CN101479336A - Fluororubber composition for peroxide crosslinking and method for producing rubber laminate - Google Patents
Fluororubber composition for peroxide crosslinking and method for producing rubber laminate Download PDFInfo
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- CN101479336A CN101479336A CNA2007800235518A CN200780023551A CN101479336A CN 101479336 A CN101479336 A CN 101479336A CN A2007800235518 A CNA2007800235518 A CN A2007800235518A CN 200780023551 A CN200780023551 A CN 200780023551A CN 101479336 A CN101479336 A CN 101479336A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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Abstract
Disclosed is a fluororubber composition for peroxide crosslinking which enables to forma a fluororubber layer excellent in adhesion to a layer made of a non-fluorine rubber. Also disclosed is a method for producing a rubber laminate. Further disclosed is an oil resistant, heat resistant rubber hose which is made of a rubber laminate produced by the method. Specifically disclosed is a fluororubber composition for peroxide crosslinking, which contains a fluororubber, a peroxide crosslinking agent, 0.05-10 parts by weight of a tackifier per 100 parts by weight of the fluororubber, and 1-100 parts by weight of a metal oxide (excepting a silica filler) and/or 1-50 parts by weight of a silica filler per 100 parts by weight of the fluororubber.
Description
Technical field
The present invention relates to contain the fluororubber composition for peroxide crosslinking of viton, peroxidation system linking agent, tackifier and metal oxide and/or silica-based weighting agent, the oil-resisting and heat-resisting rubber hose that also relates to the manufacture method of the rubber laminate that contains the fluororubber layer that forms by this fluororubber composition for peroxide crosslinking, forms by the rubber laminate that utilizes this manufacture method to obtain.
Background technology
Viton has excellent chemical proofing, solvent resistance and thermotolerance, therefore widespread use in various fields such as automotive industry, semi-conductor industry, chemical industry, for example in automobile industry, flexible pipe, sealing material of engine and peripheral device, AT device, fuel system and peripheral device etc. etc. have been used as.But,, aspect the various characteristicses such as ageing resistance, weathering resistance, processibility, oil-proofness, fuel oil resistance, fuel perviousness more strict requirement is being proposed at present for these materials that constitutes by viton along with environment control in recent years.
Though viton demonstrates the characteristic of aforesaid various excellences, its price is expensive, is 10～20 times of common elastomeric material, and the winter hardiness existing problems, and only the material of making flexible pipe etc. with viton has problems at aspects such as cost, winter hardiness.And in the past as oil fuel with the acrylonitrile butadiene copolymer rubber of flexible pipe or silicon rubber being inferior to viton aspect the various characteristicses such as thermotolerance, oil-proofness, ageing resistance, the requirement that it is improved is arranged always.
So people develop and use thin viton as internal layer and the outer flexible pipe class that is made of non-viton such as epichloro hydrin rubbers.Like this by flexible pipe is made of viton and non-viton, thereby problems such as cost and winter hardiness improve, but non-viton such as viton and epichloro hydrin rubber lacks cementability, has difficult point in the practicality.
As the method that solves such problem, known have in the mixing material of acrylonitrile-butadiene rubber and polyvinyl chloride, add the rubber combination (for example, referring to TOHKEMY 2000-273241 communique) that organo-peroxide, tackifiers (then property is paid drug), tackifier (drug is paid in adhesion) form.Although in the document, put down in writing the cementability that this rubber combination can obtain the excellence of the binding property of excellence of the fluororubber layer when uncrosslinked and the fluororubber layer when crosslinked simultaneously, but in this TOHKEMY 2000-273241 communique, for add tackifiers, the composition of non-fluororubber layer improved by tackifier and the improvement of fluororubber layer is not studied.Do not study for the bonding of material except that the mixing material of acrylonitrile-butadiene rubber and polyvinyl chloride and viton in addition yet.
In addition, as the fluoro-rubber composite that is added with tackifier, known have a fluoro-rubber composite (for example, referring to TOHKEMY 2005-113017 communique) that is made of viton, coumarone-indene resin, phenol-formaldehyde resin, polyterpene resin, terpenes-resol or xylene formal dehyde resin.But described fluoro-rubber composite is the composition of the low repulsion characteristic when having improved high temperature, and does not study for the cementability of this fluoro-rubber composite and non-fluororubber layer.In addition, in an embodiment, the content that the low repulsion characteristic when only disclosing for polyvalent alcohol sulfuration with the high temperature of fluoro-rubber composite is improved, and specifically put down in writing with fluoro-rubber composite for peroxide cure.
In addition, known by mixed metal oxide in viton or non-viton with the method for the cementability of improvement viton and non-viton (for example also have, brochure is disclosed No. 03/039858 referring to the world), be weighting agent with the method (for example, referring to TOHKEMY 2003-19772 communique) of the cementability of improvement viton and non-viton by mixed silica in viton or non-viton.And in the embodiment of these patent documentations, carried out press vulcanization, if use employed vapor crosslinking method in the manufacturing of the flexible pipe class of reality, then there is the tendency of bonding force variation.
In addition, known also have silicon rubber and the bonding method (for example, referring to Japanese Unexamined Patent Application Publication 2002-524305 communique) of fluoropolymer that comprises viton.But in the embodiment of Japanese Unexamined Patent Application Publication 2002-524305 communique, also carried out press vulcanization,, then had the tendency of bonding force variation if use employed vapor crosslinking method in the manufacturing of the flexible pipe class of reality.And find to add the tendency that the dehydrofluorination treatment agent has variation such as the compression set of making.
Thereby, still there are not the fluoro-rubber composite of the cementability that can substantially improve fluororubber layer and non-fluororubber layer or the rubber laminate that constitutes by this fluoro-rubber composite at present.
Summary of the invention
The object of the present invention is to provide a kind of can form with the fluororubber composition for peroxide crosslinking of the fluororubber layer of the adaptation excellence of the layer that forms by non-viton and contain by this fluoro-rubber composite form layer the manufacture method of rubber laminate.The present invention also aims to provide a kind of oil-resisting and heat-resisting rubber hose that forms by the rubber laminate that utilizes this manufacture method to obtain.
Promptly, the present invention relates to a kind of fluororubber composition for peroxide crosslinking, said composition contains viton, peroxidation system linking agent, is the tackifier of 0.05～10 weight part and is that the metal oxide of 4～100 weight parts (does not wherein comprise silica-based weighting agent with respect to 100 weight part viton with respect to 100 weight part viton.Below identical) and/or be the silica-based weighting agent of 1～50 weight part.
