WO2022260057A1 - Curable composition - Google Patents
Curable composition Download PDFInfo
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- WO2022260057A1 WO2022260057A1 PCT/JP2022/023045 JP2022023045W WO2022260057A1 WO 2022260057 A1 WO2022260057 A1 WO 2022260057A1 JP 2022023045 W JP2022023045 W JP 2022023045W WO 2022260057 A1 WO2022260057 A1 WO 2022260057A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 176
- -1 silane compound Chemical class 0.000 claims abstract description 215
- 229910000077 silane Inorganic materials 0.000 claims abstract description 156
- 150000001875 compounds Chemical class 0.000 claims abstract description 127
- 125000000962 organic group Chemical group 0.000 claims abstract description 98
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 83
- 125000004429 atom Chemical group 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 125000001033 ether group Chemical group 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 230000005494 condensation Effects 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 91
- 125000000217 alkyl group Chemical group 0.000 claims description 73
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 46
- 125000002947 alkylene group Chemical group 0.000 claims description 45
- 125000001153 fluoro group Chemical group F* 0.000 claims description 36
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 26
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 25
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 24
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 23
- 150000004756 silanes Chemical class 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000002619 bicyclic group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 4
- 239000007859 condensation product Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 110
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 107
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 63
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 48
- 239000003431 cross linking reagent Substances 0.000 description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 38
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 36
- 239000002904 solvent Substances 0.000 description 24
- 239000000377 silicon dioxide Substances 0.000 description 20
- 125000000524 functional group Chemical group 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 17
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 125000003709 fluoroalkyl group Chemical group 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 7
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 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 7
- 125000005647 linker group Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 6
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 6
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 5
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004382 potting Methods 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 3
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000002292 Radical scavenging effect Effects 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000005998 bromoethyl group Chemical group 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000004956 cyclohexylene group Chemical group 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 239000000945 filler Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 3
- 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 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 description 2
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical group CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical group CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- QFWAHMAYYWUGTI-UHFFFAOYSA-N methyl-tris(prop-1-enoxy)silane Chemical compound CC=CO[Si](C)(OC=CC)OC=CC QFWAHMAYYWUGTI-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- MDEBUWYIMGRYKD-UHFFFAOYSA-N n-[diacetamido(3-aminopropyl)silyl]acetamide Chemical compound CC(=O)N[Si](NC(C)=O)(NC(C)=O)CCCN MDEBUWYIMGRYKD-UHFFFAOYSA-N 0.000 description 1
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XGIZTLFJCDBRDD-UHFFFAOYSA-N phenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C1=CC=CC=C1 XGIZTLFJCDBRDD-UHFFFAOYSA-N 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
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 125000005570 polycyclic cycloalkylene group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- CVYOLMWBQAWRMY-UHFFFAOYSA-N prop-1-enyl-bis(prop-1-en-2-yloxy)silane Chemical compound CC=C[SiH](OC(=C)C)OC(=C)C CVYOLMWBQAWRMY-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- OTTUQUOINFJTBJ-UHFFFAOYSA-N tetrakis(2-ethoxyethyl) silicate Chemical compound CCOCCO[Si](OCCOCC)(OCCOCC)OCCOCC OTTUQUOINFJTBJ-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical group CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical group CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- DBXDLSPMDNQBBQ-UHFFFAOYSA-N tris(2-methoxyethoxy)-phenylsilane Chemical compound COCCO[Si](OCCOC)(OCCOC)C1=CC=CC=C1 DBXDLSPMDNQBBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
Definitions
- the present invention relates to curable compositions.
- Patent Literature 1 describes a rubber having a cured film of a room-temperature-curable perfluoro(poly)ether composition formed on the surface thereof, and exhibits releasability, solvent resistance, chemical resistance, weather resistance, It is described that a rubber imparted with water repellency, oil repellency, etc. is provided.
- Patent Documents 2 to 7 describe moisture-curable compositions having a perfluoro(poly)ether structure.
- the cured product of the perfluoro(poly)ether composition can be used as a rubber with water repellency, oil repellency, etc., so when used as an adhesive, the stability of the bonded part can be maintained at a high level.
- fluorine compounds generally do not have good affinity with non-fluorinated substances. Therefore, there is always a demand for adhesives with good adhesion. Accordingly, an object of the present invention is to provide a curable composition that gives a cured product having excellent adhesion to various substrates.
- each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group; R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group; p is independently at each occurrence an integer from 0 to 3; provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2; q is independently at each occurrence an integer from 0 to 3; provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2; R 5 is independently at each occurrence a j+1 valent organic group; R 6 is independently at each occurrence -R 22 -R 21 -R 23 -; R 21 is independently at each occurrence a cycloalkylene-containing group; R 22 is independently at each occurrence a single bond or
- the curable composition of the present invention includes (a) a compound having two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group, and a perfluoro (poly) ether group.
- each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group; R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group; p is independently at each occurrence an integer from 0 to 3; provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2; q is independently at each occurrence an integer from 0 to 3; provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2; R 5 is independently at each occurrence a j+1 valent organic group; R 6 is independently at each occurrence -R 22 -R 21 -R 23 -; R 21 is independently at each occurrence a cycloalkylene-containing group; R 22 is independently at each occurrence a single bond or a divalent organic group; R 23 is independently at each
- a divalent to decavalent organic group means a divalent to decavalent group containing carbon.
- Such divalent to decavalent organic groups are not particularly limited, but include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
- the divalent organic group is not particularly limited, but includes a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.
- hydrocarbon group means a group containing carbon and hydrogen from which one hydrogen atom has been removed from the molecule.
- hydrocarbon groups include, but are not limited to, hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups. , an aromatic hydrocarbon group, and the like.
- the above "aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
- Hydrocarbon groups may also contain one or more ring structures.
- Such hydrocarbon groups may have one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain.
- the substituents of the "hydrocarbon group” are not particularly limited, but include, for example, halogen atoms; C 1-6 alkyl optionally substituted by one or more halogen atoms group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C 6-10 aryl groups and 5-10 membered heteroaryl groups.
- alkyl groups and phenyl groups can be unsubstituted or substituted unless otherwise specified.
- Substituents of such groups are not particularly limited, but for example, one or more groups selected from halogen atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups mentioned.
- hydrolyzable group means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being eliminated from the backbone of a compound by a hydrolysis reaction.
- R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group.
- Halogen atoms include fluorine, chlorine, bromine and iodine atoms, with chlorine atoms being preferred.
- the Si atoms bonded to at least one group selected from the group consisting of hydroxyl groups and hydrolyzable groups are present at both ends of the molecular main chain of the PFPE-containing silane compound (a).
- the molecular main chain of the PFPE-containing silane compound (a) represents the relatively longest linking chain in the molecule of the PFPE-containing silane compound (a).
- the perfluoro(poly)ether group represented by PFPE 1 above is independently -R F -R FE - at each occurrence.
- R F above is -(C f F 2f )-, where f is an integer of 1-10.
- the above RFE has the formula: -( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 - is a divalent fluoropolyether group represented by
- a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 or more and 200 or less, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 or more, more preferably 10 or more, for example 10 or more and 200 or less.
- each repeating unit enclosed in parentheses with subscript a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula.
- Each occurrence of X 10 is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. provided that when all X 10 are hydrogen atoms or chlorine atoms, at least one of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or greater.
- the perfluoro(poly)ether group having the structure represented by -R F -R FE - may be referred to as "PFPE 1 ".
- the curable composition of the present invention can have a low glass transition temperature (Tg) of the cured product.
- Tg glass transition temperature
- the -PFPE 1 - moiety herein is a polymer structure that combines one or more types of fluoroalkyl ether structures. a1 to a8 or the sum thereof refers to the number of repeating units of the fluoroalkyl ether structure in the polymer, but these values are average values in one structural unit in the polymer and are approximate values for those skilled in the art. is understood.
- PFPE 1 is represented by -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -
- the value of a1 is the (OCF 2 ) a1 unit of each -PFPE 1 -moiety.
- a1 and a2 are each independently integers of 0 or more and 200 or less, and in one preferred embodiment, a1 and a2 are each independently integers of 1 or more and 200 or less.
- the values of a1 and a2 are preferably independently integers of 1 or more and 50 or less.
- the sum of a1 and a2 is preferably 20 or more, more preferably 30 or more, and even more preferably 40 or more.
- a3, a4, a5, a6, a7 and a8 are each independently preferably an integer of 0 or more and 30 or less, more preferably an integer of 20 or less, and particularly preferably an integer of 10 or less and more preferably an integer of 5 or less, and may be 0.
- the sum of a3, a4, a5, a6, a7 and a8 is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less.
- repeating units may be linear or branched. Moreover, even if the repeating units have the same number of carbon atoms, PFPE 1 can have two or more types of different straight-chain or branched-chain structures at the same time. These repeating units are preferably linear.
- -(OC 8 F 16 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) -, - (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) -, - (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) -, - (OCF 2 CF 2 CF 2 CF 2 CF(CF 3 )CF 2
- - ( OC7F14 )- is - ( OCF2CF2CF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2CF2 ) - , - ( OCF2CF ( CF3 ) CF2CF2CF2 )-,- ( OCF2CF2CF ( CF3 ) CF2CF2CF2 )-, - ( OCF2CF2CF ( CF 3 ) CF 2 CF 2 )-, - (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ) )-, - (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ))-, etc.
- - (OCF12 )- is - ( OCF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2 ) - , - ( OCF2CF (CF 3 )CF 2 CF 2 CF 2 )-,-(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-,-(OCF 2 CF 2 CF(CF 3 )CF 2 )-,-(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )-,- It may be (OCF 2 CF 2 CF 2 CF(CF 3 ))- or the like, but is preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-.
- - ( OC5F10 )- is - ( OCF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2 )-, - ( OCF2CF ( CF3 ) CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 ))-, but preferably -( OCF 2 CF 2 CF 2 CF 2 CF 2 )—.
- -( OC4F8 )- is - ( OCF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2 )-, - ( OCF2CF ( CF3 ) CF2 )- , -( OCF2CF2CF ( CF3 ))-, -(OC( CF3 ) 2CF2 )-, -( OCF2C (CF3)2 ) - , -(OCF ( CF3 )CF( Any of CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-.
- -(OC 3 F 6 )- (that is, in the above formula, X 10 is a fluorine atom) is represented by -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -( OCF 2 CF(CF 3 ))—, preferably —(OCF 2 CF 2 CF 2 )—.
- -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, but is preferably -(OCF 2 CF 2 )- be.
- the unit denoted by -(C f F 2f )- is the structure located at the left end of PFPE1 .
- the value of f is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 6 or less, and more preferably an integer of 1 or more and 4 or less. More preferably, the value of f is the same value as the number of carbon atoms contained in any one of the repeating units of PFPE 1 .
- a unit represented by -(C f F 2f )- may be linear or branched.
- the unit represented by -(C f F 2f )- is, for example, -(CF 2 )-, -(CF 2 CF 2 )-, -(CF(CF 3 ))-, -(CF 2 CF 2 CF 2 )-,-(CF(CF 3 )CF 2 )-,-(CF 2 CF(CF 3 ))-,-(CF 2 CF 2 CF 2 )-,-(CF 2 CF( CF 3 )CF 2 )-, -(CF 2 CF 2 CF(CF 3 ))-, -(CF(CF 2 CF 3 )CF 2 )-, -(CF(CF 2 CF 3 )CF 2 )-, -(CF(CF 2 CF 3 )CF 2 )-, -(CF 2 C(CF 3 ) 2 CF 2 )- and other structures can be taken.
- PFPE 1 in the PFPE-containing silane compound (a) of the present invention can be prepared as a perfluoropolyether group, in addition to these repeating units, an oxygen atom and a perfluoroalkylene having 9 or more carbon atoms It may have a repeating unit consisting of a group.
- PFPE 1 has linear repeating units.
- the molecular mobility of the PFPE-containing silane compound (a) at low temperatures is less likely to decrease.
- the physical property values (e.g., elastic modulus at low temperature) of the PFPE-containing silane compound (a) can be less likely to decrease than the values at room temperature, so it is applicable to a wide temperature range. is also possible.
- elastic modulus indicates dynamic elastic modulus, more specifically storage elastic modulus.
- R FE is, at each occurrence, independently each of the following formulas (f1)-(f5): - (OC 3 F 6 ) a3 - (f1) [In the formula, a3 is an integer of 5 to 200. ]; - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f2) [Wherein, a4 and a3 are each independently an integer of 0 to 30, a2 and a1 are each independently an integer of 1 to 200, and the sum of a4, a3, a2 and a1 is 5
- the order of existence of each repeating unit enclosed in parentheses with subscript a4, a3, a2 or a1 is arbitrary in the formula.
- R 6 is OCF 2 or OC 2 F 4 and R 7 is selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of two or three groups independently selected from these groups, and g is an integer from 2-100.
- a2 is an integer of 1 to 200
- a6, a5, a4, a3 and a1 are each independently an integer of 0 to 200
- a6, a5, a4, a3, a2 and a1 is at least 5, and the order of existence of each repeating unit bracketed with a6, a5, a4, a3, a2 or a1 is arbitrary in the formula.
- a1 is an integer of 1 to 200
- a6, a5, a4, a3 and a2 are each independently an integer of 0 to 200
- It is a group represented by
- a3 is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35.
- the above formula (f1) is preferably a group represented by -(OCF 2 CF 2 CF 2 ) a3 - or -(OCF(CF 3 )CF 2 ) a3 -, more preferably -(OCF 2 It is a group represented by CF 2 CF 2 ) a3 —.
- a2 and a1 are each independently an integer of preferably 5 or more and 200 or less, more preferably 10-200.
- the sum of a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
- the above formula ( f2 ) is preferably - ( OCF2CF2CF2CF2 ) a4- ( OCF2CF2CF2 ) a3- ( OCF2CF2 ) a2- ( OCF2 ) It is a group represented by a1- .
- formula (f2) may be a group represented by -(OC 2 F 4 ) a2 -(OCF 2 ) a1 -.
- R 6 is preferably OC 2 F 4 .
- R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or 2 independently selected from these groups, or A combination of three groups, more preferably a group selected from OC 3 F 6 and OC 4 F 8 .
- the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, but for example -OC 2 F 4 OC 3 F 6 -, -OC 2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ , -OC2F4OC2F4OC _
- g is an integer of preferably 3 or more, more preferably 5 or more. Said g is preferably an integer of 50 or less.
- OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear. is a chain.
- the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
- a2 is preferably an integer of 1-100, more preferably an integer of 5-100.
- the sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- a1 is preferably an integer of 1 to 100, more preferably an integer of 5 or more and 100 or less.
- the sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- R FE is a group represented by the formula (f1).
- R FE is a group represented by the formula (f2).
- R FE is a group represented by the formula (f3).
- R FE is a group represented by the formula (f4).
- R FE is a group represented by the formula (f5).
- the values of a1, a2, a3, a4, a5, a6, a7 and a8 are not particularly limited as long as they satisfy their respective ranges.
- the rubber properties can be easily maintained even at low temperatures, and the composition can be made suitable for use at low temperatures.
- the use of many structures represented by -(OC 2 F 4 ) a2 - is more advantageous for the formation of hardened products that are resistant to decomposition at high temperatures.
- the structure and composition of PFPE 1 can be appropriately adjusted according to the physical properties required for the final application.
- the ratio of a2 to a1 is preferably 0.1 to 10, more preferably 0.1. 2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85.
- a2/a1 ratio is preferably 0.1 to 10, more preferably 0.1. 2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85.
- the surface treatment layer obtained from this compound has improved slipperiness, friction durability and chemical resistance (for example, durability against artificial perspiration).
- the smaller the a2/a1 ratio the more improved the lubricity and friction durability of the surface treatment layer.
- the stability of the compound can be further enhanced. The higher the a2/a1 ratio, the more stable the compound.
- the a2/a1 ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.
- the a2/a1 ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.
- PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -(OC 3 F 6 ) a3 -(OC 4 F 8 ) a4 - (wherein , f is an integer of 1 or more and 4 or less, a1 and a2 are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and a3 and a4 are each independently an integer of 0 or more and 30 or less, and the order of existence of each repeating unit enclosed in parentheses with subscript a1, a2, a3 or a4 is arbitrary in the formula).
- PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OCF 2 CF 2 ) a2 -(OCF 2 CF 2 CF 2 ) a3 -(OCF 2 CF 2 CF 2 ) a4 -.
- PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -, where f is 1 or 2 and a1 and a2 are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less; is optional within).
- PFPE 1 has the formula: -(C f F 2f )-(OCF 2 ) a1 -(OCF 2 CF 2 ) a2l -(OCF(CF 3 )) a2′ -(OCF 2 CF 2 CF 2 ) a3l -(OCF 2 CF(CF 3 ) ) a3′ -(OCF(CF 3 )CF 2 ) a3′′ -(OCF 2 CF 2 CF 2 ) a4 ⁇
- f is an integer of 1 or more and 4 or less
- a1, a2l, a2′, a3l, a3′, a3′′ and a4 are each independently an integer of 0 or more and 200 or less
- a2l and a2 ' is equal to a2
- the sum of a3l, a3' and a3" is equal to a3, the sum of a1, a2l
- PFPE 1 has branched perfluoroalkyl groups, particularly perfluoropropyl groups.
- Specific examples include the following structures. - (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 ) - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 )) - - (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 CF 2 ) - - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 ) )-
- the cured product of the curable composition of the present invention is difficult to decompose at high temperatures.
- the phrase "hardly decomposing at high temperatures” means that the 1% decomposition temperature of the cured product is relatively high. That is, the curable composition of the present invention can contribute to the formation of cured products that can be used over a wide temperature range.
- 1% decomposition temperature means the temperature at which 1% by mass of the cured product decomposes with respect to the entire cured product.
- the 1% decomposition temperature means a value measured by thermogravimetry/differential heat (TG/DTA), specifically, in an air atmosphere, with a temperature increase rate of 10 ° C./min, 25 ° C. to 600 ° C. measured in the range of Examples of the TG/DTA include DTG-60 manufactured by SHIMADZU.
- the number average molecular weight of the -PFPE 1 - moiety can range from 2,000 to 200,000, preferably from 3,000 to 100,000.
- the number average molecular weight is a value measured by 19 F-NMR.
- the number average molecular weight of the -PFPE 1 - moiety can range from 2,000 to 10,000, preferably from 2,000 to 5,000.
- the viscosity of the curable composition can be low and the handleability can be improved.
- the curable composition having the number average molecular weight of the -PFPE 1 - moiety as described above is also advantageous from the viewpoint of suppressing the viscosity when used together with a solvent to form a solution.
- the number average molecular weight of the -PFPE 1 - moiety can range from 10,000 to 100,000, preferably from 10,000 to 50,000.
- physical properties such as elongation properties after curing of the curable composition can be improved.
- k is not particularly limited as long as the PFPE-containing silane compound (a) can be prepared, but it is preferably an integer of 1 or more and 5 or less. This makes it possible to provide a large number of moieties that are thought to contribute to deep-part curability of the curable composition in one molecule.
- R5 is a group that acts as a linker connecting the terminal silicon atom and the amide bond.
- R5 independently at each occurrence represents a j+ 1 valent organic group.
- the value of j represents the number of silicon atom-containing groups present at the ends of the PFPE-containing silane compound (a), and is in the range of 1-9.
- R 5 independently at each occurrence represents a divalent to decavalent organic group. Therefore, R 5 may be any group as long as it is a divalent to decavalent organic group in which the PFPE-containing silane compound (a) can stably exist.
- the definition of the “divalent to decavalent organic group” is as shown above.
- R 5 examples include those described as moieties corresponding to R 5 in formulas (A) to (D) described later.
- R 5 is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group. Therefore, the value of j is preferably 1-6, more preferably 1-3, even more preferably 1.
- R 5 preferably does not have a heteroatom or aromatic structure on the molecular chain directly connecting the silicon atom and the amide bond, and more preferably does not have an aromatic structure.
- R 5 is preferably an optionally heteroatom-containing aliphatic hydrocarbon group, more preferably an unsubstituted aliphatic hydrocarbon group, and still more preferably a divalent alkylene group.
- R 5 is more preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, and more specifically, methylene group, ethylene group, propylene group, methylethylene group, butylene group, hexa methylene group and the like.
- the two R5's present in the PFPE - containing silane compound (a) may be the same or different, but are preferably the same to facilitate preparation of the compound.
- R 21 is independently on each occurrence a cycloalkylene-containing group
- R 22 is independently on each occurrence a single bond or a divalent organic group
- R 23 is independently on each occurrence Independently, it is a single bond or a divalent organic group.
- the perfluoro(poly)ether group-containing silane compound contained in the curable composition of the present invention contains a cycloalkylene group between amide bonds. Since the value of k in general formula (I) is 1 or more, the compound represented by general formula (I) has at least one alicyclic structure group represented by R 6 .
- the present invention is based on the discovery that the introduction of an alicyclic structure into a PFPE-containing compound enhances adhesion to a substrate when used as an adhesive.
- cycloalkylene means a divalent saturated monocyclic or polycyclic aliphatic hydrocarbon. Such cycloalkylenes may optionally have ring hydrogen atoms replaced by one or more substituents.
- the substituents of the above cycloalkylene are not particularly limited, but for example, a halogen atom, a C 1-6 alkyl group optionally substituted with one or more halogen atoms, a C 2-6 alkenyl group, a C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 aryl group and 5 One or more groups selected from to 10-membered heteroaryl groups are included.
- said substituent is a C 1-6 alkyl group, preferably a methyl or ethyl group, more preferably a methyl group.
- the cycloalkylene-containing group may contain a plurality of cycloalkylenes, preferably 1 to 3, more preferably 1 or 2 cycloalkylenes.
- the cycloalkylene-containing group contains one cycloalkylene.
- the cycloalkylene-containing group contains two cycloalkylenes.
- R 21 is independently at each occurrence a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms.
- the above polycyclic cycloalkylene may be any of condensed type, spiro type, and bridged type.
- the cycloalkylene is monocyclic.
- the cycloalkylene is bicyclic.
- the cycloalkylene is tricyclic.
- each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group
- each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group.
- R 22 and R 23 above are directly attached to the cycloalkylene of R 21 .
- R 21 is independently at each occurrence a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms
- R 22 at each occurrence is Each independently is a single bond or a C 1-6 alkylene group
- each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group.
- R 21 is optionally substituted cyclohexanediyl
- R 22 and R 23 above are each independently a single bond or a C 1-6 alkylene group, meta or para to each other.
- the optionally substituted cyclohexanediyl is unsubstituted.
- the optionally substituted cyclohexanediyl is substituted by a C 1-6 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group.
- the number of such substituents may preferably be 1-5, more preferably 1-3.
- R 21 includes optionally substituted alkylenebis(cyclohexyl), preferably methylenebis(cyclohexyl), and R 22 and R 23 above are each independently a single bond or C 1-6 alkylene groups and are attached to each other at the 4,4' positions.
- an optionally substituted alkylenebis(cyclohexyl) is unsubstituted.
- the optionally substituted alkylenebis(cyclohexyl) is substituted by a C 1-6 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group.
- the number of such substituents may preferably be 2-5, more preferably 2-4.
- R 6 is the following group in which a ring hydrogen atom may be substituted: [Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
- R 6 is the following group in which a ring hydrogen atom may be substituted: [Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
- R 6 include the following groups.
- the R6 moiety is, for example, a compound having a reactive functional group at both ends of PFPE1 that can form a bond with R5 or R6 via an amide bond ( hereinafter, such a compound is referred to as a "PFPE modified form").
- PFPE modified form a compound having an ester group at the end thereof is sometimes referred to as a "modified PFPE ester", and can be introduced by reacting a diamine.
- the number of R6 moieties in the molecular chain (in other words the value of k) can be manipulated by adjusting the quantity relationships of the reactants.
- the PFPE-containing silane compound (a) has a structure represented by R 3 p R 4 3-p Si— or R 3 q R 4 3-q Si— as its molecular terminal structure.
- the definitions of R 3 , R 4 , p and q are as given above. That is, the PFPE-containing silane compound (a) has a structure in which at least one hydroxyl group or hydrolyzable group is bonded to a silicon atom at the molecular terminal.
- "Hydrolyzable group” has the same meaning as above. Different groups may be mixed in R 3 and R 4 in one molecule or in one molecular terminal structure.
- the PFPE-containing silane compound (a) has at least two terminal structures.
- the value of j is one. That is, in a preferred embodiment, the PFPE-containing silane compound (a) is a linear molecule having silicon at both ends to which hydrolyzable groups are bonded.
- each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group.
- R 3 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
- R 4 is a hydroxyl group or a hydrolyzable group, preferably a hydrolyzable group.
- hydrolyzable groups are as described above, among these, especially -OR, where R represents a substituted or unsubstituted alkyl group of 1 to 4 carbon atoms ), ie an alkoxy group.
- alkoxy groups include unsubstituted alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy and isobutoxy groups; substituted alkoxy groups such as chloromethoxy groups. Among them, a methoxy group or an ethoxy group is more preferable.
- the PFPE-containing silane compound (a) has a structure in which two or three hydroxyl groups or hydrolyzable groups are bonded to silicon atoms.
- the structure of the molecular terminal of the PFPE-containing silane compound (a) is preferably a trialkoxysilyl group, more preferably a trimethoxysilyl group.
- R 7 are all hydrogen atoms
- R 5 is a divalent alkylene group
- R 6 is a group having two cyclohexyl groups
- j is 1. and p and q are zero.
- the PFPE-containing silane compound (a) may be used singly or as a mixture of two or more.
- a structure in which a silyl group and optionally a linker moiety are not introduced at one or both terminal portions of the modified PFPE or the compound in which the modified PFPE is linked at R 6 can result.
- a compound that does not contain a silyl group on at least one of both ends of the molecular chain composed of PFPE 1 may be referred to as "non-terminated modified PFPE".
- non-terminated modified PFPE The higher the purity of the compound represented by formula (I), the better.
- Non-terminated PFPE modifications may be included.
- a compound having a structure in which an ester group, a hydroxyl group, or an alkylene-OH group is bonded may be included.
- the purity of the PFPE-containing silane compound (a) used in the preparation of the curable composition can be measured by the extent to which silyl groups are introduced at the terminals, or the degree of terminalization with silane.
- the termination rate is obtained from the ratio of the portion having a silyl group introduced into the portion to the total amount of substances not sandwiched by R 6 among the 1 portion of PFPE.
- the termination rate is preferably 90 mol % or more, more preferably 93 mol % or more, and even more preferably 95 mol % or more. Within this range, the compound having both ends of the molecule silylated can be contained in a sufficient amount, and the function as a curable composition can be sufficiently exhibited.
- the termination ratio can be determined, for example, by NMR measurement.
- the CF 2 group present at the end of PFPE 1 that is, the CF 2 group adjacent to the amide group bonded to the linker was measured by 19 F NMR to determine which It is possible to determine the extent to which silyl groups have been introduced.
- the termination rate can be calculated by NMR measurement of the different portions depending on whether the terminal is silylated or not, and the method is as follows. well known to those skilled in the art.
- the PFPE-containing silane compound (a) is preferably at least one compound represented by Formula (A), (B), (C), or (D).
- Each group and subscript appearing in the following formulas can correspond to the groups and subscripts appearing in the above general formula, respectively, and a person skilled in the art can grasp the correspondence between them.
- the PFPE-containing silane compound (A) represented by the above formulas (A), (B), (C) and (D) will be described below.
- PFPE 1 , R 6 and R 7 have the same meanings as above.
- each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group.
- Hydrolyzable groups are as defined above. That is, R 13 can correspond to R 4 in the above general formula.
- each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. That is, R 14 can correspond to R 3 in the above general formula.
- each occurrence of R 11 independently represents a hydrogen atom or a halogen atom.
- a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
- each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group and propyl group.
- R 11′′ , R 12′′ , R 13′′ and R 14′′ have the same meanings as R 11 , R 12 , R 13 and R 14 , respectively.
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group means that n1 is an integer of 1 to 3 and (-SiR 13 n1 R 14 3-n1 ) or (-SiR 13′′ n1 R 14′′ 3-n1 ).
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n1 ) unit or each (-SiR 13′′ n1 R 14′′ 3-n1 ) unit, It is preferably 1 to 3, more preferably 3. wherein at least two n1's are integers from 1 to 3, ie not all n1's are 0 at the same time. That is, in the formula, there are at least two R 13 or R 13′′ bonded Si atoms.
- the —SiR 13 n1 R 14 3-n1 structure ( That is, there are at least two structures selected from the group consisting of -SiR 13 " moieties) and -SiR 13'' n1 R 14'' 3-n1 structures where n1 is 1 or greater (ie, -SiR 13'' moieties). That is, n1 can correspond to the value of 3-p or 3-q in the above general formula.
- Si atoms bonded to at least one group selected from the group consisting of hydroxyl groups and hydrolyzable groups are present at both ends of the molecular main chain. That is, in formula (A), at least one -SiR 13 n1 R 14 3-n1 structure (i.e., -SiR 13 moiety) in which n1 is 1 or more, and at least one in which n1 is 1 or more- A SiR 13′′ n1 R 14′′ 3-n1 structure (ie, the —SiR 13′′ portion) is present.
- each X 1 independently represents a single bond or a divalent to decavalent organic group linked to the amide bond.
- the X 1 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (A), and a base material. It is understood to be part of the linker connecting the silane moieties that provide the binding ability. Therefore, X 1 may be a single bond or any organic group as long as the compound represented by formula (A) can exist stably. That is, it is understood that X 1 corresponds to part of R 5 in the above general formula together with X 2 and a hydrocarbon group linked thereto, which will be described later.
- the group described as X 1 is bonded to the amide bond adjacent to the group represented by PFPE 1 on the left side of the description, and to the parenthesized group on the right side.
- the group described as X 1 is a group that binds in the opposite direction, for example, -C 6 H 4 in the case of -CO-C 6 H 4 -, as long as it can be prepared as a stable compound. Included are those in which the phenylene group is attached to the amide bond adjacent to the group represented by PFPE 1 , described as -CO-.
- X 1 can be X e .
- X e represents a single bond or a divalent to decavalent organic group, preferably a single bond or —C 6 H 4 — (that is, —phenylene—, hereinafter referred to as a phenylene group), —O— (ether group ), —CO— (carbonyl group), —NR 40 —, and —SO 2 —, and represents a divalent to decavalent organic group having at least one selected from the group consisting of;
- Each R 40 above independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
- the above -C 6 H 4 -, -CO-, -NR 40 - or -SO 2 - is preferably contained in the molecular main chain of the PFPE-containing silane compound (A).
- X e is more preferably a single bond or —C 6 H 4 —, —CONR 40 —, —CONR 40 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —O—CO having at least one selected from the group consisting of -NR 40 -, -SO 2 NR 40 -, -SO 2 NR 40 -C 6 H 4 -, -SO 2 -, and -SO 2 -C 6 H 4 - It represents a divalent to decavalent organic group.
- ⁇ 1 is an integer of 1 to 9 and may vary depending on the valence of X1.
- ⁇ 1 is the value obtained by subtracting 1 from the valence of X1.
- ⁇ 1 is 1 when X 1 is a single bond or a divalent organic group. That is, ⁇ 1 can correspond to the value of j in the above general formula.
- X 1 is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group and ⁇ 1 is 1-3.
- X 1 is a divalent organic group and ⁇ 1 is 1.
- the formula (A) is represented by the following formula (A').
- Examples of X 1 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound.
- R 31 represents a single bond, —(CH 2 ) s′ — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s′ —, s′ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2;
- X a represents -(X b ) l' -, X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 33 ) 2 -, -( selected from the group consisting of Si(R 33 ) 2 O) m'
- R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group may be substituted by a substituent of However, when R 31 is a single bond or p′ is 0, X a is not —CONR 34 — or —NR 34 —.
- l' in the above formula is 1.
- X 1 above is -(R 31 ) p' -(X a ) q' -R 32 -.
- R 32 represents a single bond, -(CH 2 ) t' - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t' -.
- t' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3.
- R 32 (typically a hydrogen atom in R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group; may have been
- X 1 above is single bond, a C 1-20 alkylene group, —R 31 —X c —R 32 —, or —X d —R 32 — [In the formula, R 31 and R 32 have the same meanings as above. ] can be
- the alkylene group is a group having a -(C ⁇ H 2 ⁇ )- structure, may be substituted or unsubstituted, and may be linear or branched.
- X 1 above is single bond, a C 1-20 alkylene group, —(CH 2 ) s′ —X c —, —(CH 2 ) s′ —X c —(CH 2 ) t′ —, -X d -, or -X d -(CH 2 ) t' - [In the formula, s' and t' have the same meanings as described above. ] is.
- X 1 is -X f -, —X f —C 1-20 alkylene group, -Xf- ( CH2 ) s' - Xc- , —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ — —X f —X d —, or —X f —X d —(CH 2 ) t′ — is.
- s' and t' have the same meanings as above.
- X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group.
- a hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably unsubstituted there is
- Xf may be linear or branched, preferably linear.
- X c is -O-, -S-, -C(O)O-, -CONR 34- , -O-CONR 34- , —Si(R 33 ) 2 —, —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —, —O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —, —O—(CH 2 ) u′ —Si(R 33 ) 2 —O—Si(R 33 ) 2 —CH 2 CH 2 —Si(R 33 ) 2 —O—Si(R 33 ) 2 —, —O—(CH 2 ) u′ —Si(OCH 3 ) 2 OSi(OCH 3 ) 2 —, —(CH 2 ) u′ —(Si(R 33 ) 2 O) m
- X d is -S-, -C(O)O-, —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —, —(CH 2 ) u′ —N(R 34 )—, -(o-, m- or p-phenylene)-Si(R 33 ) 2 -, -CONR 34- , —CONR 34 —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —, —CONR 34 —(CH 2 ) u′ —N(R 34 )—, or —CONR 34 —(o-, m- or p-phenylene)—Si(R 33 ) 2 — [In the formula, each symbol has the same meaning as described above. ] represents
- the above X 1 is -X f -, —X f —C 1-20 alkylene group, -Xf- ( CH2 ) s' - Xc- , —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ — —X f —X d —, or —X f —X d —(CH 2 ) t′ — [In the formula, X f , s′ and t′ have the same meanings as above.
- R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group). ] It is a group represented by
- X 1 above is -Xf- ( CH2 ) s' - Xc- , —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ — —X f —X d —, or —X f —X d —(CH 2 ) t′ —
- X f , s′ and t′ have the same meanings as above.
- X c is —CONR 34 —
- X d is -CONR 34 -
- Each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group).
- ] is a group represented by
- X 1 above is single bond, a C 1-20 alkylene group, —(CH 2 ) s′ —X c —(CH 2 ) t′ —, or —X d —(CH 2 ) t′ — [In the formula, each symbol has the same meaning as described above. ] can be However, at this time, X d is not -CONR 34 -.
- X 1 above is single bond, a C 1-20 alkylene group, —(CH 2 ) s′ —O—(CH 2 ) t′ —, —(CH 2 ) s′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ —, —(CH 2 ) s′ —O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ — or —(CH 2 ) s' -O-( CH2 ) t' -Si( R33 ) 2- ( CH2 ) u' - Si ( R33 ) 2- ( CvH2v )- [Wherein, R 33 , m′, s′, t′ and u′ have the same meanings as above, v is an integer of 1 to 20,
- -(C v H 2v )- may be linear or branched, for example -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2- , -CH(CH 3 )-, -CH(CH 3 )CH 2 -.
- the above X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) may have been
- the X 1 group can be other than a —O—C 1-6 alkylene group.
- X 1 groups include, for example, the groups: [wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CF 2 O(CH 2 ) 3 —, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, and -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 - (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.) is a group selected from E is -(CH 2 )
- X 1 above include: single bond, —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2
- X 1 is single bond, —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 OCF 2 CHFOCF 2 —, —CH 2 OCF 2 CHFOCF 2 CF 2 —, -CH2OCF2CHFOCF2CF2CF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2CF2- , _ _ _ _ _ -CH2OCH2CF2CF
- X 1 is single bond, -CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- , -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 6- , -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2CONH ( CH2 ) 6- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), -CF2 - CON( CH3 )-( CH2 ) 6- , -CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl), -CF2 - CON( CH3 )-( CH2 )
- X 1 represents X e′ .
- X e′ is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 51 —C 6 H 4 —R 52 —, —R 51 —CONR 40 —R 52 —, —R 51 —CONR 40 —C 6 H 4 -R 52 -, -R 51 -CO-R 52 -, -R 51 -CO-C 6 H 4 -R 52 -, -R 51 -SO 2 NR 40 -R 52 -, -R 51 - SO 2 NR 40 -C 6 H 4 -R 52 -, -R 51 -SO 2 -R 52 -, or -R 51 -SO 2 -C 6 H 4 -R 52 -.
- R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms (provided that when R 51 is linked to —CONR 40 —, R 51 is not a single bond); A single bond or an alkylene group having 1 to 3 carbon atoms is preferred.
- R40 has the same meaning as above.
- the above alkylene groups are substituted or unsubstituted, preferably unsubstituted. Examples of substituents for the alkylene group include halogen atoms, preferably fluorine atoms.
- the alkylene group is linear or branched, preferably linear.
- X e' is single bond, -X f -, an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, —C 6 H 4 —R 52′ —, -R 52' -, —C 6 H 4 —R 52′ —, -X f -CONR 4' -R 52' -, -Xf - CONR4' - C6H4 - R52'-, -CO-R 52'- , —CO—C 6 H 4 —R 52′ —, —SO 2 NR 4′ —R 52′ —, —SO 2 NR 4′ —C 6 H 4 —R 52′ —, —SO 2 —R 52′ —, —SO 2 —R 52′
- the alkylene group is substituted or unsubstituted, and examples of substituents of the alkylene group include halogen atoms, preferably fluorine atoms.
- R 4' is a hydrogen atom or a methyl group.
- X e' is preferably -X f -, an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -R 52' -, —C 6 H 4 —R 52′ —, -X f -CONR 4' -R 52' -, -Xf - CONR4' - C6H4 - R52'-, —R 51′ —CONR 4′ —, —R 51′ —CONR 4′ —C 6 H 4 —, -X f -CONR 4' -, -Xf - CONR4' - C6H4-, -R 51' -CONR 4' -, or -R 51' -CONR 4' -C 6 H
- X e' is more preferably single bond, -R 52' -, —C 6 H 4 —R 52′ —, -X f -CONR 4' -R 52' -, -Xf - CONR4' - C6H4 - R52'-, —R 51′ —CONR 4′ —, —R 51′ —CONR 4′ —C 6 H 4 —, -C6H4- , —X f —CONR 4′ —, or —X f —CONR 4′ —C 6 H 4 —, can be
- X e′ include, for example, single bond, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.), —CF 2 —C 1-6 alkylene group, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -CF2 - CONH-, -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2 - CON( CH3 )-, -CF2 - CON( CH3 )CH2-, -CF2 - CON( CH3 )-( CH2 ) 2- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CH2 -CONH-, —CH 2 —CON
- preferable X e′ is single bond, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.), —CF 2 —C 1-6 alkylene group, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2 - CON( CH3 )-, -CF2 - CON( CH3 )CH2-, -CF2 - CON( CH3 )-( CH2 ) 2- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CH2 -CONH-, —CH 2 —CON
- more preferable X e′ is single bond, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2 - CON( CH3 )-, -CF2 - CON( CH3 )CH2-, -CF2 - CON( CH3 )-( CH2 ) 2- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CH2 -CONH-, —CH 2 —CONH—CH 2 —, -CH 2 -CONH-(CH 2 ) 2 -, -CH 2 -CONH-(CH 2 ) 3 -, -CF2- CH2 - CONH-, -CF2- CH2 - CONH-, -CF2- CH2 - CONH-,
- X e' is a single bond.
- X 1 is a group of the formula: -(R 16 ) x -(CFR 17 ) y -(CH 2 ) z -.
- x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized repeating unit in the formula is optional in
- each occurrence of R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group.
- R 16 is an oxygen atom or a divalent polar group.
- the "lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, which are substituted with one or more fluorine atoms. good too.
- each occurrence of R 17 is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
- the "lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro A methyl group, a pentafluoroethyl group, more preferably a trifluoromethyl group.
- X 1 is preferably of the formula: -(O) x -(CF 2 ) y -(CH 2 ) z - (wherein x, y and z have the same meanings as above and The order of existence of each repeating unit enclosed in a square is arbitrary in the formula).
- the group represented by the above formula: -(O) x -(CF 2 ) y -(CH 2 ) z - includes, for example, -(O) x' -(CH 2 ) z '' -O-[(CH 2 ) z''' -O-] z ''' and -(O) x' -(CF2) y ''-( CH2 ) z ''-O-[ ( CH2 ) z''' -O- ] z"" (wherein x' is 0 or 1, y", z" and z''' are each independently an integer from 1 to 10, z"" is 0 or 1 The left ends of these groups are bonded to the PFPE side.
- X 1 is -O-CFR 20 -(CF 2 ) e' -.
- Each R 20 above independently represents a fluorine atom or a lower fluoroalkyl group.
- the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably It is a trifluoromethyl group.
- the above e' are each independently 0 or 1.
- R 20 is a fluorine atom and e' is 1.
- examples of X 1 groups include the following groups: [In the formula, each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; In each X 1 group, one of T is attached to the amide bond linking PFPE 1 in the backbone of the molecule with the following groups: —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CF 2 O(CH 2 ) 3 —, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, or -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 - [In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group,
- Ts are —(CH 2 ) n′′ — (where n′′ is an integer from 2 to 6) attached to groups opposite PFPE on the molecular backbone and, if present, the remaining
- Each T can independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group.
- the left side is bonded to the amide bond that connects to the group represented by PFPE 1
- the right side is bonded to the opposite side of the group represented by PFPE 1 .
- the radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. , hindered amines, hindered phenols, or triazines.
- the UV-absorbing group is not particularly limited as long as it can absorb UV rays. Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
- preferred radical-scavenging groups or UV-absorbing groups include is mentioned.
- each occurrence of X 2 independently represents a single bond or a divalent organic group.
- X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably -(CH 2 ) u - (where u is an integer of 0 to 2).
- each t is independently an integer of 1-10. In preferred embodiments, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2-10, preferably an integer from 2-6.
- a preferred compound of formula (A) is represented by the following formula (A'): [In the formula: PFPE 1 , R 6 and R 7 are each independently as defined above; each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group; each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; each occurrence of R 11 independently represents a hydrogen atom or a halogen atom; each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group; R 11′′ , R 12′′ , R 13′′ and R 14′′ are the same as R 11 , R 12 , R 13 and R 14 respectively; n1 is an integer from 1 to 3, preferably 3; X 1 is independently at each occurrence —O—CFR 20 —(CF 2 ) e′ —; each occurrence of R 20 is independently a fluorine atom or a lower fluoroalkyl group; e′ is independently 0 or 1 at each
- the compound represented by the above formula (A) can be prepared, for example, by using a perfluoro(poly)ether derivative corresponding to the —PFPE 1 — portion as a starting material, introducing iodine at the terminal, and then converting —CH 2 CR 12 (X 2 — It can be obtained by reacting a vinyl monomer corresponding to SiR 13 n1 R 14 3-n1 )—.
- PFPE 1 , R 6 , R 7 , R 13 , R 13′′ , R 14 , R 14′′ and n1 have the same meanings as described for formula (A) above.
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group means that n1 is an integer of 1 to 3 and (SiR 13 n1 R 14 3 -n1 ) or (-SiR 13′′ n1 R 14′′ 3-n1 ).
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n1 ) unit or each (-SiR 13′′ n1 R 14′′ 3-n1 ) unit, preferably is 1 to 3, more preferably 3. wherein at least two n1's are integers from 1 to 3, ie not all n1's are 0 at the same time. That is, at least two R 13 or R 13′′ are present in the formula.
- At least one Si bonded to a hydroxyl group or a hydrolyzable group exists at each end of the molecular main chain of the PFPE-containing silane compound (a). That is, there is at least one --SiR 13 moiety and at least one --SiR 13'' moiety.
- each X 3 independently represents a divalent to decavalent organic group. That is , X3 corresponds to R5 in the above general formula.
- the X 3 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (B), and the base material. It is understood as a linker that connects a silane moiety that provides binding ability (specifically, —SiR 13 n1 R 14 3-n1 or —SiR 13′′ n1 R 14′′ 3-n1 ). Therefore, X 3 may be any organic group as long as the compound represented by formula (B) can exist stably.
- the structure described as X 3 has an amide bond linked to the group represented by PFPE 1 on the left side, and a group bracketed with ⁇ 1 on the right side, respectively. do.
- X 3 represents X e .
- Xe has the same meaning as above.
- ⁇ 1 in the above formula is an integer of 1 to 9 and can vary depending on the valence of X3.
- ⁇ 1 is the value of the valence of X3 minus one.
- ⁇ 1 is 1 when X3 is a single bond.
- X 3 above is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
- X 3 is a divalent to tetravalent organic group and ⁇ 1 is 1-3.
- X3 is a divalent organic group and ⁇ 1 is 1.
- the formula (B) is represented by the following formula (B').
- Examples of X 3 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. , and includes those other than single bonds.
- preferred specific X 3 is —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2
- X 3 is —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 OCF 2 CHFOCF 2 —, —CH 2 OCF 2 CHFOCF 2 CF 2 —, -CH2OCF2CHFOCF2CF2CF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2CF2- , _ _ _ _ _ _ -CH2OCH2CF2CF2
- X 3 is -CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- , -CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 6- , -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2CONH ( CH2 ) 6- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), -CF2 - CON( CH3 )-( CH2 ) 6- , -CF 2 -CON(Ph)-(CH 2 ) 3 -
- X 3 represents X e′ .
- X e' has the same meaning as above except that the single bond is omitted.
- formula (B) there are at least two Si bonded to hydroxyl or hydrolyzable groups. That is, in formula (B), there are at least two —SiR 13 moieties.
- a preferred compound of formula (B) is represented by the following formula (B'): [In the formula: PFPE 1 , R 6 and R 7 are as defined above; each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group; each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; R 13′′ and R 14′′ are the same as R 13 and R 14 respectively; n1 is an integer from 1 to 3, preferably 3; X 3 is an alkylene group having 1 to 20 carbon atoms, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 - or -CH 2 O(CH 2 ) 6 -. ] It is a compound represented by
- the compound represented by formula (B) above can be produced by a known method, for example, the method described in JP-A-2013-117012 or an improved method thereof.
- PFPE 1 , R 6 and R 7 have the same meanings as described for formula (A) above.
- each X 5 independently represents a divalent to decavalent organic group. That is, X5 corresponds to R5 in the above general formula.
- the X 5 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (C), and the base material. It is understood as a linker that connects a silane moiety that provides binding ability (specifically, a -SiR a k1 R b l1 R c m1 group or a -SiR a′′ k1 R b′′ l1 R c′′ m1 group). Therefore, X 5 may be any organic group as long as the compound represented by formula ( C) can exist stably.
- the structure is attached to the group represented by PFPE 1 on the left side and to the group bracketed with ⁇ 1 on the right side, respectively.
- X 5 represents X e .
- Xe has the same meaning as above.
- formula (C) is represented by the following formula (C').
- Examples of the above X 5 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. , and includes those other than single bonds.
- preferred specific X 5 is —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2
- X 5 is preferably —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 OCF 2 CHFOCF 2 —, —CH 2 OCF 2 CHFOCF 2 CF 2 —, -CH2OCF2CHFOCF2CF2CF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2CF2- , _ _ _ _ _ -CH2OCH2CF2CF2
- X 5 is -CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- , -CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 6- , -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2CONH ( CH2 ) 6- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), -CF2 - CON( CH3 )-( CH2 ) 6- , -CF 2 -CON(Ph)-(CH 2 ) 3 -
- X 5 represents X e′ .
- X e' has the same meaning as above except that the single bond is omitted.
- each occurrence of R a independently represents —Z 3 —SiR 71 p1 R 72 q1 R 73 r1 .
- Z 3 at each occurrence independently represents an oxygen atom or a divalent organic group.
- the above Z 3 is preferably a divalent organic group, and does not include those that form a siloxane bond with the terminal Si atom (Si atom to which R a is bonded) of the molecular main chain in formula (C). .
- Z 3 above is preferably a C 1-6 alkylene group, —(CH 2 ) g —O—(CH 2 ) h — (wherein g is an integer of 1 to 6, h is 1 to is an integer of 6) or -phenylene-(CH 2 ) i - (wherein i is an integer of 0 to 6), more preferably a C 1-3 alkylene group.
- These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
- Z3 is more preferably a straight-chain or branched-chain alkylene group, and still more preferably a straight-chain alkylene group.
- the number of carbon atoms constituting the alkylene group of Z 3 is preferably in the range of 1-6, more preferably in the range of 1-3.
- the alkylene group is as described above.
- each occurrence of R 71 independently represents R a′ .
- Ra' has the same meaning as Ra .
- the number of Sis connected in a straight chain via 3 Z groups is at most 5. That is, when at least one R 71 is present in the above Ra, two or more Si atoms linked in a straight chain via a Z 3 group are present in Ra. The maximum number of Si atoms linked in a straight chain is five.
- the “number of Si atoms linearly linked via Z 3 groups in R a ” is equal to the repeating number of —Z 3 —Si— linearly linked in R a . Become.
- * means the site of bonding to Si in the main chain
- ... indicates that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of the Si atom are ... means the end point of the repetition of Z 3 Si.
- the number on the right side of Si means the number of occurrences of Si linked in a straight chain via three Z groups counted from *. That is, the chain in which the Z 3 Si repeat ends at Si 2 has 2 “the number of Si atoms connected in a straight chain via the Z 3 group in Ra”.
- Si 4 and Si 5 terminate the Z 3 Si repeat, respectively, the “number of Si atoms linearly linked via the Z 3 group in Ra ” is 3, 4 and 5 is one.
- there are a plurality of Z 3 Si chains in R a but these chains do not have to all have the same length, and each may have an arbitrary length.
- the number of Si atoms linearly linked via Z 3 groups in Ra is 1 (left formula) or 2 ( right formula).
- the number of Si atoms linearly linked via the Z 3 group in R a is 1 or 2, preferably 1.
- each occurrence of R 72 independently represents a hydroxyl group or a hydrolyzable group.
- Hydrolyzable group has the same meaning as above.
- R 72 is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- each occurrence of R 73 independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
- the sum of p1, q1 and r1 is 3 for each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ).
- q1 is preferably 2 or more, such as 2 or 3, and more preferably 3, in the terminal R a ' (R a when R a ' does not exist) at the end of R a .
- At least one of the ends of R a is —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 2 R b l1 R c m1 (with the proviso that either one of l1 and m1 is 1; , the other is 0) or —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 , preferably —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 , where q1 and The sum of r1 is 3).
- the unit of (-Z 3 -SiR 72 q1 R 73 r1 ) is preferably (-Z 3 -SiR 72 3 ).
- the terminal groups of R a may all be -Si(-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si(-Z 3 -SiR 72 3 ) 3 .
- each occurrence of R a′′ independently represents —Z 3 —SiR 71 p1 R 72′′ q1 R 73 r1 .
- Z 3 , R 71 , R 73 , p1, q1 and r1 have the same meanings as above.
- R72′′ has the same meaning as R72 .
- At least one of the ends of R a′′ is —Si(—Z 3 —SiR 72′′ q1 R 73 r1 ) 2 R b′′ l1 R c′′ m1 (with the proviso that either l1 or m1 is 1 and the other is 0) or —Si(—Z 3 —SiR 72′′ q1 R 73 r1 ) 3 , preferably —Si(—Z 3 —SiR 72′′ q1 R 73 r1 ) 3 (where the sum of q1 and r1 is 3).
- the unit of (-Z 3 -SiR 72'' q1 R 73 r1 ) is preferably (-Z 3 -SiR 72'' 3 ).
- all of the terminal groups of R a may be -Si(-Z 3 -SiR 72′′ q1 R 73 r1 ) 3 , preferably –Si(-Z 3 -SiR 72′′ 3 ) 3 .
