CN104245308A - Laminate - Google Patents

Laminate Download PDF

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Publication number
CN104245308A
CN104245308A CN201380021741.1A CN201380021741A CN104245308A CN 104245308 A CN104245308 A CN 104245308A CN 201380021741 A CN201380021741 A CN 201380021741A CN 104245308 A CN104245308 A CN 104245308A
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CN
China
Prior art keywords
laminate
fluorubber
layer
fluoro
fluororubber layer
Prior art date
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Pending
Application number
CN201380021741.1A
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Chinese (zh)
Inventor
桑岛祐己
大谷充宏
增井利昭
稻叶刚志
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Daikin Industries Ltd
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Daikin Industries Ltd
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Publication of CN104245308A publication Critical patent/CN104245308A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)

Abstract

The purpose of the present invention is to provide a laminate wherein a non-fluorine rubber layer and a fluorine rubber layer are able to be firmly adhered to each other without using an adhesive and without subjecting the non-fluorine rubber layer and the fluorine rubber layer to a surface treatment. The present invention is a laminate which is provided with a fluorine rubber layer (B) and a non-fluorine rubber layer (A) that is laminated on the fluorine rubber layer (B). This laminate is characterized in that: the non-fluorine rubber layer (A) is formed from a non-fluorine rubber composition, and the non-fluorine rubber composition contains (a1) an unvulcanized non-fluorine rubber, (a2) at least one compound that is selected from the group consisting of 1,8-diazabicyclo(5.4.0)undecene-7 salts and 1,8-diazabicyclo(5.4.0)undecene-7, (a3) magnesium oxide and (a4) silica; and the fluorine rubber layer (B) is formed from a fluorine rubber composition that contains (b1) a fluorine rubber.

Description

Laminate
Technical field
The present invention relates to laminate.
Background technology
Fluorubber demonstrates excellent chemical proofing, solvent resistance and heat resistance, is thus widely used in the various fields such as auto industry, semi-conductor industry, chemical industry.Such as, in automobile industry, be used as the flexible pipe (hose), encapsulant etc. of engine and peripheral device, AT device, fuel system and peripheral device etc.
Although fluorubber that show various excellent specific property as described above, compared with common elastomeric material, its price is very expensive, from the viewpoint of cost, is only problematic with the material that fluorubber makes flexible pipe etc.In addition, the acrylonitrile-butadiene copolymer rubber in the past used as fuel area density flexible pipe is inferior to fluorubber in the various characteristics such as heat resistance, oil resistivity, resistance to ag(e)ing, requires to improve it.
Based on above-mentioned background, there is motion to propose and fluorubber and non-fluorubber are share.Such as, describe a kind of hose in patent document 1, it uses thin fluorubber as internal layer, and skin is made up of non-fluorubber such as ECDs.But, lack cementability between the non-fluororubber layer such as fluororubber layer and ECD, practicality have problems.
In order to improve the cementability of fluororubber layer and non-fluororubber layer, to be investigated in non-fluororubber layer mixture 1,8-diazabicyclo (5.4.0)-ten one carbon-7-alkene salt (DBU salt) as the method for bonding mixed agent; The method etc. of mixture epoxy resin in non-fluororubber layer.But, even if use these methods, also sufficient cementability cannot be given.
In order to solve problem as described above, such as, a kind of manufacture method of fluoropolymer lamination body is described in patent document 2, it is for having the manufacture method of the fluoropolymer lamination body of the operation of fluoropolymer layer (A) and non-fluororubber layer (B) lamination, the feature of this manufacture method is, above-mentioned fluoropolymer layer (A) is formed by the fluoro-containing copolymer composition comprising fluoropolymer and vulcanizing agent, above-mentioned non-fluororubber layer (B) is formed by the non-fluoro-rubber composite comprising non-fluorubber and bonding mixed agent, above-mentioned bonding mixed agent is for being selected from by 1, the phthalate of 8-diazabicyclo (5.4.0)-ten one carbon-7-alkene, caprylate, toluene fulfonate and phenolate, and there is substituting group or not there is at least one in the group of substituent imidazoles composition.
In addition, to provide rubber layer and fluororesin layer by for the purpose of the sulfuration laminate of strong bond, a kind of laminate is described in patent document 3, it is the laminate possessing rubber layer (A) and the fluororesin layer (B) of lamination on rubber layer (A), and the feature of this laminate is: rubber layer (A) is the layer formed by rubber composition for vulcanization; Rubber composition for vulcanization contains: half finished rubber (a1); Be selected from by 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt, 1,5-diazabicyclo (the 4.3.0)-ninth of the ten Heavenly Stems-5-alkene salt, 1, at least one compound (a2) in the group that 8-diazabicyclo (5.4.0) 11 carbon-7-alkene and 1,5-diazabicyclo (4.3.0)-ninth of the ten Heavenly Stems ,-5-alkene formed; Magnesia (a3); And silica (a4); Relative to the half finished rubber (a1) of 100 mass parts, compound (a2) is greater than 1.0 mass parts and is below 5.0 mass parts; Fluororesin layer (B) is the layer formed by fluoro-containing copolymer composition; Fluoro-containing copolymer composition contains fluoropolymer (b1), and this fluoropolymer (b1) has the copolymerization units from CTFE.
Prior art document
Patent document
Patent document 1: International Publication No. 2006/082843 pamphlet
Patent document 2: Japanese Unexamined Patent Publication 2011-116004 publication
Patent document 3: International Publication No. 2011/001756 pamphlet
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and a kind ofly can not use cement and by the laminate of fluororubber layer and fluororubber layer strong bond under do not implement surface-treated situation to each layer of non-fluororubber layer and fluororubber layer.
For solving the scheme of problem
The present invention relates to a kind of laminate, it is for possessing the laminate of fluororubber layer (B) and the non-fluororubber layer (A) in the upper lamination of fluororubber layer (B), the feature of this laminate is, non-fluororubber layer (A) is the layer formed by non-fluoro-rubber composite, and non-fluoro-rubber composite contains: unvulcanized non-fluorubber (a1); Be selected from least one compound (a2) in the group be made up of 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt and 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene; Magnesia (a3); With silica (a4), fluororubber layer (B) is the layer formed by the fluoro-rubber composite containing fluorubber (b1).
Unvulcanized non-fluorubber (a1) is preferably acrylonitrile-butadiene rubber (NBR) or its hydride.
Fluorubber (b1) is preferably selected from least one fluorubber in the group be made up of vinylidene fluoride-hexafluoropropene system fluorubber and vinylidene fluoride-hexafluoropropene-tetrafluoroethene system fluorubber.
The blend amount of non-fluoro-rubber composite preferred compound (a2) is 0.7 mass parts ~ 5.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.
Non-fluoro-rubber composite is preferably also containing at least one vulcanizing agent (a5) be selected from the group that is made up of sulfur sulfide system vulcanizing agent and peroxide vulcanizing system vulcanizing agent.
Non-fluoro-rubber composite is preferably further containing at least one slaine (a6) be selected from the group that is made up of carbamic acid slaine and thiazole system slaine.
Compound (a2) is preferably 8-benzyl-1,8-diazabicyclo (5.4.0)-ten one carbon-7-alkene chloride.
