JP5282635B2 - Fluorine-containing curable composition and method for producing the same - Google Patents
Fluorine-containing curable composition and method for producing the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 41
- 239000011737 fluorine Substances 0.000 title claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 11
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 7
- -1 Dimethylphenylsilylene group Chemical group 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000005661 hydrophobic surface Effects 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 13
- 239000000295 fuel oil Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
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- 229920001971 elastomer Polymers 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 238000012856 packing Methods 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- BUCJHJXFXUZJHL-UHFFFAOYSA-N 1-ethylcyclohexan-1-ol Chemical compound CCC1(O)CCCCC1 BUCJHJXFXUZJHL-UHFFFAOYSA-N 0.000 description 1
- YTCHAEAIYHLXBK-UHFFFAOYSA-N 2-chloro-1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=C(Cl)C(F)(F)F YTCHAEAIYHLXBK-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- MQSZOZMNAJHVML-UHFFFAOYSA-N 3-phenylbut-1-yn-1-ol Chemical compound OC#CC(C)C1=CC=CC=C1 MQSZOZMNAJHVML-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QDGONURINHVBEW-UHFFFAOYSA-N dichlorodifluoroethylene Chemical group FC(F)=C(Cl)Cl QDGONURINHVBEW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- LBSKEFWQPNVWTP-UHFFFAOYSA-N pent-1-yn-3-ol Chemical compound CCC(O)C#C LBSKEFWQPNVWTP-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、低粘度で成形し易く、耐熱性、耐薬品性、耐溶剤性及び機械的強度に優れ、特に燃料油透過性を低減化し得る硬化物を与える含フッ素硬化性組成物及びその製造方法に関するものである。 The present invention relates to a fluorine-containing curable composition that is easy to mold with a low viscosity, is excellent in heat resistance, chemical resistance, solvent resistance and mechanical strength, and particularly provides a cured product that can reduce fuel oil permeability and its production. It is about the method.
１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する直鎖状パーフルオロポリエーテル化合物、１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物、及びヒドロシリル化反応触媒からなる組成物から、耐熱性、耐薬品性、耐溶剤性、離型性、撥水性、撥油性、耐候性等に優れた硬化物が得られることは、特許第２９９０６４６号公報等により知られている。
このような組成物は、ほとんどの用途において、これで十分な性能を有しているが、ＨＣ排出物低減化などの近年の環境問題に対応するため、さらに燃料油透過性の低減化が求められている。
しかしながら、このような燃料油透過性を低減化し得る硬化物を与える適当な含フッ素硬化性組成物がないのが実情である。
A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and at least two hydrogen atoms bonded to a silicon atom in one molecule It is possible to obtain a cured product excellent in heat resistance, chemical resistance, solvent resistance, releasability, water repellency, oil repellency, weather resistance, etc. from a composition comprising an organosilicon compound having a hydrosilylation reaction catalyst Patent No. 2990646 is known.
Such a composition has sufficient performance in most applications, but in order to cope with recent environmental problems such as reduction of HC emissions, further reduction of fuel oil permeability is required. It has been.
However, in reality, there is no appropriate fluorine-containing curable composition that provides a cured product that can reduce the fuel oil permeability.
本発明は、上記事情に鑑みなされたもので、低粘度で成形し易く、耐熱性、耐薬品性、耐溶剤性及び機械的強度に優れ、特に燃料油透過性を低減化し得る硬化物を与える含フッ素硬化性組成物及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a cured product that is easy to mold with low viscosity, excellent in heat resistance, chemical resistance, solvent resistance, and mechanical strength, and in particular, can reduce fuel oil permeability. It aims at providing a fluorine-containing curable composition and its manufacturing method.
本発明者等は、上記目的を達成するために検討した結果、
（ａ）下記一般式（１）
で表される数平均分子量３，０００〜１００，０００の直鎖状パーフルオロポリエーテル化合物：１００質量部、
（ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する含フッ素有機ケイ素化合物：（ａ）成分中のアルケニル基に対する（ｂ）成分中のＳｉＨ基のモル比が０．４〜５．０となる量、
（ｃ）白金族金属化合物からなるヒドロシリル化反応触媒：白金族金属換算で組成物全量に対して０．１〜１，０００ｐｐｍ、
（ｄ）シリカ系充填材：１〜１００質量部、
（ｅ）下記一般式（２）で示される
ＣＦ 2 ＝ＣＸＲ 1 （２）
（式中、Ｘは水素原子又はハロゲン原子であり、Ｒ 1 はハロゲン原子又は１〜１０個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基はヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を含む、溶融点が１００〜２００℃の熱可塑性フッ素系樹脂：１〜１００質量部
を含有してなることを特徴とする含フッ素硬化性組成物によれば、低粘度で成形し易く、耐熱性、耐薬品性、耐溶剤性及び機械的強度に優れ、特に燃料油透過性を低減化し得る硬化物を与えることを知見するとともに、該含フッ素硬化性組成物の製造に際し、（ｅ）成分を、該（ｅ）成分の溶融点以上の温度で、（ａ）成分、又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合することを特徴とする含フッ素硬化性組成物の製造方法によれば、各成分が均一な組成物が得られることを知見し本発明をなすに至った。
As a result of studies conducted by the inventors to achieve the above-described object,
(A) The following general formula (1)
A linear perfluoropolyether compound having a number average molecular weight of 3,000 to 100,000 represented by : 100 parts by mass,
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst comprising a platinum group metal compound : 0.1 to 1,000 ppm with respect to the total amount of the composition in terms of platinum group metal ,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) represented by the following general formula (2)
CF 2 = CXR 1 (2)
(In the formula, X is a hydrogen atom or a halogen atom, R 1 is a halogen atom or an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, or an aryl group. Or may be partially or completely halogenated.)
