JP2014009286A - Fluoro rubber composition and method of manufacturing the same - Google Patents
Fluoro rubber composition and method of manufacturing the same Download PDFInfo
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- JP2014009286A JP2014009286A JP2012146571A JP2012146571A JP2014009286A JP 2014009286 A JP2014009286 A JP 2014009286A JP 2012146571 A JP2012146571 A JP 2012146571A JP 2012146571 A JP2012146571 A JP 2012146571A JP 2014009286 A JP2014009286 A JP 2014009286A
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 161
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 238000004381 surface treatment Methods 0.000 claims abstract description 35
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- 150000002978 peroxides Chemical class 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 21
- 239000012790 adhesive layer Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000000704 physical effect Effects 0.000 claims description 7
- 229920001897 terpolymer Polymers 0.000 claims description 6
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000006234 thermal black Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 239000000523 sample Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005259 measurement Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- -1 bisphenol phosphonium salt Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000011243 crosslinked material Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- VYNQWGXTLZDYFX-UHFFFAOYSA-N 1-benzoylperoxyhexyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(CCCCC)OOC(=O)C1=CC=CC=C1 VYNQWGXTLZDYFX-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- IEMBFTKNPXENSE-UHFFFAOYSA-N 2-(2-methylpentan-2-ylperoxy)propan-2-yl hydrogen carbonate Chemical compound CCCC(C)(C)OOC(C)(C)OC(O)=O IEMBFTKNPXENSE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VFTWMPNBHNNMAV-UHFFFAOYSA-N 2-tert-butylperoxy-1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C(OOC(C)(C)C)=C1 VFTWMPNBHNNMAV-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HZTNYDWTDTYXQC-UHFFFAOYSA-N bis(prop-2-ynyl) benzene-1,4-dicarboxylate Chemical compound C#CCOC(=O)C1=CC=C(C(=O)OCC#C)C=C1 HZTNYDWTDTYXQC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- PNWOTXLVRDKNJA-UHFFFAOYSA-N tert-butylperoxybenzene Chemical compound CC(C)(C)OOC1=CC=CC=C1 PNWOTXLVRDKNJA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、各種工業分野で、例えば、シール材として使用されるフッ素ゴム組成物およびその製造方法に関し、特に、ゴム硬度(Duro-A)５０以下の柔らかい硬度特性を有することはもとより、従来技術では達し得なかったレベルの非粘着性を有するフッ素ゴム組成物およびその製造方法に関する。 The present invention relates to a fluororubber composition used as a sealing material in various industrial fields, for example, and a method for producing the same. In particular, the present invention has a soft hardness characteristic with a rubber hardness (Duro-A) of 50 or less, as well as the prior art. The present invention relates to a fluororubber composition having a level of non-stickiness that could not be achieved and a method for producing the same.
フッ素ゴム組成物は、優れたゴム弾性に加えて、耐熱性、耐油性、耐薬品性および耐オゾン性にも優れており、バルブ、パッキン、シーリング材として幅広く用いられている。そして、これらのものは、シール性を保持するために用いられることが多く、例えば、金属やプラスチック等と接触したままの状態で用いられることが多い。 In addition to excellent rubber elasticity, the fluororubber composition is excellent in heat resistance, oil resistance, chemical resistance, and ozone resistance, and is widely used as a valve, packing, and sealing material. And these things are often used in order to maintain a sealing property, for example, are often used in the state which contacted the metal, the plastics, etc., for example.
しかしながら、フッ素ゴム組成物は、その表面が粘着性を有するが故に、金属やプラスチックと接触した状態が長時間に亘ると、フッ素ゴム組成物と金属等が互いに粘着してしまい、例えば、開閉バルブの弁として用いた場合、開閉バルブとしての本来の開閉機能が損なわれてしまうことがあり、また、パッキンとして用いた場合に、定期的に行われる交換作業が極めて困難な状態に陥ってしまうという問題が生じ得る。 However, since the surface of the fluororubber composition is sticky, the fluororubber composition and the metal stick to each other when they are in contact with metal or plastic for a long time. When used as a valve, the original opening / closing function as an opening / closing valve may be impaired, and when used as a packing, periodic replacement work is extremely difficult. Problems can arise.
このような問題を解決するために、従来より、例えば、ゴムそのものが持つ硬度や弾性特性をある程度維持させたまま、ゴム表面の粘着性を低減させることのできる種々の技術的提案がなされている。 In order to solve such problems, for example, various technical proposals have been made that can reduce the adhesiveness of the rubber surface while maintaining the hardness and elastic properties of the rubber itself to some extent. .
例えば、特開平１１−２５５９３０公報（特許文献１）には、リン系の架橋剤を含有する表面処理液でゴム表面を表面処理することにより形成されてなる非粘着層を備えるフッ素ゴム組成物の提案がなされている。 For example, JP-A-11-255930 (Patent Document 1) discloses a fluororubber composition comprising a non-adhesive layer formed by surface-treating a rubber surface with a surface treatment liquid containing a phosphorus-based crosslinking agent. Proposals have been made.
また、特開平０６−１１６４６４公報（特許文献２）には、固体状フッ素ゴム、液体状フッ素ゴム、炭素数８以上のアルキル基を有する脂肪族アミンおよびパーフルオロポリエーテルを含有してなる低硬度フッ素ゴム組成物の提案がなされている。 Japanese Patent Laid-Open No. 06-116464 (Patent Document 2) discloses a low hardness comprising a solid fluororubber, a liquid fluororubber, an aliphatic amine having an alkyl group having 8 or more carbon atoms, and perfluoropolyether. Proposals of fluororubber compositions have been made.
また、特開２００４−２５０５２０公報（特許文献３）には、フッ化ビニリデン−パーフルオロ（メチルビニルエーテル）−テトラフルオロエチレン３元共重合体またはフッ化ビニリデン−ヘキサフルオロプロペン共重合体１００重量部に、１００℃における粘度が５００〜３０００ｃｐｓである液状フッ素ゴム１０〜５０重量部、さらに有機過酸化物０．５〜５重量部および多官能性不飽和化合物０．５〜１０重量部を添加、あるいはポリオール系加硫剤０．５〜１０重量部を添加してなる加硫性フッ素ゴム組成物の提案がなされている。 JP-A-2004-250520 (Patent Document 3) discloses that 100 parts by weight of vinylidene fluoride-perfluoro (methyl vinyl ether) -tetrafluoroethylene terpolymer or vinylidene fluoride-hexafluoropropene copolymer is used. 10 to 50 parts by weight of a liquid fluororubber having a viscosity at 100 ° C. of 500 to 3000 cps, 0.5 to 5 parts by weight of an organic peroxide and 0.5 to 10 parts by weight of a polyfunctional unsaturated compound, or A vulcanizable fluororubber composition obtained by adding 0.5 to 10 parts by weight of a polyol vulcanizing agent has been proposed.
上記の各提案においては、ある程度の柔らかいゴム硬度特性を有し、かつ、ある程度までの非粘着性を担保することができるフッ素ゴム組成物の提案がなされている。しかしながら、非粘着性に関する要求について際限はなく、特に、ゴム硬度(Duro-A)５０以下の柔らかい硬度特性を有するフッ素ゴム組成物であって、従来レベルよりも格段と優れた非粘着性を有するフッ素ゴム組成物およびその製造方法の提案が強く望まれている。 In each of the above proposals, there has been proposed a fluororubber composition that has a certain degree of soft rubber hardness characteristics and can ensure a certain degree of non-adhesiveness. However, there is no limit to the requirements regarding non-adhesiveness, and in particular, it is a fluororubber composition having a soft hardness characteristic with a rubber hardness (Duro-A) of 50 or less, and has non-adhesive properties far superior to conventional levels. A proposal of a fluororubber composition and a method for producing the same is strongly desired.