The invention still further relates to a kind of sulfuration laminate, it is characterized in that, it heats above-mentioned laminate and obtains, and the non-fluororubber layer of sulfuration (A1) has cured bonding with vulcanised fluororubbers layer (B1).
Sulfuration laminate of the present invention is preferably flexible pipe or pipe, is laminated with vulcanised fluororubbers layer (B1) in the inner side of the non-fluororubber layer of sulfuration (A1).
The effect of invention
Laminate of the present invention can not use cement and by non-fluororubber layer and fluororubber layer strong bond under do not implement surface-treated situation to each layer of non-fluororubber layer and fluororubber layer.
Detailed description of the invention
The feature of laminate of the present invention is, it possesses fluororubber layer (B) and the non-fluororubber layer (A) in the upper lamination of fluororubber layer (B).
Below each layer is described.
(A) non-fluororubber layer
Non-fluororubber layer (A) is the layer formed by non-fluoro-rubber composite.
Non-fluoro-rubber composite contains unvulcanized non-fluorubber (a1); Be selected from least one compound (a2) in the group be made up of 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt and 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene; Magnesia (a3); With silica (a4) as neccessary composition.
By share compound (a2), magnesia (a3) and silica (a4) in non-fluoro-rubber composite, even if do not use cement and do not implement surface treatment to each layer of non-fluororubber layer (A) and fluororubber layer (B), the sulfuration laminate obtained by laminate of the present invention also can the non-fluororubber layer of bonding sulfuration and vulcanised fluororubbers layer securely.
Therefore, when by non-fluororubber layer (A) and fluororubber layer (B) lamination, namely can low cost easily carry out shaping without the need to specially combining complicated procedures of forming.Further, shaping due to the commonsense method of extrusion molding and so on can be utilized to carry out, thus also can carry out filming, also can improve in flexibility.
Non-fluoro-rubber composite can to comprise in vulcanizing agent (a5) and slaine (a6) at least one further as optional member.If not especially fluoro-rubber composite comprises vulcanizing agent (a5) and slaine (a6), then the sulfuration laminate obtained by laminate of the present invention can make the non-fluororubber layer of sulfuration bonding more firmly with vulcanised fluororubbers layer.Hereinafter vulcanizing agent (a5) and slaine (a6) are described.
As the concrete example of unvulcanized non-fluorubber (a1), diene series rubber, ethylene propylene diene rubber, silicon rubber, butyl rubber, ECD, the acrylic rubber etc. such as such as acrylonitrile-butadiene rubber (NBR) or its hydride (HNBR), butadiene-styrene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR) can be enumerated.
As unvulcanized non-fluorubber (a1), from the viewpoint of the preferred diene series rubber that heat resistance, oil resistivity, weatherability, extrusion molding are good, more preferably NBR or HNBR.
Non-fluoro-rubber composite comprises and is selected from by 1, at least one compound (a2) in the group that 8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt (hereinafter also referred to as " DBU salt ") and 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene (hereinafter also referred to as " DBU ") form.Compound (a2) is preferably 0.7 mass parts ~ 5.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.Compound (a2) is more preferably more than 1.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.Compound (a2) if very few, then likely cannot obtain sufficient bonding force.In addition, compound (a2) is more preferably below 4.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts, more preferably below 3.5 mass parts, is particularly preferably below 3.0 mass parts.Compound (a2) is if too much, then likely suppress sulfuration.
Compound (a2) is for being selected from least one compound in the group that is made up of DBU salt and DBU.
As DBU salt, the carbonate of DBU, long-chain fat race carboxylate, aromatic carboxylic acid salt, phthalate, tosilate, phenolate, phenol resin salt, naphthoate, caprylate, oleate, formates, linear phenolic resin salt, villaumite (preferred 8-benzyl-1,8-diazabicyclo (5.4.0)-ten one carbon-7-alkene chloride (DBU-B)) etc. can be enumerated.
From the view point of raising adhesive strength, compound (a2) is preferably selected from least one compound in the group be made up of the formates of the phenolate of the naphthoate of DBU, DBU-B, DBU, DBU, the phthalate of DBU and DBU.Compound (a2) is more preferably at least one compound in the group being selected from and being made up of the phthalate of DBU, DBU-B and DBU, more preferably DBU-B.
Non-fluoro-rubber composite also can quaternary ammonium salt beyond inclusion compound (a2).As the quaternary ammonium salt beyond compound (a2), 1,5-diazabicyclo (4.3.0)--5-alkene salt in the ninth of the ten Heavenly Stems (DBN salt), 1,5-diazabicyclo (4.3.0)--5-alkene in ninth of the ten Heavenly Stems (DBN) etc. can be enumerated.
As DBN salt, the carbonate of DBN, long-chain fat race carboxylate, aromatic carboxylic acid salt, phthalate, tosilate, phenolate, phenol resin salt, naphthoate, caprylate, oleate, formates, linear phenolic resin salt, villaumite etc. can be enumerated.
Non-fluoro-rubber composite comprises magnesia (a3).From the aspect of cementability, rubber physical property, the blend amount of magnesia (a3) is preferably 3 mass parts ~ 20 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts, is particularly preferably 5 mass parts ~ 15 mass parts.The laminate with ad hoc structure of the present invention is required composition with magnesia (a3), and in the sulfuration laminate thus obtained by laminate of the present invention, the non-fluororubber layer of sulfuration is bonding securely with vulcanised fluororubbers layer.
Non-fluoro-rubber composite comprises silica (a4).As silica (a4), alkaline silicon dioxide, acid silicon dioxide can be used, from the aspect of cementability, preferably use alkaline silicon dioxide.As alkaline silicon dioxide, Carplex 1120 (manufacture of DSL Japan company) can be enumerated.In addition, from the aspect of cementability, rubber physical property, the blend amount of silica (a4) is preferably 10 mass parts ~ 40 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts, is particularly preferably 15 mass parts ~ 25 mass parts.The laminate with ad hoc structure of the present invention is with silica (a4) for neccessary composition, and in the sulfuration laminate thus obtained by laminate of the present invention, the non-fluororubber layer of sulfuration is bonding securely with vulcanised fluororubbers layer.
Vulcanizing agent (a5) can use existing known vulcanizing agent according to the vulcanizing system of non-fluoro-rubber composite.By carrying out sulfuration to unvulcanized non-fluorubber (a1), the mechanical strengths such as the hot strength of the non-fluororubber layer of obtained sulfuration being improved, good elasticity can also be obtained.
As the vulcanizing system that can be used in the present invention, the any system in sulfur sulfide system, polyamine vulcanizing system, polyol vulcanized system, peroxide vulcanizing system, imidazoles vulcanizing system, triazine vulcanizing system, oxazole vulcanizing system, thiazole vulcanizing system can be adopted, but in half finished rubber containing cure group (crosslink sites (cure site)), suitably can select vulcanizing system according to the kind of crosslink sites or according to the characteristic of giving the laminate after sulfuration and purposes.
As vulcanizing agent (a5), the any vulcanizing agent in vulcanizing system employing sulfur sulfide system vulcanizing agent, polyamine vulcanizing system vulcanizing agent, polyol vulcanized system vulcanizing agent, peroxide vulcanizing system vulcanizing agent, imidazoles vulcanizing system vulcanizing agent, triazine vulcanizing system vulcanizing agent, oxazole vulcanizing system vulcanizing agent, thiazole vulcanizing system vulcanizing agent can be corresponded to, can be used alone or share.