- SiR 72 (specifically, a group represented by —SiR 71 p1 R 72 q1 R 73 r1 , where q1 is an integer of 1 to 3)
- SiR 72′′ (specifically, —SiR 71 p1 R 72′′ q1 a group represented by R 73 r1 , wherein q1 is an integer of 1 to 3)
- SiR b (specifically, a group represented by —SiR a k1 R b l1 R c m1 , with the proviso that l1 is an integer of 1 to 3)
- SiR b′′ (specifically, a group represented by —SiR a′′ k1 R b′′ l1 R c′′ m1 , where l1 is an integer of 1 to 3)
- R b and R b′′ will be described later.
- At least one Si bonded to a hydroxyl group or a hydrolyzable group exists at each end of the molecular main chain of the PFPE-containing silane compound (A). That is, there is at least one structure of SiR 72 and/or SiR b and there is at least one structure of SiR 72'' and/or SiR b' '.
- each occurrence of R b independently represents a hydroxyl group or a hydrolyzable group.
- R b above is preferably a hydroxyl group, —OR, —OCOR, —ON ⁇ C(R) 2 , —N(R) 2 , —NHR, halogen (wherein R is a substituted or unsubstituted represents an alkyl group having 1 to 4 carbon atoms), more preferably -OR.
- R includes unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
- an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group. More preferably, R b is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- R b′′ has the same meaning as R b .
- each occurrence of R c independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
- R c′′ has the same meaning as R c .
- the sum of k1, l1 and m1 is 3 for each (SiR a k1 R b l1 R c m1 ) or (SiR a′′ k1 R b′′ l1 R c′′ m1 ).
- k1 is preferably 1 to 3, more preferably 3.
- the compound represented by formula (C) above can be synthesized, for example, as described in International Publication No. 2014/069592.
- PFPE 1 , R 6 and R 7 have the same meanings as described for formula (A) above.
- each X 7 independently represents a single bond or a divalent to decavalent organic group.
- X 7 is a perfluoro(poly)ether moiety (that is, -PFPE 1 - moiety) that mainly provides water repellency and surface slipperiness, etc., and a base material. It is understood as a linker that connects the portion that provides the binding ability (ie, the group bracketed with ⁇ 1). Therefore, X 7 may be a single bond or any organic group as long as the compound represented by formula (D) can exist stably.
- the structure described as X 7 has an amide bond adjacent to the group represented by PFPE 1 on the left side, and a group bracketed with ⁇ 1 on the right side, respectively. do.
- X 7 represents X e .
- Xe has the same meaning as above.
- ⁇ 1 is an integer from 1 to 9, and ⁇ 1 can vary depending on the valence of X7 .
- ⁇ 1 is the valence of X7 minus one.
- ⁇ 1 is 1 when X7 is a single bond.
- X 7 above is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group and ⁇ 1 is 1-3.
- X 7 is a divalent organic group and ⁇ 1 is 1.
- the formula (D) is represented by the following formula (D').
- Examples of the above X 7 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. are listed.
- preferred specific X 7 is single bond, —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2
- more preferred specific X 7 is —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2- CH2 - O - CH2-, —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 OCF 2 CHFOCF 2 —, —CH 2 OCF 2 CHFOCF 2 CF 2 —, -CH2OCF2CHFOCF2CF2CF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2- , _ _ _ _ -CH2OCH2CF2CF2OCF2CF2- , _ _ _ _ _ _ -CH2OCH2CF
- X 7 is -CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- , -CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-, -CH2- , -(CH 2 ) 2 -, -(CH 2 ) 3 -, -( CH2 ) 6- , -CF2CONH- , -CF2CONHCH2- , -CF2CONH ( CH2 ) 2- , -CF2CONH ( CH2 ) 3- , -CF2CONH ( CH2 ) 6- , -CF2 - CON( CH3 )-( CH2 ) 3- , -CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl), -CF2 - CON( CH3 )-( CH2 ) 6- , -CF 2 -CON(Ph)-(CH 2 ) 3 -
- X 7 represents X e′ .
- Xe' has the same meaning as above.
- X e' is a single bond.
- each occurrence of R d independently represents -Z 4 -CR 81 p2 R 82 q2 R 83 r2 .
- Z 4 at each occurrence independently represents an oxygen atom or a divalent organic group.
- the above Z 4 is preferably a C 1-6 alkylene group, —(CH 2 ) g —O—(CH 2 ) h — (wherein g is an integer of 0 to 6, for example an integer of 1 to 6 and h is an integer from 0 to 6, such as an integer from 1 to 6) or -phenylene-(CH 2 ) i - (wherein i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
- each occurrence of R 81 independently represents R d′ .
- Rd' has the same meaning as Rd .
- R d there are at most 5 C atoms which are linearly linked via Z 4 groups. That is, when at least one R 81 is present in R d above, there are two or more C atoms linked in a straight chain via a Z 4 group in R d , but via such a Z 4 group
- the maximum number of C atoms linked in a straight chain is five.
- the “number of C atoms linearly linked via Z 4 groups in R d ” is equal to the repeating number of —Z 4 —C— linearly linked in R d . Become.
- the number of C atoms linearly linked via Z 4 groups in R d is 1 (left formula) or 2 ( right formula).
- the number of C atoms linearly linked via the Z 4 group of R d is 1 or 2, preferably 1.
- each occurrence of R 82 independently represents -Y-SiR 85 n2 R 86 3-n2 .
- Each occurrence of Y independently represents a divalent organic group.
- Y is a C 1-6 alkylene group, —(CH 2 ) g′ —O—(CH 2 ) h′ —, wherein g′ is an integer of 0-6, such as 1-6 is an integer and h' is an integer of 0 to 6, such as an integer of 1 to 6) or -phenylene-(CH 2 ) i' - (wherein i' is an integer of 0 to 6) ).
- These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
- Y can be a C 1-6 alkylene group or -phenylene-(CH 2 ) i' -.
- light resistance particularly ultraviolet resistance, can be higher.
- R 85 above independently represents a hydroxyl group or a hydrolyzable group.
- hydrolyzable group includes those similar to formula (C).
- R 85 is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl or methyl group, especially a methyl group.
- R 86 above independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- n2 is an integer of 0 to 3 independently for each (-Y-SiR 85 n2 R 86 3-n2 ) unit or each (-Y-SiR 85′′ n2 R 86′′ 3-n2 ) unit; An integer of 1 to 3 is preferred, 2 or 3 is more preferred, and 3 is particularly preferred. R 85′′ and R 86′′ will be described later.
- R 83 above independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
- q2 is preferably 2 or more, for example 2 or 3, more preferably 3, at the terminal R d ' (R d when R d ' is absent) in R d .
- At least one of the terminal groups of R d is —C(—Y—SiR 85 n2 R 86 3-n2 ) 2 (specifically —C(—Y—SiR 85 n2 R 86 3— n2 ) 2 R 83 ) or -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 .
- n2 is an integer of 1-3.
- the unit of (-Y-SiR 85 n2 R 86 3-n2 ) is preferably (-Y-SiR 85 3 ).
- the terminal portions of R d may all be -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 3 ) 3 .
- the terminal of the group represented by (CR d k2 R e 12 R f m2 ) is C(-Y-SiR 85 n2 R 86 3-n2 ) 2 R f ) or C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably C(-Y-SiR 85 n2 R 86 3-n2 ) 3 .
- n2 is an integer of 1-3.
- the unit of (-Y-SiR 85 n2 R 86 3-n2 ) is preferably (-Y-SiR 85 3 ).
- the terminal ends of the above groups may all be -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 3 ) 3 .
- each occurrence of R d′′ independently represents —Z 4 —CR 81 p2 R 82′′ q2 R 83 r2 .
- Z 4 , R 81 , R 83 , p2, q2 and r2 have the same meanings as above.
- R 82′′ at each occurrence independently represents —Y—SiR 85′′ n2 R 86′′ 3-n2 , wherein Y and n2 have the same meanings as above.
- R 85′′ , and R 86′′ has the same meaning as R 85 and R 86 respectively.
- q2 is preferably 2 or more, such as 2 or 3, more preferably 3, at the terminal R d ' (R d '' when R d ' is absent) at the end of R d ''. be.
- At least one of the terminal ends of R d′′ is —C(—Y-SiR 85′′ n2 R 86′′ 3-n2 ) 2 (specifically —C(—Y-SiR 85′′ n2 R 86′′ 3-n2 ) 2 R 83 ) or —C(-Y-SiR 85′′ n2 R 86′′ 3-n2 ) 3 , preferably —C(-Y-SiR 85′′ n2 R 86′′ 3-n2 ) 3 , where n2 is an integer from 1 to 3, wherein the unit (-Y-SiR 85′′ n2 R 86′′ 3-n2 ) is preferably (-Y-SiR 85′′ 3 ).
- the terminal portions of R d can all be -C(-Y-SiR 85′′ n2 R 86′′ 3-n2 ) 3 , preferably -C(-Y-SiR 85′′ 3 ) 3 .
- the terminal of the group represented by (CR d′′ k2 R e′′ 12 R f′′ m2 ) is C(—Y—SiR 85′′ n2 R 86′′ 3-n2 ) 2 R f′′ ) or C(-Y-SiR 85''n2 R 86'' 3 -n2 ) 3 , preferably C(-Y-SiR 85''n2 R 86'' 3 -n2 ) 3 .
- n2 is an integer of 1-3.
- the unit of (--Y--SiR 85′′ n2 R 86′′ 3-n2 ) is preferably (--Y--SiR 85′′ 3 ). It may be C(--Y--SiR 85′′ n2 R 86′′ 3-n2 ) 3 , preferably --C(--Y--SiR 85′′ 3 ) 3 .
- each occurrence of R e independently represents -Y-SiR 85 n2 R 86 3-n2 .
- Y, R 85 , R 86 and n2 have the same meanings as described for R 82 above.
- R e′′ at each occurrence independently represents —Y—SiR 85′′ n2 R 86′′ 3-n2 , wherein R 85′′ , R 86′′ , Y, and n2 are Same meaning as above.
- each occurrence of R f independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group.
- each occurrence of R f independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- R f′′ has the same meaning as R f .
- the sum of k2, l2 and m2 is 3.
- At least one k2 is 2 or 3, preferably 3.
- k2 is 2 or 3, preferably 3.
- l2 is 2 or 3, preferably 3.
- n2 is an integer of 1-3.
- the group represented by —C—(Y—SiR 85 n2 R 86 3-n2 ) 2 is one or more, and —C—(Y—SiR 85′′ n2 R 86 ′′ 3-n2 ) It is preferable that one or more groups represented by 2 are present (in the formula, n2 is an integer of 1 to 3).
- the group represented by —C—(Y—SiR 85 n2 R 86 3-n2 ) 3 is one or more, and —C—(Y—SiR 85′′ n2 R 86 ′′ 3-n2 ) It is preferable that one or more groups represented by 3 are present (in the formula, n2 is an integer of 1 to 3).
- n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3.
- the compound represented by formula (D) above can be produced by combining known methods.
- the PFPE-containing silane compound (a) is represented by formula (B) or (C).
- the PFPE-containing silane compound (a) is represented by formula (A), (C) or (D).
- the PFPE-containing silane compound (a) has 2 or more, preferably 3 or more Si atoms having a hydroxyl group or a hydrolyzable group at at least one end.
- the PFPE-containing silane compound (a) described above is not particularly limited, but in one embodiment, it can have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Within this range, it is preferred to have a number average molecular weight of 2,000 to 50,000, more preferably 2,500 to 30,000, still more preferably 3,000 to 10,000. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
- the curable composition of the present invention includes, as a cross-linking agent, a compound having at least two OR 2 groups bonded to Si atoms (where R 2 is independently at each occurrence a hydrogen atom or a monovalent organic groups) (excluding those falling under (a) above) or partial hydrolysis condensates thereof (hereinafter also referred to as "crosslinking agents").
- the cross-linking agent in the present invention performs a cross-linking reaction (condensation reaction) with the PFPE-containing silane compound (a) (specifically, the hydroxyl group or hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (a)). is a compound.
- the group R2 at each occurrence is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group means a group containing monovalent carbon. Examples of such monovalent organic groups include, but are not particularly limited to, monovalent hydrocarbon groups.
- the hydrocarbon group has the same meaning as above.
- the cross-linking agent (b) has a structure different from that of the PFPE-containing silane compound (a).
- the cross-linking agent (b) preferably does not have a perfluoro(poly)ether moiety.
- the cross-linking agent (b) may or may not have reactive functional groups other than Si—OR 2 groups, alkenyl groups and alkynyl groups. preferably does not have a reactive functional group of
- other reactive functional groups refer to primary amino groups, epoxy groups, (meth)acryloyl groups, (meth)acryloxy groups, mercapto groups, isocyanato groups, and the like.
- the cross-linking agent (b) will be described separately as (B1) a cross-linking agent having no reactive functional group and (B2) a cross-linking agent having a reactive functional group.
- Cross-linking agents having no reactive functional group include, for example, R 1 n Si(OR 2 ) 4-n (wherein R 1 is independently at each occurrence a substituted or unsubstituted 1 is a valent hydrocarbon group, each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group, and n is 0, 1 or 2). can be mentioned.
- each occurrence of R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 12 carbon atoms.
- R 1 is specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as a decyl group; Cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; Aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; aralkyl group; alkenyl group such as vinyl group, allyl group, propenyl group and butenyl group;
- n is preferably 1 or 2.
- cross-linking agent having no reactive functional group examples include organosilicon compounds represented by (B1-1) to (B1-3) below.
- (B1) a cross-linking agent having no reactive functional group is represented by the following formula (B1-1) or (B1-2), at least two silanols per molecule A compound having a group can be mentioned.
- each occurrence of R g1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
- R g1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.
- Alkyl groups such as decyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; Vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and cyclohexenyl alkenyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group; Substituted groups (eg, chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, nonafluorohexyl group) can be mentioned.
- aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group
- aralkyl group such
- each occurrence of R g2 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
- R g2 include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, and hexamethylene; cycloalkylene groups such as cyclohexylene, phenylene, tolylene, and xylylene.
- arylene groups such as groups, naphthylene groups, and biphenylene groups; groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc.; be.
- Rg2 is preferably a methylene group, ethylene group, propylene group, butylene group, hexamethylene group, cyclohexylene group and phenylene group, and particularly preferably ethylene group, propylene group, butylene group and phenylene group.
- Compounds having a silanol group in the molecule include one or a combination of two or more of R g1 3 SiO 1/2 , R g1 2 SiO 2/2 , R g1 SiO 3/2 and SiO 4/2 units. Examples include resinous compounds composed of bonds with silanol groups. The structural units in the resinous compound may be directly bonded to each other, or may be bonded via a divalent or higher hydrocarbon group.
- ⁇ 1 is independently an integer of 1 or more at each occurrence. ⁇ 1 is preferably 2 or more, more preferably 5 or more, and preferably 50 or less, more preferably 20 or less.
- the compound represented by formula (B1-1) or (B1-2) preferably does not have a PFPE 1 structure in its molecular structure.
- the cross-linking agent having no reactive functional group is an organosilicon compound represented by formula (B1-3): can be Here, the units containing OR g3 and the units containing R g4 do not need to be arranged as shown in the above formula (B1-3). It is understood that
- R g3 has the same meaning as R 2 .
- R g3 above is a moiety capable of reacting with a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (a).
- R g3 is preferably a monovalent organic group.
- each occurrence of R g4 is independently a monovalent organic group.
- R g4 is preferably a substituted or unsubstituted monovalent hydrocarbon group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
- R g4 is specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as a decyl group; Cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; Aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; aralkyl group; alkenyl group such as vinyl group, allyl group, propenyl group and butenyl group; alkynyl group such as ethynyl group and propynyl group; Groups substituted with halogen atom
- ⁇ 3 is 2 or 3.
- the cross-linking agent having no reactive functional group is a compound represented by the formula: R 1 n Si(OR 2 ) 4-n .
- the (B1) cross-linking agent having no reactive functional group is tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane.
- Alkoxy groups such as silane, phenyltriethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, dimethyldiethoxysilane and 3-chloropropyltrimethoxysilane and partial hydrolytic condensates thereof Containing compounds; tetrakis(2-ethoxyethoxy)silane, methyltris(2-methoxyethoxy)silane, vinyl(2-ethoxyethoxy)silane and phenyltris(2-methoxyethoxy)silane, and partial hydrolytic condensates thereof substituted alkoxy group-containing compounds; methyltripropenoxysilane, methyltriisopropenoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, dimethyldiisopropenoxysilane and methylvinyl
- the cross-linking agent having a reactive functional group is a compound that not only contributes to the cross-linking reaction (condensation reaction) of the PFPE-containing silane compound (a), but also functions as an adhesion imparting agent.
- the curable composition of the present invention may further contain such a compound as the component (b) in addition to the above (B1).
- B2 As the component, A compound represented by can be used.
- R g3 and R g4 have the same meanings as above.
- each occurrence of R g6 independently represents R g8 -R g7 -.
- R g7 independently represents a single bond, an oxygen atom or a divalent organic group.
- the divalent organic groups are as described above.
- R g7 is preferably an alkylene group having 1 to 10 carbon atoms or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain.
- R g7 is more preferably an alkylene group having 1 to 3 carbon atoms, CH2CH2 - NH - CH2CH2CH2 , or CH2 - O - CH2CH2CH2 .
- R g8 is a reactive functional group.
- R g8 above is preferably each independently at each occurrence a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group or an isocyanato group, more preferably a primary is a tertiary amino group.
- ⁇ 4 is 2 or 3, more preferably 3.
- ⁇ 5 is 0 or 1.
- ⁇ 6 is 1 or 2, preferably 1.
- the sum of ⁇ 4, ⁇ 5 and ⁇ 6 is four.
- ⁇ 4 is 3, ⁇ 5 is 0 and ⁇ 6 is 1.
- cross-linking agents having reactive functional groups include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltriacetamidosilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3 -substituted or unsubstituted amino group-containing silanes such as aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane; Epoxy group-containing silane
- the cross-linking agent (b) does not have a group represented by PFPE 1 in the molecular chain.
- the molecular weight of the cross-linking agent (b) is 1,000 or less, preferably 600 or less, more preferably 250 or less.
- the lower limit of the molecular weight of the cross-linking agent may be 90 or more, or 120 or more.
- the cross-linking agent (b) Only one type of the cross-linking agent (b) may be used, or two or more types may be used at the same time. When two or more are used in combination, any of two or more of (B1) may be used in combination, two or more of (B2) may be used in combination, and one or more of each of (B1) and (B2) may be used in combination.
- the crosslinker (b) preferably contains at least one kind of (B1).
- (B1) and (D) described later, (B2) and (D), or (B1) and (B2) and (D) can be used in combination. Preferably, (B1) and (D) are used in combination.
- the crosslinking agent (b) may be contained in the curable composition in an amount of, for example, 0.1 parts by mass or more, specifically 0.3 parts by mass or more, relative to 100 parts by mass of the PFPE-containing silane compound (a). , 30 parts by mass or less, specifically 20 parts by mass or less, more specifically 10 parts by mass or less.
- the total content of the components (B1) and (B2) relative to the PFPE-containing silane compound (a) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, from the viewpoint of crosslinkability. It is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
- the total content of components (B1) and (B2) relative to the silane compound (a) containing PFPE is preferably 0.1 to 30% by mass, more preferably 0.3 to 20% by mass, from the viewpoint of crosslinkability. %, particularly preferably 0.3 to 10% by weight.
- the content of component (B1) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and particularly preferably 50 to 100% by mass with respect to the total of components (B1) and (B2). is.
- Preferred contents of components (B1) and (B2) relative to PFPE-containing silane compound (a) are the total preferred content of components (B1) and (B2) relative to PFPE-containing silane compound (a) and (B1) and ( Each can be calculated from the preferred content of component (B1) with respect to the total of components B2).
- the crosslinking agent (b) can be contained in the curable composition in an amount of, for example, 0.1 to 30 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound (a), specifically 0.3 to 30 parts by mass. 10 parts by mass, more specifically, 0.3 to 5.0 parts by mass.
- the cross-linking agent (b) contains, for example, 1 mol or more of —OR 2 groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a) in the curable composition. Specifically, it can contain 2 mol or more.
- the cross-linking agent (b) can contain, for example, 30 mol or less of —OR 2 groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). may contain 20 mol or less, more specifically 10 mol or less.
- the cross-linking agent (b) may contain —OR 2 groups, for example, in the range of 1 to 30 mol per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). can be included, specifically in the range of 2 to 20 moles.
- the condensation catalyst (c) is a component that promotes hydrolytic condensation between the PFPE-containing silane compound (a) and the cross-linking agent (b).
- the condensation catalyst a metal-based catalyst, an organic acid-based catalyst, an inorganic acid-based catalyst, a base-based catalyst, or the like can be used. From the viewpoint of the curing speed of the composition, the condensation catalyst is preferably a metal-based catalyst.
- metal atoms contained in the metal-based catalyst include titanium, zirconium, and tin.
- organic tin compounds or alkoxytitanium compounds are preferred.
- a compound having an alkoxide (--O--R h ) as a ligand can be used.
- R h is preferably an alkyl group having 1 to 4 carbon atoms. The use of such catalysts promotes the condensation reaction.
- R h is more preferably an alkyl group having 1 to 3 carbon atoms.
- the use of such catalysts particularly promotes the condensation reaction.
- the catalyst is easily dissolved or dispersed in the curable composition, and can contribute to promotion of uniform reaction.
- the above catalyst can contribute to the formation of a transparent cured product of the curable composition with less foreign substances.
- Preferred metal-based catalysts include carboxylic acid metal salts such as iron octoate, manganese octoate, zinc octoate, tin naphtate, tin caprylate, tin oleate; Organotin compounds such as acetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, dioctyltin dilaurate, dimethyltin dineodecanoate; tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetra-n - organic titaniums such as butoxytitanium, tetraisobutoxytitanium, diisopropoxytitanium bis(ethylacetoacetate), 1,3-propanedioxytitanium bis(ethylacetoacetate); aluminum trisacetylace
- organic acid-based catalyst examples include compounds having carboxylic acid, sulfonic acid, and phosphoric acid. Specifically, acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and alkylphosphoric acid etc. can be mentioned.
- Examples of the inorganic acid-based catalyst include hydrochloric acid and sulfuric acid.
- Examples of the basic catalyst include ammonia, amine compounds such as triethylamine and diethylamine, dialkylhydroxylamine such as dimethylhydroxyamine and diethylhydroxylamine, and guanidyl compounds such as tetramethylguanidine and guanidyl group-containing silanes or siloxanes.
- the above condensation catalyst is preferably contained in the curable composition of the present invention in an amount of 0.01 to 10.0 parts by mass, and 0.03 to 5.0 parts by mass, based on 100 parts by mass of the PFPE-containing silane compound (a). It is more preferable to contain parts by mass.
- the above condensation catalysts may be used alone or in combination of two or more.
- the curable composition of the present invention can contain further components other than the PEPE-containing silane compound (a), the cross-linking agent (b), and the condensation catalyst (c) as long as they do not impair the effects of the present invention.
- Such components include (d) an adhesion imparting agent, (a2) a perfluoro(poly)ether group-containing silane compound represented by general formula (II) described later, (e) an inorganic filler, and (f) a surface treatment.
- Silica (g) other PFPE-containing silane compounds, (h) solvents, and (i) various additives (hereinafter sometimes abbreviated as "component (d)").
- the compound used as an adhesion-imparting agent in the curable composition of the present invention contains two or more alkoxysilyl groups in one molecule, and the groups connecting the alkoxysilyl groups are —O— groups; and A compound that is a group other than a group having a siloxane bond, or a partial hydrolysis condensate thereof (excluding those corresponding to (a)) (hereinafter, two or more alkoxysilyl groups in one molecule It is also referred to as a contained adhesiveness imparting agent.).
- Component (d) is a component that improves the adhesion of the cured product of the composition to substrates such as glass, metal and plastic.
- Component (d) undergoes a cross-linking reaction with hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a) or Si—OR 2 groups of the cross-linking agent (b) during curing of the curable composition. (condensation reaction).
- component (d) the adhesiveness of the cured product of the composition to substrates such as glass, metal, and plastic is greatly improved.
- the component (d) may or may not have a reactive functional group.
- the group that connects the alkoxysilyl groups is an --O-- group; and a group other than a group having a siloxane bond.
- the group connecting the alkoxysilyl groups is preferably a group containing a nitrogen atom and/or a carbonyl group, and in addition to the nitrogen atom and/or the carbonyl group, -O- more preferably a group containing a group, an alkenylene group and/or an alkylene group.
- component (d) is a group consisting of alkoxysilyl group-containing isocyanurate compounds, alkoxysilyl group-containing carbasilatrane compounds, alkoxysilyl group-containing fumarate ester compounds, and alkoxysilyl group-containing amine compounds.
- a more selected compound is preferable, and an alkoxysilyl group-containing isocyanurate compound or an alkoxysilyl group-containing carbasilatrane compound is particularly preferable.
- alkoxysilyl group-containing isocyanurate compounds include tris(3-trialkoxysilylpropyl) isocyanurates such as tris(3-trimethoxysilylpropyl) isocyanurate and tris(3-triethoxysilylpropyl) isocyanurate. be done.
- alkoxysilyl group-containing carbasilatrane compounds examples include the following compounds: are mentioned.
- alkoxysilyl group-containing fumaric acid ester compounds include bis(3-trimethoxysilylpropyl) fumarate and bis(3-triethoxysilylpropyl) fumarate.
- Alkoxysilyl group-containing amine compounds include bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl) ) amines and the like.
- the (d) component may be a compound in which some of the hydrogen atoms are substituted with fluorine atoms.
- a component may use only 1 type and may use 2 or more types simultaneously.
- the content of component (d) in the PFPE-containing silane compound (a) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of adhesion to the substrate. It is preferably 0.05% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
- the content of component (d) relative to the silane compound (a) containing PFPE is preferably 30% by mass or less, more preferably 0.01 to 30% by mass, and still more preferably, from the viewpoint of adhesion to the substrate. is 0.02 to 20% by weight, particularly preferably 0.05 to 10% by weight.
- the content of component (d) is preferably 0 to 90% by mass, more preferably 1 to 70% by mass, and particularly preferably 1 to 50% by mass, based on the total of components (b) and (d). is.
- Component (d) may contain, for example, 1 mol or more of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of PFPE-containing silane compound (a) in the curable composition. Specifically, it can contain 2 mol or more. Component (d) can contain, for example, 30 mol or less of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). It can contain 20 moles or less, more specifically, it can contain 10 moles or less.
- Component (d) can contain, for example, 1 to 30 mol of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a), Specifically, it can be included in the range of 2 to 20 mol.
- the curable composition of the present invention contains (a2) the following general formula (II) as a PFPE-containing silane compound other than (a): [Wherein, R 3 , R 4 , R 5 , R 6 , R 7 , PFPE 1 , p, q, and j are as defined above] It may further contain a perfluoro(poly)ether group-containing silane compound represented by.
- k in formula (I) is 0 corresponds to the PFPE-containing silane compound (a2) represented by general formula (II).
- the meaning of each group in the PFPE-containing silane compound (a2) is the same as the definition described above for the PFPE-containing silane compound (a), and the same can be adopted as preferred embodiments.
- the structure that can be represented by the above formula (I) is not included in the PFPE-containing silane compound (a2).
- a preferable PFPE-containing silane compound (a2) is a compound in which R 5 is a divalent alkylene group and j is 2 in the general formula (II).
- a compound having a structure excluding repeating units corresponding to - can be mentioned. That is, compounds having the following structures can be mentioned.
- the PFPE-containing silane compound (a2) may be used singly or as a mixture of two or more.
- the PFPE-containing silane compounds (a) and (a2) can be mixed in any ratio.
- the weight ratio of said PFPE-containing silane compounds (a) and (a2) ranges from 10:90 to 90:10, more preferably from 80:20 to 20:80. By setting the content within this range, it is possible to obtain a good curable composition with well-balanced compatibility and crack resistance.
- the PFPE-containing silane compound (a2) is a compound in which R5 is a divalent alkylene group, j is 2 , and p and q are both 0.
- One aspect of the PFPE-containing silane compound (a2) is at least one compound represented by the following formula (A2), (B2), (C2) or (D2).
- the compound represented by the above formula (A2), (B2), (C2) or (D2) is represented by the formula (A), (B), (C) or (D) described above for (a).
- the PFPE-containing silane compound that is used it corresponds to the compound where r is 0.
- the contents of the groups present in each formula are also as explained in the above formula (A), (B), (C) or (D).
- the curable composition further comprises a PFPE-containing silane compound (a) or a PFPE-containing silane compound other than (a2). good too.
- the curable composition of the present invention is, for example, a compound represented by the following formula (G-1), (G-2), (G-3) or (G-4) (hereinafter referred to as "PFPE-containing silane compound (b)”).
- Rf 2 independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
- alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms may be linear or branched. preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms is.
- Rf 2 above is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group or C 1 -16 perfluoroalkyl group, more preferably C 1-16 perfluoroalkyl group.
- the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched and having 1 to 6 carbon atoms, especially C 1 to 6 carbon atoms.
- k is an integer of 1-9, and k' is an integer of 1-9.
- k and k' can vary depending on the valence of X 11' .
- the sum of k and k' is the same as the valence of X 11' .
- the sum of k and k′ is 10, such as k is 9 and k′ is 1, k is 5 and k′ is 5, or k is 1 and k' can be nine.
- k and k' are 1 when X 11' is a divalent organic group.
- k and k' are 1 when X 11' is a single bond.
- X 11′ is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group.
- X 11′ is a divalent to tetravalent organic group
- k is 1 to 3
- k′ is 1.
- X 11' is a divalent organic group, k is 1 and k' is 1.
- each occurrence of i′ is independently an integer of 0 to 3, preferably 0 to 2, and more preferably 0.
- at least one i′ in the formula is an integer between 0 and 2, ie not all i′ are 3 at the same time.
- at least one OR 3 is present in formula (G-1).
- k is an integer of 1-9, and k' is an integer of 1-9.
- k and k' can vary depending on the valence of X12 ' .
- the sum of k and k' is the same as the valence of X 12' .
- the sum of k and k′ is 10, such as k is 9 and k′ is 1, k is 5 and k′ is 5, or k is 1 and k' can be nine.
- k and k' are 1 when X 12' is a divalent organic group.
- k and k' are 1 when X 12' is a single bond.
- X 12′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
- X 12′ is a divalent to tetravalent organic group
- k is 1 to 3
- k′ is 1.
- X 12' is a divalent organic group, k is 1 and k' is 1.
- k1 is an integer of 1-9
- k1' is an integer of 1-9
- k1 and k1' can vary depending on the valence of X13 ' .
- the sum of k1 and k1' is the same as the valence of X13 ' .
- the sum of k1 and k1′ is 10, such as k1 is 9 and k1′ is 1, k1 is 5 and k1′ is 5, or k1 is 1 and k1' can be nine.
- k1 and k1' are 1 when X 13' is a divalent organic group.
- k1 and k1' are 1 when X 13' is a single bond.
- the above X 13′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
- X 13′ is a divalent to tetravalent organic group
- k1 is 1 to 3
- k1′ is 1.
- X 13' is a divalent organic group
- k1 is 1 and k1' is 1.
- k2 is an integer of 1-9
- k2' is an integer of 1-9
- k2 and k2' can vary depending on the valence of X14 ' .
- the sum of k2 and k2' is the same as the valence of X14 ' .
- the sum of k2 and k2′ is 10, such as k2 is 9 and k2′ is 1, k2 is 5 and k2′ is 5, or k2 is 1 and k2' can be nine.
- k2 and k2' are 1 when X 14' is a divalent organic group.
- k2 and k2' are 1 when X 14' is a single bond.
- X 14′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
- X 14' is a divalent to tetravalent organic group
- k2 is 1-3
- k2' is 1.
- X 14' is a divalent organic group
- k2 is 1 and k2' is 1.
- the PFPE-containing silane compound (b) can be a compound represented by formula (G-1), (G-3) or (G-4). Adhesion to the substrate can be further improved by using such a silane compound.
- the PFPE-containing silane compound (b) has two or more, preferably three or more Si atoms having hydroxyl groups or hydrolyzable groups at the terminals.
- compounds represented by formulas (A), (B), (C) and (D) (hereinafter also referred to as "(1) component"), and formula (G- 1), compounds represented by (G-2), (G-3) and (G-4) (hereinafter also referred to as “(2) component”), the formula (G-1) , (G-2), (G-3) and (G-4) is 0.1 mol % or more and 35 mol % or less.
- the lower limit of the content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the total of components (1) and (2) is preferably It can be 0.1 mol %, more preferably 0.2 mol %, still more preferably 0.5 mol %, even more preferably 1 mol %, particularly preferably 2 mol %, especially 5 mol %.
- the upper limit of the content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the total of components (1) and (2) is preferably It can be 35 mol %, more preferably 30 mol %, even more preferably 20 mol %, still more preferably 15 mol % or 10 mol %.
- the content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the sum of components (1) and (2) is preferably 0.00. 1 mol % or more and 30 mol % or less, more preferably 0.1 mol % or more and 20 mol % or less, still more preferably 0.2 mol % or more and 10 mol % or less, still more preferably 0.5 mol % or more and 10 mol % Below, it is particularly preferably 1 mol % or more and 10 mol % or less, for example, 2 mol % or more and 10 mol % or less, or 5 mol % or more and 10 mol % or less.
- the curable composition can contribute to the formation of a cured product with good friction durability.
- the combination of the components (1) and (2) is preferably a combination of the compound represented by the formula (A) and the compound represented by the formula (G-1), the formula (B) A combination of a compound represented by the formula (G-2) and a compound represented by the formula (G-2), a combination of a compound represented by the formula (C) and a compound represented by the formula (G-3), or a combination of the compound represented by the formula (D) and a compound represented by Formula (G-4).
- t is preferably 2 or more, more preferably an integer of 2-10, and still more preferably an integer of 2-6.
- t is preferably 2 or more, more preferably an integer of 2-10, and still more preferably an integer of 2-6.
- l2 is preferably 2 or 3, more preferably 3.
- the compound represented by formula (C) has a structure represented by -Si-(Z 3 -SiR 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 at the terminal. and more preferably have a structure represented by -Si- ( Z 3 -SiR 72 3 ) 3 ; 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 , more preferably -Si-(Z 3 -SiR 72 3 ) 3 .
- the group represented by —Si—(Z 3 —SiR 72 3 ) 2 is -Si-R a 2 R b m1 R c n1 , wherein R a is a group represented by -Z 3 -SiR 72 3 , and the sum of m1 and n1 is 1; -Si-R a 2 R b m2 R c n2 in which R a is a group represented by -Z 3 -SiR 72 3 and the sum of m2 and n2 is 1, or -Si-R 71 2 R In 72 q1 R 73 r1 , the terminal of R 71 is a group represented by —Z 3 —SiR 72 3 , and the sum of q1 and r1 is 1.
- m4 is preferably 2 or 3, more preferably 3.
- the compound represented by formula (D) is terminally end-C-(Y-SiR 85 3 ) 2 (specifically, -C-(Y-SiR 85 3 ) 2 R 83 ) or -C-(Y-SiR 85 3 ) 3 structure, more preferably -C-(Y-SiR 85 3 ) 3 structure; , -C-(Y-SiR 85 3 ) 2 (specifically, -C-(Y-SiR 85 3 ) 2 R 83 ) or -C-(Y-SiR 85 3 ) 3 structure, and It preferably has a —C—(Y—SiR 85 3 ) 3 structure.
- the curable composition can contribute to the formation of a cured product having higher durability (for example, abrasion resistance).
- the PFPE-containing silane compound (b) can also be a compound represented by the following formula (G-5).
- OR g3 represents a hydrolyzable group.
- ⁇ 3 is 2 or 3.
- Rf 1 is a monovalent fluorinated (poly)ether group.
- Rf 1 includes CF 3 O—, CF 3 CF 2 O—, CF 3 CF 2 CF 2 O—, (CF 3 ) 2 CFO—, or CF 3 CF 2 CF 2 CF at the CF 2 end of PFPE 1 . Structures in which 2 O- and the like are bonded are exemplified.
- R g5 is a divalent organic group.
- the divalent organic group has the same meaning as above.
- R g5 may contain, for example, one or more of an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, and may contain an amide bond or a sulfonamide bond, a substituted or unsubstituted It can be a divalent hydrocarbon group.
- the divalent hydrocarbon group preferably has 2 to 20 carbon atoms.
- substituted or unsubstituted divalent hydrocarbon groups that do not contain an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom and do not contain an amide bond or a sulfonamide bond include an ethylene group, Alkylene groups such as a propylene group, a methylethylene group, a butylene group and a hexamethylene group; Cycloalkylene groups such as a cyclohexylene group; Arylene groups such as a phenylene group, a tolylene group, a xylylene group, a naphthylene group and a biphenylene group; combinations with arylene groups; and groups in which some or all of the hydrogen atoms of these alkylene groups and arylene groups are substituted with halogen atoms.
- the oxygen atom is —O—
- the nitrogen atom is —NR g51 —
- R g51 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group
- a sulfur atom is included as —S—.
- divalent hydrocarbon groups include the following. In the following formulas, Me represents a methyl group, Ph represents a phenyl group, and in each of the following formulas, one Rf group is bonded to the left side.
- the curable composition of the present invention may further contain an inorganic filler in order to suppress fluidity of the composition.
- an inorganic filler having a primary particle size of 0.01 to 0.1 ⁇ m is preferably used.
- the primary particle size of the inorganic filler is preferably 0.02 to 0.08 ⁇ m, more preferably 0.03 to 0.07 ⁇ m.
- the measured value of the primary particle size is the measured value by electron microscopy.
- the fluidity value measured by the fluidity test described below is an indicator of the fluidity of the composition.
- the fluidity value of the composition is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less. When the fluidity value is within the above range, the composition does not flow out after application, and a composition with suppressed fluidity can be obtained. If the fluidity value of the composition exceeds 15 mm, the composition spreads excessively during application, and the cured product of the composition tends to have poor sealability.
- Fluidity test 0.1 g of the curable composition was applied to an aluminum plate inclined at 45 degrees, and the distance (mm) flowed after 10 seconds was measured, and the value was taken as the fluidity value.
- the fluidity value of the composition can be adjusted by (a) the type and blending amount of the PFPE-containing silane compound; the type, particle size, and blending amount of the filler; the presence or absence of addition of a solvent, the blending amount, and the like.
- the primary particle size of the filler has a large effect on the fluidity value of the composition. It becomes easy to set the fluidity value of the product to 15 mm or less.
- Inorganic fillers include reinforcing fillers such as fumed titanium oxide; oxides such as silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, and aluminum oxide; calcium carbonate, magnesium carbonate, zinc carbonate, etc. carbonates; silicates such as aluminosilicate, calcium silicate and mica; talc; conductive fillers such as carbon black, copper powder and nickel powder; Examples include those treated with a hydrophobizing agent such as octamethylcyclotetrasiloxane.
- the inorganic filler is preferably carbon black or calcium carbonate, more preferably carbon black.
- the blending amount of component (e) is preferably adjusted appropriately so that the fluidity value of the curable composition in a fluidity test is 15 mm or less.
- the inorganic filler is preferably contained in the composition in an amount of 1 to 500 parts by mass, preferably 1 to 200 parts by mass, based on 100 parts by mass of (a) the silane compound containing PFPE. More preferably, it is 1 to 100 parts by mass.
- the curable composition of the present invention may further contain (f) surface-treated silica as an inorganic filler.
- the surface-treated silica is a component that suppresses the fluidity of the composition and imparts mechanical strength to the cured product of the composition.
- surface treatment refers to covalently treating silanol groups with different groups using a compound having reactivity with silanol groups on the silica surface.
- silica examples include fumed silica, calcined silica, silica aerogel, precipitated silica, and pulverized silica.
- fumed silica is preferable from the viewpoint of suppressing the fluidity of the composition and imparting mechanical strength to the cured product of the composition in a small amount.
- silazane compounds hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)tetramethyldisilazane, 1, 3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, heptamethyldisilazane, 2,2,4,4 ,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, 1,1,3,3-tetramethyldisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, etc.
- alkoxysilane compounds methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyl trimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, etc.), chlorosilane compounds (methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc.), octamethyl Examples include treatment with cyclotetrasiloxane, dimethylsiloxane oligomer
- silica surface can be hydrophobized with a small treatment amount.
- Hexamethyldisilazane and dimethyldichlorosilane are particularly preferred. Hexamethyldisilazane is preferred from the viewpoint of the degree of treatment and the stability (inactivation) of the surface state after treatment.
- These surface treatment agents may be blended with silica during preparation of the curable composition and kneaded to treat the surface of silica. Alternatively, commercially available materials may be used.
- the BET specific surface area of (f) the surface-treated silica is preferably 50 to 500 m 2 /g from the viewpoint of suppressing the fluidity of the curable composition and imparting high mechanical strength to the cured product. , 80 to 400 m 2 /g, more preferably 100 to 300 m 2 /g.
- the surface-treated silica may have carbon on the surface derived from the carbon of the hydrocarbon group such as the alkyl group possessed by the surface treatment agent. Since the hydrocarbon group is effective in hydrophobizing the silica surface, it is represented by —Si—(CH 3 ) n (where n is a value of 1 to 3, preferably 3) as exemplified above.
- the surface is treated with a compound having a structure that
- the degree of surface treatment at this time can be represented by the amount of carbon on the silica surface.
- the surface-treated silica preferably has a carbon content on the particle surface of 0.8% by mass or more, more preferably 2.0% by mass or more. More preferably, it is 3.0% by mass or more.
- the amount of carbon is 0.8% by mass or more, the degree of surface treatment increases with the amount of carbon, so the stability of the surface state is further improved.
- the upper limit of the carbon content is not particularly limited, it is preferably 20% by mass or less, more preferably 12% by mass or less, and even more preferably 8% by mass or less.
- a method for measuring the amount of carbon is known, and it can be determined from the amount of the surface treatment agent used for the surface treatment, and it can also be determined by a technique such as elemental analysis.
- the surface-treated silica is preferably contained in the curable composition in an amount of 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and still more preferably 100 parts by mass of the silane compound containing (a) PFPE. is 3 to 30 parts by mass.
- the curable composition may contain a solvent.
- a solvent for example, a fluorine atom-containing solvent
- the concentration of the solvent may be, for example, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 20 parts by mass with respect to 100 parts by mass of the curable composition. It may be less than or equal to parts by mass.
- the composition when using the curable composition, may be diluted with a solvent depending on the application and purpose.
- a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc. to a desired concentration.
- a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc.
- the curable composition may further contain various additives.
- various additives are not particularly limited, for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter referred to as "fluorine-containing Oil"), stabilizer (dehydrating agent, molecular sieve, magnesium sulfate or methyl orthoformate), viscosity modifier, fluorescent agent, colorant, heat resistance improver, cold resistance improver, rust inhibitor, liquid reinforcement It may contain an agent or the like.
- fluorine-containing oil examples include, but are not limited to, compounds represented by the following general formula (III) (perfluoro(poly)ether compounds).
- III perfluoro(poly)ether compounds.
- Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
- Rf 6 is , a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom
- Rf 5 and Rf 6 is more preferably each independently a C 1-3 perfluoroalkyl group.
- a', b', c' and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, , a′, b′, c′ and d′ are at least 1, preferably 1-300, more preferably 20-300.
- the order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' is arbitrary in the formula.
- -(OC 4 F 8 )- is -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF(CF 3 ))-,-(OC(CF 3 ) 2 CF 2 )-,-(OCF 2 C(CF 3 ) 2 )-,-(OCF (CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-.
- -(OC 3 F 6 )- is any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))- Well, preferably -(OCF 2 CF 2 CF 2 )-.
- -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, but is preferably -(OCF 2 CF 2 )-.
- perfluoro(poly)ether compounds represented by general formula (III) include compounds represented by any of the following general formulas (IIIa) and (IIIb) (one or a mixture of two or more good).
- Rf 5 and Rf 6 are as described above; in formula (IIIa), b'' is an integer of 1 or more and 100 or less; is each independently an integer of 1 or more and 30 or less, and c''' and d''' are each independently an integer of 1 or more and 300 or less.
- the fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000.
- the compound represented by formula (IIIa) preferably has a number average molecular weight of 2,000 to 8,000.
- the compound represented by formula (IIIb) has a number average molecular weight of 3,000 to 8,000.
- the compound represented by formula (IIIb) has a number average molecular weight of 8,000 to 30,000.
- the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the PFPE-containing silane compound (a). Preferably, it can be contained in an amount of 1-5 parts by weight.
- the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf' is a C5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer.
- Rf'-F and the chlorotrifluoroethylene oligomer are preferable in that they have a high affinity with (A) the PFPE-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group.
- the curable composition can form a more flexible cured composition.
- the average molecular weight of the fluorine-containing oil is larger than the average molecular weight of the PFPE-containing silane compound (a) (or the compound represented by formula (A), (B), (C) or (D)). You may With such an average molecular weight, it is possible to obtain more excellent friction durability and surface slipperiness in a cured product formed using the curable composition.
- the average molecular weight of the fluorine-containing oil is smaller than the average molecular weight of the PFPE-containing silane compound (a) (or the compound represented by formula (A), (B), (C) or (D)). You may By setting such an average molecular weight, it is possible to contribute to the formation of a cured product having high friction durability and high surface slipperiness while suppressing deterioration in the transparency of the cured product formed using the curable composition. .
- coloring agents include pigments and dyes.
- heat resistance improvers examples include red iron oxide and cerium oxide.
- liquid reinforcing agents include network polysiloxanes composed of triorganosiloxy units and SiO2 units.
- the curable composition can be produced by uniformly kneading the essential components (a) to (c) and the optional component (d) below using a mixing means such as a universal kneader or a kneader. can.
- a mixing means such as a universal kneader or a kneader.
- the order of addition of each component is arbitrary, but after adding and dispersing an optional component such as a filler into the mixture of component (a) and optionally other silane compounds, the remaining components such as a cross-linking agent and a catalyst are added. It is preferred to add and mix the ingredients.
- composition of such a curable composition may be configured as a so-called one-liquid type or as a two-liquid type, and the two may be mixed at the time of use, depending on the application.
- a cured product of the curable composition of the present invention can be used, for example, as a potting material, a sealing material, and the like. Moreover, since it exhibits high adhesion to the base material, it can be used effectively as an adhesive.
- the cured product of the curable composition of the present invention is filled, for example, in a gap of an electronic member (for example, a gap between a housing and a printed circuit board, or a gap between a resin-molded metal terminal and a mold resin). After drying, it can be used.
- the object to be treated is preferably washed with acetone, hydrofluoroether or the like and then dried. Furthermore, in addition to the above cleaning, pretreatment with UV ozone, oxygen plasma, or the like can further improve the abrasion resistance of the cured product.
- the walls of the voids, etc. Prior to the treatment with the curable composition of the present invention, if necessary, the walls of the voids, etc. are subjected to primer treatment to improve the adhesiveness of the potting material formed from the curable composition, Abrasion resistance can be further improved.
- the primer treatment may be performed according to a conventional method under the same conditions as those for the primer treatment when using a silane coupling agent.
- base materials include metals such as aluminum, copper, nickel, iron, brass, and stainless steel; polyester resins such as epoxy resins, polyethylene terephthalate and polybutylene terephthalate resins; Engineering plastics such as polyphenylene sulfide resin; glass and the like can be used.
- the temperature during the treatment there is no particular limitation on the temperature during the treatment, and usually the treatment should be performed at room temperature.
- the treatment time is also not particularly limited, but can be, for example, 5 minutes to 1 hour.
- the curable composition can be cured at room temperature.
- a curable composition is particularly useful as a composition for forming a potting material.
- the composition when using the curable composition of the present invention, may be diluted with a solvent depending on its use and purpose.
- a solvent used for dilution the above-exemplified fluorine type solvents can be used.
- it may be dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc. to a desired concentration.
- a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc.
- it is preferable to use the above solvents in thin film coating applications.
- the curable composition of the present invention When used as an adhesive for metal or plastic substrates, it exhibits high adhesion to substrates, and is therefore particularly suitable for use around electrical and electronic components and vehicle-mounted components. useful as an agent.
- a cured product of the curable composition of the present invention can have good elastic modulus, chemical resistance, acid resistance, and base resistance. Furthermore, it has a low glass transition temperature, can suppress an increase in elastic modulus at low temperatures, and has a high decomposition temperature.
- the cured product of such a curable composition of the present invention can be used in automobile parts (e.g., sealing materials, specifically, gaskets), chemical plants, electrical and electronic parts such as semiconductor manufacturing equipment, and cold regions (e.g. - 50° C. or less) and automobile parts that can be used under high temperature conditions.
- PFPE-containing silane compound (a) represented by the following formula.
- the resulting PFPE-containing silane compound (a) was identified by 19 F-NMR analysis as containing -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 97 mol %.
- PFPE-containing silane compound (b) represented by the following formula.
- the resulting PFPE-containing silane compound (b) was identified by 19 F-NMR analysis as —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 2 (CH 3 ) and the raw material —CF 2 — By comparing the integrated values of the COOCH 2 CH 3 peaks, the silane termination rate was calculated to be 97 mol %.
- R′ in the following formula 85 mol % of CH 3 and 15 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
- PFPE-containing silane compound (b) (R'O) 2 ( CH3 )Si - CH2CH2CH2-NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - C6H10 - CH2 -C6H10 -NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n -OCF2 - CONH - CH2CH2CH2 - Si(OR') 2 ( CH3 ) (m ⁇ 12, n ⁇ 12)
- PFPE-containing silane compound (c) represented by the following formula.
- the resulting PFPE-containing silane compound (c) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 99 mol %.
- R′ in the following formula 91 mol % of CH 3 and 9 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
- PFPE-containing silane compound (d) represented by the following formula.
- the resulting PFPE-containing silane compound (d) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 2 (CH 3 ) and the raw material -CF 2 - By comparing the peak integral values of COOCH 2 CH 3 , the silane termination rate was calculated to be 100 mol %.
- R′ in the following formula 88 mol % of CH 3 and 12 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
- PFPE-containing silane compound (e) represented by the following formula.
- the resulting PFPE-containing silane compound (e) was identified by 19 F-NMR analysis as containing —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 3 and the starting material —CF 2 —COOCH 2 CH 3 . were compared, and the silane termination rate was calculated to be 99 mol %.
- Example 1 Preparation of curable composition
- Example 2 A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (b) was used instead of the PFPE-containing silane compound (a).
- Example 3 Example except that 0.1 part by mass of dibutylbis(triethoxysiloxy)tin was used instead of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst, and 0.5 part by mass of 3-aminopropyltriethoxylan was added. 1 to prepare a curable composition.
- Example 4 80 parts by mass of silane compound (a) containing PFPE, 20 parts by mass of silane compound (c) containing PFPE, 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, and 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst are mixed.
- a curable composition was prepared by weighing in a plastic container for the above and stirring using a rotation/revolution mixer.
- Example 5 In addition to the composition of Example 4, 0.3 parts by mass of tris(3-trimethoxysilylpropyl)isocyanurate was further added to prepare a curable composition.
- Example 6 In addition to the composition of Example 5, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition. Here, the amount of carbon in the fumed silica used in this example was 3.5% by mass.
- Example 7 60 parts of PFPE-containing silane compound (a), 40 parts of PFPE-containing silane compound (d), 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, 0.3 parts by mass of tris(3-trimethoxysilylpropyl) isocyanurate, And 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst were weighed into a mixing plastic container and stirred using a rotation/revolution mixer to prepare a curable composition.
- Example 8 A curable composition was prepared in the same manner as in Example 7, except that the blending ratio of the PFPE-containing silane compound (a) to the PFPE-containing silane compound (d) was changed to 80:20.
- Example 9 In addition to the composition of Example 8, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition.
- composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (e) was used instead of the PFPE-containing silane compound (a), and the amount of methyltrimethoxysilane was changed to 2 parts by mass. .