Described tackifier are preferably that to be selected from by coumarone resin, rosin derivative, phenol-terpenic series resin and oil be more than one tackifier in the group formed of hydrocarbon resin.
Described metal oxide is preferably more than one the oxide compound that is selected from the group of being made up of magnesium oxide, calcium oxide, titanium dioxide, aluminum oxide, ferric oxide and zinc oxide.
Described metal oxide is magnesium oxide more preferably.
In addition, the present invention relates to the manufacture method of rubber laminate,
This method comprises the operation that forms rubber laminate and carries out the bonding operation of interlayer,
In the operation of described formation rubber laminate, will be by above-mentioned fluororubber composition for peroxide crosslinking fluororubber layer that forms and the non-fluororubber layer lamination that forms by the non-fluoro-rubber composite that contains non-viton and peroxidation system linking agent, form rubber laminate
In the bonding operation of interlayer resulting rubber laminate is carried out peroxide crosslinking described carrying out, it is bonding to carry out interlayer.
Described non-viton is preferably silicon rubber.
Described peroxide crosslinking is preferably vapor crosslinking.
In addition, the present invention relates to a kind of oil-resisting and heat-resisting rubber hose, this oil-resisting and heat-resisting rubber hose is to be formed by the rubber laminate that utilizes above-mentioned manufacture method to obtain.
Description of drawings
Fig. 1 is the explanatory view that is used for the test film of determining bonding strength.
Embodiment
The present invention relates to a kind of fluororubber composition for peroxide crosslinking, said composition contains viton, peroxidation system linking agent, is the tackifier of 0.05～10 weight part and is the metal oxide of 4～100 weight parts and/or is the silica-based weighting agent of 1～50 weight part with respect to 100 weight part viton with respect to 100 weight part viton.
In the present invention, as viton, can enumerate non-perfluor viton and perfluor viton.In addition, the perfluor viton is meant 90 moles of rubber that are made of perfluorinated monomers more than the % in its structural unit.
As non-perfluor viton, can enumerate vinylidene fluoride (hereinafter referred to as VdF) is viton, tetrafluoroethylene (hereinafter referred to as TFE)/propylene is a viton, TFE/ propylene/VdF is a viton, ethene/R 1216 (hereinafter referred to as HFP) is a viton, ethene/HFP/VdF is a viton, ethene/HFP/TFE is a viton, fluorosilicone is that viton or fluorine phosphonitrile are viton etc., these non-perfluor viton can be distinguished use separately, also can arbitrary combination use in the scope of not damaging effect of the present invention, wherein preferably using VdF is viton, the TFE/ propylene is a viton.
As Vdf is viton, preferably the viton of representing with following general formula (1):
—(M
1)—(M
2)—(N
1)— (1)
(in the formula, structural unit M
1Be to be derived from VdF (m
1) structural unit, structural unit M
2Be to be derived from fluorine-containing ethylenic monomer (m
2) structural unit, structural unit N
1Be be derived from can with monomer (m
1) and monomer (m
2) monomer (n of copolymerization
1) repeating unit).
Among the VdF shown in general formula (1) is viton, preferably contain 25～85 moles of % structural unit M
1, 75～15 moles of % structural unit M
2VdF be viton, more preferably contain 30～80 moles of % structural unit M
1, 70～20 moles of % structural unit M
2VdF be viton, further preferably contain 40～70 moles of % structural unit M
1, 60～30 moles of % structural unit M
2VdF be viton.With respect to structural unit M
1With structural unit M
2Total amount, preferred structure unit N
1Be 0～10 mole of %.
As fluorine-containing ethylenic monomer (m
2), can enumerate for example fluorochemical monomers such as TFE, trifluorochloroethylene (hereinafter referred to as CTFE), trifluoro-ethylene, HFP, trifluoro propene, tetrafluoeopropene, five fluorine propylene, trifluoro butylene, tetrafluoro iso-butylene, perfluor (alkyl vinyl ether) (hereinafter referred to as PAVE), vinyl fluoride, in these monomers, preferred TFE, HFP, PAVE.And these monomers can be distinguished use separately, and perhaps arbitrary combination is used.
As monomer (n
1), can be monomer arbitrarily, as long as can with monomer (m
1) and monomer (m
2) copolymerization gets final product, and for example can enumerate ethene, propylene, alkyl vinyl ether, the monomer of cross-linking part etc. is provided, and in these monomers, preferably provides the monomer of cross-linking part.But more preferably provide the monomer of the cross-linking part of peroxide crosslinking.
As such monomer that cross-linking part is provided, can enumerate such perfluor (6,6-dihydro-6-iodo-3-oxa--1-hexene) of putting down in writing in for example Japanese special fair 5-63482 communique, the Japanese kokai publication hei 7-316234 communique, perfluor (5-iodo-3-oxa--1-amylene) etc. and contain the iodine monomer; The brominated monomer of putting down in writing in the Japanese kokai publication hei 4-505341 communique; The monomer of such cyano-containing of putting down in writing in Japanese kokai publication hei 4-505345 communique, the Japanese kokai publication hei 5-500070 communique, carboxylic monomer, contain the monomer of alkoxy carbonyl etc.
In addition, as the monomer that cross-linking part is provided, can enumerate VdF for example, with general formula (2) expression contain iodine monomer or brominated monomer, with general formula (3) expression contain iodine monomer or brominated monomer, with the monomer of the expression of general formula (4) expression, with the monomer of general formula (5) expression etc.