Such as, when unvulcanized non-fluorubber (a1) is for the non-fluorubber of diene series (NBR, SBR, BR etc.), usual employing sulfur sulfide system and peroxide vulcanizing system, be thus also preferably selected from least one in the group be made up of sulfur sulfide system vulcanizing agent and peroxide vulcanizing system vulcanizing agent as vulcanizing agent.Be more preferably sulfur sulfide system vulcanizing agent.
The addition of vulcanizing agent (a5) is preferably 0.5 mass parts ~ 15.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.Addition is more preferably below below 10.0 mass parts, more preferably 5.0 mass parts, is particularly preferably below 3.0 mass parts, and is more preferably more than 1.0 mass parts.
As sulfur sulfide system vulcanizing agent, powder sulphur, sedimentation sulphur, colloid sulphur, surface treatment sulphur, insoluble sulfur, sulfur chloride, sulfur dichloride, disulphide, polysulfide etc. can be exemplified.
The blend amount of sulfur sulfide system vulcanizing agent is preferably 1.0 mass parts ~ 10.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.If it is insufficient to cross cementability at least, become tendency really up to the mark if cross to have at most.
As peroxide vulcanizing system vulcanizing agent, as preferably enumerating the organic peroxide easily producing peroxylradicals under the existence of heat or redox system.
As organic peroxide, such as 1 can be exemplified, 1-bis(t-butylperoxy)-3, 5, 5-trimethyl-cyclohexane, 2, 5-dimethylhexane-2, 5-dihydroxy peroxide, di-tert-butyl peroxide, t-butylcumylperoxide, cumyl peroxide, α, α '-bis(t-butylperoxy)-to diisopropyl benzene, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy)-3-hexin, benzoyl peroxide, tert-butyl hydroperoxide benzene, 2, 5-dimethyl-2, 5-bis-(benzoyl peroxide) hexane, the peroxidating maleic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate etc.Dialkyl compound is preferably among these.Usually kind and blend amount is selected according to the amount, decomposition temperature etc. of activity-O-O-.Blend amount is usually 0.1 mass parts ~ 15.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts, is preferably 0.3 mass parts ~ 5.0 mass parts.
Slaine (a6) is preferably selected from least one in the group be made up of carbamic acid slaine and thiazole system slaine.
As above-mentioned carbamic acid slaine, the zinc salt (ZnMDC) of such as dimethyl dithiocarbamate can be enumerated, the zinc salt (ZnEDC) of DECTC, the zinc salt (ZnBDC) of dibutyl dithiocaarbamate salt, the molysite (FeMDC) of dimethyl dithiocarbamate, the zinc salt (ZnEPDC) of ethylphenyl dithiocarbamate salt, the zinc salt of N-pentamethylene dithiocar-bamate, the zinc salt of dibenzyl aminodithioformic acid salt, the sodium salt (NaMDC) of dimethyl dithiocarbamate, the sodium salt (NaEDC) of DECTC, the sodium salt (NaBDC) of dibutyl dithiocaarbamate salt, the mantoquita (CuMDC) of dimethyl dithiocarbamate, the tellurium salt (TeEDC) etc. of DECTC.These materials can be used alone or share two or more.Among these, from the viewpoint of cementability, rubber physical property, preferably use ZnMDC, ZnEDC or ZnBDC.
As above-mentioned thiazole system slaine, preferably use the zinc salt (ZnMBT) of mercaptobenzothiazoler.
Relative to the unvulcanized non-fluorubber (a1) of 100 mass parts, the blend amount of slaine (a6) is preferably 0.01 mass parts ~ 3.0 mass parts, is more preferably 0.01 mass parts ~ 0.5 mass parts, is particularly preferably 0.05 mass parts ~ 0.3 mass parts.Slaine (a6) if blend amount very few, then find that vulcanized rubber physical property has the tendency of variation; If too much, then find that unvulcanized physical property has the tendency of variation.
In order to give the characteristic being different from unvulcanized non-fluorubber (a1) to non-fluororubber layer (A), non-fluoro-rubber composite can contain resin.As resin, such as PVC, Chloropolystyrene, chlorosulfonation polystyrene ethene (Network ロ ロ ス Le ホ Application Port リ ス チ レ Application エ チ レ Application), vinyl-vinyl acetate copolymer etc. can be enumerated.Such as, when non-fluoro-rubber composite contains NBR and PVC, ozone resistance can be made to be improved.In this case, the blend amount of PVC is preferably 10 mass parts ~ 70 mass parts relative to 100 mass parts NBR.
In addition, in the present invention, according to object or needs, can the conventional additive of mixture institute's mixture in common non-fluoro-rubber composite, such as can mixture filler, processing aid, plasticizer, softening agent, age resister, colouring agent, stabilizing agent, bonding auxiliary agent, antitack agent, conductivity-imparting agent, thermal conductivity imparting agent, the surface not various additive such as sticky agent, tackifier, softness-conferring agent, improved heat resistance agent, fire retardant, ultra-violet absorber, oil resistivity improving agent, blowing agent, antiscorching agent, lubricant, epoxy resin.In addition, also can the one kind or two or more conventional vulcanizing agent different from above-mentioned substance of mixture or vulcanization accelerator.Wherein, the blend amount of these additives is in the scope of the layers cementing power without detriment to the sulfuration laminate obtained by laminate of the present invention.
As filler, the metal oxides such as calcium oxide, titanium dioxide, aluminium oxide can be enumerated; The metal hydroxides such as magnesium hydroxide, aluminium hydroxide, calcium hydroxide; The carbonate such as magnesium carbonate, aluminium carbonate, calcium carbonate, brium carbonate; The silicate such as magnesium silicate, calcium silicates, sodium metasilicate, alumina silicate; The sulfate such as aluminum sulfate, calcium sulfate, barium sulfate; Synthetic hydrotalcite; The metal sulfides such as molybdenum bisuphide, iron sulfide, copper sulfide; Diatomite, asbestos, lithopone (zinc sulphide/barium sulphide), graphite, carbon black, fluorocarbons, calcirm-fluoride, coke, quartz micropowder, zinc white, talcum, mica powder, wollastonite, carbon fiber, aramid fiber, various whisker, glass fibre, organic reinforcing agent, organic filler etc.
As processing aid, the higher fatty acids such as stearic acid, oleic acid, palmitic acid, laurate can be enumerated; The higher fatty acid salt such as odium stearate, zinc stearate; The high fatty acid amide such as stearmide, oleamide; The high-grade aliphatic esters such as ethyl oleate; The senior aliphatic amine such as stearylamine, oleyl amine; The petroleum such as Brazil wax, ceresine wax; The polyglycols such as ethylene glycol, glycerine, diethylene glycol (DEG); The aliphatic hydrocarbon such as vaseline, alkane; Silicon-type oil, silicon-type polymer, low molecular weight polyethylene, phthalate, phosphoric acid ester, rosin, (halogenation) dialkylamine, (halogenation) dialkyl sulfone, surfactant etc.
As plasticizer, such as phthalic acid derivatives, adipic acid derivative or sebacic acid derivative can be enumerated; As softening agent, such as lubricating oil, process oil, coal tar, castor oil, calcium stearate can be enumerated; As age resister, such as phenylenediamine, phosphate (salt) class, quinolines, cresols class, phenol, metal dithiocarbamate etc. can be enumerated.