このような実状のもとに本発明は創案されたものであり、その目的は、ゴム硬度(Duro-A)５０以下の柔らかい硬度特性を有するフッ素ゴム組成物であって、従来レベルよりも格段と優れた非粘着性を有するフッ素ゴム組成物およびその製造方法を提供することにある。 The present invention was devised based on such a situation, and an object thereof is a fluororubber composition having a soft hardness characteristic with a rubber hardness (Duro-A) of 50 or less, which is much higher than the conventional level. Another object of the present invention is to provide a fluororubber composition having excellent non-stickiness and a method for producing the same.
上述してきた課題を解決するために、本発明のフッ素ゴム組成物は、パーオキサイド架橋タイプ（架橋剤としてパーオキサイドが用いられる）のフッ素ゴム１００重量部と、液状フッ素ゴム２０〜３０重量部と、カーボンブラック１〜７重量部を含むフッ素ゴム架橋物と、該フッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理して形成してなる非粘着層と、を有するように構成される。 In order to solve the above-described problems, the fluororubber composition of the present invention comprises a peroxide crosslinking type (peroxide is used as a crosslinking agent) 100 parts by weight, a liquid fluororubber 20 to 30 parts by weight, A cross-linked fluororubber containing 1 to 7 parts by weight of carbon black, and a non-adhesive layer formed by surface-treating the surface of the cross-linked fluororubber with a surface treatment agent containing a phosphorus-based cross-linking agent. Configured to have.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記リン系の架橋剤が、所定の構造式で示されるビスフェノールホスホニウム塩からなるように構成される。 Further, as a preferred embodiment of the fluororubber composition of the present invention, the phosphorus-based crosslinking agent is constituted by a bisphenol phosphonium salt represented by a predetermined structural formula.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記非粘着層が形成された部位におけるゴム硬度(Duro-A)が５０以下であるように構成される。 In addition, as a preferred embodiment of the fluororubber composition of the present invention, the rubber hardness (Duro-A) at the portion where the non-adhesive layer is formed is configured to be 50 or less.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記フッ素ゴム架橋物におけるカーボンブラック含有量が、１〜５重量部であるように構成される。 Moreover, as a preferable aspect of the fluororubber composition of this invention, it is comprised so that carbon black content in the said fluororubber crosslinked material may be 1-5 weight part.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記フッ素ゴムは、２種以上の単量体を共重合させて得られるパーオキサイド架橋タイプ（架橋剤としてパーオキサイドが用いられる）のフッ素ゴムを主成分としてなるように構成される。 Further, as a preferred embodiment of the fluororubber composition of the present invention, the fluororubber is a peroxide cross-linking type (peroxide is used as a cross-linking agent) obtained by copolymerizing two or more monomers. It is comprised so that it may become a main component.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記フッ素ゴムは、フッ化ビニリデン（ＶＤＦ）と、テトラフルオロエチレン（ＴＦＥ）と、パーフロロメチルビニルエーテルとを共重合して得られる三元系共重合体、またはテトラフルオロエチレン（ＴＦＥ）と、ヘキサフルオロプロピレン（ＨＦＰ）とを共重合して得られる二元系共重合体のフッ素ゴムであるように構成される。 As a preferred embodiment of the fluororubber composition of the present invention, the fluororubber is a ternary system obtained by copolymerizing vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and perfluoromethyl vinyl ether. It is configured to be a fluoropolymer of a copolymer or a binary copolymer obtained by copolymerizing tetrafluoroethylene (TFE) and hexafluoropropylene (HFP).
また、本発明のフッ素ゴム組成物の好ましい態様として、前記液状フッ素ゴムは、常温で液体のフッ素ゴムであり、架橋しないゴム成分としての物性を備えてなるように構成される。 As a preferred embodiment of the fluororubber composition of the present invention, the liquid fluororubber is a fluororubber that is liquid at room temperature, and is configured to have physical properties as a rubber component that is not crosslinked.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記カーボンブラックは、平均粒子径１５〜３５０ｎｍ、比表面積７〜１５０ｍ2／ｇの範囲の物性を備えてなるように構成される。 As a preferred embodiment of the fluororubber composition of the present invention, the carbon black is configured to have physical properties in the range of an average particle size of 15 to 350 nm and a specific surface area of 7 to 150 m 2 / g.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記カーボンブラックは、平均粒子径２４０〜３２０ｎｍ、比表面積７〜１１ｍ2／ｇの範囲の物性を備えるサーマルブラックであるように構成される。 Moreover, as a preferable aspect of the fluororubber composition of the present invention, the carbon black is configured to be a thermal black having physical properties in an average particle diameter of 240 to 320 nm and a specific surface area of 7 to 11 m 2 / g.
また、本発明のフッ素ゴム組成物の好ましい態様として、前記非粘着層がシール部位を構成してなるように構成される。 Moreover, as a preferable aspect of the fluororubber composition of the present invention, the non-adhesive layer is configured to constitute a seal portion.
本発明のフッ素ゴム組成物の製造方法は、前記記載のフッ素ゴム架橋物の表面に、主成分としてリン系の架橋剤を含有する表面処理液を付着させた後、熱処理するように構成される。 The method for producing a fluororubber composition of the present invention is configured to heat-treat after a surface treatment liquid containing a phosphorus-based cross-linking agent as a main component is attached to the surface of the cross-linked fluororubber described above. .
また、本発明のフッ素ゴム組成物の製造方法の好ましい態様として、前記リン系の架橋剤が、所定の構造式で示されるビスフェノールホスホニウム塩からなるように構成される。 Further, as a preferred embodiment of the method for producing a fluororubber composition of the present invention, the phosphorus-based crosslinking agent is constituted by a bisphenolphosphonium salt represented by a predetermined structural formula.
本発明のフッ素ゴム組成物は、フッ素ゴム組成物のベースとなるパーオキサイド架橋タイプ（架橋剤としてパーオキサイドが用いられる）のフッ素ゴム１００重量部と、液状フッ素ゴム２０〜３０重量部と、カーボンブラック１〜７重量部を含むフッ素ゴム架橋物と、該フッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理して形成してなる非粘着層と、を有して構成されているので、ゴム硬度(Duro-A)５０以下の柔らかい硬度特性を有するフッ素ゴム組成物であって、従来レベルよりも格段と優れた非粘着性を有するフッ素ゴム組成物を実現させることができる。 The fluororubber composition of the present invention comprises a peroxide crosslinking type (peroxide is used as a crosslinking agent) 100 parts by weight of a fluororubber composition, 20-30 parts by weight of liquid fluororubber, carbon A fluororubber crosslinked product containing 1 to 7 parts by weight of black, and a non-adhesive layer formed by surface-treating the surface of the fluororubber crosslinked product with a surface treatment agent containing a phosphorus-based crosslinking agent. Therefore, a fluororubber composition having a soft hardness characteristic with a rubber hardness (Duro-A) of 50 or less and having a non-adhesiveness far superior to the conventional level is realized. be able to.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明のフッ素ゴム組成物は、フッ素ゴム組成物のベースとなるフッ素ゴム１００重量部と、液状フッ素ゴム２０〜３０重量部と、カーボンブラック１〜７重量部を含むフッ素ゴム架橋物と、そのフッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理してなる非粘着層と、を有して構成される。通常、本発明のフッ素ゴム組成物における非粘着層は、シール部位として作用するように使用され、当該非粘着層を例えば金属やプラスチック等の当接相手と押圧・接触させた状態で用いることができる。 The fluororubber composition of the present invention comprises a fluororubber crosslinked product comprising 100 parts by weight of fluororubber as a base of the fluororubber composition, 20-30 parts by weight of liquid fluororubber, and 1-7 parts by weight of carbon black, A non-adhesive layer formed by surface-treating the surface of the cross-linked fluororubber with a surface treatment agent containing a phosphorus-based cross-linking agent. Usually, the non-adhesive layer in the fluororubber composition of the present invention is used so as to act as a seal part, and the non-adhesive layer is used in a state of being pressed and brought into contact with a contact partner such as metal or plastic. it can.