General formula (2):
CY
1 2＝CY
1—R
f 1CHR
1X
1 (2)
(in the formula, Y
1Be hydrogen atom, fluorine atom or CH
3, R
f 1Be fluoro alkylidene group, perfluorinated alkylidene, fluoro polyoxy alkylidene or perfluor polyoxy alkylidene, R
1Be hydrogen atom or CH
3, X
1Be iodine atom or bromine atoms);
General formula (3):
CY
2 2＝CY
2—R
f 2CF
2X
2 (3)
(in the formula, Y
2Be hydrogen atom, fluorine atom or CH
3, R
f 2Be fluoro alkylidene group, perfluorinated alkylidene, fluoro polyoxy alkylidene or perfluor polyoxy alkylidene, X
2Be iodine atom or bromine atoms);
General formula (4):
CF
2＝CFO—R
f 3—CFR
3—X
3 (4)
(in the formula, R
f 3Be fluoro alkylidene group, perfluorinated alkylidene, fluoro polyoxy alkylidene or perfluor polyoxy alkylidene, R
3Be fluorine atom or CF
3, X
3Be cyano group, carboxyl or alkoxy carbonyl);
General formula (5):
CY
4 2＝CF
2CF
2O—R
f 4—CFR
4—X
4 (5)
(in the formula, Y
4Be fluorine atom or hydrogen atom, R
f 4Be fluoro alkylidene group, perfluorinated alkylidene, fluoro polyoxy alkylidene or perfluor polyoxy alkylidene, R
4Be fluorine atom or CF
3, X
4Be cyano group, carboxyl or alkoxy carbonyl),
These monomers can use separately, perhaps can arbitrary combination use.
Described iodine atom, bromine atoms, cyano group, carboxyl, alkoxy carbonyl can play a role as cross-linking set, and particularly iodine atom, bromine atoms, cyano group can play a role as the cross-linking set of peroxide crosslinking.
As such VdF is viton, specifically, can preferably enumerate VdF/HFP is that rubber, VdF/HFP/TFE are that rubber, VdF/CTFE are that rubber, VdF/CTFE/TFE are that rubber, VdF/PAVE are that rubber, VdF/TFE/PAVE are that rubber, VdF/HFP/PAVE are that rubber, VdF/HFP/TFE/PAVE are that rubber, VdF/TFE/ propylene are that rubber, VdF/ ethene/HFP are rubber etc.
As the TFE/ propylene is viton, is preferably as follows the viton of general formula (6) expression:
-(M
3)-(M
4)-(N
2)- (6)
(in the formula, structural unit M
3Be to be derived from TFE (m
3) structural unit, structural unit M
4Be to be derived from propylene (m
4) structural unit, structural unit N
2Be be derived from can with monomer (m
3) and monomer (m
4) monomer (n of copolymerization
2) repeating unit).
Among the TFE/ propylene shown in general formula (6) is viton, preferably contain 40～70 moles of % structural unit M
3, 60～30 moles of % structural unit M
4Viton, more preferably contain 50～60 moles of % structural unit M
3, 50～40 moles of % structural unit M
4Viton.With respect to structural unit M
3With structural unit M
4Total amount, preferred structure unit N
2Be 0～40 mole of %.
As monomer (n
2), can be any monomer, as long as can with monomer (m
3) and monomer (m
4) copolymerization gets final product, and the monomer of cross-linking part preferably is provided.But more preferably provide the monomer of the cross-linking part of peroxide crosslinking.
As such monomer that cross-linking part is provided, can enumerate the example identical with above-mentioned example, among described monomer, the monomer that contains iodine atom, bromine atoms, cyano group is preferred especially owing to the cross-linking part that peroxide crosslinking can be provided.
As the perfluor viton, preferably with the perfluor viton of following general formula (7) expression:
—(M
5)—(M
6)—(N
3)— (7)
(in the formula, structural unit M
5Be to be derived from TFE (m
5) structural unit, structural unit M
6Be to be derived from PAVE (m
6) structural unit, structural unit N
3Be be derived from can with monomer (m
5) and the monomer (n of monomer (m6) copolymerization
3) repeating unit).
Among the perfluor viton shown in general formula (7), preferably contain 50～90 moles of % structural unit M
5, 10～50 moles of % structural unit M
6The perfluor viton, more preferably contain 50～80 moles of % structural unit M
5, 20～50 moles of % structural unit M
6The perfluor viton, further preferably contain 55～70 moles of % structural unit M
5, 30～45 moles of % structural unit M
6The perfluor viton.With respect to structural unit M
5With structural unit M
6Total amount, structural unit N
3Be preferably 0～5 mole of %, more preferably 0～2 mole of %.If described perfluor viton is in beyond these compositing ranges, then trends towards losing as the character of rubber elastomer and become character near resin.
As PAVE (m
6), can enumerate for example perfluor (methylvinylether), perfluor (propyl vinyl ether) etc., these monomers can be distinguished use separately, perhaps can arbitrary combination use.
In addition, as monomer (n
3), can be monomer arbitrarily, as long as can with monomer (m
5) and monomer (m
6) copolymerization gets final product, and can enumerate above-mentioned monomer etc., in these monomers, preferably provides the monomer of cross-linking part.
As such monomer that cross-linking part is provided, can enumerate the example identical with above-mentioned example.
Described iodine atom, bromine atoms, cyano group, carboxyl, alkoxy carbonyl can play a role as cross-linking set, and particularly iodine atom, bromine atoms, cyano group can play a role as the cross-linking set of peroxide crosslinking.
As the concrete example of described perfluor viton, can enumerate the international viton that No. 97/24381 brochure, Japanese Patent Publication 61-57324 communique, the special fair 4-81608 communique of Japan, Japanese special fair 5-13961 communique etc. are put down in writing etc. that disclose.
For viton of the present invention, as above-mentioned non-perfluor viton and perfluor viton and the formation that constitutes principal monomer shown in the example, and also can use copolymerization such as the monomer that cross-linking part is provided (such as having a plurality of vinyl or a plurality of allylic polyfunctional monomers etc.), modified monomer that will be except that above-mentioned aptly and the material that obtains.And, also can wait to promote the dehydrogenation fluoric acid to make the two keys that generate in the molecule as cross-linking set by enforcement thermal treatment.
Consider from the aspect of thermotolerance, compression set, processibility, cost, among the above-mentioned viton, preferably contain the unitary viton of VdF, more preferably have the unitary viton of VdF unit and HFP, further preferred VdF/TFE/HFP is a viton.
More than Shuo Ming viton can utilize usual method manufacturing, as preferred manufacture method, can enumerate as the manufacturing process of viton and known iodine transfer polymerization method.End at the fluoroelastomer that uses iodine transfer polymerization method to obtain imports iodine atom or bromine atoms, can form the cross-linking set of peroxide crosslinking.Polymerizing conditions such as the temperature during as polymerization, time suit to determine to get final product according to monomeric kind and target elastomerics.