Non-fluoro-rubber composite passes through unvulcanized non-fluorubber (a1); Be selected from least one compound (a2) in the group be made up of 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt and 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene; Magnesia (a3); With silica (a4); Vulcanizing agent (a5) when needing further; Slaine (a6) and other additive carry out mixing preparation.
Mixing can such as less than 100 DEG C temperature uses mill (open roll), Banbury, pressure kneader etc. carry out.
Sulfurizing time (the T of non-fluoro-rubber composite 90) be preferably less than 18 minutes.Be more preferably less than 15 minutes, more preferably less than 13 minutes.To T 90lower limit be not particularly limited, be such as more than 1 minute.Above-mentioned non-fluoro-rubber composite, owing to being above-mentioned formation, thus can make cure time shorten, productivity ratio is improved.T 90for at 160 DEG C to maximum torque (M h) and minimal torque value (M l) carry out measuring and the value obtained, it is by { (M h)-(M l) × 0.9+M lthe value tried to achieve.M hand M lfor the value measured based on JIS K 6300-2.
Next the fluororubber layer (B) in laminate of the present invention is described.
(B) fluororubber layer
Fluororubber layer (B) is the layer formed by fluoro-rubber composite.Fluoro-rubber composite contains fluorubber (b1).
Above-mentioned fluorubber (b1) can be unvulcanized fluorubber, also can be vulcanised fluororubbers.
As fluorubber (b1), can enumerate the fluorubber of such as peroxide curable, can polyol vulcanized fluorubber, can the fluorubber etc. of polyamine sulfuration.Fluorubber as above-mentioned peroxide curable is not particularly limited, as long as be the fluorubber at the position with peroxide curable.Position as above-mentioned peroxide curable is not particularly limited, and can enumerate such as atomic iodine, bromine atoms etc.
Can the fluorubber of polyol vulcanized be not particularly limited as above-mentioned, as long as can the fluorubber at position of polyol vulcanized for having.The position of polyol vulcanized can be not particularly limited as above-mentioned, the position etc. such as with vinylidene fluoride (VdF) unit can be enumerated.As the method importing above-mentioned sulfide site, the method etc. that the monomer copolymerization of sulfide site can be provided when the polymerization of fluorubber can be enumerated.
As above-mentioned fluorubber (b1), can enumerate that vinylidene fluoride (VdF)/hexafluoropropene (HFP) is fluorubber, VdF/HFP/ tetrafluoroethene (TFE) is fluorubber, TFE/ propylene system fluorubber, TFE/ propylene/VdF system fluorubber, ethene/HFP system fluorubber, ethene/HFP/VdF system fluorubber, ethene/HFP/TFE system fluorubber, VdF/TFE/ perfluoroalkyl vinyl ether (PAVE) are fluorubber, VdF/CTFE system fluorubber etc.
From the viewpoint of heat resistance, compression set, processability, cost, above-mentioned fluorubber (b1) is more preferably the fluorubber (VdF system fluorubber) containing VdF unit, is more preferably selected from least one fluorubber in the group be made up of VdF-HFP system fluorubber and VdF-HFP-TFE system fluorubber.
As above-mentioned fluorubber (b1), be not limited to a kind in above explanation, also can use two or more, can also use after their sulfurations.
In addition, the preferred fluorine-containing rate of fluorubber (b1) used in the present invention is fluorubber, the more preferably fluorine-containing rate of more than 64 quality % is the fluorubber of more than 66 quality %.The higher limit of fluorine-containing rate is not particularly limited, is preferably below 74 quality %.If fluorine-containing rate is less than 64 quality %, then chemical proofing, fuel-resistant oiliness, fuel crossover have the tendency of variation.
Above-mentioned fluoro-rubber composite can comprise fluorubber (b1) and fluororesin, above-mentioned fluorubber (b1) can under the existence of fluororesin and vulcanizing agent, under melting condition by the vulcanised fluororubbers of unvulcanized fluorubber dynamic vulcanization process.By carrying out dynamic vulcanization process so to unvulcanized fluorubber, the flexibility of the fluororubber layer formed by above-mentioned fluoro-rubber composite can be improved, because of but preferred.
Herein, so-called dynamic vulcanization process refers to and uses Banbury, pressure kneader, extruder etc. carry out melting mixing to unvulcanized fluorubber and make the situation of its dynamic vulcanization simultaneously.Among these, from the viewpoint of applying high shear force, the extruders such as preferred double screw extruder.By carrying out dynamic vulcanization process, the phase structure of fluororesin and vulcanised fluororubbers can be controlled.
In addition, more than the temperature for fluororesin generation melting is meaned under so-called melting condition.Suitable temperature range is different according to the difference of the glass transition temperature of the fusing point of fluororesin and unvulcanized fluorubber, but preferably 120 DEG C ~ 330 DEG C, be more preferably 130 DEG C ~ 320 DEG C.If temperature is lower than 120 DEG C, then the tendency be dispersed with in coarsening between fluororesin and fluorubber; If higher than 330 DEG C, then fluorubber has the tendency that heat deterioration occurs.
The fluoro-rubber composite obtained can have following structure: fluororesin forms continuous phase and the structure of vulcanised fluororubbers formation decentralized photo; Or fluororesin and vulcanised fluororubbers form common continuous print structure.Wherein preferably fluororesin forms continuous phase and the structure of vulcanised fluororubbers formation decentralized photo.
Even if when by unvulcanized fluorubber dispersion to form matrix (matrix), along with the carrying out of vulcanization reaction, unvulcanized fluorubber becomes vulcanised fluororubbers, thus melt viscosity rises, and vulcanised fluororubbers becomes decentralized photo or vulcanised fluororubbers and fluororesin and forms altogether (bicontinuous) structure continuously.
In addition, the fluororesin of fluoro-rubber composite forms continuous phase and also can contain the common continuous structure of fluororesin and vulcanised fluororubbers in a part for the structure of vulcanised fluororubbers formation decentralized photo.
If form such structure, then the sulfuration laminate obtained by laminate of the present invention can demonstrate more excellent fuel-barrier, heat resistance, chemical proofing and oil resistivity.The average mark shot footpath of above-mentioned vulcanised fluororubbers is preferably 0.01 μm ~ 30 μm, be more preferably 0.1 μm ~ 20 μm, more preferably 0.1 μm ~ 10 μm.If average mark shot footpath is less than 0.01 μm, then mobility has the tendency of reduction; If more than 30 μm, then the intensity of products formed has the tendency of reduction.
Fluorubber (b1) in above-mentioned fluoro-rubber composite is preferably 3/97 ~ 80/20 (fluorubber (b1)/fluororesin) with the mass ratio of fluororesin.If the mass ratio of fluororesin is less than 80/20 (fluorubber (b1)/fluororesin), then the improvement effect of the low permeability of fuel or low temperature resistant degradation property reduces, if the mass ratio of fluororesin is greater than 3/97 on the other hand, then the caoutchouc elasticity of script is significantly impaired, compression set is significantly deteriorated or hardness significantly improves, because of but not preferred.From the viewpoint of balancedly improving the low permeability of fuel, low temperature resistant degradation property and caoutchouc elasticity, above-mentioned mass ratio (fluorubber (b1)/fluororesin) is more preferably 5/95 ~ 70/30, more preferably 10/90 ~ 50/50.
