[go: up one dir, main page]

WO2007111334A1 - Composition de fluoroélastomère, composition de fluororesine, et moulage de celles-ci - Google Patents

Composition de fluoroélastomère, composition de fluororesine, et moulage de celles-ci Download PDF

Info

Publication number
WO2007111334A1
WO2007111334A1 PCT/JP2007/056406 JP2007056406W WO2007111334A1 WO 2007111334 A1 WO2007111334 A1 WO 2007111334A1 JP 2007056406 W JP2007056406 W JP 2007056406W WO 2007111334 A1 WO2007111334 A1 WO 2007111334A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
composition
containing elastomer
crosslinking
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/056406
Other languages
English (en)
Japanese (ja)
Inventor
Tomihiko Yanagiguchi
Shintaro Ogata
Toshiki Ichisaka
Haruhisa Masuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of WO2007111334A1 publication Critical patent/WO2007111334A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

  • Fluorine-containing elastomer composition Fluorine-containing elastomer composition, fluororesin composition, and molded article formed from the composition
  • the present invention relates to a fluorine-containing elastomer composition containing a fluorine-containing elastomer and sericite, a fluorine resin composition containing a crosslinked fluororubber obtained by crosslinking the composition, and a composition formed from the composition.
  • a fluorine-containing elastomer composition containing a fluorine-containing elastomer and sericite
  • a fluorine resin composition containing a crosslinked fluororubber obtained by crosslinking the composition and a composition formed from the composition.
  • Fluorine-containing elastomers have excellent chemical resistance, solvent resistance, and heat resistance, and therefore are used as sealing materials in harsh environments, such as automobile industry, semiconductor industry, and chemical industry. Widely used!
  • thermoplastic resins such as polyphenylene sulfide-based resins, ethylene-bulb alcohol-based resins, and liquid-crystalline polyester-based resins are known as materials having excellent fuel barrier properties.
  • a polymer alloy of fluorine rubber and fluorine resin is known (for example, see JP-A-61-57641).
  • a thin film of the barrier layer is required, and further improvement in the noirality is required for the thin film.
  • the present invention relates to a fluorine-containing elastomer composition containing fluorine-containing elastomer and sericite.
  • the amount of added sericite is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer.
  • the present invention also relates to a molded article, a hose, and a tube formed from the fluorine-containing elastomer composition.
  • the present invention relates to a fluorine resin composition
  • a fluorine resin composition comprising a fluorine resin (A) and a crosslinked fluorine rubber (B) obtained by crosslinking the fluorine-containing elastomer yarn and composition.
  • the cross-linked fluororubber (B) is obtained by dynamically cross-linking the fluorine-containing elastomer composition under the melting condition of the fluororesin (A).
  • the present invention relates to a molded article, a hose, and a tube in which the fluororesin composition strength is also formed.
  • the present invention relates to a fluorine-containing elastomer composition containing fluorine-containing elastomer and sericite.
  • the sericite used in the present invention is a flake-like filler, and by adding sericite, the fuel barrier property of a molded product having a fluorine-containing elastomer composition or a fluorinated resin composition is remarkably improved. And high mechanical strength can be obtained.
  • the sericite may be natural sericite or synthetic sericite.
  • Sericite can be obtained by a grinding method such as wet grinding or dry grinding.
  • the wet pulverization has a clear surface, and the dry pulverization has the characteristics of simple manufacturing process and low cost.
  • the aspect ratio (flatness) of sericite is preferably 10 or more, more preferably 20 or more, still more preferably 50 or more, and particularly preferably 100 or more. If the aspect ratio is less than 10, sufficient fuel barrier properties tend not to be obtained.
  • the aspect ratio is the ratio of the major axis to the thickness of the sericite crystal.
  • the average particle size is preferably 20 ⁇ m or less, more preferably 5 ⁇ m or less. Above 20 ⁇ m, differential scattering is difficult and mechanical strength tends to decrease.
  • the amount of sericite added is preferably 2 to 40 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer so that the sericite power is 50 to 50 parts by weight. It is more preferable to add so that it is 3 to 40 parts by weight. It is more preferable to add so that it is 5 to 30 parts by weight. It is particularly preferable to add 10 to 25 parts by weight. More preferably, it is added so as to be part. If the sericite content is less than 2 parts by weight, sufficient fuel barrier properties tend not to be obtained. If the sericite content exceeds 50 parts by weight, it becomes difficult to finely disperse the sericite and the mechanical strength tends to decrease significantly.
  • the fluorine-containing elastomer is not particularly limited, and examples thereof include fluororubber ( a ), thermoplastic fluororubber (b), and rubber compositions having these fluororubber strengths. More preferably, the fluororubber (a) is used.
  • the fluororubber (a) examples include non-perfluorofluororubber ( a -1) and perfluorofluororubber ( a- 2).
  • the Pafuruorofutsu containing rubbers, Chi caries its constituent units refers to the 90 mole 0/0 or consisting par full O b monomer.
  • Non-perfluorofluorinated rubber (a-1) includes bi-lidene fluoride (hereinafter referred to as VdF) based fluoro rubber, tetrafluoroethylene (hereinafter referred to as TFE) Z propylene based fluoro rubber. , TFEZ propylene ZVdF fluorine rubber, ethylene Z hexafluoropropylene (hereinafter referred to as HFP) fluorine rubber, ethylene ZHFPZVdF fluorine rubber, ethylene ZHF P / TFE fluorine rubber, fluorosilicone fluorine Rubber, fluorophosphazene-based fluororubber, etc. These can be used alone or in any combination as long as the effects of the present invention are not impaired. VdF-based fluororubber, TFEZ It is preferable to use ropylene-based fluororubber.
  • VdF-based fluororubber those represented by the following general formula (1) are preferable.
  • 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, preferably those containing structural units M 2 75 to 15 mol%, the structural unit M 1 30-80 mole 0/0, the more preferred instrument structural unit M 1 is intended to include structural units M 2 70 to 20 mol% 70 to 80 mol%, those comprising structural units M 2 30 to 20 mol% Further preferred.
  • the structural unit N 1 is preferably 0 to 10 mol% based on the total amount of the structural unit M 1 and the structural unit M 2 U.
  • Examples of the fluorine-containing ethylenic monomer (m 2 ) include TFE, black trifluoroethylene (hereinafter referred to as CTFE), trifluoroethylene, HFP, trifluoropropylene, and tetrafluoro.
  • Fluorine-containing monomers such as propylene, pentafluoropropylene, trifluorobutene, tetrafluoroloy sobutene, perfluoro (alkyl butyl ether) (hereinafter referred to as PAVE), vinyl fluoride, and the like.