Fluororubber composition for peroxide crosslinking of the present invention is the composition that contains peroxidation system linking agent, by utilizing this peroxidation system linking agent to carry out crosslinked, can have C-C at cross-linking set, therefore compare with the crosslinked system of polyamine with the polyol crosslink system that has carbon-oxygen bond at cross-linking set, have excellent chemical proofing and anti-steam with the two keys of carbon-nitrogen.
In addition, in fluororubber composition for peroxide crosslinking of the present invention, preferably constitute as much as possible crosslinked in the peroxide crosslinking mode, this is favourable to the bonding of viton and non-viton, and does not preferably contain the polyol crosslink agent in fluororubber composition for peroxide crosslinking of the present invention.
As the peroxidation system linking agent that uses among the present invention, get final product so long as in the presence of heat or reducto oxydative system, can easily produce the organo-peroxide of peroxylradicals, specifically, for example can enumerate 1, two (tert-butyl hydroperoxide)-3 of 1-, 5, the 5-trimethyl-cyclohexane, 2,5-dimethylhexane-2,5-diperoxy hydrogen, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, α, α-two (tert-butyl hydroperoxide) is to diisopropyl benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide, tert-butyl peroxide benzene, the tert-butyl hydroperoxide toxilic acid, tert-butylperoxy isopropyl carbonate etc.Among these, preferred 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane.
With respect to 100 weight part viton, the addition of peroxidation system linking agent is preferably 0.05～10 weight part, 0.1～10 weight part more preferably, and more preferably 0.3～7.0 weight part is preferably 1～5 weight part especially.When linking agent during less than 0.05 weight part, the degree of crosslinking deficiency, therefore there are the impaired tendencies of performance such as the thermotolerance of moulding product and oil-proofness, if linking agent surpasses 10 weight parts, then owing to the cross-linking density too high tendency that exists crosslinking time to prolong that becomes, and also be not preferred economically, have the tendency of the forming process reduction of resulting fluoro-rubber composite in addition.
In addition, in the peroxidation system is crosslinked, preferably use crosslinking coagent and peroxidation system linking agent to share.
As crosslinking coagent, for example can enumerate, triallyl cyanurate, cyanacrylate (TAIC), three vinylformic acid formals (triacrylformal), the trimellitic acid triallyl, N, N '-meta-phenylene bismaleimide, terephthalic acid diine propyl ester, Phthalic acid, diallyl ester, the tetraallyl terephthalamide, the triallyl phosphoric acid ester, bismaleimides, fluoridize cyanacrylate (1,3,5-three (2,3,3-three fluoro-2-propenyl)-1,3,5-triazines-2,4, the 6-triketone), three (diallyl amine) s-triazine, triallyl phosphite, N, N-diallyl acrylamide, 1,6-divinyl ten difluoro hexanes, six allyl group phosphamides, N, N, N ', N '-tetraallyl phthalic diamide, N, N, N ', N '-tetraallyl Malonamide, the trivinyl isocyanuric acid ester, 2,4,6-trivinyl methyl trisiloxanes, three (5-norbornylene-2-methylene radical) cyanurate, triallyl phosphorous acid ester etc.Among crosslinking coagent, consider preferred cyanacrylate (TAIC) from the aspect of the rerum natura of bridging property, cross-linking agent.
With respect to 100 weight part viton, the addition of crosslinking coagent is preferably 0.1～20 weight part, 0.3～10 weight part more preferably, and more preferably 0.5～10 weight part is preferably 1～6 weight part especially.If crosslinking coagent is less than 0.1 weight part, then crosslinking time can extend to the practical degree of being unable to stand, and the compression set of resulting moulding product, thermotolerance and oil-proofness have the tendency of reduction, if crosslinking coagent surpasses 20 weight parts, the then compression set of moulding product, thermotolerance reduce, and the forming process of resulting fluoro-rubber composite has the tendency of reduction.
In addition, fluororubber composition for peroxide crosslinking of the present invention is owing to contain tackifier, thereby with the adaptation excellence of the non-fluororubber layer that forms by the non-fluoro-rubber composite that contains non-viton and peroxidation system linking agent, therefore with resulting rubber laminate when crosslinked, can be crosslinked bonding and can not occur two layers and peel off.Thus, even utilize and the crosslinked vapor crosslinking method that is difficult to obtain bonding strength of comparing of pressurization, also can obtain sufficient adhesion strength.And can not damage the characteristic of compression set etc., can improve cementability.
The softening temperature of tackifier is preferably below 200 ℃, more preferably below 120 ℃.If softening temperature is greater than 200 ℃, not fusion of tackifier when then crosslinked, existence can not obtain the tendency of sufficient bonding force, and the tackifier infusibility melts when mixing, exists bad tendency easily takes place to disperse.
As tackifier, can enumerate coumarone resin, phenol-terpenic series resin, oil is hydrocarbon resin, rosin derivative etc.These materials can be used alone, but also also mix together.
As coumarone resin, can enumerate coumarone-indene resin.
As phenol-terpenic series resin, can enumerate p-tert-butylphenol-acetylene resin, phenol-formaldehyde resin, terpenes-resol, polyterpene resin, xylene formal dehyde resin, alkyl phenolic resin etc.
As oil is hydrocarbon resin, can enumerate polymkeric substance, isoprene resin, hydrogenated hydrocarbon resins, hydro carbons binder resin, aggretion type particular polyesters, polybutene, atactic polypropylene(APP), liquid polybutadiene, lower molecular weight isoprene-isobutylene rubber of aromatic hydrocarbon resin, aliphatic hydrocarbon resin, fatty family cyclic hydrocarbon resin, unsaturated hydrocarbons etc.
As rosin derivative, wood rosin, the methyl ester of staybelite, the triethyleneglycol ester of staybelite, the pentaerythritol ester of staybelite, hydrogenated wood rosin glycerol ester, the high-melting-point ester that can enumerate rosiny pentaerythritol ester, rosiny glyceryl ester, staybelite, height hydrogenation is the glyceryl ester of resin, polymerized rosin, polymerized rosin, zinc resinate, hardened rosin, rosin series tackifier etc.
In addition, as other tackifier, mixture, the rosin that can enumerate resinous acid and amine-sodium resinate is the cocondensate of tackifier, synthetic resins and phthalic ester etc.
Among these tackifier, consider that from the aspect of the cementability of viton and non-viton more preferably being selected from by coumarone resin, phenol-terpenic series resin, oil is more than one tackifier in the group formed of hydrocarbon resin, rosin derivative.