以下、本発明のフッ素ゴム組成物を各構成要件ごとに説明する。
〔フッ素ゴム架橋物の説明〕
Hereinafter, the fluororubber composition of the present invention will be described for each component.
[Description of cross-linked fluororubber]
＜フッ素ゴム組成物のベースとなるフッ素ゴムの説明＞
本発明におけるフッ素ゴム架橋物（フッ素ゴム加硫物と実質的に同義）は、特に、フッ化ビニリデン系のフッ素ゴムをベースにして構成することが望ましく、例えば、２種以上の単量体（特に２種または３種の単量体が好ましい）を共重合させて得られるパーオキサイド架橋タイプ（架橋剤としてパーオキサイドが用いられる）のフッ素ゴムを主成分とすることが好ましい。
<Description of fluororubber as a base of fluororubber composition>
The cross-linked fluororubber in the present invention (substantially synonymous with fluororubber vulcanizate) is particularly preferably formed on the basis of vinylidene fluoride fluororubber, for example, two or more monomers ( In particular, it is preferable that the main component is a peroxide crosslinking type (peroxide is used as a crosslinking agent) fluororubber obtained by copolymerizing two or three monomers.
後述する本願所定の表面処理との組み合わせ使用において、パーオキサイド架橋タイプのフッ素ゴムは、ポリオール架橋タイプのそれよりも表面処理後の硬度が高くなり難いことが実験的に確認されている。これについては、後述の具体的な実験結果を参照されたい。 It has been experimentally confirmed that the peroxide cross-linking type fluororubber is less likely to have higher hardness after the surface treatment than that of the polyol cross-linking type in combination use with the predetermined surface treatment described later. For this, see the specific experimental results described below.
このようなフッ素ゴムの具体例としては、フッ化ビニリデン／テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、フッ化ビニリデン／テトラフルオロエチレン／パーフロロメチルビニルエーテル、テトラフルオロエチレン／プロピレン／フッ化ビニリデン共重合体、テトラフルオロエチレン／プロピレン／フッ化ビニル共重合体等の三元系共重合体や；フッ化ビニリデン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／プロピレン共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、ヘキサフルオロプロピレン／エチレン共重合体、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体等の二元系共重合体が挙げられる。 Specific examples of such fluororubbers include vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene / perfluoromethyl vinyl ether, tetrafluoroethylene / propylene / vinylidene fluoride copolymer Polymers, terpolymers such as tetrafluoroethylene / propylene / vinyl fluoride copolymer; vinylidene fluoride / hexafluoropropylene copolymer, tetrafluoroethylene / propylene copolymer, tetrafluoroethylene / hexafluoro Examples thereof include binary copolymers such as a propylene copolymer, a hexafluoropropylene / ethylene copolymer, and a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer.
これらの中でも特に、フッ化ビニリデン（ＶＤＦ）と、テトラフルオロエチレン（ＴＦＥ）と、ヘキサフルオロプロピレン（ＨＦＰ）とを共重合して得られる三元系共重合体、フッ化ビニリデンと、テトラフルオロエチレンと、パーフロロメチルビニルエーテルとを共重合して得られる三元系共重合体、またはテトラフルオロエチレン（ＴＦＥ）と、ヘキサフルオロプロピレン（ＨＦＰ）とを共重合して得られる二元系共重合体のフッ素ゴムを用いることが好ましい。 Among these, in particular, a terpolymer obtained by copolymerizing vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and hexafluoropropylene (HFP), vinylidene fluoride, and tetrafluoroethylene. And a terpolymer obtained by copolymerizing perfluoromethyl vinyl ether, or a binary copolymer obtained by copolymerizing tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) It is preferable to use fluororubber.
フッ素ゴムの架橋剤としては、上述したように、パーオキサイド（有機過酸化物）が好適に用いられる。前述したようにパーオキサイド（有機過酸化物）の架橋剤により架橋されるタイプのゴムが特に、本願所定の表面処理においても硬度が高くなり難いためである。 As the fluororubber crosslinking agent, as described above, peroxide (organic peroxide) is preferably used. This is because, as described above, the type of rubber that is cross-linked by a peroxide (organic peroxide) cross-linking agent is particularly difficult to increase in hardness even in the predetermined surface treatment of the present application.
本発明でいうパーオキサイド架橋タイプのフッ素ゴムとは、架橋剤としてパーオキサイドを用いることを前提とする趣旨である。 The peroxide cross-linking type fluororubber referred to in the present invention is based on the premise that peroxide is used as a cross-linking agent.
具体的な架橋剤としては、１，１−ジ（ｔ−ヘキシルパーオキシ）−３，５，５−トリメチルシクロヘキサン、２，５−ジメチルヘキサンー２，５−ジヒドロパーオキシド、ジ−ｔ−ブチルパーオキシド、ｔ−ブチルクミルパーオキシド、ジクミルパーオキシド、α−α´−ビス（ｔ−ブチルパーオキシ）−ｐ−ジイソプロピルベンゼン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）−ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）−ヘキシン−３、ジベンゾイルパーオキシド、ｔ−ブチルパーオキシベンゼン、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシマレイン酸、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート等が挙げられる。このような架橋剤の含有量は、フッ素ゴム１００重量部に対して、０．１〜５重量部程度とされる。 Specific crosslinking agents include 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl. Peroxide, t-butylcumyl peroxide, dicumyl peroxide, α-α'-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxide Oxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, dibenzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5- Examples include di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-hexylperoxyisopropyl monocarbonate, and the like. The content of such a crosslinking agent is about 0.1 to 5 parts by weight with respect to 100 parts by weight of the fluororubber.
本発明におけるフッ素ゴム架橋物は、共架橋剤を含有することが好ましい。具体的な共架橋剤としては、例えば、トリアリルシアネート、トリアリルイソシアネート、トリアクリルホルマール、トリアリルトリメリテート、ジプロパルギルテレフタレート、ジアリルフタレート、テトラアリルテレフタールアミド、トリアリルホスフェート等が挙げられる。このような共架橋剤の含有量は、フッ素ゴム１００重量部に対して、０．５〜５重量部程度とされる。 The cross-linked fluororubber in the present invention preferably contains a co-crosslinking agent. Specific examples of the co-crosslinking agent include triallyl cyanate, triallyl isocyanate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, and the like. The content of such a co-crosslinking agent is about 0.5 to 5 parts by weight with respect to 100 parts by weight of the fluororubber.