  • TFE, HFP, and PAVE are preferred.
  • the monomer (n 1 ) may be any one that is copolymerizable with the monomer (m 1 ) and the monomer (m 2 ). Any of these may be used, and examples thereof include ethylene, propylene, alkyl butyl ether, and a monomer that gives a crosslinking site. Among these, a monomer that gives a crosslinking site is preferable.
  • CY 1 CY 1 -R 1 CHR 1 X 1 (2)
  • n is an integer of 1 to 3
  • X 2 is a cyano group, a carboxyl group, an alkoxycarbonyl group, a bromine atom
  • the iodine atom, bromine atom, cyan group, carboxyl group, and alkoxycarbonyl group can function as a crosslinking point.
  • VdF fluorororubbers include VdFZHFP rubber, VdFZHFP ZTFE rubber, VdFZCTFE rubber, VdFZCTFEZTFE rubber, VdFZPAVE rubber, VdFZTFEZPAVE rubber, VdFZHFPZPAVE rubber, VdFZHFPZPAVE rubber, VdFZTFEZ propylene rubber, VdFZ ethylene ZHFP rubber and the like are preferable.
  • TFEZ propylene fluorine rubber preferably those represented by the following general formula (4) / ⁇ one (M 3) one (M 4) -! (N 2) one (4)
  • 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 )
  • the structural unit M 3 is 40 70 mol%, the structural unit M 4 of 60 to 30 mol%, including ones more preferably preferably tool the structural unit M 3 50-60 mole 0/0, the structural unit M 4 fifty to forty mole 0/0 containing It is a waste.
  • 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 .
  • V may be used as long as it is copolymerizable with the monomer (m 3 ) and the monomer (m 4 ). Preferred to be a monomer that gives.
  • Examples of the monomer that gives such a cross-linking site include perfluoro (6, 6 dihydro-1, 6-3, oxa) as described in JP-B-5-63482 and JP-A-7-316234, for example. 1) iodine-containing monomers such as 1-hexene) and perfluoro (5-3 oxa 1 pentene), benzene-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 alkoxycarboxyl group-containing monomer as described in JP-A-5-500070.
  • perfluoro fluororubber (a-2) those represented by the following general formula (5) are preferable: 1 (M 5 ) 1 (M 6 )-(N 3 ) 1 (5)
  • 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 mol% preferably those comprising structural units M 6 10 to 50 mol% instrument more preferably the structural unit M 5 and 50 to 80 mole 0/0, which the structural unit M 6 comprising 20 to 50 mole 0/0, further preferred properly structural unit M 5 and 55 to 70 mole 0/0, the structural unit M 6 are those containing 30 to 45 mole 0/0.
  • the structural unit N 3 is preferably 0 to 5 mol%, more preferably 0 to 2 mol%, based on the total amount of the structural unit M 5 and the structural unit M 6 .
  • Examples of PAVE (m 6 ) include perfluoro (methyl vinyl ether), perfluoro (propyl butyl ether), and the like. Can be used in combination.
  • the monomer (n) the monomer (m 5 ) and any of the above monomers that can be copolymerized with the monomer (m 6 ) may be used. Among these, a monomer that gives a crosslinking site is preferable.
  • Examples of monomers that give such a crosslinking site include VdF, the general formula (2), (3
  • strong perfluorinated rubber examples include WO 97Z24381 pamphlet, JP-B 61-57324, JP-B 4-81608, JP-B 5-
  • Examples thereof include fluororubber described in Japanese Patent No. 13961.
  • the fluororubber ( a ) preferably has a number average molecular weight of 1,000 to 500,000! /.
  • non-perfluorofluorororubber (a-1) and perfluorofluororubber (a-2) are the constitution of the main monomer. Those obtained by copolymerizing a polymerizable monomer or the like can also be suitably used.
  • a fluororubber containing a VdF unit is preferred from the viewpoint of heat resistance, compression set, workability, and cost.
  • a fluororubber having a VdF unit and an HFP unit is more preferred.
  • VdFZTFEZHFP is preferably at least one rubber selected from the group consisting of VdFZHFP-based fluororubber, VdFZTFEZ HFP-based fluororubber, and TFEZ propylene-based fluororubber. More preferred is fluororubber.
  • -2) is a power that can be produced by a conventional method.
  • a known iodine transfer polymerization method can be given as a production method of fluororubber.
  • Polymerization conditions such as temperature and time during polymerization may be appropriately determined depending on the type of monomer and the desired elastomer.
  • a composition comprising the fluororubber (a) and the thermoplastic fluororubber (b) as described above can also be used.
  • the fluorine-containing elastomer scratch, in the fluorine-containing elastomer first composition of the present invention it is more preferably from 20 to 98 weight 0/0 is a preferred tool 30-95 wt%.
  • the fluorine-containing elastomer composition of the present invention preferably contains a crosslinking agent, but the type of the crosslinking agent is not particularly limited, depending on the type of fluorine-containing elastomer and the melt-kneading conditions. And can be selected as appropriate.
  • the crosslinking system used in the present invention is appropriately selected depending on the type of the cure site or the use of the obtained molded product. That's fine.
  • the crosslinking system any of a polyamine crosslinking system, a polyol crosslinking system, a peroxide crosslinking system, an imidazole crosslinking system, a triazine crosslinking system, an oxazole crosslinking system, and a thiazole crosslinking system can be employed.
  • a polyol crosslinking system in which a polyamine crosslinking system, a polyol crosslinking system, and a peroxide crosslinking system are preferable, and a polyol in which a peroxide crosslinking system is more preferable, since both fuel barrier properties and processability are possible.
  • a cross-linking system or a combined cross-linking system of a polyol cross-linking system and a peroxide cross-linking system is particularly preferred.
  • the cross-linking by the polyol cross-linking system is preferable in that it has a carbon-oxygen bond at the cross-linking point, and has a feature that the compression set is small and the moldability is excellent.
  • V has a carbon-carbon bond at the crosslinking point, so a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine crosslinking system having a carbon-nitrogen double bond. Compared with, it is characterized by excellent chemical resistance and steam resistance.
  • crosslinked by polyamine crosslinking When crosslinked by polyamine crosslinking, it has a carbon-nitrogen double bond at the crosslinking point and is characterized by excellent dynamic mechanical properties. However, compression set tends to increase as compared with the case of crosslinking using a polyol crosslinking system or a peroxide crosslinking system.
  • polyamine cross-linking agent examples include hexamethylenediamine carbamate, N, N, i-dicinnamylidene 1, 6 hexamethylenediamine, 4, 4'-bis (aminocyclohexenole ) Polyamine compounds such as methane power rubamate. Of these, N, N'-dicinnamylidene 1, 6 hexamethylenediamine is preferred!
  • polyol cross-linking agent a compound conventionally known as a fluororubber cross-linking agent can be used.
  • a polyhydroxy compound particularly a polyhydroxy aromatic compound having excellent heat resistance.
  • a compound is preferably used.