- Cohesive failure rate 80% or more 3 Cohesive failure rate 60% or more and less than 80% 2: Cohesive failure rate 30% or more and less than 60% 1: Cohesive failure rate less than 30%
- the curable compositions of Examples that is, the curable compositions using the PFPE-containing silane compound having a cyclic hydrocarbon group in the general formula (I) had a high cohesive failure rate and excellent adhesion. rice field.
- a comparative example that is, when a compound having no cyclic hydrocarbon group in general formula (I) was used, peeling occurred between the curable composition and the substrate. That is, the curable compositions of Examples were superior in terms of effectiveness as adhesives.
- fluidity test 0.1 g of the curable composition prepared in Examples 6 and 9 was applied in a circle using a syringe to an aluminum plate (in accordance with JIS H 4000 A1050P) inclined at 45 degrees, and the distance flowed after 10 seconds (mm) was measured and taken as the fluidity value.
- the fluidity value is more preferably in the range of 10 mm or less, particularly preferably 5 mm or less.
- the compositions of Examples 6 and 9 both had a fluidity value of 3 mm, indicating that the fluidity of the composition was suppressed.
- the present invention provides a curable composition that can be cured by humidity at room temperature and has excellent adhesion to substrates. Since the curable composition of the present invention has excellent adhesiveness due to its good adhesion, the curable composition of the present invention has high reliability in adhesion and can be suitably used around electric and electronic parts and parts for vehicles.
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Abstract
A curable composition comprising: a perfluoro(poly)ether group–containing silane compound represented by general formula (I) (the radicals in the formula are defined in the description); (b) an organosilicon compound having at least two of an OR2 group bonded to a Si atom (wherein each appearance of R2 independently represents a hydrogen atom or a monovalent organic group), or a partial hydrolysis-condensation product of said compound; and (c) a condensation catalyst.
Description
本発明は、硬化性組成物に関する。
The present invention relates to curable compositions.
ある種のフルオロ(ポリ)エーテル系化合物を含む組成物は、優れた撥水性、撥油性等を有する。例えば、特許文献1には、室温硬化型パーフルオロ(ポリ)エーテル組成物の硬化皮膜が表面に形成されたゴムについて記載されており、離型性、耐溶剤性、耐薬品性、耐候性、撥水性、撥油性等が付与されたゴムが提供されると記載されている。特許文献1の実施例には、パーフルオロ(ポリ)エーテル構造として、(OCF2CF(CF3))mOCF2CF2O(CF(CF3)CF2O)n(式中、m+n=90)を有する化合物を用いた組成物が記載されている。また、特許文献2~7には、パーフルオロ(ポリ)エーテル構造を有する湿気硬化性の組成物が記載されている。
Compositions containing certain fluoro(poly)ether compounds have excellent water repellency, oil repellency, and the like. For example, Patent Literature 1 describes a rubber having a cured film of a room-temperature-curable perfluoro(poly)ether composition formed on the surface thereof, and exhibits releasability, solvent resistance, chemical resistance, weather resistance, It is described that a rubber imparted with water repellency, oil repellency, etc. is provided. Examples of Patent Document 1 include (OCF 2 CF(CF 3 )) m OCF 2 CF 2 O(CF(CF 3 )CF 2 O) n (where m+n= 90) have been described. Furthermore, Patent Documents 2 to 7 describe moisture-curable compositions having a perfluoro(poly)ether structure.
パーフルオロ(ポリ)エーテル組成物の硬化物は撥水性、撥油性等を備えたゴムとして利用することができるため、接着剤とすると、接着部の安定性を高く保つことができる。しかしながら、フッ素化合物は概して非フッ素系の物質との親和性が良好ではない。このため、良好な密着性を備えた接着剤に対する需要が常に存在する。そこで本発明の課題は、各種基材に対する密着性に優れた硬化物を与える硬化性組成物を提供することにある。
The cured product of the perfluoro(poly)ether composition can be used as a rubber with water repellency, oil repellency, etc., so when used as an adhesive, the stability of the bonded part can be maintained at a high level. However, fluorine compounds generally do not have good affinity with non-fluorinated substances. Therefore, there is always a demand for adhesives with good adhesion. Accordingly, an object of the present invention is to provide a curable composition that gives a cured product having excellent adhesion to various substrates.
本発明の第1の要旨によれば、
(a)下記式(I):
[式中:
R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
R4は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
pは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 pR4 3-p)jにおいて少なくとも1つのSiR3 pR4 3-pは、pが0~2の整数であり、
qは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 qR4 3-q)jにおいて少なくとも1つのSiR3 qR4 3-qは、qが0~2の整数であり、
R5は、各出現においてそれぞれ独立して、j+1価の有機基であり、
R6は、各出現においてそれぞれ独立して、-R22-R21-R23-であり、
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、
R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R23は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基であり、
PFPE1は、各出現においてそれぞれ独立して、-RF-RFE-であり、
RFは、-(CfF2f)-であり(ここで、fは1~10の整数である)、
RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
(式中:
a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0~200の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5であり、添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり、
X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である)
で表される2価のフルオロポリエーテル基であり、
jは、各出現において独立して、1~9の整数であり、
kは、1以上の整数である]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物;
(b)Si原子と結合したOR2基を少なくとも2個有する化合物(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(ただし、前記(a)に該当するものを除く)またはその部分加水分解縮合物;並びに
(c)縮合触媒
を含む、硬化性組成物が提供される。 According to the first gist of the present invention,
(a) the following formula (I):
[In the formula:
each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group;
R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
p is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2;
q is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2;
R 5 is independently at each occurrence a j+1 valent organic group;
R 6 is independently at each occurrence -R 22 -R 21 -R 23 -;
R 21 is independently at each occurrence a cycloalkylene-containing group;
R 22 is independently at each occurrence a single bond or a divalent organic group;
R 23 is independently at each occurrence a single bond or a divalent organic group;
R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group;
PFPE 1 is independently at each occurrence -R F -R FE -;
R F is -(C f F 2f )-, where f is an integer from 1 to 10;
R FE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
(in the formula:
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 and the order of existence of each repeating unit enclosed in parentheses with subscripts a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula,
X 10 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom, with the proviso that when all X 10 are hydrogen atoms or chlorine atoms, a1, a2, a4, a5, a6, a7 and at least one of a8 is an integer of 1 or more)
A divalent fluoropolyether group represented by
j is independently at each occurrence an integer from 1 to 9;
k is an integer of 1 or more]
A perfluoro (poly) ether group-containing silane compound represented by;
(b) a compound having at least two OR 2 groups bonded to Si atoms (wherein each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group) (provided that the above (a ) or a partial hydrolytic condensate thereof; and (c) a condensation catalyst.
(a)下記式(I):
[式中:
R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
R4は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
pは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 pR4 3-p)jにおいて少なくとも1つのSiR3 pR4 3-pは、pが0~2の整数であり、
qは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 qR4 3-q)jにおいて少なくとも1つのSiR3 qR4 3-qは、qが0~2の整数であり、
R5は、各出現においてそれぞれ独立して、j+1価の有機基であり、
R6は、各出現においてそれぞれ独立して、-R22-R21-R23-であり、
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、
R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R23は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基であり、
PFPE1は、各出現においてそれぞれ独立して、-RF-RFE-であり、
RFは、-(CfF2f)-であり(ここで、fは1~10の整数である)、
RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
(式中:
a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0~200の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5であり、添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり、
X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である)
で表される2価のフルオロポリエーテル基であり、
jは、各出現において独立して、1~9の整数であり、
kは、1以上の整数である]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物;
(b)Si原子と結合したOR2基を少なくとも2個有する化合物(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(ただし、前記(a)に該当するものを除く)またはその部分加水分解縮合物;並びに
(c)縮合触媒
を含む、硬化性組成物が提供される。 According to the first gist of the present invention,
(a) the following formula (I):
[In the formula:
each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group;
R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
p is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2;
q is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2;
R 5 is independently at each occurrence a j+1 valent organic group;
R 6 is independently at each occurrence -R 22 -R 21 -R 23 -;
R 21 is independently at each occurrence a cycloalkylene-containing group;
R 22 is independently at each occurrence a single bond or a divalent organic group;
R 23 is independently at each occurrence a single bond or a divalent organic group;
R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group;
PFPE 1 is independently at each occurrence -R F -R FE -;
R F is -(C f F 2f )-, where f is an integer from 1 to 10;
R FE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
(in the formula:
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 and the order of existence of each repeating unit enclosed in parentheses with subscripts a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula,
X 10 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom, with the proviso that when all X 10 are hydrogen atoms or chlorine atoms, a1, a2, a4, a5, a6, a7 and at least one of a8 is an integer of 1 or more)
A divalent fluoropolyether group represented by
j is independently at each occurrence an integer from 1 to 9;
k is an integer of 1 or more]
A perfluoro (poly) ether group-containing silane compound represented by;
(b) a compound having at least two OR 2 groups bonded to Si atoms (wherein each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group) (provided that the above (a ) or a partial hydrolytic condensate thereof; and (c) a condensation catalyst.
本発明によると、基材との密着性に優れた湿気硬化性の硬化性組成物を提供することができる。
According to the present invention, it is possible to provide a moisture-curable curable composition with excellent adhesion to substrates.
以下、本発明の硬化性組成物について説明する。本発明の硬化性組成物は、(a)水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上、および、パーフルオロ(ポリ)エーテル基を有する化合物であって、下記式(I):
[式中:
R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
R4は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
pは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 pR4 3-p)jにおいて少なくとも1つのSiR3 pR4 3-pは、pが0~2の整数であり、
qは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 qR4 3-q)jにおいて少なくとも1つのSiR3 qR4 3-qは、qが0~2の整数であり、
R5は、各出現においてそれぞれ独立して、j+1価の有機基であり、
R6は、各出現においてそれぞれ独立して、-R22-R21-R23-であり、
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、
R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R23は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基であり、
PFPE1は、各出現においてそれぞれ独立して、-RF-RFE-であり、
RFは、-(CfF2f)-であり(ここで、fは1~10の整数である)、
RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
(式中:
a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0~200の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5であり、添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり、
X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である)
で表される2価のフルオロポリエーテル基であり、
jは、各出現において独立して、1~9の整数であり、
kは、1以上の整数である]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物(以下において、「PFPE含有シラン化合物(a)」と称することがある)、
(b)Si原子と結合したOR2基(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)を少なくとも2個有する有機ケイ素化合物(ただし、PFPE含有シラン化合物(a)を除く)またはその部分加水分解縮合物(以下において、「架橋剤(b)」と称することがある)、および
縮合触媒(c)
を有する。 The curable composition of the present invention is described below. The curable composition of the present invention includes (a) a compound having two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group, and a perfluoro (poly) ether group. with the following formula (I):
[In the formula:
each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group;
R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
p is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2;
q is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2;
R 5 is independently at each occurrence a j+1 valent organic group;
R 6 is independently at each occurrence -R 22 -R 21 -R 23 -;
R 21 is independently at each occurrence a cycloalkylene-containing group;
R 22 is independently at each occurrence a single bond or a divalent organic group;
R 23 is independently at each occurrence a single bond or a divalent organic group;
R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group;
PFPE 1 is independently at each occurrence -R F -R FE -;
R F is -(C f F 2f )-, where f is an integer from 1 to 10;
RFE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
(in the formula:
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 and the order of existence of each repeating unit enclosed in parentheses with subscripts a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula,
X 10 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom, with the proviso that when all X 10 are hydrogen atoms or chlorine atoms, a1, a2, a4, a5, a6, a7 and at least one of a8 is an integer of 1 or more)
A divalent fluoropolyether group represented by
j is independently at each occurrence an integer from 1 to 9;
k is an integer of 1 or more]
A perfluoro (poly) ether group-containing silane compound represented by (hereinafter sometimes referred to as "PFPE-containing silane compound (a)"),
( b ) an organosilicon compound ( with the proviso that PFPE containing silane compound (a)) or a partial hydrolysis condensate thereof (hereinafter sometimes referred to as "crosslinking agent (b)"), and a condensation catalyst (c)
have
[式中:
R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
R4は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
pは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 pR4 3-p)jにおいて少なくとも1つのSiR3 pR4 3-pは、pが0~2の整数であり、
qは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 qR4 3-q)jにおいて少なくとも1つのSiR3 qR4 3-qは、qが0~2の整数であり、
R5は、各出現においてそれぞれ独立して、j+1価の有機基であり、
R6は、各出現においてそれぞれ独立して、-R22-R21-R23-であり、
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、
R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R23は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基であり、
PFPE1は、各出現においてそれぞれ独立して、-RF-RFE-であり、
RFは、-(CfF2f)-であり(ここで、fは1~10の整数である)、
RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
(式中:
a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0~200の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5であり、添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり、
X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である)
で表される2価のフルオロポリエーテル基であり、
jは、各出現において独立して、1~9の整数であり、
kは、1以上の整数である]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物(以下において、「PFPE含有シラン化合物(a)」と称することがある)、
(b)Si原子と結合したOR2基(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)を少なくとも2個有する有機ケイ素化合物(ただし、PFPE含有シラン化合物(a)を除く)またはその部分加水分解縮合物(以下において、「架橋剤(b)」と称することがある)、および
縮合触媒(c)
を有する。 The curable composition of the present invention is described below. The curable composition of the present invention includes (a) a compound having two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group, and a perfluoro (poly) ether group. with the following formula (I):
[In the formula:
each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group;
R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
p is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2;
q is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2;
R 5 is independently at each occurrence a j+1 valent organic group;
R 6 is independently at each occurrence -R 22 -R 21 -R 23 -;
R 21 is independently at each occurrence a cycloalkylene-containing group;
R 22 is independently at each occurrence a single bond or a divalent organic group;
R 23 is independently at each occurrence a single bond or a divalent organic group;
R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group;
PFPE 1 is independently at each occurrence -R F -R FE -;
R F is -(C f F 2f )-, where f is an integer from 1 to 10;
RFE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
(in the formula:
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 and the order of existence of each repeating unit enclosed in parentheses with subscripts a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula,
X 10 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom, with the proviso that when all X 10 are hydrogen atoms or chlorine atoms, a1, a2, a4, a5, a6, a7 and at least one of a8 is an integer of 1 or more)
A divalent fluoropolyether group represented by
j is independently at each occurrence an integer from 1 to 9;
k is an integer of 1 or more]
A perfluoro (poly) ether group-containing silane compound represented by (hereinafter sometimes referred to as "PFPE-containing silane compound (a)"),
( b ) an organosilicon compound ( with the proviso that PFPE containing silane compound (a)) or a partial hydrolysis condensate thereof (hereinafter sometimes referred to as "crosslinking agent (b)"), and a condensation catalyst (c)
have
なお、本明細書において用いられる場合、「2~10価の有機基」とは、炭素を含有する2~10価の基を意味する。かかる2~10価の有機基としては、特に限定されないが、炭化水素基からさらに1~9個の水素原子を脱離させた2~10価の基が挙げられる。2価の有機基としては、特に限定されるものではないが、炭化水素基からさらに1個の水素原子を脱離させた2価の基が挙げられる。
As used herein, "a divalent to decavalent organic group" means a divalent to decavalent group containing carbon. Such divalent to decavalent organic groups are not particularly limited, but include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group. The divalent organic group is not particularly limited, but includes a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.
本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、分子から1個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、1つまたはそれ以上の置換基により置換されていてもよい、炭素原子数1~20の炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、1つまたはそれ以上の環構造を含んでいてもよい。なお、かかる炭化水素基は、その末端または分子鎖中に、1つまたはそれ以上のN、O、S、Si、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。
As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen from which one hydrogen atom has been removed from the molecule. Examples of such hydrocarbon groups include, but are not limited to, hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups. , an aromatic hydrocarbon group, and the like. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures. Such hydrocarbon groups may have one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain.
本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子;1個またはそれ以上のハロゲン原子により置換されていてもよい、C1-6アルキル基、C2-6アルケニル基、C2-6アルキニル基、C3-10シクロアルキル基、C3-10不飽和シクロアルキル基、5~10員のヘテロシクリル基、5~10員の不飽和ヘテロシクリル基、C6-10アリール基および5~10員のヘテロアリール基から選択される1個またはそれ以上の基が挙げられる。
As used herein, the substituents of the "hydrocarbon group" are not particularly limited, but include, for example, halogen atoms; C 1-6 alkyl optionally substituted by one or more halogen atoms group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C 6-10 aryl groups and 5-10 membered heteroaryl groups.
本明細書において、アルキル基およびフェニル基は、特記しない限り、非置換であっても、置換されていてもよい。かかる基の置換基としては、特に限定されないが、例えば、ハロゲン原子、C1-6アルキル基、C2-6アルケニル基およびC2-6アルキニル基から選択される1個またはそれ以上の基が挙げられる。
In this specification, alkyl groups and phenyl groups can be unsubstituted or substituted unless otherwise specified. Substituents of such groups are not particularly limited, but for example, one or more groups selected from halogen atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups mentioned.
(PFPE含有シラン化合物(a))
上記PFPE含有シラン化合物(a)は、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上、および、パーフルオロ(ポリ)エーテル基を有し、かつ、パーフルオロ(ポリ)エーテル基が連結する-C(=O)NH-で示される構造を少なくとも一つ有する化合物である。 (PFPE-containing silane compound (a))
The PFPE-containing silane compound (a) has two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group, and a perfluoro(poly)ether group, and , a compound having at least one structure represented by -C(=O)NH- to which a perfluoro(poly)ether group is linked.
上記PFPE含有シラン化合物(a)は、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子を2以上、および、パーフルオロ(ポリ)エーテル基を有し、かつ、パーフルオロ(ポリ)エーテル基が連結する-C(=O)NH-で示される構造を少なくとも一つ有する化合物である。 (PFPE-containing silane compound (a))
The PFPE-containing silane compound (a) has two or more Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group, and a perfluoro(poly)ether group, and , a compound having at least one structure represented by -C(=O)NH- to which a perfluoro(poly)ether group is linked.
「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応を受け得る基を意味し、すなわち、加水分解反応により、化合物の主骨格から脱離し得る基を意味する。加水分解可能な基の例としては、-OR、-OCOR、-O-N=CR2、-NR2、-NHR、ハロゲン原子(これら式中、Rは、置換または非置換の炭素原子数1~4のアルキル基を示す)などが挙げられ、好ましくは-OR(即ち、アルコキシ基)である。Rの例には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基などの非置換アルキル基;クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、これらの中では、塩素原子が好ましい。
A "hydrolyzable group", as used herein, means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being eliminated from the backbone of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR, -OCOR, -ON=CR 2 , -NR 2 , -NHR, halogen atoms (wherein R is a substituted or unsubstituted 1 carbon atom -OR (that is, an alkoxy group) is preferred. Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group. Halogen atoms include fluorine, chlorine, bromine and iodine atoms, with chlorine atoms being preferred.
上記水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子は、PFPE含有シラン化合物(a)の分子主鎖の両末端に存在する。本明細書において、PFPE含有シラン化合物(a)の分子主鎖とは、PFPE含有シラン化合物(a)の分子中で相対的に最も長い結合鎖を表す。
The Si atoms bonded to at least one group selected from the group consisting of hydroxyl groups and hydrolyzable groups are present at both ends of the molecular main chain of the PFPE-containing silane compound (a). As used herein, the molecular main chain of the PFPE-containing silane compound (a) represents the relatively longest linking chain in the molecule of the PFPE-containing silane compound (a).
上記PFPE1で示されるパーフルオロ(ポリ)エーテル基は、各出現においてそれぞれ独立して、-RF-RFE-である。
The perfluoro(poly)ether group represented by PFPE 1 above is independently -R F -R FE - at each occurrence.
上記RFは、-(CfF2f)-であり、ここで、fは1~10の整数である。
R F above is -(C f F 2f )-, where f is an integer of 1-10.
上記RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
で表される2価のフルオロポリエーテル基である。式中、a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0以上200以下の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5以上であり、より好ましくは10以上、例えば10以上200以下である。添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくは水素原子またはフッ素原子であり、より好ましくはフッ素原子である。ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である。以下において、上記-RF-RFE-で表される構造を有するパーフルオロ(ポリ)エーテル基を、「PFPE1」と称することがある。本発明の硬化性組成物は、上記のようなPFPE1を有することにより、その硬化物が低いガラス転移温度(Tg)を有し得る。本明細書における-PFPE1-部分は、1種類または複数種類のフルオロアルキルエーテル構造を組み合わせてなるポリマー構造である。a1~a8またはそれらの和は、ポリマー中のフルオロアルキルエーテル構造の繰り返し単位数を指すが、これらの値は、ポリマー中の一構造単位における平均値であり、近似値であることが当業者には理解される。例えばPFPE1が-(CfF2f)-(OCF2)a1-(OC2F4)a2-で表されている場合、a1の値は各-PFPE1-部分の(OCF2)a1単位の数の平均を、a2の値は各-PFPE1-部分の(OC2F4)a2単位の数の平均をそれぞれ表し、a1+a2=のように記載されている場合、各繰り返し単位の合計の平均がその値(近似値)であることを表す。 The above RFE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
is a divalent fluoropolyether group represented by In the formula, a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 or more and 200 or less, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 or more, more preferably 10 or more, for example 10 or more and 200 or less. The order of existence of each repeating unit enclosed in parentheses with subscript a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula. Each occurrence of X 10 is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. provided that when all X 10 are hydrogen atoms or chlorine atoms, at least one of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or greater. Hereinafter, the perfluoro(poly)ether group having the structure represented by -R F -R FE - may be referred to as "PFPE 1 ". By including PFPE 1 as described above, the curable composition of the present invention can have a low glass transition temperature (Tg) of the cured product. The -PFPE 1 - moiety herein is a polymer structure that combines one or more types of fluoroalkyl ether structures. a1 to a8 or the sum thereof refers to the number of repeating units of the fluoroalkyl ether structure in the polymer, but these values are average values in one structural unit in the polymer and are approximate values for those skilled in the art. is understood. For example, if PFPE 1 is represented by -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -, then the value of a1 is the (OCF 2 ) a1 unit of each -PFPE 1 -moiety. and the value of a2 represents the average number of (OC 2 F 4 ) a2 units in each -PFPE 1 -moiety, respectively, and when written as a1+a2=, the total number of each repeat unit Indicates that the average is that value (approximate value).
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
で表される2価のフルオロポリエーテル基である。式中、a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0以上200以下の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5以上であり、より好ましくは10以上、例えば10以上200以下である。添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくは水素原子またはフッ素原子であり、より好ましくはフッ素原子である。ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である。以下において、上記-RF-RFE-で表される構造を有するパーフルオロ(ポリ)エーテル基を、「PFPE1」と称することがある。本発明の硬化性組成物は、上記のようなPFPE1を有することにより、その硬化物が低いガラス転移温度(Tg)を有し得る。本明細書における-PFPE1-部分は、1種類または複数種類のフルオロアルキルエーテル構造を組み合わせてなるポリマー構造である。a1~a8またはそれらの和は、ポリマー中のフルオロアルキルエーテル構造の繰り返し単位数を指すが、これらの値は、ポリマー中の一構造単位における平均値であり、近似値であることが当業者には理解される。例えばPFPE1が-(CfF2f)-(OCF2)a1-(OC2F4)a2-で表されている場合、a1の値は各-PFPE1-部分の(OCF2)a1単位の数の平均を、a2の値は各-PFPE1-部分の(OC2F4)a2単位の数の平均をそれぞれ表し、a1+a2=のように記載されている場合、各繰り返し単位の合計の平均がその値(近似値)であることを表す。 The above RFE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
is a divalent fluoropolyether group represented by In the formula, a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 or more and 200 or less, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 or more, more preferably 10 or more, for example 10 or more and 200 or less. The order of existence of each repeating unit enclosed in parentheses with subscript a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula. Each occurrence of X 10 is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. provided that when all X 10 are hydrogen atoms or chlorine atoms, at least one of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or greater. Hereinafter, the perfluoro(poly)ether group having the structure represented by -R F -R FE - may be referred to as "PFPE 1 ". By including PFPE 1 as described above, the curable composition of the present invention can have a low glass transition temperature (Tg) of the cured product. The -PFPE 1 - moiety herein is a polymer structure that combines one or more types of fluoroalkyl ether structures. a1 to a8 or the sum thereof refers to the number of repeating units of the fluoroalkyl ether structure in the polymer, but these values are average values in one structural unit in the polymer and are approximate values for those skilled in the art. is understood. For example, if PFPE 1 is represented by -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -, then the value of a1 is the (OCF 2 ) a1 unit of each -PFPE 1 -moiety. and the value of a2 represents the average number of (OC 2 F 4 ) a2 units in each -PFPE 1 -moiety, respectively, and when written as a1+a2=, the total number of each repeat unit Indicates that the average is that value (approximate value).
一の態様において上記a1およびa2はそれぞれ独立して、0以上200以下の整数であるが、一の好ましい態様において、a1およびa2は、それぞれ独立して1以上200以下の整数である。a1およびa2の値は、好ましくはそれぞれ独立して1以上50以下の整数である。a1およびa2の和は、好ましくは20以上、より好ましくは30以上、さらに好ましくは40以上である。
In one embodiment, a1 and a2 are each independently integers of 0 or more and 200 or less, and in one preferred embodiment, a1 and a2 are each independently integers of 1 or more and 200 or less. The values of a1 and a2 are preferably independently integers of 1 or more and 50 or less. The sum of a1 and a2 is preferably 20 or more, more preferably 30 or more, and even more preferably 40 or more.
一の態様において上記a3、a4、a5、a6、a7およびa8はそれぞれ独立して、好ましくは0以上30以下の整数であり、より好ましくは20以下の整数であり、特に好ましくは10以下の整数であり、さらに好ましくは5以下の整数であり、0であってもよい。
In one embodiment, a3, a4, a5, a6, a7 and a8 are each independently preferably an integer of 0 or more and 30 or less, more preferably an integer of 20 or less, and particularly preferably an integer of 10 or less and more preferably an integer of 5 or less, and may be 0.
一の態様において、a3、a4、a5、a6、a7およびa8の和は、好ましくは30以下、より好ましくは20以下、さらに好ましくは10以下、特に好ましくは5以下である。
In one aspect, the sum of a3, a4, a5, a6, a7 and a8 is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less.
これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよい。また、同じ炭素数の繰り返し単位であっても、各々の直鎖状または分岐鎖状の異なる構造を2種類以上同時にPFPE1中に有することができる。これら繰り返し単位としては、好ましくは直鎖状である。例えば、-(OC8F16)-は、-(OCF2CF2CF2CF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2CF2CF2CF2)-、-(OCF2CF2CF(CF3)CF2CF2CF2CF2)-、-(OCF2CF2CF2CF(CF3)CF2CF2CF2)-、-(OCF2CF2CF2CF2CF(CF3)CF2CF2)-、-(OCF2CF2CF2CF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF2CF2CF2CF(CF3))-等であってもよいが、好ましくは-(OCF2CF2CF2CF2CF2CF2CF2CF2)-である。-(OC7F14)-は、-(OCF2CF2CF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2CF2CF2)-、-(OCF2CF2CF(CF3)CF2CF2CF2)-、-(OCF2CF2CF2CF(CF3)CF2CF2)-、-(OCF2CF2CF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF2CF2CF(CF3))-等であってもよいが、好ましくは-(OCF2CF2CF2CF2CF2CF2CF2)-である。-(OC6F12)-は、-(OCF2CF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2CF2)-、-(OCF2CF2CF(CF3)CF2CF2)-、-(OCF2CF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF2CF(CF3))-等であってもよいが、好ましくは-(OCF2CF2CF2CF2CF2CF2)-である。-(OC5F10)-は、-(OCF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2)-、-(OCF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF(CF3))-等であってもよいが、好ましくは-(OCF2CF2CF2CF2CF2)-である。-(OC4F8)-は、-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-および-(OCF2CF(C2F5))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2CF2)-である。-(OC3F6)-(即ち、上記式中、X10はフッ素原子である)は、-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-および-(OCF2CF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2)-である。また、-(OC2F4)-は、-(OCF2CF2)-および-(OCF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2)-である。
These repeating units may be linear or branched. Moreover, even if the repeating units have the same number of carbon atoms, PFPE 1 can have two or more types of different straight-chain or branched-chain structures at the same time. These repeating units are preferably linear. For example, -(OC 8 F 16 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,- (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) -, - (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) -, - (OCF 2 CF 2 CF 2 CF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF(CF 3 ))-, etc., but preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )—. - ( OC7F14 )- is - ( OCF2CF2CF2CF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2CF2CF2 ) - , - ( OCF2CF ( CF3 ) CF2CF2CF2CF2 )-,- ( OCF2CF2CF ( CF3 ) CF2CF2CF2 )-, - ( OCF2CF2CF2CF ( CF 3 ) CF 2 CF 2 )-, - (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ) CF 2 )-, - (OCF 2 CF 2 CF 2 CF 2 CF 2 CF (CF 3 ))-, etc. Although it may be present, it is preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-. - ( OC6F12 )- is - ( OCF2CF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2CF2 ) - , - ( OCF2CF (CF 3 )CF 2 CF 2 CF 2 )-,-(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-,-(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )-,- It may be (OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ))- or the like, but is preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-. - ( OC5F10 )- is - ( OCF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2 )-, - ( OCF2CF ( CF3 ) CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 ))-, but preferably -( OCF 2 CF 2 CF 2 CF 2 CF 2 )—. -( OC4F8 )- is - ( OCF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2 )-, - ( OCF2CF ( CF3 ) CF2 )- , -( OCF2CF2CF ( CF3 ))-, -(OC( CF3 ) 2CF2 )-, -( OCF2C (CF3)2 ) - , -(OCF ( CF3 )CF( Any of CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )- (that is, in the above formula, X 10 is a fluorine atom) is represented by -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -( OCF 2 CF(CF 3 ))—, preferably —(OCF 2 CF 2 CF 2 )—. -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, but is preferably -(OCF 2 CF 2 )- be.
-(CfF2f)-で示される単位は、PFPE1の左側末端に位置する構造である。fの値は1以上10以下の整数であり、1以上6以下の整数であることが好ましく、1以上4以下の整数であることがより好ましい。fの値は、PFPE1の有する繰り返し単位のいずれか1つあたりに含まれる炭素数と同じ値であることが、より好ましい。-(CfF2f)-で示される単位は、直鎖状であっても、分枝鎖状であってもよい。したがって、-(CfF2f)-で示される単位は、例えば、-(CF2)-のほか、-(CF2CF2)-、-(CF(CF3))-、-(CF2CF2CF2)-、-(CF(CF3)CF2)-、-(CF2CF(CF3))-、-(CF2CF2CF2CF2)-、-(CF2CF(CF3)CF2)-、-(CF2CF2CF(CF3))-、-(CF(CF2CF3)CF2)-、-(CF2CF(CF2CF3))-、-(CF2C(CF3)2CF2)-等の構造をとることができる。
The unit denoted by -(C f F 2f )- is the structure located at the left end of PFPE1 . The value of f is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 6 or less, and more preferably an integer of 1 or more and 4 or less. More preferably, the value of f is the same value as the number of carbon atoms contained in any one of the repeating units of PFPE 1 . A unit represented by -(C f F 2f )- may be linear or branched. Therefore, the unit represented by -(C f F 2f )- is, for example, -(CF 2 )-, -(CF 2 CF 2 )-, -(CF(CF 3 ))-, -(CF 2 CF 2 CF 2 )-,-(CF(CF 3 )CF 2 )-,-(CF 2 CF(CF 3 ))-,-(CF 2 CF 2 CF 2 CF 2 )-,-(CF 2 CF( CF 3 )CF 2 )-, -(CF 2 CF 2 CF(CF 3 ))-, -(CF(CF 2 CF 3 )CF 2 )-, -(CF 2 CF(CF 2 CF 3 ))-, -(CF 2 C(CF 3 ) 2 CF 2 )- and other structures can be taken.
本発明のPFPE含有シラン化合物(a)におけるPFPE1は、パーフルオロポリエーテル基として調製が可能なものであれば、これらの繰り返し単位の他に、酸素原子および炭素原子数9以上のパーフルオロアルキレン基からなる繰り返し単位を有していてもよい。
If PFPE 1 in the PFPE-containing silane compound (a) of the present invention can be prepared as a perfluoropolyether group, in addition to these repeating units, an oxygen atom and a perfluoroalkylene having 9 or more carbon atoms It may have a repeating unit consisting of a group.
一の態様において、PFPE1は直鎖状の繰り返し単位を有する。本態様では、PFPE含有シラン化合物(a)の低温における分子の運動性が低下しにくくなる。直鎖状の繰り返し単位を有することにより、PFPE含有シラン化合物(a)の物性値(例えば、低温における弾性率)が、室温における値と比べて低下しにくくなり得るため、広い温度範囲に適用することも可能となる。なお、本明細書において、「弾性率」は、動的弾性率、より具体的には貯蔵弾性率を示す。
In one aspect, PFPE 1 has linear repeating units. In this aspect, the molecular mobility of the PFPE-containing silane compound (a) at low temperatures is less likely to decrease. By having a linear repeating unit, the physical property values (e.g., elastic modulus at low temperature) of the PFPE-containing silane compound (a) can be less likely to decrease than the values at room temperature, so it is applicable to a wide temperature range. is also possible. In this specification, "elastic modulus" indicates dynamic elastic modulus, more specifically storage elastic modulus.
一の態様において、RFEは、各出現においてそれぞれ独立して、下記式(f1)~(f5):
-(OC3F6)a3- (f1)
[式中、a3は、5~200の整数である。];
-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f2)
[式中、a4およびa3は、それぞれ独立して、0~30の整数であり、a2およびa1は、それぞれ独立して1~200の整数であり、 a4、a3、a2およびa1の和は5以上であり、添字a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序 は、式中において任意である。];
-(R6-R7)g- (f3)
[式中、R6は、OCF2またはOC2F4であり、R7は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から独立して選択される2または3つの基の組み合わせであり、gは、2~100の整数である。];
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f4)
[式中、a2は、1~200の整数であり、a6、a5、a4、a3およびa1は、それぞれ独立して0~200の整数であって、a6、a5、a4、a3、a2およびa1の和は少なくとも5であり、また、a6、a5、a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f5)
[式中、a1は、1~200の整数であり、a6、a5、a4、a3およびa2は、それぞれ独立して0~200の整数であって、a6、a5、a4、a3、a2およびa1の和は少なくとも5であり、また、a6、a5、a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である。 In one aspect, R FE is, at each occurrence, independently each of the following formulas (f1)-(f5):
- (OC 3 F 6 ) a3 - (f1)
[In the formula, a3 is an integer of 5 to 200. ];
- (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f2)
[Wherein, a4 and a3 are each independently an integer of 0 to 30, a2 and a1 are each independently an integer of 1 to 200, and the sum of a4, a3, a2 and a1 is 5 The order of existence of each repeating unit enclosed in parentheses with subscript a4, a3, a2 or a1 is arbitrary in the formula. ];
-(R 6 -R 7 ) g - (f3)
wherein R 6 is OCF 2 or OC 2 F 4 and R 7 is selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of two or three groups independently selected from these groups, and g is an integer from 2-100. ];
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f4)
[Wherein, a2 is an integer of 1 to 200, a6, a5, a4, a3 and a1 are each independently an integer of 0 to 200, a6, a5, a4, a3, a2 and a1 is at least 5, and the order of existence of each repeating unit bracketed with a6, a5, a4, a3, a2 or a1 is arbitrary in the formula. ]
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f5)
[Wherein, a1 is an integer of 1 to 200, a6, a5, a4, a3 and a2 are each independently an integer of 0 to 200, a6, a5, a4, a3, a2 and a1 is at least 5, and the order of existence of each repeating unit bracketed with a6, a5, a4, a3, a2 or a1 is arbitrary in the formula. ]
It is a group represented by
-(OC3F6)a3- (f1)
[式中、a3は、5~200の整数である。];
-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f2)
[式中、a4およびa3は、それぞれ独立して、0~30の整数であり、a2およびa1は、それぞれ独立して1~200の整数であり、 a4、a3、a2およびa1の和は5以上であり、添字a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序 は、式中において任意である。];
-(R6-R7)g- (f3)
[式中、R6は、OCF2またはOC2F4であり、R7は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から独立して選択される2または3つの基の組み合わせであり、gは、2~100の整数である。];
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f4)
[式中、a2は、1~200の整数であり、a6、a5、a4、a3およびa1は、それぞれ独立して0~200の整数であって、a6、a5、a4、a3、a2およびa1の和は少なくとも5であり、また、a6、a5、a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f5)
[式中、a1は、1~200の整数であり、a6、a5、a4、a3およびa2は、それぞれ独立して0~200の整数であって、a6、a5、a4、a3、a2およびa1の和は少なくとも5であり、また、a6、a5、a4、a3、a2またはa1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である。 In one aspect, R FE is, at each occurrence, independently each of the following formulas (f1)-(f5):
- (OC 3 F 6 ) a3 - (f1)
[In the formula, a3 is an integer of 5 to 200. ];
- (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f2)
[Wherein, a4 and a3 are each independently an integer of 0 to 30, a2 and a1 are each independently an integer of 1 to 200, and the sum of a4, a3, a2 and a1 is 5 The order of existence of each repeating unit enclosed in parentheses with subscript a4, a3, a2 or a1 is arbitrary in the formula. ];
-(R 6 -R 7 ) g - (f3)
wherein R 6 is OCF 2 or OC 2 F 4 and R 7 is selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of two or three groups independently selected from these groups, and g is an integer from 2-100. ];
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f4)
[Wherein, a2 is an integer of 1 to 200, a6, a5, a4, a3 and a1 are each independently an integer of 0 to 200, a6, a5, a4, a3, a2 and a1 is at least 5, and the order of existence of each repeating unit bracketed with a6, a5, a4, a3, a2 or a1 is arbitrary in the formula. ]
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f5)
[Wherein, a1 is an integer of 1 to 200, a6, a5, a4, a3 and a2 are each independently an integer of 0 to 200, a6, a5, a4, a3, a2 and a1 is at least 5, and the order of existence of each repeating unit bracketed with a6, a5, a4, a3, a2 or a1 is arbitrary in the formula. ]
It is a group represented by
上記式(f1)において、a3は、好ましくは5~200、より好ましくは10~100、さらに好ましくは15~50、例えば25~35の整数である。上記式(f1)は、好ましくは、-(OCF2CF2CF2)a3-または-(OCF(CF3)CF2)a3-で表される基であり、より好ましくは、-(OCF2CF2CF2)a3-で表される基である。
In the above formula (f1), a3 is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35. The above formula (f1) is preferably a group represented by -(OCF 2 CF 2 CF 2 ) a3 - or -(OCF(CF 3 )CF 2 ) a3 -, more preferably -(OCF 2 It is a group represented by CF 2 CF 2 ) a3 —.
上記式(f2)において、a2およびa1は、それぞれ独立して、好ましくは5以上200以下、より好ましくは10~200の整数である。また、a4、a3、a2およびa1の和は、好ましくは5以上であり、より好ましくは10以上であり、例えば15以上または20以上であってもよい。一の態様において、上記式(f2)は、好ましくは、-(OCF2CF2CF2CF2)a4-(OCF2CF2CF2)a3-(OCF2CF2)a2-(OCF2)a1-で表される基である。別の態様において、式(f2)は、-(OC2F4)a2-(OCF2)a1-で表される基であってもよい。
In the above formula (f2), a2 and a1 are each independently an integer of preferably 5 or more and 200 or less, more preferably 10-200. The sum of a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula ( f2 ) is preferably - ( OCF2CF2CF2CF2 ) a4- ( OCF2CF2CF2 ) a3- ( OCF2CF2 ) a2- ( OCF2 ) It is a group represented by a1- . In another embodiment, formula (f2) may be a group represented by -(OC 2 F 4 ) a2 -(OCF 2 ) a1 -.
上記式(f3)において、R6は、好ましくは、OC2F4である。上記(f3)において、R7は、好ましくは、OC2F4、OC3F6およびOC4F8から選択される基であるか、あるいは、これらの基から独立して選択される2または3つの基の組み合わせであり、より好ましくは、OC3F6およびOC4F8から選択される基である。OC2F4、OC3F6およびOC4F8から独立して選択される2または3つの基の組み合わせとしては、特に限定されないが、例えば-OC2F4OC3F6-、-OC2F4OC4F8-、-OC3F6OC2F4-、-OC3F6OC3F6-、-OC3F6OC4F8-、-OC4F8OC4F8-、-OC4F8OC3F6-、-OC4F8OC2F4-、-OC2F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4-、および-OC4F8OC2F4OC2F4-等が挙げられる。上記式(f3)において、gは、好ましくは3以上、より好ましくは5以上の整数で ある。上記gは、好ましくは50以下の整数である。上記式(f3)において、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、上記式(f3)は、好ましくは、-(OC2F4-OC3F6)g-または-(OC2F4-OC4F8)g-である。
In formula (f3) above, R 6 is preferably OC 2 F 4 . In (f3) above, R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or 2 independently selected from these groups, or A combination of three groups, more preferably a group selected from OC 3 F 6 and OC 4 F 8 . The combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, but for example -OC 2 F 4 OC 3 F 6 -, -OC 2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8 OC 2 F 4 OC 2 F 4 - and the like. In the above formula (f3), g is an integer of preferably 3 or more, more preferably 5 or more. Said g is preferably an integer of 50 or less. In formula (f3) above, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear. is a chain. In this aspect, the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
上記式(f4)において、a2は、好ましくは、1~100の整数、より好ましくは5~100の整数である。a6、a5、a4、a3、a2およびa1の和は、好ましくは5以上であり、より好ましくは10以上、例えば10以上100以下である。
In the above formula (f4), a2 is preferably an integer of 1-100, more preferably an integer of 5-100. The sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
上記式(f5)において、a1は、好ましくは、1~100の整数、より好ましくは5以上100以下の整数である。a6、a5、a4、a3、a2およびa1の和は、好ましくは5以上であり、より好ましくは10以上、例えば10以上100以下である。
In the above formula (f5), a1 is preferably an integer of 1 to 100, more preferably an integer of 5 or more and 100 or less. The sum of a6, a5, a4, a3, a2 and a1 is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
一の態様において、上記RFEは、上記式(f1)で表される基である。
In one aspect, R FE is a group represented by the formula (f1).
一の態様において、上記RFEは、上記式(f2)で表される基である。
In one aspect, R FE is a group represented by the formula (f2).
一の態様において、上記RFEは、上記式(f3)で表される基である。
In one aspect, R FE is a group represented by the formula (f3).
一の態様において、上記RFEは、上記式(f4)で表される基である。
In one aspect, R FE is a group represented by the formula (f4).
一の態様において、上記RFEは、上記式(f5)で表される基である。
In one aspect, R FE is a group represented by the formula (f5).
上記PFPE1において、a1、a2、a3、a4、a5、a6、a7およびa8の値は、それぞれの範囲を満たしていれば、各々の値の間での数量関係は特に制限されない。例えば、-(OCF2)a1-で示される構造を多く用いると、低温でもゴム特性を維持しやすくなり、低温使用にも適した組成物とすることができる。また、-(OC2F4)a2-で示される構造を多く用いると、高温において分解しにくい硬化物の形成により有利である。最終的な用途に求められる物性に応じて、PFPE1の構造、組成は適宜調整することができる。ただし、上記RFEにおいて、a1およびa2がともに0ではないとき、a1に対するa2の比(以下、「a2/a1比」という)は、好ましくは0.1~10であり、より好ましくは0.2~5であり、さらに好ましくは0.2~2であり、さらにより好ましくは0.2~1.5であり、特に好ましくは0.2~0.85である。a2/a1比を10以下にすることにより、この化合物から得られる表面処理層の滑り性、摩擦耐久性および耐ケミカル性(例えば、人工汗に対する耐久性)がより向上する。a2/a1比がより小さいほど、表面処理層の滑り性および摩擦耐久性はより向上する。一方、a2/a1比を0.1以上にすることにより、化合物の安定性をより高めることができる。a2/a1比がより大きいほど、化合物の安定性はより向上する。
In the above PFPE 1 , the values of a1, a2, a3, a4, a5, a6, a7 and a8 are not particularly limited as long as they satisfy their respective ranges. For example, if many structures represented by -(OCF 2 ) a1 - are used, the rubber properties can be easily maintained even at low temperatures, and the composition can be made suitable for use at low temperatures. Also, the use of many structures represented by -(OC 2 F 4 ) a2 - is more advantageous for the formation of hardened products that are resistant to decomposition at high temperatures. The structure and composition of PFPE 1 can be appropriately adjusted according to the physical properties required for the final application. However, in the RFE , when both a1 and a2 are not 0, the ratio of a2 to a1 (hereinafter referred to as "a2/a1 ratio") is preferably 0.1 to 10, more preferably 0.1. 2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and particularly preferably 0.2 to 0.85. By setting the a2/a1 ratio to 10 or less, the surface treatment layer obtained from this compound has improved slipperiness, friction durability and chemical resistance (for example, durability against artificial perspiration). The smaller the a2/a1 ratio, the more improved the lubricity and friction durability of the surface treatment layer. On the other hand, by setting the a2/a1 ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the a2/a1 ratio, the more stable the compound.
一の態様において、上記a2/a1比は、好ましくは0.2~0.95であり、より好ましくは0.2~0.9である。
In one aspect, the a2/a1 ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.
一の態様において、耐熱性の観点から、上記a2/a1比は、好ましくは1.0以上であり、より好ましくは1.0~2.0である。
In one aspect, from the viewpoint of heat resistance, the a2/a1 ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.
好ましい一態様において、PFPE1は、-(CfF2f)-(OCF2)a1-(OC2F4)a2-(OC3F6)a3-(OC4F8)a4-(式中、fは1以上4以下の整数であり、a1およびa2は、それぞれ独立して1以上200以下、好ましくは5以上200以下、より好ましくは10以上200以下の整数であり、a3およびa4は、それぞれ独立して0以上30以下の整数であり、添字a1、a2、a3またはa4を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である)である。好ましくは、PFPE1は、-(CfF2f)-(OCF2)a1-(OCF2CF2)a2-(OCF2CF2CF2)a3-(OCF2CF2CF2CF2)a4-である。一のより好ましい態様において、PFPE1は、-(CfF2f)-(OCF2)a1-(OC2F4)a2-(式中、fは1または2であり、a1およびa2は、それぞれ独立して1以上200以下、好ましくは5以上200以下、より好ましくは10以上200以下の整数であり、添字a1またはa2を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である)である。
In one preferred embodiment, PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -(OC 3 F 6 ) a3 -(OC 4 F 8 ) a4 - (wherein , f is an integer of 1 or more and 4 or less, a1 and a2 are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and a3 and a4 are each independently an integer of 0 or more and 30 or less, and the order of existence of each repeating unit enclosed in parentheses with subscript a1, a2, a3 or a4 is arbitrary in the formula). Preferably, PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OCF 2 CF 2 ) a2 -(OCF 2 CF 2 CF 2 ) a3 -(OCF 2 CF 2 CF 2 CF 2 ) a4 -. In one more preferred embodiment, PFPE 1 is -(C f F 2f )-(OCF 2 ) a1 -(OC 2 F 4 ) a2 -, where f is 1 or 2 and a1 and a2 are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less; is optional within).
別の好ましい一態様において、PFPE1は、式:
-(CfF2f)-(OCF2)a1-(OCF2CF2)a2l-(OCF(CF3))a2’-(OCF2CF2CF2)a3l-(OCF2CF(CF3))a3’-(OCF(CF3)CF2)a3”-(OCF2CF2CF2CF2)a4-
(ここで、fは、1以上4以下の整数であり、a1、a2l、a2’、a3l、a3’、a3”およびa4は、それぞれ独立して0以上200以下の整数であり、a2lおよびa2’の和はa2に等しく、a3l、a3’およびa3”の和はa3に等しく、a1、a2l、a2’、a3l、a3’、a3”およびa4の和は5以上であり、各繰り返し単位の存在順序は、式中において任意である)で示される2価のパーフルオロ(ポリ)エーテル基である。一態様としてより好ましい例において、PFPE1は、上記式においてa1が0以上50以下の整数であり、a2が0以上50以下の整数であり、a3が0以上30以下の整数であり、a4が0以上30以下の整数であり、a1、a2、a3およびa4の和が5以上200以下である、2価のパーフルオロ(ポリ)エーテル基である。一態様としてさらに好ましい例において、PFPE1は、-(OCF2CF(CF3))a3’-および/または-(OCF(CF3)CF2)a3”-で示される繰り返し単位を有するパーフルオロ(ポリ)エーテル基である。すなわち、別のより好ましい一態様において、PFPE1は、分岐状のパーフルオロアルキル基、特にパーフルオロプロピル基を有する。具体的な例としては、以下のような構造を挙げることができる。
-(CfF2f)-(OCF2CF(CF3))a3’-(OCF2CF2)-(OCF(CF3)CF2)a3”-(OCF(CF3))-
-(CfF2f)-(OCF2CF(CF3))a3’-(OCF2CF2CF2CF2)--(OCF(CF3)CF2)a3”-(OCF(CF3))- In another preferred embodiment, PFPE 1 has the formula:
-(C f F 2f )-(OCF 2 ) a1 -(OCF 2 CF 2 ) a2l -(OCF(CF 3 )) a2′ -(OCF 2 CF 2 CF 2 ) a3l -(OCF 2 CF(CF 3 ) ) a3′ -(OCF(CF 3 )CF 2 ) a3″ -(OCF 2 CF 2 CF 2 CF 2 ) a4 −
(Here, f is an integer of 1 or more and 4 or less, a1, a2l, a2′, a3l, a3′, a3″ and a4 are each independently an integer of 0 or more and 200 or less, and a2l and a2 ' is equal to a2, the sum of a3l, a3' and a3" is equal to a3, the sum of a1, a2l, a2', a3l, a3', a3" and a4 is greater than or equal to 5, and the sum of each repeating unit is The order of existence is arbitrary in the formula) is a divalent perfluoro(poly)ether group represented by In a more preferred embodiment, PFPE 1 is an integer in which a1 is 0 or more and 50 or less in the above formula and a2 is an integer of 0 or more and 50 or less, a3 is an integer of 0 or more and 30 or less, a4 is an integer of 0 or more and 30 or less, and the sum of a1, a2, a3 and a4 is 5 or more and 200 or less is a divalent perfluoro(poly)ether group, In a more preferred embodiment, PFPE 1 is -(OCF 2 CF(CF 3 )) a3' - and/or -(OCF(CF 3 )CF 2 ) a3″ is a perfluoro(poly)ether group having a repeating unit represented by —. That is, in another more preferred aspect, PFPE 1 has branched perfluoroalkyl groups, particularly perfluoropropyl groups. Specific examples include the following structures.