A fluorine-containing fluorine-containing resin comprising: 1 to 100 parts by mass of a thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C. containing a copolymer unit derived from at least one monomer having a structure According to the curable composition, it has been found that it is easy to mold with low viscosity, has excellent heat resistance, chemical resistance, solvent resistance and mechanical strength, and in particular provides a cured product that can reduce fuel oil permeability. In the production of the fluorine-containing curable composition, the component (e) is added to the component (a) or the mixture of the component (a) and the component (d) at a temperature equal to or higher than the melting point of the component (e). After mixing, according to the method for producing a fluorinated curable composition characterized in that the remaining components are added and mixed, it has been found that a uniform composition can be obtained for each component, and the present invention has been made. .
従って、本発明は、下記含フッ素硬化性組成物及びその製造方法を提供する。
請求項１：
（ａ）下記一般式（１）
で表される数平均分子量３，０００〜１００，０００の直鎖状パーフルオロポリエーテル化合物：１００質量部、
（ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する含フッ素有機ケイ素化合物：（ａ）成分中のアルケニル基に対する（ｂ）成分中のＳｉＨ基のモル比が０．４〜５．０となる量、
（ｃ）白金族金属化合物からなるヒドロシリル化反応触媒：白金族金属換算で組成物全量に対して０．１〜１，０００ｐｐｍ、
（ｄ）シリカ系充填材：１〜１００質量部、
（ｅ）下記一般式（２）で示される
ＣＦ 2 ＝ＣＸＲ 1 （２）
（式中、Ｘは水素原子又はハロゲン原子であり、Ｒ 1 はハロゲン原子又は１〜１０個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基はヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を含む、溶融点が１００〜２００℃の熱可塑性フッ素系樹脂：１〜１００質量部
を含有してなることを特徴とする含フッ素硬化性組成物。
請求項２：
（ｂ）成分が、１分子中に１個以上の一価のパーフルオロ基、一価のパーフルオロオキシ基、二価のパーフルオロ基又は二価のパーフルオロオキシ基を有し、かつケイ素原子に結合した水素原子を２個以上有する含フッ素有機ケイ素化合物であることを特徴とする請求項１記載の含フッ素硬化性組成物。
請求項３：
（ｄ）成分が、ＢＥＴ比表面積３０ｍ2／ｇ以上で表面が疎水化処理されたシリカ系充填材であることを特徴とする請求項１又は２記載の含フッ素硬化性組成物。
請求項４：
請求項１〜３のいずれか１項に記載の含フッ素硬化性組成物の製造に際し、（ｅ）成分を、該（ｅ）成分の溶融点以上の温度で、（ａ）成分、又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合することを特徴とする含フッ素硬化性組成物の製造方法。
Therefore, this invention provides the following fluorine-containing curable composition and its manufacturing method.
Claim 1:
(A) The following general formula (1)
A linear perfluoropolyether compound having a number average molecular weight of 3,000 to 100,000 represented by : 100 parts by mass,
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst comprising a platinum group metal compound : 0.1 to 1,000 ppm with respect to the total amount of the composition in terms of platinum group metal ,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) represented by the following general formula (2)
CF 2 = CXR 1 (2)
(In the formula, X is a hydrogen atom or a halogen atom, R 1 is a halogen atom or an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, or an aryl group. Or may be partially or completely halogenated.)
A fluorine-containing fluorine-containing resin comprising: 1 to 100 parts by mass of a thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C. containing a copolymer unit derived from at least one monomer having a structure Curable composition.
Claim 2 :
The component (b) has one or more monovalent perfluoro group, monovalent perfluorooxy group, divalent perfluoro group or divalent perfluorooxy group in one molecule, and a silicon atom fluorinated curable composition of claim 1 Symbol mounting, characterized in that a fluorine-containing organic silicon compound having at least two hydrogen atoms bonded to.
Claim 3 :
The fluorine-containing curable composition according to claim 1 or 2 , wherein the component (d) is a silica-based filler having a BET specific surface area of 30 m 2 / g or more and having a hydrophobic surface.
Claim 4 :
In producing the fluorine-containing curable composition according to any one of claims 1 to 3, the component (e) is added at a temperature equal to or higher than the melting point of the component (e), the component (a), or (a A method for producing a fluorine-containing curable composition, wherein the remaining component is added and mixed after being added to and mixed with a mixture of the component)) and the component (d).
本発明によれば、低粘度で成形し易く、耐熱性、耐薬品性、耐溶剤性及び機械的強度に優れ、特に燃料油透過性を低減化し得る硬化物を与える含フッ素硬化性組成物及びその製造方法を提供することができるので、自動車や化学機器、化学プラント等のゴム部材の用途に有用である。 According to the present invention, a fluorine-containing curable composition that provides a cured product that has low viscosity, is easy to mold, is excellent in heat resistance, chemical resistance, solvent resistance, and mechanical strength, and can reduce fuel oil permeability. Since the manufacturing method can be provided, it is useful for the use of rubber members such as automobiles, chemical equipment, and chemical plants.
以下、本発明を更に詳細に説明する。
［（ａ）成分］
本発明の（ａ）成分は、１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する数平均分子量が３，０００〜１００，０００の直鎖状パーフルオロポリエーテル化合物である。
Hereinafter, the present invention will be described in more detail.
[(A) component]
The component (a) of the present invention is a linear chain having a number average molecular weight of 3,000 to 100,000 having at least two alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain. It is a perfluoropolyether compound.
ここで、パーフルオロポリエーテル構造としては、
−ＣaＦ2aＯ−
（式中、ａは１〜６の整数である。）
の多数の繰り返し単位を含むもので、例えば下記一般式（２）で示されるものなどが挙げられる。
-C a F 2a O-
(In the formula, a is an integer of 1 to 6.)
And a compound represented by the following general formula (2).
上記式−ＣaＦ2aＯ−で示される繰り返し単位は、例えば下記の単位等が挙げられる。
なお、上記パーフルオロポリエーテル構造は、これらの繰り返し単位の１種単独で構成されていてもよいし、２種以上の組み合わせであってもよい。
−ＣＦ2Ｏ−
−ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−Ｃ（ＣＦ3）2Ｏ−
これらの中では、特に下記単位が好適である。
−ＣＦ2Ｏ−
−ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
Examples of the repeating unit represented by the above formula —C a F 2a O— include the following units.