  • the polyhydroxy aromatic compound is not particularly limited, and examples thereof include 2, 2 bis (4 hydroxyphenol) propane (hereinafter referred to as bisphenol A), 2, 2 bis (4 hydroxyphenol). ) Perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3 dihydroxybenzene, 1,7 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 4,4'-dihydroxydiphenyl 4, 4 'dihydroxystilbene, 2, 6 dihydroxyanthracene, hydroquinone, catechol, 2, 2-bis (4-hydroxyphenol) butane (hereinafter referred to as bisphenol B), 4, 4-bis (4— Hydroxyphenol) valeric acid, 2, 2 bis (4 hydroxyphenol) tetrafluorodiclonal propane, 4, 4, dihydroxydiphenol Ninoles norephone, 4, 4, dihydroxydiphenyl ketone, tri (4-hydroxyphenol) methane, 3, 3 ', 5, 5, monot
  • the peroxide cross-linking agent may be an organic peroxide compound that can easily generate a peroxide radical in the presence of heat or a redox system.
  • polyhydroxy aromatic compounds are preferred because polyhydroxy compounds are excellent in heat resistance because they are excellent in moldability with small compression set such as molded articles obtained.
  • Bisphenol AF is more preferred.
  • the addition amount of the crosslinking agent is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer, and more preferably 0.1 to 10 parts by weight. 0.3 to 7.0 parts by weight is even more preferred. 1 to 5 parts by weight is particularly preferred. If the cross-linking agent is less than 0.05 parts by weight, the degree of cross-linking is insufficient, and the performance of the molded product tends to be impaired, such as heat resistance and oil resistance. 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. In addition, it is not economically preferable, and the molding processability of the resulting fluorinated resin composition tends to decrease.
  • a crosslinking assistant is usually used in combination with the polyol crosslinking agent.
  • the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.
  • a crosslinking aid for the polyol crosslinking system generally an organic compound is used.
  • the onium compound is not particularly limited, and examples thereof include an ammonium compound such as a quaternary ammonium salt, a phosphonium compound such as a quaternary phosphonium salt, an oxonium compound, a sulfone compound, Examples include cyclic amines and monofunctional amine compounds, among which quaternary ammonium salts and quaternary phosphonium salts are preferred.
  • tetraptylammonum bromide tetraptylammonum chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, tetraptylammonium hydrogensulfate, tetraptyl Quaternary ammonium salts such as ammonium hydroxide; 8—methyl-1,8 diazabicyclo [5, 4, 0] —7 undecse-um chloride, 8—methyl-1,8 diazabicyclo [5, 4, 0] — 7 Undesse-muai odide, 8-methyl-1,8 diazabicyclo [5, 4, 0] —7 Undesse-umhide mouth, 8—methyl-1,8 diazabicyclo [5, 4, 0] —7 Undeceumumsulfate, 8 ethyl 1, 8 Gizabicyclo [5, 4, 0] —7 Undese-Um
  • Cyclic amines such as undecene 7; monofunctional amines such as benzylmethylamine and benzylethanolamine; tetrabutylphosphomum chloride, benzyltriphenylphosphomum chloride (hereinafter referred to as BTPPC), And quaternary phosphonium salts such as benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tribubutylphosphoryl chloride, tributyl-2-methoxypropylphosphonium chloride, and benzylphenol (dimethylamino) phosphonium chloride. It is done.
  • DBU-B and BTPPC are preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.
  • crosslinking aid a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, a chlorine-free crosslinking aid disclosed in JP-A-11-147891 Use agent.
  • crosslinking assistants for organic peroxides include triaryl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N, 1 m-phenol-bismaleimide, Dipropargyl terephthalate, diallyl phthalate, tetralyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1, 3, 5 HJ (2, 3, 3 ⁇ !; Funole P 2 P P Peninole) 1, 3, 5 HJ Azin 1, 2, 4, 6 Trion), Tris (Dialylamine) S Triazine, Trisyl phosphite, N, N-Diallylacrylamide, 1, 6 Divilde decafluor mouth Hexane, hexarylphosphoramide, N, N, ⁇ ', ⁇ , monotetraarylphthalamide, ⁇ , ⁇ , ⁇ ', ⁇ , Examples of crosslinking assistant
  • the addition amount of the crosslinking aid is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer, and more preferably 0.1 to 10 parts by weight. More preferably, it is 0.3 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight. If the crosslinking aid is less than 0.1 parts by weight, the crosslinking time becomes unusable for practical use, and the heat resistance and oil resistance of the resulting molded product tend to be lowered. Furthermore, in addition to the crosslinking time becoming too fast, the compression set of the molded product also decreases, and the moldability of the resulting fluororesin composition tends to decrease.
  • the fluorine-containing elastomer composition of the present invention may be prepared by adding usual additives, for example, a filler, a processing aid, a plasticizer, a colorant, and the like, as needed, to a composition that can be used as a fluorine-containing elastomer.
  • Antioxidants, anti-aging agents, ozone degrading agents, UV absorbers, etc. can be blended, and each of these can be blended with one or more conventional crosslinking agents and crosslinking aids different from the above.
  • the ingredients can be prepared by mixing using conventional elastomer processing machines such as open rolls, Banbury mixers, aders and the like. This method using a hermetic mixer can also be prepared by the co-coagulation method with the emulsion mixing force.
  • the obtained fluorine-containing elastomer composition is crosslinked and molded according to a conventional method.
  • it is molded by compression molding, injection molding, extrusion molding, calender molding, or melt molding in a solvent and then by die molding or coating.
  • the crosslinking conditions vary depending on the molding method and the shape of the molded product, but are generally in the range of several seconds to 180 minutes at 100 to 200 ° C. Further, secondary crosslinking may be performed in order to stabilize the physical properties of the crosslinked product.
  • the secondary cross-linking condition is 150 to 300 ° C for 30 minutes to 30 hours.
  • the fuel permeability coefficient of the molded article formed from the fluorine-containing elastomer composition of the present invention is preferably 35 g ⁇ mm / m 2 ⁇ day or less, and preferably 30 g ⁇ / ⁇ day or less. Yo More preferably, it is 25 g'mm / m 2 'day or less.
  • the lower limit value of the fuel permeation coefficient is not particularly limited, and the lower value is preferable. If the fuel permeation coefficient exceeds 35 g'mm / m 2 'day, the fuel barrier property is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product, which is not economically preferable. The lower the fuel permeation coefficient, the better the fuel permeation prevention capability. Conversely, the fuel permeation coefficient is large, V, and the fuel permeates easily! /.
  • the fuel permeability coefficient was measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials.
  • the cup method is a moisture permeability test method stipulated in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time.
  • the fuel permeation coefficient is measured according to this cup method.
  • the tensile strength at break of the molded article formed from the fluorine-containing elastomer composition of the present invention is preferably 6 MPa or more, more preferably 8 MPa, and particularly preferably lOMPa. .