Be not particularly limited as above-mentioned fluororesin, from the aspect good with the compatibility of VdF system fluorubber, preferably comprise the fluororesin of the fluorine-containing ethylenic polymer of at least one.Above-mentioned fluorine-containing ethylenic polymer is not particularly limited, such as, preferably there is the construction unit of at least one from fluorine-containing ethylenic monomer.As above-mentioned fluorine-containing ethylenic monomer, tetrafluoroethene (TFE) can be enumerated, with formula (2):
CF 2＝CF-Rf 2 (2)
(in formula, Rf 2expression-CF 3or-ORf 3(Rf 3to be carbon number be 1 ~ 5 perfluoroalkyl)) perfluoroolefine such as the perfluor ethylenically unsaturated compounds that represents; CTFE (CTFE), trifluoro-ethylene, hexafluoro-isobutene, vinylidene fluoride (VdF), PVF, formula (3):
CH 2＝CX 3(CF 2) nX 4 (3)
(in formula, X 3represent hydrogen atom or fluorine atom, X 4represent hydrogen atom, fluorine atom or chlorine atom, n represents the integer of 1 ~ 10.) etc. fluoroolefin etc.
Above-mentioned fluorine-containing ethylenic polymer can have from can with the construction unit of the monomer of above-mentioned fluorine-containing ethylenic monomer copolymerization, as such monomer, the non-fluorine ethylenic monomer beyond above-mentioned fluoroolefin, perfluoroolefine can be enumerated.Be not particularly limited as above-mentioned non-fluorine ethylenic monomer, such as ethene, propylene, alkyl vinyl ethers etc. can be enumerated.Herein, alkyl vinyl ether refers to have the alkyl vinyl ether that carbon number is the alkyl of 1 ~ 5.
Among these, from the low permeability of fuel of the sulfuration laminate obtained by laminate of the present invention and the good aspect of cold resistance, preferred following fluorine-containing ethylenic polymer.
(1) ethene be made up of TFE and ethene/TFE based copolymer (ETFE)
(2) by TFE and TFE-perfluor (alkyl vinyl ether) copolymer (PFA) formed with the perfluor ethylenically unsaturated compounds that formula (2) represents or TFE/HFP based copolymer (FEP)
(3) by TFE, VdF and TFE/VdF/ perfluor (alkyl vinyl ether) copolymer formed with the perfluor ethylenically unsaturated compounds that formula (2) represents or TFE/HFP/VdF copolymer
(4) polyvinylidene fluoride (PVdF)
(5) the CTFE/TFE/ perfluor ethylenically unsaturated compounds based copolymer that forms of CTFE-TFE copolymer or the perfluor ethylenically unsaturated compounds that represented by CTFE, TFE and formula (2)
Wherein more preferably with the fluorine-containing ethylenic polymer that (1), (2), (5) represent.
Below, the preferred fluorine-containing ethylenic polymer of (1), (2), (5) is described.
(1)ETFE
When ETFE, be preferred from the aspect of the low permeability of fuel showing excellence.The mol ratio that contains of TFE unit and ethylene unit is preferably 20:80 ~ 90:10, is more preferably 37:63 ~ 85:15, is particularly preferably 38:62 ~ 80:20.In addition the 3rd composition can be contained, as the 3rd composition, as long as just can not limit its kind with TFE and ethylene copolymer.As the 3rd composition, usually use with following formula:
CH 2=CX 5rf 4, CF 2=CFRf 4, CF 2=CFORf 4, CH 2=C (Rf 4) 2(in formula, X 5represent hydrogen atom or fluorine atom, Rf 4represent containing or the fluoro-alkyl of not ether-containing key oxygen atom) monomer that represents, more preferably with CH among these 2=CX 5rf 4the fluorine-containing vinyl monomer represented, particularly preferably Rf 4carbon number be the monomer of 1 ~ 8.
As the concrete example of the fluorine-containing vinyl monomer that above-mentioned formula represents, can 1 be enumerated, 1-dihydro perfluor-1-propylene, 1, 1-dihydro perfluor-1-butylene, 1, 1, 5-tri-hydrogen perfluor-1-amylene, 1, 1, 7-tri-hydrogen perfluor-1-heptene, 1, 1, 2-tri-hydrogen perfluor-1-hexene, 1, 1, 2-tri-hydrogen perfluor-1-octene, 2, 2, 3, 3, 4, 4, 5, 5-octafluoro amyl group vinyl ethers, perfluor (methyl vinyl ether), perfluor (propyl vinyl ether), hexafluoropropene, perfluor-1-butylene, 3, 3, the fluoro-2-of 3-tri-(trifluoromethyl)-1-propylene, 2, 3, 3, 4, 4, 5, the fluoro-1-amylene of 5-seven (CH 2=CFCF 2cF 2cF 2h) etc.
Relative to fluorine-containing ethylenic polymer, the content of above-mentioned 3rd composition is preferably 0.1 % by mole ~ 10 % by mole, is more preferably 0.1 % by mole ~ 5 % by mole, is particularly preferably 0.2 % by mole ~ 4 % by mole.
(2) PFA or FEP
When PFA or FEP, from heat resistance is especially excellent and the aspect that can show the excellent low permeability of fuel is preferred.Be not particularly limited as PFA or FEP, be preferably by TFE unit 70 % by mole ~ 99 % by mole with perfluor ethylenically unsaturated compounds unit 1 % by mole ~ 30 % by mole copolymers formed that formula (2) represents, be more preferably by TFE unit 80 % by mole ~ 97 % by mole and perfluor ethylenically unsaturated compounds unit 3 % by mole ~ 20 % by mole copolymers formed of representing with formula (2).When TFE unit is less than 70 % by mole, mechanical properties has the tendency of reduction; If more than 99 % by mole, fusing point becomes too high, and mouldability has the tendency of reduction.In addition, 3rd composition can be contained by TFE with the fluorine-containing ethylenic polymer that the perfluor ethylenically unsaturated compounds that formula (2) represents is formed, as the 3rd composition, as long as the perfluor ethylenically unsaturated compounds copolymerization that can represent with TFE and formula (2) does not then limit its kind.
(5) CTFE-TFE copolymer or CTFE/TFE/ perfluor ethylenically unsaturated compounds based copolymer
When CTFE-TFE copolymer, the mol ratio that contains of CTFE unit and TFE unit is preferably CTFE:TFE=2:98 ~ 98:2, is more preferably 5:95 ~ 90:10.If CTFE unit is less than 2 % by mole, then has the low permeability of fuel and be deteriorated and the tendency of melt-processed difficulty, if more than 98 % by mole, then heat resistance time shaping, chemical proofing are deteriorated sometimes.In addition, preferably by the copolymerization of perfluor ethylenically unsaturated compounds, relative to the total of CTFE unit and TFE unit, preferred perfluor ethylenically unsaturated compounds unit is 0.1 % by mole ~ 10 % by mole, CTFE unit and TFE unit add up to 90 % by mole ~ 99.9 % by mole.If perfluor ethylenically unsaturated compounds unit is less than 0.1 % by mole, then mouldability, environmental stress crack resistance and stress cracking resistance are easily deteriorated; If more than 10 % by mole, then the low permeability of fuel, heat resistance, mechanical property, productivity ratio etc. have the tendency of variation.In addition, as CTFE/TFE/ perfluor ethylenically unsaturated compounds based copolymer, more preferably perfluor ethylenically unsaturated compounds is CTFE/TFE/ perfluor (alkyl vinyl ether) copolymer of the perfluor ethylenically unsaturated compounds represented with formula (2).