In addition, the said perfluoropolyether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
-CF 2 O-
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3 ) CF 2 O-
-CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-
-C (CF 3) 2 O-
Of these, the following units are particularly preferred.
-CF 2 O-
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3 ) CF 2 O-
この（ａ）成分の直鎖状パーフルオロポリエーテル化合物におけるアルケニル基としては、炭素数２〜８、特に２〜６で、かつ末端にＣＨ2＝ＣＨ−構造を有するものが好ましく、例えば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等の末端にＣＨ2＝ＣＨ−構造を有する基、特にビニル基、アリル基等が好ましい。 As the alkenyl group in the linear perfluoropolyether compound of component (a), those having 2 to 8 carbon atoms, particularly 2 to 6 and having a CH 2 ═CH— structure at the terminal are preferable. A group having a CH 2 ═CH— structure at the terminal, such as a vinyl group or an allyl group, such as a group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group or a hexenyl group is preferred.
かかる（ａ）成分としては、下記一般式で表される化合物を挙げることができる。
ＣＨ2＝ＣＨ−（Ｘ）p−Ｒｆ1−（Ｘ’）p−ＣＨ＝ＣＨ2 （３）
ＣＨ2＝ＣＨ−（Ｘ）p−Ｑ−Ｒｆ1−Ｑ−（Ｘ’）p−ＣＨ＝ＣＨ2 （４）
［式中、Ｘは独立に−ＣＨ2−、−ＣＨ2Ｏ−、−ＣＨ2ＯＣＨ2−又は−Ｙ−ＮＲ1−ＣＯ−（但し、Ｙは−ＣＨ2−又は下記構造式（Ｚ）で示される基であり、Ｒ1は水素原子、メチル基、フェニル基又はアリル基である。）であり、Ｘ’は独立に−ＣＨ2−、−ＯＣＨ2−、−ＣＨ2ＯＣＨ2−又は−ＣＯ−ＮＲ2−Ｙ’−（但し、Ｙ’は−ＣＨ2−又は下記構造式（Ｚ’）で示される基であり、Ｒ2は水素原子、メチル基、フェニル基又はアリル基である。）
で表される基である。Ｒｆ1は二価のパーフルオロポリエーテル構造であり、上記式（２）、即ち−（ＣaＦ2aＯ）q−で示される繰り返し単位を含むものが好ましい。Ｑは炭素数１〜１５の二価の炭化水素基であり、エーテル結合を含んでいてもよく、具体的にはアルキレン基、エーテル結合を含んでいてもよいアルキレン基である。ｐは独立に０又は１である。］
Examples of the component (a) include compounds represented by the following general formula.
CH 2 = CH- (X) p -Rf 1 - (X ') p -CH = CH 2 (3)
CH 2 = CH- (X) p -Q-Rf 1 -Q- (X ') p -CH = CH 2 (4)
[-CH 2 wherein, X is independently -, - CH 2 O -, - CH 2 OCH 2 - or -Y-NR 1 -CO- (where, Y is -CH 2 - or the following structural formula (Z) And R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group.) And X ′ is independently —CH 2 —, —OCH 2 —, —CH 2 OCH 2 — or —CO—NR 2 —Y′— (where Y ′ is —CH 2 — or a group represented by the following structural formula (Z ′), and R 2 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group. .)
It is group represented by these. Rf 1 is a divalent perfluoropolyether structure, and preferably contains a repeating unit represented by the above formula (2), that is, — (C a F 2a O) q —. Q is a C1-C15 divalent hydrocarbon group which may contain an ether bond, specifically an alkylene group or an alkylene group which may contain an ether bond. p is independently 0 or 1. ]
このような（Ａ）成分の直鎖状パーフルオロポリエーテル化合物としては、特に下記一般式（１）で示されるものが好適である。
上記式（１）の直鎖状パーフルオロポリエーテル化合物は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による数平均分子量が３，０００〜１００，０００、特に３，０００〜３０，０００であることが望ましい。数平均分子量が３，０００未満では、必要とされる耐薬品性を満たすことができない可能性があるので好ましくなく、数平均分子量が１００，０００を超えると、他成分との相溶性に問題を生じる場合があるので好ましくない。 The linear perfluoropolyether compound of the above formula (1) preferably has a number average molecular weight of 3,000 to 100,000, particularly 3,000 to 30,000, as determined by gel permeation chromatography (GPC). . If the number average molecular weight is less than 3,000, the required chemical resistance may not be satisfied, which is not preferable. If the number average molecular weight exceeds 100,000, there is a problem in compatibility with other components. Since it may occur, it is not preferable.
一般式（１）で表される直鎖状パーフルオロポリエーテル化合物の具体例としては、下記式で表されるものが挙げられる。 Specific examples of the linear perfluoropolyether compound represented by the general formula (1) include those represented by the following formula.
更に本発明では、上記式（１）の直鎖状パーフルオロポリエーテル化合物を目的に応じた所望の数平均分子量に調節するため、予め上記したような直鎖状パーフルオロポリエーテル化合物を分子内にＳｉＨ基を２個含有する有機ケイ素化合物と通常の方法及び条件でヒドロシリル化反応させ、鎖長延長した生成物を（ａ）成分として使用することも可能である。
これらの直鎖状フルオロポリエーテル化合物は１種を単独で又は２種以上を組み合わせて使用できる。
Furthermore, in the present invention, in order to adjust the linear perfluoropolyether compound of the above formula (1) to a desired number average molecular weight according to the purpose, It is also possible to use, as a component (a), a product obtained by subjecting an organosilicon compound containing two SiH groups to a hydrosilylation reaction in the usual manner and conditions and extending the chain length.
These linear fluoropolyether compounds can be used singly or in combination of two or more.