  • the upper limit of the tensile strength at break is not particularly limited. If the tensile strength at break is less than 6 MPa, it tends to be unsuitable for molded products that require mechanical strength.
  • the present invention also relates to a fluorine resin composition
  • a fluorine resin composition comprising a fluorine resin (A) and a crosslinked fluororubber (B) obtained by crosslinking the fluorine-containing elastomer composition.
  • Fluororesin (A) is not particularly limited, but at least one fluorine-containing resin Preferred is a fluorine resin containing the ethylenic polymer (a).
  • R 2 is —CF or OR 3
  • R 3 is a perfluoroalkyl having 3 to 5 carbon atoms, f 3 ff
  • Perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: CT FE, trifluoroethylene, hexafluoroisobutene, VdF, fluorinated butyl, general formula (7):
  • X 3 is a hydrogen atom or a fluorine atom
  • X 4 is a hydrogen atom, a fluorine atom or a chlorine atom
  • n is an integer of 1 to 10
  • Fluoro refin etc. can be given.
  • the fluorine-containing ethylenic polymer (a) may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer.
  • Non-fluorinated ethylenic monomers other than the above-mentioned fluororefin and perfluororefin can be mentioned.
  • Examples of the non-fluorinated ethylenic monomer include ethylene, propylene, and alkyl butyl ethers.
  • the alkyl bulle ether is an alkyl bur ether having an alkyl group having 1 to 5 carbon atoms.
  • the fluorine-containing ethylenic polymer (a) has the heat resistance, chemical resistance, oil resistance, and ease of molding processability of the obtained fluorocoagulant composition.
  • ETFE ethylene TFE copolymer
  • TFE PAVE copolymer PFA
  • TFE-HFP copolymer FEP
  • Ethylene TFE—HFP copolymer composed of TFE, ethylene and a perfluoroethylenically unsaturated compound represented by the general formula (1), ethylene TFE-PAVE copolymer,
  • PVDF Polyvinylidene fluoride
  • the molar ratio of TFE units to ethylene units is preferably 20:80 to 90:10 62:38 to 90:10 is preferred, 63:37 to 80:20 is particularly preferred, 0 or
  • the third component may be! /, And the type of the third component is not limited as long as it is copolymerizable with TFE and ethylene.
  • the third component usually the following formula
  • R 4 monomers having 1 to 8 carbon atoms are particularly preferred.
  • the content of the third component is 0. 1 to the fluorine-containing ethylenic polymer (a): LO mol% are preferred, 0.1 to 5 mole 0/0, more preferably tool 0. 2 to 4 mol 0/0 are particularly preferred.
  • T It is an FE units 90 to 99 mole 0/0 and formula (1) per full O represented by b ethylenically unsaturated compound unit 10 mol% Ca also the fluorine-containing ethylenic polymer (a) Is more preferable.
  • the fluorine-containing ethylenic polymer (a) composed of TFE and the perfluoroethylenically unsaturated compound represented by the general formula (1) is a third component which may contain a third component.
  • the type is not limited as long as it is copolymerizable with TFE and the perfluoroethylenically unsaturated compound represented by the general formula (1).
  • the melting point of the fluorine-containing ethylenic polymer (a) is preferably 150 to 310 ° C, more preferably 150 to 290 ° C, and 170 to 250 ° C. Is more preferable. If the melting point of the fluorinated ethylenic polymer ( a ) is less than 150 ° C, the heat resistance of the resulting fluorocobalt composition tends to decrease, and if it exceeds 310 ° C, the fluorinated resin (A) When the fluorine-containing elastomer composition is dynamically cross-linked in the molten state of fluorine resin (A) in the presence of cerite and sericite, the melting temperature is set to be higher than the melting point of the fluorine-containing ethylenic polymer (a). Although necessary, the fluorine-containing elastomer composition tends to be thermally deteriorated.
  • the weight ratio of fluorinated resin (A) Z-crosslinked fluorororubber (B) is preferably 98Z2 to 40Z60, more preferably 95/5 to 50/50 weight%, more preferably force S, 83/17 More preferably, it is ⁇ 50 / 50 parts by weight.
  • the weight ratio of fluorinated resin ( ⁇ ) exceeds 98 ⁇ 2, sufficient flexibility tends not to be imparted, and when it is less than 40 ⁇ 60, the cross-linked fluororubber ( ⁇ ) does not disperse uniformly and becomes partially co-continuous. There is a tendency for the mechanical strength to decrease significantly and the fluidity to decrease significantly.
  • the fluorinated resin composition of the present invention can be obtained by uniformly dispersing the crosslinked fluorinated rubber ( ⁇ ⁇ ) containing sericite in the fluorinated resin ( ⁇ ). In a molten state, it is preferable to dynamically crosslink the fluorine-containing elastomer composition so that at least a part of the composition is crosslinked.
  • the dynamic crosslinking treatment means that the fluorine-containing elastomer composition is dynamically cross-linked simultaneously with melt kneading using a Banbury mixer, a pressure mixer, an extruder, or the like.
  • a Banbury mixer a pressure mixer
  • an extruder such as a twin screw extruder because a high shear force can be applied.
  • the molten state means a state at a temperature at which the fluorine resin (soot) melts. Melting The temperature to be changed varies depending on the glass transition temperature and Z or melting point of the fluororesin (A), but is preferably 120 to 330 ° C, more preferably 130 to 320 ° C. If the temperature is less than 120 ° C, the dispersion between the fluorocobalt (A) and the fluorine-containing elastomer composition tends to become coarse, and if it exceeds 330 ° C, the fluorine-containing elastomer composition Tend to heat deteriorate.
  • the obtained fluorinated resin composition has a structure in which the fluorinated resin (A) forms a continuous phase and the crosslinked fluorinated rubber (B) forms a dispersed phase, or the fluorinated resin composition (A) is crosslinked with the fluorinated resin (A).
  • the fluororubber (B) can have a structure that forms a co-continuity, and among them, the fluororesin (A) forms a continuous phase and the cross-linked fluororubber (B) forms a dispersed phase. Preferred to have.
  • the fluorine-containing elastomer composition forms an initial dispersion matrix! /,
  • the fluorine-containing elastomer composition becomes a crosslinked fluororubber (B) as the crosslinking reaction proceeds.
  • the melt viscosity is increased, and the crosslinked fluororubber (B) becomes a dispersed phase or forms a co-continuous phase with the fluorocarbon resin (A).
  • the fluororesin composition of the present invention exhibits excellent heat resistance, chemical resistance and oil resistance, as well as high fuel barrier properties and good moldability. It becomes.
  • the average dispersed particle size of the crosslinked fluororubber (B) is preferably 0.01-30 ⁇ m. If the average dispersed particle size is less than 0.01 m, the fluidity tends to decrease, and if it exceeds 30 / z m, the strength of the resulting fluorocobalt composition tends to decrease.
  • the preferred fluorinated resin composition of the present invention is that the preferred fluorinated resin (A) forms a continuous phase, and the crosslinked fluororubber (B) forms a dispersed phase. It is also possible to include a co-continuous structure of fluorine resin (A) and crosslinked fluororubber (B) as part of the structure.
