WO2007148759A1 - Composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde et procédé de fabrication d'un stratifié de caoutchouc - Google Patents

Composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde et procédé de fabrication d'un stratifié de caoutchouc Download PDF

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Publication number
WO2007148759A1
WO2007148759A1 PCT/JP2007/062511 JP2007062511W WO2007148759A1 WO 2007148759 A1 WO2007148759 A1 WO 2007148759A1 JP 2007062511 W JP2007062511 W JP 2007062511W WO 2007148759 A1 WO2007148759 A1 WO 2007148759A1
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fluororubber
rubber
crosslinking
peroxide
weight
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PCT/JP2007/062511
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English (en)
Japanese (ja)
Inventor
Kazuyoshi Kawasaki
Katsusada Tokuhira
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to CN2007800235518A priority Critical patent/CN101479336B/zh
Priority to JP2008522512A priority patent/JP5239857B2/ja
Publication of WO2007148759A1 publication Critical patent/WO2007148759A1/fr

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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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • the present invention relates to a fluororubber composition for peroxide crosslinking containing a fluororubber, a peroxide-based crosslinking agent, a tackifier, and a metal oxide and / or a silica-based filler, and the fluororubber composition for peroxide crosslinking.
  • the present invention relates to a method for producing a rubber laminate including a fluororubber layer formed from a product, and an oil resistant / heat resistant rubber hose formed from the rubber laminate obtained from the production method.
  • Fluorororubber has been widely used in various fields such as automobile industry, semiconductor industry, chemical industry and the like because it exhibits excellent chemical resistance, solvent resistance and heat resistance.
  • automobile industry Is used as hoses and sealing materials for engines and peripheral devices, AT devices, fuel systems and peripheral devices.
  • these fluororubber materials also have stricter demands on various properties such as aging resistance, weather resistance, processability, oil resistance, fuel oil resistance, and fuel permeability. This is the current situation.
  • fluororubber exhibits the above-mentioned excellent characteristics, its price is 10 to 20 times that of ordinary rubber materials, and there is a problem with cold resistance.
  • materials such as cost and cold resistance.
  • acrylic nitrile monobutadiene copolymer rubber and silicone rubber which have been used as a fuel oil hose, have been changed to fluoro rubber in terms of various properties such as heat resistance, oil resistance, and aging resistance. It was inferior and its improvement was required.
  • hoses made of non-fluorinated rubber such as epichlorohydrin rubber have been developed as a thin layer using fluoro rubber as an inner layer and outer layer.
  • non-fluororubbers such as fluororubber and epichlorohydrin rubber have practical problems with poor adhesion. .
  • acrylonitrile butadiene rubber and polychlorinated A rubber composition in which an organic peroxide, an adhesion-imparting agent, and a tackifier are added to a blend material with bulle is known (see, for example, JP-A-2000-273241).
  • the rubber composition can achieve both excellent adhesiveness to the fluororubber layer at the time of non-crosslinking and excellent adhesiveness to the fluororubber layer at the time of crosslinking, it is described in JP-A-2000- In the 273241 publication, an adhesion-imparting agent and a tackifier are added to improve the non-fluorine rubber layer, and improvement of the fluororubber layer has not been studied. In addition, adhesion of fluororubber and other materials other than blends of acrylonitrile-butadiene rubber and polychlorinated butyl rubber has been studied.
  • fluororubber composition to which a tackifier is added
  • a fluorororubber composition comprising fluororubber, coumarone 'indene resin, phenol' formaldehyde resin, polyterpene resin, terpene 'phenol resin or xylene' formaldehyde resin. It is known (see, for example, JP 2005-113017 A).
  • the fluororubber composition has improved low resilience characteristics at high temperature, and the adhesiveness with the non-fluororubber layer has not been studied.
  • the examples only disclose that the low resilience characteristics at high temperature of the polyol vulcanized fluororubber composition are improved, and the fluoro rubber composition for peroxide vulcanization is specifically described. It has not been.
  • a method for improving the adhesion between fluororubber and non-fluororubber by blending a metal oxide with fluororubber or non-fluororubber see, for example, WO 03/039858 pamphlet
  • fluorine A method for improving the adhesion between fluororubber and non-fluororubber by blending a silica-based filler with rubber or non-fluororubber (for example, see JP-A-2003-19772) is known.
  • press vulcanization is carried out, and when the steam cross-linking method used in the actual production of hoses is used, the adhesion tends to be inferior.
  • the present invention relates to a peroxide-crosslinking fluororubber composition capable of forming a fluororubber layer excellent in adhesion to a layer formed from non-fluororubber, and a layer formed from the fluororubber composition. It aims at providing the manufacturing method of the rubber laminated body containing this. Another object of the present invention is to provide an oil and heat resistant rubber hose formed from the rubber laminate obtained from the production method.
  • the present invention relates to fluororubber, peroxide cross-linking agent, 0.05 to 100 parts by weight of fluororubber: 4 to 100 parts by weight of tackifier and 100 parts by weight of fluororubber.
  • the present invention relates to a peroxide-crosslinking fluororubber composition containing parts by weight of a metal oxide (excluding silica-based fillers; the same applies hereinafter) and / or 1 to 50 parts by weight of a silica-based filler.