［（ｂ）成分］
（ｂ）成分の含フッ素有機ケイ素化合物は上記（ａ）成分の架橋剤、鎖長延長剤として作用するものである。（ａ）成分との相溶性、分散性、硬化後の均一性を考慮して、１分子中に１個以上の一価のパーフルオロ基、一価のパーフルオロオキシ基、二価のパーフルオロ基又は二価のパーフルオロオキシ基を有していて、１分子中にケイ素原子に結合した水素原子を少なくとも２個、好ましくは３個以上有する有機ケイ素化合物であれば特に制限されるものではない。
[Component (b)]
The fluorine-containing organosilicon compound as component (b) acts as a crosslinking agent and chain extender as component (a). In consideration of compatibility with component (a), dispersibility, and uniformity after curing, one or more monovalent perfluoro group, monovalent perfluorooxy group, divalent perfluoro in one molecule There is no particular limitation as long as it is an organosilicon compound having a group or a divalent perfluorooxy group and having at least 2, preferably 3 or more hydrogen atoms bonded to a silicon atom in one molecule. .
上記一又は二価のパーフルオロ基、パーフルオロオキシ基としては、下記一般式で示される基を例示することができる。
ＣgＦ2g+1−
（式中、ｇは１〜２０、好ましくは２〜１０の整数である。）
−ＣgＦ2g−
（式中、ｇは１〜２０、好ましくは２〜１０の整数である。）
−（ＣＦ2Ｏ）c−（ＣＦ2ＣＦ2Ｏ）d−ＣＦ2−
（但し、ｃ及びｄはそれぞれ１〜５０の整数である。）
Examples of the monovalent or divalent perfluoro group and perfluorooxy group include groups represented by the following general formula.
C g F 2g + 1 −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
−C g F 2g −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
- (CF 2 O) c - (CF 2 CF 2 O) d -CF 2 -
(However, c and d are each an integer of 1 to 50.)
また、これらの一又は二価のパーフルオロアルキル基、パーフルオロオキシ基は、ケイ素原子に直接結合していてもよいが、ケイ素原子と二価の連結基を介して結合していてもよい。ここで、二価の連結基としては、アルキレン基、アリーレン基やこれらの組み合わせでも、あるいはこれらにエ一テル結合酸素原子やアミド結合、カルボニル結合等を介在するものであってもよく、例えば炭素数２〜１２のものが好ましく、下記の基等が挙げられる。
−ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2ＯＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2−ＮＨ−ＣＯ−
−ＣＨ2ＣＨ2ＣＨ2−Ｎ（Ｐｈ）−ＣＯ−（但し、Ｐｈはフェニル基である。）
−ＣＨ2ＣＨ2ＣＨ2−Ｎ（ＣＨ3）−ＣＯ−
−ＣＨ2ＣＨ2ＣＨ2−Ｏ−ＣＯ−
These mono- or divalent perfluoroalkyl groups and perfluorooxy groups may be directly bonded to the silicon atom, but may be bonded to the silicon atom via a divalent linking group. Here, the divalent linking group may be an alkylene group, an arylene group, or a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, or the like interposed therebetween. The thing of number 2-12 is preferable and the following group etc. are mentioned.
—CH 2 CH 2 —
—CH 2 CH 2 CH 2 —
-CH 2 CH 2 CH 2 OCH 2 -
—CH 2 CH 2 CH 2 —NH—CO—
—CH 2 CH 2 CH 2 —N (Ph) —CO— (where Ph is a phenyl group)
-CH 2 CH 2 CH 2 -N ( CH 3) -CO-
—CH 2 CH 2 CH 2 —O—CO—
また、この（ｂ）成分の有機ケイ素化合物における上記一価又は二価の含フッ素置換基以外のケイ素原子に結合した一価の置換基としては、例えばメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基、オクチル基、デシル基等のアルキル基；フェニル基、トリル基、ナフチル基等のアリール基；ベンジル基、フェニルエチル基等のアラルキル基：あるいはこれらの基の水素原子の一部が塩素原子、シアノ基等で置換された例えばクロロメチル基、クロロプロピル基、シアノエチル基等の炭素数１〜２０の非置換又は置換炭化水素基が挙げられる。 Examples of the monovalent substituent bonded to the silicon atom other than the monovalent or divalent fluorine-containing substituent in the organosilicon compound of component (b) include, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. Alkyl groups such as hexyl group, cyclohexyl group, octyl group and decyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenylethyl group: or one of hydrogen atoms of these groups Examples thereof include an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms such as a chloromethyl group, a chloropropyl group, and a cyanoethyl group in which a part is substituted with a chlorine atom, a cyano group, or the like.
（ｂ）成分の含フッ素有機ケイ素化合物は、環状でも鎖状でもよく、更に三次元網状でもよい。更に、この含フッ素有機ケイ素化合物における分子中のケイ素原子数は特に制限されないが、通常２〜６０、特に３〜３０程度が好ましい。 The fluorine-containing organosilicon compound as component (b) may be cyclic or chain-like, and may be a three-dimensional network. Further, the number of silicon atoms in the molecule in the fluorine-containing organosilicon compound is not particularly limited, but usually 2 to 60, particularly about 3 to 30 is preferable.
この様な有機ケイ素化合物としては、例えば下記のような化合物が挙げられ、これらの化合物は単独で使用しても、２種類以上を併用してもよい。なお、下記式でＭｅはメチル基、Ｐｈはフェニル基を示す。 Examples of such organosilicon compounds include the following compounds, and these compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.
（ｂ）成分の配合量は、通常（ａ）成分中に含まれるビニル基、アリル基、シクロアルケニル基等のアルケニル基１モルに対して、（ｂ）成分中のヒドロシリル基、即ちＳｉＨ基の合計量が好ましくは０．４〜５．０モル、より好ましくは０．８〜３．０モル供給する量が好適である。（ｂ）成分中の配合量が少なすぎると架橋度合いが不十分で硬化物の強度が不足する場合があり、多すぎても同様に硬化物の強度が不足する場合がある。また、この（ｂ）成分は１種単独で使用してもいいし、２種以上のものを併用してもよい。 The blending amount of the component (b) is usually that of the hydrosilyl group in the component (b), that is, the SiH group, with respect to 1 mol of the alkenyl group such as vinyl group, allyl group, cycloalkenyl group, etc. The total amount is preferably 0.4 to 5.0 mol, more preferably 0.8 to 3.0 mol. If the amount of component (b) is too small, the degree of crosslinking may be insufficient and the strength of the cured product may be insufficient, and if too large, the strength of the cured product may be insufficient. Moreover, this (b) component may be used individually by 1 type, and may use 2 or more types together.