  • Fuel permeability coefficient of a molded article using a fluorine ⁇ composition of the present invention it is more favorable 20g'mmZm 2 'd is preferably ay is less instrument 10g'mmZm 2' is day or less More preferably, it is 5 g-mmZm 2 'day or less.
  • the lower limit value of the fuel permeation coefficient is not particularly limited, and it is preferably as low as possible. If the fuel permeation coefficient exceeds 20 g-mm / day • m 2 , the fuel barrier property is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product, which is not economically preferable.
  • the lower the fuel permeability coefficient The ability to prevent fuel permeation is improved. Conversely, when the fuel permeation coefficient is large, the fuel permeates.
  • the fuel permeation coefficient can be measured using the same method as described above.
  • the tensile modulus of elasticity is 400 MPa or less, more preferably 350 MPa or less, and even more preferably 300 MPa or less.
  • the lower limit value of the tensile elastic modulus is not particularly limited and is preferably as low as possible. If the tensile modulus of elasticity exceeds OOMPa, the flexibility of the molded product is impaired, and the assemblability is liable to deteriorate and the degree of freedom in design tends to be extremely limited.
  • the tensile strength at break of a molded article using the fluororesin composition of the present invention is preferably lOMPa or more, more preferably 15 MPa or more, and particularly preferably 20 MPa or more. preferable.
  • the upper limit of the tensile strength at break is not particularly limited. If the tensile breaking strength is less than 15 MPa, it tends to be unsuitable for molded products that require mechanical strength.
  • the fluorine resin composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester and polyurethane, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents.
  • An agent, an ultraviolet absorber, an antioxidant, a release agent, a foaming agent, a fragrance, an oil, a softening agent, and the like can be added as long as the effects of the present invention are not affected.
  • the fluorinated resin composition of the present invention can be molded using a general molding method or molding apparatus.
  • the molding method for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding and the like can be adopted, and the fluororesin composition of the present invention is intended for use. Depending on the shape, it is formed into a molded body of any shape.
  • the present invention relates to a force relating to a molded article obtained by using the fluorine-containing elastomer composition or the fluorine resin composition of the present invention.
  • the molded article includes a sheet or a film.
  • the molded body includes a laminate structure including a layer formed from the fluorine-containing elastomer composition or fluorine resin composition of the present invention and a layer formed from other materials.
  • the other materials may be selected appropriately according to the required characteristics and intended use.
  • examples of such other materials include polyolefin (eg, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene propylene copolymer, polypropylene, etc.), nylon, polyester, salt Thermoplastic polymers such as vinyl resin (PVC) and salt vinylidene resin (PVDC), crosslinked rubber such as ethylene-propylene-gene rubber, butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, metal, glass, Wood, ceramic, etc. can be raised.
  • PVC vinyl resin
  • PVDC salt vinylidene resin
  • crosslinked rubber such as ethylene-propylene-gene rubber, butyl rubber, nitrile rubber, silicone rubber, acrylic rubber, metal, glass, Wood, ceramic, etc. can be raised.
  • a layer formed from the fluorine-containing elastomer composition or the fluorine resin composition of the present invention and a base material layer formed from another material are used.
  • An adhesive layer may be interposed. By interposing the adhesive layer, the layer formed from the fluororesin composition of the present invention and the base material layer formed from another material can be firmly joined and integrated.
  • Examples of the adhesive used in the adhesive layer include acid anhydride modified products of gen-based polymers; acid anhydride modified products of polyolefins; polymer polyols (eg, glycol compounds such as ethylene glycol and propylene glycol, and adipic acid) Polyester polyols obtained by polycondensation of dibasic acids of the above; partial conjugated products of copolymers of vinyl acetate and vinyl chloride, etc.) and polyisocyanate compounds (eg, 2, 4 tolylene diisocyanate, etc.) (For example, a reaction product of a diol compound such as 1,6 hexamethylene glycol and a diisocyanate compound such as 2,4 tolylene diisocyanate in a molar ratio of 1: 2; trio such as trimethylolpropane) 1 to 3 molar ratio of 1 to 3 compound and diisocyanate compound such as 2,4 tolylene diisocyanate Response product, etc.); or the like can be used.
  • the fluororesin composition strength of the present invention when producing a laminated structure having a layer in which the fluororesin composition strength of the present invention is formed and a layer having other material strength, it is formed from the fluororesin composition of the present invention as necessary.
  • Surface treatment may be performed on the layer.
  • the surface treatment is not particularly limited as long as it is a treatment method that enables adhesion, for example, plasma discharge treatment, corona discharge treatment or other discharge treatment, wet metal sodium Z naphthalene treatment. Etc. It is done.
  • a primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When primer treatment is performed, the surface of the layer formed from the non-surface-treated fluororesin composition can be primed. Plasma discharge treatment, corona discharge treatment, metal sodium z naphthalene solution treatment, etc. are applied beforehand. It is more effective if the surface of the layer formed from the fluorinated resin composition is further primed
  • the fluorine-containing elastomer composition, fluorine resin composition, and molded product using the composition of the present invention include, for example, a semiconductor manufacturing apparatus, a liquid crystal panel manufacturing apparatus, a plasma panel manufacturing apparatus, and a plasma addressed liquid crystal panel.
  • Semiconductor related fields such as field emission display panels and solar cell substrates; Automotive field; Aircraft field; Rocket field; Ship field; Chemical field such as plant; Pharmaceutical field such as pharmaceutical; Photo field such as developing machine; Printing machine In the fields such as printing field such as painting equipment; coating field such as coating equipment; analysis ⁇ physics and chemistry machine field; food plant equipment field; nuclear power plant equipment field; steel field such as iron plate processing equipment; general industrial field; electrical field; Although it can be used preferably, among these, it can be used more preferably in the automobile field.
  • gaskets In the automotive field, gaskets, shaft seals, valve stem seals, seals and hoses can be used for engines and peripherals.