- (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 ) - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 )) -
- (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 CF 2 CF 2 ) - - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 ) )-
-(CfF2f)-(OCF2)a1-(OCF2CF2)a2l-(OCF(CF3))a2’-(OCF2CF2CF2)a3l-(OCF2CF(CF3))a3’-(OCF(CF3)CF2)a3”-(OCF2CF2CF2CF2)a4-
(ここで、fは、1以上4以下の整数であり、a1、a2l、a2’、a3l、a3’、a3”およびa4は、それぞれ独立して0以上200以下の整数であり、a2lおよびa2’の和はa2に等しく、a3l、a3’およびa3”の和はa3に等しく、a1、a2l、a2’、a3l、a3’、a3”およびa4の和は5以上であり、各繰り返し単位の存在順序は、式中において任意である)で示される2価のパーフルオロ(ポリ)エーテル基である。一態様としてより好ましい例において、PFPE1は、上記式においてa1が0以上50以下の整数であり、a2が0以上50以下の整数であり、a3が0以上30以下の整数であり、a4が0以上30以下の整数であり、a1、a2、a3およびa4の和が5以上200以下である、2価のパーフルオロ(ポリ)エーテル基である。一態様としてさらに好ましい例において、PFPE1は、-(OCF2CF(CF3))a3’-および/または-(OCF(CF3)CF2)a3”-で示される繰り返し単位を有するパーフルオロ(ポリ)エーテル基である。すなわち、別のより好ましい一態様において、PFPE1は、分岐状のパーフルオロアルキル基、特にパーフルオロプロピル基を有する。具体的な例としては、以下のような構造を挙げることができる。
-(CfF2f)-(OCF2CF(CF3))a3’-(OCF2CF2)-(OCF(CF3)CF2)a3”-(OCF(CF3))-
-(CfF2f)-(OCF2CF(CF3))a3’-(OCF2CF2CF2CF2)--(OCF(CF3)CF2)a3”-(OCF(CF3))- In another preferred embodiment, PFPE 1 has the formula:
-(C f F 2f )-(OCF 2 ) a1 -(OCF 2 CF 2 ) a2l -(OCF(CF 3 )) a2′ -(OCF 2 CF 2 CF 2 ) a3l -(OCF 2 CF(CF 3 ) ) a3′ -(OCF(CF 3 )CF 2 ) a3″ -(OCF 2 CF 2 CF 2 CF 2 ) a4 −
(Here, f is an integer of 1 or more and 4 or less, a1, a2l, a2′, a3l, a3′, a3″ and a4 are each independently an integer of 0 or more and 200 or less, and a2l and a2 ' is equal to a2, the sum of a3l, a3' and a3" is equal to a3, the sum of a1, a2l, a2', a3l, a3', a3" and a4 is greater than or equal to 5, and the sum of each repeating unit is The order of existence is arbitrary in the formula) is a divalent perfluoro(poly)ether group represented by In a more preferred embodiment, PFPE 1 is an integer in which a1 is 0 or more and 50 or less in the above formula and a2 is an integer of 0 or more and 50 or less, a3 is an integer of 0 or more and 30 or less, a4 is an integer of 0 or more and 30 or less, and the sum of a1, a2, a3 and a4 is 5 or more and 200 or less is a divalent perfluoro(poly)ether group, In a more preferred embodiment, PFPE 1 is -(OCF 2 CF(CF 3 )) a3' - and/or -(OCF(CF 3 )CF 2 ) a3″ is a perfluoro(poly)ether group having a repeating unit represented by —. That is, in another more preferred aspect, PFPE 1 has branched perfluoroalkyl groups, particularly perfluoropropyl groups. Specific examples include the following structures.
- (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 ) - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 )) -
- (C f F 2f ) - (OCF 2 CF (CF 3 )) a3' - (OCF 2 CF 2 CF 2 CF 2 ) - - (OCF (CF 3 ) CF 2 ) a3'' - (OCF (CF 3 ) )-
本発明の硬化性組成物は、その硬化物が高温で分解しにくい。本明細書において、硬化物が「高温で分解しにくい」とは、その硬化物の1%分解温度が比較的高い温度にあることをいう。即ち、本発明の硬化性組成物は、広い温度範囲で使用可能な硬化物の形成に寄与し得る。本明細書において、「1%分解温度」とは、硬化物全体に対して、該硬化物の1質量%が分解する温度を意味する。1%分解温度は、熱重量・示差熱(TG/DTA)によって測定された値を意味し、具体的には、Air雰囲気下で、昇温レートを10℃/分とし、25℃~600℃の範囲で測定する。上記TG/DTAとしては、例えば、SHIMADZU社製DTG-60を挙げることができる。
The cured product of the curable composition of the present invention is difficult to decompose at high temperatures. In the present specification, the phrase "hardly decomposing at high temperatures" means that the 1% decomposition temperature of the cured product is relatively high. That is, the curable composition of the present invention can contribute to the formation of cured products that can be used over a wide temperature range. As used herein, "1% decomposition temperature" means the temperature at which 1% by mass of the cured product decomposes with respect to the entire cured product. The 1% decomposition temperature means a value measured by thermogravimetry/differential heat (TG/DTA), specifically, in an air atmosphere, with a temperature increase rate of 10 ° C./min, 25 ° C. to 600 ° C. measured in the range of Examples of the TG/DTA include DTG-60 manufactured by SHIMADZU.
-PFPE1-部分の数平均分子量は、2,000~20万の範囲にあり得、3,000~10万の範囲にあることが好ましい。上記数平均分子量は、19F-NMRにより測定される値とする。
The number average molecular weight of the -PFPE 1 - moiety can range from 2,000 to 200,000, preferably from 3,000 to 100,000. The number average molecular weight is a value measured by 19 F-NMR.
一の態様において、-PFPE1-部分の数平均分子量は、2,000~10,000の範囲にあり得、2,000~5,000の範囲にあることが好ましい。上記のような-PFPE1-部分の数平均分子量を有することにより、硬化性組成物の粘度が低く、ハンドリング性が良好になり得る。上記のような-PFPE1-部分の数平均分子量を有する硬化性組成物は、例えば、溶剤とともに用い溶液状態とした場合の粘度の抑制の点からも有利である。
In one embodiment, the number average molecular weight of the -PFPE 1 - moiety can range from 2,000 to 10,000, preferably from 2,000 to 5,000. By having the number average molecular weight of the -PFPE 1 - portion as described above, the viscosity of the curable composition can be low and the handleability can be improved. The curable composition having the number average molecular weight of the -PFPE 1 - moiety as described above is also advantageous from the viewpoint of suppressing the viscosity when used together with a solvent to form a solution.
一の態様において、-PFPE1-部分の数平均分子量は、10,000~100,000の範囲にあり得、10,000~50,000の範囲にあることが好ましい。上記のような-PFPE1-部分の数平均分子量を有することにより、硬化性組成物の硬化後の伸び特性等の物性が良好になり得る。
In one embodiment, the number average molecular weight of the -PFPE 1 - moiety can range from 10,000 to 100,000, preferably from 10,000 to 50,000. By having the number average molecular weight of the -PFPE 1 - moiety as described above, physical properties such as elongation properties after curing of the curable composition can be improved.
上記PFPE含有シラン化合物(a)の一般式(I)におけるkは、該一般式(I)中の下記式:
-PFPE1-C(=O)NR7-R6-NR7C(=O)-
で示される構造の繰り返し単位の数を表す。kの値は1以上である。したがって、上記PFPE含有シラン化合物(a)は、-PFPE1-の両末端に-C(=O)NR7-で示される構造を有する単位が少なくとも2つ存在する。すなわち、上記PFPE含有シラン化合物(a)は、-C(=O)NR7-で示される構造を少なくとも4つ有する。kの値は、上記PFPE含有シラン化合物(a)が調製可能な範囲であれば特に制限されないが、1以上5以下の整数であることが好ましい。これにより、硬化性組成物の深部硬化性に寄与しうると考えられる部分を1分子中に多数設けることができる。 k in the general formula (I) of the PFPE-containing silane compound (a) is represented by the following formula in the general formula (I):
-PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-
represents the number of repeating units in the structure shown. The value of k is 1 or more. Therefore, the PFPE-containing silane compound (a) has at least two units having a structure represented by -C(=O)NR 7 - at both ends of -PFPE 1 -. That is, the PFPE-containing silane compound (a) has at least four structures represented by -C(=O)NR 7 -. The value of k is not particularly limited as long as the PFPE-containing silane compound (a) can be prepared, but it is preferably an integer of 1 or more and 5 or less. This makes it possible to provide a large number of moieties that are thought to contribute to deep-part curability of the curable composition in one molecule.
-PFPE1-C(=O)NR7-R6-NR7C(=O)-
で示される構造の繰り返し単位の数を表す。kの値は1以上である。したがって、上記PFPE含有シラン化合物(a)は、-PFPE1-の両末端に-C(=O)NR7-で示される構造を有する単位が少なくとも2つ存在する。すなわち、上記PFPE含有シラン化合物(a)は、-C(=O)NR7-で示される構造を少なくとも4つ有する。kの値は、上記PFPE含有シラン化合物(a)が調製可能な範囲であれば特に制限されないが、1以上5以下の整数であることが好ましい。これにより、硬化性組成物の深部硬化性に寄与しうると考えられる部分を1分子中に多数設けることができる。 k in the general formula (I) of the PFPE-containing silane compound (a) is represented by the following formula in the general formula (I):
-PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-
represents the number of repeating units in the structure shown. The value of k is 1 or more. Therefore, the PFPE-containing silane compound (a) has at least two units having a structure represented by -C(=O)NR 7 - at both ends of -PFPE 1 -. That is, the PFPE-containing silane compound (a) has at least four structures represented by -C(=O)NR 7 -. The value of k is not particularly limited as long as the PFPE-containing silane compound (a) can be prepared, but it is preferably an integer of 1 or more and 5 or less. This makes it possible to provide a large number of moieties that are thought to contribute to deep-part curability of the curable composition in one molecule.
本発明は特定の理論に束縛されるものではないが、-C(=O)NR7-で表される構造はカルボニル基の酸素およびR7が水素の場合の水素原子とが、水分子との水素結合の形成に関与しうる。一分子中における-C(=O)NR7-で示される構造の数が増えることで、水素結合を生じる部分を多く備えることになり、硬化性組成物の硬化に関与する水分との親和性が増加する。このため、硬化性組成物の深部まで硬化反応が起こりやすくなり、好ましいと考えられる。したがって、前記一般式(I)においてkの値が1以上であることにより、PFPE含有シラン化合物(a)1分子あたりに含まれるアミド結合の数が多くなる。この構造が、水素結合による水分子との親和性向上をもたらしうるものであり、硬化性組成物の良好な深部硬化性に寄与するものと考えることができる。
Although the present invention is not bound by any particular theory, the structure represented by -C (=O) NR - can participate in the formation of hydrogen bonds between By increasing the number of structures represented by -C(=O)NR 7 - in one molecule, it is equipped with a large number of parts that generate hydrogen bonds, and affinity with moisture involved in curing of the curable composition increases. For this reason, the curing reaction tends to occur deep in the curable composition, which is considered preferable. Therefore, when the value of k in the general formula (I) is 1 or more, the number of amide bonds contained in one molecule of the PFPE-containing silane compound (a) increases. This structure can bring about improved affinity with water molecules through hydrogen bonding, and can be considered to contribute to good deep-part curability of the curable composition.
前記-C(=O)NR7-で表される構造におけるR7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基を表す。R7は1分子あたり少なくとも4個存在するが、R7が水素である、すなわち、-C(=O)NH-で示される構造を有することで、得られる硬化性組成物が深部まで良好に硬化するようになるため好ましい。R7のうち少なくとも3つは水素原子であることが好ましく、全てのR7が水素原子であることがより好ましい。R7の一部が水素原子である場合において、上記PFPE含有シラン化合物(a)中のどの位置にあるR7が水素原子であるかは特に制限されない。上記PFPE含有シラン化合物(a)の調製において、原料の選択により-C(=O)NH-で示される構造が導入される位置を制御することができる。
Each occurrence of R 7 in the structure represented by -C(=O)NR 7 - independently represents a hydrogen atom or a C 1-20 alkyl group. At least four R 7 are present per molecule, and when R 7 is hydrogen, that is, by having a structure represented by -C(=O)NH-, the obtained curable composition can penetrate well to the deep part. It is preferable because it becomes hardened. At least three of R7 are preferably hydrogen atoms, and more preferably all R7 are hydrogen atoms. When part of R 7 is a hydrogen atom, there is no particular limitation on the position of the hydrogen atom in the PFPE-containing silane compound (a). In the preparation of the above PFPE-containing silane compound (a), the position at which the structure represented by -C(=O)NH- is introduced can be controlled by selecting raw materials.
上記PFPE含有シラン化合物(a)は、前記-C(=O)NR7-で表される構造が、その窒素原子を介してR5またはR6で表される有機基と結合する。
In the PFPE-containing silane compound (a), the structure represented by -C(=O)NR 7 - is bonded to the organic group represented by R 5 or R 6 through the nitrogen atom.
R5は、末端のケイ素原子とアミド結合とを連結するリンカーとして作用する基である。R5は、各出現において独立して、j+1価の有機基を表す。ここで、jの値は、上記PFPE含有シラン化合物(a)の末端に存在するケイ素原子を含む基の数を表し、その値は1~9の範囲である。よって、R5は、各出現において独立して、2~10価の有機基を表す。従って、当該R5は、上記PFPE含有シラン化合物(a)が安定に存在し得る2~10価の有機基であれば、いずれの基であってもよい。「2~10価の有機基」の定義は、先に示したとおりである。R5の具体的な例としては、後述する式(A)ないし(D)においてR5に対応する部分として記載されているものを挙げることができる。R5は、好ましくは2~7価であり、より好ましくは2~4価であり、さらに好ましくは2価の有機基である。したがって、jの値は、好ましくは1~6であり、より好ましくは1~3であり、さらに好ましくは1である。
R5 is a group that acts as a linker connecting the terminal silicon atom and the amide bond. R5 independently at each occurrence represents a j+ 1 valent organic group. Here, the value of j represents the number of silicon atom-containing groups present at the ends of the PFPE-containing silane compound (a), and is in the range of 1-9. Thus, R 5 independently at each occurrence represents a divalent to decavalent organic group. Therefore, R 5 may be any group as long as it is a divalent to decavalent organic group in which the PFPE-containing silane compound (a) can stably exist. The definition of the “divalent to decavalent organic group” is as shown above. Specific examples of R 5 include those described as moieties corresponding to R 5 in formulas (A) to (D) described later. R 5 is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group. Therefore, the value of j is preferably 1-6, more preferably 1-3, even more preferably 1.
R5は、ケイ素原子とアミド結合とを直接連結する分子鎖上にヘテロ原子または芳香族の構造を有していないことが好ましく、芳香族の構造を有していないことがより好ましい。R5としては、場合によりヘテロ原子を有していてもよい脂肪族炭化水素基であることが好ましく、より好ましくは非置換の脂肪族炭化水素であり、さらに好ましくは2価のアルキレン基である。R5としてより好ましくはC1-20アルキレン基であり、さらに好ましくはC1-6アルキレン基であり、特に具体的には、メチレン基、エチレン基、プロピレン基、メチルエチレン基、ブチレン基、ヘキサメチレン基等である。上記PFPE含有シラン化合物(a)中に存在する二つのR5は、同じであってもよく、異なっていてもよいが、化合物の調製が容易となることから、同じであることが好ましい。また、R5は、j+1個の結合手を有していることになるが、どの結合手で-C(=O)NR7-部分と結合していてもよい。
R 5 preferably does not have a heteroatom or aromatic structure on the molecular chain directly connecting the silicon atom and the amide bond, and more preferably does not have an aromatic structure. R 5 is preferably an optionally heteroatom-containing aliphatic hydrocarbon group, more preferably an unsubstituted aliphatic hydrocarbon group, and still more preferably a divalent alkylene group. . R 5 is more preferably a C 1-20 alkylene group, more preferably a C 1-6 alkylene group, and more specifically, methylene group, ethylene group, propylene group, methylethylene group, butylene group, hexa methylene group and the like. The two R5's present in the PFPE - containing silane compound (a) may be the same or different, but are preferably the same to facilitate preparation of the compound. In addition, although R 5 has j+1 bonds, it may be bonded to the -C(=O)NR 7 - moiety with any bond.
R6は、前記-C(=O)NR7-で表される構造同士を連結する、2価の有機基であり、各出現においてそれぞれ独立して、-R22-R21-R23-で表される。
R 6 is a divalent organic group that connects the structures represented by -C(=O)NR 7 -, and each occurrence is independently -R 22 -R 21 -R 23 - is represented by
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、R23は、各出現においてそれぞれ独立して、単結合または二価の有機基である。本発明の硬化性組成物に含まれるパーフルオロ(ポリ)エーテル基含有シラン化合物は、アミド結合間にシクロアルキレン基を含有する。一般式(I)ではkの値が1以上であるので、一般式(I)で示される化合物は、R6で示される脂環式構造の基を少なくとも1つ有する。本発明は、脂環式構造をPFPE含有化合物に導入することで、接着剤としたときの基材との密着性がより高まることを見出したことによるものである。
R 21 is independently on each occurrence a cycloalkylene-containing group, R 22 is independently on each occurrence a single bond or a divalent organic group, and R 23 is independently on each occurrence Independently, it is a single bond or a divalent organic group. The perfluoro(poly)ether group-containing silane compound contained in the curable composition of the present invention contains a cycloalkylene group between amide bonds. Since the value of k in general formula (I) is 1 or more, the compound represented by general formula (I) has at least one alicyclic structure group represented by R 6 . The present invention is based on the discovery that the introduction of an alicyclic structure into a PFPE-containing compound enhances adhesion to a substrate when used as an adhesive.
上記シクロアルキレンは、2価の飽和単環式または多環式脂肪族炭化水素を意味する。かかるシクロアルキレンは、環の水素原子が、1つまたはそれ以上の置換基により置換されていてもよい。
The above cycloalkylene means a divalent saturated monocyclic or polycyclic aliphatic hydrocarbon. Such cycloalkylenes may optionally have ring hydrogen atoms replaced by one or more substituents.
上記シクロアルキレンの置換基としては、特に限定されないが、例えば、ハロゲン原子、1個またはそれ以上のハロゲン原子により置換されていてもよい、C1-6アルキル基、C2-6アルケニル基、C2-6アルキニル基、C3-10シクロアルキル基、C3-10不飽和シクロアルキル基、5~10員のヘテロシクリル基、5~10員の不飽和ヘテロシクリル基、C6-10アリール基および5~10員のヘテロアリール基から選択される1個またはそれ以上の基が挙げられる。好ましい態様において、当該置換基は、C1-6アルキル基、好ましくはメチル基またはエチル基、より好ましくはメチル基である。
The substituents of the above cycloalkylene are not particularly limited, but for example, a halogen atom, a C 1-6 alkyl group optionally substituted with one or more halogen atoms, a C 2-6 alkenyl group, a C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 aryl group and 5 One or more groups selected from to 10-membered heteroaryl groups are included. In a preferred embodiment, said substituent is a C 1-6 alkyl group, preferably a methyl or ethyl group, more preferably a methyl group.
上記シクロアルキレン含有基は、複数のシクロアルキレンを含んでいてもよく、好ましくは1~3個、より好ましくは1または2個のシクロアルキレンを含む。
The cycloalkylene-containing group may contain a plurality of cycloalkylenes, preferably 1 to 3, more preferably 1 or 2 cycloalkylenes.
一の態様において、上記シクロアルキレン含有基は、シクロアルキレンを1個含む。
In one aspect, the cycloalkylene-containing group contains one cycloalkylene.
別の態様において、上記シクロアルキレン含有基は、シクロアルキレンを2個含む。
In another aspect, the cycloalkylene-containing group contains two cycloalkylenes.
好ましい態様において、R21は、各出現においてそれぞれ独立して、炭素数5~12の単環式、二環式または三環式シクロアルキレン基を含有する基である。
In preferred embodiments, R 21 is independently at each occurrence a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms.
上記多環式シクロアルキレンは、縮合型、スピロ型、架橋型のいずれであってもよい。
The above polycyclic cycloalkylene may be any of condensed type, spiro type, and bridged type.
一の態様において、上記シクロアルキレンは、単環式である。
In one aspect, the cycloalkylene is monocyclic.
別の態様において、上記シクロアルキレンは、二環式である。
In another aspect, the cycloalkylene is bicyclic.
別の態様において、上記シクロアルキレンは、三環式である。
In another aspect, the cycloalkylene is tricyclic.
好ましい態様において、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基である。
In preferred embodiments, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. be.
上記R22およびR23は、R21のシクロアルキレンに直接結合する。
R 22 and R 23 above are directly attached to the cycloalkylene of R 21 .
好ましい態様において、R21は、各出現においてそれぞれ独立して、炭素数5~12の単環式、二環式または三環式シクロアルキレン基を含有する基であり、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基である。
In preferred embodiments, R 21 is independently at each occurrence a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms, and R 22 at each occurrence is Each independently is a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group.
好ましい態様において、R21は、置換されていてもよいシクロヘキサンジイルであり、上記R22およびR23は、それぞれ独立して、単結合またはC1-6アルキレン基であり、互いにメタ位またはパラ位に結合する。一の態様において、置換されていてもよいシクロヘキサンジイルは、非置換である。別の態様において、置換されていてもよいシクロヘキサンジイルは、C1-6アルキル基、好ましくはメチル基またはエチル基、より好ましくはメチル基により置換されている。かかる置換基の数は、好ましくは1~5個、より好ましくは1~3個であり得る。
In a preferred embodiment, R 21 is optionally substituted cyclohexanediyl, and R 22 and R 23 above are each independently a single bond or a C 1-6 alkylene group, meta or para to each other. bind to In one aspect, the optionally substituted cyclohexanediyl is unsubstituted. In another aspect the optionally substituted cyclohexanediyl is substituted by a C 1-6 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group. The number of such substituents may preferably be 1-5, more preferably 1-3.
好ましい態様において、R21は、置換されていてもよいアルキレンビス(シクロヘキシル)、好ましくはメチレンビス(シクロヘキシル)を含み、上記R22およびR23は、それぞれ独立して、単結合またはC1-6アルキレン基であり、互いに4,4’位に結合する。一の態様において、置換されていてもよいアルキレンビス(シクロヘキシル)は、非置換である。別の態様において、置換されていてもよいアルキレンビス(シクロヘキシル)は、C1-6アルキル基、好ましくはメチル基またはエチル基、より好ましくはメチル基により置換されている。かかる置換基の数は、好ましくは2~5個、より好ましくは2~4個であり得る。
In a preferred embodiment, R 21 includes optionally substituted alkylenebis(cyclohexyl), preferably methylenebis(cyclohexyl), and R 22 and R 23 above are each independently a single bond or C 1-6 alkylene groups and are attached to each other at the 4,4' positions. In one aspect, an optionally substituted alkylenebis(cyclohexyl) is unsubstituted. In another aspect, the optionally substituted alkylenebis(cyclohexyl) is substituted by a C 1-6 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group. The number of such substituents may preferably be 2-5, more preferably 2-4.
好ましい態様において、R6は、環の水素原子が置換されていてもよい下記の基:
[式中、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R24は、各出現においてそれぞれ独立して、C1-6アルキレン基、好ましくは-CH2CH2-または-CH2-である。]から選択される基である。 In a preferred embodiment, R 6 is the following group in which a ring hydrogen atom may be substituted:
[Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
[式中、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R24は、各出現においてそれぞれ独立して、C1-6アルキレン基、好ましくは-CH2CH2-または-CH2-である。]から選択される基である。 In a preferred embodiment, R 6 is the following group in which a ring hydrogen atom may be substituted:
[Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
さらに好ましい態様において、R6は、環の水素原子が置換されていてもよい下記の基:
[式中、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R24は、各出現においてそれぞれ独立して、C1-6アルキレン基、好ましくは-CH2CH2-または-CH2-である。]から選択される基である。 In a further preferred embodiment, R 6 is the following group in which a ring hydrogen atom may be substituted:
[Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
[式中、R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、R24は、各出現においてそれぞれ独立して、C1-6アルキレン基、好ましくは-CH2CH2-または-CH2-である。]から選択される基である。 In a further preferred embodiment, R 6 is the following group in which a ring hydrogen atom may be substituted:
[Wherein, each occurrence of R 22 is independently a single bond or a C 1-6 alkylene group, and each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group. and R 24 is independently at each occurrence a C 1-6 alkylene group, preferably -CH 2 CH 2 - or -CH 2 -. ] is a group selected from
R6部分は、例えばPFPE1の両末端に、アミド結合を介してR5またはR6と結合を形成可能な反応性官能基を有する化合物(以下、このような化合物を「PFPE変性体」といい、例えば末端がエステル基の場合の当該化合物を「PFPEエステル変性体」ということがある)に対し、ジアミンを作用させることにより、導入することができる。分子鎖中のR6部分の個数(換言するとkの値)は、反応物の量関係を調整することで操作することができる。
The R6 moiety is, for example, a compound having a reactive functional group at both ends of PFPE1 that can form a bond with R5 or R6 via an amide bond ( hereinafter, such a compound is referred to as a "PFPE modified form"). For example, a compound having an ester group at the end thereof is sometimes referred to as a "modified PFPE ester"), and can be introduced by reacting a diamine. The number of R6 moieties in the molecular chain (in other words the value of k) can be manipulated by adjusting the quantity relationships of the reactants.
上記PFPE含有シラン化合物(a)は、その分子末端の構造として、R3
pR4
3-pSi-またはR3
qR4
3-qSi-で表される構造を有する。R3、R4、p、qの定義は、先に示したとおりである。すなわち、上記PFPE含有シラン化合物(a)の分子末端には、水酸基または加水分解可能な基が少なくとも1つケイ素原子に結合した構造が存在する。「加水分解可能な基」は、上記と同意義である。1分子または1つの分子末端構造中のR3、R4には、各々異なる基が混在していてもよい。水酸基または加水分解可能な基が2つまたは3つケイ素原子に結合した構造は、分子の各末端にj個存在する。jの値は1~9の範囲である。したがって、PFPE含有シラン化合物(a)は、少なくとも2個の上記末端構造を有している。好ましくはjの値は1である。すなわち、好ましい一態様において、PFPE含有シラン化合物(a)は、加水分解可能な基が結合したケイ素を両末端に有する、直鎖状の分子である。
The PFPE-containing silane compound (a) has a structure represented by R 3 p R 4 3-p Si— or R 3 q R 4 3-q Si— as its molecular terminal structure. The definitions of R 3 , R 4 , p and q are as given above. That is, the PFPE-containing silane compound (a) has a structure in which at least one hydroxyl group or hydrolyzable group is bonded to a silicon atom at the molecular terminal. "Hydrolyzable group" has the same meaning as above. Different groups may be mixed in R 3 and R 4 in one molecule or in one molecular terminal structure. Structures in which two or three hydroxyl groups or hydrolyzable groups are bonded to silicon atoms are present at each end of the molecule. The value of j ranges from 1-9. Therefore, the PFPE-containing silane compound (a) has at least two terminal structures. Preferably the value of j is one. That is, in a preferred embodiment, the PFPE-containing silane compound (a) is a linear molecule having silicon at both ends to which hydrolyzable groups are bonded.
上記式中、R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基である。R3として好ましくは炭素原子数1~22のアルキル基、より好ましくは炭素原子数1~4のアルキル基である。
In the above formula, each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group. R 3 is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
R4は、水酸基または加水分解可能な基であるが、加水分解可能な基であることが好ましい。加水分解可能な基の例としては、先に記載したとおりであるが、これらの中でも、特に、-OR(ここで、Rは、置換または非置換の炭素原子数1~4のアルキル基を示す)、即ち、アルコキシ基が好ましい。アルコキシ基の例には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基などの非置換アルコキシ基;クロロメトキシ基などの置換アルコキシ基が挙げられる。それらの中でも、メトキシ基またはエトキシ基がより好ましい。
R 4 is a hydroxyl group or a hydrolyzable group, preferably a hydrolyzable group. Examples of hydrolyzable groups are as described above, among these, especially -OR, where R represents a substituted or unsubstituted alkyl group of 1 to 4 carbon atoms ), ie an alkoxy group. Examples of alkoxy groups include unsubstituted alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy and isobutoxy groups; substituted alkoxy groups such as chloromethoxy groups. Among them, a methoxy group or an ethoxy group is more preferable.
pまたはqは、それぞれ0~3の整数である。ただし、(SiR3
pR4
3-p)jにおいて少なくとも1つのSiR3
pR4
3-pは、pが0~2の整数であり、(SiR3
qR4
3-q)jにおいて少なくとも1つのSiR3
qR4
3-qは、qが0~2の整数である。pまたはqは、それぞれ0または1である。0であることが好ましい。したがって、PFPE含有シラン化合物(a)は、水酸基または加水分解可能な基が2つまたは3つケイ素原子に結合した構造を有する。また、PFPE含有シラン化合物(a)の分子末端の構造は、トリアルコキシシリル基であることが好ましく、トリメトキシシリル基であることがより好ましい。
p or q is an integer from 0 to 3 respectively. provided that at least one SiR 3 p R 4 3 - p in (SiR 3 p R 4 3 - p ) j is an integer of 0 to 2 , and at least In one SiR 3 q R 4 3-q , q is an integer of 0-2. p or q is 0 or 1, respectively. 0 is preferred. Therefore, the PFPE-containing silane compound (a) has a structure in which two or three hydroxyl groups or hydrolyzable groups are bonded to silicon atoms. The structure of the molecular terminal of the PFPE-containing silane compound (a) is preferably a trialkoxysilyl group, more preferably a trimethoxysilyl group.
特に好ましい態様において、PFPE含有シラン化合物(a)は、R7が全て水素原子であり、R5が2価のアルキレン基であり、R6がシクロヘキシル基を2つ有する基であり、jが1であり、pおよびqが0である、化合物である。PFPE含有シラン化合物(a)は、1種の化合物を単独で用いてもよく、2種以上の混合物として用いてもよい。
In a particularly preferred embodiment, in the PFPE-containing silane compound (a), R 7 are all hydrogen atoms, R 5 is a divalent alkylene group, R 6 is a group having two cyclohexyl groups, and j is 1. and p and q are zero. The PFPE-containing silane compound (a) may be used singly or as a mixture of two or more.
PFPE含有シラン化合物(a)の調製方法によっては、PFPE変性体またはPFPE変性体がR6で連結された化合物の、片方または両方の末端部分にシリル基および場合によりリンカー部分が導入されていない構造の化合物が生じ得る。以下、このようなPFPE1から構成される分子鎖両末端の少なくとも一方にシリル基を含まない化合物を「非末端化PFPE変性体」と表記することがある。一般式(I)で表される化合物の純度は高い方が好ましい。つまりこのような非末端化PFPE変性体の含有割合は小さい方が好ましいが、硬化性組成物としての機能を損なわない範囲において、硬化性組成物の調製に用いられるPFPE含有シラン化合物(a)は非末端化PFPE変性体を含んでいてもよい。例えば、前記一般式(I)の場合、{-PFPE1-C(=O)NR7-R6-NR7C(=O)-}k-PFPE1-で示される構造にカルボン酸基、エステル基、水酸基またはアルキレン-OH基が結合したような構造の化合物を含んでいてもよい。
Depending on the method for preparing the PFPE-containing silane compound (a), a structure in which a silyl group and optionally a linker moiety are not introduced at one or both terminal portions of the modified PFPE or the compound in which the modified PFPE is linked at R 6 can result. Hereinafter, such a compound that does not contain a silyl group on at least one of both ends of the molecular chain composed of PFPE 1 may be referred to as "non-terminated modified PFPE". The higher the purity of the compound represented by formula (I), the better. In other words, it is preferable that the content of such non-terminated PFPE modified product is small, but the PFPE-containing silane compound (a) used for preparing the curable composition is Non-terminated PFPE modifications may be included. For example, in the case of general formula (I), {-PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-} k -PFPE 1 - has a carboxylic acid group, A compound having a structure in which an ester group, a hydroxyl group, or an alkylene-OH group is bonded may be included.
硬化性組成物の調製に用いられるPFPE含有シラン化合物(a)の純度は、シリル基がどの程度末端に導入されているか、シランでの末端化率をその尺度とすることができる。末端化率は、PFPE1部分のうち、R6で挟まれていないものの物質量の合計に対し、当該部分にシリル基が導入されているものの割合により求められる。末端化率は90モル%以上であることが好ましく、93モル%以上であることがより好ましく、95モル%以上であることがさらに好ましい。この範囲とすることで、分子の両末端がシリル化された化合物を十分な量で含有することができ、硬化性組成物としての機能を十分に発揮することができる。
末端化率は、例えばNMR測定により決定することができる。一般式(I)の化合物の場合、PFPE1の末端に存在するCF2基、即ちリンカーと結合しているアミド基に隣接するCF2基を19F NMRで測定することで、分子末端にどの程度シリル基が導入されているかを求めることができる。一般式(I)の化合物とは異なる構造を有する化合物においても、末端がシリル化されたものとそうでないものとで異なる部分のNMR測定によって末端化率を算出することができ、その方法は、当業者にとって周知である。 The purity of the PFPE-containing silane compound (a) used in the preparation of the curable composition can be measured by the extent to which silyl groups are introduced at the terminals, or the degree of terminalization with silane. The termination rate is obtained from the ratio of the portion having a silyl group introduced into the portion to the total amount of substances not sandwiched by R 6 among the 1 portion of PFPE. The termination rate is preferably 90 mol % or more, more preferably 93 mol % or more, and even more preferably 95 mol % or more. Within this range, the compound having both ends of the molecule silylated can be contained in a sufficient amount, and the function as a curable composition can be sufficiently exhibited.
The termination ratio can be determined, for example, by NMR measurement. In the case of the compound of general formula (I), the CF 2 group present at the end of PFPE 1 , that is, the CF 2 group adjacent to the amide group bonded to the linker was measured by 19 F NMR to determine which It is possible to determine the extent to which silyl groups have been introduced. Even in a compound having a structure different from that of the compound of general formula (I), the termination rate can be calculated by NMR measurement of the different portions depending on whether the terminal is silylated or not, and the method is as follows. well known to those skilled in the art.
末端化率は、例えばNMR測定により決定することができる。一般式(I)の化合物の場合、PFPE1の末端に存在するCF2基、即ちリンカーと結合しているアミド基に隣接するCF2基を19F NMRで測定することで、分子末端にどの程度シリル基が導入されているかを求めることができる。一般式(I)の化合物とは異なる構造を有する化合物においても、末端がシリル化されたものとそうでないものとで異なる部分のNMR測定によって末端化率を算出することができ、その方法は、当業者にとって周知である。 The purity of the PFPE-containing silane compound (a) used in the preparation of the curable composition can be measured by the extent to which silyl groups are introduced at the terminals, or the degree of terminalization with silane. The termination rate is obtained from the ratio of the portion having a silyl group introduced into the portion to the total amount of substances not sandwiched by R 6 among the 1 portion of PFPE. The termination rate is preferably 90 mol % or more, more preferably 93 mol % or more, and even more preferably 95 mol % or more. Within this range, the compound having both ends of the molecule silylated can be contained in a sufficient amount, and the function as a curable composition can be sufficiently exhibited.
The termination ratio can be determined, for example, by NMR measurement. In the case of the compound of general formula (I), the CF 2 group present at the end of PFPE 1 , that is, the CF 2 group adjacent to the amide group bonded to the linker was measured by 19 F NMR to determine which It is possible to determine the extent to which silyl groups have been introduced. Even in a compound having a structure different from that of the compound of general formula (I), the termination rate can be calculated by NMR measurement of the different portions depending on whether the terminal is silylated or not, and the method is as follows. well known to those skilled in the art.
以下、上記PFPE含有シラン化合物(a)の一態様として、具体的な構造について詳述する。上記PFPE含有シラン化合物(a)は、式(A)、(B)、(C)、または(D)で表される少なくとも1種の化合物であることが好ましい。以下の式において現れる各基および添え字は、それぞれ前記一般式に現れる基および添え字に対応させることができ、当業者であれば各々の対応関係を把握することができるものである。
A specific structure will be described in detail below as one aspect of the PFPE-containing silane compound (a). The PFPE-containing silane compound (a) is preferably at least one compound represented by Formula (A), (B), (C), or (D). Each group and subscript appearing in the following formulas can correspond to the groups and subscripts appearing in the above general formula, respectively, and a person skilled in the art can grasp the correspondence between them.
(式中、PFPE1、R6、R7は、上記と同定義である。)
(In the formula, PFPE 1 , R 6 and R 7 have the same definitions as above.)
以下、上記式(A)、(B)、(C)および(D)で表されるPFPE含有シラン化合物(A)について説明する。
The PFPE-containing silane compound (A) represented by the above formulas (A), (B), (C) and (D) will be described below.
上記式中、PFPE1、R6、R7は、上記と同意義である。
In the above formula, PFPE 1 , R 6 and R 7 have the same meanings as above.
上記式中、R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。加水分解可能な基は、上記と同意義である。即ち、R13は、上記一般式のR4に対応させることができる。
In the above formula, each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group. Hydrolyzable groups are as defined above. That is, R 13 can correspond to R 4 in the above general formula.
上記式中、R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基、好ましくは炭素原子数1~4のアルキル基を表す。即ち、R14は、上記一般式のR3に対応させることができる。
In the above formula, each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. That is, R 14 can correspond to R 3 in the above general formula.
上記式中、R11は、各出現において、それぞれ独立して、水素原子またはハロゲン原子を表す。ハロゲン原子は、好ましくはヨウ素原子、塩素原子またはフッ素原子であり、より好ましくはフッ素原子である。
In the above formula, each occurrence of R 11 independently represents a hydrogen atom or a halogen atom. A halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
上記式中、R12は、各出現において、それぞれ独立して、水素原子または低級アルキル基を表す。低級アルキル基は、好ましくは炭素原子数1~20のアルキル基であり、より好ましくは炭素原子数1~6のアルキル基であり、例えばメチル基、エチル基、プロピル基等が挙げられる。
In the above formula, each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group and propyl group.
上記式中、R11”、R12”、R13”、およびR14”は、それぞれ、R11、R12、R13、およびR14と同意義である。
In the above formulas, R 11″ , R 12″ , R 13″ and R 14″ have the same meanings as R 11 , R 12 , R 13 and R 14 , respectively.
上記式(A)において、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子とは、n1が1~3の整数であり、かつ(-SiR13
n1R14
3-n1)または(-SiR13”
n1R14”
3-n1)に含まれるSi原子を示す。
In the above formula (A), the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group means that n1 is an integer of 1 to 3 and (-SiR 13 n1 R 14 3-n1 ) or (-SiR 13″ n1 R 14″ 3-n1 ).
上記式中、n1は、(-SiR13
n1R14
3-n1)単位毎、または(-SiR13”
n1R14”
3-n1)単位毎に独立して、0~3の整数であり、好ましくは1~3であり、より好ましくは3である。式中、少なくとも2つのn1が1~3の整数であり、即ち、すべてのn1が同時に0になることはない。即ち、式中、少なくとも2つはR13またはR13”の結合したSi原子が存在する。言い換えると、式(A)において、n1が1以上である-SiR13
n1R14
3-n1構造(即ち、-SiR13部分)およびn1が1以上である-SiR13”
n1R14”
3-n1構造(即ち、-SiR13”部分)からなる群より選ばれる構造が少なくとも2つ存在する。即ち、n1は、上記一般式の3-pまたは3-qの値に対応させることができる。
In the above formula, n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n1 ) unit or each (-SiR 13″ n1 R 14″ 3-n1 ) unit, It is preferably 1 to 3, more preferably 3. wherein at least two n1's are integers from 1 to 3, ie not all n1's are 0 at the same time. That is, in the formula, there are at least two R 13 or R 13″ bonded Si atoms. In other words, in formula (A), the —SiR 13 n1 R 14 3-n1 structure ( That is, there are at least two structures selected from the group consisting of -SiR 13 " moieties) and -SiR 13'' n1 R 14'' 3-n1 structures where n1 is 1 or greater (ie, -SiR 13'' moieties). That is, n1 can correspond to the value of 3-p or 3-q in the above general formula.
好ましくは、式(A)において、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子は、分子主鎖の両末端に存在する。即ち、式(A)において、少なくとも1の、n1が1以上である-SiR13
n1R14
3-n1構造(即ち、-SiR13部分)、および、少なくとも1の、n1が1以上である-SiR13”
n1R14”
3-n1構造(即ち、-SiR13”部分)が存在する。
Preferably, in formula (A), Si atoms bonded to at least one group selected from the group consisting of hydroxyl groups and hydrolyzable groups are present at both ends of the molecular main chain. That is, in formula (A), at least one -SiR 13 n1 R 14 3-n1 structure (i.e., -SiR 13 moiety) in which n1 is 1 or more, and at least one in which n1 is 1 or more- A SiR 13″ n1 R 14″ 3-n1 structure (ie, the —SiR 13″ portion) is present.
上記式中、X1は、それぞれ独立して、アミド結合に連結する単結合または2~10価の有機基を表す。当該X1は、式(A)で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロ(ポリ)エーテル部(即ち、-PFPE1-部)と、基材との結合能を提供するシラン部とを連結するリンカーの一部と解される。従って、当該X1は、式(A)で表される化合物が安定に存在し得るものであれば、単結合であってもよく、いずれの有機基であってもよい。即ち、X1は、後述するX2およびそれに連結する炭化水素基とともに、上記一般式におけるR5の一部に対応することが理解される。なお、本明細書において、X1として記載している基は、記載の左側がPFPE1で表される基に隣接するアミド結合に、右側が括弧でくくられた基に、それぞれ結合する。ただし、X1として記載している基は、それが安定な化合物として調製できるものである限り、逆方向に結合する基、例えば、-CO-C6H4-であれば-C6H4-CO-と記載される、フェニレン基がPFPE1で表される基に隣接するアミド結合に結合するものを包含する。
In the above formula, each X 1 independently represents a single bond or a divalent to decavalent organic group linked to the amide bond. The X 1 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (A), and a base material. It is understood to be part of the linker connecting the silane moieties that provide the binding ability. Therefore, X 1 may be a single bond or any organic group as long as the compound represented by formula (A) can exist stably. That is, it is understood that X 1 corresponds to part of R 5 in the above general formula together with X 2 and a hydrocarbon group linked thereto, which will be described later. In this specification, the group described as X 1 is bonded to the amide bond adjacent to the group represented by PFPE 1 on the left side of the description, and to the parenthesized group on the right side. However, the group described as X 1 is a group that binds in the opposite direction, for example, -C 6 H 4 in the case of -CO-C 6 H 4 -, as long as it can be prepared as a stable compound. Included are those in which the phenylene group is attached to the amide bond adjacent to the group represented by PFPE 1 , described as -CO-.
別の態様において、X1は、Xeであり得る。Xeは、単結合または2~10価の有機基を表し、好ましくは、単結合または-C6H4-(すなわち-フェニレン-。以下、フェニレン基を示す。)、-O-(エーテル基)、-CO-(カルボニル基)、-NR40-および-SO2-からなる群より選ばれる少なくとも1つを有する2~10価の有機基を表す。上記R40は、それぞれ独立して、水素原子、フェニル基、またはC1~6アルキル基(好ましくはメチル基)を表し、好ましくは水素原子、またはメチル基である。上記の-C6H4-、-CO-、-NR40-または-SO2-は、PFPE含有シラン化合物(A)の分子主鎖中に含まれることが好ましい。
In another aspect, X 1 can be X e . X e represents a single bond or a divalent to decavalent organic group, preferably a single bond or —C 6 H 4 — (that is, —phenylene—, hereinafter referred to as a phenylene group), —O— (ether group ), —CO— (carbonyl group), —NR 40 —, and —SO 2 —, and represents a divalent to decavalent organic group having at least one selected from the group consisting of; Each R 40 above independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group. The above -C 6 H 4 -, -CO-, -NR 40 - or -SO 2 - is preferably contained in the molecular main chain of the PFPE-containing silane compound (A).
Xeは、より好ましくは、単結合または-C6H4-、-CONR40-、-CONR40-C6H4-、-CO-、-CO-C6H4-、-O-CO-NR40-、-SO2NR40-、-SO2NR40-C6H4-、-SO2-、および-SO2-C6H4-からなる群より選ばれる少なくとも1つを有する2~10価の有機基を表す。上記の-C6H4-、-CONR40-、-CONR40-C6H4-、-CO-、-CO-C6H4-、-SO2NR40-、-SO2NR40-C6H4-、-SO2-、または-SO2-C6H4-は、PFPE含有シラン化合物(A)の分子主鎖中に含まれることが好ましい。
X e is more preferably a single bond or —C 6 H 4 —, —CONR 40 —, —CONR 40 —C 6 H 4 —, —CO—, —CO—C 6 H 4 —, —O—CO having at least one selected from the group consisting of -NR 40 -, -SO 2 NR 40 -, -SO 2 NR 40 -C 6 H 4 -, -SO 2 -, and -SO 2 -C 6 H 4 - It represents a divalent to decavalent organic group. The above -C 6 H 4 -, -CONR 40 -, -CONR 40 -C 6 H 4 -, -CO-, -CO-C 6 H 4 -, -SO 2 NR 40 -, -SO 2 NR 40 - C 6 H 4 —, —SO 2 —, or —SO 2 —C 6 H 4 — is preferably included in the molecular backbone of the PFPE-containing silane compound (A).
上記式中、α1は1~9の整数であり、X1の価数に応じて変化し得る。式(A)において、α1はX1の価数から1を引いた値である。X1が単結合または2価の有機基であるときには、α1は1である。即ち、α1は、上記一般式のjの値に対応させることができる。
In the above formula, α1 is an integer of 1 to 9 and may vary depending on the valence of X1. In formula (A), α1 is the value obtained by subtracting 1 from the valence of X1. α1 is 1 when X 1 is a single bond or a divalent organic group. That is, α1 can correspond to the value of j in the above general formula.
上記X1は、好ましくは2~7価であり、より好ましくは2~4価であり、さらに好ましくは2価の有機基である。
X 1 is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X1は2~4価の有機基であり、α1は1~3である。
In one embodiment, X 1 is a divalent to tetravalent organic group and α1 is 1-3.
別の態様において、X1は2価の有機基であり、α1は1である。この場合、式(A)は、下記式(A’)で表される。
In another embodiment, X 1 is a divalent organic group and α1 is 1. In this case, the formula (A) is represented by the following formula (A').
上記X1の例としては、PFPE1基に連結するアミド基と結合を形成しうるもので化合物を安定に調製可能なものであれば特に限定されないが、例えば、下記式:
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、好ましくは水素原子であり、
m’は、各出現において、それぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現において、それぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0または1であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。ただし、R31が単結合であるかp’が0であるとき、Xaは、-CONR34-または-NR34-ではない。 Examples of X 1 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound.
-(R 31 ) p' -(X a ) q' -
[In the formula:
R 31 represents a single bond, —(CH 2 ) s′ — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s′ —,
s′ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2;
X a represents -(X b ) l' -,
X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 33 ) 2 -, -( selected from the group consisting of Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CONR 34 -, -O-CONR 34 -, -NR 34 - and -(CH 2 ) n' -; represents a group that
R 33 at each occurrence independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group and
each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom,
m′ at each occurrence is independently an integer from 1 to 100, preferably an integer from 1 to 20;
n′ at each occurrence is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3;
l' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p' is 0 or 1;
q' is 0 or 1;
Here, at least one of p' and q' is 1, and the order of existence of each repeating unit bracketed with p' or q' is arbitrary.]
A divalent group represented by is mentioned. Here, R 31 and X a (typically hydrogen atoms of R 31 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group may be substituted by a substituent of However, when R 31 is a single bond or p′ is 0, X a is not —CONR 34 — or —NR 34 —.
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、好ましくは水素原子であり、
m’は、各出現において、それぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現において、それぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0または1であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。ただし、R31が単結合であるかp’が0であるとき、Xaは、-CONR34-または-NR34-ではない。 Examples of X 1 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound.
-(R 31 ) p' -(X a ) q' -
[In the formula:
R 31 represents a single bond, —(CH 2 ) s′ — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s′ —,
s′ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2;
X a represents -(X b ) l' -,
X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 33 ) 2 -, -( selected from the group consisting of Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CONR 34 -, -O-CONR 34 -, -NR 34 - and -(CH 2 ) n' -; represents a group that
R 33 at each occurrence independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group and
each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom,
m′ at each occurrence is independently an integer from 1 to 100, preferably an integer from 1 to 20;
n′ at each occurrence is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3;
l' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p' is 0 or 1;
q' is 0 or 1;
Here, at least one of p' and q' is 1, and the order of existence of each repeating unit bracketed with p' or q' is arbitrary.]
A divalent group represented by is mentioned. Here, R 31 and X a (typically hydrogen atoms of R 31 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group may be substituted by a substituent of However, when R 31 is a single bond or p′ is 0, X a is not —CONR 34 — or —NR 34 —.
一の態様において、上記式におけるl’は、1である。
In one aspect, l' in the above formula is 1.
好ましくは、上記X1は、-(R31)p’-(Xa)q’-R32-である。R32は、単結合、-(CH2)t’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)t’-である。t’は、1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。ここに、R32(典型的にはR32中の水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
Preferably, X 1 above is -(R 31 ) p' -(X a ) q' -R 32 -. R 32 represents a single bond, -(CH 2 ) t' - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t' -. t' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. wherein R 32 (typically a hydrogen atom in R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group; may have been
好ましくは、上記X1は、
単結合、
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。なお、アルキレン基とは、-(CδH2δ)-構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。 Preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—R 31 —X c —R 32 —, or —X d —R 32 —
[In the formula, R 31 and R 32 have the same meanings as above. ]
can be The alkylene group is a group having a -(C δ H 2δ )- structure, may be substituted or unsubstituted, and may be linear or branched.
単結合、
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。なお、アルキレン基とは、-(CδH2δ)-構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。 Preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—R 31 —X c —R 32 —, or —X d —R 32 —
[In the formula, R 31 and R 32 have the same meanings as above. ]
can be The alkylene group is a group having a -(C δ H 2δ )- structure, may be substituted or unsubstituted, and may be linear or branched.
より好ましくは、上記X1は、
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-、
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。 More preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —X c —,
—(CH 2 ) s′ —X c —(CH 2 ) t′ —,
-X d -, or -X d -(CH 2 ) t' -
[In the formula, s' and t' have the same meanings as described above. ]
is.
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-、
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。 More preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —X c —,
—(CH 2 ) s′ —X c —(CH 2 ) t′ —,
-X d -, or -X d -(CH 2 ) t' -
[In the formula, s' and t' have the same meanings as described above. ]
is.
さらに好ましくは、上記X1は、
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
である。式中、s’およびt’は、上記と同意義である。
上記式中、Xfは、炭素原子数1~6、好ましくは炭素原子数1~4、より好ましくは炭素原子数1~2のアルキレン基、例えばメチレン基である。Xf中の水素原子は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Xfは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。 More preferably, the above X 1 is
-X f -,
—X f —C 1-20 alkylene group,
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
is. In the formula, s' and t' have the same meanings as above.
In the above formula, X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group. A hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably unsubstituted there is Xf may be linear or branched, preferably linear.
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
である。式中、s’およびt’は、上記と同意義である。
上記式中、Xfは、炭素原子数1~6、好ましくは炭素原子数1~4、より好ましくは炭素原子数1~2のアルキレン基、例えばメチレン基である。Xf中の水素原子は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Xfは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。 More preferably, the above X 1 is
-X f -,
—X f —C 1-20 alkylene group,
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
is. In the formula, s' and t' have the same meanings as above.
In the above formula, X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group. A hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably unsubstituted there is Xf may be linear or branched, preferably linear.
上記式中、Xcは、
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-(CH2)u’-N(R34)-、
-(o-、m-またはp-フェニレン)-Si(R33)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。但し、R31が単結合である場合、Xcは、-CONR34-を末端に有する基ではない。好ましくは-O-である。 In the above formula, X c is
-O-,
-S-,
-C(O)O-,
-CONR 34- ,
-O-CONR 34- ,
—Si(R 33 ) 2 —,
—(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —Si(R 33 ) 2 —O—Si(R 33 ) 2 —CH 2 CH 2 —Si(R 33 ) 2 —O—Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —Si(OCH 3 ) 2 OSi(OCH 3 ) 2 —,
—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—(CH 2 ) u′ —N(R 34 )—,
-(o-, m- or p-phenylene)-Si(R 33 ) 2 -,
—CONR 34 —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—CONR 34 —(CH 2 ) u′ —N(R 34 )—, or —CONR 34 —(o-, m- or p-phenylene)—Si(R 33 ) 2 —
[Wherein, R 33 , R 34 and m′ have the same meanings as above,
u' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. ] represents. However, when R 31 is a single bond, X c is not a group terminating with —CONR 34 —. -O- is preferred.
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-(CH2)u’-N(R34)-、
-(o-、m-またはp-フェニレン)-Si(R33)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。但し、R31が単結合である場合、Xcは、-CONR34-を末端に有する基ではない。好ましくは-O-である。 In the above formula, X c is
-O-,
-S-,
-C(O)O-,
-CONR 34- ,
-O-CONR 34- ,
—Si(R 33 ) 2 —,
—(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —Si(R 33 ) 2 —O—Si(R 33 ) 2 —CH 2 CH 2 —Si(R 33 ) 2 —O—Si(R 33 ) 2 —,
—O—(CH 2 ) u′ —Si(OCH 3 ) 2 OSi(OCH 3 ) 2 —,
—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—(CH 2 ) u′ —N(R 34 )—,
-(o-, m- or p-phenylene)-Si(R 33 ) 2 -,
—CONR 34 —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—CONR 34 —(CH 2 ) u′ —N(R 34 )—, or —CONR 34 —(o-, m- or p-phenylene)—Si(R 33 ) 2 —
[Wherein, R 33 , R 34 and m′ have the same meanings as above,
u' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. ] represents. However, when R 31 is a single bond, X c is not a group terminating with —CONR 34 —. -O- is preferred.
