll, 20 parts by weight of hydrotalcite (DHT-4A, manufactured by Kyowa chemical industry Co., Ltd.), 1 part by weight of polyoxyethylene stearyl ether phosphoric acid (Fuosufa Nord PL-210: Toho Chemical Industry Co., Ltd.), 0.5 parts by weight (6-aminohexyl) carbamate (Diak No.1: DuPont Co.), 2 parts by weight of 1,3-di -o - to obtain a tolyl guanidine (Nocceler DT, Ouchi Shinko chemical industrial Co., Ltd.) were added and kneaded to uncrosslinked rubber composition for 10 minutes (rubber compound) (composition containing ACM).
[0111]
　"Layer adjustment fluorine rubber composition forming the (2)"
　(fluorine-based rubber composition)
　The fluorine-based rubber composition, DAI-EL DC-2270F: using (manufactured by Daikin Industries polyol-crosslinkable fluorine-based rubber compound) . DAI-EL DC-2270F is, fluorine-based rubber Besides polyol crosslinking agent (bisphenol AF), a crosslinking accelerator (a quaternary onium salt), filler, a composition comprising a acid acceptor.
[0112]
　"Preparation of the laminate, evaluation"
　(T-peel preparation of the laminate for test)
　above, the composition and the fluorine-based rubber composition containing ACM, respectively put into a separating sheet. Then (compositions and fluorine-based rubber composition containing ACM) unvulcanized rubber sheets minute out 50 g, were each sandwiched up and down individually Lumirror (oriented polyester (polyethylene terephthalate) film). Each unvulcanized rubber sheet vertically is sandwiched by Lumirror, with 50 ton press molding machine, and pressed for 2 minutes at 120 ° C., t (thickness) = 1 mm, making the 20cm square unvulcanized rubber sheet did.
[0113]
　Then, the after press has been performed, the unvulcanized rubber sheet obtained from the resulting unvulcanized rubber sheet [Layer (1)] and a fluorine-based rubber composition because Oyo composition comprising an ACM [ the layer (2)] was cut into this press dimensions which each (15cm × 15cm × t = 1mm). Peeling the upper and lower Lumirror after cutting was then superimposed each unvulcanized rubber sheet. When overlaying the portion of the unvulcanized rubber sheet (width 3 cm, length 15cm: Peeling gripping white during the test) in a Teflon (registered trademark) state tucked resin sheet (t = 0.2 mm) , it superimposed the unvulcanized rubber sheet.
[0114]
　It said portion Teflon® resin sheet is sandwiched and superimposed unvulcanized rubber sheet was allowed, and pressed (the pressing) at 180 ° C. 10 min with 100 ton press molding machine, the thickness 2mm crosslinked rubber sheet (laminate) was adjusted.
[0115]
　Crosslinked rubber sheet (laminate) of Teflon (registered trademark) removing the resin sheet, in the manner of the described crosslinked rubber sheet (laminate) was subjected to T-peel test.
[0116]
　The results are shown in Table 1.
[0117]
　[Examples 2 to 12]
　instead of the ACM composition forming the layer (1) used in Example 1, except for using ACM composition obtained by adding various additives in amounts as described in Table 1 , the laminate obtained in the same manner as in example 1, by the method described in example 1, was subjected to T-peel test.
[0118]
　The results are shown in Table 1-1 and Table 1-2.
[0119]
　[Comparative Example 1]
　in place of the ACM composition forming the layer (1) used in Example 1, in the amount listed in Table 1-2 [inorganic compound such as hydrotalcite (B) is not blended] except for using, to produce a laminate performed in the same manner as in example 1, by the method described in example 1, it was subjected to T-peel test.
[0120]
　The results are shown in Table 1-2.
[0121]
　[Reference Example 1]
　in place of the ACM composition forming the layer (1) used in Example 1, in the amount listed in Table 1-2 [inorganic compound such as hydrotalcite (B) is not blended] except for using, to produce a laminate performed in the same manner as in example 1, by the method described in example 1, it was subjected to T-peel test.
[0122]
　The results are shown in Table 1-2.
[0123]
[Table 1-1]

[0124]
[Table 1-2]