  • the molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable for industrial hoses, industrial tubes, fuel hoses, and fuel tubes.
  • Sericite (Sericite) (manufactured by Yodogawa Industries Co., Ltd., Yodogawa My Force Z20, shape: phosphorus flake, aspect ratio: 110, average particle size: 2 / ⁇ ⁇ )
  • sheath 1 S shape: granular, average particle size: 0.07 m
  • Polyol-based cross-linking agent 2, 2-bis (4-hydroxyphenol) perfluoropropane (Daikin Industries, Ltd., trade name Bisphenol AF) [0112] ⁇ Crosslinking aid 1>
  • BTPPC Benzyltriphenylphospho-um chloride
  • This fluorine-containing elastomer composition was subjected to crosslinking by first pressing at 170 ° C for 15 minutes, followed by crosslinking in an oven at 230 ° C for 24 hours by oven crosslinking. A shape was obtained.
  • the tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test of the molded product were measured by the following methods. The results are shown in Table 1.
  • a molded article formed from a fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the amount of sericite added was changed to the amount shown in Table 1.
  • the tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.
  • a molded article formed from a fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the amount of sericite added was changed to the amount shown in Table 1.
  • the tensile strength at break (Tb), tensile elongation at break (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.
  • a molded article formed from the fluorine-containing elastomer composition was obtained in the same manner as in Example 1, except that sericite was not added.
  • Tensile strength at break (Tb) and tensile fracture The elongation (Eb), hardness (Shore A), and fuel permeation test were measured by the following methods. The results are shown in Table 1.
  • a molded article formed from the fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the sericite was changed to the carbon filler and the addition amount was changed to the amount shown in Table 1.
  • the tensile breaking strength (Tb), tensile breaking elongation (Eb), hardness (Shore A), and fuel permeation test of the molded product were measured by the following methods. The results are shown in Table 1.
  • Kneading method Roll kneading
  • compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 are subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to obtain a sheet having a thickness of 2 mm, and the measurement is performed according to JIS-K6251.
  • compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 are subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to obtain a sheet having a thickness of 2 mm, and the measurement is performed according to JIS-K6253.
  • compositions shown in Examples 1 to 4 and Comparative Examples 1 to 5 were subjected to primary press crosslinking and secondary oven crosslinking under standard crosslinking conditions to produce sheet test pieces having a thickness of 0.5 mm.
  • SUS container open area 1.
  • 26 X 10 "V) with 20mL of volume the sheet-shaped test piece Is set in a container open part and sealed to obtain a test body.
  • the specimen was placed in the apparatus (40 ° C), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was obtained by the following formula.
  • the fluorine-containing elastomer compositions obtained by 2 and 3 are the same as those in Examples 1 and 2. Although it has the same hardness as the fluorine-containing elastomer composition, it has poor fuel permeability. In order to give the comparative fluorine-containing elastomer composition the same fuel permeability as the fluorine-containing elastomer composition of the example, it is necessary to add a large amount of My power. Due to the high hardness, it is not suitable as an elastomer composition.
  • the fluorine-containing elastomer compositions obtained in the examples have a low fuel permeability coefficient, excellent balance between fuel barrier properties and flexibility, and sufficient mechanical strength (breaking strength). I understood.
  • Table 3 shows the results of measurement of tensile strength at break, tensile elongation at break, tensile elastic modulus, MFR, and fuel barrier properties by the following methods using the above-described fluorocoagulant (A) alone.
  • Fluorine-containing resin composition was prepared in the same manner as in Example 5 except that 1 part by weight of sericite was mixed with 100 parts by weight of fluorine-containing elastomer to prepare a compound of fluororubber (b-2). Each was manufactured.
  • Table 3 shows the results of measuring the tensile strength at break, tensile elongation at break, tensile modulus, MFR, and fuel barrier properties by the following methods using the obtained fluorocoagulant composition.
  • Comparative Example 9 Fluorine-containing elastomer 1 2 100 parts by weight kneaded 55 parts by weight of sericite to prepare a fluorine rubber (b-3) compound. The thing was manufactured. Table 3 shows the results of measurement of tensile strength at break, tensile elongation at break, tensile elastic modulus, MFR, and fuel barrier properties by the following methods using the obtained fluorocoagulant composition.
  • the fluorine resin composition produced in Examples 5 to 9 and Comparative Examples 6 to 9 was set in a mold, and then heated with a heat press. Hold at 60 ° C high and temperature (280 ° C) for 15-30 minutes, make the dynamic vulcanized composition into a molten state, then apply a 3MPa load for 1 minute, compress it, and then press the sheet A test specimen is prepared.
  • a sheet-like test piece having a thickness of 0.5 mm was produced by the above method.
  • the specimen is placed in the open part of the vessel and sealed to make a specimen.
  • the specimen is placed in a thermostatic device (60 ° C), and the weight of the specimen is measured.
  • the fuel permeability coefficient was calculated by the following formula.
  • the fluorine-containing elastomer 2 and sericite were kneaded by a roll by a conventional method to prepare crosslinkable fluorine-containing elastomer compositions (b-1 to b-3) shown in Table 2.
  • the kneading of the fluororesin (A) and the crosslinkable fluorine-containing elastomer composition (b-l to b-3) was performed using a laboplast mill (manufactured by Toyo Seiki Seisakusho).
  • the total amount of the fluorinated resin (A) and the crosslinkable fluorine-containing elastomer composition to be kneaded was adjusted so that the total volume was 77% by volume of the total volume of the kneaded part of the lab plast mill.
  • the temperature of the lab plast mill was set to 40 ° C higher than the melting point (220 ° C) of the fluororesin (A) used in the composition, and the temperature (260 ° C).
  • a molded article having excellent heat resistance, chemical resistance, and oil resistance, and having excellent fuel barrier properties and high mechanical properties can be obtained.
  • a fluorine-containing elastomer composition which can be provided is provided.
  • the present invention also provides a molded article having excellent fuel barrier properties, heat resistance, chemical resistance, oil resistance and flexibility by including a crosslinked fluororubber obtained by crosslinking the fluorine-containing elastomer composition.
  • a fluororesin composition that can be obtained and can be melt-molded can be provided.