上記式中、Xdは、
-S-、
-C(O)O-、
-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-(CH2)u’-N(R34)-、
-(o-、m-またはp-フェニレン)-Si(R33)2-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。 In the above formula, X d is
-S-,
-C(O)O-,
—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—(CH 2 ) u′ —N(R 34 )—,
-(o-, m- or p-phenylene)-Si(R 33 ) 2 -,
-CONR 34- ,
—CONR 34 —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—CONR 34 —(CH 2 ) u′ —N(R 34 )—, or —CONR 34 —(o-, m- or p-phenylene)—Si(R 33 ) 2 —
[In the formula, each symbol has the same meaning as described above. ]
represents
-S-、
-C(O)O-、
-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-(CH2)u’-N(R34)-、
-(o-、m-またはp-フェニレン)-Si(R33)2-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。 In the above formula, X d is
-S-,
-C(O)O-,
—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—(CH 2 ) u′ —N(R 34 )—,
-(o-, m- or p-phenylene)-Si(R 33 ) 2 -,
-CONR 34- ,
—CONR 34 —(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —,
—CONR 34 —(CH 2 ) u′ —N(R 34 )—, or —CONR 34 —(o-, m- or p-phenylene)—Si(R 33 ) 2 —
[In the formula, each symbol has the same meaning as described above. ]
represents
特に好ましくは、上記X1は、
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。 Particularly preferably, the above X 1 is
-X f -,
—X f —C 1-20 alkylene group,
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
[In the formula, X f , s′ and t′ have the same meanings as above. ]
and
X c is —O—, or —CONR 34 —,
X d is -CONR 34 -,
Each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group). ]
It is a group represented by
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。 Particularly preferably, the above X 1 is
-X f -,
—X f —C 1-20 alkylene group,
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
[In the formula, X f , s′ and t′ have the same meanings as above. ]
and
X c is —O—, or —CONR 34 —,
X d is -CONR 34 -,
Each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group). ]
It is a group represented by
一の態様において、上記X1は、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。 In one aspect, X 1 above is
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
[In the formula, X f , s′ and t′ have the same meanings as above. ]
and
X c is —CONR 34 —,
X d is -CONR 34 -,
Each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group). ]
is a group represented by
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。 In one aspect, X 1 above is
-Xf- ( CH2 ) s' - Xc- ,
—X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
—X f —X d —, or —X f —X d —(CH 2 ) t′ —
[In the formula, X f , s′ and t′ have the same meanings as above. ]
and
X c is —CONR 34 —,
X d is -CONR 34 -,
Each occurrence of R 34 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group). ]
is a group represented by
一の態様において、上記X1は、
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。但し、このときXdは、-CONR34-ではない。 In one aspect, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —X c —(CH 2 ) t′ —, or —X d —(CH 2 ) t′ —
[In the formula, each symbol has the same meaning as described above. ]
can be However, at this time, X d is not -CONR 34 -.
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。但し、このときXdは、-CONR34-ではない。 In one aspect, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —X c —(CH 2 ) t′ —, or —X d —(CH 2 ) t′ —
[In the formula, each symbol has the same meaning as described above. ]
can be However, at this time, X d is not -CONR 34 -.
好ましくは、上記X1は、
単結合、
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2-(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。 Preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —O—(CH 2 ) t′ —,
—(CH 2 ) s′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ —,
—(CH 2 ) s′ —O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ — or —(CH 2 ) s' -O-( CH2 ) t' -Si( R33 ) 2- ( CH2 ) u' - Si ( R33 ) 2- ( CvH2v )-
[Wherein, R 33 , m′, s′, t′ and u′ have the same meanings as above, v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3 is an integer. ]
is.
単結合、
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2-(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。 Preferably, X 1 above is
single bond,
a C 1-20 alkylene group,
—(CH 2 ) s′ —O—(CH 2 ) t′ —,
—(CH 2 ) s′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ —,
—(CH 2 ) s′ —O—(CH 2 ) u′ —(Si(R 33 ) 2 O) m′ —Si(R 33 ) 2 —(CH 2 ) t′ — or —(CH 2 ) s' -O-( CH2 ) t' -Si( R33 ) 2- ( CH2 ) u' - Si ( R33 ) 2- ( CvH2v )-
[Wherein, R 33 , m′, s′, t′ and u′ have the same meanings as above, v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3 is an integer. ]
is.
上記式中、-(CvH2v)-は、直鎖であっても、分枝鎖であってもよく、例えば、-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH(CH3)-、-CH(CH3)CH2-であり得る。
In the above formula, -(C v H 2v )- may be linear or branched, for example -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2- , -CH(CH 3 )-, -CH(CH 3 )CH 2 -.
上記X1基は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基(好ましくは、C1-3パーフルオロアルキル基)から選択される1個またはそれ以上の置換基により置換されていてもよい。
The above X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) may have been
一の態様において、X1基は、-O-C1-6アルキレン基以外であり得る。
In one aspect, the X 1 group can be other than a —O—C 1-6 alkylene group.
別の態様において、X1基としては、例えば下記の基が挙げられる:
[式中、R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、および
-(1,3-フェニレン)-Si(R42)2-(CH2)2-
(式中、R42は、それぞれ独立して、水素原子、C1-6のアルキル基またはC1-6のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。)
から選択される基であり、
Eは、-(CH2)ne-(neは2~6の整数)であり、
Dは、分子主鎖のPFPE1基がある側に結合し、Eは、PFPE1がある側と反対の基に結合する。] In another aspect, X 1 groups include, for example, the groups:
[wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
D is
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CF 2 O(CH 2 ) 3 —,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -, and -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 -
(In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
is a group selected from
E is -(CH 2 ) ne - (ne is an integer of 2 to 6),
D is attached to the side of the molecular backbone with the PFPE 1 group, and E is attached to the group opposite the side with the PFPE 1 group. ]
[式中、R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、および
-(1,3-フェニレン)-Si(R42)2-(CH2)2-
(式中、R42は、それぞれ独立して、水素原子、C1-6のアルキル基またはC1-6のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。)
から選択される基であり、
Eは、-(CH2)ne-(neは2~6の整数)であり、
Dは、分子主鎖のPFPE1基がある側に結合し、Eは、PFPE1がある側と反対の基に結合する。] In another aspect, X 1 groups include, for example, the groups:
[wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
D is
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CF 2 O(CH 2 ) 3 —,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -, and -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 -
(In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
is a group selected from
E is -(CH 2 ) ne - (ne is an integer of 2 to 6),
D is attached to the side of the molecular backbone with the PFPE 1 group, and E is attached to the group opposite the side with the PFPE 1 group. ]
上記X1の具体的な例としては、例えば:
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Specific examples of X 1 above include:
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Specific examples of X 1 above include:
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
上記の中では、X1は、
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、または
-OCFHCF2-、
であることが好ましい。 In the above, X 1 is
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —, or —OCFHCF 2 —,
is preferably
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、または
-OCFHCF2-、
であることが好ましい。 In the above, X 1 is
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —, or —OCFHCF 2 —,
is preferably
上記の中では、より好ましくは、X1は、
単結合、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably, X 1 is
single bond,
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
単結合、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably, X 1 is
single bond,
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
一の態様において、X1は、Xe’を表す。Xe’は、単結合、炭素原子数1~6のアルキレン基、-R51-C6H4-R52-、-R51-CONR40-R52-、-R51-CONR40-C6H4-R52-、-R51-CO-R52-、-R51-CO-C6H4-R52-、-R51-SO2NR40-R52-、-R51-SO2NR40-C6H4-R52-、-R51-SO2-R52-、または-R51-SO2-C6H4-R52-である。R51およびR52は、それぞれ独立して、単結合または炭素原子数1~6のアルキレン基(但し、R51が-CONR40-と連結する場合、R51は単結合ではない)を表し、好ましくは単結合または炭素原子数1~3のアルキレン基である。R40は上記と同意義である。上記アルキレン基は、置換または非置換であり、好ましくは非置換である。上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。上記アルキレン基は、直鎖状または分枝鎖状であり、直鎖状であることが好ましい。
In one aspect, X 1 represents X e′ . X e′ is a single bond, an alkylene group having 1 to 6 carbon atoms, —R 51 —C 6 H 4 —R 52 —, —R 51 —CONR 40 —R 52 —, —R 51 —CONR 40 —C 6 H 4 -R 52 -, -R 51 -CO-R 52 -, -R 51 -CO-C 6 H 4 -R 52 -, -R 51 -SO 2 NR 40 -R 52 -, -R 51 - SO 2 NR 40 -C 6 H 4 -R 52 -, -R 51 -SO 2 -R 52 -, or -R 51 -SO 2 -C 6 H 4 -R 52 -. R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms (provided that when R 51 is linked to —CONR 40 —, R 51 is not a single bond); A single bond or an alkylene group having 1 to 3 carbon atoms is preferred. R40 has the same meaning as above. The above alkylene groups are substituted or unsubstituted, preferably unsubstituted. Examples of substituents for the alkylene group include halogen atoms, preferably fluorine atoms. The alkylene group is linear or branched, preferably linear.
好ましい態様において、Xe’は、
単結合、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-C6H4-R52’-、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-CO-R52’-、
-CO-C6H4-R52’-、
-SO2NR4’-R52’-、
-SO2NR4’-C6H4-R52’-、
-SO2-R52’-、
-SO2-C6H4-R52’-、
-R51’-C6H4-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-R51’-CO-、
-R51’-CO-C6H4-、
-R51’-SO2NR4’-、
-R51’-SO2NR4’-C6H4-、
-R51’-SO2-、
-R51’-SO2-C6H4-、
-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-CO-、
-CO-C6H4-、
-SO2NR4’-、
-SO2NR4’-C6H4-、
-SO2-、または
-SO2-C6H4-
(式中、R51’およびR52’は、それぞれ独立して、炭素原子数1~6、好ましくは炭素原子数1~3の直鎖のアルキレン基である。上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。R4’は、水素原子またはメチル基である。)
であり得る。 In a preferred embodiment, X e' is
single bond,
-X f -,
an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group,
—C 6 H 4 —R 52′ —,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
-CO-R 52'- ,
—CO—C 6 H 4 —R 52′ —,
—SO 2 NR 4′ —R 52′ —,
—SO 2 NR 4′ —C 6 H 4 —R 52′ —,
—SO 2 —R 52′ —,
—SO 2 —C 6 H 4 —R 52′ —,
—R 51′ —C 6 H 4 —,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
—R 51′ —CO—,
—R 51′ —CO—C 6 H 4 —,
—R 51′ —SO 2 NR 4′ —,
—R 51′ —SO 2 NR 4′ —C 6 H 4 —,
—R 51′ —SO 2 —,
—R 51′ —SO 2 —C 6 H 4 —,
-C6H4- ,
-X f -CONR 4' -,
-Xf - CONR4' - C6H4-,
-CO-,
—CO—C 6 H 4 —,
—SO 2 NR 4′ —,
-SO2NR4' - C6H4- ,
—SO 2 —, or —SO 2 —C 6 H 4 —
(wherein R 51′ and R 52′ are each independently a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As described above, the alkylene group is substituted or unsubstituted, and examples of substituents of the alkylene group include halogen atoms, preferably fluorine atoms.R 4' is a hydrogen atom or a methyl group.)
can be
単結合、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-C6H4-R52’-、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-CO-R52’-、
-CO-C6H4-R52’-、
-SO2NR4’-R52’-、
-SO2NR4’-C6H4-R52’-、
-SO2-R52’-、
-SO2-C6H4-R52’-、
-R51’-C6H4-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-R51’-CO-、
-R51’-CO-C6H4-、
-R51’-SO2NR4’-、
-R51’-SO2NR4’-C6H4-、
-R51’-SO2-、
-R51’-SO2-C6H4-、
-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-CO-、
-CO-C6H4-、
-SO2NR4’-、
-SO2NR4’-C6H4-、
-SO2-、または
-SO2-C6H4-
(式中、R51’およびR52’は、それぞれ独立して、炭素原子数1~6、好ましくは炭素原子数1~3の直鎖のアルキレン基である。上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。R4’は、水素原子またはメチル基である。)
であり得る。 In a preferred embodiment, X e' is
single bond,
-X f -,
an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group,
—C 6 H 4 —R 52′ —,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
-CO-R 52'- ,
—CO—C 6 H 4 —R 52′ —,
—SO 2 NR 4′ —R 52′ —,
—SO 2 NR 4′ —C 6 H 4 —R 52′ —,
—SO 2 —R 52′ —,
—SO 2 —C 6 H 4 —R 52′ —,
—R 51′ —C 6 H 4 —,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
—R 51′ —CO—,
—R 51′ —CO—C 6 H 4 —,
—R 51′ —SO 2 NR 4′ —,
—R 51′ —SO 2 NR 4′ —C 6 H 4 —,
—R 51′ —SO 2 —,
—R 51′ —SO 2 —C 6 H 4 —,
-C6H4- ,
-X f -CONR 4' -,
-Xf - CONR4' - C6H4-,
-CO-,
—CO—C 6 H 4 —,
—SO 2 NR 4′ —,
-SO2NR4' - C6H4- ,
—SO 2 —, or —SO 2 —C 6 H 4 —
(wherein R 51′ and R 52′ are each independently a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. As described above, the alkylene group is substituted or unsubstituted, and examples of substituents of the alkylene group include halogen atoms, preferably fluorine atoms.R 4' is a hydrogen atom or a methyl group.)
can be
上記の中で、Xe’は、好ましくは、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-R51’-CONR4’-、または
-R51’-CONR4’-C6H4-、
であり得る。式中、Xf、R51’およびR52’は、それぞれ上記と同意義である。 In the above, X e' is preferably
-X f -,
an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
-X f -CONR 4' -,
-Xf - CONR4' - C6H4-,
-R 51' -CONR 4' -, or -R 51' -CONR 4' -C 6 H 4 -,
can be In the formula, X f , R 51′ and R 52′ have the same meanings as above.
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-R51’-CONR4’-、または
-R51’-CONR4’-C6H4-、
であり得る。式中、Xf、R51’およびR52’は、それぞれ上記と同意義である。 In the above, X e' is preferably
-X f -,
an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
-X f -CONR 4' -,
-Xf - CONR4' - C6H4-,
-R 51' -CONR 4' -, or -R 51' -CONR 4' -C 6 H 4 -,
can be In the formula, X f , R 51′ and R 52′ have the same meanings as above.
上記の中で、Xe’は、より好ましくは、
単結合、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-C6H4-、
-Xf-CONR4’-、または
-Xf-CONR4’-C6H4-、
であり得る。 Among the above, X e' is more preferably
single bond,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
-C6H4- ,
—X f —CONR 4′ —, or —X f —CONR 4′ —C 6 H 4 —,
can be
単結合、
-R52’-、
-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-C6H4-、
-Xf-CONR4’-、または
-Xf-CONR4’-C6H4-、
であり得る。 Among the above, X e' is more preferably
single bond,
-R 52' -,
—C 6 H 4 —R 52′ —,
-X f -CONR 4' -R 52' -,
-Xf - CONR4' - C6H4 - R52'-,
—R 51′ —CONR 4′ —,
—R 51′ —CONR 4′ —C 6 H 4 —,
-C6H4- ,
—X f —CONR 4′ —, or —X f —CONR 4′ —C 6 H 4 —,
can be
本態様において、Xe’の具体例としては、例えば、
単結合、
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2-CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
-CO-、
-CO-C6H4-、
-C6H4-、
-SO2NH-、
-SO2NH-CH2-、
-SO2NH-(CH2)2-、
-SO2NH-(CH2)3-、
-SO2NH-C6H4-、
-SO2N(CH3)-、
-SO2N(CH3)-CH2-、
-SO2N(CH3)-(CH2)2-、
-SO2N(CH3)-(CH2)3-、
-SO2N(CH3)-C6H4-、
-SO2-、
-SO2-CH2-、
-SO2-(CH2)2-、
-SO2-(CH2)3-、または
-SO2-C6H4-
などが挙げられる。 In this aspect, specific examples of X e′ include, for example,
single bond,
an alkylene group having 1 to 6 carbon atoms,
a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.),
—CF 2 —C 1-6 alkylene group,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2 - CONH-,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CO-,
—CO—C 6 H 4 —,
-C6H4- ,
-SO2NH- ,
-SO2NH - CH2-,
-SO2NH- ( CH2 ) 2- ,
—SO 2 NH—(CH 2 ) 3 —,
-SO2NH - C6H4- ,
-SO2N ( CH3 )-,
-SO2N ( CH3 ) -CH2- ,
-SO2N ( CH3 )-( CH2 ) 2- ,
-SO2N ( CH3 )-( CH2 ) 3- ,
-SO2N ( CH3 ) -C6H4- ,
-SO2- ,
—SO 2 —CH 2 —,
—SO 2 —(CH 2 ) 2 —,
—SO 2 —(CH 2 ) 3 —, or —SO 2 —C 6 H 4 —
etc.
単結合、
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2-CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
-CO-、
-CO-C6H4-、
-C6H4-、
-SO2NH-、
-SO2NH-CH2-、
-SO2NH-(CH2)2-、
-SO2NH-(CH2)3-、
-SO2NH-C6H4-、
-SO2N(CH3)-、
-SO2N(CH3)-CH2-、
-SO2N(CH3)-(CH2)2-、
-SO2N(CH3)-(CH2)3-、
-SO2N(CH3)-C6H4-、
-SO2-、
-SO2-CH2-、
-SO2-(CH2)2-、
-SO2-(CH2)3-、または
-SO2-C6H4-
などが挙げられる。 In this aspect, specific examples of X e′ include, for example,
single bond,
an alkylene group having 1 to 6 carbon atoms,
a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.),
—CF 2 —C 1-6 alkylene group,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2 - CONH-,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CO-,
—CO—C 6 H 4 —,
-C6H4- ,
-SO2NH- ,
-SO2NH - CH2-,
-SO2NH- ( CH2 ) 2- ,
—SO 2 NH—(CH 2 ) 3 —,
-SO2NH - C6H4- ,
-SO2N ( CH3 )-,
-SO2N ( CH3 ) -CH2- ,
-SO2N ( CH3 )-( CH2 ) 2- ,
-SO2N ( CH3 )-( CH2 ) 3- ,
-SO2N ( CH3 ) -C6H4- ,
-SO2- ,
—SO 2 —CH 2 —,
—SO 2 —(CH 2 ) 2 —,
—SO 2 —(CH 2 ) 3 —, or —SO 2 —C 6 H 4 —
etc.
上記列挙の中で、好ましいXe’としては、
単結合、
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
などが挙げられる。 Among the above enumeration, preferable X e′ is
single bond,
an alkylene group having 1 to 6 carbon atoms,
a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.),
—CF 2 —C 1-6 alkylene group,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- ,
-CF2 - CON( CH3 ) -C6H4- ,
etc.
単結合、
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
などが挙げられる。 Among the above enumeration, preferable X e′ is
single bond,
an alkylene group having 1 to 6 carbon atoms,
a perfluoroalkylene group having 1 to 6 carbon atoms (eg, -CF 2 -, -(CF 2 ) 2 -, etc.),
—CF 2 —C 1-6 alkylene group,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- ,
-CF2 - CON( CH3 ) -C6H4- ,
etc.
上記列挙の中で、より好ましいXe’としては、
単結合、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、または
-CF2-CON(CH3)-C6H4-、
などが挙げられる。 Among the above enumeration, more preferable X e′ is
single bond,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- , or -CF2 - CON( CH3 ) -C6H4- ,
etc.
単結合、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、または
-CF2-CON(CH3)-C6H4-、
などが挙げられる。 Among the above enumeration, more preferable X e′ is
single bond,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2 - CON( CH3 )-,
-CF2 - CON( CH3 )CH2-,
-CF2 - CON( CH3 )-( CH2 ) 2- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CH2 -CONH-,
—CH 2 —CONH—CH 2 —,
-CH 2 -CONH-(CH 2 ) 2 -,
-CH 2 -CONH-(CH 2 ) 3 -,
-CF2- CH2 - CONH-,
-CF2- CH2 - CONH - CH2-,
-CF2- CH2 - CONH-( CH2 ) 2- ,
-CF2- CH2 - CONH-( CH2 ) 3- ,
-C6H4- ,
—CH 2 —CON(CH 3 )—CH 2 —,
-CH 2 -CON(CH 3 )-(CH 2 ) 2 -,
-CH 2 -CON(CH 3 )-(CH 2 ) 3 -,
-CF2 - CONH- C6H4- ,
-CF2 - CON( CH3 ) -C6H4- ,
-CF2- CH2 - CON( CH3 ) -CH2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 2- ,
-CF2- CH2 - CON( CH3 )-( CH2 ) 3- , or -CF2 - CON( CH3 ) -C6H4- ,
etc.
一の態様において、Xe’は、単結合である。
In one aspect, X e' is a single bond.
さらに別の態様において、X1は、式:-(R16)x-(CFR17)y-(CH2)z-で表される基である。式中、x、yおよびzは、それぞれ独立して、0~10の整数であり、x、yおよびzの和は1以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。
In yet another aspect, X 1 is a group of the formula: -(R 16 ) x -(CFR 17 ) y -(CH 2 ) z -. In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized repeating unit in the formula is optional in
上記式中、R16は、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、-NR18-(式中、R18は、水素原子または有機基を表す)または2価の有機基である。好ましくは、R16は、酸素原子または2価の極性基である。
In the above formula, each occurrence of R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group. be. Preferably, R 16 is an oxygen atom or a divalent polar group.
上記「2価の極性基」としては、特に限定されないが、-C(O)-、および-C(=NR19)-(式中、R19は、水素原子または低級アルキル基を表す)が挙げられる。当該「低級アルキル基」は、例えば、炭素原子数1~6のアルキル基、例えばメチル基、エチル基、n-プロピル基であり、これらは、1個またはそれ以上のフッ素原子により置換されていてもよい。
The above-mentioned "divalent polar group" is not particularly limited, but -C(O)- and -C(=NR 19 )- (wherein R 19 represents a hydrogen atom or a lower alkyl group). mentioned. The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, which are substituted with one or more fluorine atoms. good too.
上記式中、R17は、各出現においてそれぞれ独立して、水素原子、フッ素原子または低級フルオロアルキル基であり、好ましくはフッ素原子である。当該「低級フルオロアルキル基」は、例えば、炭素原子数1~6、好ましくは炭素原子数1~3のフルオロアルキル基、好ましくは炭素原子数1~3のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。
In the above formula, each occurrence of R 17 is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro A methyl group, a pentafluoroethyl group, more preferably a trifluoromethyl group.
この態様において、X1は、好ましくは、式:-(O)x-(CF2)y-(CH2)z-(式中、x、yおよびzは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である)で表される基である。
In this aspect, X 1 is preferably of the formula: -(O) x -(CF 2 ) y -(CH 2 ) z - (wherein x, y and z have the same meanings as above and The order of existence of each repeating unit enclosed in a square is arbitrary in the formula).
上記式:-(O)x-(CF2)y-(CH2)z-で表される基としては、例えば、-(O)x’-(CH2)z”-O-[(CH2)z’’’-O-]z””、および-(O)x’-(CF2)y”-(CH2)z”-O-[(CH2)z’’’-O-]z””(式中、x’は0または1であり、y”、z”およびz’’’は、それぞれ独立して、1~10の整数であり、z””は、0または1である)で表される基が挙げられる。なお、これらの基は左端がPFPE側に結合する。
The group represented by the above formula: -(O) x -(CF 2 ) y -(CH 2 ) z - includes, for example, -(O) x' -(CH 2 ) z '' -O-[(CH 2 ) z''' -O-] z '''' and -(O) x' -(CF2) y ''-( CH2 ) z ''-O-[ ( CH2 ) z''' -O- ] z"" (wherein x' is 0 or 1, y", z" and z''' are each independently an integer from 1 to 10, z"" is 0 or 1 The left ends of these groups are bonded to the PFPE side.
別の好ましい態様において、X1は、-O-CFR20-(CF2)e’-である。
In another preferred embodiment, X 1 is -O-CFR 20 -(CF 2 ) e' -.
上記R20は、それぞれ独立して、フッ素原子または低級フルオロアルキル基を表す。ここで低級フルオロアルキル基は、例えば炭素原子数1~3のフルオロアルキル基、好ましくは炭素原子数1~3のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。
Each R 20 above independently represents a fluorine atom or a lower fluoroalkyl group. Here, the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably It is a trifluoromethyl group.
上記e’は、それぞれ独立して、0または1である。
The above e' are each independently 0 or 1.
一の具体例において、R20はフッ素原子であり、e’は1である。
In one embodiment, R 20 is a fluorine atom and e' is 1.
さらに別の態様において、X1基の例として、下記の基が挙げられる:
[式中、
R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各X1基において、Tのうち一つは、分子主鎖のPFPE1に連結するアミド結合に結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、または
-(1,3-フェニレン)-Si(R42)2-(CH2)2-
[式中、R42は、それぞれ独立して、水素原子、C1-6のアルキル基またはC1-6のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。]
であり、別のTのいくつかは、分子主鎖のPFPEと反対の基に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りのTは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。なお、上記態様においても、X1として記載している基において、左側がPFPE1で表される基に連結するアミド結合に、右側がPFPE1で表される基の逆側に、それぞれ結合する。 In yet another aspect, examples of X 1 groups include the following groups:
[In the formula,
each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
In each X 1 group, one of T is attached to the amide bond linking PFPE 1 in the backbone of the molecule with the following groups:
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CF 2 O(CH 2 ) 3 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -, or -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 -
[In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
and some of the other Ts are —(CH 2 ) n″ — (where n″ is an integer from 2 to 6) attached to groups opposite PFPE on the molecular backbone and, if present, the remaining Each T can independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group. Also in the above embodiment, in the group described as X 1 , the left side is bonded to the amide bond that connects to the group represented by PFPE 1 , and the right side is bonded to the opposite side of the group represented by PFPE 1 . .
[式中、
R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各X1基において、Tのうち一つは、分子主鎖のPFPE1に連結するアミド結合に結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、または
-(1,3-フェニレン)-Si(R42)2-(CH2)2-
[式中、R42は、それぞれ独立して、水素原子、C1-6のアルキル基またはC1-6のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。]
であり、別のTのいくつかは、分子主鎖のPFPEと反対の基に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りのTは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。なお、上記態様においても、X1として記載している基において、左側がPFPE1で表される基に連結するアミド結合に、右側がPFPE1で表される基の逆側に、それぞれ結合する。 In yet another aspect, examples of X 1 groups include the following groups:
[In the formula,
each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
In each X 1 group, one of T is attached to the amide bond linking PFPE 1 in the backbone of the molecule with the following groups:
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CF 2 O(CH 2 ) 3 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -, or -(1,3-phenylene)-Si(R 42 ) 2 -(CH 2 ) 2 -
[In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
and some of the other Ts are —(CH 2 ) n″ — (where n″ is an integer from 2 to 6) attached to groups opposite PFPE on the molecular backbone and, if present, the remaining Each T can independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group. Also in the above embodiment, in the group described as X 1 , the left side is bonded to the amide bond that connects to the group represented by PFPE 1 , and the right side is bonded to the opposite side of the group represented by PFPE 1 . .
ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、またはトリアジン類の残基が挙げられる。
The radical scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation. , hindered amines, hindered phenols, or triazines.
紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換および未置換安息香酸もしくはサリチル酸化合物のエステル類、アクリレートまたはアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。
The UV-absorbing group is not particularly limited as long as it can absorb UV rays. Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
好ましい態様において、好ましいラジカル捕捉基または紫外線吸収基としては、
が挙げられる。 In a preferred embodiment, preferred radical-scavenging groups or UV-absorbing groups include
is mentioned.
が挙げられる。 In a preferred embodiment, preferred radical-scavenging groups or UV-absorbing groups include
is mentioned.
上記式(A)中、X2は、各出現においてそれぞれ独立して、単結合または2価の有機基を表す。X2は、好ましくは、炭素原子数1~20のアルキレン基であり、より好ましくは、-(CH2)u-(式中、uは、0~2の整数である)である。
In formula (A) above, each occurrence of X 2 independently represents a single bond or a divalent organic group. X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably -(CH 2 ) u - (where u is an integer of 0 to 2).
上記式中、tは、それぞれ独立して、1~10の整数である。好ましい態様において、tは1~6の整数である。別の好ましい態様において、tは2~10の整数であり、好ましくは2~6の整数である。
In the above formula, each t is independently an integer of 1-10. In preferred embodiments, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2-10, preferably an integer from 2-6.
好ましい式(A)で示される化合物は、下記式(A’):
[式中:
PFPE1、R6およびR7は、それぞれ独立して、上記定義のとおりであり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、およびR14”は、それぞれ、R11、R12、R13、およびR14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X1は、各出現においてそれぞれ独立して、-O-CFR20-(CF2)e’-であり;
R20は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり;
e’は、各出現においてそれぞれ独立して、0または1であり;
X2は、-(CH2)u-であり;
uは、各出現においてそれぞれ独立して、0~2の整数であり;
tは、各出現においてそれぞれ独立して、2~10の整数である。]
で表される化合物である。 A preferred compound of formula (A) is represented by the following formula (A'):
[In the formula:
PFPE 1 , R 6 and R 7 are each independently as defined above;
each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group;
each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
each occurrence of R 11 independently represents a hydrogen atom or a halogen atom;
each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group;
R 11″ , R 12″ , R 13″ and R 14″ are the same as R 11 , R 12 , R 13 and R 14 respectively;
n1 is an integer from 1 to 3, preferably 3;
X 1 is independently at each occurrence —O—CFR 20 —(CF 2 ) e′ —;
each occurrence of R 20 is independently a fluorine atom or a lower fluoroalkyl group;
e′ is independently 0 or 1 at each occurrence;
X 2 is -(CH 2 ) u -;
u is independently at each occurrence an integer from 0 to 2;
t is independently an integer from 2 to 10 at each occurrence. ]
It is a compound represented by
[式中:
PFPE1、R6およびR7は、それぞれ独立して、上記定義のとおりであり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、およびR14”は、それぞれ、R11、R12、R13、およびR14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X1は、各出現においてそれぞれ独立して、-O-CFR20-(CF2)e’-であり;
R20は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり;
e’は、各出現においてそれぞれ独立して、0または1であり;
X2は、-(CH2)u-であり;
uは、各出現においてそれぞれ独立して、0~2の整数であり;
tは、各出現においてそれぞれ独立して、2~10の整数である。]
で表される化合物である。 A preferred compound of formula (A) is represented by the following formula (A'):
[In the formula:
PFPE 1 , R 6 and R 7 are each independently as defined above;
each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group;
each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
each occurrence of R 11 independently represents a hydrogen atom or a halogen atom;
each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group;
R 11″ , R 12″ , R 13″ and R 14″ are the same as R 11 , R 12 , R 13 and R 14 respectively;
n1 is an integer from 1 to 3, preferably 3;
X 1 is independently at each occurrence —O—CFR 20 —(CF 2 ) e′ —;
each occurrence of R 20 is independently a fluorine atom or a lower fluoroalkyl group;
e′ is independently 0 or 1 at each occurrence;
X 2 is -(CH 2 ) u -;
u is independently at each occurrence an integer from 0 to 2;
t is independently an integer from 2 to 10 at each occurrence. ]
It is a compound represented by
上記式(A)で表される化合物は、例えば、-PFPE1-部分に対応するパーフルオロ(ポリ)エーテル誘導体を原料として、末端にヨウ素を導入した後、-CH2CR12(X2-SiR13
n1R14
3-n1)-に対応するビニルモノマーを反応させることにより得ることができる。
The compound represented by the above formula (A) can be prepared, for example, by using a perfluoro(poly)ether derivative corresponding to the —PFPE 1 — portion as a starting material, introducing iodine at the terminal, and then converting —CH 2 CR 12 (X 2 — It can be obtained by reacting a vinyl monomer corresponding to SiR 13 n1 R 14 3-n1 )—.
上記式(B)中、PFPE1、R6、R7、R13、R13”、R14、R14”およびn1は、上記式(A)に関する記載と同意義である。
In formula (B) above, PFPE 1 , R 6 , R 7 , R 13 , R 13″ , R 14 , R 14″ and n1 have the same meanings as described for formula (A) above.
上記式(B)において、水酸基および加水分解可能な基からなる群より選ばれる少なくとも1の基と結合したSi原子とは、n1が1~3の整数であり、かつ(SiR13
n1R14
3-n1)または(-SiR13”
n1R14”
3-n1)に含まれるSi原子を示す。
In the above formula (B), the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group means that n1 is an integer of 1 to 3 and (SiR 13 n1 R 14 3 -n1 ) or (-SiR 13″ n1 R 14″ 3-n1 ).
上記式中、n1は、(-SiR13
n1R14
3-n1)単位毎または(-SiR13”
n1R14”
3-n1)単位毎に独立して、0~3の整数であり、好ましくは1~3であり、より好ましくは3である。式中、少なくとも2つのn1が1~3の整数であり、即ち、すべてのn1が同時に0になることはない。即ち、式中、少なくとも2つはR13またはR13”が存在する。即ち、式(B)において、n1が1以上である-SiR13
n1R14
3-n1構造(即ち、-SiR13部分)およびn1が1以上である-SiR13”
n1R14”
3-n1構造(即ち、-SiR13”部分)からなる群より選ばれる構造が少なくとも2つ存在する。
In the above formula, n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n1 ) unit or each (-SiR 13″ n1 R 14″ 3-n1 ) unit, preferably is 1 to 3, more preferably 3. wherein at least two n1's are integers from 1 to 3, ie not all n1's are 0 at the same time. That is, at least two R 13 or R 13″ are present in the formula. That is, in formula (B), the —SiR 13 n1 R 14 3-n1 structure in which n1 is 1 or more (that is, the —SiR 13 moiety ) and —SiR 13″ n1 R 14″ 3-n1 structures where n1 is 1 or greater (ie, the —SiR 13″ portion).
より好ましくは、式(B)においては、水酸基または加水分解可能な基に結合したSiがPFPE含有シラン化合物(a)の分子主鎖の両末端にそれぞれ少なくとも1つ存在する。即ち、-SiR13部分が少なくとも1つ存在し、かつ-SiR13”部分が少なくとも1つ存在する。
More preferably, in formula (B), at least one Si bonded to a hydroxyl group or a hydrolyzable group exists at each end of the molecular main chain of the PFPE-containing silane compound (a). That is, there is at least one --SiR 13 moiety and at least one --SiR 13'' moiety.
上記式中、X3は、それぞれ独立して、2~10価の有機基を表す。すなわち、X3は、上記一般式のR5に対応する。当該X3は、式(B)で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロ(ポリ)エーテル部(即ち、-PFPE1-部)と、基材との結合能を提供するシラン部(具体的には、-SiR13
n1R14
3-n1または-SiR13”
n1R14”
3-n1)とを連結するリンカーと解される。従って、当該X3は、式(B)で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。なお、本明細書において、X3として記載している構造は、左側がPFPE1で表される基に連結するアミド結合に、右側がβ1を付して括弧でくくられた基に、それぞれ結合する。
In the above formula, each X 3 independently represents a divalent to decavalent organic group. That is , X3 corresponds to R5 in the above general formula. The X 3 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (B), and the base material. It is understood as a linker that connects a silane moiety that provides binding ability (specifically, —SiR 13 n1 R 14 3-n1 or —SiR 13″ n1 R 14″ 3-n1 ). Therefore, X 3 may be any organic group as long as the compound represented by formula (B) can exist stably. In the present specification, the structure described as X 3 has an amide bond linked to the group represented by PFPE 1 on the left side, and a group bracketed with β1 on the right side, respectively. do.
別の態様において、X3は、Xeを表す。Xeは、上記と同意義である。
In another aspect, X 3 represents X e . Xe has the same meaning as above.
上記式中のβ1は、1~9の整数であり、X3の価数に応じて変化し得る。式(B)において、β1はX3の価数の値から1を引いた値である。X3が単結合であるときには、β1は1である。
β1 in the above formula is an integer of 1 to 9 and can vary depending on the valence of X3. In equation (B), β1 is the value of the valence of X3 minus one. β1 is 1 when X3 is a single bond.
上記X3は、好ましくは2~7価、より好ましくは2~4価、さらに好ましくは2価の有機基である。
X 3 above is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X3は2~4価の有機基であり、β1は1~3である。
In one embodiment, X 3 is a divalent to tetravalent organic group and β1 is 1-3.
別の態様において、X3は2価の有機基であり、β1は1である。この場合、式(B)は、下記式(B’)で表される。
In another embodiment, X3 is a divalent organic group and β1 is 1. In this case, the formula (B) is represented by the following formula (B').
上記X3の例としては、PFPE1基に連結するアミド基と結合を形成しうるもので化合物を安定に調製可能なものであれば特に限定されないが、例えば、X1に関して記載したものと同様のもので、単結合以外のものが挙げられる。
Examples of X 3 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. , and includes those other than single bonds.
中でも、好ましい具体的なX3は、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 3 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 3 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
上記の中では、X3は、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 In the above, X 3 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 In the above, X 3 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
上記の中では、より好ましくは、X3は、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 3 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 3 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
別の好ましい態様において、X3は、Xe’を表す。Xe’は、単結合が除外されるほかは上記と同意義である。
In another preferred embodiment, X 3 represents X e′ . X e' has the same meaning as above except that the single bond is omitted.
一の態様において、式(B)において、水酸基または加水分解可能な基に結合したSiが少なくとも2つ存在する。即ち、式(B)において、-SiR13部分が少なくとも2つ存在する。
In one embodiment, in formula (B) there are at least two Si bonded to hydroxyl or hydrolyzable groups. That is, in formula (B), there are at least two —SiR 13 moieties.
好ましい式(B)で示される化合物は、下記式(B’):
[式中:
PFPE1、R6およびR7は、上記定義のとおりであり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R13”、およびR14”は、それぞれ、R13、およびR14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X3は、炭素数1~20のアルキレン基、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-である。]
で表される化合物である。 A preferred compound of formula (B) is represented by the following formula (B'):
[In the formula:
PFPE 1 , R 6 and R 7 are as defined above;
each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group;
each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
R 13″ and R 14″ are the same as R 13 and R 14 respectively;
n1 is an integer from 1 to 3, preferably 3;
X 3 is an alkylene group having 1 to 20 carbon atoms, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 - or -CH 2 O(CH 2 ) 6 -. ]
It is a compound represented by
[式中:
PFPE1、R6およびR7は、上記定義のとおりであり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R13”、およびR14”は、それぞれ、R13、およびR14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X3は、炭素数1~20のアルキレン基、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-である。]
で表される化合物である。 A preferred compound of formula (B) is represented by the following formula (B'):
[In the formula:
PFPE 1 , R 6 and R 7 are as defined above;
each occurrence of R 13 independently represents a hydroxyl group or a hydrolyzable group;
each occurrence of R 14 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
R 13″ and R 14″ are the same as R 13 and R 14 respectively;
n1 is an integer from 1 to 3, preferably 3;
X 3 is an alkylene group having 1 to 20 carbon atoms, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 - or -CH 2 O(CH 2 ) 6 -. ]
It is a compound represented by
上記式(B)で表される化合物は、公知の方法、例えば特開2013-117012号公報に記載の方法またはその改良方法により製造することができる。
The compound represented by formula (B) above can be produced by a known method, for example, the method described in JP-A-2013-117012 or an improved method thereof.
上記式(C)中、PFPE1、R6、R7は、上記式(A)に関する記載と同意義である。
In formula (C) above, PFPE 1 , R 6 and R 7 have the same meanings as described for formula (A) above.
上記式中、X5は、それぞれ独立して、2~10価の有機基を表す。すなわち、X5は、上記一般式のR5に対応する。当該X5は、式(C)で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロ(ポリ)エーテル部(即ち、-PFPE1-部)と、基材との結合能を提供するシラン部(具体的には、-SiRa
k1Rb
l1Rc
m1基、または-SiRa”
k1Rb”
l1Rc”
m1基)とを連結するリンカーと解される。従って、当該X5は、式(C)で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。なお、本明細書において、X5として記載している構造は、左側がPFPE1で表される基に、右側がγ1を付して括弧でくくられた基に、それぞれ結合する。
In the above formula, each X 5 independently represents a divalent to decavalent organic group. That is, X5 corresponds to R5 in the above general formula. The X 5 is a perfluoro(poly)ether portion (that is, -PFPE 1 - portion) that mainly provides water repellency and surface slipperiness in the compound represented by formula (C), and the base material. It is understood as a linker that connects a silane moiety that provides binding ability (specifically, a -SiR a k1 R b l1 R c m1 group or a -SiR a″ k1 R b″ l1 R c″ m1 group). Therefore, X 5 may be any organic group as long as the compound represented by formula ( C) can exist stably. The structure is attached to the group represented by PFPE 1 on the left side and to the group bracketed with γ1 on the right side, respectively.
別の態様において、X5は、Xeを表す。Xeは、上記と同意義である。
In another aspect, X 5 represents X e . Xe has the same meaning as above.
別の態様において、式(C)は、下記式(C’)で表される。
In another aspect, formula (C) is represented by the following formula (C').
上記X5の例としては、PFPE1基に連結するアミド基と結合を形成しうるもので化合物を安定に調製可能なものであれば特に限定されないが、例えば、X1に関して記載したものと同様のもので、単結合以外のものが挙げられる。
Examples of the above X 5 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. , and includes those other than single bonds.
中でも、好ましい具体的なX5は、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 5 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 5 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
上記の中では、X5は、好ましくは、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 In the above, X 5 is preferably
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 In the above, X 5 is preferably
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
上記の中では、より好ましくは、X5は、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 5 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 5 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
別の好ましい態様において、X5は、Xe’を表す。Xe’は、単結合が除外されるほかは上記と同意義である。
In another preferred embodiment, X 5 represents X e′ . X e' has the same meaning as above except that the single bond is omitted.
上記式中、Raは、各出現においてそれぞれ独立して、-Z3-SiR71
p1R72
q1R73
r1を表す。
In the above formula, each occurrence of R a independently represents —Z 3 —SiR 71 p1 R 72 q1 R 73 r1 .
式中、Z3は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表す。
In the formula, Z 3 at each occurrence independently represents an oxygen atom or a divalent organic group.
上記Z3は、好ましくは、2価の有機基であり、式(C)における分子主鎖の末端のSi原子(Raが結合しているSi原子)とシロキサン結合を形成するものを含まない。
The above Z 3 is preferably a divalent organic group, and does not include those that form a siloxane bond with the terminal Si atom (Si atom to which R a is bonded) of the molecular main chain in formula (C). .
上記Z3は、好ましくは、C1-6アルキレン基、-(CH2)g-O-(CH2)h-(式中、gは、1~6の整数であり、hは、1~6の整数である)または、-フェニレン-(CH2)i-(式中、iは、0~6の整数である)であり、より好ましくはC1-3アルキレン基である。これらの基は、例えば、フッ素原子、C1-6アルキル基、C2-6アルケニル基、およびC2-6アルキニル基から選択される1個またはそれ以上の置換基により置換されていてもよい。紫外線耐久性を特に良好とする観点からは、上記Z3は、より好ましくは、直鎖状または分枝鎖状のアルキレン基であり、さらに好ましくは直鎖状のアルキレン基である。上記Z3のアルキレン基を構成する炭素原子数は、好ましくは1~6の範囲にあり、より好ましくは1~3の範囲にある。なお、アルキレン基については上記のとおりである。
Z 3 above is preferably a C 1-6 alkylene group, —(CH 2 ) g —O—(CH 2 ) h — (wherein g is an integer of 1 to 6, h is 1 to is an integer of 6) or -phenylene-(CH 2 ) i - (wherein i is an integer of 0 to 6), more preferably a C 1-3 alkylene group. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. . From the viewpoint of particularly good UV resistance, Z3 is more preferably a straight-chain or branched-chain alkylene group, and still more preferably a straight-chain alkylene group. The number of carbon atoms constituting the alkylene group of Z 3 is preferably in the range of 1-6, more preferably in the range of 1-3. The alkylene group is as described above.
式中、R71は、各出現においてそれぞれ独立して、Ra’を表す。Ra’は、Raと同意義である。
In the formula, each occurrence of R 71 independently represents R a′ . Ra' has the same meaning as Ra .
Ra中、Z3基を介して直鎖状に連結されるSiは最大で5個である。即ち、上記Raにおいて、R71が少なくとも1つ存在する場合、Ra中にZ3基を介して直鎖状に連結されるSi原子が2個以上存在するが、かかるZ3基を介して直鎖状に連結されるSi原子の数は最大で5個である。なお、「Ra中のZ3基を介して直鎖状に連結されるSi原子の数」とは、Ra中において直鎖状に連結される-Z3-Si-の繰り返し数と等しくなる。
In Ra, the number of Sis connected in a straight chain via 3 Z groups is at most 5. That is, when at least one R 71 is present in the above Ra, two or more Si atoms linked in a straight chain via a Z 3 group are present in Ra. The maximum number of Si atoms linked in a straight chain is five. The “number of Si atoms linearly linked via Z 3 groups in R a ” is equal to the repeating number of —Z 3 —Si— linearly linked in R a . Become.
例えば、下記にRa中においてZ3基を介してSi原子が連結された一例を示す。
For example, an example in which a Si atom is linked via a Z 3 group in Ra is shown below.
上記式において、*は、主鎖のSiに結合する部位を意味し、…は、Z3Si以外の所定の基が結合していること、即ち、Si原子の3本の結合手がすべて…である場合、Z3Siの繰り返しの終了箇所を意味する。また、Siの右肩の数字は、*から数えたZ3基を介して直鎖状に連結されたSiの出現数を意味する。即ち、Si2でZ3Si繰り返しが終了している鎖は「Ra中のZ3基を介して直鎖状に連結されるSi原子の数」が2個であり、同様に、Si3、Si4およびSi5でZ3Si繰り返しが終了している鎖は、それぞれ、「Ra中のZ3基を介して直鎖状に連結されるSi原子の数」が3、4および5個である。なお、上記の式から明らかなように、Ra中には、Z3Si鎖が複数存在するが、これらはすべて同じ長さである必要はなく、それぞれ任意の長さであってもよい。
In the above formula, * means the site of bonding to Si in the main chain, ... indicates that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of the Si atom are ... means the end point of the repetition of Z 3 Si. In addition, the number on the right side of Si means the number of occurrences of Si linked in a straight chain via three Z groups counted from *. That is, the chain in which the Z 3 Si repeat ends at Si 2 has 2 “the number of Si atoms connected in a straight chain via the Z 3 group in Ra”. , Si 4 and Si 5 terminate the Z 3 Si repeat, respectively, the “number of Si atoms linearly linked via the Z 3 group in Ra ” is 3, 4 and 5 is one. As is clear from the above formula, there are a plurality of Z 3 Si chains in R a , but these chains do not have to all have the same length, and each may have an arbitrary length.
好ましい態様において、下記に示すように、「Ra中のZ3基を介して直鎖状に連結されるSi原子の数」は、すべての鎖において、1個(左式)または2個(右式)である。
In a preferred embodiment, as shown below, "the number of Si atoms linearly linked via Z 3 groups in Ra" is 1 (left formula) or 2 ( right formula).
一の態様において、Ra中のZ3基を介して直鎖状に連結されるSi原子の数は1個または2個、好ましくは1個である。
In one embodiment, the number of Si atoms linearly linked via the Z 3 group in R a is 1 or 2, preferably 1.
式中、R72は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。「加水分解可能な基」は、上記と同意義である。
In the formula, each occurrence of R 72 independently represents a hydroxyl group or a hydrolyzable group. "Hydrolyzable group" has the same meaning as above.
好ましくは、R72は、-OR(式中、Rは、置換または非置換のC1-3アルキル基、より好ましくはメチル基を表す)である。
Preferably, R 72 is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
式中、R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素原子数1~20のアルキル基、より好ましくは炭素原子数1~6のアルキル基、さらに好ましくはメチル基である。
In the formula, each occurrence of R 73 independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
式中、p1は、各出現においてそれぞれ独立して、0~3の整数であり;q1は、各出現においてそれぞれ独立して、0~3の整数であり;r1は、各出現においてそれぞれ独立して、0~3の整数である。ただし、(-Z3-SiR71
p1R72
q1R73
r1)毎において、p1、q1およびr1の和は3である。
wherein p1 is independently at each occurrence an integer from 0 to 3; q1 is independently at each occurrence an integer from 0 to 3; r1 is independently at each occurrence is an integer from 0 to 3. However, the sum of p1, q1 and r1 is 3 for each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ).
好ましい態様において、Ra中の末端のRa’(Ra’が存在しない場合、Ra)において、上記q1は、好ましくは2以上、例えば2または3であり、より好ましくは3である。
In a preferred embodiment, q1 is preferably 2 or more, such as 2 or 3, and more preferably 3, in the terminal R a ' (R a when R a ' does not exist) at the end of R a .
好ましい態様において、Raの末端部の少なくとも1つは、-Si(-Z3-SiR72
q1R73
r1)2Rb
l1Rc
m1(ただし、l1およびm1のいずれか一方が1であり、他方は0である)または-Si(-Z3-SiR72
q1R73
r1)3、好ましくは-Si(-Z3-SiR72
q1R73
r1)3であり得る(ここで、q1およびr1の合計は3である)。式中、(-Z3-SiR72
q1R73
r1)の単位は、好ましくは(-Z3-SiR72
3)である。さらに好ましい態様において、Raの末端部は、すべて-Si(-Z3-SiR72
q1R73
r1)3、好ましくは-Si(-Z3-SiR72
3)3であり得る。
In a preferred embodiment, at least one of the ends of R a is —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 2 R b l1 R c m1 (with the proviso that either one of l1 and m1 is 1; , the other is 0) or —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 , preferably —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 , where q1 and The sum of r1 is 3). In the formula, the unit of (-Z 3 -SiR 72 q1 R 73 r1 ) is preferably (-Z 3 -SiR 72 3 ). In a further preferred embodiment, the terminal groups of R a may all be -Si(-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si(-Z 3 -SiR 72 3 ) 3 .
上記式中、Ra”は、各出現においてそれぞれ独立して、-Z3-SiR71
p1R72”
q1R73
r1を表す。Z3、R71、R73、p1、q1、およびr1は、上記と同意義である。R72”は、R72と同意義である。
In the above formula, each occurrence of R a″ independently represents —Z 3 —SiR 71 p1 R 72″ q1 R 73 r1 . Z 3 , R 71 , R 73 , p1, q1 and r1 have the same meanings as above. R72″ has the same meaning as R72 .
好ましい態様において、Ra”の末端部の少なくとも1つは、-Si(-Z3-SiR72”
q1R73
r1)2Rb”
l1Rc”
m1(ただし、l1およびm1のいずれか一方が1であり、他方は0である)または-Si(-Z3-SiR72”
q1R73
r1)3、好ましくは-Si(-Z3-SiR72”
q1R73
r1)3であり得る(ここで、q1およびr1の合計は3である)。式中、(-Z3-SiR72”
q1R73
r1)の単位は、好ましくは(-Z3-SiR72”
3)である。さらに好ましい態様において、Raの末端部は、すべて-Si(-Z3-SiR72”
q1R73
r1)3、好ましくは-Si(-Z3-SiR72”
3)3であり得る。
In a preferred embodiment, at least one of the ends of R a″ is —Si(—Z 3 —SiR 72″ q1 R 73 r1 ) 2 R b″ l1 R c″ m1 (with the proviso that either l1 or m1 is 1 and the other is 0) or —Si(—Z 3 —SiR 72″ q1 R 73 r1 ) 3 , preferably —Si(—Z 3 —SiR 72″ q1 R 73 r1 ) 3 (where the sum of q1 and r1 is 3). In the formula, the unit of (-Z 3 -SiR 72'' q1 R 73 r1 ) is preferably (-Z 3 -SiR 72'' 3 ). In a further preferred embodiment, all of the terminal groups of R a may be -Si(-Z 3 -SiR 72″ q1 R 73 r1 ) 3 , preferably –Si(-Z 3 -SiR 72″ 3 ) 3 .