本発明におけるフッ素ゴム架橋物は、架橋助剤を含有することが好ましい。具体的架橋助剤としては、酸化亜鉛等が挙げられる。 The cross-linked fluororubber in the present invention preferably contains a cross-linking aid. Specific examples of the crosslinking aid include zinc oxide.
本発明におけるフッ素ゴム架橋物は、カーボンブラックを含有しており、その含有量は、フッ素ゴム１００重量部に対して、１〜７重量部、より好ましくは１〜５重量部とされる。 The fluororubber cross-linked product in the present invention contains carbon black, and the content thereof is 1 to 7 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the fluororubber.
このカーボンブラックの含有量が７重量部を超えると、ゴム硬度が高くなる傾向が生じるとともに、本願の表面処理との関係において粘着性の顕著な低減効果が発現しなくなる傾向が見られるために好ましくない。また、カーボンブラックの含有量が１重量部未満となると、含有量が７重量部を超える場合と同様に、本願の表面処理との関係において表面処理の効果が発現し難くなってしまい、粘着性の顕著な低減効果が発現しなくなる傾向が見られるために好ましくない。 When the carbon black content exceeds 7 parts by weight, the rubber hardness tends to be high, and a significant reduction effect of adhesiveness tends not to be exhibited in relation to the surface treatment of the present application. Absent. In addition, when the content of carbon black is less than 1 part by weight, the effect of the surface treatment becomes difficult to be expressed in relation to the surface treatment of the present application, as in the case where the content exceeds 7 parts by weight. This is not preferable because a remarkable reduction effect of is not observed.
用いられるカーボンブラックとしては、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック等が挙げられる。 Examples of the carbon black used include furnace black, acetylene black, thermal black, and channel black.
このようなカーボンブラックとしては、平均粒子径１５〜３５０ｎｍ、比表面積７〜１５０ｍ2／ｇの範囲のものが好適に使用可能である。特に、後述する液状フッ素ゴムの使用適量領域に合わせ易くゴム硬度の調整の簡便化を図るためには、平均粒子径２４０〜３２０ｎｍ、比表面積７〜１１ｍ2／ｇの範囲のサーマルブラックを用いるのが好適であるが、必ずしも、この範囲の物性のものに限定されるわけではない。 As such carbon black, those having an average particle diameter of 15 to 350 nm and a specific surface area of 7 to 150 m 2 / g can be suitably used. In particular, thermal black having an average particle diameter of 240 to 320 nm and a specific surface area of 7 to 11 m 2 / g is used in order to easily adjust the rubber hardness so that it can be easily adjusted to the appropriate amount of liquid fluororubber to be described later. Is preferable, but is not necessarily limited to the physical properties in this range.
さらに、本発明におけるフッ素ゴム架橋物には、液状フッ素ゴムが２０〜３０重量部含有される。 Furthermore, 20-30 weight part of liquid fluororubber is contained in the fluororubber crosslinked material in this invention.
液状フッ素ゴムとは、常温で液体のフッ素ゴムであり、ソリッドのフッ素ゴムの加工性改良や低硬度化などの用途に使用される。また、液状フッ素ゴムは、架橋しないゴム成分である。液状フッ素ゴムの含有割合が、２０重量部未満となると、ゴム硬度を低下させる作用が十分でなくなるとともに、本願の表面処理との関係において粘着性の顕著な低減効果が発現しなくなる傾向が見られるために好ましくない。この一方で、液状フッ素ゴムの含有割合が、３０重量部を超えると、液状フッ素ゴムの含有量があまりに多くなり過ぎると、機械的強度が失われてしまい、シール材等としての本来のゴム機能がなくなってしまうという不都合が生じる。 The liquid fluororubber is a fluororubber that is liquid at room temperature, and is used for applications such as improving the workability and reducing the hardness of solid fluororubber. Liquid fluororubber is a rubber component that is not crosslinked. When the content ratio of the liquid fluororubber is less than 20 parts by weight, there is a tendency that the effect of reducing the rubber hardness is not sufficient, and the effect of significantly reducing tackiness is not exhibited in relation to the surface treatment of the present application. Therefore, it is not preferable. On the other hand, when the content ratio of the liquid fluororubber exceeds 30 parts by weight, if the content of the liquid fluororubber is too large, the mechanical strength is lost, and the original rubber function as a sealing material or the like. The inconvenience of disappearing occurs.
このような液状フッ素ゴムは、一般に、水に不溶であり、低級のケトンやエステルに可溶の溶解性を有する。具体的な製品名の一例として、「ダイエル（登録商標）Ｇ−１０１」を挙げることができる。 Such a liquid fluororubber is generally insoluble in water and has solubility in lower ketones and esters. An example of a specific product name is “DAIEL (registered trademark) G-101”.
その他の添加剤として、充填剤（カーボンブラックを除く）、滑剤等の加工助剤、潤滑剤、難燃剤、帯電防止剤、着色剤等を含有させてもよい。 As other additives, fillers (excluding carbon black), processing aids such as lubricants, lubricants, flame retardants, antistatic agents, colorants, and the like may be included.
充填剤としては、例えば、フッ素樹脂、ガラス繊維、炭素繊維等が挙げられる。加工助剤としては、高級脂肪酸のアルカリ金属塩等が挙げられ、特に、ステアリン酸塩、ラウリン酸塩が好ましい。 Examples of the filler include fluororesin, glass fiber, and carbon fiber. Examples of the processing aid include alkali metal salts of higher fatty acids, and stearates and laurates are particularly preferable.
本発明に用いられるフッ素ゴム架橋物は、上述してきたフッ素ゴム、液状フッ素ゴム、カーボンブラック、架橋剤、共架橋剤、架橋助剤、その他の添加剤を配合・添加した後、ニーダー等の混練機を用いてゴム混練物を形成し、このゴム混練物を金型を用いて所定の形状に成形し、熱架橋（熱加硫）を行うことにより製造することができる。 The fluororubber cross-linked product used in the present invention is blended and added to the above-described fluororubber, liquid fluororubber, carbon black, cross-linking agent, co-crosslinking agent, cross-linking aid, and other additives, and then kneaded such as a kneader. A rubber kneaded material is formed using a machine, the rubber kneaded material is molded into a predetermined shape using a mold, and is manufactured by thermal crosslinking (thermal vulcanization).
本発明のフッ素ゴム組成物は、上述してきたフッ素ゴム架橋物と、当該フッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理することにより、フッ素ゴム架橋物の表面に形成された非粘着層とを有して構成される。つまり、架橋したフッ素ゴム架橋物の表面を所望の表面処理することによって、本発明のフッ素ゴム組成物が形成される。表面処理は、フッ素ゴム架橋物の表面全体とすることもできるし、所望の一部の表面のみとすることもでき、特に限定されるものではない。 The fluororubber composition of the present invention is obtained by surface-treating the above-mentioned fluororubber crosslinked product and the surface of the fluororubber crosslinked product with a surface treatment agent containing a phosphorus-based crosslinking agent. The non-adhesive layer is formed. That is, the surface of the crosslinked fluororubber crosslinked product is subjected to a desired surface treatment to form the fluororubber composition of the present invention. The surface treatment can be performed on the entire surface of the cross-linked fluororubber, or only on a desired partial surface, and is not particularly limited.