Landscapes

  • 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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une composition de fluoroélastomère qui possède simultanément des performances de barrière aux combustibles et de propriétés mécaniques satisfaisantes ; et une composition de fluororésine ayant une excellente résistance à la perméation de combustibles. En outre, l'invention concerne un article moulé, un tuyau et un tube produits à partir de la composition. L'invention concerne en outre une composition de fluoroélastomère comprenant un fluoroélastomère et de la séricite. L'invention concerne également une composition de fluororésine comprenant de la fluororésine (A) et du caoutchouc fluoré réticulé (B) obtenu par réticulation de la composition de fluoroélastomère. L'invention concerne en outre un article moulé, un tuyau et un tube composés de la composition.
PCT/JP2007/056406 2006-03-29 2007-03-27 Composition de fluoroélastomère, composition de fluororesine, et moulage de celles-ci Ceased WO2007111334A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006091265 2006-03-29
JP2006-091265 2006-03-29
JP2006-144012 2006-05-24
JP2006144012 2006-05-24

Publications (1)

Publication Number Publication Date
WO2007111334A1 true WO2007111334A1 (fr) 2007-10-04

Family

ID=38541251

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/056406 Ceased WO2007111334A1 (fr) 2006-03-29 2007-03-27 Composition de fluoroélastomère, composition de fluororesine, et moulage de celles-ci

Country Status (1)