Among these, from the aspect excellent especially with the compatibility of the VdF system fluorubber being preferably used as above-mentioned fluorubber, preferred ETFE.
The fusing point of above-mentioned fluorine-containing ethylenic polymer is preferably 120 DEG C ~ 340 DEG C, be more preferably 150 DEG C ~ 330 DEG C, more preferably 170 DEG C ~ 320 DEG C.If the fusing point of fluorine-containing ethylenic polymer is less than 120 DEG C, then there is the tendency of oozing out during its sulfuration in fluororubber layer (B); If more than 340 DEG C, then there is the tendency being difficult to mix with VdF system fluorubber.
In the sulfuration laminate obtained by laminate of the present invention, for the reason that the non-fluororubber layer of sulfuration can be made bonding more firmly with vulcanised fluororubbers layer, at least one polyfunctional compound can be added in above-mentioned fluoro-rubber composite.Above-mentioned polyfunctional compound is the compound of the functional group in 1 molecule with more than 2 identical or different structures.
As the functional group that above-mentioned polyfunctional compound has, as long as there is reactive functional group for carbonyl, carboxyl, halogen formoxyl, amide groups, alkylene, amino, NCO, hydroxyl, epoxy radicals etc. are usually known, just can use arbitrarily.The compound with these functional groups is not only high with the compatibility of fluorubber, and can react with the above-mentioned functional group of fluororesin, can expect that cementability improves further.
Above-mentioned fluoro-rubber composite preferably comprises vulcanizing agent further.As above-mentioned vulcanizing agent, suitably can select according to the vulcanizing system of the fluorubber of institute's mixture.Specifically, peroxidating system vulcanizing agent, polyalcohol system vulcanizing agent etc. can be selected according to object.Be not particularly limited as above-mentioned peroxidating system vulcanizing agent, such as organic peroxide can be enumerated.As above-mentioned organic peroxide, under the existence of heat or redox system, preferably easily produce the organic peroxide of peroxylradicals, such as 1 can be exemplified, 1-bis(t-butylperoxy)-3, 5, 5-trimethyl-cyclohexane, 2, 5-dimethylhexane-2, 5-dihydroxy peroxide, di-tert-butyl peroxide, t-butylcumylperoxide, cumyl peroxide, α, α '-bis(t-butylperoxy)-to diisopropyl benzene, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy)-3-hexin, benzoyl peroxide, tert-butyl hydroperoxide benzene, 2, 5-dimethyl-2, 5-bis-(benzoyl peroxide) hexane, the peroxidating maleic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate etc.Wherein preferred dialkyl compound.Usually, consumption is suitably selected according to the amount, decomposition temperature etc. of activity-O-O-.Relative to 100 mass parts fluorubber, consumption is generally 0.1 mass parts ~ 15 mass parts, is preferably 0.3 mass parts ~ 5 mass parts.
When organic peroxide is used as vulcanizing agent, vulcanization aid or co-curing agent can be share.Be not particularly limited as above-mentioned vulcanization aid or co-curing agent, vulcanization aid as escribed above and co-curing agent can be enumerated.Among these, from the viewpoint of cure, sulfide physical property, preferred cyanacrylate (TAIC).
As the blend amount of above-mentioned vulcanization aid or co-curing agent, be preferably 0.2 mass parts ~ 10 mass parts relative to 100 mass parts fluorubber, be more preferably 0.5 mass parts ~ 6 mass parts, more preferably 1 mass parts ~ 5 mass parts.If vulcanizing agent is less than 0.2 mass parts, then vulcanization density reduces, and compression set has the tendency of increase; If more than 10 mass parts, then vulcanization density is too high, thus there is crackly tendency when compressing.
Be not particularly limited as above-mentioned polyalcohol system vulcanizing agent, such as, be applicable to using polyol, from the viewpoint of excellent heat resistance, be particularly suitable for use polyhydroxy aromatic compound.Be not particularly limited as above-mentioned polyhydroxy aromatic compound, can enumerate such as: 2, two (4-hydroxy phenyl) propane (hereinafter referred to bisphenol-A) of 2-, 2, two (4-hydroxy phenyl) perfluoropropane (hereinafter referred to bisphenol AF) of 2-, resorcinol, 1, 3-dihydroxy benzenes, 1, 7-dihydroxy naphthlene, 2, 7-dihydroxy naphthlene, 1, 6-dihydroxy naphthlene, 4, 4 '-dihydroxybiphenyl, stilbazo, 4 '-glycol, 2, 6-dihydroxy-anthracene, hydroquinones, catechol, 2, two (4-hydroxy phenyl) butane (hereinafter referred to bisphenol b) of 2-, 4, two (4-hydroxy phenyl) valeric acid of 4-, 2, two (4-hydroxy phenyl) the tetrafluoro dichloropropane of 2-, 4, 4 '-dihydroxydiphenylsulisomer, 4, 4 '-dihydroxy benaophenonel, three (4-hydroxy phenyl) methane, 3, 3 ', 5, 5 '-tetrachlorobisphenol A, 3, 3 ', 5, 5 '-tetrabromobisphenol A etc.These polyhydroxy aromatic compounds can be alkali metal salt, alkali salt etc., but when using acid to carry out copolymer precipitating, preferably do not use above-mentioned slaine.
As above-mentioned polyalcohol system vulcanizing agent, little from the viewpoint of the compression set of the fluorubber after sulfuration, mouldability is excellent, preferred polyol; For the reason of excellent heat resistance, more preferably polyhydroxy aromatic compound, further preferred bisphenol AF.
Relative to 100 mass parts fluorubber, the blend amount of above-mentioned polyalcohol system vulcanizing agent is preferably 0.2 mass parts ~ 10 mass parts, is more preferably 0.5 mass parts ~ 6 mass parts, more preferably 1 mass parts ~ 3 mass parts.If above-mentioned blend amount is less than 0.2 mass parts, then have that vulcanization density reduces, compression set becomes large tendency; If more than 10 mass parts, then because vulcanization density is too high, thus have when compressing the tendency being easy to break.
In addition, also vulcanization accelerator can be used together with polyalcohol system vulcanizing agent.If use vulcanization accelerator, then by promoting to form molecule internal double bond to promote vulcanization reaction in the reaction of fluorubber main chain dehydrogenation fluoric acid.
In fluoro-rubber composite, can the mixture additive of mixture in fluoro-rubber composite usually as required, such as filler, processing aid, plasticizer, colouring agent, stabilizing agent, bonding auxiliary agent, acid-acceptor, releasing agent, conductivity-imparting agent, heat conductivity imparting agent, surface be the various additive such as sticky agent, softness-conferring agent, improved heat resistance agent, fire retardant not, also can mixture a kind or more plant and above-mentioned different conventional vulcanizing agent or vulcanization accelerator.