以下、フッ素ゴム架橋物の表面に形成される非粘着層について説明する。
〔非粘着層の説明〕
本発明における非粘着層は、上述したように主成分としてリン系の架橋剤を含有する表面処理液で、フッ素ゴム架橋物の表面を表面処理することによって形成される。
Hereinafter, the non-adhesive layer formed on the surface of the cross-linked fluororubber will be described.
[Description of non-adhesive layer]
The non-adhesive layer in the present invention is formed by surface-treating the surface of the cross-linked fluororubber with a surface treatment liquid containing a phosphorus-based crosslinking agent as a main component as described above.
本発明で用いられるリン系の架橋剤は、下記一般式（１）の構造式で示されるビスフェノールホスホニウム塩であることが好ましい。 The phosphorus-based crosslinking agent used in the present invention is preferably a bisphenol phosphonium salt represented by the structural formula of the following general formula (1).
上記一般式（１）中、ＲおよびＲ’は、それぞれ、水素または置換もしくは非置換の炭素数１〜６のアルキル基（特に好ましくは、炭素数１〜４のアルキル基）を示す。これの中でさらにＲおよびＲ’の好ましい形態は、メチル基、エチル基である。ＲおよびＲ’は同一の置換基であってもよいし、異なった置換基であってもよい。これらは、１種のみならず２種以上併用してもよい。 In the general formula (1), R and R ′ each represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (particularly preferably, an alkyl group having 1 to 4 carbon atoms). Among these, preferred forms of R and R ′ are methyl group and ethyl group. R and R 'may be the same substituent or different substituents. These may be used alone or in combination of two or more.
このようなリン系の架橋剤を用いることによって、上述のフッ素ゴム架橋物の特別な配合（特に、カーボンブラック量と液体フッ素ゴム量）と、リン系の架橋剤による表面処理とが相俟って、従来得られたこともないような特性、すなわち、ゴム硬度(Duro-A)が５０以下の柔らかい硬度でありながら、従来レベルをはるかに超え、ゴム表面の粘着性が格段に小さいフッ素ゴム組成物を得ることができる。もちろん、シール性を維持するためのゴム弾性とのバランスも非常に良い。 By using such a phosphorus-based crosslinking agent, a special blend of the above-mentioned fluororubber crosslinked product (particularly, the amount of carbon black and the amount of liquid fluororubber) and surface treatment with a phosphorus-based crosslinking agent are combined. Fluoro rubber with properties that have never been obtained before, that is, rubber hardness (Duro-A) is soft hardness of 50 or less, far exceeding the conventional level, and the rubber surface has much lower adhesiveness. A composition can be obtained. Of course, the balance with the rubber elasticity for maintaining the sealing performance is also very good.
このようなリン系の架橋剤は、通常、溶媒中に混合されることによって、ゴム表面の表面処理液となる。リン系の架橋剤の含有量は、溶媒１００重量部に対して、５〜１５重量部、好ましくは８〜１２重量部とされる。この含有量が多くなり過ぎると、反応過剰となり表面が過度に硬化してしまいシール性が低下するという不都合が生じ、また含有量が少な過ぎると、反応が不十分となり満足のいく非粘着性が得られないという不都合が生じる。
溶媒としては、例えば、アセトン、メチルエチルケトン、メチルアルコール等の溶媒が好適に用いられる。
Such a phosphorus-based crosslinking agent is usually mixed in a solvent to become a surface treatment solution for the rubber surface. The content of the phosphorus-based crosslinking agent is 5 to 15 parts by weight, preferably 8 to 12 parts by weight with respect to 100 parts by weight of the solvent. If this content is too high, the reaction will be excessive and the surface will be excessively hardened, resulting in a disadvantage that the sealing performance will be lowered.If the content is too low, the reaction will be insufficient and satisfactory non-adhesiveness will occur. The inconvenience that it cannot be obtained occurs.
As the solvent, for example, a solvent such as acetone, methyl ethyl ketone, or methyl alcohol is preferably used.
このようなリン系の架橋剤による処理によって形成された非粘着層の表面を、元素分析（ＥＤＳ：energy dispersive X-ray spectrometry）という手法で分析すると、リン元素の存在を確認することができる。 When the surface of the non-adhesive layer formed by the treatment with such a phosphorus-based crosslinking agent is analyzed by a technique called elemental analysis (EDS: energy dispersive X-ray spectrometry), the presence of the phosphorus element can be confirmed.
〔フッ素ゴム組成物の製造方法〕
次いで、本発明のフッ素ゴム組成物の製造方法について説明する。
[Method for producing fluororubber composition]
Subsequently, the manufacturing method of the fluororubber composition of this invention is demonstrated.
まず最初に、上記所定のリン系の架橋剤を含有する表面処理液を準備し、この表面処理液を被処理体であるフッ素ゴム架橋物の表面に付着させる。付着に際しては、表面処理液の溶液中にフッ素ゴム架橋物の表面を浸漬させたり（浸漬法）、フッ素ゴム架橋物の表面に表面処理液を吹き付けたり（吹き付け法）、フッ素ゴム架橋物の表面（一部分または全部）に表面処理液を塗布したりする方法（塗布法）等が挙げられる。これらの付着法のうち、どの方法を選択するかは、非粘着性の度合い、コスト等を考慮しつつ適宜選定すればよい。例えば、浸漬法の場合、１５分程度、好ましくは１０分程度の処理とすることができる。 First, a surface treatment liquid containing the predetermined phosphorus-based cross-linking agent is prepared, and this surface treatment liquid is adhered to the surface of a fluororubber cross-linked product that is an object to be treated. At the time of adhesion, the surface of the fluororubber crosslinked product is immersed in the surface treatment solution solution (immersion method), or the surface treatment solution is sprayed on the surface of the fluororubber crosslinked product (spraying method). Examples thereof include a method (coating method) or the like in which a surface treatment liquid is applied to (a part or all of). Of these adhesion methods, which method is selected may be appropriately selected in consideration of the degree of non-adhesiveness, cost, and the like. For example, in the case of the immersion method, the treatment can be performed for about 15 minutes, preferably about 10 minutes.
このように表面処理液を付着されたフッ素ゴム架橋物は、その後、熱処理されることが好ましい。好適な熱処理条件は、温度１８０℃〜２４０℃程度、処理時間４時間〜２４時間程度とされる。 Thus, it is preferable that the fluororubber crosslinked material to which the surface treatment liquid is attached is then heat-treated. Suitable heat treatment conditions are a temperature of about 180 ° C. to 240 ° C. and a processing time of about 4 hours to 24 hours.
浸漬法により表面処理が行われた場合には、通常さらに、未反応物を除去するために水またはアルコールで洗浄が行われ、しかる後、もう一度、温度１００℃〜１５０℃程度、処理時間３０分〜６０分程度の条件で再熱処理され、処理を完了させるようにすることが望ましい。 When the surface treatment is performed by the dipping method, usually, further washing with water or alcohol is performed to remove unreacted substances, and then again, the temperature is about 100 ° C. to 150 ° C., and the treatment time is 30 minutes. It is desirable that the heat treatment is performed again for about 60 minutes to complete the treatment.