Country Link
WO (1) WO2007111334A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009128363A1 (fr) * 2008-04-14 2009-10-22 Nok株式会社 Matériau d'étanchéité en fluoro-caoutchouc présentant de bonnes propriétés d'étanchéité sous charge à haute et basse température
JP2011168630A (ja) * 2010-02-16 2011-09-01 Nok Corp 耐燃料透過性の良好な耐寒フッ素ゴム組成物
CN112812474A (zh) * 2021-01-07 2021-05-18 广州机械科学研究院有限公司 一种抗变形氟橡胶及其制备方法与应用
JP7251005B1 (ja) * 2022-03-29 2023-04-03 住友理工株式会社 燃料用ホース
CN116554619A (zh) * 2023-06-26 2023-08-08 上海芯密科技有限公司 一种氟橡胶弹性体及其制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111377A (ja) * 1984-11-05 1986-05-29 Mitsubishi Petrochem Co Ltd フツ素系樹脂プライマ−
JPH0289633A (ja) * 1988-05-20 1990-03-29 Sumitomo Electric Ind Ltd フッ素樹脂被覆物
JPH08176390A (ja) * 1994-12-22 1996-07-09 Dainippon Ink & Chem Inc 熱可塑性樹脂組成物
JPH08319391A (ja) * 1995-05-25 1996-12-03 Nippon Pillar Packing Co Ltd 摺動用部材
JPH10219062A (ja) * 1997-02-06 1998-08-18 Nichias Corp 熱可塑性エラストマー組成物、その製造法および成形品
JP2002212370A (ja) * 2001-01-23 2002-07-31 Nok Corp フッ素ゴム加硫成形物
JP2002241619A (ja) * 2001-02-19 2002-08-28 Kuraray Co Ltd ガソリンバリア性に優れた樹脂組成物
WO2003000792A1 (fr) * 2001-06-26 2003-01-03 Daikin Industries, Ltd. Composition de resine et procede de production associe, fil electrique a mousse isolante
JP2004501258A (ja) * 2000-06-20 2004-01-15 フロイデンベルク　−　ノク　ジェネラル　パートナーシップ フッ化炭素ポリマーを基剤とする熱可塑性加硫ゴム
JP2004217892A (ja) * 2002-12-27 2004-08-05 Nok Corp フッ素ゴム系シール材用組成物及びフッ素ゴム系シール材
JP2004346087A (ja) * 2002-04-23 2004-12-09 Yunimatekku Kk 含フッ素エラストマーおよびその組成物
JP2005219972A (ja) * 2004-02-05 2005-08-18 National Institute Of Advanced Industrial & Technology 形状と構造を制御した雲母系粉体、及びその製造方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111377A (ja) * 1984-11-05 1986-05-29 Mitsubishi Petrochem Co Ltd フツ素系樹脂プライマ−
JPH0289633A (ja) * 1988-05-20 1990-03-29 Sumitomo Electric Ind Ltd フッ素樹脂被覆物
JPH08176390A (ja) * 1994-12-22 1996-07-09 Dainippon Ink & Chem Inc 熱可塑性樹脂組成物
JPH08319391A (ja) * 1995-05-25 1996-12-03 Nippon Pillar Packing Co Ltd 摺動用部材
JPH10219062A (ja) * 1997-02-06 1998-08-18 Nichias Corp 熱可塑性エラストマー組成物、その製造法および成形品
JP2004501258A (ja) * 2000-06-20 2004-01-15 フロイデンベルク　−　ノク　ジェネラル　パートナーシップ フッ化炭素ポリマーを基剤とする熱可塑性加硫ゴム
JP2002212370A (ja) * 2001-01-23 2002-07-31 Nok Corp フッ素ゴム加硫成形物
JP2002241619A (ja) * 2001-02-19 2002-08-28 Kuraray Co Ltd ガソリンバリア性に優れた樹脂組成物
WO2003000792A1 (fr) * 2001-06-26 2003-01-03 Daikin Industries, Ltd. Composition de resine et procede de production associe, fil electrique a mousse isolante
JP2004346087A (ja) * 2002-04-23 2004-12-09 Yunimatekku Kk 含フッ素エラストマーおよびその組成物
JP2004217892A (ja) * 2002-12-27 2004-08-05 Nok Corp フッ素ゴム系シール材用組成物及びフッ素ゴム系シール材
JP2005219972A (ja) * 2004-02-05 2005-08-18 National Institute Of Advanced Industrial & Technology 形状と構造を制御した雲母系粉体、及びその製造方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009128363A1 (fr) * 2008-04-14 2009-10-22 Nok株式会社 Matériau d'étanchéité en fluoro-caoutchouc présentant de bonnes propriétés d'étanchéité sous charge à haute et basse température
JP2009256418A (ja) * 2008-04-14 2009-11-05 Nok Corp 高／低温負荷シール性が良好なフッ素ゴム系シール材
US20110034639A1 (en) * 2008-04-14 2011-02-10 Nok Corporation Fluororubber-based sealing material having good sealing properties under high/low temperature load
US8563660B2 (en) 2008-04-14 2013-10-22 Nok Corporation Fluororubber-based sealing material having good sealing properties under high/low temperature load
JP2011168630A (ja) * 2010-02-16 2011-09-01 Nok Corp 耐燃料透過性の良好な耐寒フッ素ゴム組成物
CN112812474A (zh) * 2021-01-07 2021-05-18 广州机械科学研究院有限公司 一种抗变形氟橡胶及其制备方法与应用
CN112812474B (zh) * 2021-01-07 2022-11-18 广州机械科学研究院有限公司 一种抗变形氟橡胶及其制备方法与应用
JP7251005B1 (ja) * 2022-03-29 2023-04-03 住友理工株式会社 燃料用ホース
WO2023187992A1 (fr) * 2022-03-29 2023-10-05 住友理工株式会社 Tuyau pour carburants
CN116554619A (zh) * 2023-06-26 2023-08-08 上海芯密科技有限公司 一种氟橡胶弹性体及其制备方法
CN116554619B (zh) * 2023-06-26 2024-03-08 上海芯密科技有限公司 一种氟橡胶弹性体及其制备方法

Similar Documents

Publication Publication Date Title
JP4910704B2 (ja) 熱可塑性重合体組成物
KR100846941B1 (ko) 열가소성 중합체 조성물
JP5273048B2 (ja) 含フッ素樹脂および架橋フッ素ゴムを含む熱可塑性樹脂組成物
JP5652469B2 (ja) 含フッ素エラストマー組成物および該組成物からなる成形品
KR101397843B1 (ko) 가교성 불소 고무 조성물, 불소 고무 성형품 및 그의 제법
JP2008308657A (ja) 燃料部品
CN101065440B (zh) 热塑性聚合物组合物
JP5120251B2 (ja) 熱可塑性重合体組成物および該組成物からなる成形体
WO2007111334A1 (fr) Composition de fluoroélastomère, composition de fluororesine, et moulage de celles-ci
JP2007191576A (ja) 熱可塑性重合体組成物、熱可塑性樹脂組成物、それを用いた成形品および熱可塑性樹脂組成物の製造方法
JP7436910B2 (ja) フッ素ゴム組成物および成形体
JP2010209275A (ja) ポリマー組成物及び成形体
WO2007135938A1 (fr) Matériau de barrière contre un combustible et article moulé formé à partir de celui-ci
JP2024095578A (ja) フッ素ゴム組成物、成形体および燃料ホース
JP2023177692A (ja) 含フッ素エラストマー組成物、成形体および燃料ホース
JP2007277348A (ja) フッ素樹脂組成物の製造方法および該製造方法から得られるフッ素樹脂組成物
JP2007224086A (ja) フッ素樹脂組成物およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07739844

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 07739844

Country of ref document: EP

Kind code of ref document: A1