With respect to 100 weight part viton, the addition of tackifier is 0.05～10 weight part, is preferably 0.1～5 weight part, more preferably 0.1～2 weight part.If tackifier are less than 0.05 weight part, then there is the tendency that can not obtain sufficient bonding force, if tackifier above 10 weight parts, then exist compression set, thermotolerance, the oil-proofness of moulding product to reduce and the tendency of the forming process reduction of resulting fluoro-rubber composite.
Fluororubber composition for peroxide crosslinking of the present invention also contains metal oxide and/or silica-based weighting agent.
By containing metal oxide, the bonding force of viton and non-viton is improved.
As metal oxide, can enumerate magnesium oxide, calcium oxide, titanium dioxide, aluminum oxide, ferric oxide, zinc oxide etc., consider from the aspect that surfactivity is high, be preferably selected from more than one the oxide compound in the group of forming by magnesium oxide, calcium oxide, titanium dioxide, aluminum oxide, ferric oxide and zinc oxide, more preferably magnesium oxide.
And the particle diameter of above-mentioned metal oxide is preferably more than the 0.1 μ m, more preferably more than the 0.5 μ m, and then is preferably more than the 1.0 μ m.If particle diameter less than 0.1 μ m, then may be difficult to mix in viton, perhaps the moulding product hardening that is formed by fluoro-rubber composite loses elastic tendency.As the upper limit of particle diameter, be preferably below the 500 μ m, more preferably below the 50 μ m, more preferably below the 10 μ m.If particle diameter is greater than 500 μ m, then the particulate specific surface area diminishes, the tendency that exists bonding force to reduce.
With respect to 100 weight part viton, the addition of metal oxide is 4～100 weight parts, is preferably 5～50 weight parts, more preferably 8～40 weight parts, more preferably 8～20 weight parts.If if metal oxide surpasses 100 weight parts, then there is the too high tendency of hardness of moulding product in the tendency that metal oxide less than 4 weight parts, then exists the bonding strength of viton and non-viton to reduce.
In addition, by containing silica-based weighting agent, thereby improved the bonding strength of viton and non-viton.
As silica-based weighting agent, can enumerate wet silicon dioxide, dry type silicon-dioxide, diatomite, silica powder etc., preferred wet silicon dioxide, dry type silicon-dioxide.
With respect to 100 weight part viton, the addition of silica-based weighting agent is 1～50 weight part, is preferably 3～30 weight parts.If if silica-based weighting agent surpasses 50 weight parts, then there is the too high tendency of hardness of moulding product in the tendency that silica-based weighting agent less than 1 weight part, then exists the bonding strength of viton and non-viton to reduce.
In addition; also can sneak into the additive that is blended in usually in the fluoro-rubber composite as required; for example various additives such as weighting agent, processing aid, softening agent, tinting material, stablizer, bonding auxiliary agent, acid acceptor, release agent, electroconductibility imparting agent, heat conductivity imparting agent, flexibility imparting agent, improved heat resistance agent, fire retardant can also be sneaked into linking agent and crosslinking coagents commonly used different with crosslinking coagent with above-mentioned linking agent more than a kind or a kind.
Above-mentioned fluoro-rubber composite is by using compounding rubber device commonly used that viton, peroxidation system linking agent, tackifier and metal oxide and/or silica-based weighting agent, in case of necessity other Synergist S-421 95s such as crosslinking coagent, packing material are carried out mixing obtaining.As the compounding rubber device, can use roller, kneader, Banbury, Banbury mixer, twin screw extruder etc.
In addition, in the scope that does not influence effect of the present invention, can in fluororubber composition for peroxide crosslinking of the present invention, add other polymkeric substance such as polyethylene, polypropylene, polymeric amide, polyester, urethane; Inorganic fillers such as the carbon black except that metal oxide and silica-based weighting agent, barium sulfate; Pigment, fire retardant, lubricant, photostabilizer, weather-proof stablizer, static inhibitor, UV light absorber, antioxidant, release agent, whipping agent, spices, oil, softening agent (gentle Softization drug) etc.
Fluororubber composition for peroxide crosslinking of the present invention can use general method for processing forming and shaping and processing device to wait forming process.As method for processing forming, can adopt any means such as for example injection molding, extrusion moulding, compression molding, blow molding, calendering formation, vacuum forming, according to application target fluoro-rubber composite of the present invention is shaped to the formed body of shape arbitrarily.
In addition, the present invention relates to the manufacture method of rubber laminate, this method comprises the operation that forms rubber laminate and carries out the bonding operation of interlayer, in the operation of described formation rubber laminate, will be by above-mentioned fluororubber composition for peroxide crosslinking fluororubber layer that forms and the non-fluororubber layer lamination that forms by the non-fluoro-rubber composite that contains non-viton and peroxidation system linking agent, form rubber laminate, carry out in the bonding operation of interlayer described, resulting rubber laminate is carried out peroxide crosslinking, and it is bonding to carry out interlayer.
As non-viton, be not particularly limited, can enumerate polybutadiene rubber, styrene butadiene rubbers, acrylonitrile-butadiene rubber or its hydride, natural rubber, polyisoprene, PBR, ethylene-propylene rubber, ethylene-propylene termonomer multipolymer, sovprene, chloroprene copolymer, poly--the 1-chloroprene, 1-chloroprene-butadienecopolymer, chlorinatedpolyethylene, chlorosulfonated polyethylene, chlorinated butyl rubber or brominated butyl rubber, acrylic rubber, silicon rubber, the multipolymer of epichloro hydrin rubber and other unsaturated epoxy compounds etc., vinyl-vinyl acetate copolymer, α, alpha, beta-unsaturated nitriles-conjugated diene copolymer rubber or its hydride; Acrylate and vinyl compound, olefin(e) compound, diolefin, α, β-ethene is multipolymer of unsaturated carboxylic acid etc. etc., in these non-viton, consider preferred acrylonitrile-butadiene rubber or its hydride, acrylic rubber, silicon rubber from the aspect of excellent heat resistance; Acrylate and vinyl compound, olefin(e) compound, diolefin, α, β-ethene is the multipolymer of unsaturated carboxylic acid etc., the more preferably silicon rubber of thermotolerance the best.
And,, preferably used the non-viton of the peroxide crosslinking system of organo-peroxide from considering with the aspect of the cementability of viton.