  • the tackifier is preferably at least one tackifier selected from the group consisting of coumarone resins, rosin derivatives, phenol terpene resins, and petroleum hydrocarbon resins.
  • the metal oxide is preferably at least one oxide selected from the group consisting of magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, iron oxide and zinc oxide.
  • the metal oxide is preferably magnesium oxide.
  • the present invention provides a fluorine rubber layer formed from the peroxide crosslinking fluororubber composition
  • a step of forming a rubber laminate by laminating a non-fluorine rubber layer formed from a non-fluorine rubber and a non-fluorine rubber composition containing a peroxide-based crosslinking agent, and subjecting the resulting rubber laminate to peroxide crosslinking The present invention relates to a method for producing a rubber laminate including a bonding step.
  • Non-fluorine rubber strength Silicone rubber is preferable.
  • the present invention provides an oil resistance 'anti-resistance formed from a rubber laminate obtained from the above production method. It relates to a thermal rubber hose.
  • FIG. 1 is an explanatory view of a test piece for measuring adhesive strength.
  • the present invention relates to fluororubber, peroxide-based crosslinking agent, fluororubber 100 parts by weight.
  • the present invention relates to a fluororubber composition.
  • examples of the fluoro rubber include non-perfluoro fluoro rubber and perfluoro fluoro rubber.
  • perfluoro fluorororubber is, among its structural units,
  • Non-perfluorofluorororubbers include vinylidene fluoride (hereinafter referred to as VdF) fluorine rubber, tetrafluoroethylene (hereinafter referred to as TFE) Z propylene fluororubber, TF E / propylene / VdF fluorine rubber, ethylene / hexafluoropropylene (hereinafter referred to as HF P) fluorine rubber, ethylene / HFP / VdF fluorine rubber, ethylene / HFP / TF E fluorine rubber, fluorosilicone fluorine Examples include rubbers, fluorophosphazene-based fluoro rubbers, and the like. These can be used alone or in any combination as long as the effects of the present invention are not impaired. VdF-based fluoro rubber, TFEZ propylene It is preferable to use a fluorinated rubber.
  • VdF-based fluororubber As the VdF-based fluororubber, the following general formula (1):
  • the structural unit M 1 is a structural unit derived from VdF (m 1 )
  • the structural unit M 2 is a structural unit derived from a fluorinated ethylenic monomer (m 2 )
  • the structural unit N 1 is It is a repeating unit derived from a monomer (n 1 ) that is copolymerizable with a monomer (m 1 ) and a monomer (m 2 )
  • the structural unit M 1 25 to 85 mole 0/0, 75 of the structural unit M 2: preferably those containing 15 mol% instrument structural units A structural unit containing 30 to 80 moles of M 1 and 0 to 0 , and a structural unit M 2 of 70 to 20 mole% is more preferable. 40 to 70 moles of M 1 %, The structural unit M 2 further preferably contains 60 to 30 mol%.
  • the structural unit N 1 is preferably 0 to 10 mol% with respect to the total amount of the structural unit M 1 and the structural unit M 2 .
  • Examples of the fluorine-containing ethylenic monomer (m 2 ) include TFE, black trifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, HFP, trifluoropropylene, and tetrafluoro. Forces that include fluorine-containing monomers such as propylene, pentafluoropropylene, trifluorobutene, tetrafluoroloybutene, perfluoro (alkyl butyl ether) (hereinafter referred to as PAVE), and vinyl fluoride. , TFE, HFP and PAVE are preferred. These can be used alone or in any combination.
  • any monomer (m 1 ) and monomer (m 2 ) can be used as long as they are copolymerizable with the monomer (m 1 ).
  • ethylene, propylene, alkyl Examples include butyl ether and a monomer that gives a crosslinking site. Among them, a monomer that gives a crosslinking site is preferable. More preferred is a monomer that provides a crosslinking site capable of peroxide crosslinking.
  • a monomer that gives such a crosslinking site for example, perfluoro (6, 6 dihydro 6-hydroxy 3-oxa) described in JP-B-5-63482 and JP-A-7-316234 is disclosed.
  • Iodine-containing monomers such as hexene
  • perfluoro 5-iodo-3-oxa 1 pentene
  • nitrogen-containing monomers described in JP-A-4-505341, JP-A-4-505345
  • nitrogen-containing monomers described in JP-A-4-505341, JP-A-4-505345 examples thereof include a cyano group-containing monomer, a carboxyl group-containing monomer, and an alkoxycarbonyl group-containing monomer as described in JP-A-5-500070.
  • examples of the monomer that gives a crosslinking site include VdF and general formula (2):
  • CY 1 CY 1 -R 1 CHR 1 X 1 (2)
  • CY 2 CY 2 -R 2 CF X 2 (3) (Where Y 2 is a hydrogen atom, fluorine atom or CH, R 2 is a fluoroalkylene group,
  • a fluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, X 2 is an iodine atom or a bromine atom
  • R 3 is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group
  • R 3 is a fluorine atom or CF
  • X 3 is a cyano group. , Carboxyl group or alkoxycarbonyl group
  • the iodine atom, bromine atom, cyano group, carboxyl group, and alkoxycarbonyl group can function as a crosslinking point.
  • the iodine atom, bromine atom, and cyano group function as a crosslinking point for peroxide crosslinking. can do.