Fluoro-rubber composite can carry out mixing obtaining by using usually compounding rubber device used to other additives such as fluorubber and vulcanizing agent if desired, vulcanization aid, co-curing agent, vulcanization accelerator, packing materials.As above-mentioned compounding rubber device, roller, kneader, Banbury, banbury, double screw extruder etc. can be used.
Although laminate of the present invention forms simple and easy and cost is low, but there is low temperature properties, chemical proofing, flexibility, consider from this point, laminate of the present invention is preferably the bilayer laminated body be only made up of fluororubber layer (B) and non-fluororubber layer (A).
In addition, laminate of the present invention also can for being laminated with the laminate of more than 3 layers of the polymeric layer (C) different with fluororubber layer (B) from non-fluororubber layer (A) at the one side (face of the non-fluororubber layer of non-lamination (A)) of fluororubber layer (B); Can also for being laminated with the laminate of more than 3 layers of the polymeric layer (C) different with fluororubber layer (B) from non-fluororubber layer (A) at the one side (face of non-lamination fluororubber layer (B)) of non-fluororubber layer (A).
In addition, can, for being laminated with the laminate of more than 3 layers of non-fluororubber layer (A) in the both sides of fluororubber layer (B), also can be the laminate being laminated with more than 3 layers of fluororubber layer (B) in the both sides of non-fluororubber layer (A).
Be not particularly limited as above-mentioned polymeric layer (C), the purposes etc. according to the sulfuration laminate obtained by laminate of the present invention is suitably determined.
Sulfuration laminate of the present invention obtains possessing fluororubber layer (B) and heating at the laminate of the non-fluororubber layer (A) of the upper lamination of fluororubber layer (B), and the non-fluororubber layer of sulfuration (A1) has cured bonding with vulcanised fluororubbers layer (B1).
By to possessing fluororubber layer (B) and heating at the laminate of the present invention of the non-fluororubber layer (A) of the upper lamination of fluororubber layer (B), the sulfuration laminate of the non-fluororubber layer of sulfuration (A1) and vulcanised fluororubbers layer (B1) bonding by Vulcanization can be obtained.
The non-fluororubber layer of sulfuration (A1) makes non-fluororubber layer (A) sulfuration form by above-mentioned heating.
Vulcanised fluororubbers layer (B1) carries out above-mentioned heating to fluororubber layer (B) and forms.When carrying out above-mentioned heating to unvulcanized fluororubber layer (B), vulcanised fluororubbers layer (B1) by above-mentioned heating, the fluorubber (b1) in fluororubber layer (B) is cured.
By above-mentioned heating, non-fluororubber layer (A) cures, and can obtain the sulfuration laminate of the non-fluororubber layer of sulfuration (A1) and vulcanised fluororubbers layer (B1) bonding by Vulcanization.
Above-mentioned heating can by will unvulcanized non-fluororubber layer (A) and sulfuration or unvulcanized fluororubber layer (B) superimposed and carry out heating to carry out.By heating, non-fluororubber layer (A) sulfuration can be made.Further, in fluororubber layer (B) in unvulcanized situation, fluororubber layer (B) sulfuration can also be made.
As the condition heated, carry out under the condition at least making non-fluororubber layer (A) sulfuration.In fluororubber layer (B) for uncrosslinked, can carry out under the condition making non-fluororubber layer (A) and fluororubber layer (B) sulfuration.
The actual conditions heated suitably determines according to the kind of used vulcanizing agent etc., usually within 1 minute ~ 24 hours, is carried out by the heating temperatures at 150 DEG C ~ 300 DEG C.
As the method heated, use the method that at least can make non-fluororubber layer (A) sulfuration.In fluororubber layer (B) for uncrosslinked, use the method that can make non-fluororubber layer (A) and fluororubber layer (B) sulfuration.
As the method heated, can adopt the vulcanization process carrying out heating, can be the method usually used such as steam vulcanization (cure) certainly, also can be the vulcanization process under normal pressure, pressurization, decompression, can also be aerial vulcanization process in addition.
Sulfuration lamination style of the present invention is as obtained as follows: use extruder to extrude fluoro-rubber composite and non-fluoro-rubber composite respectively, make unvulcanized non-fluorine sheet rubber and unvulcanized fluorubber sheet, by unvulcanized non-fluorine sheet rubber and unvulcanized fluorubber sheet superimposed, be inserted in the mould of oneself heating and carry out bonding by Vulcanization, thus obtain sulfuration laminate of the present invention.
In addition, sulfuration laminate of the present invention also can obtain as follows: utilize extruder fluoro-rubber composite and non-fluoro-rubber composite to be extruded with more than 2 layers or 2 layers simultaneously or utilize the extruder of more than 2 or 2 on la m, extrude outside layer, extruder is utilized to extrude the unvulcanized laminate containing la m and outside layer and carry out integrated thus, then carry out heating to carry out bonding by Vulcanization, thus obtain sulfuration laminate of the present invention.
In addition, sulfuration lamination style of the present invention is as also obtained as follows: by by above-mentioned carry out dynamic vulcanization process the sheet that forms of the vulcanised fluororubbers that obtains and fluororesin and unvulcanized non-fluorine sheet rubber superimposed, be inserted in the mould of oneself heating and carry out bonding by Vulcanization, thus obtain sulfuration laminate of the present invention.
Sulfuration laminate of the present invention is the laminate having the low permeability of fuel, low temperature resistant degradation property, chemical proofing, oil resistivity, heat resistance concurrently, flexible pipe, pipe, container, encapsulant etc. as fuel periphery are useful, particularly as the engine of automobile and the fuel area density flexible pipe of peripheral device, AT device, fuel system and peripheral device etc. or manage useful.
Sulfuration laminate of the present invention is preferably flexible pipe or pipe, is laminated with vulcanised fluororubbers layer (B1) in the inner side of the non-fluororubber layer of sulfuration (A1).
Such as, fuel area density flexible pipe or pipe preferably there is following laminated structure: be configured with vulcanised fluororubbers layer (A1) at the innermost layer of flexible pipe or pipe, be configured with the non-fluororubber layer of sulfuration (B1) at its skin.
Embodiment
Next the present invention will be described to enumerate embodiment, but the present invention is not limited only to described embodiment.
Carry out describing to the fluororesin used in embodiment and comparative example and assay method thereof below.
(vulcanization characteristics)
For obtained non-fluoro-rubber composite, use vulcameter (curelastometer) II type (manufacture of model: JSR curelastometer, JSR company), measure maximum torque (M at 160 DEG C h) and minimal torque value (M l), obtain induction time (T 10) and sulfurizing time (T 90).Measurement result is shown in table 2.It should be noted that, T 10for reaching { (M h)-(M l) × 0.1+M ltime, T 90for reaching { (M h)-(M l) × 0.9+M ltime, M hand M lfor the value of carrying out measuring based on JIS K 6300-2.
(adhesive strength)
Obtained laminate is cut into the strip that width 10mm × length 40mm × often overlaps 3, peels off mold release film and form bare terminal end, make test film.For this test film, use AUTOGRAPH (the AGS-J 5kN that Shimadzu Corporation manufactures), based on the method recorded in JIS K 6256 (the adhesive test method of cross-linked rubber), carry out disbonded test at 25 DEG C with the draw speed of 50mm/ minute.About the evaluation of cementability, separation mode is observed, evaluate by following benchmark.The result obtained is shown in table 2.