また、塗布法により表面処理が行われた場合には、通常、最初の熱処理が行われた後、水またはアルコールで洗浄が行われ、しかる後乾燥して処理を完了させるようにすることが望ましい。 Further, when the surface treatment is performed by a coating method, it is usually desirable that after the first heat treatment is performed, the surface is washed with water or alcohol, and then dried to complete the treatment. .
以下、具体的実施例を挙げて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to specific examples.
〔実施例１〕
まず最初に、下記に示す要領でフッ素ゴム架橋物およびフッ素ゴム架橋物の表面処理液を、それぞれ作製し、準備した。
[Example 1]
First, a fluororubber crosslinked product and a fluororubber crosslinked product surface treatment solution were respectively prepared and prepared in the following manner.
＜フッ素ゴム架橋物の作製＞
（フッ素ゴム）
以下に示すパーオキサイド架橋タイプのフッ素ゴム（便宜上、当該フッ素ゴムを「タイプＡ」と称する）を用いた。
・フッ化ビニリデン／テトラフルオロエチレン／パーフロロメチルビニルエーテル３元共重合体（商品名「ダイエルＬＴ３０３Ｌ」；ダイキン工業（株）社製；パーオキサイド架橋タイプ）…１００重量部
<Preparation of cross-linked fluororubber>
(Fluoro rubber)
The following peroxide-crosslinking type fluororubber (for convenience, the fluororubber is referred to as “type A”) was used.
・ Vinylidene fluoride / tetrafluoroethylene / perfluoromethyl vinyl ether terpolymer (trade name “DAIEL LT303L”; manufactured by Daikin Industries, Ltd .; peroxide crosslinking type): 100 parts by weight
（液状フッ素ゴム）
・ダイエルＧ−１０１（ダイキン工業社製） …２０重量部
(Liquid fluoro rubber)
・ Daiel G-101 (Daikin Kogyo Co., Ltd.) 20 parts by weight
（カーボンブラック）
・サーマックスＮ９９０（Cancarb 社製）；平均粒子径２８０ｎｍ …１重量部
(Carbon black)
・ Thermax N990 (manufactured by Cancarb); average particle size 280 nm: 1 part by weight
（架橋助剤）
・酸化亜鉛（二種を使用）……３重量部
(Crosslinking aid)
・ Zinc oxide (use two types) ...... 3 parts by weight
（共架橋剤）
・ＴＡＩＣ：日本化成社製、トリアリルイソシアネート …３重量部
(Co-crosslinking agent)
・ TAIC: Nippon Kasei Co., Ltd., triallyl isocyanate: 3 parts by weight
（架橋剤）
・パーヘキサ２５Ｂ−４０（日本油脂社製）；２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン） …３重量部
(Crosslinking agent)
・ Perhexa 25B-40 (manufactured by NOF Corporation); 2,5-dimethyl-2,5-di (t-butylperoxy) hexane) 3 parts by weight
上記の配合用の原料を用いて、ゴムコンパウンドを得て、これを１７０℃、１０分間熱架橋（加硫）して固体状のフッ素ゴム架橋物（加硫物）を得た。 A rubber compound was obtained using the above raw materials for blending, and this was thermally crosslinked (vulcanized) at 170 ° C. for 10 minutes to obtain a solid fluororubber crosslinked product (vulcanized product).
＜表面処理液の作製＞
メチルアルコール１００重量部に、上記式（１）で表されるビスフェノールホスホニウム塩を１０重量部、加硫剤を１０重量部含有させて作製した表面処理液を準備した。
なお、上記式（１）において、ＲおよびＲ’は、それぞれ、メチル基とした。
<Preparation of surface treatment liquid>
A surface treatment solution prepared by containing 10 parts by weight of a bisphenolphosphonium salt represented by the above formula (1) and 10 parts by weight of a vulcanizing agent in 100 parts by weight of methyl alcohol was prepared.
In the above formula (1), R and R ′ were each a methyl group.
＜具体的な表面処理操作に基づくサンプルの作製＞
上記の表面処理液に上記の固体状のフッ素ゴム架橋物を２０℃で１０分間浸漬させ、その後、フッ素ゴム架橋物の表面をメチルアルコール水溶液で洗浄し、乾燥させ、しかる後、２００℃、１０時間の再熱処理を施し、実施例１のサンプルを作製した。
<Preparation of sample based on specific surface treatment operation>
The solid fluororubber crosslinked product is immersed in the surface treatment solution at 20 ° C. for 10 minutes, and then the surface of the fluororubber crosslinked product is washed with a methyl alcohol aqueous solution and dried. The sample of Example 1 was prepared by performing a reheat treatment for a period of time.
このようにして作製した実施例１のサンプルについて下記の要領でゴム表面の粘着試験を行い、粘着力（固着力）を求めた。なお、粘着試験は表面処理操作前と、表面処理操作後の双方で行い、処理前後のそれぞれの粘着力（固着力）を求めた。 For the sample of Example 1 produced in this manner, an adhesion test on the rubber surface was performed in the following manner to determine the adhesion (adhesion). In addition, the adhesion test was performed both before and after the surface treatment operation, and the adhesion strength (adhesion force) before and after the treatment was obtained.
また、表面処理された表面の硬度（Duro-A）を測定し、この硬度の測定についても、表面処理操作前と、表面処理操作後の双方で行い、処理前後のそれぞれの硬度を求めた。 In addition, the hardness (Duro-A) of the surface-treated surface was measured, and the hardness was measured both before and after the surface treatment operation, and the respective hardness before and after the treatment was obtained.
また、表面処理操作後のフッ素ゴム架橋物の常態物性（引っ張り強さおよび伸び）を、常法にて求めた。 In addition, normal properties (tensile strength and elongation) of the crosslinked fluororubber after the surface treatment operation were determined by a conventional method.
（ゴム表面の粘着試験）
表面処理操作前と表面処理操作後のフッ素ゴム架橋物についてそれぞれ、表面層のプローブタック値を測定した。プローブタック値は、ＪＩＳ Ｚ０２３７のプローブタック試験方法に基づいて測定した。具体的には、試験片（幅＝約２５ｍｍ、長さ＝約２５ｍｍ）をプローブタック試験装置に取付け、実施例および比較例の表面層にプローブを、一定荷重をかけながら一定時間接触させた後、プローブを表面層から垂直方向に引き剥がすのに要する力を求め、これをプローブタック値とした。
(Rubber surface adhesion test)
The probe tack value of the surface layer was measured for each of the fluororubber crosslinked products before and after the surface treatment operation. The probe tack value was measured based on the probe tack test method of JIS Z0237. Specifically, after attaching a test piece (width = about 25 mm, length = about 25 mm) to the probe tack test apparatus and bringing the probe into contact with the surface layer of the example and the comparative example for a certain period of time while applying a certain load. The force required to peel the probe from the surface layer in the vertical direction was determined, and this was used as the probe tack value.
プローブとしては、ステンレスＳＵＳ製の円柱プローブ（直径＝５．１ｍｍ）を用い、接触荷重を１００ｇｆ、接触時間を３秒、引き剥がし速さを６００ｍｍ／分とし、３回測定した後の平均値を算出した。 As a probe, a cylindrical probe made of stainless steel (diameter = 5.1 mm) was used, the contact load was 100 gf, the contact time was 3 seconds, the peeling speed was 600 mm / min, and the average value after three measurements was taken. Calculated.