  • VdF fluorororubbers include VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, and VdF / PAVE rubber.
  • VdF / TFE / PAVE rubber, VdFZHFPZPAVE rubber, VdF / HFPZ TFE / PAVE rubber, VdFZTFEZ propylene rubber, VdF / ethylene / HFP rubber and the like are preferable.
  • the structural unit M 3 is a structural unit derived from TFE (m 3 )
  • the structural unit M 4 is a structural unit derived from propylene (m 4 )
  • the structural unit N 2 is a monomer (m 3 ) And copolymerization with monomer (m 4 ) It is a repeating unit derived from a possible monomer (n 2 )
  • the structural unit N 2 is preferably 0 to 40 mol% with respect to the total amount of the structural unit M 3 and the structural unit M 4 .
  • the monomer (n 2 ) may be any monomer as long as it is copolymerizable with the monomer (m 3 ) and the monomer (m 4 ). It is preferable that A monomer that provides a crosslinking site capable of peroxide crosslinking is more preferred.
  • Examples of the monomer that gives such a crosslinking site include those mentioned above.
  • these monomers iodine atom, bromine atom, and cyano group-containing monomers are particularly suitable for crosslinking sites for peroxide crosslinking. This is preferable for giving.
  • structural unit M 5 is a structural unit derived from TFE (m 5 )
  • structural unit M 6 is a structural unit derived from PAVE (m 6 )
  • structural unit N 3 is a monomer (m 5 ).
  • the structural unit M 5 50 to 90 molar% more preferably preferably those comprising structural units M 6 10 to 50 mol% instrument structure unit M 5 50-80 Monore 0/0, which the structural unit M 6 comprising 20 to 50 mole 0/0, more preferably a structural unit M 5 55 to 70 mol%, 30 to the structural unit M 6 Contains 45 mol%.
  • PAVE examples include perfluoro (methyl vinyl ether), perfluoro mouth (propyl butyl ether) and the like. Can be used in combination.
  • the monomer (n 3 ) may be any monomer as long as it is copolymerizable with the monomer (m 5 ) and the monomer (m 6 ). Among these, a monomer that gives a crosslinking site is preferable.
  • Examples of the monomer that gives such a crosslinking site include those mentioned above.
  • force and perfluoro fluororubber include WO 97/24381 pamphlet, JP-B 61-57324, JP-B 4-81608, JP-B 5-13961, etc. And fluororubber described in the above.
  • a polymer or a copolymer of a modified monomer or the like can be suitably used. It is also possible to accelerate the dehydrofluoric acid by heat treatment, etc. to generate a double bond in the molecule as a crosslinking point.
  • a fluororubber containing VdF units is preferred from the viewpoint of heat resistance, compression set, workability, and cost. More preferred is VdF / TFE / HFP fluororubber.
  • the fluororubber described above can be produced by a conventional method, and as a preferred production method, a known iodine transfer polymerization method can be given as a production method of the fluororubber.
  • An iodine atom or a bromine atom is introduced into the terminal of the fluorine-containing elastomer obtained by using the silicon transfer polymerization method, and can serve as a crosslinking point for peroxide crosslinking.
  • the polymerization conditions such as temperature and time during polymerization may be appropriately determined according to the type of monomer and the desired elastomer.
  • the peroxide-crosslinking fluororubber composition of the present invention contains a peroxide-based crosslinking agent, and is crosslinked with the peroxide-based crosslinking agent, so that carbon-carbon at the crosslinking point. Excellent chemical resistance and steam resistance compared to polyol cross-linking systems with carbon-oxygen bonds at the cross-linking points and polyamine cross-linking systems with carbon-nitrogen double bonds. It is.
  • fluororubber composition for peroxide crosslinking of the present invention it is advantageous in bonding of fluororubber and non-fluororubber that as many bridges as possible are composed of peroxide crosslinks. It is preferable that it does not contain agents.
  • the peroxide cross-linking agent used in the present invention may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system.
  • the addition amount of the peroxide-based crosslinking agent is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the fluororubber, more preferably 0.1 to 10 parts by weight. It is more preferable that the content is 0.3 to 7.0 parts by weight: It is particularly preferable to be 5 to 5 parts by weight. If the cross-linking agent is less than 0.05 parts by weight, the degree of cross-linking is insufficient, and the performance such as heat resistance and oil resistance of the molded product tends to be impaired. If it exceeds 10 parts by weight, the cross-linking density is high. In addition to being liable to be too long, the crosslinking time tends to be long, and in addition, it is economically preferable, and the molding cacheability of the resulting fluororubber composition tends to decrease.
  • crosslinking aid examples include triaryl cyanurate, triallyl isocyanurate ( ⁇ C), triacryl formal, trilinole trimellitate, N, N'_m_phenylene bismale. Imido, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1, 3, 3 tris (2, 3, 3 trifanolate low 2 propylene) Ninore) 1, 3, 5 Triazine-2, 4, 6-trione), Tris (dialylamine) -S-triazine, triallyl phosphite, N, N diary-noraretalinoleamide, 1, 6 _Divinyl dodecafluor Xanthane, hexaryl phosphoramide, N, N, ⁇ , N, monotetraarylphthalamide, N, N, N ′, N, mono
  • the addition amount of the crosslinking aid is preferably 0.:! To 20 parts by weight with respect to 100 parts by weight of the fluororubber. 0.3 to 10 parts by weight is more preferable. Preferred 0.5 to: More preferably 10 parts by weight, and particularly preferably 1 to 6 parts by weight. If the crosslinking aid is less than 0.1 part by weight, the crosslinking time becomes unusable for practical use, and the compression set, heat resistance and oil resistance of the resulting molded product tend to decrease. If it exceeds 20 parts by weight, the compression set and heat resistance of the molded product tend to decrease, and the moldability of the resulting fluororubber composition tends to decrease.