As silicon rubber, comprise and utilize condensation reaction, addition reaction or organo-peroxide to carry out crosslinked silicon rubber, from considering, preferably used the silicon rubber of the peroxide crosslinking system of organo-peroxide with the aspect of the cementability of viton.
In addition, as the peroxidation system linking agent that in non-fluoro-rubber composite, adds, the same linking agent of peroxidation system linking agent that can enumerate Yu in fluoro-rubber composite, add, wherein preferred 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, dicumyl peroxide.
In addition, can also use crosslinking coagent with linking agent, as crosslinking coagent, the same crosslinking coagent of peroxidation system linking agent that also can enumerate Yu in fluoro-rubber composite, add, consider preferred cyanacrylate (TAIC) from the aspect of the rerum natura of bridging property, cross-linking agent.
As the combined amount of linking agent, with respect to the non-viton of 100 weight parts, its combined amount is preferably 0.2～10 weight part, more preferably 0.5～8 weight part.If the tendency that linking agent less than 0.2 weight part, then exists cross-linking density reduction and compression set to increase, if linking agent surpasses 10 weight parts, then cross-linking density excessively raises, and therefore has tendency frangible when compressing.
As the combined amount of crosslinking coagent, with respect to the non-viton of 100 weight parts, its combined amount is preferably 0.2～10 weight part, more preferably 0.5～8 weight part.If the combined amount of crosslinking coagent is less than 0.2 weight part, then rate of crosslinking is slack-off, therefore the tendency that exists all rerum naturas such as productivity deterioration, compression set to worsen, if the combined amount of crosslinking coagent surpasses 10 weight parts, then rate of crosslinking becomes too fast, therefore exists incipient scorch or the bad tendency of moulding easily take place.
In addition, in non-fluoro-rubber composite, unless beyond the viton, peroxide cross-linking agent, can also add Synergist S-421 95 commonly used in the art such as acid acceptor, toughener, weighting agent, softening agent, antiaging agent as required.Particularly, by mixing above-mentioned metal oxide, silica-based weighting agent, can make the bonding more firm of viton and non-viton.
Non-fluoro-rubber composite and above-mentioned fluoro-rubber composite are similarly by using compounding rubber device commonly used to carry out mixing obtaining.
Lamination method to laminate is not particularly limited, and can use common lamination method.For example can make laminate: utilize forcing machine with fluoro-rubber composite with non-fluoro-rubber composite is two-layer extrudes or utilize 2 forcing machines to extrude outside layer simultaneously on la m by following method, form the interior pipe rubber layer that constitutes by la m and outside layer thus, utilize forcing machine to extrude the outer tube rubber layer again, form one, next make them crosslinked bonding, make laminate thus.
In addition, also can make laminate: utilize open roll and pressing machine etc. will be respectively flaky fluoro-rubber composite and non-fluoro-rubber composite is overlapping then makes them crosslinked bonding to form one, produce laminate thus by following method.
As crosslinked condition, get final product according to the suitable decision of kind of employed linking agent etc., carry out 1 minute～24 hours firing 140～300 ℃ temperature usually.
In addition, as cross-linking method, normally used methods such as mold pressing is crosslinked, vapor crosslinking are certainly used, and both can under normal pressure, pressurization, decompression or in air, carry out crosslinking reaction, also can carry out crosslinking reaction under the condition arbitrarily, in these conditions, consider preferred crosslinked, the vapor crosslinking of mold pressing from the normality rerum natura of operation, moulding product, the aspect of compression set.The more preferably vapor crosslinking from the aspect of operation, productivity.
Utilize in the rubber laminate that manufacture method of the present invention obtains, because the fluororubber layer that is had is by added peroxidation system linking agent in viton, the fluoro-rubber composite of tackifier and metal oxide and/or silica-based weighting agent forms, therefore with the adaptation excellence of the non-fluororubber layer that constitutes by non-fluoro-rubber composite, can make and have both chemical proofing, oil-proofness, thermotolerance, the rubber laminate of winter hardiness, this rubber laminate is useful as the oil-resisting and heat-resisting rubber hose, particularly as the engine and the peripheral device of automobile, the AT device, the flexible pipe of fuel system and peripheral device etc. is useful.
Purposes as the rubber laminate that utilizes manufacture method of the present invention to obtain is not particularly limited, and for example can enumerate the engine body of engine for automobile, main motion system, valve actuation system, lubricating and cooling system, fuel system, air-breathing exhaust system; The transmission mechanism system of drive system; The maneuvering system on chassis; The drift stop system; The basic parts of electric of Denso product, control be parts of electric, equipment parts of electric etc. require thermotolerance, oil-proofness, oil fuel patience, anti-engine cool with non-freezing solution, the packing ring of anti-steam or the gasket class sealing materials such as (self-sealing packing pad, piston ring, fracture Gask-O-Seal, mechanical seal, oil-sealing arrangements etc.) of non-contact type and contact-type etc.
Sealing material as the engine body that is used for engine for automobile, be not particularly limited, for example can enumerate sealing materials such as packing ring, circular rings, gasket, synchronizing jugged with closure such as cylinder head gaskets, cylinder head sealing cover, oil pan packing, general packing ring etc.
Sealing material as the main motion system that is used for engine for automobile is not particularly limited, and can enumerate for example gland seal device such as crankshaft seal spare, camshaft seal etc.
Sealing material as the valve actuation system that is used for engine for automobile is not particularly limited, and can enumerate valve rod oil-sealing arrangement of engine valve for example etc.
Sealing material as the lubricating and cooling system that is used for engine for automobile is not particularly limited, and can enumerate seal washer of oil cooler for example etc.
Sealing material as being used for the engine for automobile fuel system is not particularly limited, and can enumerate packing seal element, fuel tank gasket of oil-sealing arrangement, the fuel container of petrolift for example etc.; Fuel tube junctor circular rings etc.; The injector packing ring of fuel injection device, injector sealing-ring, injector circular rings etc.; The flange washer of vaporizer etc.
Sealing material as the air-breathing exhaust system that is used for engine for automobile is not particularly limited, and can enumerate for example induction manifold gasket, the exhaust manifold gasket of manifold; The butterfly gasket of throttling valve; The turboshaft seal apparatus of turbo-supercharger etc.