［（ｃ）成分］
（ｃ）成分のヒドロシリル化反応触媒としては、遷移金属、例えばＰｔ、Ｒｈ、Ｐｄ等の白金族金属やこれら遷移金属の化合物などが好ましく使用される。本発明では、これら化合物が一般に貴金属の化合物で高価格であることから、比較的入手しやすい白金化合物が好適に用いられる。白金化合物としては、具体的に塩化白金酸又は塩化白金酸とエチレン等のオレフインとの錯体、アルコールやピニルシロキサンとの錯体、白金／シリカ、アルミナ又はカーボン等を例示することができるが、これらに限定されるものではない。
[Component (c)]
As the hydrosilylation reaction catalyst of component (c), transition metals, for example, platinum group metals such as Pt, Rh, and Pd, and compounds of these transition metals are preferably used. In the present invention, since these compounds are generally precious metal compounds and are expensive, platinum compounds that are relatively easily available are preferably used. Specific examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and olefin such as ethylene, a complex of alcohol or pinylsiloxane, platinum / silica, alumina or carbon. It is not limited to.
白金化合物以外の白金族金属化合物としては、ロジウム、ルテニウム、イリジウム、パラジウム系化合物等が知られており、例えばＲｈＣｌ（ＰＰｈ3）3、ＲｈＣｌ（ＣＯ）（ＰＰｈ3）2、ＲｈＣ１（Ｃ2Ｈ4）2、Ｒｕ3（ＣＯ）12、ＩｒＣｌ（ＣＯ）（ＰＰｈ3）2、Ｐｄ（ＰＰｈ3）4等が挙げられる（なお、Ｐｈはフェニル基を示す）。これらの触媒の使用量は、特に制限されるものではなく、触媒量で所望とする硬化速度を得ることができるが、経済的見地又は良好な硬化物を得るためには組成物全量に対して０．１〜１，０００ｐｐｍ（白金族金属換算）、より好ましくは０．１〜５００ｐｐｍ（同上）程度の範囲とするのがよい。 As platinum group metal compounds other than platinum compounds, rhodium, ruthenium, iridium, palladium compounds and the like are known. For example, RhCl (PPh 3 ) 3 , RhCl (CO) (PPh 3 ) 2 , RhC1 (C 2 H 4 ) 2 , Ru 3 (CO) 12 , IrCl (CO) (PPh 3 ) 2 , Pd (PPh 3 ) 4 (Ph represents a phenyl group). The amount of these catalysts used is not particularly limited, and a desired curing rate can be obtained with the amount of catalyst. However, in order to obtain an economical viewpoint or a good cured product, the total amount of the composition is used. It is good to set it as the range of about 0.1-1,000 ppm (platinum group metal conversion), More preferably about 0.1-500 ppm (same as the above).
［（ｄ）成分］
本発明の（ｄ）成分は、シリカ系充填材である。シリカ系充填材としては、石英やガラスを粉砕した粉砕シリカ、一旦溶融してから球粒状に成形する溶融シリカ、ケイ酸ソーダに鉱酸を加えて製造される湿式シリカ、シラン化合物を燃焼させて製造される乾式シリカなどが挙げられるが、機械的強度を向上させる観点から、ＢＥＴ比表面積が３０ｍ2／ｇ以上のシリカ系充填材が良く、湿式シリカ、乾式シリカがこれに該当するが、吸着水分が少ない乾式シリカが好適である。さらに、ポリマー成分との濡れ性を考慮すると、シリカフィラー表面が疎水化処理されたものが好ましい。シリカフィラー表面の疎水化処理が施されていないと、十分な機械的強度が得られない、組成物の粘度が異常に高くなるなどの弊害が生じやすい。
（ｄ）成分の配合量は、（ａ）成分１００質量部に対して１〜１００質量部である。１質量部未満ではフィラーの補強性効果が十分に得られない場合があり、１００質量部を超えると組成物の粘度が高くなり、作業性を損なう可能性がある。
[Component (d)]
The component (d) of the present invention is a silica-based filler. Silica-based fillers include pulverized silica obtained by pulverizing quartz and glass, fused silica that is once melted and then formed into spherical particles, wet silica produced by adding a mineral acid to sodium silicate, and silane compounds. Examples include dry silica produced, but from the viewpoint of improving mechanical strength, a silica-based filler having a BET specific surface area of 30 m 2 / g or more is good, and wet silica and dry silica fall under this category. Dry silica with low moisture is preferred. Furthermore, when the wettability with the polymer component is taken into consideration, it is preferable that the silica filler surface be subjected to a hydrophobic treatment. If the surface of the silica filler is not hydrophobized, it is liable to cause adverse effects such as insufficient mechanical strength and abnormally high viscosity of the composition.
(D) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (a) component. If the amount is less than 1 part by mass, the reinforcing effect of the filler may not be sufficiently obtained. If the amount exceeds 100 parts by mass, the viscosity of the composition increases, and workability may be impaired.
［（ｅ）成分］
本発明の（ｅ）成分は、溶融点が１００〜２００℃の熱可塑性フッ素系樹脂である。このような化合物は下記一般式（２）で示される
ＣＦ2＝ＣＸＲ1 （２）
（式中、Ｘは水素原子又はハロゲン原子であり、Ｒ1はハロゲン原子又は１〜１０個好ましくは１〜６個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基は酸素若しくは窒素のようなヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を含むものである。
[(E) component]
The component (e) of the present invention is a thermoplastic fluororesin having a melting point of 100 to 200 ° C. Such a compound is represented by the following general formula (2): CF 2 = CXR 1 (2)
(In the formula, X is a hydrogen atom or a halogen atom, R 1 is a halogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, a cyclic alkyl group, or an aryl group. The group may contain one or more heteroatoms such as oxygen or nitrogen, and may be partially or fully halogenated.)
And a copolymer unit derived from at least one monomer having the following structure.