  • the peroxide cross-linking fluororubber composition of the present invention contains a tackifier, thereby forming a non-fluororubber formed from a non-fluororubber and a non-fluorine rubber composition containing a peroxide-based cross-linking agent. Since the adhesiveness with the layer is excellent, when the obtained rubber laminate is crosslinked, the two layers can be crosslinked and bonded without being peeled off. As a result, sufficient adhesive strength can be obtained even by the steam cross-linking method in which adhesive strength is difficult to obtain than press cross-linking. Further, it is possible to improve the adhesion without impairing properties such as compression set.
  • the softening point of the tackifier is preferably 200 ° C or lower, more preferably 120 ° C or lower. When the softening point exceeds 200 ° C, the tackifier does not melt even during crosslinking, and there is a tendency that sufficient adhesive strength cannot be obtained.In addition, the tackifier melts during kneading, causing a poor dispersion. It tends to be easy.
  • Examples of the tackifier include coumarone resin, phenol'terpene resin, petroleum hydrocarbon resin, rosin derivative and the like. These can be used alone or in combination.
  • Examples of the coumarone resin include coumarone 'indene resin.
  • phenol'terpene resin examples include p_tertiary butylphenol'acetylene resin, phenol'formaldehyde resin, terpene'phenol resin, polyterpene resin, xylene.formaldehyde resin, alkylphenol resin, and the like.
  • Examples of petroleum hydrocarbon resins include aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, unsaturated hydrocarbon polymers, isoprene resins, and hydrogenated hydrocarbon resins. And hydrocarbon-based tackifying resins, polymerized special polyesters, polybutene, atactic 'polypropylene, liquid polybutadiene, and low molecular weight butyl rubber.
  • rosin derivatives include rosin pentaerythritolol 'ester, rosin glycerone ester, hydrogenated rosin, highly hydrogenated wood rosin, hydrogenated rosin methyl ester, hydrogenated rosin triethylene.
  • tackifiers include resin acid and ammine-resin soap mixtures, turpentine tackifiers, synthetic resins and phthalate ester co-condensates.
  • one or more selected from the group consisting of coumarone resin, phenol'terpene resin, petroleum hydrocarbon resin, and rosin derivative A tackifier is more preferred.
  • the addition amount of the tackifier is 0.05 to 10 parts by weight with respect to 100 parts by weight of the fluororubber, and preferably 0.0 to 5 parts by weight. More preferably, it is 2 parts by weight. If the tackifier is less than 0.05 parts by weight, sufficient adhesion tends not to be obtained, and if it exceeds 10 parts by weight, the compression set, heat resistance, and oil resistance of the molded product will be reduced and obtained. Hook There exists a tendency for the molding cache property of a base rubber composition to fall.
  • the peroxide-crosslinking fluororubber composition of the present invention further contains a metal oxide and / or a silica-based filler.
  • the adhesive strength between the fluororubber and the non-fluororubber is improved.
  • the metal oxide examples include magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, iron oxide, and zinc oxide. From the viewpoint of high surface activity, magnesium oxide and calcium oxide. More preferably, the oxide is one or more oxides selected from the group consisting of titanium oxide, aluminum oxide, iron oxide, and oxide oxide.
  • the particle diameter of the metal oxide is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more. 1. Ozm or more Further preferred.
  • the upper limit of the particle diameter is preferably 500 / im or less, more preferably 50 ⁇ or less, and even more preferably 10 / im or less.
  • the particle diameter exceeds 500 / m, the specific surface area of the particles tends to be small and the adhesive strength tends to be low.
  • the addition amount of the metal oxide is 4 to 100 parts by weight with respect to 100 parts by weight of the fluororubber, and preferably 5 to 50 parts by weight, more preferably 8 to 40 parts by weight. More preferably, it is 8 to 20 parts by weight. If the metal oxide is less than 4 parts by weight, the adhesive strength between fluororubber and non-fluororubber tends to decrease, and if it exceeds 100 parts by weight, the hardness of the molded product tends to increase too much.
  • a silica-based filler improves the adhesive strength between fluororubber and non-fluororubber.
  • silica-based filler examples include wet silica, dry silica, diatomaceous earth, quartz powder, and the like. Wet silica and dry silica are preferable.
  • the amount of silica filler added is 1 to 50 parts by weight with respect to 100 parts by weight of the fluororubber,
  • the silica filler is less than 1 part by weight, There is a tendency for the adhesive strength between the rubber and the non-fluororubber to decrease.
  • additives blended in the fluororubber composition for example, fillers, processing aids, plasticizers, colorants, stabilizers, adhesion aids, acid acceptors, release agents
  • Various additives such as a conductivity imparting agent, a thermal conductivity imparting agent, a flexibility imparting agent, a heat resistance improving agent and a flame retardant can be combined.