Sealing material as the actuator system that is used for engine for automobile is not particularly limited, and can enumerate the relevant bearing seal of transmission mechanism for example, oil-sealing arrangement, circular rings, gasket etc.; The circular rings of automatic gear-box, gasket class etc.
Sealing material as the drift stop system that is used for engine for automobile is not particularly limited, and can enumerate for example oil-sealing arrangement, circular rings, gasket etc.; The piston cup of master cylinder (rubber bowl) etc.; Clamp sealing member, shield cap class etc.
Sealing material as the equipment Denso product that are used for engine for automobile is not particularly limited, and can enumerate circular rings, gasket of air conditioner for automobile for example etc.
, be not particularly limited with purposes in addition as automobile, for example can enumerate the gasket of the oil resistant in the transportation equipments such as boats and ships, aircraft, chemical-resistant resistance, heat-resisting, anti-steam or weather-proof usefulness, circular rings, other sealing materials; Same gasket in the chemical device, circular rings, sealing material; Same gasket, circular rings, sealing material in food factories machine and the food machine (comprising household supplies); Same gasket in the nuclear power station machine, circular rings, sealing material; Same gasket in the general industry product, circular rings, sealing material etc.
Among these purposes, the rubber laminate that is obtained by manufacture method of the present invention is preferably used as the oil-resisting and heat-resisting rubber hose especially.
Embodiment
The present invention will be described to enumerate embodiment below, but the present invention also only is not limited to described embodiment.
＜crosslinking feature 〉
For the fluoro-rubber composite that obtains in embodiment and the comparative example, when 1 mold pressing is crosslinked, use JSR type Curelastometer II type, obtain 160 ℃ cross-linking curve, and, obtain MV minium viscosity (ML), high viscosity (MH), induction time (T10) and best crosslinking time (T90) by the variation of moment of torsion.
＜normality rerum natura 〉
The crosslinked of thickness 2mm that use is formed by the fluoro-rubber composite that obtains in embodiment and comparative example, use tensile testing machine (Tensilon, ORIENTEC makes), based on JIS K6251 (1993), under 500mm/ minute condition, 23 ℃ tensile break strength (TB), tension fracture elongation rate (EB) and 100% modulus (M100) are measured with No. 5, dumb-bell shape.
＜hardness 〉
The crosslinked of thickness 2mm that use is formed by the fluoro-rubber composite that obtains in embodiment and comparative example uses TYPE A sclerometer (trade(brand)name: ASKER, polymer gauge society makes), measures based on JIS K 6253 (1997).
＜compression set 〉
Based on JIS K 6301, to 200 ℃ * 24 hours compression set of circular rings (P-24) measure (under the 25% pressurization compression in 200 ℃ keep 24 hours after, the sample of placing after 30 minutes in 25 ℃ thermostatic chamber is measured).
＜heat-resistant aging 〉
Based on JIS K 6257 A-2 methods, use crosslinked, after the thermal ageing of implementing 200 ℃ * 72 hours and 230 ℃ * 72 hours is handled, obtain the variation of TB, EB and hardness.
＜oil-proofness 〉
Based on JIS K 6258, use crosslinked, in testing with lubricating oil No.3 oil, JIS carries out 175 ℃ * 72 hours dip test, obtain variation, volume change and the mass change of TB, EB and hardness.
Each composition in table 1, table 2 and the table 3 below is shown respectively.
＜viton 〉
FKM1: but the ternary fluororubber (VdF/TFE/HFP=50/20/30 (mole %)) of the peroxide crosslinking that iodine transfer polymerization legal system produces utilized.Mooney viscosity is 50 (ML1+10,100 ℃).
FKM2: but the binary viton (VdF/HFP=78/22 (mole %)) of the peroxide crosslinking that iodine transfer polymerization legal system produces utilized.Mooney viscosity is 69 (ML1+10,100 ℃).
＜silicon rubber 〉
Silicon rubber: the silicone sizing material (trade(brand)name: KE551-U) that Shin-Etsu Chemial Co., Ltd makes
＜linking agent 〉
Linking agent 1: the PERHEXA 25B (trade(brand)name) that NOF Corp makes
(2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane))
Linking agent 2: the C-8B (trade(brand)name) that Shin-Etsu Chemial Co., Ltd makes
(containing 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane)
＜crosslinking coagent 〉
TAIC: the cyanacrylate that Nippon Kasei Chemical Company makes
＜metal oxide 〉
Magnesium oxide: the KYOWAMAG 150 (trade(brand)name) that Kyowa Chemical Industry Co., Ltd makes, size-grade distribution (microtrack method) 10%:1.48 μ m, 50%:5.92 μ m, 90%:14.16 μ m
＜silica-based weighting agent 〉
Silicon-dioxide: Japan Silica Co., the wet silicon dioxide Nipsil VN3 that Ltd. makes
＜tackifier 〉
Escron G90:(trade(brand)name) the coumarone resin softening temperature of chemical industry Co., Ltd. of Nippon Steel manufacturing is about 90 ℃
TACKROL 101:(trade(brand)name) the non-response type alkyl phenolic resin softening temperature of Sumitomo Chemical Company Ltd's manufacturing is 78～105 ℃
Petrosin PR-100:(trade(brand)name) the fragrant family hydrocarbon resin softening temperature of Mitsui Chemicals, Inc's manufacturing is about 100 ℃
QUINTON B170:(trade(brand)name) petroleum resin (the synthetic polyterpene resin C=4～5 hydrocarbon-fraction polymkeric substance) softening temperature made of Japanese Zeon Co., Ltd. is about 70 ℃
HARIESTER TF:(trade(brand)name) the Abietyl modified glyceryl ester softening temperature of Harima Chemicals Co., Ltd. manufacturing is 83 ℃
HARIESTER P:(trade(brand)name) the Abietyl modified tetramethylolmethane softening temperature of Harima Chemicals Co., Ltd. manufacturing is 102 ℃
＜weighting agent 〉
The carbon black ThermaxN-990 (trade(brand)name) that MT carbon: Cancarb makes
Embodiment 1～7
Prescription according to table 1 mixes viton respectively, carries out mixingly on open roll, prepares fluoro-rubber composite (1)～(7).It is crosslinked in 160 ℃ 10 minutes mold pressing to be carried out in fluoro-rubber composite (1)～(7) of preparing, and crosslinked in 180 ℃ of bakings of implementing 4 hours again, producing thickness is that crosslinked of 2mm and the quilt of circular rings (P-24) are tested sample.The bridging property of this fluoro-rubber composite (1)～(7), the normality rerum natura and the compression set of cross-linking agent are measured, be the results are shown in table 1.And, the heat-resistant aging and the oil-proofness of the cross-linking agent of fluoro-rubber composite (1) are measured.The results are shown in table 2.