（ゴム硬度(Duro-A)）
表面処理操作前と表面処理操作後のフッ素ゴム架橋物について、ＪＩＳ Ｋ６２５３に基づいてゴム硬度(Duro-A)を求めた。
本発明の目標値は、５０以下である。
上記の測定項目の測定値を下記表１に示した。
(Rubber hardness (Duro-A))
The rubber hardness (Duro-A) of the cross-linked fluororubber before and after the surface treatment operation was determined based on JIS K6253.
The target value of the present invention is 50 or less.
The measured values of the above measurement items are shown in Table 1 below.
〔実施例２〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から２重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、実施例２のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[Example 2]
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 2 parts by weight. Other than that, the sample of Example 2 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔実施例３〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から５重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、実施例３のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
Example 3
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 5 parts by weight. Otherwise, the sample of Example 3 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔実施例４〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から７重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、実施例４のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
Example 4
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 7 parts by weight. Otherwise, the sample of Example 4 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例１〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から０重量部（含有量零）に変えた。それ以外は上記実施例１のサンプルと同様な要領で、比較例１のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 1]
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 0 part by weight (zero content). Otherwise, the sample of Comparative Example 1 was prepared in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例２〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から１０重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、比較例２のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 2]
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 10 parts by weight. Otherwise, the sample of Comparative Example 2 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例３〕
上記実施例１のサンプルにおいて、カーボンブラックの含有量を１重量部から３０重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、比較例３のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 3]
In the sample of Example 1, the carbon black content was changed from 1 part by weight to 30 parts by weight. Otherwise, the sample of Comparative Example 3 was prepared in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例４〕
上記実施例２のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から０重量部（含有量零）に変えた。それ以外は上記実施例２のサンプルと同様な要領で、比較例４のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 4]
In the sample of Example 2, the content of the liquid fluororubber was changed from 20 parts by weight to 0 parts by weight (zero content). Otherwise, the sample of Comparative Example 4 was produced in the same manner as the sample of Example 2 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例５〕
上記実施例２のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から５重量部に変えた。それ以外は上記実施例２のサンプルと同様な要領で、比較例５のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 5]
In the sample of Example 2, the content of the liquid fluororubber was changed from 20 parts by weight to 5 parts by weight. Otherwise, the sample of Comparative Example 5 was produced in the same manner as the sample of Example 2 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例６〕
上記実施例１のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から１０重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、比較例６のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 6]
In the sample of Example 1, the content of the liquid fluororubber was changed from 20 parts by weight to 10 parts by weight. Otherwise, the sample of Comparative Example 6 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔＊比較例７〕
上記実施例４のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から１０重量部に変えた。それ以外は上記実施例４のサンプルと同様な要領で、比較例７のサンプルを作製した。そして、上記の要領で測定項目の測定値を求め、その結果を下記表１に示した。
[* Comparative Example 7]
In the sample of Example 4, the content of the liquid fluororubber was changed from 20 parts by weight to 10 parts by weight. Otherwise, the sample of Comparative Example 7 was prepared in the same manner as the sample of Example 4 above. And the measured value of the measurement item was calculated | required in said way, and the result was shown in following Table 1.
〔実施例５〕
上記実施例１のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から３０重量部に変えた。それ以外は上記実施例１のサンプルと同様な要領で、実施例５のサンプルを作製した。そして、上記の要領で測定項目の測定値を求めた。結果を下記表１に示した。
Example 5
In the sample of Example 1, the content of the liquid fluororubber was changed from 20 parts by weight to 30 parts by weight. Other than that, the sample of Example 5 was produced in the same manner as the sample of Example 1 above. And the measured value of the measurement item was calculated | required in said way. The results are shown in Table 1 below.
〔実施例６〕
上記実施例４のサンプルにおいて、液状フッ素ゴムの含有量を２０重量部から３０重量部に変えた。それ以外は上記実施例４のサンプルと同様な要領で、実施例６のサンプルを作製した。そして、上記の要領で測定項目の測定値を求めた。結果を下記表１に示した。
Example 6
In the sample of Example 4, the content of the liquid fluororubber was changed from 20 parts by weight to 30 parts by weight. Otherwise, the sample of Example 6 was produced in the same manner as the sample of Example 4 above. And the measured value of the measurement item was calculated | required in said way. The results are shown in Table 1 below.
〔＊比較例８〕
上記実施例４のサンプルにおいて、パーオキサイド架橋タイプのフッ素ゴムをポリオール架橋型のフッ素ゴム「ダイニオンＦＣ−２１７６」（住友スリーエム社製）に変えた（便宜上、当該フッ素ゴムを「タイプＢ」と称する）。
[* Comparative Example 8]
In the sample of Example 4, the peroxide-crosslinking type fluororubber was changed to a polyol-crosslinking type fluororubber “Dinion FC-2176” (manufactured by Sumitomo 3M Limited) (for convenience, the fluororubber is referred to as “type B”). ).
それに伴い、全体の配合も以下のように変えた。すなわち、ポリオール架橋型のフッ素ゴム「ダイニオンＦＣ−２１７６」（住友スリーエム社製）１００重量部に対し、液状フッ素ゴム「ダイエルＧ−１０１」２０重量部、カーボンブラック「サーマックスＮ９９０」７重量部、加工助剤としての「モールドウィズＩＮＴ−５４」（ＡＸＥＬ社製）０．５重量部、架橋助剤としての「キョーワマグ １５０」（協和化学工業社製）３重量部、架橋促進助剤としての「カルビット」（近江化学工業社製）６重量部を配合し、上記と同様にして比較例６のサンプルを作製した。そして、上記の要領で測定項目の測定値を求めた。結果を下記表１に示した。 Accordingly, the overall formulation was changed as follows. That is, with respect to 100 parts by weight of polyol-crosslinked fluororubber “Dinion FC-2176” (manufactured by Sumitomo 3M), 20 parts by weight of liquid fluororubber “Daiel G-101”, 7 parts by weight of carbon black “Thermax N990”, "Mold with INT-54" (manufactured by AXEL) as a processing aid, 0.5 parts by weight of "Kyowa Mag 150" (manufactured by Kyowa Chemical Industry Co., Ltd.) as a crosslinking aid, " 6 parts by weight of “Calbit” (Omi Chemical Co., Ltd.) was blended, and a sample of Comparative Example 6 was prepared in the same manner as described above. And the measured value of the measurement item was calculated | required in said way. The results are shown in Table 1 below.
〔＊比較例９〕
従来技術の特許文献２（特開平０６−１１６４６４公報）の表１の配合処方３で示されるサンプルを比較例９として作製した。もちろん当該比較例９においては、粘着性を低下させるための配合として、Ｎ，Ｎ−ジメチルオクタデシルアミンとパーフルオロエーテルが含有されているため、本願所定の表面処理操作は行なっていない。結果を下記表１に示した。
[* Comparative Example 9]
A sample shown in Formulation 3 of Table 1 of Patent Document 2 (Japanese Patent Laid-Open No. 06-116464) of the prior art was produced as Comparative Example 9. Of course, in the comparative example 9, N, N-dimethyloctadecylamine and perfluoroether are contained as a composition for reducing the adhesiveness, and therefore the predetermined surface treatment operation of the present application is not performed. The results are shown in Table 1 below.
以上の実験結果を下記表１に纏めて示した。 The above experimental results are summarized in Table 1 below.