  • One or more agents may be added.
  • the fluororubber composition includes a fluororubber, a peroxide-based crosslinking agent, a tackifier, a metal oxide and / or a silica-based filler, and if necessary, a crosslinking aid, a filler.
  • Other compounding agents can be obtained by kneading using a commonly used rubber kneader.
  • a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.
  • the peroxide-crosslinking fluororubber composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, metal oxides, carbon blacks other than silica-based fillers, Inorganic fillers such as barium sulfate, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, release agents, foaming agents, fragrances, oils, softening agents Etc. can be applied in a range that does not affect the effects of the present invention.
  • polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, metal oxides, carbon blacks other than silica-based fillers, Inorganic fillers such as barium sulfate, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, release agents, foaming agents, fragrances, oils, softening agents Etc.
  • the peroxide-crosslinking fluorororubber composition of the present invention can be molded using a general molding method or molding apparatus.
  • a general molding method or molding apparatus for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding, etc. can be adopted, and the fluororubber composition of the present invention is used for the purpose of use. In response, it is formed into a molded body of any shape.
  • the present invention provides a fluorine rubber layer formed from the peroxide crosslinking fluororubber composition
  • a step of forming a rubber laminate by laminating a non-fluorine rubber layer formed from a non-fluorine rubber and a non-fluorine rubber composition containing a peroxide-based crosslinking agent, and subjecting the resulting rubber laminate to peroxide crosslinking The present invention relates to a method for producing a rubber laminate including a bonding step.
  • Non-fluorine rubber is not particularly limited, but polybutadiene rubber, styrene-butadiene rubber, acrylonitrile butadiene rubber or its hydride, natural rubber, polyisoprene, propylene butadiene rubber, ethylene propylene rubber, ethylene —Propylene monotermonomer copolymer, polychloroprene, black polyprene copolymer, poly 1 _ cloguchi butadiene, 1 _ chloro butadiene monobutadiene copolymer, chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated Or copolymer of brominated butyl rubber, acrylic rubber, silicone rubber, epichlorohydrin rubber and other unsaturated epoxides, ethylene-butyl acetate copolymer, _unsaturated nitrile-conjugated diene copolymer Polymer Rubber or its hydride, acrylic acid Forces such as
  • acrylonitrile-butadiene rubber or Its hydrides acrylic rubbers, silicone rubbers, copolymers of acrylic acid esters and bur compounds, olefin compounds, gen compounds, ⁇ , ethylenically unsaturated carboxylic acids, etc. are preferred and have the best heat resistance Silicone rubber is preferred.
  • Silicone rubber includes those crosslinked by condensation reaction, addition reaction, or organic peroxide. From the viewpoint of adhesion to fluororubber, a peroxide crosslinking system using an organic peroxide is used. Silicone rubber is preferred.
  • examples of the peroxide-based crosslinking agent added to the non-fluorine rubber composition include the same peroxide-based crosslinking agents as those added to the fluorine-rubber composition, among which 2,5-dimethyl 1,2,5-di (t_butylperoxy) hexane and dicumyl peroxide are preferred.
  • a crosslinking aid can be used together with the crosslinking agent, and the crosslinking aid may be the same as the peroxide-based crosslinking agent added to the fluorine rubber composition.
  • TAIC triallyl isocyanurate
  • the blending amount of the crosslinking agent is 0.2 to 10 parts by weight with respect to 100 parts by weight of the non-fluororubber. Preferred 0.5 to 8 parts by weight is more preferred. If the crosslinking agent is less than 0.2 parts by weight, the crosslinking density tends to be low and compression set tends to increase. If the crosslinking agent exceeds 10 parts by weight, the crosslinking density becomes too high, and it tends to crack during compression. Tend.
  • the blending amount of the crosslinking aid is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the non-fluororubber, and more preferably 0.5 to 8 parts by weight. If the blending amount of the crosslinking aid is less than 0.2 parts by weight, the crosslinking rate becomes slow, so the productivity tends to deteriorate, and various physical properties such as compression set tend to deteriorate. Scorches and molding defects tend to occur because the speed is too high.
  • the non-fluorororubber composition includes, as necessary, an acid acceptor, a reinforcing agent, a filler, a plasticizer, an anti-aging agent, and the like in the technical field. Additives commonly used in odor can be added. In particular, by blending the metal oxide and the silica-based filler, adhesion between the fluororubber and the non-fluororubber can be further strengthened.
  • the non-fluororubber composition can be obtained by kneading using a commonly used rubber kneading apparatus in the same manner as the fluororubber composition.
  • the method for laminating the laminate is not particularly limited, and an ordinary laminating method can be used.
  • the inner layer and the outer layer force can be increased by extruding the fluororubber composition and the non-fluororubber composition simultaneously with an extruder, or by extruding the outer layer onto the inner layer with two extruders.
  • a tube rubber layer is formed, and the outer tube rubber layer is further extruded and integrated by an extruder, and then crosslinked and adhered.
  • the fluororubber composition formed into a sheet form with an open roll, a press, or the like and the non-fluororubber composition can be integrated by being overlapped and then cross-linked and produced.