式(C)においては、水酸基または加水分解可能な基に結合したSiが少なくとも2つ存在する。即ち、SiR72(具体的には-SiR71
p1R72
q1R73
r1で表される基、ただし、q1が1~3の整数)、SiR72”(具体的には、-SiR71
p1R72”
q1R73
r1で表される基、ただし、q1が1~3の整数)、SiRb(具体的には、-SiRa
k1Rb
l1Rc
m1で表される基、ただし、l1が1~3の整数)、およびSiRb”(具体的には、-SiRa”
k1Rb”
l1Rc”
m1で表される基、ただし、l1が1~3の整数)からなる群より選ばれる構造が少なくとも2つ存在する。Rb、およびRb”については後述する。
In formula (C), there are at least two Si bonded to hydroxyl groups or hydrolyzable groups. That is, SiR 72 (specifically, a group represented by —SiR 71 p1 R 72 q1 R 73 r1 , where q1 is an integer of 1 to 3), SiR 72″ (specifically, —SiR 71 p1 R 72″ q1 a group represented by R 73 r1 , wherein q1 is an integer of 1 to 3), SiR b (specifically, a group represented by —SiR a k1 R b l1 R c m1 , with the proviso that l1 is an integer of 1 to 3) and SiR b″ (specifically, a group represented by —SiR a″ k1 R b″ l1 R c″ m1 , where l1 is an integer of 1 to 3) There are at least two preferred structures. R b and R b″ will be described later.
より好ましくは、式(C)においては、水酸基または加水分解可能な基に結合したSiが、PFPE含有シラン化合物(A)の分子主鎖の両末端にそれぞれ少なくとも1つ存在する。即ち、SiR72および/またはSiRbの構造が少なくとも1つ存在し、かつSiR72”および/またはSiRb”の構造が少なくとも1つ存在する。
More preferably, in formula (C), at least one Si bonded to a hydroxyl group or a hydrolyzable group exists at each end of the molecular main chain of the PFPE-containing silane compound (A). That is, there is at least one structure of SiR 72 and/or SiR b and there is at least one structure of SiR 72'' and/or SiR b' '.
上記式中、Rbは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。
In the above formula, each occurrence of R b independently represents a hydroxyl group or a hydrolyzable group.
上記Rbは、好ましくは、水酸基、-OR、-OCOR、-O-N=C(R)2、-N(R)2、-NHR、ハロゲン(これら式中、Rは、置換または非置換の炭素原子数1~4のアルキル基を示す)であり、より好ましくは-ORである。Rは、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基などの非置換アルキル基;クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。より好ましくは、Rbは、-OR(式中、Rは、置換または非置換のC1-3アルキル基、より好ましくはメチル基を表す)である。
R b above is preferably a hydroxyl group, —OR, —OCOR, —ON═C(R) 2 , —N(R) 2 , —NHR, halogen (wherein R is a substituted or unsubstituted represents an alkyl group having 1 to 4 carbon atoms), more preferably -OR. R includes unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group. More preferably, R b is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
上記式中、Rb”は、Rbと同意義である。
In the above formula, R b″ has the same meaning as R b .
上記式中、Rcは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素原子数1~20のアルキル基、より好ましくは炭素原子数1~6のアルキル基、さらに好ましくはメチル基である。
In the above formula, each occurrence of R c independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
上記式中、Rc”は、Rcと同意義である。
In the above formula, R c″ has the same meaning as R c .
式中、k1は、各出現においてそれぞれ独立して、0~3の整数であり;l1は、各出現においてそれぞれ独立して、0~3の整数であり;m1は、各出現においてそれぞれ独立して、0~3の整数である。ただし、(SiRa
k1Rb
l1Rc
m1)毎または(SiRa”
k1Rb”
l1Rc”
m1)毎において、k1、l1およびm1の和は、3である。
wherein k1 is independently at each occurrence an integer from 0 to 3; l1 is independently at each occurrence an integer from 0 to 3; m1 is independently at each occurrence is an integer from 0 to 3. However, the sum of k1, l1 and m1 is 3 for each (SiR a k1 R b l1 R c m1 ) or (SiR a″ k1 R b″ l1 R c″ m1 ).
一の態様において、k1は、1~3であることが好ましく、3であることがより好ましい。
In one aspect, k1 is preferably 1 to 3, more preferably 3.
上記式(C)で表される化合物は、例えば、国際公開第2014/069592号に記載のように合成することができる。
The compound represented by formula (C) above can be synthesized, for example, as described in International Publication No. 2014/069592.
上記式(D)中、PFPE1、R6、R7は、上記式(A)に関する記載と同意義である。
In formula (D) above, PFPE 1 , R 6 and R 7 have the same meanings as described for formula (A) above.
上記式中、X7は、それぞれ独立して、単結合または2~10価の有機基を表す。当該X7は、式(D)で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロ(ポリ)エーテル部(即ち、-PFPE1-部)と、基材との結合能を提供する部(即ち、δ1を付して括弧でくくられた基)とを連結するリンカーと解される。従って、当該X7は、式(D)で表される化合物が安定に存在し得るものであれば、単結合であってもよく、いずれの有機基であってもよい。なお、本明細書において、X7として記載している構造は、左側がPFPE1で表される基に隣接するアミド結合に、右側がδ1を付して括弧でくくられた基に、それぞれ結合する。
In the above formula, each X 7 independently represents a single bond or a divalent to decavalent organic group. In the compound represented by formula (D), X 7 is a perfluoro(poly)ether moiety (that is, -PFPE 1 - moiety) that mainly provides water repellency and surface slipperiness, etc., and a base material. It is understood as a linker that connects the portion that provides the binding ability (ie, the group bracketed with δ1). Therefore, X 7 may be a single bond or any organic group as long as the compound represented by formula (D) can exist stably. In the present specification, the structure described as X 7 has an amide bond adjacent to the group represented by PFPE 1 on the left side, and a group bracketed with δ1 on the right side, respectively. do.
別の態様において、X7は、Xeを表す。Xeは、上記と同意義である。
In another aspect, X 7 represents X e . Xe has the same meaning as above.
上記式中、δ1は1~9の整数であり、δ1は、X7の価数に応じて変化し得る。式(D)においては、δ1はX7の価数から1を引いた値である。X7が単結合であるときには、δ1は1である。
In the above formula, δ1 is an integer from 1 to 9, and δ1 can vary depending on the valence of X7 . In formula (D), δ1 is the valence of X7 minus one. δ1 is 1 when X7 is a single bond.
上記X7は、好ましくは2~7価、より好ましくは2~4価、さらに好ましくは2価の有機基である。
X 7 above is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X7は2~4価の有機基であり、δ1は1~3である。
In one embodiment, X 7 is a divalent to tetravalent organic group and δ1 is 1-3.
別の態様において、X7は2価の有機基であり、δ1は1である。この場合、式(D)は、下記式(D’)で表される。
In another embodiment, X 7 is a divalent organic group and δ1 is 1. In this case, the formula (D) is represented by the following formula (D').
上記X7の例としては、PFPE1基に連結するアミド基と結合を形成しうるもので化合物を安定に調製可能なものであれば特に限定されないが、例えば、X1に関して記載したものと同様のものが挙げられる。
Examples of the above X 7 are not particularly limited as long as they can form a bond with the amide group linked to the PFPE 1 group and can stably prepare the compound. are listed.
中でも、好ましい具体的なX7は、
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 7 is
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-CONH-(CH 2 ) 2 NH(CH 2 ) 3 -,
-CONH-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
1,3-フェニレン、
-(1,3-フェニレン)-Si(CH3)2-(CH2)2-
などが挙げられる。 Among them, preferred specific X 7 is
single bond,
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CH2OCH2 ( CH2 ) 7CH2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2Si ( OCH3) 2OSi ( OCH3) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH3) 2OSi ( OCH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 3- ,
-CH2OCH2CH2CH2Si ( OCH3 ) 2OSi ( OCH3 ) 2 ( CH2 ) 2- ,
-CH2OCH2CH2CH2Si ( OCH2CH3 ) 2OSi ( OCH2CH3 ) 2 ( CH2 ) 2- ,
—(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CO-,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-CONH-(CH 2 ) 2 NH(CH 2 ) 3 -,
-CONH-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-S-(CH 2 ) 3 -,
-(CH 2 ) 2 S(CH 2 ) 3 -,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 —,
—(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 —,
—C(O)O—(CH 2 ) 3 —,
—C(O)O—(CH 2 ) 6 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 2 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —(CH 2 ) 3 —,
—CH 2 —O—(CH 2 ) 3 —Si(CH 3 ) 2 —(CH 2 ) 2 —Si(CH 3 ) 2 —CH(CH 3 )—CH 2 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
1,3-phenylene,
-(1,3-phenylene)-Si(CH 3 ) 2 -(CH 2 ) 2 -
etc.
上記の中で、より好ましい具体的なX7は、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 Among the above, more preferred specific X 7 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。 Among the above, more preferred specific X 7 is
—CH 2 OCH 2 —,
—CH 2 O(CH 2 ) 2 —,
—CH 2 O(CH 2 ) 3 —,
—CH 2 O(CH 2 ) 6 —,
-CF2- CH2 - O - CH2-,
—CF 2 —CH 2 —O—(CH 2 ) 2 —,
—CF 2 —CH 2 —O—(CH 2 ) 3 —,
—CF 2 —CH 2 —O—(CH 2 ) 6 —,
—CH 2 OCF 2 CHFOCF 2 —,
—CH 2 OCF 2 CHFOCF 2 CF 2 —,
-CH2OCF2CHFOCF2CF2CF2- , _ _ _
-CH2OCH2CF2CF2OCF2- , _ _ _
-CH2OCH2CF2CF2OCF2CF2- , _ _ _ _
-CH2OCH2CF2CF2OCF2CF2CF2- , _ _ _ _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2- , _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2- , _ _
-CH2OCH2CF2CF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2- , _ _
-CH2OCH2CHFCF2OCF2CF2- , _ _ _
-CH2OCH2CHFCF2OCF2CF2CF2- , _ _ _ _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2- ,
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2- , _
-CH2OCH2CHFCF2OCF ( CF3 ) CF2OCF2CF2CF2- , _ _
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-(CH 2 ) 4 -,
-(CH 2 ) 5 -,
-( CH2 ) 6- ,
-CF2- ,
-(CF 2 ) 2 -,
—CF 2 —CH 2 —,
—CF 2 —(CH 2 ) 2 —,
—CF 2 —(CH 2 ) 3 —,
—CF 2 —(CH 2 ) 4 —,
—CF 2 —(CH 2 ) 5 —,
—CF 2 —(CH 2 ) 6 —,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
—CH 2 O—CONH—(CH 2 ) 3 —,
—CH 2 O—CONH—(CH 2 ) 6 —,
-OCH2- ,
—O(CH 2 ) 3 —,
-OCFHCF2- ,
is preferably
上記の中では、より好ましくは、X7は、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 7 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-(CH2)2NH(CH2)3-、
-(CH2)6NH(CH2)3-、
である。 Among the above, more preferably X 7 is
-CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2- ,
-CF2 - CH2OCF2CHFOCF2CF2CF2 - C ( O)NH - CH2-,
-CH2- ,
-(CH 2 ) 2 -,
-(CH 2 ) 3 -,
-( CH2 ) 6- ,
-CF2CONH- ,
-CF2CONHCH2- ,
-CF2CONH ( CH2 ) 2- ,
-CF2CONH ( CH2 ) 3- ,
-CF2CONH ( CH2 ) 6- ,
-CF2 - CON( CH3 )-( CH2 ) 3- ,
-CF 2 -CON(Ph)-(CH 2 ) 3 - (wherein Ph means phenyl),
-CF2 - CON( CH3 )-( CH2 ) 6- ,
-CF 2 -CON(Ph)-(CH 2 ) 6 - (wherein Ph means phenyl),
-( CH2 ) 2NH ( CH2 ) 3- ,
-( CH2 ) 6NH ( CH2 ) 3- ,
is.
より好ましい態様において、X7は、Xe’を表す。Xe’は、上記と同意義である。一の態様において、Xe’は、単結合である。
In a more preferred embodiment X 7 represents X e′ . Xe' has the same meaning as above. In one aspect, X e' is a single bond.
上記式中、Rdは、各出現においてそれぞれ独立して、-Z4-CR81
p2R82
q2R83
r2を表す。
In the above formula, each occurrence of R d independently represents -Z 4 -CR 81 p2 R 82 q2 R 83 r2 .
式中、Z4は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表す。
In the formula, Z 4 at each occurrence independently represents an oxygen atom or a divalent organic group.
上記Z4は、好ましくは、C1-6アルキレン基、-(CH2)g-O-(CH2)h-(式中、gは、0~6の整数、例えば1~6の整数であり、hは、0~6の整数、例えば1~6の整数である)または、-フェニレン-(CH2)i-(式中、iは、0~6の整数である)であり、より好ましくはC1-3アルキレン基である。これらの基は、例えば、フッ素原子、C1-6アルキル基、C2-6アルケニル基、およびC2-6アルキニル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
The above Z 4 is preferably a C 1-6 alkylene group, —(CH 2 ) g —O—(CH 2 ) h — (wherein g is an integer of 0 to 6, for example an integer of 1 to 6 and h is an integer from 0 to 6, such as an integer from 1 to 6) or -phenylene-(CH 2 ) i - (wherein i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
式中、R81は、各出現においてそれぞれ独立して、Rd’を表す。Rd’は、Rdと同意義である。
In the formula, each occurrence of R 81 independently represents R d′ . Rd' has the same meaning as Rd .
Rd中、Z4基を介して直鎖状に連結されるC原子は最大で5個である。即ち、上記Rdにおいて、R81が少なくとも1つ存在する場合、Rd中にZ4基を介して直鎖状に連結されるC原子が2個以上存在するが、かかるZ4基を介して直鎖状に連結されるC原子の数は最大で5個である。なお、「Rd中のZ4基を介して直鎖状に連結されるC原子の数」とは、Rd中において直鎖状に連結される-Z4-C-の繰り返し数と等しくなる。
In R d there are at most 5 C atoms which are linearly linked via Z 4 groups. That is, when at least one R 81 is present in R d above, there are two or more C atoms linked in a straight chain via a Z 4 group in R d , but via such a Z 4 group The maximum number of C atoms linked in a straight chain is five. The “number of C atoms linearly linked via Z 4 groups in R d ” is equal to the repeating number of —Z 4 —C— linearly linked in R d . Become.
好ましい態様において、下記に示すように、「Rd中のZ4基を介して直鎖状に連結されるC原子の数」は、すべての鎖において、1個(左式)または2個(右式)である。
In a preferred embodiment, as shown below, "the number of C atoms linearly linked via Z 4 groups in R d " is 1 (left formula) or 2 ( right formula).
一の態様において、RdのZ4基を介して直鎖状に連結されるC原子の数は1個または2個、好ましくは1個である。
In one embodiment, the number of C atoms linearly linked via the Z 4 group of R d is 1 or 2, preferably 1.
式中、R82は、各出現においてそれぞれ独立して、-Y-SiR85
n2R86
3-n2を表す。
In the formula, each occurrence of R 82 independently represents -Y-SiR 85 n2 R 86 3-n2 .
Yは、各出現においてそれぞれ独立して、2価の有機基を表す。
Each occurrence of Y independently represents a divalent organic group.
好ましい態様において、Yは、C1-6アルキレン基、-(CH2)g’-O-(CH2)h’-(式中、g’は、0~6の整数、例えば1~6の整数であり、h’は、0~6の整数、例えば1~6の整数である)または、-フェニレン-(CH2)i’-(式中、i’は、0~6の整数である)である。これらの基は、例えば、フッ素原子、C1-6アルキル基、C2-6アルケニル基、およびC2-6アルキニル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
In a preferred embodiment, Y is a C 1-6 alkylene group, —(CH 2 ) g′ —O—(CH 2 ) h′ —, wherein g′ is an integer of 0-6, such as 1-6 is an integer and h' is an integer of 0 to 6, such as an integer of 1 to 6) or -phenylene-(CH 2 ) i' - (wherein i' is an integer of 0 to 6) ). These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
一の態様において、Yは、C1-6アルキレン基または-フェニレン-(CH2)i’-であり得る。Yが上記の基である場合、光耐性、特に紫外線耐久性がより高くなり得る。
In one aspect, Y can be a C 1-6 alkylene group or -phenylene-(CH 2 ) i' -. When Y is the above group, light resistance, particularly ultraviolet resistance, can be higher.
上記R85は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。
Each occurrence of R 85 above independently represents a hydroxyl group or a hydrolyzable group.
上記「加水分解可能な基」とは、式(C)と同様のものが挙げられる。
The above "hydrolyzable group" includes those similar to formula (C).
好ましくは、R85は、-OR(式中、Rは、置換または非置換のC1-3アルキル基、より好ましくはエチル基またはメチル基、特にメチル基を表す)である。
Preferably, R 85 is -OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl or methyl group, especially a methyl group.
上記R86は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素原子数1~20のアルキル基、より好ましくは炭素原子数1~6のアルキル基、さらに好ましくはメチル基である。
Each occurrence of R 86 above independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
n2は、(-Y-SiR85
n2R86
3-n2)単位毎、または(-Y-SiR85”
n2R86”
3-n2)単位毎に独立して、0~3の整数を表し、好ましくは1~3の整数、より好ましくは2または3、特に好ましくは3である。R85”、およびR86”については後述する。
n2 is an integer of 0 to 3 independently for each (-Y-SiR 85 n2 R 86 3-n2 ) unit or each (-Y-SiR 85″ n2 R 86″ 3-n2 ) unit; An integer of 1 to 3 is preferred, 2 or 3 is more preferred, and 3 is particularly preferred. R 85″ and R 86″ will be described later.
上記R83は、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表し、好ましくは水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素原子数1~20のアルキル基、より好ましくは炭素原子数1~6のアルキル基、さらに好ましくはメチル基である。
Each occurrence of R 83 above independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group.
式中、p2は、各出現においてそれぞれ独立して、0~3の整数であり;q2は、各出現においてそれぞれ独立して、0~3の整数であり;r2は、各出現においてそれぞれ独立して、0~3の整数である。ただし、(-Z4-CR81
p2R82
q2R83
r2)毎、または(-Z4-CR81
p2R82”
q2R83
r2)毎において、p2、q2およびr2の和は3である。R82”については後述する。
wherein p2 is independently at each occurrence an integer from 0 to 3; q2 is independently at each occurrence an integer from 0 to 3; r2 is independently at each occurrence is an integer from 0 to 3. provided that for each (-Z 4 -CR 81 p2 R 82 q2 R 83 r2 ) or (-Z 4 -CR 81 p2 R 82″ q2 R 83 r2 ) the sum of p2, q2 and r2 is 3 The R 82″ will be described later.
好ましい態様において、Rd中の末端のRd’(Rd’が存在しない場合、Rd)において、上記q2は、好ましくは2以上、例えば2または3であり、より好ましくは3である。
In a preferred embodiment, q2 is preferably 2 or more, for example 2 or 3, more preferably 3, at the terminal R d ' (R d when R d ' is absent) in R d .
好ましい態様において、Rdの末端部の少なくとも1つは、-C(-Y-SiR85
n2R86
3-n2)2(具体的には、-C(-Y-SiR85
n2R86
3-n2)2R83)または-C(-Y-SiR85
n2R86
3-n2)3、好ましくは-C(-Y-SiR85
n2R86
3-n2)3であり得る。ここで、n2は1~3の整数である。式中、(-Y-SiR85
n2R86
3-n2)の単位は、好ましくは(-Y-SiR85
3)である。さらに好ましい態様において、Rdの末端部は、すべて-C(-Y-SiR85
n2R86
3-n2)3、好ましくは-C(-Y-SiR85
3)3であり得る。
In a preferred embodiment, at least one of the terminal groups of R d is —C(—Y—SiR 85 n2 R 86 3-n2 ) 2 (specifically —C(—Y—SiR 85 n2 R 86 3— n2 ) 2 R 83 ) or -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 . Here, n2 is an integer of 1-3. In the formula, the unit of (-Y-SiR 85 n2 R 86 3-n2 ) is preferably (-Y-SiR 85 3 ). In a further preferred embodiment, the terminal portions of R d may all be -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 3 ) 3 .
より好ましい態様において、(CRd
k2Re
l2Rf
m2)で表される基の末端は、C(-Y-SiR85
n2R86
3-n2)2Rf)またはC(-Y-SiR85
n2R86
3-n2)3、好ましくはC(-Y-SiR85
n2R86
3-n2)3である。ここで、n2は1~3の整数である。式中、(-Y-SiR85
n2R86
3-n2)の単位は、好ましくは(-Y-SiR85
3)である。さらに好ましい態様において、上記基の末端部は、すべて-C(-Y-SiR85
n2R86
3-n2)3、好ましくは-C(-Y-SiR85
3)3であり得る。
In a more preferred embodiment, the terminal of the group represented by (CR d k2 R e 12 R f m2 ) is C(-Y-SiR 85 n2 R 86 3-n2 ) 2 R f ) or C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably C(-Y-SiR 85 n2 R 86 3-n2 ) 3 . Here, n2 is an integer of 1-3. In the formula, the unit of (-Y-SiR 85 n2 R 86 3-n2 ) is preferably (-Y-SiR 85 3 ). In a further preferred embodiment, the terminal ends of the above groups may all be -C(-Y-SiR 85 n2 R 86 3-n2 ) 3 , preferably -C(-Y-SiR 85 3 ) 3 .
上記式中、Rd”は、各出現においてそれぞれ独立して、-Z4-CR81
p2R82”
q2R83
r2を表す。Z4、R81、R83、p2、q2、およびr2は上記と同意義である。R82”は、各出現においてそれぞれ独立して、-Y-SiR85”
n2R86”
3-n2を表す。ここで、Y、およびn2は、上記と同意義である。R85”、およびR86”は、それぞれ、R85、およびR86と同意義である。
In the above formula, each occurrence of R d″ independently represents —Z 4 —CR 81 p2 R 82″ q2 R 83 r2 . Z 4 , R 81 , R 83 , p2, q2 and r2 have the same meanings as above. R 82″ at each occurrence independently represents —Y—SiR 85″ n2 R 86″ 3-n2 , wherein Y and n2 have the same meanings as above. R 85″ , and R 86″ has the same meaning as R 85 and R 86 respectively.
好ましい態様において、Rd”中の末端のRd’(Rd’が存在しない場合、Rd”)において、上記q2は、好ましくは2以上、例えば2または3であり、より好ましくは3である。
In a preferred embodiment, q2 is preferably 2 or more, such as 2 or 3, more preferably 3, at the terminal R d ' (R d '' when R d ' is absent) at the end of R d ''. be.
好ましい態様において、Rd”の末端部の少なくとも1つは、-C(-Y-SiR85”
n2R86”
3-n2)2(具体的には、-C(-Y-SiR85”
n2R86”
3-n2)2R83)または-C(-Y-SiR85”
n2R86”
3-n2)3、好ましくは-C(-Y-SiR85”
n2R86”
3-n2)3であり得る。ここで、n2は1~3の整数である。式中、(-Y-SiR85”
n2R86”
3-n2)の単位は、好ましくは(-Y-SiR85”
3)である。さらに好ましい態様において、Rdの末端部は、すべて-C(-Y-SiR85”
n2R86”
3-n2)3、好ましくは-C(-Y-SiR85”
3)3であり得る。
In preferred embodiments, at least one of the terminal ends of R d″ is —C(—Y-SiR 85″ n2 R 86″ 3-n2 ) 2 (specifically —C(—Y-SiR 85″ n2 R 86″ 3-n2 ) 2 R 83 ) or —C(-Y-SiR 85″ n2 R 86″ 3-n2 ) 3 , preferably —C(-Y-SiR 85″ n2 R 86″ 3-n2 ) 3 , where n2 is an integer from 1 to 3, wherein the unit (-Y-SiR 85″ n2 R 86″ 3-n2 ) is preferably (-Y-SiR 85″ 3 ). In a further preferred embodiment, the terminal portions of R d can all be -C(-Y-SiR 85″ n2 R 86″ 3-n2 ) 3 , preferably -C(-Y-SiR 85″ 3 ) 3 .
より好ましい態様において、(CRd”
k2Re”
l2Rf”
m2)で表される基の末端は、C(-Y-SiR85”
n2R86”
3-n2)2Rf”)またはC(-Y-SiR85”
n2R86”
3-n2)3、好ましくはC(-Y-SiR85”
n2R86”
3-n2)3である。ここで、n2は1~3の整数である。式中、(-Y-SiR85”
n2R86”
3-n2)の単位は、好ましくは(-Y-SiR85”
3)である。さらに好ましい態様において、上記基の末端部は、すべて-C(-Y-SiR85”
n2R86”
3-n2)3、好ましくは-C(-Y-SiR85”
3)3であり得る。
In a more preferred embodiment, the terminal of the group represented by (CR d″ k2 R e″ 12 R f″ m2 ) is C(—Y—SiR 85″ n2 R 86″ 3-n2 ) 2 R f″ ) or C(-Y-SiR 85''n2 R 86'' 3 -n2 ) 3 , preferably C(-Y-SiR 85''n2 R 86'' 3 -n2 ) 3 . Here, n2 is an integer of 1-3. In the formula, the unit of (--Y--SiR 85″ n2 R 86″ 3-n2 ) is preferably (--Y--SiR 85″ 3 ). It may be C(--Y--SiR 85″ n2 R 86″ 3-n2 ) 3 , preferably --C(--Y--SiR 85″ 3 ) 3 .
上記式中、Reは、各出現においてそれぞれ独立して、-Y-SiR85
n2R86
3-n2を表す。ここに、Y、R85、R86およびn2は、上記R82における記載と同意義である。
In the above formula, each occurrence of R e independently represents -Y-SiR 85 n2 R 86 3-n2 . Here, Y, R 85 , R 86 and n2 have the same meanings as described for R 82 above.
上記式中、Re”は、各出現においてそれぞれ独立して、-Y-SiR85”
n2R86”
3-n2を表す。ここで、R85”、R86”、Y、およびn2は、上記と同意義である。
In the above formula, R e″ at each occurrence independently represents —Y—SiR 85″ n2 R 86″ 3-n2 , wherein R 85″ , R 86″ , Y, and n2 are Same meaning as above.
上記式中、Rfは、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表す。好ましくは、Rfは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素原子数1~20のアルキル基、より好ましくは炭素原子数1~6のアルキル基、さらに好ましくはメチル基である。
In the above formula, each occurrence of R f independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group. Preferably, each occurrence of R f independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
上記式中、Rf”は、Rfと同意義である。
In the above formula, R f″ has the same meaning as R f .
式中、k2は、各出現においてそれぞれ独立して、0~3の整数であり;l2は、各出現においてそれぞれ独立して、0~3の整数であり;m2は、各出現においてそれぞれ独立して、0~3の整数である。ただし、k2、l2およびm2の和は3である。
wherein k2 is independently at each occurrence an integer from 0 to 3; l2 is independently at each occurrence an integer from 0 to 3; m2 is independently at each occurrence is an integer from 0 to 3. However, the sum of k2, l2 and m2 is 3.
一の態様において、少なくとも1つのk2は2または3であり、好ましくは3である。
In one aspect, at least one k2 is 2 or 3, preferably 3.
一の態様において、k2は2または3であり、好ましくは3である。
In one aspect, k2 is 2 or 3, preferably 3.
一の態様において、l2は2または3であり、好ましくは3である。
In one aspect, l2 is 2 or 3, preferably 3.
上記式(D)において、-Y-SiR85で表される基および-Y-SiR85”で表される基よりなる群より選ばれる基が2以上存在する。上記式(D)において、好ましくは、-Y-SiR85で表される基が1以上、かつ-Y-SiR85”で表される基が1以上存在する。
より好ましくは、2以上の-Y-SiR85 n2R86 3-n2で表される基に結合した炭素原子が1以上存在し、2以上の-Y-SiR85” n2R86” 3-n2で表される基に結合した炭素原子が1以上存在する。式中、n2は1~3の整数である。
即ち、-C-Rd k2(Y-SiR85 n2R86 3-n2)l2Rf m2で表される基(ただし、l2は2または3であり、k2、l2およびm2の合計は3である)および-C-R81 p2(Y-SiR85 n2R86 3-n2)q2R83 r2で表される基(ただし、q2は2または3であり、p2、q2およびr2の合計は3である)から選ばれる基が1以上、かつ、-C-Rd k2(Y-SiR85” n2R86” 3-n2)l2Rf m2で表される基(ただし、l2は2または3であり、k2、l2およびm2の合計は3である)および-C-R81 p2(Y-SiR85” n2R86” 3-n2)q2R83 r2で表される基(ただし、q2は2または3であり、p2、q2およびr2の合計は3である)で表される基が1以上存在することが好ましい(式中、n2は1~3の整数である)。 In the above formula (D), there are two or more groups selected from the group consisting of a group represented by -Y-SiR 85 and a group represented by -Y-SiR 85″ . In the above formula (D), preferably contains one or more groups represented by -Y-SiR 85 and one or more groups represented by -Y-SiR 85″ .
More preferably, there are one or more carbon atoms bonded to two or more groups represented by -Y-SiR 85 n2 R 86 3-n2 , and two or more -Y-SiR 85″ n2 R 86″ 3-n2 There are one or more carbon atoms bonded to the group represented by. In the formula, n2 is an integer of 1-3.
That is, a group represented by —C—R d k2 (Y—SiR 85 n2 R 86 3-n2 ) l2 R f m2 (provided that l2 is 2 or 3 and the sum of k2, l2 and m2 is 3). ) and a group represented by —C—R 81 p2 (Y—SiR 85 n2 R 86 3-n2 ) q2 R 83 r2 (provided that q2 is 2 or 3, and the sum of p2, q2 and r2 is 3 ) and a group represented by —C—R d k2 (Y—SiR 85″ n2 R 86″ 3-n2 ) l2 R f m2 (where l2 is 2 or 3 and the sum of k2, l2 and m2 is 3) and a group represented by —C—R 81 p2 (Y—SiR 85″ n2 R 86″ 3-n2 ) q2 R 83 r2 (provided that q2 is 2 or 3, and the sum of p2, q2 and r2 is 3).
より好ましくは、2以上の-Y-SiR85 n2R86 3-n2で表される基に結合した炭素原子が1以上存在し、2以上の-Y-SiR85” n2R86” 3-n2で表される基に結合した炭素原子が1以上存在する。式中、n2は1~3の整数である。
即ち、-C-Rd k2(Y-SiR85 n2R86 3-n2)l2Rf m2で表される基(ただし、l2は2または3であり、k2、l2およびm2の合計は3である)および-C-R81 p2(Y-SiR85 n2R86 3-n2)q2R83 r2で表される基(ただし、q2は2または3であり、p2、q2およびr2の合計は3である)から選ばれる基が1以上、かつ、-C-Rd k2(Y-SiR85” n2R86” 3-n2)l2Rf m2で表される基(ただし、l2は2または3であり、k2、l2およびm2の合計は3である)および-C-R81 p2(Y-SiR85” n2R86” 3-n2)q2R83 r2で表される基(ただし、q2は2または3であり、p2、q2およびr2の合計は3である)で表される基が1以上存在することが好ましい(式中、n2は1~3の整数である)。 In the above formula (D), there are two or more groups selected from the group consisting of a group represented by -Y-SiR 85 and a group represented by -Y-SiR 85″ . In the above formula (D), preferably contains one or more groups represented by -Y-SiR 85 and one or more groups represented by -Y-SiR 85″ .
More preferably, there are one or more carbon atoms bonded to two or more groups represented by -Y-SiR 85 n2 R 86 3-n2 , and two or more -Y-SiR 85″ n2 R 86″ 3-n2 There are one or more carbon atoms bonded to the group represented by. In the formula, n2 is an integer of 1-3.
That is, a group represented by —C—R d k2 (Y—SiR 85 n2 R 86 3-n2 ) l2 R f m2 (provided that l2 is 2 or 3 and the sum of k2, l2 and m2 is 3). ) and a group represented by —C—R 81 p2 (Y—SiR 85 n2 R 86 3-n2 ) q2 R 83 r2 (provided that q2 is 2 or 3, and the sum of p2, q2 and r2 is 3 ) and a group represented by —C—R d k2 (Y—SiR 85″ n2 R 86″ 3-n2 ) l2 R f m2 (where l2 is 2 or 3 and the sum of k2, l2 and m2 is 3) and a group represented by —C—R 81 p2 (Y—SiR 85″ n2 R 86″ 3-n2 ) q2 R 83 r2 (provided that q2 is 2 or 3, and the sum of p2, q2 and r2 is 3).
一の態様において、上記式(D)において、-C-(Y-SiR85
n2R86
3-n2)2で表される基が1以上、かつ-C-(Y-SiR85”
n2R86”
3-n2)2で表される基が1以上存在することが好ましい(式中、n2は1~3の整数である。)。
In one embodiment, in formula (D) above, the group represented by —C—(Y—SiR 85 n2 R 86 3-n2 ) 2 is one or more, and —C—(Y—SiR 85″ n2 R 86 ″ 3-n2 ) It is preferable that one or more groups represented by 2 are present (in the formula, n2 is an integer of 1 to 3).
一の態様において、上記式(D)において、-C-(Y-SiR85
n2R86
3-n2)3で表される基が1以上、かつ-C-(Y-SiR85”
n2R86”
3-n2)3で表される基が1以上存在することが好ましい(式中、n2は1~3の整数である。)。
In one embodiment, in formula (D) above, the group represented by —C—(Y—SiR 85 n2 R 86 3-n2 ) 3 is one or more, and —C—(Y—SiR 85″ n2 R 86 ″ 3-n2 ) It is preferable that one or more groups represented by 3 are present (in the formula, n2 is an integer of 1 to 3).
上記式(D)中、n2は1~3の整数であり、および、少なくとも1つのq2は2または3であるか、あるいは、少なくとも1つのl2は2または3である。
In the above formula (D), n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3.
上記式(D)中、式中、-Y-SiR85
n2R86
3-n2基または-Y-SiR85”
n2R86”
3-n2基が少なくとも2存在することが好ましい。上記式(D)中、-Y-SiR85
n2R86
3-n2基が1以上存在し、かつ-Y-SiR85”
n2R86”
3-n2基が1以上存在することがより好ましい。即ち、-SiR85を含む基および-SiR85”を含む基が、PFPE含有シラン化合物(A)の分子主鎖の両末端に存在することが好ましい。
In formula (D) above, it is preferred that at least two -Y-SiR 85 n2 R 86 3-n2 groups or -Y-SiR 85″ n2 R 86″ 3-n2 groups are present. More preferably, one or more -Y-SiR 85 n2 R 86 3-n2 groups and one or more -Y-SiR 85″ n2 R 86″ 3-n2 groups are present in the above formula (D). That is, it is preferred that the group containing —SiR 85 and the group containing —SiR 85″ are present at both ends of the molecular main chain of the PFPE-containing silane compound (A).
上記式(D)で表される化合物は、公知の方法を組み合わせることにより製造することができる。
The compound represented by formula (D) above can be produced by combining known methods.
好ましい態様において、PFPE含有シラン化合物(a)は、式(B)または(C)で表される。
In a preferred embodiment, the PFPE-containing silane compound (a) is represented by formula (B) or (C).
一の態様において、PFPE含有シラン化合物(a)は、式(A)、(C)または(D)で表される。
In one aspect, the PFPE-containing silane compound (a) is represented by formula (A), (C) or (D).
一の態様において、PFPE含有シラン化合物(a)は、少なくとも一方の末端に、水酸基または加水分解可能な基を有するSi原子を2個以上、好ましくは3個以上有する。
In one aspect, the PFPE-containing silane compound (a) has 2 or more, preferably 3 or more Si atoms having a hydroxyl group or a hydrolyzable group at at least one end.
上記したPFPE含有シラン化合物(a)は、特に限定されるものではないが、一の態様において、5×102~1×105の数平均分子量を有し得る。かかる範囲のなかでも、2,000~50,000、より好ましくは2,500~30,000、さらに好ましくは3,000~10,000の数平均分子量を有することが好ましい。なお、本発明において、数平均分子量は、19F-NMRにより測定される値とする。
The PFPE-containing silane compound (a) described above is not particularly limited, but in one embodiment, it can have a number average molecular weight of 5×10 2 to 1×10 5 . Within this range, it is preferred to have a number average molecular weight of 2,000 to 50,000, more preferably 2,500 to 30,000, still more preferably 3,000 to 10,000. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
(架橋剤(b))
本発明の硬化性組成物には、架橋剤として、Si原子と結合したOR2基を少なくとも2個有する化合物(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(ただし、前記(a)に該当するものを除く)またはその部分加水分解縮合物が含まれる(以下、「架橋剤」ともいう。)。本発明における架橋剤は、PFPE含有シラン化合物(a)(具体的には、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基)と架橋反応(縮合反応)をする化合物である。PFPE含有シラン化合物(a)と架橋剤(b)とを含むことにより、硬化性組成物から得られる硬化物の物性(例えば、引張強度、弾性率)が良好になる。 (Crosslinking agent (b))
The curable composition of the present invention includes, as a cross-linking agent, a compound having at least two OR 2 groups bonded to Si atoms (where R 2 is independently at each occurrence a hydrogen atom or a monovalent organic groups) (excluding those falling under (a) above) or partial hydrolysis condensates thereof (hereinafter also referred to as "crosslinking agents"). The cross-linking agent in the present invention performs a cross-linking reaction (condensation reaction) with the PFPE-containing silane compound (a) (specifically, the hydroxyl group or hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (a)). is a compound. By containing the PFPE-containing silane compound (a) and the cross-linking agent (b), the physical properties (eg, tensile strength, elastic modulus) of the cured product obtained from the curable composition are improved.
本発明の硬化性組成物には、架橋剤として、Si原子と結合したOR2基を少なくとも2個有する化合物(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(ただし、前記(a)に該当するものを除く)またはその部分加水分解縮合物が含まれる(以下、「架橋剤」ともいう。)。本発明における架橋剤は、PFPE含有シラン化合物(a)(具体的には、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基)と架橋反応(縮合反応)をする化合物である。PFPE含有シラン化合物(a)と架橋剤(b)とを含むことにより、硬化性組成物から得られる硬化物の物性(例えば、引張強度、弾性率)が良好になる。 (Crosslinking agent (b))
The curable composition of the present invention includes, as a cross-linking agent, a compound having at least two OR 2 groups bonded to Si atoms (where R 2 is independently at each occurrence a hydrogen atom or a monovalent organic groups) (excluding those falling under (a) above) or partial hydrolysis condensates thereof (hereinafter also referred to as "crosslinking agents"). The cross-linking agent in the present invention performs a cross-linking reaction (condensation reaction) with the PFPE-containing silane compound (a) (specifically, the hydroxyl group or hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (a)). is a compound. By containing the PFPE-containing silane compound (a) and the cross-linking agent (b), the physical properties (eg, tensile strength, elastic modulus) of the cured product obtained from the curable composition are improved.
架橋剤(b)において、基R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である。1価の有機基は、1価の炭素を含有する基を意味する。かかる1価の有機基としては、特に限定されないが、1価の炭化水素基が挙げられる。炭化水素基は上記と同意義である。
In crosslinker (b), the group R2 at each occurrence is independently a hydrogen atom or a monovalent organic group. A monovalent organic group means a group containing monovalent carbon. Examples of such monovalent organic groups include, but are not particularly limited to, monovalent hydrocarbon groups. The hydrocarbon group has the same meaning as above.
架橋剤(b)は、PFPE含有シラン化合物(a)とは異なる構造を有する。架橋剤(b)は、パーフルオロ(ポリ)エーテル部を有さないことが好ましい。架橋剤(b)は、Si-OR2基、アルケニル基およびアルキニル基以外の他の反応性官能基を有していてもよく、有していなくてもよいが、架橋性の点で、他の反応性官能基を有していないことが好ましい。本発明において、他の反応性官能基とは、第1級アミノ基、エポキシ基、(メタ)アクリロイル基、(メタ)アクリロキシ基、メルカプト基、イソシアナト基等を指す。以下、架橋剤(b)を、(B1)反応性官能基を有さない架橋剤、(B2)反応性官能基を有する架橋剤と分けて説明する。
The cross-linking agent (b) has a structure different from that of the PFPE-containing silane compound (a). The cross-linking agent (b) preferably does not have a perfluoro(poly)ether moiety. The cross-linking agent (b) may or may not have reactive functional groups other than Si—OR 2 groups, alkenyl groups and alkynyl groups. preferably does not have a reactive functional group of In the present invention, other reactive functional groups refer to primary amino groups, epoxy groups, (meth)acryloyl groups, (meth)acryloxy groups, mercapto groups, isocyanato groups, and the like. Hereinafter, the cross-linking agent (b) will be described separately as (B1) a cross-linking agent having no reactive functional group and (B2) a cross-linking agent having a reactive functional group.
<<(B1)反応性官能基を有さない架橋剤>>
(B1)反応性官能基を有さない架橋剤としては、例えばR1 nSi(OR2)4-n(式中、R1は、各出現においてそれぞれ独立して、置換または非置換の1価の炭化水素基であり、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、nは、0、1または2である)で表される有機ケイ素化合物を挙げることができる。 <<(B1) Cross-linking agent having no reactive functional group>>
(B1) Cross-linking agents having no reactive functional group include, for example, R 1 n Si(OR 2 ) 4-n (wherein R 1 is independently at each occurrence a substituted or unsubstituted 1 is a valent hydrocarbon group, each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group, and n is 0, 1 or 2). can be mentioned.
(B1)反応性官能基を有さない架橋剤としては、例えばR1 nSi(OR2)4-n(式中、R1は、各出現においてそれぞれ独立して、置換または非置換の1価の炭化水素基であり、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、nは、0、1または2である)で表される有機ケイ素化合物を挙げることができる。 <<(B1) Cross-linking agent having no reactive functional group>>
(B1) Cross-linking agents having no reactive functional group include, for example, R 1 n Si(OR 2 ) 4-n (wherein R 1 is independently at each occurrence a substituted or unsubstituted 1 is a valent hydrocarbon group, each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group, and n is 0, 1 or 2). can be mentioned.
R1は、各出現においてそれぞれ独立して、炭素原子数1~12の置換または非置換の1価の炭化水素基であることが好ましい。R1は、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基;シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基;フェニル基、トリル基、キシリル基、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、フェニルプロピル基等のアラルキル基;ビニル基、アリル基、プロペニル基、ブテニル基等のアルケニル基;エチニル基、プロピニル基等のアルキニル基;および、これらの基の水素原子の一部または全部をフッ素、塩素、臭素等のハロゲン原子等で置換した基(例えば、クロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基、3,3,4,4,5,5,6,6,6-ノナフルオロヘキシル基)等を挙げることができる。
Preferably, each occurrence of R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group of 1 to 12 carbon atoms. R 1 is specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as a decyl group; Cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; Aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; aralkyl group; alkenyl group such as vinyl group, allyl group, propenyl group and butenyl group; alkynyl group such as ethynyl group and propynyl group; Groups substituted with halogen atoms (e.g., chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group), etc. can be mentioned.
R2は、各出現においてそれぞれ独立して、CH3-、C2H5-、C3H7-、CF3CH2-、CH3CO-、CH2=C(CH3)-、CH3CH2C(CH3)=N-、(CH3)2N-、(C2H5)2N-、CH2=C(OC2H5)-、(CH3)2C=C(OC8H17)-、または
であることが好ましい。R2は、置換または非置換の炭素原子数1~3のアルキル基であることがより好ましく、特に好ましくは、CH3-またはC2H5-である。 R 2 is independently at each occurrence CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, CH 2 =C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N-, (CH 3 ) 2 N-, (C 2 H 5 ) 2 N-, CH 2 =C(OC 2 H 5 )-, (CH 3 ) 2 C=C (OC 8 H 17 )-, or
is preferably R 2 is more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, particularly preferably CH 3 — or C 2 H 5 —.
であることが好ましい。R2は、置換または非置換の炭素原子数1~3のアルキル基であることがより好ましく、特に好ましくは、CH3-またはC2H5-である。 R 2 is independently at each occurrence CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, CH 2 =C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N-, (CH 3 ) 2 N-, (C 2 H 5 ) 2 N-, CH 2 =C(OC 2 H 5 )-, (CH 3 ) 2 C=C (OC 8 H 17 )-, or
is preferably R 2 is more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, particularly preferably CH 3 — or C 2 H 5 —.
nは、1または2であることが好ましい。
n is preferably 1 or 2.
(B1)反応性官能基を有さない架橋剤としては、さらに、以下の(B1-1)~(B1-3)で表される有機ケイ素化合物を挙げることができる。一の態様において、(B1)反応性官能基を有さない架橋剤は、以下の式(B1-1)または(B1-2)で表されるような、1分子中に少なくとも2個のシラノール基を有する化合物を挙げることができる。
(B1) Examples of the cross-linking agent having no reactive functional group further include organosilicon compounds represented by (B1-1) to (B1-3) below. In one aspect, (B1) a cross-linking agent having no reactive functional group is represented by the following formula (B1-1) or (B1-2), at least two silanols per molecule A compound having a group can be mentioned.
式(B1-1)および(B1-2)中、Rg1は、各出現においてそれぞれ独立して、置換または非置換の炭素原子数1~8の1価炭化水素基である。Rg1としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基;シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基;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、イソブテニル基、ヘキセニル基、シクロヘキセニル基等のアルケニル基;フェニル基、トリル基、キシリル基、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、フェニルプロピル基等のアラルキル基;およびこれらの基の水素原子の一部または全部をハロゲン原子で置換した基(例えば、クロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基、ノナフルオロヘキシル基)が挙げられる。
In formulas (B1-1) and (B1-2), each occurrence of R g1 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specific examples of R g1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. , Alkyl groups such as decyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; Vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and cyclohexenyl alkenyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group; Substituted groups (eg, chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, nonafluorohexyl group) can be mentioned.
式(B1-2)中、Rg2は、各出現においてそれぞれ独立して、置換または非置換の炭素原子数1~20であり、好ましくは、炭素原子数2~10の2価炭化水素基である。Rg2としては、具体的には、メチレン基、エチレン基、プロピレン基、メチルエチレン基、ブチレン基、ヘキサメチレン基等のアルキレン基;シクロヘキシレン基等のシクロアルキレン基、フェニレン基、トリレン基、キシリレン基、ナフチレン基、ビフェニレン基等のアリーレン基;これらの基の水素原子の一部または全部をハロゲン原子等で置換した基;およびこれらの置換または非置換のアルキレン基、アリーレン基の組合せが例示される。この中で、Rg2としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基、シクロヘキシレン基およびフェニレン基が好ましく、特にエチレン基、プロピレン基、ブチレン基およびフェニレン基が好ましい。
分子内にシラノール基を有する化合物としては、Rg1 3SiO1/2、Rg1 2SiO2/2、Rg1SiO3/2、およびSiO4/2単位の1種または2種以上の組合せとシラノール基との結合で構成される樹脂状化合物が挙げられる。上記樹脂状化合物中の構成単位同士は、直接結合していてもよいし、2価以上の炭化水素基を介して結合していてもよい。 In formula (B1-2), each occurrence of R g2 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms. be. Specific examples of R g2 include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, and hexamethylene; cycloalkylene groups such as cyclohexylene, phenylene, tolylene, and xylylene. arylene groups such as groups, naphthylene groups, and biphenylene groups; groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc.; be. Among these, Rg2 is preferably a methylene group, ethylene group, propylene group, butylene group, hexamethylene group, cyclohexylene group and phenylene group, and particularly preferably ethylene group, propylene group, butylene group and phenylene group.
Compounds having a silanol group in the molecule include one or a combination of two or more of R g1 3 SiO 1/2 , R g1 2 SiO 2/2 , R g1 SiO 3/2 and SiO 4/2 units. Examples include resinous compounds composed of bonds with silanol groups. The structural units in the resinous compound may be directly bonded to each other, or may be bonded via a divalent or higher hydrocarbon group.
分子内にシラノール基を有する化合物としては、Rg1 3SiO1/2、Rg1 2SiO2/2、Rg1SiO3/2、およびSiO4/2単位の1種または2種以上の組合せとシラノール基との結合で構成される樹脂状化合物が挙げられる。上記樹脂状化合物中の構成単位同士は、直接結合していてもよいし、2価以上の炭化水素基を介して結合していてもよい。 In formula (B1-2), each occurrence of R g2 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms. be. Specific examples of R g2 include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, and hexamethylene; cycloalkylene groups such as cyclohexylene, phenylene, tolylene, and xylylene. arylene groups such as groups, naphthylene groups, and biphenylene groups; groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc.; be. Among these, Rg2 is preferably a methylene group, ethylene group, propylene group, butylene group, hexamethylene group, cyclohexylene group and phenylene group, and particularly preferably ethylene group, propylene group, butylene group and phenylene group.
Compounds having a silanol group in the molecule include one or a combination of two or more of R g1 3 SiO 1/2 , R g1 2 SiO 2/2 , R g1 SiO 3/2 and SiO 4/2 units. Examples include resinous compounds composed of bonds with silanol groups. The structural units in the resinous compound may be directly bonded to each other, or may be bonded via a divalent or higher hydrocarbon group.
式(B1-1)または(B1-2)中、ε1は、各出現においてそれぞれ独立して、1以上の整数である。ε1は、好ましくは2以上、より好ましくは5以上であり、好ましくは50以下、より好ましくは20以下である。
In formula (B1-1) or (B1-2), ε1 is independently an integer of 1 or more at each occurrence. ε1 is preferably 2 or more, more preferably 5 or more, and preferably 50 or less, more preferably 20 or less.
式(B1-1)または(B1-2)で表される化合物は、分子構造中にPFPE1構造を有しないことが好ましい。
The compound represented by formula (B1-1) or (B1-2) preferably does not have a PFPE 1 structure in its molecular structure.
(B1)反応性官能基を有さない架橋剤は、式(B1-3)で表される有機ケイ素化合物:
であることができる。ここで、ORg3を含む単位およびRg4を含む単位は上記式(B1-3)で示されるとおりに配列している必要はなく、例えば、両者が交互に存在する等、その配列順が任意であることが理解される。 (B1) The cross-linking agent having no reactive functional group is an organosilicon compound represented by formula (B1-3):
can be Here, the units containing OR g3 and the units containing R g4 do not need to be arranged as shown in the above formula (B1-3). It is understood that
であることができる。ここで、ORg3を含む単位およびRg4を含む単位は上記式(B1-3)で示されるとおりに配列している必要はなく、例えば、両者が交互に存在する等、その配列順が任意であることが理解される。 (B1) The cross-linking agent having no reactive functional group is an organosilicon compound represented by formula (B1-3):
can be Here, the units containing OR g3 and the units containing R g4 do not need to be arranged as shown in the above formula (B1-3). It is understood that
式(B1-3)中、Rg3は、R2と同意義である。上記Rg3は、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基と反応し得る部分である。
In formula (B1-3), R g3 has the same meaning as R 2 . R g3 above is a moiety capable of reacting with a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound (a).
Rg3は、1価の有機基であることが好ましい。
R g3 is preferably a monovalent organic group.
式(B1-3)において、Rg3は、より好ましくは、各出現においてそれぞれ独立して、CH3-、C2H5-、C3H7-、CF3CH2-、CH3CO-、CH2=C(CH3)-、CH3CH2C(CH3)=N-、(CH3)2N-、(C2H5)2N-、CH2=C(OC2H5)-、(CH3)2C=C(OC8H17)-、または
である。 In formula (B1-3), R g3 is more preferably CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, each independently at each occurrence. , CH 2 ═C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N—, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, CH 2 ═C(OC 2 H 5 )-, (CH 3 ) 2 C=C(OC 8 H 17 )-, or
is.