このようなモノマーの例としては、テトラフルオロエチレン、ビニリデンフルオライド、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、２-クロロペンタフルオロプロペン、ジクロロジフルオロエチレン、パーフルオロアルキルビニルエーテル、たとえばＣＦ3ＯＣＦ＝ＣＦ2またはＣＦ3ＣＦ2ＣＦ2ＯＣＦ＝ＣＦ2、及びそれらの混合物などが挙げられる。 Examples of such monomers include tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, 2-chloropentafluoropropene, dichlorodifluoroethylene, perfluoroalkyl vinyl ethers such as CF 3 OCF═CF 2 or CF 3 CF 2 CF 2 OCF═CF 2 , and mixtures thereof.
また、フッ素化された上記した複数種のモノマーと共重合される、実質的にフッ素化されていないオレフィン系のモノマーとしては、下記一般式（３）で示される
ＣＨ2＝ＣＸＲ2 （３）
（式中、Ｘは水素原子又はハロゲン原子であり、 Ｒ2はＲ2及びＸが共にフッ素原子であることはないという条件付きで、水素原子、ハロゲン原子、１〜１０個好ましくは１〜６個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基は酸素若しくは窒素のようなヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を必要に応じて含んでもよい。
Further, as a substantially non-fluorinated olefin-based monomer copolymerized with the above-mentioned plural types of fluorinated monomers, CH 2 = CXR 2 (3) represented by the following general formula (3)
(In the formula, X is a hydrogen atom or a halogen atom, R 2 is a hydrogen atom, a halogen atom, 1-10, preferably 1-6, provided that R 2 and X are not both fluorine atoms. Alkyl groups having 1 carbon atom, cyclic alkyl groups, or aryl groups, these groups may contain one or more heteroatoms such as oxygen or nitrogen, and may be partially or fully halogenated May be.)
If necessary, it may contain copolymerized units derived from at least one monomer having the structure:
このようなモノマーの例としては、エチレン、プロピレン、１−ブテン、イソブテンなどが挙げられる。 Examples of such monomers include ethylene, propylene, 1-butene, isobutene and the like.
また、これらモノマー単位から誘導される共重合体の例としては、フッ化ビニリデンとヘキサフルオロプロピレンの共重合体、テトラフルオロエチレンとヘキサフルオロプロピレンとフッ化ビニリデンの共重合体、テトラフルオロエチレンとヘキサフルオロプロピレンとエチレン又はプロピレンの共重合体、テトラフルオロエチレンとプロピレンの共重合体、テトラフルオロエチレンとフッ化ビニリデンとプロピレンの共重合体などが挙げられる。 Examples of copolymers derived from these monomer units include copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. Examples thereof include a copolymer of fluoropropylene and ethylene or propylene, a copolymer of tetrafluoroethylene and propylene, a copolymer of tetrafluoroethylene, vinylidene fluoride, and propylene.
（ｅ）成分は、上記共重合体単位を含み、溶融点が１００〜２００℃、曲げ弾性率（試験方法：ＡＳＴＭＤ７９０）が５０〜３００ＭＰａ、好ましくは７０〜２５０ＭＰａの熱可塑性フッ素系樹脂が望ましい。
このような熱可塑性フッ素系樹脂としては、具体的には、テトラフルオロエチレン、ヘキサフルオロプロピレン、及びフッ化ビニリデンを共重合したものが挙げられる。上記の特性を得るためにはテトラフルオロエチレン３０〜７０質量％、ヘキサフルオロプロピレン１０〜３０質量％、フッ化ビニリデン５〜５０質量％の共重合体が例示される。
The component (e) includes the above-described copolymer unit, and a thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C. and a flexural modulus (test method: ASTM D790) of 50 to 300 MPa, preferably 70 to 250 MPa is desirable.
Specific examples of such thermoplastic fluororesins include those obtained by copolymerizing tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. In order to obtain the above characteristics, a copolymer of 30 to 70% by mass of tetrafluoroethylene, 10 to 30% by mass of hexafluoropropylene, and 5 to 50% by mass of vinylidene fluoride is exemplified.
このような熱可塑性フッ素系樹脂は商業的に入手可能であり、例えば、ダイニオン社（Ｄｙｎｅｏｎ）のＴＨＶシリーズ、ソルベイ社（Ｓｏｌｖａｙ）のＫＹＮＥＲ、セントラル硝子社のセフラルソフト、ダイキン社のダイエルサーモプラスチック、旭硝子社のＡＦＬＡＳなどが挙げられる。 Such thermoplastic fluororesins are commercially available, for example, Dyneon's THV series, Solvay's KYNER, Central Glass' Cefral Soft, Daikin's Daiel Thermoplastic, Examples include AFLAS from Asahi Glass.
（ｅ）成分の配合においては、（ｅ）成分の溶融点以上で行わなければならない。溶融点未満では、（ｅ）成分が固体状を維持する為、組成物中に均一に分散することができない。（ｅ）成分の溶融点以上で混合することによって、溶融した状態でせん断応力をかけ、均一分散させることが可能となる。
（ｅ）成分の配合量は、（ａ）成分１００質量部に対して１〜１００質量部である。好ましくは、３〜５０質量部である。少なすぎると、燃料透過低減化の十分な効果が得られない場合があり、多すぎると、硬化物のゴム特性を損なう可能性がある。
In blending the component (e), it must be carried out at a temperature higher than the melting point of the component (e). If it is less than the melting point, the component (e) maintains a solid state, and thus cannot be uniformly dispersed in the composition. By mixing at or above the melting point of the component (e), it is possible to apply a shear stress in the molten state and uniformly disperse it.
(E) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (a) component. Preferably, it is 3-50 mass parts. If the amount is too small, a sufficient effect of reducing fuel permeation may not be obtained. If the amount is too large, the rubber properties of the cured product may be impaired.