  • the crosslinking conditions may be appropriately determined depending on the kind of the crosslinking agent used, but the firing is usually performed at a temperature of 140 to 300 ° C for 1 minute to 24 hours.
  • crosslinking method not only a conventionally used method such as press crosslinking and steam crosslinking, but also under normal pressure, increased pressure, reduced pressure, and in air, under any conditions
  • press crosslinking and steam crosslinking are preferred from the viewpoints of workability, normal physical properties of molded products, and compression set.
  • Steam cross-linking is preferred from the viewpoint of workability and productivity.
  • the rubber laminate obtained by the production method of the present invention is a fluororubber composition obtained by adding a peroxide-based crosslinking agent, a tackifier, and a metal oxide and / or a silica-based filler to fluororubber. Since it has a fluororubber layer formed from the above, a rubber laminate having excellent adhesion to a non-fluororubber layer made of a non-fluororubber composition and having both chemical resistance, oil resistance, heat resistance, and cold resistance can be obtained. It is useful as an oil-resistant / heat-resistant rubber hose, especially as a hose for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices.
  • the use of the rubber laminate obtained by the production method of the present invention is not particularly limited.
  • the seal material used for the engine body of an automobile engine is not particularly limited.
  • a cylinder head gasket, a cylinder head cover gasket, an oil pan packing, a gasket such as a general gasket, an O-ring, a packing, a timing Examples include sealing materials such as belt cover gaskets.
  • the seal material used in the main motion system of the automobile engine is not particularly limited, and examples thereof include a shaft seal such as a crankshaft seal and a camshaft seal.
  • the seal material used in the valve train of an automobile engine is not particularly limited, and examples thereof include a valve stem oil seal of an engine valve.
  • the sealant used in the lubricant / cooling system of the automobile engine is not particularly limited, and examples thereof include a seal gasket of an engine oil cooler.
  • the sealing material used in the engine fuel system for automobiles is not particularly limited. For example, an oil seal for a fuel pump, a filler seal for a fuel tank, a tank packing, a connector O link for a fuel tube, etc. Injector / cushion ring of fuel injector, cushion ring, injector seal ring, injector ⁇ ring, etc.
  • the sealing material used in the intake / exhaust system of an automobile engine is not particularly limited.
  • a manifold hold intake manifold seal for example, a manifold hold intake manifold seal, an exhaust manifold hold packing, and a slot slot.
  • Nore body packing and turbocharged turbine shaft seal for example, a manifold hold intake manifold seal, an exhaust manifold hold packing, and a slot slot.
  • the seal material used in the transmission system of an automobile engine is not particularly limited.
  • a transmission-related bearing seal for example, a transmission-related bearing seal, an oil seal, an O-ring, a knocker, etc.
  • O Rings and packings are examples.
  • the seal material used in the brake system of the automobile engine is not particularly limited.
  • an oil seal for example, an O-ring, a knocker, a master cylinder piston cup (rubber cup), etc.
  • Examples include carrier seals and boots.
  • the sealing material used for the electrical equipment of the automobile engine is not particularly limited, and examples thereof include a car air conditioner ring and packing.
  • Applications other than those for automobiles are not particularly limited, for example, oil-resistant, chemical-resistant, heat-resistant, steam-resistant or weather-resistant packing, O-rings, and other sealing materials in transport engines such as ships and airplanes; Similar packings, o-rings, seals in engineering plants; similar packings, o-rings, seals in food plant equipment and food equipment (including household items); similar packings, o-rings, seals in nuclear plant equipment Materials: The same packings, o-rings, and sealing materials for general industrial parts.
  • the rubber laminate obtained from the production method of the present invention is particularly preferably used as an oil resistant and heat resistant rubber hose.
  • JIS K6253 (1997) using a type A durometer (trade name: ASKER, manufactured by Kobunshi Keiki Co., Ltd.) using a 2 mm thick crosslinked sheet made of the fluororubber composition obtained in the examples and comparative examples. ) To measure.
  • JIS K6301 measure the compression set of ⁇ ring ( ⁇ -24) at 200 ° CX for 24 hours (after holding at 25 ° C under compression at 200 ° C for 24 hours, in a constant temperature room at 25 ° C Measure the sample left for 30 minutes).
  • heat aging treatment is performed at 200 ° C for 72 hours and 230 ° C for 72 hours using a crosslinked sheet, and then changes in TB, EB and hardness are obtained.
  • JIS K6258 a 175 ° CX 7 2 hour immersion test was performed in JIS test lubricant No. 3 oil using a cross-linked sheet, and TB, EB, hardness change, volume change rate and mass change Find the conversion rate.
  • Fluoro rubber> FKMl: Peroxide-crosslinkable ternary fluororubber (VdF / TFE / HFP 50/20/30 (mol 0 /.)) Manufactured by iodine transfer polymerization. Mooney viscosity is 50 (ML1 + 10, 100.C).
  • the Mooney viscosity is 69 (ML1 + 10, 100 ° C).
  • Silicone rubber Silicone rubber compound (trade name: KE551-U) manufactured by Shin-Etsu Chemical Co., Ltd.
  • Cross-linking agent 1 Perhexa 25B (trade name) manufactured by Nippon Oil & Fats Co., Ltd.
  • Crosslinking agent 2 C_8B (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.
  • TAIC Triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.