である。 In formula (B1-3), R g3 is more preferably CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, each independently at each occurrence. , CH 2 ═C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N—, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, CH 2 ═C(OC 2 H 5 )-, (CH 3 ) 2 C=C(OC 8 H 17 )-, or
is.
式(B1-3)中、Rg4は、各出現においてそれぞれ独立して、1価の有機基である。Rg4は、置換または非置換の1価の炭化水素基であることが好ましく、炭素原子数1~12の置換または非置換の1価の炭化水素基であることがより好ましい。Rg4は、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基;シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基;フェニル基、トリル基、キシリル基、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、フェニルプロピル基等のアラルキル基;ビニル基、アリル基、プロペニル基、ブテニル基等のアルケニル基;エチニル基、プロピニル基等のアルキニル基;および、これらの基の水素原子の一部または全部をフッ素、塩素、臭素等のハロゲン原子等で置換した基(例えば、クロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基、3,3,4,4,5,5,6,6,6-ノナフルオロヘキシル基等を挙げることができる。
In formula (B1-3), each occurrence of R g4 is independently a monovalent organic group. R g4 is preferably a substituted or unsubstituted monovalent hydrocarbon group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. R g4 is specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as a decyl group; Cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; Aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; aralkyl group; alkenyl group such as vinyl group, allyl group, propenyl group and butenyl group; alkynyl group such as ethynyl group and propynyl group; Groups substituted with halogen atoms (e.g., chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc.) can be mentioned.
式(B1-3)中、ε3は、2または3である。
In formula (B1-3), ε3 is 2 or 3.
好ましくは、(B1)反応性官能基を有さない架橋剤は、式:R1
nSi(OR2)4-nで表される化合物である。
Preferably, (B1) the cross-linking agent having no reactive functional group is a compound represented by the formula: R 1 n Si(OR 2 ) 4-n .
好ましい態様において、(B1)反応性官能基を有さない架橋剤は、テトラメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、フェニルトリメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ビニルトリエトキシシラン、フェニルトリエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、ジメチルジメトキシシラン、ビニルメチルジメトキシシラン、ジメチルジエトキシシランおよび3-クロロプロピルトリメトキシシラン並びにそれらの部分加水分解縮合物のようなアルコキシ基含有化合物;テトラキス(2-エトキシエトキシ)シラン、メチルトリス(2-メトキシエトキシ)シラン、ビニル(2-エトキシエトキシ)シランおよびフェニルトリス(2-メトキシエトキシ)シラン並びにそれらの部分加水分解縮合物のような置換アルコキシ基含有化合物;メチルトリプロペノキシシラン、メチルトリイソプロペノキシシラン、ビニルトリイソプロペノキシシラン、フェニルトリイソプロペノキシシラン、ジメチルジイソプロペノキシシランおよびメチルビニルジイソプロペノキシシラン並びにそれらの部分加水分解縮合物のようなエノキシ基含有化合物;メチルトリアセトキシシランおよびそれらの部分加水分解縮合物のようなアシルオキシ基含有化合物等が例示される。
In a preferred embodiment, the (B1) cross-linking agent having no reactive functional group is tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane. Alkoxy groups such as silane, phenyltriethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, dimethyldiethoxysilane and 3-chloropropyltrimethoxysilane and partial hydrolytic condensates thereof Containing compounds; tetrakis(2-ethoxyethoxy)silane, methyltris(2-methoxyethoxy)silane, vinyl(2-ethoxyethoxy)silane and phenyltris(2-methoxyethoxy)silane, and partial hydrolytic condensates thereof substituted alkoxy group-containing compounds; methyltripropenoxysilane, methyltriisopropenoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, dimethyldiisopropenoxysilane and methylvinyldiisopropenoxysilane, and their Enoxy group-containing compounds such as partial hydrolysis condensates; acyloxy group-containing compounds such as methyltriacetoxysilane and partial hydrolysis condensates thereof are exemplified.
<<(B2)反応性官能基を有する架橋剤>>
(B2)反応性官能基を有する架橋剤は、PFPE含有シラン化合物(a)の架橋反応(縮合反応)に寄与するだけではなく、接着性付与剤としても機能する化合物である。本発明の硬化性組成物は、(b)成分として、上記(B1)に加えてこのような化合物を更に含んでいてもよい。(B2)成分としては、
で表される化合物を使用することができる。 <<(B2) Cross-linking agent having a reactive functional group>>
(B2) The cross-linking agent having a reactive functional group is a compound that not only contributes to the cross-linking reaction (condensation reaction) of the PFPE-containing silane compound (a), but also functions as an adhesion imparting agent. The curable composition of the present invention may further contain such a compound as the component (b) in addition to the above (B1). (B2) As the component,
A compound represented by can be used.
(B2)反応性官能基を有する架橋剤は、PFPE含有シラン化合物(a)の架橋反応(縮合反応)に寄与するだけではなく、接着性付与剤としても機能する化合物である。本発明の硬化性組成物は、(b)成分として、上記(B1)に加えてこのような化合物を更に含んでいてもよい。(B2)成分としては、
で表される化合物を使用することができる。 <<(B2) Cross-linking agent having a reactive functional group>>
(B2) The cross-linking agent having a reactive functional group is a compound that not only contributes to the cross-linking reaction (condensation reaction) of the PFPE-containing silane compound (a), but also functions as an adhesion imparting agent. The curable composition of the present invention may further contain such a compound as the component (b) in addition to the above (B1). (B2) As the component,
A compound represented by can be used.
式(B2)中、Rg3およびRg4は上記と同意義である。
In formula (B2), R g3 and R g4 have the same meanings as above.
式(B2)中、Rg6は、各出現においてそれぞれ独立して、Rg8-Rg7-を表す。
In formula (B2), each occurrence of R g6 independently represents R g8 -R g7 -.
Rg7は、各出現においてそれぞれ独立して、単結合、酸素原子または2価の有機基を表す。2価の有機基は上記のとおりである。
Each occurrence of R g7 independently represents a single bond, an oxygen atom or a divalent organic group. The divalent organic groups are as described above.
Rg7は、好ましくは、炭素原子数1~10のアルキレン基、または、炭素原子数1~10であり主鎖中に窒素原子または酸素原子を含む基である。
R g7 is preferably an alkylene group having 1 to 10 carbon atoms or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain.
Rg7は、より好ましくは、
炭素原子数1~3のアルキレン基、
CH2CH2-NH-CH2CH2CH2、または
CH2-O-CH2CH2CH2である。 R g7 is more preferably
an alkylene group having 1 to 3 carbon atoms,
CH2CH2 - NH - CH2CH2CH2 , or CH2 - O - CH2CH2CH2 .
炭素原子数1~3のアルキレン基、
CH2CH2-NH-CH2CH2CH2、または
CH2-O-CH2CH2CH2である。 R g7 is more preferably
an alkylene group having 1 to 3 carbon atoms,
CH2CH2 - NH - CH2CH2CH2 , or CH2 - O - CH2CH2CH2 .
Rg8は、反応性官能基である。上記Rg8は、好ましくは、各出現においてそれぞれ独立して、第1級アミノ基、エポキシ基、(メタ)アクリロイル基、(メタ)アクリロキシ基、メルカプト基またはイソシアナト基であり、より好ましくは第1級アミノ基である。
R g8 is a reactive functional group. R g8 above is preferably each independently at each occurrence a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group or an isocyanato group, more preferably a primary is a tertiary amino group.
式(B2)中、ε4は2または3、より好ましくは3である。式(B2)中、ε5は0または1である。式(B2)中、ε6は、1または2、好ましくは1である。ただし、ε4、ε5およびε6の和は4である。特に好ましくは、ε4は、3、ε5は、0かつ、ε6は、1である。
In formula (B2), ε4 is 2 or 3, more preferably 3. In formula (B2), ε5 is 0 or 1. In formula (B2), ε6 is 1 or 2, preferably 1. However, the sum of ε4, ε5 and ε6 is four. Particularly preferably, ε4 is 3, ε5 is 0 and ε6 is 1.
(B2)反応性官能基を有する架橋剤としては、例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリイソプロポキシシラン、3-アミノプロピルトリアセトアミドシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-メチル-3-アミノプロピルトリメトキシシラン、 N-フェニル-3-アミノプロピルトリメトキシシラン、N,N-ジメチル-3-アミノプロピルトリメトキシシランのような置換または非置換のアミノ基含有シラン;3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3,4-エポキシシクロヘキシルエチルトリメトキシシランのようなエポキシ基含有シラン;3-イソシアナトプロピルトリメトキシシラン、3-イソシアナトプロピルトリエトキシシラン、3-イソシアナトプロピルメチルジメトキシシランのようなイソシアナト基含有シラン;3-アクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシランのような(メタ)アクリロキシ基含有シラン;3-メルカプトプロピルトリメトキシシランのようなメルカプト基含有シラン;および第1級アミノ基含有シランとエポキシ基含有シランの混合物あるいは反応物が例示される。
(B2) Examples of cross-linking agents having reactive functional groups include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltriacetamidosilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3 -substituted or unsubstituted amino group-containing silanes such as aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane; Epoxy group-containing silanes such as ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 - isocyanato group-containing silanes such as isocyanatopropylmethyldimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane silanes containing (meth)acryloxy groups such as 3-methacryloxypropylmethyldiethoxysilane; silanes containing mercapto groups such as 3-mercaptopropyltrimethoxysilane; and silanes containing primary amino groups and epoxy groups. Mixtures or reactants are exemplified.
一の態様において、架橋剤(b)は、分子鎖中にPFPE1で表される基を有しない。
In one aspect, the cross-linking agent (b) does not have a group represented by PFPE 1 in the molecular chain.
一の態様において、架橋剤(b)の分子量は、1,000以下であり、好ましくは600以下、より好ましくは250以下である。架橋剤の分子量の下限値は、90以上であってもよく、120以上であってもよい。
In one aspect, the molecular weight of the cross-linking agent (b) is 1,000 or less, preferably 600 or less, more preferably 250 or less. The lower limit of the molecular weight of the cross-linking agent may be 90 or more, or 120 or more.
架橋剤(b)は、1種のみを用いてもよいし、2種以上を同時に用いてもよい。2種以上併用する場合、(B1)を2種以上併用、(B2)を2種以上併用、(B1)と(B2)の各1種以上の併用のいずれであってもよい。架橋性の観点から、架橋剤(b)は、少なくとも(B1)を1種以上含有することが好ましい。また、架橋性および基材との密着性の観点から、(B1)と後述する(D)、(B2)と(D)または(B1)と(B2)と(D)とを併用することが好ましく、(B1)と(D)を併用することがより好ましい。
Only one type of the cross-linking agent (b) may be used, or two or more types may be used at the same time. When two or more are used in combination, any of two or more of (B1) may be used in combination, two or more of (B2) may be used in combination, and one or more of each of (B1) and (B2) may be used in combination. From the viewpoint of crosslinkability, the crosslinker (b) preferably contains at least one kind of (B1). In addition, from the viewpoint of crosslinkability and adhesion to the substrate, (B1) and (D) described later, (B2) and (D), or (B1) and (B2) and (D) can be used in combination. Preferably, (B1) and (D) are used in combination.
架橋剤(b)は、硬化性組成物中、PFPE含有シラン化合物(a)100質量部に対して、例えば、0.1質量部以上含み得、具体的には0.3質量部以上含み得、30質量部以下含み得、具体的には20質量部以下、より具体的には10質量部以下含み得る。
The crosslinking agent (b) may be contained in the curable composition in an amount of, for example, 0.1 parts by mass or more, specifically 0.3 parts by mass or more, relative to 100 parts by mass of the PFPE-containing silane compound (a). , 30 parts by mass or less, specifically 20 parts by mass or less, more specifically 10 parts by mass or less.
PFPE含有シラン化合物(a)に対する(B1)および(B2)成分の合計含有量は、架橋性の観点から、0.1質量%以上であることが好ましく、より好ましくは0.3質量%以上であり、また、30質量%以下であることが好ましく、より好ましくは20質量%以下、特に好ましくは10質量%以下である。
The total content of the components (B1) and (B2) relative to the PFPE-containing silane compound (a) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, from the viewpoint of crosslinkability. It is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
PFPE含有シラン化合物(a)に対する(B1)および(B2)成分の合計含有量は、架橋性の観点から、0.1~30質量%であることが好ましく、より好ましくは0.3~20質量%、特に好ましくは0.3~10質量%である。
The total content of components (B1) and (B2) relative to the silane compound (a) containing PFPE is preferably 0.1 to 30% by mass, more preferably 0.3 to 20% by mass, from the viewpoint of crosslinkability. %, particularly preferably 0.3 to 10% by weight.
(B1)成分の含有量は、(B1)および(B2)成分の合計に対して10~100質量%であることが好ましく、より好ましくは20~100質量%、特に好ましくは50~100質量%である。PFPE含有シラン化合物(a)に対する(B1)および(B2)成分の好ましい含有量は、PFPE含有シラン化合物(a)に対する(B1)および(B2)成分の合計の好ましい含有量並びに(B1)および(B2)成分の合計に対する(B1)成分の好ましい含有量から、それぞれ算出することができる。
The content of component (B1) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and particularly preferably 50 to 100% by mass with respect to the total of components (B1) and (B2). is. Preferred contents of components (B1) and (B2) relative to PFPE-containing silane compound (a) are the total preferred content of components (B1) and (B2) relative to PFPE-containing silane compound (a) and (B1) and ( Each can be calculated from the preferred content of component (B1) with respect to the total of components B2).
架橋剤(b)は、硬化性組成物中、PFPE含有シラン化合物(a)100質量部に対して、例えば、0.1~30質量部含むことができ、具体的には、0.3~10質量部含むことができ、より具体的には、0.3~5.0質量部含むことができる。
The crosslinking agent (b) can be contained in the curable composition in an amount of, for example, 0.1 to 30 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound (a), specifically 0.3 to 30 parts by mass. 10 parts by mass, more specifically, 0.3 to 5.0 parts by mass.
架橋剤(b)は、硬化性組成物中、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、例えば、-OR2基を1モル以上含むことができ、具体的には、2モル以上含むことができる。架橋剤(b)は、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、例えば、-OR2基を30モル以下含むことができ、具体的には20モル以下含むことができ、より具体的には10モル以下含むことができる。
The cross-linking agent (b) contains, for example, 1 mol or more of —OR 2 groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a) in the curable composition. Specifically, it can contain 2 mol or more. The cross-linking agent (b) can contain, for example, 30 mol or less of —OR 2 groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). may contain 20 mol or less, more specifically 10 mol or less.
架橋剤(b)は、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、-OR2基を、例えば1~30モルの範囲で含むことができ、具体的には、2~20モルの範囲含むことができる。
The cross-linking agent (b) may contain —OR 2 groups, for example, in the range of 1 to 30 mol per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). can be included, specifically in the range of 2 to 20 moles.
<縮合触媒>
縮合触媒(c)は、上記PFPE含有シラン化合物(a)と上記架橋剤(b)との加水分解縮合を促進する成分である。 <Condensation catalyst>
The condensation catalyst (c) is a component that promotes hydrolytic condensation between the PFPE-containing silane compound (a) and the cross-linking agent (b).
縮合触媒(c)は、上記PFPE含有シラン化合物(a)と上記架橋剤(b)との加水分解縮合を促進する成分である。 <Condensation catalyst>
The condensation catalyst (c) is a component that promotes hydrolytic condensation between the PFPE-containing silane compound (a) and the cross-linking agent (b).
上記縮合触媒としては、金属系触媒、有機酸系触媒、無機酸系触媒、塩基系触媒等を用いることができる。組成物の硬化速度の観点から、縮合触媒としては金属系触媒であることが好ましい。
As the condensation catalyst, a metal-based catalyst, an organic acid-based catalyst, an inorganic acid-based catalyst, a base-based catalyst, or the like can be used. From the viewpoint of the curing speed of the composition, the condensation catalyst is preferably a metal-based catalyst.
上記金属系触媒に含まれる金属原子としては、例えば、チタン、ジルコニウム、スズ等を挙げることができる。特に、有機スズ化合物またはアルコキシチタン類であることが好ましい。
Examples of metal atoms contained in the metal-based catalyst include titanium, zirconium, and tin. In particular, organic tin compounds or alkoxytitanium compounds are preferred.
上記金属系触媒の一態様としては、配位子としてアルコキシド(-O-Rh)を有する化合物を用いることができる。
As one aspect of the metal-based catalyst, a compound having an alkoxide (--O--R h ) as a ligand can be used.
上記金属系触媒としてアルコキシドを有する化合物を用いる場合、上記Rhとしては、炭素原子数1~4のアルキル基が好ましい。このような触媒を用いると、縮合反応がより促進される。
When a compound having an alkoxide is used as the metal-based catalyst, R h is preferably an alkyl group having 1 to 4 carbon atoms. The use of such catalysts promotes the condensation reaction.
上記金属系触媒としてアルコキシドを有する化合物を用いる場合、上記Rhとしては、炭素原子数1~3のアルキル基がより好ましい。このような触媒を用いると、縮合反応が特に促進される。上記触媒は、硬化性組成物に溶解または分散しやすく、均一な反応の促進に寄与し得る。上記触媒は、異物が少なく、透明な硬化性組成物の硬化物の形成に寄与し得る。
When a compound having an alkoxide is used as the metal-based catalyst, R h is more preferably an alkyl group having 1 to 3 carbon atoms. The use of such catalysts particularly promotes the condensation reaction. The catalyst is easily dissolved or dispersed in the curable composition, and can contribute to promotion of uniform reaction. The above catalyst can contribute to the formation of a transparent cured product of the curable composition with less foreign substances.
好ましい金属系触媒としては、鉄オクトエート、マンガンオクトエート、亜鉛オクトエート、スズナフテート、スズカプリレート、スズオレートのようなカルボン酸金属塩;ジブチルスズジアセテート、ジブチルスズジオクトエート、ジブチルスズジラウレート、ジブチルスズジオレート、ジフェニルスズジアセテート、酸化ジブチルスズ、ジブチルスズジメトキシド、ジブチルビス(トリエトキシシロキシ)スズ、ジオクチルスズジラウレート、ジメチルスズジネオデカノエートのような有機スズ化合物;テトラエトキシチタン、テトラプロポキシチタン、テトライソプロポキシチタン、テトラn-ブトキシチタン、テトライソブトキシチタン、ジイソプロポキシチタンビス(エチルアセトアセテート)、1,3-プロパンジオキシチタンビス(エチルアセトアセテート)のような有機チタン類;アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート、トリエトキシアルミニウムなどの有機アルミニウム;ジルコニウムテトラアセチルアセトナート、テトライソプロポキシジルコニウム、テトラプロポキシジルコニウム、テトラn-ブトキシジルコニウム、テトライソブトキシジルコニウム、トリブトキシジルコニウムアセチルアセトネート、トリブトキシジルコニウムステアレートなどの有機ジルコニウム化合物が挙げられる。
Preferred metal-based catalysts include carboxylic acid metal salts such as iron octoate, manganese octoate, zinc octoate, tin naphtate, tin caprylate, tin oleate; Organotin compounds such as acetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, dioctyltin dilaurate, dimethyltin dineodecanoate; tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetra-n - organic titaniums such as butoxytitanium, tetraisobutoxytitanium, diisopropoxytitanium bis(ethylacetoacetate), 1,3-propanedioxytitanium bis(ethylacetoacetate); aluminum trisacetylacetonate, aluminum trisethylacetoacetate , diisopropoxyaluminum ethylacetoacetate, triethoxyaluminum; Examples include organozirconium compounds such as tributoxyzirconium stearate.
上記有機酸系触媒としては、例えば、カルボン酸、スルホン酸、リン酸を有する化合物を挙げることができ、具体的には、酢酸、トリフルオロ酢酸、メタンスルホン酸、トルエンゼンスルホン酸、アルキルリン酸等を挙げることができる。
Examples of the organic acid-based catalyst include compounds having carboxylic acid, sulfonic acid, and phosphoric acid. Specifically, acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and alkylphosphoric acid etc. can be mentioned.
上記無機酸系触媒としては、例えば、塩酸、硫酸等を挙げることができる。
Examples of the inorganic acid-based catalyst include hydrochloric acid and sulfuric acid.
上記塩基系触媒としては、例えばアンモニア、トリエチルアミン、ジエチルアミン等のアミン化合物、ジメチルヒドロキシアミン、ジエチルヒドロキシルアミンなどのジアルキルヒドロキシルアミン、テトラメチルグアニジン、グアニジル基含有シランもしくはシロキサン等のグアニジル化合物が例示される。
Examples of the basic catalyst include ammonia, amine compounds such as triethylamine and diethylamine, dialkylhydroxylamine such as dimethylhydroxyamine and diethylhydroxylamine, and guanidyl compounds such as tetramethylguanidine and guanidyl group-containing silanes or siloxanes.
上記縮合触媒は、本発明の硬化性組成物中、PFPE含有シラン化合物(a)100質量部に対して、0.01~10.0質量部含まれることが好ましく、0.03~5.0質量部含まれることがより好ましい。
The above condensation catalyst is preferably contained in the curable composition of the present invention in an amount of 0.01 to 10.0 parts by mass, and 0.03 to 5.0 parts by mass, based on 100 parts by mass of the PFPE-containing silane compound (a). It is more preferable to contain parts by mass.
上記縮合触媒は、1種のみを用いてもよいし、2種以上を同時に用いてもよい。
The above condensation catalysts may be used alone or in combination of two or more.
(更なる成分)
本発明の硬化性組成物は、本発明の効果を損なわない範囲で、上記PEPE含有シラン化合物(a)、架橋剤(b)、縮合触媒(c)以外の更なる成分を含むことができる。このような成分として、(d)接着性付与剤、(a2)後述する一般式(II)で示されるパーフルオロ(ポリ)エーテル基含有シラン化合物、(e)無機充填剤、(f)表面処理シリカ、(g)その他PFPE含有シラン化合物、(h)溶剤、(i)各種添加剤等が挙げられる(以下、「(d)成分」などと略記することがある)。 (additional ingredients)
The curable composition of the present invention can contain further components other than the PEPE-containing silane compound (a), the cross-linking agent (b), and the condensation catalyst (c) as long as they do not impair the effects of the present invention. Such components include (d) an adhesion imparting agent, (a2) a perfluoro(poly)ether group-containing silane compound represented by general formula (II) described later, (e) an inorganic filler, and (f) a surface treatment. Silica, (g) other PFPE-containing silane compounds, (h) solvents, and (i) various additives (hereinafter sometimes abbreviated as "component (d)").
本発明の硬化性組成物は、本発明の効果を損なわない範囲で、上記PEPE含有シラン化合物(a)、架橋剤(b)、縮合触媒(c)以外の更なる成分を含むことができる。このような成分として、(d)接着性付与剤、(a2)後述する一般式(II)で示されるパーフルオロ(ポリ)エーテル基含有シラン化合物、(e)無機充填剤、(f)表面処理シリカ、(g)その他PFPE含有シラン化合物、(h)溶剤、(i)各種添加剤等が挙げられる(以下、「(d)成分」などと略記することがある)。 (additional ingredients)
The curable composition of the present invention can contain further components other than the PEPE-containing silane compound (a), the cross-linking agent (b), and the condensation catalyst (c) as long as they do not impair the effects of the present invention. Such components include (d) an adhesion imparting agent, (a2) a perfluoro(poly)ether group-containing silane compound represented by general formula (II) described later, (e) an inorganic filler, and (f) a surface treatment. Silica, (g) other PFPE-containing silane compounds, (h) solvents, and (i) various additives (hereinafter sometimes abbreviated as "component (d)").
<(d)接着性付与剤>
本発明の硬化性組成物において接着性付与剤として用いられる化合物は、1分子中に2個以上のアルコキシシリル基を含有し、かつ、アルコキシシリル基間を連結する基が-O-基;およびシロキサン結合を有する基以外の基である化合物、またはその部分加水分解縮合物(ただし、(a)に該当するものを除く。)である(以下、1分子中に2個以上のアルコキシシリル基を含有する接着性付与剤ともいう。)。(d)成分は、組成物の硬化物の、ガラス、金属、プラスチック等の基材への密着性を向上させる成分である。 <(d) Adhesion imparting agent>
The compound used as an adhesion-imparting agent in the curable composition of the present invention contains two or more alkoxysilyl groups in one molecule, and the groups connecting the alkoxysilyl groups are —O— groups; and A compound that is a group other than a group having a siloxane bond, or a partial hydrolysis condensate thereof (excluding those corresponding to (a)) (hereinafter, two or more alkoxysilyl groups in one molecule It is also referred to as a contained adhesiveness imparting agent.). Component (d) is a component that improves the adhesion of the cured product of the composition to substrates such as glass, metal and plastic.
本発明の硬化性組成物において接着性付与剤として用いられる化合物は、1分子中に2個以上のアルコキシシリル基を含有し、かつ、アルコキシシリル基間を連結する基が-O-基;およびシロキサン結合を有する基以外の基である化合物、またはその部分加水分解縮合物(ただし、(a)に該当するものを除く。)である(以下、1分子中に2個以上のアルコキシシリル基を含有する接着性付与剤ともいう。)。(d)成分は、組成物の硬化物の、ガラス、金属、プラスチック等の基材への密着性を向上させる成分である。 <(d) Adhesion imparting agent>
The compound used as an adhesion-imparting agent in the curable composition of the present invention contains two or more alkoxysilyl groups in one molecule, and the groups connecting the alkoxysilyl groups are —O— groups; and A compound that is a group other than a group having a siloxane bond, or a partial hydrolysis condensate thereof (excluding those corresponding to (a)) (hereinafter, two or more alkoxysilyl groups in one molecule It is also referred to as a contained adhesiveness imparting agent.). Component (d) is a component that improves the adhesion of the cured product of the composition to substrates such as glass, metal and plastic.
(d)成分は、硬化性組成物の硬化の際にPFPE含有シラン化合物(a)のSi原子に結合した水酸基もしくは加水分解可能な基または架橋剤(b)のSi-OR2基と架橋反応(縮合反応)をする化合物である。(d)成分を含むことにより、組成物の硬化物のガラス、金属、プラスチック等の基材への密着性がより大きく向上する。
Component (d) undergoes a cross-linking reaction with hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a) or Si—OR 2 groups of the cross-linking agent (b) during curing of the curable composition. (condensation reaction). By including the component (d), the adhesiveness of the cured product of the composition to substrates such as glass, metal, and plastic is greatly improved.
(d)成分は、反応性官能基を有していてもよく、有していなくてもよい。(d)成分において、アルコキシシリル基間を連結する基は、-O-基;およびシロキサン結合を有する基以外の基である。基材への密着性の観点から、アルコキシシリル基間を連結する基は、窒素原子および/またはカルボニル基を含む基であることが好ましく、窒素原子および/またはカルボニル基に加え、さらに-O-基、アルケニレン基および/またはアルキレン基を含む基であることがより好ましい。
The component (d) may or may not have a reactive functional group. In the component (d), the group that connects the alkoxysilyl groups is an --O-- group; and a group other than a group having a siloxane bond. From the viewpoint of adhesion to the substrate, the group connecting the alkoxysilyl groups is preferably a group containing a nitrogen atom and/or a carbonyl group, and in addition to the nitrogen atom and/or the carbonyl group, -O- more preferably a group containing a group, an alkenylene group and/or an alkylene group.
(d)成分におけるアルコキシシリル基間を連結する基としては、
-O-C(=O)-C=C-C(=O)-O-、または
を含む基であることがさらに好ましく、
-(CH2)b-O-C(=O)-C=C-C(=O)-O-(CH2)b-、
または
(式中、R5は、各出現においてそれぞれ独立して、炭素数1~4のアルキル基であり、好ましくはメチル基またはエチル基であり、bおよびcは、各出現において独立して、1~8の整数であり、好ましくは1~4の整数である。)であることが特に好ましい。 (d) As the group connecting the alkoxysilyl groups in the component,
-O-C(=O)-C=C-C(=O)-O-, or
It is more preferably a group containing
-(CH 2 ) b -O-C(=O)-C=C-C(=O)-O-(CH 2 ) b -,
or
(wherein R 5 is independently at each occurrence an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group; b and c are at each occurrence independently 1 is an integer of ∼8, preferably an integer of 1 to 4).
-O-C(=O)-C=C-C(=O)-O-、または
を含む基であることがさらに好ましく、
-(CH2)b-O-C(=O)-C=C-C(=O)-O-(CH2)b-、
または
(式中、R5は、各出現においてそれぞれ独立して、炭素数1~4のアルキル基であり、好ましくはメチル基またはエチル基であり、bおよびcは、各出現において独立して、1~8の整数であり、好ましくは1~4の整数である。)であることが特に好ましい。 (d) As the group connecting the alkoxysilyl groups in the component,
-O-C(=O)-C=C-C(=O)-O-, or
It is more preferably a group containing
-(CH 2 ) b -O-C(=O)-C=C-C(=O)-O-(CH 2 ) b -,
or
(wherein R 5 is independently at each occurrence an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group; b and c are at each occurrence independently 1 is an integer of ∼8, preferably an integer of 1 to 4).
基材に対する密着性の観点から、(d)成分は、アルコキシシリル基含有イソシアヌレート化合物、アルコキシシリル基含有カルバシラトラン化合物、アルコキシシリル基含有フマル酸エステル化合物およびアルコキシシリル基含有アミン化合物からなる群より選択される化合物であることが好ましく、特に好ましくはアルコキシシリル基含有イソシアヌレート化合物またはアルコキシシリル基含有カルバシラトラン化合物である。
From the viewpoint of adhesion to substrates, component (d) is a group consisting of alkoxysilyl group-containing isocyanurate compounds, alkoxysilyl group-containing carbasilatrane compounds, alkoxysilyl group-containing fumarate ester compounds, and alkoxysilyl group-containing amine compounds. A more selected compound is preferable, and an alkoxysilyl group-containing isocyanurate compound or an alkoxysilyl group-containing carbasilatrane compound is particularly preferable.
アルコキシシリル基含有イソシアヌレート化合物としては、例えば、トリス(3-トリメトキシシリルプロピル)イソシアヌレート、トリス(3-トリエトキシシリルプロピル)イソシアヌレート等のトリス(3-トリアルコキシシリルプロピル)イソシアヌレートが挙げられる。
Examples of alkoxysilyl group-containing isocyanurate compounds include tris(3-trialkoxysilylpropyl) isocyanurates such as tris(3-trimethoxysilylpropyl) isocyanurate and tris(3-triethoxysilylpropyl) isocyanurate. be done.
アルコキシシリル基含有カルバシラトラン化合物としては、例えば、以下の化合物:
が挙げられる。 Examples of alkoxysilyl group-containing carbasilatrane compounds include the following compounds:
are mentioned.
が挙げられる。 Examples of alkoxysilyl group-containing carbasilatrane compounds include the following compounds:
are mentioned.
アルコキシシリル基含有フマル酸エステル化合物としては、例えば、ビス(3-トリメトキシシリルプロピル)フマレート、ビス(3-トリエトキシシリルプロピル)フマレート等が挙げられる。アルコキシシリル基含有アミン化合物としては、ビス(3-トリメトキシシリルプロピル)アミン、ビス(3-トリエトキシシリルプロピル)アミン、トリス(3-トリメトキシシリルプロピル)アミン、トリス(3-トリエトキシシリルプロピル)アミン等が挙げられる。
Examples of alkoxysilyl group-containing fumaric acid ester compounds include bis(3-trimethoxysilylpropyl) fumarate and bis(3-triethoxysilylpropyl) fumarate. Alkoxysilyl group-containing amine compounds include bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl) ) amines and the like.
(d)成分は、水素原子の一部がフッ素原子で置換された化合物であってもよい。(d)成分は、1種のみを用いてもよいし、2種以上を同時に用いてもよい。
The (d) component may be a compound in which some of the hydrogen atoms are substituted with fluorine atoms. (d) A component may use only 1 type and may use 2 or more types simultaneously.
PFPE含有シラン化合物(a)に対する(d)成分の含有量は、基材との密着性の観点から、0.01質量%以上であることが好ましく、より好ましくは0.02質量%以上、さらに好ましくは0.05質量%以上であり、また、30質量%以下であることが好ましく、より好ましくは20質量%以下、さらに好ましくは10質量%以下である。
The content of component (d) in the PFPE-containing silane compound (a) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of adhesion to the substrate. It is preferably 0.05% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
PFPE含有シラン化合物(a)に対する(d)成分の含有量は、基材との密着性の観点から、30質量%以下であることが好ましく、より好ましくは0.01~30質量%、さらに好ましくは0.02~20質量%、特に好ましくは0.05~10質量%である。
The content of component (d) relative to the silane compound (a) containing PFPE is preferably 30% by mass or less, more preferably 0.01 to 30% by mass, and still more preferably, from the viewpoint of adhesion to the substrate. is 0.02 to 20% by weight, particularly preferably 0.05 to 10% by weight.
(d)成分の含有量は、(b)および(d)成分の合計に対して0~90質量%であることが好ましく、より好ましくは1~70質量%、特に好ましくは1~50質量%である。
The content of component (d) is preferably 0 to 90% by mass, more preferably 1 to 70% by mass, and particularly preferably 1 to 50% by mass, based on the total of components (b) and (d). is.
(d)成分は、硬化性組成物中、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、例えば、アルコキシシリル基を1モル以上含むことができ、具体的には、2モル以上含むことができる。(d)成分は、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、例えば、アルコキシシリル基を30モル以下含むことができ、具体的には20モル以下含むことができ、より具体的には10モル以下含むことができる。
Component (d) may contain, for example, 1 mol or more of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of PFPE-containing silane compound (a) in the curable composition. Specifically, it can contain 2 mol or more. Component (d) can contain, for example, 30 mol or less of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a). It can contain 20 moles or less, more specifically, it can contain 10 moles or less.
(d)成分は、PFPE含有シラン化合物(a)のSi原子に結合した水酸基または加水分解可能な基1モルに対して、アルコキシシリル基を、例えば1~30モルの範囲で含むことができ、具体的には2~20モルの範囲含むことができる。
Component (d) can contain, for example, 1 to 30 mol of alkoxysilyl groups per 1 mol of hydroxyl groups or hydrolyzable groups bonded to Si atoms of the PFPE-containing silane compound (a), Specifically, it can be included in the range of 2 to 20 mol.
<PFPE含有シラン化合物(a2)>
本発明の硬化性組成物は、(a)以外のPFPE含有シラン化合物として、(a2)下記一般式(II):
[式中、R3、R4、R5、R6、R7、PFPE1、p、q、jは、上記定義のとおりである]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物をさらに含んでいてもよい。PFPE含有シラン化合物(a2)は、前記PFPE含有シラン化合物(a)と類似の構造を有するが、-PFPE1-C(=O)NR7-R6-NR7C(=O)-で示される構造を有さないものである。換言すると、前記式(I)におけるkを0とした場合が、一般式(II)で示されるPFPE含有シラン化合物(a2)に相当する。PFPE含有シラン化合物(a2)におけるそれぞれの基の意味するところは、先にPFPE含有シラン化合物(a)について記載した定義と同じであり、好ましい態様としても同じものを採用することができる。ただし、前記式(I)として表すことができる構造については、PFPE含有シラン化合物(a2)には含めない。好ましいPFPE含有シラン化合物(a2)としては、前記一般式(II)において、R5が2価のアルキレン基であり、jが2である、化合物である。このような、式(I)で示される化合物より短い分子構造を有するPFPE含有シラン化合物を硬化性組成物に配合することで、組成物の相溶性がより良好になり、硬化性組成物の取り扱い性がより良好になる。さらに、硬化物としたときに耐クラック性が優れた硬化性組成物を得ることができる。具体的なPFPE含有シラン化合物(a2)の非限定的な例としては、(a)として挙げた化合物から、-PFPE1-C(=O)NR7-R6-NR7C(=O)-に対応する繰り返し単位を除いた構造を有する化合物が挙げられる。すなわち、以下のような構造の化合物を挙げることができる。
(CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)29-(OCF2CF2)17-OCF2-CONH-CH2CH2CH2-Si(OCH3)3 <PFPE-containing silane compound (a2)>
The curable composition of the present invention contains (a2) the following general formula (II) as a PFPE-containing silane compound other than (a):
[Wherein, R 3 , R 4 , R 5 , R 6 , R 7 , PFPE 1 , p, q, and j are as defined above]
It may further contain a perfluoro(poly)ether group-containing silane compound represented by. The PFPE-containing silane compound (a2) has a structure similar to that of the PFPE-containing silane compound (a), but is represented by -PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-. It does not have a structure that can be In other words, the case where k in formula (I) is 0 corresponds to the PFPE-containing silane compound (a2) represented by general formula (II). The meaning of each group in the PFPE-containing silane compound (a2) is the same as the definition described above for the PFPE-containing silane compound (a), and the same can be adopted as preferred embodiments. However, the structure that can be represented by the above formula (I) is not included in the PFPE-containing silane compound (a2). A preferable PFPE-containing silane compound (a2) is a compound in which R 5 is a divalent alkylene group and j is 2 in the general formula (II). By blending such a PFPE-containing silane compound having a shorter molecular structure than the compound represented by formula (I) into the curable composition, the compatibility of the composition is improved, and the handling of the curable composition is improved. better sex. Furthermore, it is possible to obtain a curable composition having excellent crack resistance when cured. Non-limiting examples of specific PFPE-containing silane compounds (a2) include -PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O) from the compounds listed as (a). A compound having a structure excluding repeating units corresponding to - can be mentioned. That is, compounds having the following structures can be mentioned.
( CH3O )3Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) 29- ( OCF2CF2 ) 17 - OCF2 - CONH - CH2CH2CH2 - Si ( OCH3 ) 3
本発明の硬化性組成物は、(a)以外のPFPE含有シラン化合物として、(a2)下記一般式(II):
[式中、R3、R4、R5、R6、R7、PFPE1、p、q、jは、上記定義のとおりである]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物をさらに含んでいてもよい。PFPE含有シラン化合物(a2)は、前記PFPE含有シラン化合物(a)と類似の構造を有するが、-PFPE1-C(=O)NR7-R6-NR7C(=O)-で示される構造を有さないものである。換言すると、前記式(I)におけるkを0とした場合が、一般式(II)で示されるPFPE含有シラン化合物(a2)に相当する。PFPE含有シラン化合物(a2)におけるそれぞれの基の意味するところは、先にPFPE含有シラン化合物(a)について記載した定義と同じであり、好ましい態様としても同じものを採用することができる。ただし、前記式(I)として表すことができる構造については、PFPE含有シラン化合物(a2)には含めない。好ましいPFPE含有シラン化合物(a2)としては、前記一般式(II)において、R5が2価のアルキレン基であり、jが2である、化合物である。このような、式(I)で示される化合物より短い分子構造を有するPFPE含有シラン化合物を硬化性組成物に配合することで、組成物の相溶性がより良好になり、硬化性組成物の取り扱い性がより良好になる。さらに、硬化物としたときに耐クラック性が優れた硬化性組成物を得ることができる。具体的なPFPE含有シラン化合物(a2)の非限定的な例としては、(a)として挙げた化合物から、-PFPE1-C(=O)NR7-R6-NR7C(=O)-に対応する繰り返し単位を除いた構造を有する化合物が挙げられる。すなわち、以下のような構造の化合物を挙げることができる。
(CH3O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)29-(OCF2CF2)17-OCF2-CONH-CH2CH2CH2-Si(OCH3)3 <PFPE-containing silane compound (a2)>
The curable composition of the present invention contains (a2) the following general formula (II) as a PFPE-containing silane compound other than (a):
[Wherein, R 3 , R 4 , R 5 , R 6 , R 7 , PFPE 1 , p, q, and j are as defined above]
It may further contain a perfluoro(poly)ether group-containing silane compound represented by. The PFPE-containing silane compound (a2) has a structure similar to that of the PFPE-containing silane compound (a), but is represented by -PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O)-. It does not have a structure that can be In other words, the case where k in formula (I) is 0 corresponds to the PFPE-containing silane compound (a2) represented by general formula (II). The meaning of each group in the PFPE-containing silane compound (a2) is the same as the definition described above for the PFPE-containing silane compound (a), and the same can be adopted as preferred embodiments. However, the structure that can be represented by the above formula (I) is not included in the PFPE-containing silane compound (a2). A preferable PFPE-containing silane compound (a2) is a compound in which R 5 is a divalent alkylene group and j is 2 in the general formula (II). By blending such a PFPE-containing silane compound having a shorter molecular structure than the compound represented by formula (I) into the curable composition, the compatibility of the composition is improved, and the handling of the curable composition is improved. better sex. Furthermore, it is possible to obtain a curable composition having excellent crack resistance when cured. Non-limiting examples of specific PFPE-containing silane compounds (a2) include -PFPE 1 -C(=O)NR 7 -R 6 -NR 7 C(=O) from the compounds listed as (a). A compound having a structure excluding repeating units corresponding to - can be mentioned. That is, compounds having the following structures can be mentioned.
( CH3O )3Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) 29- ( OCF2CF2 ) 17 - OCF2 - CONH - CH2CH2CH2 - Si ( OCH3 ) 3
PFPE含有シラン化合物(a2)は、1種の化合物を単独で用いてもよく、2種以上の混合物として用いてもよい。PFPE含有シラン化合物(a)と(a2)とは、任意の割合で混合することができる。好ましくは、前記PFPE含有シラン化合物(a)と(a2)の質量比は、10:90~90:10の範囲であり、より好ましくは80:20~20:80の範囲である。この範囲とすることで、より相溶性と耐クラック性のバランスが取れた、良好な硬化性組成物とすることができる。
The PFPE-containing silane compound (a2) may be used singly or as a mixture of two or more. The PFPE-containing silane compounds (a) and (a2) can be mixed in any ratio. Preferably, the weight ratio of said PFPE-containing silane compounds (a) and (a2) ranges from 10:90 to 90:10, more preferably from 80:20 to 20:80. By setting the content within this range, it is possible to obtain a good curable composition with well-balanced compatibility and crack resistance.
特に好ましい態様において、PFPE含有シラン化合物(a2)は、R5が2価のアルキレン基であり、jが2であり、pおよびqが共に0である、化合物である。
In a particularly preferred embodiment, the PFPE-containing silane compound (a2) is a compound in which R5 is a divalent alkylene group, j is 2 , and p and q are both 0.
PFPE含有シラン化合物(a2)の一態様は、以下の式(A2)、(B2)、(C2)または(D2)で表される少なくとも1種の化合物である。
上記式(A2)、(B2)、(C2)または(D2)で表される化合物は、(a)について先に述べた式(A)、(B)、(C)または(D)で表されるPFPE含有シラン化合物において、rが0である場合の化合物に相当する。また、各式中に存在する基の示す内容も、前記式(A)、(B)、(C)または(D)において説明されたとおりである。 One aspect of the PFPE-containing silane compound (a2) is at least one compound represented by the following formula (A2), (B2), (C2) or (D2).
The compound represented by the above formula (A2), (B2), (C2) or (D2) is represented by the formula (A), (B), (C) or (D) described above for (a). In the PFPE-containing silane compound that is used, it corresponds to the compound where r is 0. Further, the contents of the groups present in each formula are also as explained in the above formula (A), (B), (C) or (D).
上記式(A2)、(B2)、(C2)または(D2)で表される化合物は、(a)について先に述べた式(A)、(B)、(C)または(D)で表されるPFPE含有シラン化合物において、rが0である場合の化合物に相当する。また、各式中に存在する基の示す内容も、前記式(A)、(B)、(C)または(D)において説明されたとおりである。 One aspect of the PFPE-containing silane compound (a2) is at least one compound represented by the following formula (A2), (B2), (C2) or (D2).
The compound represented by the above formula (A2), (B2), (C2) or (D2) is represented by the formula (A), (B), (C) or (D) described above for (a). In the PFPE-containing silane compound that is used, it corresponds to the compound where r is 0. Further, the contents of the groups present in each formula are also as explained in the above formula (A), (B), (C) or (D).
(g)PFPE含有シラン化合物(a)(a2)以外のPFPE含有シラン化合物
硬化性組成物は、さらに、PFPE含有シラン化合物(a)または(a2)以外のPFPEを含有するシラン化合物を含んでいてもよい。本発明の硬化性組成物は、例えば、以下の式(G-1)、(G-2)、(G-3)または(G-4)で表される化合物(以下において、「PFPE含有シラン化合物(b)」と称することがある)を含み得る。
(g) PFPE-containing silane compound (a) other than (a2) The curable composition further comprises a PFPE-containing silane compound (a) or a PFPE-containing silane compound other than (a2). good too. The curable composition of the present invention is, for example, a compound represented by the following formula (G-1), (G-2), (G-3) or (G-4) (hereinafter referred to as "PFPE-containing silane compound (b)”).
硬化性組成物は、さらに、PFPE含有シラン化合物(a)または(a2)以外のPFPEを含有するシラン化合物を含んでいてもよい。本発明の硬化性組成物は、例えば、以下の式(G-1)、(G-2)、(G-3)または(G-4)で表される化合物(以下において、「PFPE含有シラン化合物(b)」と称することがある)を含み得る。
式(G-1)、(G-2)、(G-3)および(G-4)において、式(A)、(B)、(C)および(D)に関する記載と重複する部分については、記載を省略することがある。
In formulas (G-1), (G-2), (G-3) and (G-4), the parts that overlap with the descriptions of formulas (A), (B), (C) and (D) , may be omitted.
上記式中、Rf2は、各出現において独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16のアルキル基を表す。
In the above formula, Rf 2 independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
上記1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16のアルキル基における「炭素原子数1~16のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素原子数1~6、特に炭素原子数1~3のアルキル基であり、より好ましくは直鎖の炭素原子数1~3のアルキル基である。
The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms may be linear or branched. preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms is.
上記Rf2は、好ましくは、1個またはそれ以上のフッ素原子により置換されている炭素原子数1~16のアルキル基であり、より好ましくはCF2H-C1-15フルオロアルキレン基またはC1-16パーフルオロアルキル基であり、さらに好ましくはC1-16パーフルオロアルキル基である。
Rf 2 above is preferably an alkyl group having 1 to 16 carbon atoms substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group or C 1 -16 perfluoroalkyl group, more preferably C 1-16 perfluoroalkyl group.
該炭素原子数1~16のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素原子数1~6、特に炭素原子数1~3のパーフルオロアルキル基であり、より好ましくは直鎖の炭素原子数1~3のパーフルオロアルキル基、具体的には-CF3、-CF2CF3、または-CF2CF2CF3である。
The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched and having 1 to 6 carbon atoms, especially C 1 to 6 carbon atoms. a perfluoroalkyl group having a number of 1 to 3, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF3 .
式(G-1)において、kは、1~9の整数であり、k’は、1~9の整数である。kおよびk’は、X11’の価数に応じて変化し得る。式(G-1)において、kおよびk’の和は、X11’の価数と同じである。例えば、X11’が10価の有機基である場合、kおよびk’の和は10であり、例えばkが9かつk’が1、kが5かつk’が5、またはkが1かつk’が9となり得る。また、X11’が2価の有機基である場合、kおよびk’は1である。式(G-1)においては、X11’が単結合である場合、kおよびk’は1である。
In formula (G-1), k is an integer of 1-9, and k' is an integer of 1-9. k and k' can vary depending on the valence of X 11' . In formula (G-1), the sum of k and k' is the same as the valence of X 11' . For example, when X 11′ is a decavalent organic group, the sum of k and k′ is 10, such as k is 9 and k′ is 1, k is 5 and k′ is 5, or k is 1 and k' can be nine. Also, k and k' are 1 when X 11' is a divalent organic group. In formula (G-1), k and k' are 1 when X 11' is a single bond.
上記X11’は、好ましくは2~7価であり、より好ましくは2~4価であり、さらに好ましくは2価の有機基である。
X 11′ is preferably divalent to heptavalent, more preferably divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X11’は2~4価の有機基であり、kは1~3であり、k’は1である。
In one aspect, X 11′ is a divalent to tetravalent organic group, k is 1 to 3, and k′ is 1.
別の態様において、X11’は2価の有機基であり、kは1であり、k’は1である。
In another embodiment, X 11' is a divalent organic group, k is 1 and k' is 1.
上記式(G-1)において、i’は、各出現においてそれぞれ独立して、0~3の整数であり、好ましくは0~2であり、より好ましくは0である。好ましくは、式中、少なくとも1つのi’が0~2の整数であり、即ち、すべてのi’が同時に3になることはない。換言すれば、式(G-1)中、少なくとも1つはOR3が存在する。
In formula (G-1) above, each occurrence of i′ is independently an integer of 0 to 3, preferably 0 to 2, and more preferably 0. Preferably, at least one i′ in the formula is an integer between 0 and 2, ie not all i′ are 3 at the same time. In other words, at least one OR 3 is present in formula (G-1).
式(G-2)において、kは、1~9の整数であり、k’は、1~9の整数である。kおよびk’は、X12’の価数に応じて変化し得る。式(G-2)において、kおよびk’の和は、X12’の価数と同じである。例えば、X12’が10価の有機基である場合、kおよびk’の和は10であり、例えばkが9かつk’が1、kが5かつk’が5、またはkが1かつk’が9となり得る。また、X12’が2価の有機基である場合、kおよびk’は1である。式(G-2)において、X12’が単結合である場合、kおよびk’は1である。
In formula (G-2), k is an integer of 1-9, and k' is an integer of 1-9. k and k' can vary depending on the valence of X12 ' . In formula (G-2), the sum of k and k' is the same as the valence of X 12' . For example, when X 12′ is a decavalent organic group, the sum of k and k′ is 10, such as k is 9 and k′ is 1, k is 5 and k′ is 5, or k is 1 and k' can be nine. Also, k and k' are 1 when X 12' is a divalent organic group. In formula (G-2), k and k' are 1 when X 12' is a single bond.
上記X12’は、好ましくは2~7価、より好ましくは2~4価、さらに好ましくは2価の有機基である。
X 12′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X12’は2~4価の有機基であり、kは1~3であり、k’は1である。
In one aspect, X 12′ is a divalent to tetravalent organic group, k is 1 to 3, and k′ is 1.
別の態様において、X12’は2価の有機基であり、kは1であり、k’は1である。
In another embodiment, X 12' is a divalent organic group, k is 1 and k' is 1.
式(G-2)において、i’は、(G-1)の記載と同意義である。
In formula (G-2), i' has the same meaning as described in (G-1).
上記式(G-3)において、k1は、1~9の整数であり、k1’は、1~9の整数である。k1およびk1’は、X13’の価数に応じて変化し得る。式(G-3)において、k1およびk1’の和は、X13’の価数と同じである。例えば、X13’が10価の有機基である場合、k1およびk1’の和は10であり、例えばk1が9かつk1’が1、k1が5かつk1’が5、またはk1が1かつk1’が9となり得る。また、X13’が2価の有機基である場合、k1およびk1’は1である。式(G-3)において、X13’が単結合である場合、k1およびk1’は1である。
In the above formula (G-3), k1 is an integer of 1-9, and k1' is an integer of 1-9. k1 and k1' can vary depending on the valence of X13 ' . In formula (G-3), the sum of k1 and k1' is the same as the valence of X13 ' . For example, when X 13′ is a decavalent organic group, the sum of k1 and k1′ is 10, such as k1 is 9 and k1′ is 1, k1 is 5 and k1′ is 5, or k1 is 1 and k1' can be nine. Also, k1 and k1' are 1 when X 13' is a divalent organic group. In formula (G-3), k1 and k1' are 1 when X 13' is a single bond.
上記X13’は、好ましくは2~7価、より好ましくは2~4価、さらに好ましくは2価の有機基である。
The above X 13′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X13’は2~4価の有機基であり、k1は1~3であり、k1’は1である。
In one aspect, X 13′ is a divalent to tetravalent organic group, k1 is 1 to 3, and k1′ is 1.
別の態様において、X13’は2価の有機基であり、k1は1であり、k1’は1である。
In another embodiment, X 13' is a divalent organic group, k1 is 1 and k1' is 1.