その他の成分
本発明の組成物には、（ａ）〜（ｅ）成分の他に本発明の効果を損なわない範囲で従来公知の各種の添加剤を配合することができる。このような成分としては、具体的に１−エチル−１−ヒドロキシシクロヘキサン、３−メチル−１−ブチン−３−オール、３，５−ジメチル−１−ヘキシン−３−オール、３−メチル−１−ペンチン−３−オール、フェニルブチノールなどのアセチレンアルコールや３−メチル−３−ペンテン−１−イン、３，５−ジメチル−３−ヘキセン−１−イン等のヒドロシリル化反応触媒の制御剤、酸化鉄、酸化セリウム、カーボンブラック等の顔料や、着色剤、染料、酸化防止剤、一部又は全てがフッ素変性されたオイル状化合物等が挙げられる。なお、これら任意成分の添加量は、本発明の効果を妨げない範囲で通常量とすることができる。
Other components In addition to the components (a) to (e), various conventionally known additives can be blended in the composition of the present invention as long as the effects of the present invention are not impaired. Specific examples of such components include 1-ethyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1. -Control agents for hydrosilylation reaction catalysts such as acetylene alcohols such as pentyn-3-ol and phenylbutynol, 3-methyl-3-penten-1-in, and 3,5-dimethyl-3-hexen-1-in, Examples thereof include pigments such as iron oxide, cerium oxide, and carbon black, colorants, dyes, antioxidants, oil-like compounds partially or entirely modified with fluorine. In addition, the addition amount of these arbitrary components can be made into a normal amount in the range which does not inhibit the effect of this invention.
組成物の製造方法
本発明の含フッ素硬化性組成物の製造に際しては、（ｅ）成分を、該（ｅ）成分の溶融点以上の温度で、（ａ）成分又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合する。
（ｅ）成分を、溶融点以上の温度で添加混合する意味は上述の通りである。また、（ｅ）成分を、（ａ）成分又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合する意味は、組成物がスコーチしやすくなるのを防止するためである。
Method for Producing Composition In producing the fluorine-containing curable composition of the present invention, component (e) is mixed with component (a) or component (a) and (d) at a temperature equal to or higher than the melting point of component (e). ) After adding and mixing to the mixture of components, the remaining components are added and mixed.
The meaning of adding and mixing the component (e) at a temperature equal to or higher than the melting point is as described above. In addition, after the component (e) is added to the component (a) or the mixture of the component (a) and the component (d), the remaining component is added and mixed to prevent the composition from being easily scorched. It is to do.
使用方法
本発明の組成物は、用途に応じて前記（ａ）〜（ｅ）成分の必須成分全てを１つの組成物として取り扱う、いわゆる１液タイプとして構成してもよいし、あるいは例えば前記（ａ）、（ｃ）、（ｄ）及び（ｅ）成分を一方の組成物とし、（ａ）、（ｂ）、（ｄ）及び（ｅ）成分を他方の組成物とする、いわゆる２液タイプとして構成し、使用にあたってこれを混合してもよい。
この場合も組成物の製造に際しては、上述の通り、（ｅ）成分を、該（ｅ）成分の溶融点以上の温度で、（ａ）成分又は（ａ）成分と（ｄ）成分の混合物に添加混合した後、残りの成分を添加混合し、１液タイプの組成物又は２液タイプの一方の組成物及び他方の組成物を製造することが好ましい。
Method of Use The composition of the present invention may be configured as a so-called one-component type in which all the essential components (a) to (e) are handled as one composition depending on the application, or, for example, ( A so-called two-component type in which the components a), (c), (d) and (e) are one composition and the components (a), (b), (d) and (e) are the other composition And may be mixed for use.
Also in this case, in the production of the composition, as described above, the component (e) is converted into the component (a) or the mixture of the component (a) and the component (d) at a temperature equal to or higher than the melting point of the component (e). After the addition and mixing, the remaining components are preferably added and mixed to produce one-component type composition or one-component type composition and the other composition.
また、組成物を溶解希釈して用いることも可能である。このような溶剤としては、（ａ）成分を溶解させ得るものが好ましく、例えばＣ4Ｆ10、Ｃ8Ｆ18、Ｃ4Ｆ9ＯＣＨ3、Ｃ4Ｆ9ＯＣ2Ｈ5、２−ｎ−ノナフルオロブチル−テトラフルオロフラン、トリス（ｎ−ノナフルオロブチル）アミン、メタキシレンヘキサフルオライド、パラキシレンヘキサフルオライド、ベンゾトリフルオライド等のフッ素化溶剤などが例示される。 It is also possible to use the composition after dissolving and diluting it. As such a solvent, those capable of dissolving the component (a) are preferable. For example, C 4 F 10 , C 8 F 18 , C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , 2-n- Examples include fluorinated solvents such as nonafluorobutyl-tetrafluorofuran, tris (n-nonafluorobutyl) amine, metaxylene hexafluoride, paraxylene hexafluoride, benzotrifluoride and the like.
本発明の含フッ素硬化性組成物は、常温にて放置するか、加熱することにより容易に硬化させることができるが、通常室温（例えば５〜３５℃）〜２００℃、１分間〜２４時間の範囲で熱的に硬化させるのが好ましく、このような硬化により、優れた特性を有するゴムを得ることができる。 The fluorine-containing curable composition of the present invention can be easily cured by allowing it to stand at room temperature or heating, but it is usually room temperature (for example, 5-35 ° C.) to 200 ° C., 1 minute to 24 hours. It is preferable to thermally cure in the range, and rubber having excellent characteristics can be obtained by such curing.