  • Magnesium oxide Kyowa Chemical Industry Co., Ltd. Kiyo Ichigo Mug 150 (trade name), particle size distribution (microtrack method) 10 ⁇ / ⁇ : 1. 48 ⁇ ⁇ , 50%: 5. 92 / im, 90% : 14. 16 / im
  • Escron G90 (trade name) Coumarone resin made by Nippon Steel Chemical Co., Ltd. Soft brown point approx. 90 ° C
  • Tatsukirol 101 (Product name) Non-reactive alkylphenol resin softened by Sumitomo Chemical Co., Ltd. Point 78 ⁇ : 105 ° C
  • Petrozine PR—100 (Product name) Aromatic hydrocarbon resin manufactured by Mitsui Chemicals, Inc. Softening point approx. 100 ° C
  • Harrier Star P (Product Name) Harima Kasei Co., Ltd. rosin modified pentaerythritol Softening point 102 ° C
  • MT carbon Cancarb carbon black ThermaxN— 990 (trade name)
  • the fluororubbers (1) to (7) were prepared by blending the fluororubbers according to the formulations shown in Table 1 and kneading them on an open roll.
  • the prepared fluororubber compositions (1) to (7) were subjected to press crosslinking for 10 minutes at 160 ° C, and further oven-crosslinked for 4 hours at 180 ° C.
  • a sample of the ring (P-24) was prepared.
  • Table 1 shows the measurement results of the crosslinkability, the normal properties of the cross-linked product and the compression set of the fluororubber compositions (1) to (7).
  • the cross-linked product of the fluororubber composition (1) was measured for heat aging resistance and oil resistance. The results are shown in Table 2.
  • the fluororubbers (8) were prepared by blending the fluororubbers according to the formulations shown in Table 1 and kneading them on an open roll.
  • a fluororubber composition (9) was produced in the same manner as in Example 1 except that no tackifier was added. Table 1 shows the measurement results of the crosslinkability of this fluororubber composition (9), the normal properties of the crosslinked product, and the compression set.
  • a fluororubber composition (10) was produced in the same manner as in Example 1 except that MT carbon was added in an amount of 30 parts by weight and no magnesium oxide was added. Table 1 shows the results of measurement of the crosslinkability of this fluororubber composition (10), the normal properties of the crosslinked product and the compression set.
  • Blending was carried out at the same blending ratio as in Table 1, and kneaded on an open roll to prepare an uncrosslinked fluororubber sheet having a thickness of 1 ⁇ 2 mm composed of fluororubber compositions (1) to (: 10).
  • 1 part by weight of the crosslinking agent 2 was blended with 100 parts by weight of the silicone rubber and kneaded on an open roll to prepare an uncrosslinked non-fluorinated rubber sheet having a thickness of 3.2 mm.
  • uncrosslinked fluororubber sheet 1 and uncrosslinked non-fluorinated rubber sheet 2 are stacked on top of each other, and fluororesin film 3 (thickness 150 zm, Daikin Industries, Ltd., trade name NEOFLON FEP NF — 0150 ) At this time, it is necessary to hook the interface from one end to 1 to 1.5 cm.
  • a non-adhesive part was formed with the base resin film 3 sandwiched between them, and was used as a grip for the peel test. This was preformed to a thickness of 4 mm for 30 seconds at 80 ° C. and pressed, and steam cross-linking was performed at 160 ° C. for 45 minutes using a vulcanizing can to produce a cross-linked and bonded rubber laminate.
  • oven crosslinking was performed at 180 ° C for 10 hours.
  • Table 3 shows the evaluation results of the adhesive strength before and after oven crosslinking of the resulting laminate.
  • the peroxide-crosslinking fluororubber composition of the present invention includes a tackifier and is formed from a non-fluororubber by including a metal oxide and / or a silica-based filler.
  • a fluororubber layer having excellent adhesion to the non-fluororubber layer can be formed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde permettant de former une couche de caoutchouc fluoré dont les propriétés d'adhésion à une couche faite d'un caoutchouc non fluoré sont excellentes. L'invention concerne également un procédé de fabrication d'un stratifié de caoutchouc. L'invention concerne aussi un tuyau souple en caoutchouc résistant à la chaleur et résistant à l'huile, fait d'un stratifié de caoutchouc obtenu par le procédé. L'invention concerne spécifiquement une composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde contenant un caoutchouc fluoré, un agent de réticulation par peroxyde, 0,05-10 parties en poids d'un tackifiant pour 100 parties en poids du caoutchouc fluoré, et 1-100 parties en poids d'un oxyde métallique (excepté une charge de silice) et/ou 1-50 parties en poids d'une charge de silice pour 100 parties en poids du caoutchouc fluoré.