(embodiment 1)
(preparation of fluoro-rubber composite and the making of fluorubber sheet)
8 inches of mills that serviceability temperature is adjusted to 25 DEG C are carried out mixing to the material shown in following table 1, thus obtain the fluoro-rubber composite (fluorubber sheet) of the thick sheet of about 3mm.
(preparation of non-fluoro-rubber composite and the making of unvulcanized non-fluorine sheet rubber)
8 inches of mills that serviceability temperature is adjusted to 25 DEG C are carried out mixing to the material shown in following table 2, thus obtain the non-fluoro-rubber composite (non-fluorine sheet rubber) of the thick sheet of about 3mm.
(making of laminate)
The above-mentioned non-fluoro-rubber composite (non-fluorine sheet rubber) that the above-mentioned fluoro-rubber composite (fluorubber sheet) thickness being about 3mm and thickness are about 3mm is superimposed, the resin molding (mold release film that thickness is 10 μm) in the end of side, width being about 10mm ~ 15mm is clipped in after between two sheets, obtained sheet is inserted in the mould being placed with metal sept, 160 DEG C of compactings 45 minutes, to make the thickness of obtained sheet for 2mm, thus obtain the laminate of sheet.
(embodiment 2 ~ 9 and comparative example 1 ~ 3)
The kind of the mixed agent of the non-fluoro-rubber composite of change as shown in table 2 (non-fluorine sheet rubber) and addition, prepare non-fluoro-rubber composite similarly to Example 1 in addition, and have rated vulcanization characteristics.In addition, make laminate similarly to Example 1, have rated the cementability of laminate.Result is shown in table 2.
[table 1]
(bonding evaluation)
Zero ... non-fluorine sheet rubber after sulfuration or fluorubber sheet destroy at the interface generating material of laminate, cannot be peeled off by interface.
× ... peeled off by the interface of laminate than being easier to.
Industrial applicibility
Laminate of the present invention is useful as the flexible pipe, pipe, container, encapsulant etc. of fuel periphery, particularly as the engine of automobile and the fuel area density flexible pipe of peripheral device, AT device, fuel system and peripheral device etc. or manage useful.

Claims (9)

1. a laminate, it is for possessing the laminate of fluororubber layer (B) and the non-fluororubber layer (A) in the upper lamination of fluororubber layer (B), and the feature of this laminate is,
Non-fluororubber layer (A) is the layer formed by non-fluoro-rubber composite,
Non-fluoro-rubber composite contains: unvulcanized non-fluorubber (a1); Be selected from least one compound (a2) in the group be made up of 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene salt and 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene; Magnesia (a3); With silica (a4),
Fluororubber layer (B) is the layer formed by the fluoro-rubber composite containing fluorubber (b1).
2. laminate as claimed in claim 1, wherein, unvulcanized non-fluorubber (a1) is acrylonitrile-butadiene rubber (NBR) or its hydride.
3. laminate as claimed in claim 1 or 2, wherein, fluorubber (b1) is for being selected from least one fluorubber in the group that is made up of vinylidene fluoride-hexafluoropropene system fluorubber and vinylidene fluoride-hexafluoropropene-tetrafluoroethene system fluorubber.
4. the laminate as described in claim 1,2 or 3, wherein, in non-fluoro-rubber composite, the blend amount of compound (a2) is 0.7 mass parts ~ 5.0 mass parts relative to the unvulcanized non-fluorubber (a1) of 100 mass parts.
5. the laminate as described in claim 1,2,3 or 4, wherein, non-fluoro-rubber composite is also containing at least one vulcanizing agent (a5) be selected from the group that is made up of sulfur sulfide system vulcanizing agent and peroxide vulcanizing system vulcanizing agent.
6. the laminate as described in claim 1,2,3,4 or 5, wherein, non-fluoro-rubber composite is further containing at least one slaine (a6) be selected from the group that is made up of carbamic acid slaine and thiazole system slaine.
7. the laminate as described in claim 1,2,3,4,5 or 6, wherein, compound (a2) is 8-benzyl-1,8-diazabicyclo (5.4.0)-ten one carbon-7-alkene chloride.
8. a sulfuration laminate, is characterized in that, it heats the laminate described in claim 1,2,3,4,5,6 or 7 and obtains,
The non-fluororubber layer of sulfuration (A1) has cured bonding with vulcanised fluororubbers layer (B1).
9. sulfuration laminate as claimed in claim 8, it is flexible pipe or pipe,
Vulcanised fluororubbers layer (B1) is laminated with in the inner side of the non-fluororubber layer of sulfuration (A1).
CN201380021741.1A 2012-04-25 2013-04-23 Laminate Pending CN104245308A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111201138A (en) * 2017-10-05 2020-05-26 Ａｇｃ株式会社 Method for producing laminate, and laminate
CN111344336A (en) * 2017-11-17 2020-06-26 大金工业株式会社 Member for air management system and fluororubber composition
CN111363279A (en) * 2020-03-17 2020-07-03 戚佳轩 Fluororubber composition capable of being co-vulcanized and bonded with silicone rubber, rubber product and preparation method
CN113423570A (en) * 2019-02-22 2021-09-21 大金工业株式会社 Laminated body
EP3548280B1 (en) 2016-11-29 2023-08-16 ContiTech Schlauch GmbH Multi-layer flexible hose

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103642099A (en) * 2013-12-12 2014-03-19 建新赵氏集团有限公司 Nitrile rubber material favorably adhered with fluororubber

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1282347A (en) * 1997-12-19 2001-01-31 德弘公司 Elastomer compositions for bonding to fluoropolymers
WO2011001756A1 (en) * 2009-06-30 2011-01-06 ダイキン工業株式会社 Laminate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5114826B2 (en) * 2005-02-04 2013-01-09 ダイキン工業株式会社 Crosslinkable composition and laminate comprising the same
JP2011116004A (en) * 2009-12-02 2011-06-16 Daikin Industries Ltd Method of manufacturing fluoropolymer laminate, fluoropolymer laminate obtained by the method and non-fluororubber composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1282347A (en) * 1997-12-19 2001-01-31 德弘公司 Elastomer compositions for bonding to fluoropolymers
WO2011001756A1 (en) * 2009-06-30 2011-01-06 ダイキン工業株式会社 Laminate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3548280B1 (en) 2016-11-29 2023-08-16 ContiTech Schlauch GmbH Multi-layer flexible hose
CN111201138A (en) * 2017-10-05 2020-05-26 Ａｇｃ株式会社 Method for producing laminate, and laminate
CN111201138B (en) * 2017-10-05 2021-11-16 Ａｇｃ株式会社 Method for producing laminate, and laminate
CN111344336A (en) * 2017-11-17 2020-06-26 大金工业株式会社 Member for air management system and fluororubber composition
CN111344336B (en) * 2017-11-17 2023-10-13 大金工业株式会社 Component of air management system and fluororubber composition
CN113423570A (en) * 2019-02-22 2021-09-21 大金工业株式会社 Laminated body
CN113423570B (en) * 2019-02-22 2024-05-14 大金工业株式会社 Laminate body
CN111363279A (en) * 2020-03-17 2020-07-03 戚佳轩 Fluororubber composition capable of being co-vulcanized and bonded with silicone rubber, rubber product and preparation method

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