　Example 13
　in place of the ACM composition forming the layer (1) used in Example 1 used in Example 1, a composition comprising an ECO adjusted by the following method except that the layer (1) is to prepare a laminate performed in the same manner as in example 1, by the method described in example 1, was subjected to T-peel test.
[0125]
　The results are shown in Table 2.
[0126]
　"Preparation of ECO composition forming the layer (1)"
　as a first step, using a BB-2 type Banbury mixer (manufactured by Kobe Steel), the ECO 100 parts by weight kneaded for 30 seconds element, then to , MAF carbon black 40 parts by weight (Seast 116: Tokai carbon Co., Ltd.), 1 part by weight of stearic acid (Tsubaki beads stearic acid: manufactured by NOF Corporation), magnesium oxide 3 parts by weight (Mag 150: manufactured by Kyowa chemical Kogyo Co., Ltd.), 1 part by weight of nickel dibutyldithiocarbamate manufactured by (NOCRAC NBC Ouchi Shinko chemical industrial Co.), calcium carbonate 5 parts by mass (Whiton SB (red): Bihoku Funka Kogyo Co. ), and the mixture was kneaded for 2 minutes at 140 ° C.. Thereafter, performs cleaning to increase the ram, further, subjected to 1 minute kneading, discharged at about 0.99 ° C., to obtain a first phase of the formulation.
[0127]
　Next, as a second step, the blend obtained in the first stage, 8 Inchiro - Le (Nippon Roll Co., Ltd., before the surface temperature 50 ° C. of the roll, the surface temperature of 50 ° C. of the rear roll, front roll wound rotational speed 16 rpm, the rotational speed 18 rpm) of the rear roll, 20 parts by weight of hydrotalcite (DHT-4A, manufactured by Kyowa chemical industry Co., Ltd.), 1.2 parts by weight of 2,4,6-trimercapto -S- triazine (Noccelar TCA: Ouchi Shinko chemical industrial Co., Ltd.), 0.5 part by weight of tetramethylthiuram disulfide (NOCCELER TT: Ouchi Ltd. Shinko chemical industry Co.) was kneaded for 10 minutes was added to obtain a rubber composition of uncrosslinked (rubber compound) (composition containing ECO).
[0128]
　[Examples 14-18]
　in place of the ECO composition forming the layer (1) used in Example 13, except using ECO composition obtained by adding various additives in amounts as described in Table 2 , the laminate obtained in the same manner as in example 1, by the method described in example 13, was subjected to T-peel test.
[0129]
　The results are shown in Table 2.
[0130]
　[Comparative Example 2]
　in place of the ECO composition forming the layer (1) used in Example 13, except that in the amount described in Table 2 [Inorganic compounds such as hydrotalcite (B) is not blended] is the laminate obtained in the same manner as in example 5, by the method described in example 13, it was subjected to T-peel test.
[0131]
　The results are shown in Table 2.
[0132]
　[Reference Example 2]
　in place of the ECO composition forming the layer (1) used in Example 13, except that in the amount described in Table 2 [Inorganic compounds such as hydrotalcite (B) is not blended] is the laminate obtained in the same manner as in example 5, by the method described in example 13, it was subjected to T-peel test.
[0133]
　The results are shown in Table 2.
[0134]
[Table 2]

　
　in two layers molding die using two Thereafter, steam vulcanization (150 ℃ ~ 160 ℃, 30 minutes to 50 minutes) to crosslink the multi-layer hose is heated in, and inner and outer layers hose appearance smoothness was confirmed that it is firmly adhered.
[0135]
　
　regard to the ACM composition or ECO composition described in Examples 2-8, similarly molded multilayer hose with the fluorine-based rubber, and inner and outer layers hose appearance smooth it was confirmed that is you are firmly bonded.

WE CLAIM

Following layer (1), the following layer (2) and is directly joined laminate.
　Layer (1): a halogen-based rubber (A) [excluding the fluorine-based rubber]: at least one element selected from the 100 parts by mass of group 2 element and Group 13 element-containing inorganic compounds and oxygen (B): 1 ~ 30 parts by weight comprising comprising the composition layer.
　Layer (2) except for halogen-containing rubber halogen-containing polymer (C) was prepared in which the layer (1). Layer consisting].
[Requested item 2]
　Halogen-based rubber (A) is The laminate of claim 1 is at least one selected from epichlorohydrin rubber (ECO) and acrylic rubber (ACM).
[Requested item 3]
　Halogen-containing polymer (C) is laminated body according to claim 1 is a fluorine-based rubber.
[Requested item 4]
　Layer (2) is The laminate of claim 1 comprising cross-linked with a polyol crosslinking agent.
[Requested item 5]
　The inorganic compound (B) is laminated body according to claim 1 which is a compound containing magnesium, calcium, barium, one or more elements selected from aluminum.
[Requested item 6]
　The inorganic compound (B) is laminated body according to claim 1 is at least one compound selected from magnesium oxide and hydrotalcite.
[Requested item 7]
　The laminate according to any one of claims 1 to 6, hose having at least in part.
[Requested item 8]
　Automotive, motorcycle use, industrial machinery, construction machinery or hose according to claim 7 for use in any application for agricultural machinery.
[Requested item 9]
　Hose according to claim 7 for use in turbocharger hose for automobiles.
[Requested item 10]
　Following layer (1), method for producing a laminate, which comprises directly bonding the following layer (2).
　Layer (1): a halogen-based rubber (A) [excluding the fluorine-based rubber]: at least one element selected from the 100 parts by mass of group 2 element and Group 13 element-containing inorganic compounds and oxygen (B): a layer comprising a composition comprising 10 to 30 parts by weight.
　Layer (2) except for halogen-containing rubber halogen-containing polymer (C) was prepared in which the layer (1). Layer consisting].