本発明の組成物は、種々の用途に利用することができる。すなわち、フッ素含有率が高いため、耐溶剤性、耐薬品性に優れ、また、透湿性も低く、低表面エネルギーを有するため、離型性、撥水性に優れており、耐油性を要求される自動車用ゴム部品、具体的にはフューエル・レギュレーター用ダイヤフラム、パルセーションダンパ用ダイヤフラム、オイルプレッシャースイッチ用ダイヤフラム、ＥＧＲ用ダイヤフラムなどのダイヤフラム類、キャニスタ用バルブ、パワーコントロール用バルブなどのバルブ類、クイックコネクタ用Ｏ−リング、インジェクター用Ｏ−リングなどのＯ−リング類、あるいは、オイルシール、シリンダヘッド用ガスケットなどのシール材、化学プラント用ゴム部品、具体的にはポンプ用ダイヤフラム、バルブ類、Ｏ−リング類、ホース類、パッキン類、オイルシール、ガスケットなどのシール材、インクジェットプリンタ用ゴム部品、半導体製造ライン用ゴム部品、具体的には薬品が接触する機器用のダイヤフラム、弁、Ｏ−リング、パッキン、ガスケットなどのシール材、低摩擦耐磨耗性を要求されるバルブ、分析、理化学機器用ゴム部品、具体的にはポンプ用ダイヤフラム、弁、シール部品、（Ｏ−リング、パッキンなど）、医療機器用ゴム部品、具体的にはポンプ、バルブ、ジョイント、また、テント膜材料、シーラント、成形部品、押し出し部品、被覆材、複写機ロール材料、電気用防湿コーティング材、センサー用ポッティング材、燃料電池用シール材、積層ゴム布などに有用である The composition of this invention can be utilized for various uses. That is, since the fluorine content is high, it has excellent solvent resistance and chemical resistance, and also has low moisture permeability and low surface energy, so it has excellent releasability and water repellency and requires oil resistance. Rubber parts for automobiles, specifically diaphragms for fuel regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, valves for canisters, valves for power control, quick connectors O-rings such as O-rings for injectors and O-rings for injectors, or sealing materials such as oil seals and gaskets for cylinder heads, rubber parts for chemical plants, specifically diaphragms for valves, valves, O- Rings, hoses, packings, oil seals, Sealing materials such as skets, rubber parts for inkjet printers, rubber parts for semiconductor production lines, specifically diaphragms for devices that come in contact with chemicals, valves, O-rings, packing, gaskets, low friction and abrasion resistance Valves that require wear, analysis, rubber parts for physics and chemistry equipment, specifically diaphragms for pumps, valves, seal parts, (O-rings, packing, etc.), rubber parts for medical equipment, specifically pumps, Useful for valves, joints, tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, electrical moisture-proof coating materials, sensor potting materials, fuel cell sealing materials, laminated rubber cloths, etc. is there
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、粘度は２５℃における値であり、下記式でＭｅはメチル基を表す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a viscosity is a value in 25 degreeC and Me represents a methyl group by the following formula.
［実施例１］
下記式（６）
Following formula (6)
［実施例２］
下記式（６）
[Example 2]
Following formula (6)
［比較例１］
実施例１において、ＴＨＶ５５０Ｇを配合しない以外は、同様な処方で組成物調製し、硬化シートを得た。得られた硬化シートの物性はＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１に準拠して測定した。また、燃料油透過性の測定は、実施例１と同じ方法で測定した。結果を表１に示す。
[Comparative Example 1]
In Example 1, a composition was prepared with the same formulation except that THV550G was not blended to obtain a cured sheet. The physical properties of the obtained cured sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by the same method as in Example 1. The results are shown in Table 1.
［比較例２］
実施例２において、ＴＨＶ５５０Ｇを配合しない以外は、同様な処方で組成物調製し、硬化シートを得た。得られたシートの物性はＪＩＳ Ｋ６２５３、ＪＩＳ Ｋ６２５１に準拠して測定した。また、燃料油透過性の測定は、実施例１と同じ方法で測定した。結果を表１に示す。
[Comparative Example 2]
In Example 2, a composition was prepared with the same formulation except that THV550G was not blended to obtain a cured sheet. The physical properties of the obtained sheet were measured according to JIS K6253 and JIS K6251. The fuel oil permeability was measured by the same method as in Example 1. The results are shown in Table 1.
実施例１と比較例１、並びに実施例２と比較例２とをそれぞれ比較すると、ＴＨＶ５５０Ｇを配合した実施例１、２の方が、燃料透過性が低くなっていることがわかる。 When Example 1 and Comparative Example 1 are compared with Example 2 and Comparative Example 2, respectively, it can be seen that Examples 1 and 2 containing THV550G have lower fuel permeability.
Claims (4)
で表される数平均分子量３，０００〜１００，０００の直鎖状パーフルオロポリエーテル化合物：１００質量部、
（ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する含フッ素有機ケイ素化合物：（ａ）成分中のアルケニル基に対する（ｂ）成分中のＳｉＨ基のモル比が０．４〜５．０となる量、
（ｃ）白金族金属化合物からなるヒドロシリル化反応触媒：白金族金属換算で組成物全量に対して０．１〜１，０００ｐｐｍ、
（ｄ）シリカ系充填材：１〜１００質量部、
（ｅ）下記一般式（２）で示される
ＣＦ 2 ＝ＣＸＲ 1 （２）
（式中、Ｘは水素原子又はハロゲン原子であり、Ｒ 1 はハロゲン原子又は１〜１０個の炭素原子を有するアルキル基、環状アルキル基、若しくはアリール基であり、これらの基はヘテロ原子を１個以上含んでいてもよく、また部分的に若しくは完全にハロゲン化されていてもよい。）
なる構造を有する少なくとも１種のモノマーから誘導される共重合単位を含む、溶融点が１００〜２００℃の熱可塑性フッ素系樹脂：１〜１００質量部
を含有してなることを特徴とする含フッ素硬化性組成物。 (A) The following general formula (1)
A linear perfluoropolyether compound having a number average molecular weight of 3,000 to 100,000 represented by : 100 parts by mass,
(B) a fluorine-containing organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule: the molar ratio of SiH groups in component (b) to alkenyl groups in component (a) is 0.4 to An amount of 5.0,
(C) Hydrosilylation reaction catalyst comprising a platinum group metal compound : 0.1 to 1,000 ppm with respect to the total amount of the composition in terms of platinum group metal ,
(D) Silica-based filler: 1 to 100 parts by mass,
(E) represented by the following general formula (2)
CF 2 = CXR 1 (2)
(In the formula, X is a hydrogen atom or a halogen atom, R 1 is a halogen atom or an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group, or an aryl group. Or may be partially or completely halogenated.)
A fluorine-containing fluorine-containing resin comprising: 1 to 100 parts by mass of a thermoplastic fluorine-based resin having a melting point of 100 to 200 ° C. containing a copolymer unit derived from at least one monomer having a structure Curable composition.
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