なお、上記実施例６において、液状フッ素ゴムを４０重量部含有させた場合には、機械的強度が失われてしまい、シール材等としての本来のゴム機能が十分ではなかった。 In Example 6 described above, when 40 parts by weight of liquid fluororubber was contained, the mechanical strength was lost, and the original rubber function as a sealing material or the like was not sufficient.
また、本実施例で用いたパーオキサイド架橋タイプの商品名「ダイエルＬＴ３０３Ｌ」を、他のパーオキサイド架橋タイプの商品名「バイトンＧＬＴ２００Ｓ（デュポン社製）」のフッ素ゴムに変更させた場合であっても、上記表１に示される実施例と同様な効果が発現することが確認できた。 In addition, the product name “DAIEL LT303L” of the peroxide cross-linking type used in this example is changed to a fluorine rubber of the other product name “Viton GLT200S (manufactured by DuPont)” of the peroxide cross-linking type. In addition, it was confirmed that the same effects as in the examples shown in Table 1 were exhibited.
上記表１に示される実験結果より、本発明の効果は明らかである。
すなわち、本発明のフッ素ゴム組成物は、フッ素ゴム組成物のベースとなるパーオキサイド架橋タイプ（架橋剤としてパーオキサイドが用いられる）のフッ素ゴム１００重量部と、液状フッ素ゴム２０〜３０重量部と、カーボンブラック１〜７重量部を含むフッ素ゴム架橋物と、該フッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理して形成してなる非粘着層と、を有して構成されているので、ゴム硬度(Duro-A)５０以下の柔らかい硬度特性を有するフッ素ゴム組成物であって、従来レベルよりも格段と優れた非粘着性を有するフッ素ゴム組成物を実現させることができる。
From the experimental results shown in Table 1, the effect of the present invention is clear.
That is, the fluororubber composition of the present invention comprises a peroxide crosslinking type (peroxide is used as a crosslinking agent) 100 parts by weight of a fluororubber composition, and 20 to 30 parts by weight of a liquid fluororubber. A cross-linked fluororubber containing 1 to 7 parts by weight of carbon black, and a non-adhesive layer formed by surface-treating the surface of the cross-linked fluororubber with a surface treatment agent containing a phosphorus-based cross-linking agent. A fluororubber composition having a soft hardness characteristic with a rubber hardness (Duro-A) of 50 or less, and having a non-adhesiveness far superior to the conventional level. Can be realized.
例えば、フッ素ゴム組成物をシール部材として用いることができる各種の工業分野において利用可能である。 For example, it can be used in various industrial fields in which the fluororubber composition can be used as a sealing member.
Claims (12)
該フッ素ゴム架橋物の表面をリン系の架橋剤を含有する表面処理剤で表面処理して形成してなる非粘着層と、
を有することを特徴とするフッ素ゴム組成物。 Peroxide crosslinking type (peroxide is used as a crosslinking agent) 100 parts by weight of fluorine rubber, 20 to 30 parts by weight of liquid fluororubber, and 1 to 7 parts by weight of carbon black,
A non-adhesive layer formed by surface-treating the surface of the crosslinked fluororubber with a surface treatment agent containing a phosphorus-based crosslinking agent;
A fluororubber composition comprising:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101792329B1 (en) * | 2015-06-19 | 2017-11-20 | 한국가스공사 | Rubber composition for sealing material composing silica, carbonblack, and method thereof |
| CN112592548A (en) * | 2020-11-16 | 2021-04-02 | 上海如实密封科技有限公司 | Low-temperature-resistant fluororubber composition and application thereof |
| CN114752162A (en) * | 2021-11-26 | 2022-07-15 | 浙江户润密封系统有限公司 | Conductive fluororubber for oil seal and production method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11147891A (en) * | 1997-11-14 | 1999-06-02 | Nippon Mektron Ltd | Production of vulcanization accelerator for fluorine-containing elastomer |
| JP2000080278A (en) * | 1989-06-22 | 2000-03-21 | Dyneon Llc | Bonding composition with improved bonding performance |
| JP2000290430A (en) * | 1999-04-02 | 2000-10-17 | Nippon Zeon Co Ltd | Cross-linkable fluororubber composition, cross-linked product, rubber laminate and production of rubber laminate |
| JP2002144484A (en) * | 2000-11-13 | 2002-05-21 | Nichias Corp | Cushioning material having mold release characteristics and its manufacturing method |
| JP2002212370A (en) * | 2001-01-23 | 2002-07-31 | Nok Corp | Fluororubber vulcanization molded product |
| JP2003268349A (en) * | 2002-03-13 | 2003-09-25 | Nichias Corp | Fluororubber sealing material and its treating method |
| JP2004250520A (en) * | 2003-02-19 | 2004-09-09 | Nok Corp | Fluororubber composition |
| JP2005524729A (en) * | 2002-05-02 | 2005-08-18 | デュポン ダウ エラストマーズ エルエルシー | Curable base resistant fluoroelastomer |
| JP2010126721A (en) * | 2008-11-28 | 2010-06-10 | Arai Seisakusho Co Ltd | Fluororubber composition |
| JP2012097204A (en) * | 2010-11-02 | 2012-05-24 | Unimatec Co Ltd | Blend of fluorine-containing elastomer |
-
2012
- 2012-06-29 JP JP2012146571A patent/JP6121659B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000080278A (en) * | 1989-06-22 | 2000-03-21 | Dyneon Llc | Bonding composition with improved bonding performance |
| JPH11147891A (en) * | 1997-11-14 | 1999-06-02 | Nippon Mektron Ltd | Production of vulcanization accelerator for fluorine-containing elastomer |
| JP2000290430A (en) * | 1999-04-02 | 2000-10-17 | Nippon Zeon Co Ltd | Cross-linkable fluororubber composition, cross-linked product, rubber laminate and production of rubber laminate |
| JP2002144484A (en) * | 2000-11-13 | 2002-05-21 | Nichias Corp | Cushioning material having mold release characteristics and its manufacturing method |
| JP2002212370A (en) * | 2001-01-23 | 2002-07-31 | Nok Corp | Fluororubber vulcanization molded product |
| JP2003268349A (en) * | 2002-03-13 | 2003-09-25 | Nichias Corp | Fluororubber sealing material and its treating method |
| JP2005524729A (en) * | 2002-05-02 | 2005-08-18 | デュポン ダウ エラストマーズ エルエルシー | Curable base resistant fluoroelastomer |
| JP2004250520A (en) * | 2003-02-19 | 2004-09-09 | Nok Corp | Fluororubber composition |
| JP2010126721A (en) * | 2008-11-28 | 2010-06-10 | Arai Seisakusho Co Ltd | Fluororubber composition |
| JP2012097204A (en) * | 2010-11-02 | 2012-05-24 | Unimatec Co Ltd | Blend of fluorine-containing elastomer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101792329B1 (en) * | 2015-06-19 | 2017-11-20 | 한국가스공사 | Rubber composition for sealing material composing silica, carbonblack, and method thereof |
| CN112592548A (en) * | 2020-11-16 | 2021-04-02 | 上海如实密封科技有限公司 | Low-temperature-resistant fluororubber composition and application thereof |
| CN114752162A (en) * | 2021-11-26 | 2022-07-15 | 浙江户润密封系统有限公司 | Conductive fluororubber for oil seal and production method thereof |
| CN114752162B (en) * | 2021-11-26 | 2023-07-21 | 浙江户润密封系统有限公司 | Production method of conductive fluororubber for oil seal |
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