Embodiment 8
Prescription according to table 1 mixes viton respectively, carries out mixingly on open roll, produces fluoro-rubber composite (8).
Comparative example 1
Except that not adding tackifier, produce fluoro-rubber composite (9) similarly to Example 1.The bridging property of this fluoro-rubber composite (9), the normality rerum natura and the compression set of cross-linking agent are measured, be the results are shown in table 1.
Comparative example 2
Use 30 weight part MT carbon and do not add magnesium oxide, in addition, produce fluoro-rubber composite (10) similarly to Example 1.The bridging property of this fluoro-rubber composite (10), the normality rerum natura and the compression set of cross-linking agent are measured, be the results are shown in table 1.
Table 2
| Fluoro-rubber composite | (1) |
| Condition of molding | Mold pressing is crosslinked: baking in 160 ℃ * 10 minutes is crosslinked: 180 ℃ * 4 hours |
| Heat-resistant aging 200 ℃ * 72 hours TB velocity of variation (%) EB velocity of variation (%) changes in hardness 230 ℃ * 72 hours TB velocity of variation (%) EB velocity of variation (%) changes in hardness | +6 -7 -1 -24 +25 0 |
| 175 ℃ * 72 hours TB velocity of variation (%) EB velocity of variation (%) changes in hardness volume change (%) mass changes (%) of oil-proofness JIS No.3 oil | -9 -8 -2 +2 +1 |
Embodiment 9～16 and comparative example 3～4
To mix with the same ratio of mixture of table 1, on open roll, carry out mixingly, produce the uncrosslinked viton sheet of the thickness 1.2mm that forms by fluoro-rubber composite (1)～(10).Next, in 100 weight part silicon rubber, mix 1 weight part linking agent 2, on open roll, carry out mixingly, produce the uncrosslinked non-viton sheet of thickness 3.2mm.As shown in Figure 1, uncrosslinked viton sheet 1 and uncrosslinked non-viton sheet 2 is overlapped, carry out clamping with fluororesin film 3 (thickness 150 μ m, Daikin Industries (strain) system, trade(brand)name NEOFLON FEP NF-0150) again.At this moment, until the interface that is deep into the position about 1cm～1.5cm, inserting fluororesin film 3 from an end to produce not bonding part, the pull head when making stripping test (body ろ slaps).Utilize moulding press under 80 ℃, 30 seconds condition, it to be pre-formed as the thickness of 4mm, use vulcanizing boiler, carry out 45 minutes vapor crosslinkings in 160 ℃, produce crosslinked bonding rubber laminate.
And, crosslinked in 180 ℃ of bakings of carrying out 10 hours behind vapor crosslinking.The evaluation result of the bonding strength of the crosslinked front and back of baking of resulting laminate is listed in table 3.
(bonding strength)
Peel fluoro-resin system film 3 from resulting rubber laminate, cut into the rectangle of wide 25mm * length 100mm, make test film, carry out the T stripping test, measure bonding strength in 23 ℃ of peeling rates with 50mm/ minute.And state is peeled off in observation, estimates with following benchmark.
Zero .... material damage, fracture appear in the silastic-layer side.
* .... peel off at the interface at fluororubber layer and silastic-layer.
[table 3]
Industrial applicibility
Fluororubber composition for peroxide crosslinking of the present invention is owing to contain tackifier, and contains metal oxide and/or silica-based filler, therefore can form the fluororubber layer with the adaptation excellence of the non-fluororubber layer that is formed by non-fluorubber.
Claims (8)
1. fluororubber composition for peroxide crosslinking, wherein, described composition contains viton, peroxidation system linking agent, is the tackifier of 0.05 weight part～10 weight parts and is the metal oxide except that silica-based weighting agent of 4 weight parts～100 weight parts and/or is the silica-based weighting agent of 1 weight part～50 weight parts with respect to 100 weight part viton with respect to 100 weight part viton.
2. fluororubber composition for peroxide crosslinking as claimed in claim 1, wherein, described tackifier are that being selected from by coumarone resin, rosin derivative, phenol-terpenic series resin and oil is more than one tackifier in the group formed of hydrocarbon resin.
3. fluororubber composition for peroxide crosslinking as claimed in claim 1 or 2, wherein, described metal oxide is more than one the oxide compound that is selected from the group of being made up of magnesium oxide, calcium oxide, titanium dioxide, aluminum oxide, ferric oxide and zinc oxide.
4. fluororubber composition for peroxide crosslinking as claimed in claim 3, wherein, described metal oxide is a magnesium oxide.
5. the manufacture method of a rubber laminate, this method comprise the operation that forms rubber laminate and carry out the bonding operation of interlayer,
In the operation of described formation rubber laminate, fluororubber layer that will form by the described fluororubber composition for peroxide crosslinking of claim 1～4 and the non-fluororubber layer lamination that forms by the non-fluoro-rubber composite that contains non-viton and peroxidation system linking agent, form rubber laminate
In the bonding operation of interlayer resulting rubber laminate is carried out peroxide crosslinking described carrying out, it is bonding to carry out interlayer.
6. the manufacture method of rubber laminate as claimed in claim 5, wherein, described non-viton is a silicon rubber.
7. as the manufacture method of claim 5 or 6 described rubber laminates, wherein, described peroxide crosslinking is a vapor crosslinking.
8. oil-resisting and heat-resisting rubber hose, described oil-resisting and heat-resisting rubber hose is to be formed by the rubber laminate that utilizes each described manufacture method of claim 5～7 to obtain.
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| JP173694/2006 | 2006-06-23 | ||
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| PCT/JP2007/062511 WO2007148759A1 (en) | 2006-06-23 | 2007-06-21 | Fluororubber composition for peroxide crosslinking and method for producing rubber laminate |
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- 2007-06-21 WO PCT/JP2007/062511 patent/WO2007148759A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2007148759A1 (en) | 2009-11-19 |
| CN101479336B (en) | 2012-01-11 |
| JP5239857B2 (en) | 2013-07-17 |
| WO2007148759A1 (en) | 2007-12-27 |
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