PCT/JP2007/062511 2006-06-23 2007-06-21 Composition de caoutchouc fluoré en vue d'une réticulation par un peroxyde et procédé de fabrication d'un stratifié de caoutchouc WO2007148759A1 (fr)

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JP2011005719A (ja) * 2009-06-25 2011-01-13 Daiso Co Ltd 加硫ゴム積層体
JP2011099032A (ja) * 2009-11-05 2011-05-19 Kitagawa Ind Co Ltd 制振用樹脂組成物
JP2012046618A (ja) * 2010-08-26 2012-03-08 Tokai Rubber Ind Ltd ゴム組成物およびそれを用いた自動車用燃料タンクパッキン
JP2012126015A (ja) * 2010-12-15 2012-07-05 Daikin Industries Ltd 積層体
WO2013125731A1 (fr) * 2012-02-24 2013-08-29 Daikin Industries, Ltd. Composition de caoutchouc fluoré
CN104893306A (zh) * 2015-05-21 2015-09-09 蚌埠市耀得保温容器有限公司 一种环保耐热耐老化保温瓶
US9403954B2 (en) 2012-01-20 2016-08-02 Daikin Industries, Ltd. Fluororubber composition and method for producing same
US9499678B2 (en) 2012-02-24 2016-11-22 Daikin Industries, Ltd. Fluororubber composition
US9976016B2 (en) 2012-02-24 2018-05-22 Daikin Industries, Ltd. Fluororubber composition
EP2587107B1 (fr) 2010-08-25 2018-07-11 Daikin Industries, Ltd. Tuyau souple
WO2018235581A1 (fr) * 2017-06-21 2018-12-27 オリンパス株式会社 Article élastomère moulé destiné à un dispositif médical, procédé de production d'un article élastomère moulé destiné à un dispositif médical, et dispositif médical
WO2020170025A1 (fr) * 2019-02-22 2020-08-27 Daikin Industries, Ltd. Stratifié
WO2020204079A1 (fr) * 2019-04-04 2020-10-08 Ａｇｃ株式会社 Procédé de production d'un corps multicouche, et corps multicouche
WO2020204076A1 (fr) * 2019-04-04 2020-10-08 Ａｇｃ株式会社 Stratifié et son procédé de fabrication
WO2021215263A1 (fr) * 2020-04-21 2021-10-28 三菱電線工業株式会社 Composition élastomère et matériau d'étanchéité la comprenant
CN114561071A (zh) * 2022-01-11 2022-05-31 宁波泰科威橡胶科技有限公司 耐低温纳米硅改性氟橡胶复合材料及其制备方法

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CN110511514B (zh) * 2019-08-31 2021-08-06 中国石油集团川庆钻探工程有限公司 一种耐高温高压的橡胶材料及其制备方法

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Publication number Priority date Publication date Assignee Title
JP2011005719A (ja) * 2009-06-25 2011-01-13 Daiso Co Ltd 加硫ゴム積層体
JP2011099032A (ja) * 2009-11-05 2011-05-19 Kitagawa Ind Co Ltd 制振用樹脂組成物
US11054066B2 (en) 2010-08-25 2021-07-06 Daikin Industries, Ltd. Hose
EP2587107B1 (fr) 2010-08-25 2018-07-11 Daikin Industries, Ltd. Tuyau souple
JP2012046618A (ja) * 2010-08-26 2012-03-08 Tokai Rubber Ind Ltd ゴム組成物およびそれを用いた自動車用燃料タンクパッキン
JP2012126015A (ja) * 2010-12-15 2012-07-05 Daikin Industries Ltd 積層体
US9403954B2 (en) 2012-01-20 2016-08-02 Daikin Industries, Ltd. Fluororubber composition and method for producing same
US9976016B2 (en) 2012-02-24 2018-05-22 Daikin Industries, Ltd. Fluororubber composition
WO2013125731A1 (fr) * 2012-02-24 2013-08-29 Daikin Industries, Ltd. Composition de caoutchouc fluoré
US9499678B2 (en) 2012-02-24 2016-11-22 Daikin Industries, Ltd. Fluororubber composition
JP2015509112A (ja) * 2012-02-24 2015-03-26 ダイキン工業株式会社 フッ素ゴム組成物
US20150330537A1 (en) * 2012-02-24 2015-11-19 Daikin Industries, Ltd. Fluororubber composition
US11898661B2 (en) 2012-02-24 2024-02-13 Daikin Industries, Ltd. Fluororubber composition
CN104893306A (zh) * 2015-05-21 2015-09-09 蚌埠市耀得保温容器有限公司 一种环保耐热耐老化保温瓶
WO2018235581A1 (fr) * 2017-06-21 2018-12-27 オリンパス株式会社 Article élastomère moulé destiné à un dispositif médical, procédé de production d'un article élastomère moulé destiné à un dispositif médical, et dispositif médical
WO2020170025A1 (fr) * 2019-02-22 2020-08-27 Daikin Industries, Ltd. Stratifié
WO2020204079A1 (fr) * 2019-04-04 2020-10-08 Ａｇｃ株式会社 Procédé de production d'un corps multicouche, et corps multicouche
WO2020204076A1 (fr) * 2019-04-04 2020-10-08 Ａｇｃ株式会社 Stratifié et son procédé de fabrication
WO2021215263A1 (fr) * 2020-04-21 2021-10-28 三菱電線工業株式会社 Composition élastomère et matériau d'étanchéité la comprenant
CN114561071A (zh) * 2022-01-11 2022-05-31 宁波泰科威橡胶科技有限公司 耐低温纳米硅改性氟橡胶复合材料及其制备方法
CN114561071B (zh) * 2022-01-11 2023-07-18 宁波泰科威橡胶科技有限公司 耐低温纳米硅改性氟橡胶复合材料及其制备方法

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