上記式(G-4)において、k2は、1~9の整数であり、k2’は、1~9の整数である。k2およびk2’は、X14’の価数に応じて変化し得る。式(G-4)において、k2およびk2’の和は、X14’の価数と同じである。例えば、X14’が10価の有機基である場合、k2およびk2’の和は10であり、例えばk2が9かつk2’が1、k2が5かつk2’が5、またはk2が1かつk2’が9となり得る。また、X14’が2価の有機基である場合、k2およびk2’は1である。式(G-4)において、X14’が単結合である場合、k2およびk2’は1である。
In the above formula (G-4), k2 is an integer of 1-9, and k2' is an integer of 1-9. k2 and k2' can vary depending on the valence of X14 ' . In formula (G-4), the sum of k2 and k2' is the same as the valence of X14 ' . For example, when X 14′ is a decavalent organic group, the sum of k2 and k2′ is 10, such as k2 is 9 and k2′ is 1, k2 is 5 and k2′ is 5, or k2 is 1 and k2' can be nine. Also, k2 and k2' are 1 when X 14' is a divalent organic group. In formula (G-4), k2 and k2' are 1 when X 14' is a single bond.
上記X14’は、好ましくは2~7価、より好ましくは2~4価、さらに好ましくは2価の有機基である。
X 14′ is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, still more preferably a divalent organic group.
一の態様において、X14’は2~4価の有機基であり、k2は1~3であり、k2’は1である。
In one embodiment, X 14' is a divalent to tetravalent organic group, k2 is 1-3, and k2' is 1.
別の態様において、X14’は2価の有機基であり、k2は1であり、k2’は1である。
In another embodiment, X 14' is a divalent organic group, k2 is 1 and k2' is 1.
一の態様において、PFPE含有シラン化合物(b)は、式(G-1)、(G-3)または(G-4)で表される化合物であり得る。このようなシラン化合物を用いることにより、基材への密着性をより向上させることができる。
In one embodiment, the PFPE-containing silane compound (b) can be a compound represented by formula (G-1), (G-3) or (G-4). Adhesion to the substrate can be further improved by using such a silane compound.
一の態様において、PFPE含有シラン化合物(b)は、末端に、水酸基または加水分解可能な基を有するSi原子を2個以上、好ましくは3個以上有する。
In one aspect, the PFPE-containing silane compound (b) has two or more, preferably three or more Si atoms having hydroxyl groups or hydrolyzable groups at the terminals.
一の態様において、硬化性組成物中、式(A)、(B)、(C)および(D)で表される化合物(以下、「(1)成分」ともいう)と、式(G-1)、(G-2)、(G-3)および(G-4)で表される化合物(以下、「(2)成分」ともいう)との合計に対して、式(G-1)、(G-2)、(G-3)および(G-4)で表される化合物の量は、0.1モル%以上35モル%以下である。(1)成分および(2)成分の合計に対する式(G-1)、(G-2)、(G-3)および(G-4)で表される化合物の含有量の下限は、好ましくは0.1モル%、より好ましくは0.2モル%、さらに好ましくは0.5モル%、さらにより好ましくは1モル%、特に好ましくは2モル%、特別には5モル%であり得る。(1)成分および(2)成分の合計に対する式(G-1)、(G-2)、(G-3)および(G-4)で表される化合物の含有量の上限は、好ましくは35モル%、より好ましくは30モル%、さらに好ましくは20モル%、さらにより好ましくは15モル%または10モル%であり得る。(1)成分および(2)成分の合計に対する式(G-1)、(G-2)、(G-3)および(G-4)で表される化合物の含有量は、好ましくは0.1モル%以上30モル%以下、より好ましくは0.1モル%以上20モル%以下、さらに好ましくは0.2モル%以上10モル%以下、さらにより好ましくは0.5モル%以上10モル%以下、特に好ましくは1モル%以上10モル%以下、例えば2モル%以上10モル%以下または5モル%以上10モル%以下である。(1)成分および(2)成分の含有量をかかる範囲とすることにより、硬化性組成物は、摩擦耐久性の良好な硬化物の形成に寄与し得る。
In one aspect, in the curable composition, compounds represented by formulas (A), (B), (C) and (D) (hereinafter also referred to as "(1) component"), and formula (G- 1), compounds represented by (G-2), (G-3) and (G-4) (hereinafter also referred to as “(2) component”), the formula (G-1) , (G-2), (G-3) and (G-4) is 0.1 mol % or more and 35 mol % or less. The lower limit of the content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the total of components (1) and (2) is preferably It can be 0.1 mol %, more preferably 0.2 mol %, still more preferably 0.5 mol %, even more preferably 1 mol %, particularly preferably 2 mol %, especially 5 mol %. The upper limit of the content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the total of components (1) and (2) is preferably It can be 35 mol %, more preferably 30 mol %, even more preferably 20 mol %, still more preferably 15 mol % or 10 mol %. The content of the compounds represented by formulas (G-1), (G-2), (G-3) and (G-4) with respect to the sum of components (1) and (2) is preferably 0.00. 1 mol % or more and 30 mol % or less, more preferably 0.1 mol % or more and 20 mol % or less, still more preferably 0.2 mol % or more and 10 mol % or less, still more preferably 0.5 mol % or more and 10 mol % Below, it is particularly preferably 1 mol % or more and 10 mol % or less, for example, 2 mol % or more and 10 mol % or less, or 5 mol % or more and 10 mol % or less. By setting the contents of component (1) and component (2) within such ranges, the curable composition can contribute to the formation of a cured product with good friction durability.
硬化性組成物中、(1)成分と(2)成分の組み合わせは、好ましくは式(A)で表される化合物と式(G-1)で表される化合物の組み合わせ、式(B)で表される化合物と式(G-2)で表される化合物の組み合わせ、式(C)で表される化合物と式(G-3)で表される化合物の組み合わせ、または式(D)で表される化合物と式(G-4)で表される化合物の組み合わせである。
In the curable composition, the combination of the components (1) and (2) is preferably a combination of the compound represented by the formula (A) and the compound represented by the formula (G-1), the formula (B) A combination of a compound represented by the formula (G-2) and a compound represented by the formula (G-2), a combination of a compound represented by the formula (C) and a compound represented by the formula (G-3), or a combination of the compound represented by the formula (D) and a compound represented by Formula (G-4).
式(A)および式(G-1)で表される化合物は、好ましくはtが2以上、より好ましくは2~10の整数、さらに好ましくは2~6の整数である。tを2以上とすることにより、OR3を有するSi原子が複数存在することになり、硬化性組成物により形成される硬化物において、より高い耐久性(例えば摩擦耐久性)を得ることができる。
In the compounds represented by formula (A) and formula (G-1), t is preferably 2 or more, more preferably an integer of 2-10, and still more preferably an integer of 2-6. By setting t to 2 or more, a plurality of Si atoms having OR 3 will be present, and higher durability (for example, friction durability) can be obtained in the cured product formed from the curable composition. .
式(C)および式(G-3)で表される化合物は、好ましくはl2が2または3、より好ましくは3である。
In the compounds represented by formula (C) and formula (G-3), l2 is preferably 2 or 3, more preferably 3.
好ましい態様において、式(C)で表される化合物は、末端に、-Si-(Z3-SiR72
3)2または-Si-(Z3-SiR72
3)3で表される構造を有し、さらに好ましくは-Si-(Z3-SiR72
3)3で表される構造を有し;式(G-3)で表される化合物は、末端に、-Si-(Z3-SiR72
3)2または、-Si-(Z3-SiR72
3)3で表される構造を有し、さらに好ましくは-Si-(Z3-SiR72
3)3で表される構造を有する。末端をかかる構造とすることにより、硬化性組成物により形成される硬化物において、より高い耐久性(例えば摩擦耐久性)を得ることができる。
上記-Si-(Z3-SiR72 3)2で表される基としては、具体的には、
-Si-Ra 2Rb m1Rc n1において、Raが-Z3-SiR72 3で表される基であり、m1およびn1の和が1である、
-Si-Ra 2Rb m2Rc n2において、Raが-Z3-SiR72 3で表される基であり、m2およびn2の和が1である、または
-Si-R71 2R72 q1R73 r1において、R71の末端が-Z3-SiR72 3で表される基であり、q1およびr1の和が1である、を挙げることができる。 In a preferred embodiment, the compound represented by formula (C) has a structure represented by -Si-(Z 3 -SiR 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 at the terminal. and more preferably have a structure represented by -Si- ( Z 3 -SiR 72 3 ) 3 ; 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 , more preferably -Si-(Z 3 -SiR 72 3 ) 3 . By making the ends have such a structure, it is possible to obtain higher durability (for example, friction durability) in a cured product formed from the curable composition.
Specifically, the group represented by —Si—(Z 3 —SiR 72 3 ) 2 is
-Si-R a 2 R b m1 R c n1 , wherein R a is a group represented by -Z 3 -SiR 72 3 , and the sum of m1 and n1 is 1;
-Si-R a 2 R b m2 R c n2 in which R a is a group represented by -Z 3 -SiR 72 3 and the sum of m2 and n2 is 1, or -Si-R 71 2 R In 72 q1 R 73 r1 , the terminal of R 71 is a group represented by —Z 3 —SiR 72 3 , and the sum of q1 and r1 is 1.
上記-Si-(Z3-SiR72 3)2で表される基としては、具体的には、
-Si-Ra 2Rb m1Rc n1において、Raが-Z3-SiR72 3で表される基であり、m1およびn1の和が1である、
-Si-Ra 2Rb m2Rc n2において、Raが-Z3-SiR72 3で表される基であり、m2およびn2の和が1である、または
-Si-R71 2R72 q1R73 r1において、R71の末端が-Z3-SiR72 3で表される基であり、q1およびr1の和が1である、を挙げることができる。 In a preferred embodiment, the compound represented by formula (C) has a structure represented by -Si-(Z 3 -SiR 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 at the terminal. and more preferably have a structure represented by -Si- ( Z 3 -SiR 72 3 ) 3 ; 72 3 ) 2 or -Si-(Z 3 -SiR 72 3 ) 3 , more preferably -Si-(Z 3 -SiR 72 3 ) 3 . By making the ends have such a structure, it is possible to obtain higher durability (for example, friction durability) in a cured product formed from the curable composition.
Specifically, the group represented by —Si—(Z 3 —SiR 72 3 ) 2 is
-Si-R a 2 R b m1 R c n1 , wherein R a is a group represented by -Z 3 -SiR 72 3 , and the sum of m1 and n1 is 1;
-Si-R a 2 R b m2 R c n2 in which R a is a group represented by -Z 3 -SiR 72 3 and the sum of m2 and n2 is 1, or -Si-R 71 2 R In 72 q1 R 73 r1 , the terminal of R 71 is a group represented by —Z 3 —SiR 72 3 , and the sum of q1 and r1 is 1.
式(B)および式(G-4)で表される化合物は、好ましくはm4が2または3、より好ましくは3である。
In the compounds represented by formula (B) and formula (G-4), m4 is preferably 2 or 3, more preferably 3.
好ましい態様において、式(D)で表される化合物は、末端に、-C-(Y-SiR85
3)2(具体的には、-C-(Y-SiR85
3)2R83)または-C-(Y-SiR85
3)3構造を有し、さらに好ましくは-C-(Y-SiR85
3)3構造を有し;式(G-4)で表される化合物は、末端に、-C-(Y-SiR85
3)2(具体的には、-C-(Y-SiR85
3)2R83)または-C-(Y-SiR85
3)3構造を有し、さらに好ましくは-C-(Y-SiR85
3)3構造を有する。末端をかかる構造とすることにより、硬化性組成物は、より高い耐久性(例えば摩擦耐久性)を有する硬化物の形成に寄与し得る。
In a preferred embodiment, the compound represented by formula (D) is terminally end-C-(Y-SiR 85 3 ) 2 (specifically, -C-(Y-SiR 85 3 ) 2 R 83 ) or -C-(Y-SiR 85 3 ) 3 structure, more preferably -C-(Y-SiR 85 3 ) 3 structure; , -C-(Y-SiR 85 3 ) 2 (specifically, -C-(Y-SiR 85 3 ) 2 R 83 ) or -C-(Y-SiR 85 3 ) 3 structure, and It preferably has a —C—(Y—SiR 85 3 ) 3 structure. By having such a structure at the end, the curable composition can contribute to the formation of a cured product having higher durability (for example, abrasion resistance).
PFPE含有シラン化合物(b)としては、下記式(G-5)で表される化合物であることもできる。
The PFPE-containing silane compound (b) can also be a compound represented by the following formula (G-5).
式(G-5)中、ORg3は、加水分解可能な基を表す。Rg3は、各出現においてそれぞれ独立して、CH3-、C2H5-、C3H7-、CF3CH2-、CH3CO-、CH2=C(CH3)-、CH3CH2C(CH3)=N-、(CH3)2N-、(C2H5)2N-、CH2=C(OC2H5)-、(CH3)2C=C(OC8H17)-、または
であることが好ましく、より好ましくは、CH3-またはC2H5-である。 In formula (G-5), OR g3 represents a hydrolyzable group. R g3 is independently at each occurrence CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, CH 2 =C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N-, (CH 3 ) 2 N-, (C 2 H 5 ) 2 N-, CH 2 =C(OC 2 H 5 )-, (CH 3 ) 2 C=C (OC 8 H 17 )-, or
is preferably CH 3 — or C 2 H 5 —.
であることが好ましく、より好ましくは、CH3-またはC2H5-である。 In formula (G-5), OR g3 represents a hydrolyzable group. R g3 is independently at each occurrence CH 3 —, C 2 H 5 —, C 3 H 7 —, CF 3 CH 2 —, CH 3 CO—, CH 2 =C(CH 3 )—, CH 3 CH 2 C(CH 3 )=N-, (CH 3 ) 2 N-, (C 2 H 5 ) 2 N-, CH 2 =C(OC 2 H 5 )-, (CH 3 ) 2 C=C (OC 8 H 17 )-, or
is preferably CH 3 — or C 2 H 5 —.
式(G-5)中、ε3は、2または3である。
In formula (G-5), ε3 is 2 or 3.
Rf1は1価のフッ素化(ポリ)エーテル基である。Rf1としては、上記PFPE1のCF2末端にCF3O-、CF3CF2O-、CF3CF2CF2O-、(CF3)2CFO-、またはCF3CF2CF2CF2O-等が結合された構造のものが例示される。
Rf 1 is a monovalent fluorinated (poly)ether group. Rf 1 includes CF 3 O—, CF 3 CF 2 O—, CF 3 CF 2 CF 2 O—, (CF 3 ) 2 CFO—, or CF 3 CF 2 CF 2 CF at the CF 2 end of PFPE 1 . Structures in which 2 O- and the like are bonded are exemplified.
Rg5は、2価の有機基である。2価の有機基は上記と同意義である。Rg5は、例えば、酸素原子、窒素原子、ケイ素原子およびイオウ原子の1種または2種以上を含有していてもよく、アミド結合またはスルホンアミド結合を含有してもよい、置換または非置換の2価の炭化水素基であり得る。該2価の炭化水素基は、炭素原子数2~20であることが好ましい。ここで、酸素原子、窒素原子、ケイ素原子またはイオウ原子を介在せず、かつアミド結合またはスルホンアミド結合を含有しない、置換または非置換の2価の炭化水素基の具体例としては、エチレン基、プロピレン基、メチルエチレン基、ブチレン基、ヘキサメチレン基等のアルキレン基;シクロヘキシレン基等のシクロアルキレン基;フェニレン基、トリレン基、キシリレン基、ナフチレン基、ビフェニレン基等のアリーレン基;これらアルキレン基とアリーレン基との組み合わせ;および、これらアルキレン基およびアリーレン基の水素原子の一部または全部がハロゲン原子で置換された基が挙げられる。
R g5 is a divalent organic group. The divalent organic group has the same meaning as above. R g5 may contain, for example, one or more of an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, and may contain an amide bond or a sulfonamide bond, a substituted or unsubstituted It can be a divalent hydrocarbon group. The divalent hydrocarbon group preferably has 2 to 20 carbon atoms. Here, specific examples of substituted or unsubstituted divalent hydrocarbon groups that do not contain an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom and do not contain an amide bond or a sulfonamide bond include an ethylene group, Alkylene groups such as a propylene group, a methylethylene group, a butylene group and a hexamethylene group; Cycloalkylene groups such as a cyclohexylene group; Arylene groups such as a phenylene group, a tolylene group, a xylylene group, a naphthylene group and a biphenylene group; combinations with arylene groups; and groups in which some or all of the hydrogen atoms of these alkylene groups and arylene groups are substituted with halogen atoms.
上記2価の炭化水素基において、酸素原子は-O-として、窒素原子は-NRg51-(Rg51は、水素原子または炭素原子数1~10のアルキル基またはアリール基)または-N=として、ケイ素原子は-SiRg52Rg53-(Rg52およびRg53は、各出現においてそれぞれ独立して、炭素原子数1~10のアルキル基またはアリール基)として、イオウ原子は-S-として含まれ得る。また、上記2価の炭化水素基において、アミド結合は-C(=O)NRg51-(Rg51は上記と同じ)として、またスルホンアミド結合は-SO2NRg51-(Rg51は上記と同じ)として含まれ得る。このような2価の炭化水素基の具体例としては、下記のものが挙げられる。なお、下記式でMeはメチル基、Phはフェニル基を表し、また下記の各式において、左側にRf1基が結合する。
In the above divalent hydrocarbon group, the oxygen atom is —O—, the nitrogen atom is —NR g51 — (R g51 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group) or —N= , a silicon atom is included as —SiR g52 R g53 — (R g52 and R g53 are each independently at each occurrence an alkyl or aryl group having 1 to 10 carbon atoms), and a sulfur atom is included as —S—. obtain. In the above divalent hydrocarbon group, the amide bond is -C(=O)NR g51 - (R g51 is the same as above), and the sulfonamide bond is -SO 2 NR g51 - (R g51 is the same as above). same). Specific examples of such divalent hydrocarbon groups include the following. In the following formulas, Me represents a methyl group, Ph represents a phenyl group, and in each of the following formulas, one Rf group is bonded to the left side.
(e)無機充填剤
本発明の硬化性組成物は、組成物の流動性を抑制するために無機充填剤をさらに含んでもよい。無機充填剤としては、一次粒子径が0.01~0.1μmである無機充填剤が好ましくは用いられる。(e)無機充填剤の一次粒子径を上記範囲とすることにより、塗布後に組成物が流れ出さず、流動性が抑えられた組成物を得ることができる。(e)無機充填剤の一次粒子径は、0.02~0.08μmであることが好ましく、より好ましくは0.03~0.07μmである。一次粒子径の測定値は、電子顕微鏡法による測定値である。 (e) Inorganic filler The curable composition of the present invention may further contain an inorganic filler in order to suppress fluidity of the composition. As the inorganic filler, an inorganic filler having a primary particle size of 0.01 to 0.1 μm is preferably used. (e) By setting the primary particle size of the inorganic filler within the above range, it is possible to obtain a composition with suppressed fluidity without the composition flowing out after application. (e) The primary particle size of the inorganic filler is preferably 0.02 to 0.08 μm, more preferably 0.03 to 0.07 μm. The measured value of the primary particle size is the measured value by electron microscopy.
本発明の硬化性組成物は、組成物の流動性を抑制するために無機充填剤をさらに含んでもよい。無機充填剤としては、一次粒子径が0.01~0.1μmである無機充填剤が好ましくは用いられる。(e)無機充填剤の一次粒子径を上記範囲とすることにより、塗布後に組成物が流れ出さず、流動性が抑えられた組成物を得ることができる。(e)無機充填剤の一次粒子径は、0.02~0.08μmであることが好ましく、より好ましくは0.03~0.07μmである。一次粒子径の測定値は、電子顕微鏡法による測定値である。 (e) Inorganic filler The curable composition of the present invention may further contain an inorganic filler in order to suppress fluidity of the composition. As the inorganic filler, an inorganic filler having a primary particle size of 0.01 to 0.1 μm is preferably used. (e) By setting the primary particle size of the inorganic filler within the above range, it is possible to obtain a composition with suppressed fluidity without the composition flowing out after application. (e) The primary particle size of the inorganic filler is preferably 0.02 to 0.08 μm, more preferably 0.03 to 0.07 μm. The measured value of the primary particle size is the measured value by electron microscopy.
下記流動性試験によって測定される流動性値は、組成物の流動性の指標である。組成物の流動性値は、好ましくは15mm以下であり、より好ましくは10mm以下、特に好ましくは5mm以下である。流動性値が上記範囲であると、塗布後に組成物が流れ出さず、流動性が抑えられた組成物とすることができる。組成物の流動性値が15mmを超えると塗布時に組成物が広がりすぎ、また、組成物の硬化物のシール性に劣りやすい。
流動性試験:硬化性組成物を、45度に傾斜させたアルミニウム板に0.1g塗布し、10秒後に流れた距離(mm)を測定し、その値を流動性値とする。 The fluidity value measured by the fluidity test described below is an indicator of the fluidity of the composition. The fluidity value of the composition is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less. When the fluidity value is within the above range, the composition does not flow out after application, and a composition with suppressed fluidity can be obtained. If the fluidity value of the composition exceeds 15 mm, the composition spreads excessively during application, and the cured product of the composition tends to have poor sealability.
Fluidity test: 0.1 g of the curable composition was applied to an aluminum plate inclined at 45 degrees, and the distance (mm) flowed after 10 seconds was measured, and the value was taken as the fluidity value.
流動性試験:硬化性組成物を、45度に傾斜させたアルミニウム板に0.1g塗布し、10秒後に流れた距離(mm)を測定し、その値を流動性値とする。 The fluidity value measured by the fluidity test described below is an indicator of the fluidity of the composition. The fluidity value of the composition is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less. When the fluidity value is within the above range, the composition does not flow out after application, and a composition with suppressed fluidity can be obtained. If the fluidity value of the composition exceeds 15 mm, the composition spreads excessively during application, and the cured product of the composition tends to have poor sealability.
Fluidity test: 0.1 g of the curable composition was applied to an aluminum plate inclined at 45 degrees, and the distance (mm) flowed after 10 seconds was measured, and the value was taken as the fluidity value.
組成物の流動性値は、(a)PFPE含有シラン化合物の種類、配合量;充填剤の種類、粒子径、配合量;溶剤の添加の有無、その配合量等によって調整することができる。中でも、充填剤の一次粒子径が組成物の流動性値に与える影響は大きく、(e)一次粒子径が0.01~0.1μmである無機充填剤を組成物に配合することにより、組成物の流動性値を15mm以下とすることが容易となる。
The fluidity value of the composition can be adjusted by (a) the type and blending amount of the PFPE-containing silane compound; the type, particle size, and blending amount of the filler; the presence or absence of addition of a solvent, the blending amount, and the like. Among them, the primary particle size of the filler has a large effect on the fluidity value of the composition. It becomes easy to set the fluidity value of the product to 15 mm or less.
(e)無機充填剤としては、煙霧質酸化チタン等の補強性充填剤;シリカ、珪藻土、酸化鉄、酸化亜鉛、酸化チタン、酸化アルミニウム等の酸化物;炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛等の炭酸塩;アルミノケイ酸、ケイ酸カルシウム、マイカ等のケイ酸塩;タルク;カーボンブラック、銅粉、ニッケル粉等の導電性充填剤;これらの表面をトリメチルクロロシラン、ジメチルジクロロシラン、ヘキサメチルジシラザン、オクタメチルシクロテトラシロキサン等の疎水化剤で処理したものが挙げられる。これらのなかで、(e)無機充填剤は、カーボンブラックまたは炭酸カルシウムであることが好ましく、より好ましくはカーボンブラックである。
(e) Inorganic fillers include reinforcing fillers such as fumed titanium oxide; oxides such as silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, and aluminum oxide; calcium carbonate, magnesium carbonate, zinc carbonate, etc. carbonates; silicates such as aluminosilicate, calcium silicate and mica; talc; conductive fillers such as carbon black, copper powder and nickel powder; Examples include those treated with a hydrophobizing agent such as octamethylcyclotetrasiloxane. Among these, (e) the inorganic filler is preferably carbon black or calcium carbonate, more preferably carbon black.
(e)成分の配合量は、硬化性組成物の流動性試験による流動性値が15mm以下となるように、適宜調整されることが好ましい。具体的には、(e)無機充填剤は、組成物中、(a)PFPE含有シラン化合物100質量部に対して、1~500質量部含まれることが好ましく、好ましくは1~200質量部、より好ましくは1~100質量部である。
The blending amount of component (e) is preferably adjusted appropriately so that the fluidity value of the curable composition in a fluidity test is 15 mm or less. Specifically, (e) the inorganic filler is preferably contained in the composition in an amount of 1 to 500 parts by mass, preferably 1 to 200 parts by mass, based on 100 parts by mass of (a) the silane compound containing PFPE. More preferably, it is 1 to 100 parts by mass.
(e)無機充填剤は、1種のみを用いてもよいし、2種以上を同時に用いてもよい。
(e) Only one type of inorganic filler may be used, or two or more types may be used at the same time.
(f)表面処理シリカ
本発明の硬化性組成物は、無機充填剤としてさらに(f)表面処理シリカを含んでいてもよい。表面処理シリカは、組成物の流動性を抑制し、かつ、組成物の硬化物に機械的強度を付与する成分である。本明細書において、表面処理とは、シリカ表面のシラノール基との反応性を有する化合物を用い、シラノール基を別種の基に共有結合的に処理することを指す。 (f) Surface-treated silica The curable composition of the present invention may further contain (f) surface-treated silica as an inorganic filler. The surface-treated silica is a component that suppresses the fluidity of the composition and imparts mechanical strength to the cured product of the composition. As used herein, surface treatment refers to covalently treating silanol groups with different groups using a compound having reactivity with silanol groups on the silica surface.
本発明の硬化性組成物は、無機充填剤としてさらに(f)表面処理シリカを含んでいてもよい。表面処理シリカは、組成物の流動性を抑制し、かつ、組成物の硬化物に機械的強度を付与する成分である。本明細書において、表面処理とは、シリカ表面のシラノール基との反応性を有する化合物を用い、シラノール基を別種の基に共有結合的に処理することを指す。 (f) Surface-treated silica The curable composition of the present invention may further contain (f) surface-treated silica as an inorganic filler. The surface-treated silica is a component that suppresses the fluidity of the composition and imparts mechanical strength to the cured product of the composition. As used herein, surface treatment refers to covalently treating silanol groups with different groups using a compound having reactivity with silanol groups on the silica surface.
シリカとしては、煙霧質シリカ、焼成シリカ、シリカエアロゲル、沈殿シリカ、粉砕シリカ等が挙げられる。これらのなかで、少ない配合量で、組成物の流動性を抑制し、かつ、組成物の硬化物に機械的強度を付与する点から、煙霧質シリカが好ましい。
Examples of silica include fumed silica, calcined silica, silica aerogel, precipitated silica, and pulverized silica. Among these, fumed silica is preferable from the viewpoint of suppressing the fluidity of the composition and imparting mechanical strength to the cured product of the composition in a small amount.
表面処理の方法としては、シラザン化合物(ヘキサメチルジシラザン、1,3-ジビニル-1,1,3,3-テトラメチルジシラザン、1,3-ビス(クロロメチル)テトラメチルジシラザン、1,3-ビス(3,3,3-トリフルオロプロピル)-1,1,3,3-テトラメチルジシラザン、1,3-ジフェニルテトラメチルジシラザン、ヘプタメチルジシラザン、2,2,4,4,6,6-ヘキサメチルシクロトリシラザン、オクタメチルシクロテトラシラザン、1,1,3,3-テトラメチルジシラザン、2,4,6-トリメチル-2,4,6-トリビニルシクロトリシラザン等)、アルコキシシラン化合物(メチルトリメトキシシラン、ジメチルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、n-プロピルトリメトキシシラン、n-プロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン、ヘキサデシルトリメトキシシラン等)、クロロシラン化合物(メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン等)、オクタメチルシクロテトラシロキサン、ジメチルシロキサンオリゴマー等による処理が挙げられる。これらの中で、シラザン化合物またはクロロシラン化合物で化学処理されていると、少ない処理量で、シリカ表面を疎水化処理することができる点から好ましい。特に、ヘキサメチルジシラザン、ジメチルジクロロシランが好ましい。また、処理度および処理した後の表面状態の安定性(不活性化)の点から、ヘキサメチルジシラザンが好ましい。これらの表面処理剤は、硬化性組成物の調製時にシリカとともに配合し、混練することで、シリカの表面処理を行うようにしてもよい。また、市販の材料を用いてもよい。
As a surface treatment method, silazane compounds (hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)tetramethyldisilazane, 1, 3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, heptamethyldisilazane, 2,2,4,4 ,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, 1,1,3,3-tetramethyldisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, etc. ), alkoxysilane compounds (methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyl trimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, etc.), chlorosilane compounds (methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc.), octamethyl Examples include treatment with cyclotetrasiloxane, dimethylsiloxane oligomer, and the like. Among these, chemical treatment with a silazane compound or a chlorosilane compound is preferred because the silica surface can be hydrophobized with a small treatment amount. Hexamethyldisilazane and dimethyldichlorosilane are particularly preferred. Hexamethyldisilazane is preferred from the viewpoint of the degree of treatment and the stability (inactivation) of the surface state after treatment. These surface treatment agents may be blended with silica during preparation of the curable composition and kneaded to treat the surface of silica. Alternatively, commercially available materials may be used.
硬化性組成物の流動性を抑制する観点、並びにその硬化物に高い機械的強度を付与する観点から、(f)表面処理シリカのBET比表面積は、50~500m2/gであることが好ましく、80~400m2/gであることがより好ましく、100~300m2/gであることがさらに好ましい。
また、(f)表面処理シリカには、表面処理剤が有するアルキル基など炭化水素基の炭素に由来して、表面に炭素が存在することがある。炭化水素基はシリカ表面の疎水化に有効であるため、上記例示のような-Si-(CH3)n(ここでnは1~3の値であり、3であることが好ましい)で示される構造を有する化合物で表面処理がなされていることが好ましい。このときの表面処理の度合いは、シリカ表面のカーボン量で表すことができる。表面処理シリカは、粒子表面のカーボン量が0.8質量%以上であることが好ましく、2.0質量%以上であるとより好ましい。さらに好ましくは3.0質量%以上である。カーボン量が0.8質量%以上であると、カーボンの量に伴い表面処理の程度が大きくなるために表面状態の安定性がより向上する。カーボン量の上限は特に制限されないが、20質量%以下であることが好ましく、12質量%以下であることがより好ましく、8質量%以下であることがさらに好ましい。カーボン量の測定方法は公知であり、表面処理に用いた表面処理剤の量から求めることができるほか、元素分析等の手法によっても求めることができる。 The BET specific surface area of (f) the surface-treated silica is preferably 50 to 500 m 2 /g from the viewpoint of suppressing the fluidity of the curable composition and imparting high mechanical strength to the cured product. , 80 to 400 m 2 /g, more preferably 100 to 300 m 2 /g.
In addition, (f) the surface-treated silica may have carbon on the surface derived from the carbon of the hydrocarbon group such as the alkyl group possessed by the surface treatment agent. Since the hydrocarbon group is effective in hydrophobizing the silica surface, it is represented by —Si—(CH 3 ) n (where n is a value of 1 to 3, preferably 3) as exemplified above. It is preferable that the surface is treated with a compound having a structure that The degree of surface treatment at this time can be represented by the amount of carbon on the silica surface. The surface-treated silica preferably has a carbon content on the particle surface of 0.8% by mass or more, more preferably 2.0% by mass or more. More preferably, it is 3.0% by mass or more. When the amount of carbon is 0.8% by mass or more, the degree of surface treatment increases with the amount of carbon, so the stability of the surface state is further improved. Although the upper limit of the carbon content is not particularly limited, it is preferably 20% by mass or less, more preferably 12% by mass or less, and even more preferably 8% by mass or less. A method for measuring the amount of carbon is known, and it can be determined from the amount of the surface treatment agent used for the surface treatment, and it can also be determined by a technique such as elemental analysis.
また、(f)表面処理シリカには、表面処理剤が有するアルキル基など炭化水素基の炭素に由来して、表面に炭素が存在することがある。炭化水素基はシリカ表面の疎水化に有効であるため、上記例示のような-Si-(CH3)n(ここでnは1~3の値であり、3であることが好ましい)で示される構造を有する化合物で表面処理がなされていることが好ましい。このときの表面処理の度合いは、シリカ表面のカーボン量で表すことができる。表面処理シリカは、粒子表面のカーボン量が0.8質量%以上であることが好ましく、2.0質量%以上であるとより好ましい。さらに好ましくは3.0質量%以上である。カーボン量が0.8質量%以上であると、カーボンの量に伴い表面処理の程度が大きくなるために表面状態の安定性がより向上する。カーボン量の上限は特に制限されないが、20質量%以下であることが好ましく、12質量%以下であることがより好ましく、8質量%以下であることがさらに好ましい。カーボン量の測定方法は公知であり、表面処理に用いた表面処理剤の量から求めることができるほか、元素分析等の手法によっても求めることができる。 The BET specific surface area of (f) the surface-treated silica is preferably 50 to 500 m 2 /g from the viewpoint of suppressing the fluidity of the curable composition and imparting high mechanical strength to the cured product. , 80 to 400 m 2 /g, more preferably 100 to 300 m 2 /g.
In addition, (f) the surface-treated silica may have carbon on the surface derived from the carbon of the hydrocarbon group such as the alkyl group possessed by the surface treatment agent. Since the hydrocarbon group is effective in hydrophobizing the silica surface, it is represented by —Si—(CH 3 ) n (where n is a value of 1 to 3, preferably 3) as exemplified above. It is preferable that the surface is treated with a compound having a structure that The degree of surface treatment at this time can be represented by the amount of carbon on the silica surface. The surface-treated silica preferably has a carbon content on the particle surface of 0.8% by mass or more, more preferably 2.0% by mass or more. More preferably, it is 3.0% by mass or more. When the amount of carbon is 0.8% by mass or more, the degree of surface treatment increases with the amount of carbon, so the stability of the surface state is further improved. Although the upper limit of the carbon content is not particularly limited, it is preferably 20% by mass or less, more preferably 12% by mass or less, and even more preferably 8% by mass or less. A method for measuring the amount of carbon is known, and it can be determined from the amount of the surface treatment agent used for the surface treatment, and it can also be determined by a technique such as elemental analysis.
(f)表面処理シリカは、硬化性組成物中、(a)PFPE含有シラン化合物100質量部に対して、1~100質量部含まれることが好ましく、より好ましくは2~50質量部、さらに好ましくは3~30質量部である。
(f) The surface-treated silica is preferably contained in the curable composition in an amount of 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and still more preferably 100 parts by mass of the silane compound containing (a) PFPE. is 3 to 30 parts by mass.
(f)表面処理シリカは、1種のみを用いてもよいし、2種以上を同時に用いてもよい。
(f) Only one type of surface-treated silica may be used, or two or more types may be used at the same time.
(h)溶剤
硬化性組成物は、溶剤を含んでいてもよい。この場合、硬化性組成物の用途、目的に応じて適当な溶剤(例えばフッ素原子含有溶剤)に所望の濃度に溶解して使用し得る。上記溶剤の濃度は、例えば、硬化性組成物100質量部に対して、80質量部以下であってもよく、50質量部以下であってもよく、30質量部以下であってもよく、20質量部以下であってもよい。硬化性組成物の粘度を調整する観点からは、溶剤を含むことが好ましい。溶剤を含むことにより、硬化性組成物の取り扱い性の面が良好になり得る。また、硬化性組成物から形成される硬化物の形状のコントロールが容易になり得、例えば厚みの大きな硬化物の形成が容易になり得る。 (h) Solvent The curable composition may contain a solvent. In this case, it can be used by dissolving in a suitable solvent (for example, a fluorine atom-containing solvent) to a desired concentration depending on the application and purpose of the curable composition. The concentration of the solvent may be, for example, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 20 parts by mass with respect to 100 parts by mass of the curable composition. It may be less than or equal to parts by mass. From the viewpoint of adjusting the viscosity of the curable composition, it is preferable to contain a solvent. By containing a solvent, the handling property of the curable composition can be improved. Also, the shape of the cured product formed from the curable composition can be easily controlled, and for example, the formation of a thick cured product can be facilitated.
硬化性組成物は、溶剤を含んでいてもよい。この場合、硬化性組成物の用途、目的に応じて適当な溶剤(例えばフッ素原子含有溶剤)に所望の濃度に溶解して使用し得る。上記溶剤の濃度は、例えば、硬化性組成物100質量部に対して、80質量部以下であってもよく、50質量部以下であってもよく、30質量部以下であってもよく、20質量部以下であってもよい。硬化性組成物の粘度を調整する観点からは、溶剤を含むことが好ましい。溶剤を含むことにより、硬化性組成物の取り扱い性の面が良好になり得る。また、硬化性組成物から形成される硬化物の形状のコントロールが容易になり得、例えば厚みの大きな硬化物の形成が容易になり得る。 (h) Solvent The curable composition may contain a solvent. In this case, it can be used by dissolving in a suitable solvent (for example, a fluorine atom-containing solvent) to a desired concentration depending on the application and purpose of the curable composition. The concentration of the solvent may be, for example, 80 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 20 parts by mass with respect to 100 parts by mass of the curable composition. It may be less than or equal to parts by mass. From the viewpoint of adjusting the viscosity of the curable composition, it is preferable to contain a solvent. By containing a solvent, the handling property of the curable composition can be improved. Also, the shape of the cured product formed from the curable composition can be easily controlled, and for example, the formation of a thick cured product can be facilitated.
上記溶剤としては、例えば:
パーフルオロヘキサン、CF3CF2CHCl2、CF3CH2CF2CH3、CF3CHFCHFC2F5、1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン((ゼオローラH(商品名)等)、C4F9OCH3、C4F9OC2H5、CF3CH2OCF2CHF2、C6F13CH=CH2、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、HCF2CF2CH2OH、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびCF3O(CF2CF2O)w1(CF2O)w2CF2CF3[式中、w1およびw2は、それぞれ独立して0以上1000以下の整数であり、w1またはw2を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、ただしw1およびw2の和は1以上である。]、1,1-ジクロロ-2,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-1,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1,2-トリクロロ―3,3,3-トリフルオロ-1-プロペン、1,1,1,4,4,4-ヘキサフルオロ-2-ブテン、エチルパーフルオロブチルエーテル、およびメチルパーフルオロブチルエーテルからなる群から選択されるフッ素原子含有溶剤等が挙げられる。これらの溶剤は、単独で、または、2種以上の混合物として用いることができる。 Examples of the solvent include:
Perfluorohexane , CF3CF2CHCl2 , CF3CH2CF2CH3 , CF3CHFCHFC2F5 , 1,1,1,2,2,3,3,4,4,5,5,6 _ ,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H5 , CF3CH2OCF2CHF2 , C6F13CH = CH2 , xylene hexafluoride , perfluorobenzene, methylpentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2CF2CH2OH , methyltrifluoromethanesulfonate, trifluoroacetic acid and CF3O ( CF2CF2O ) w1 ( CF2O ) w2CF2CF3 , wherein w1 and w2 are each independently It is an integer of 0 or more and 1000 or less, and the order of existence of each repeating unit enclosed in parentheses with w1 or w2 is arbitrary in the formula, provided that the sum of w1 and w2 is 1 or more.], 1 ,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3 ,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, fluorine atom-containing solvents selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene, ethyl perfluorobutyl ether, and methyl perfluorobutyl ether, etc. These solvents are They can be used singly or as a mixture of two or more.
パーフルオロヘキサン、CF3CF2CHCl2、CF3CH2CF2CH3、CF3CHFCHFC2F5、1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン((ゼオローラH(商品名)等)、C4F9OCH3、C4F9OC2H5、CF3CH2OCF2CHF2、C6F13CH=CH2、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、HCF2CF2CH2OH、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびCF3O(CF2CF2O)w1(CF2O)w2CF2CF3[式中、w1およびw2は、それぞれ独立して0以上1000以下の整数であり、w1またはw2を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、ただしw1およびw2の和は1以上である。]、1,1-ジクロロ-2,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-1,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1,2-トリクロロ―3,3,3-トリフルオロ-1-プロペン、1,1,1,4,4,4-ヘキサフルオロ-2-ブテン、エチルパーフルオロブチルエーテル、およびメチルパーフルオロブチルエーテルからなる群から選択されるフッ素原子含有溶剤等が挙げられる。これらの溶剤は、単独で、または、2種以上の混合物として用いることができる。 Examples of the solvent include:
Perfluorohexane , CF3CF2CHCl2 , CF3CH2CF2CH3 , CF3CHFCHFC2F5 , 1,1,1,2,2,3,3,4,4,5,5,6 _ ,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorolla H (trade name), etc.), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H5 , CF3CH2OCF2CHF2 , C6F13CH = CH2 , xylene hexafluoride , perfluorobenzene, methylpentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2CF2CH2OH , methyltrifluoromethanesulfonate, trifluoroacetic acid and CF3O ( CF2CF2O ) w1 ( CF2O ) w2CF2CF3 , wherein w1 and w2 are each independently It is an integer of 0 or more and 1000 or less, and the order of existence of each repeating unit enclosed in parentheses with w1 or w2 is arbitrary in the formula, provided that the sum of w1 and w2 is 1 or more.], 1 ,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3 ,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, fluorine atom-containing solvents selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene, ethyl perfluorobutyl ether, and methyl perfluorobutyl ether, etc. These solvents are They can be used singly or as a mixture of two or more.
なお、硬化性組成物から得られる硬化物を各種基材に接着させる場合、各種プライマーを併用することもできる。
When the cured product obtained from the curable composition is adhered to various substrates, various primers can be used together.
一の態様において、硬化性組成物を使用するに当たり、その用途、目的に応じて該組成物をさらに溶剤を用いて希釈して用いてもよい。希釈に用いる溶剤としては、上記に例示したフッ素原子含有溶剤を用いることができる。例えば、溶剤として1,3-ビス(トリフルオロメチル)ベンゼン、フロリナート(3M社製)、パーフルオロブチルメチルエーテル、パーフルオロブチルエチルエーテル等に所望の濃度に溶解して使用してもよい。特に、薄膜コーティング用途においては上記溶剤を使用することが好ましい。
In one embodiment, when using the curable composition, the composition may be diluted with a solvent depending on the application and purpose. As the solvent used for dilution, the fluorine atom-containing solvents exemplified above can be used. For example, it may be dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc. to a desired concentration. In particular, it is preferable to use the above solvents in thin film coating applications.
(i)各種添加剤
硬化性組成物は、さらに、各種添加剤を含んでいてもよい。各種添加剤としては、特に限定されるものではないが、例えば、含フッ素オイルとして理解され得る(非反応性の)フルオロポリエーテル化合物、好ましくはパーフルオロ(ポリ)エーテル化合物(以下、「含フッ素オイル」と言う)、安定化剤(脱水剤、モレキュラーシーブ、硫酸マグネシウムまたはオルソギ酸メチル)、粘度調節剤、蛍光剤、着色剤、耐熱性向上剤、耐寒性向上剤、防錆剤、液状補強剤等を含んでいてもよい。 (i) Various Additives The curable composition may further contain various additives. Although various additives are not particularly limited, for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter referred to as "fluorine-containing Oil"), stabilizer (dehydrating agent, molecular sieve, magnesium sulfate or methyl orthoformate), viscosity modifier, fluorescent agent, colorant, heat resistance improver, cold resistance improver, rust inhibitor, liquid reinforcement It may contain an agent or the like.
硬化性組成物は、さらに、各種添加剤を含んでいてもよい。各種添加剤としては、特に限定されるものではないが、例えば、含フッ素オイルとして理解され得る(非反応性の)フルオロポリエーテル化合物、好ましくはパーフルオロ(ポリ)エーテル化合物(以下、「含フッ素オイル」と言う)、安定化剤(脱水剤、モレキュラーシーブ、硫酸マグネシウムまたはオルソギ酸メチル)、粘度調節剤、蛍光剤、着色剤、耐熱性向上剤、耐寒性向上剤、防錆剤、液状補強剤等を含んでいてもよい。 (i) Various Additives The curable composition may further contain various additives. Although various additives are not particularly limited, for example, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter referred to as "fluorine-containing Oil"), stabilizer (dehydrating agent, molecular sieve, magnesium sulfate or methyl orthoformate), viscosity modifier, fluorescent agent, colorant, heat resistance improver, cold resistance improver, rust inhibitor, liquid reinforcement It may contain an agent or the like.
上記含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の一般式(III)で表される化合物(パーフルオロ(ポリ)エーテル化合物)が挙げられる。
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 ・・・(III) Examples of the fluorine-containing oil include, but are not limited to, compounds represented by the following general formula (III) (perfluoro(poly)ether compounds).
Rf5- ( OC4F8 ) a' -( OC3F6 ) b' - ( OC2F4 ) c' -( OCF2 ) d' - Rf6 ( III )
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 ・・・(III) Examples of the fluorine-containing oil include, but are not limited to, compounds represented by the following general formula (III) (perfluoro(poly)ether compounds).
Rf5- ( OC4F8 ) a' -( OC3F6 ) b' - ( OC2F4 ) c' -( OCF2 ) d' - Rf6 ( III )
式中、Rf5は、1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16アルキル基(好ましくは、C1-16のパーフルオロアルキル基)を表し、Rf6は、1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16アルキル基(好ましくは、C1-16パーフルオロアルキル基)、フッ素原子または水素原子を表し、Rf5およびRf6は、より好ましくは、それぞれ独立して、C1-3パーフルオロアルキル基である。
a’、b’、c’およびd’は、ポリマーの主骨格を構成するパーフルオロ(ポリ)エーテルの4種の繰り返し単位数をそれぞれ表し、互いに独立して0以上300以下の整数であって、a’、b’、c’およびd’の和は少なくとも1、好ましくは1~300、より好ましくは20~300である。添字a’、b’、c’またはd’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、-(OC4F8)-は、-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-および-(OCF2CF(C2F5))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2CF2)-である。-(OC3F6)-は、-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-および-(OCF2CF(CF3))-のいずれであってもよく、好ましくは-(OCF2CF2CF2)-である。-(OC2F4)-は、-(OCF2CF2)-および-(OCF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2)-である。 In the formula, Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf 6 is , a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, Rf 5 and Rf 6 is more preferably each independently a C 1-3 perfluoroalkyl group.
a', b', c' and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, , a′, b′, c′ and d′ are at least 1, preferably 1-300, more preferably 20-300. The order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' is arbitrary in the formula. Among these repeating units, -(OC 4 F 8 )- is -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF(CF 3 ))-,-(OC(CF 3 ) 2 CF 2 )-,-(OCF 2 C(CF 3 ) 2 )-,-(OCF (CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )- is any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))- Well, preferably -(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, but is preferably -(OCF 2 CF 2 )-.
a’、b’、c’およびd’は、ポリマーの主骨格を構成するパーフルオロ(ポリ)エーテルの4種の繰り返し単位数をそれぞれ表し、互いに独立して0以上300以下の整数であって、a’、b’、c’およびd’の和は少なくとも1、好ましくは1~300、より好ましくは20~300である。添字a’、b’、c’またはd’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、-(OC4F8)-は、-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-および-(OCF2CF(C2F5))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2CF2)-である。-(OC3F6)-は、-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-および-(OCF2CF(CF3))-のいずれであってもよく、好ましくは-(OCF2CF2CF2)-である。-(OC2F4)-は、-(OCF2CF2)-および-(OCF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2)-である。 In the formula, Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf 6 is , a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, Rf 5 and Rf 6 is more preferably each independently a C 1-3 perfluoroalkyl group.
a', b', c' and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, , a′, b′, c′ and d′ are at least 1, preferably 1-300, more preferably 20-300. The order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' is arbitrary in the formula. Among these repeating units, -(OC 4 F 8 )- is -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF(CF 3 ))-,-(OC(CF 3 ) 2 CF 2 )-,-(OCF 2 C(CF 3 ) 2 )-,-(OCF (CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )- is any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))- Well, preferably -(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, but is preferably -(OCF 2 CF 2 )-.
一般式(III)で表されるパーフルオロ(ポリ)エーテル化合物の例として、以下の一般式(IIIa)および(IIIb)のいずれかで示される化合物(1種または2種以上の混合物であってよい)が挙げられる。
Rf5-(OCF2CF2CF2)b’’-Rf6 ・・・(IIIa)
Rf5-(OCF2CF2CF2CF2)a’’’-(OCF2CF2CF2)b’’’-(OCF2CF2)c’’’-(OCF2)d’’’-Rf6 ・・・(IIIb)
これら式中、Rf5およびRf6は上記の通りであり;式(IIIa)において、b’’は1以上100以下の整数であり;式(IIIb)において、a’’’およびb’’’は、それぞれ独立して1以上30以下の整数であり、c’’’およびd’’’はそれぞれ独立して1以上300以下の整数である。添字a’’’、b’’’、c’’’、d’’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 Examples of perfluoro(poly)ether compounds represented by general formula (III) include compounds represented by any of the following general formulas (IIIa) and (IIIb) (one or a mixture of two or more good).
Rf 5 —(OCF 2 CF 2 CF 2 ) b″ —Rf 6 (IIIa)
Rf5- ( OCF2CF2CF2CF2 ) a''' - ( OCF2CF2CF2 ) b ''' - ( OCF2CF2 ) c''' - ( OCF2 ) d ''' -Rf 6 (IIIb)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (IIIa), b'' is an integer of 1 or more and 100 or less; is each independently an integer of 1 or more and 30 or less, and c''' and d''' are each independently an integer of 1 or more and 300 or less. The order in which the repeating units enclosed in parentheses with subscripts a''', b''', c''' and d''' are arbitrary in the formula.
Rf5-(OCF2CF2CF2)b’’-Rf6 ・・・(IIIa)
Rf5-(OCF2CF2CF2CF2)a’’’-(OCF2CF2CF2)b’’’-(OCF2CF2)c’’’-(OCF2)d’’’-Rf6 ・・・(IIIb)
これら式中、Rf5およびRf6は上記の通りであり;式(IIIa)において、b’’は1以上100以下の整数であり;式(IIIb)において、a’’’およびb’’’は、それぞれ独立して1以上30以下の整数であり、c’’’およびd’’’はそれぞれ独立して1以上300以下の整数である。添字a’’’、b’’’、c’’’、d’’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 Examples of perfluoro(poly)ether compounds represented by general formula (III) include compounds represented by any of the following general formulas (IIIa) and (IIIb) (one or a mixture of two or more good).
Rf 5 —(OCF 2 CF 2 CF 2 ) b″ —Rf 6 (IIIa)
Rf5- ( OCF2CF2CF2CF2 ) a''' - ( OCF2CF2CF2 ) b ''' - ( OCF2CF2 ) c''' - ( OCF2 ) d ''' -Rf 6 (IIIb)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (IIIa), b'' is an integer of 1 or more and 100 or less; is each independently an integer of 1 or more and 30 or less, and c''' and d''' are each independently an integer of 1 or more and 300 or less. The order in which the repeating units enclosed in parentheses with subscripts a''', b''', c''' and d''' are arbitrary in the formula.
上記含フッ素オイルは、1,000~30,000の数平均分子量を有していてよい。特に、式(IIIa)で表される化合物の数平均分子量は、2,000~8,000であることが好ましい。一の態様において、式(IIIb)で表される化合物の数平均分子量は、3,000~8,000である。別の態様において、式(IIIb)で表される化合物の数平均分子量は、8,000~30,000である。
The fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000. In particular, the compound represented by formula (IIIa) preferably has a number average molecular weight of 2,000 to 8,000. In one aspect, the compound represented by formula (IIIb) has a number average molecular weight of 3,000 to 8,000. In another aspect, the compound represented by formula (IIIb) has a number average molecular weight of 8,000 to 30,000.
硬化性組成物中、含フッ素オイルは、PFPE含有シラン化合物(a)100質量部に対して、例えば0~500質量部、好ましくは0~100質量部、より好ましくは1~50質量部、さらに好ましくは1~5質量部で含まれ得る。
In the curable composition, the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the PFPE-containing silane compound (a). Preferably, it can be contained in an amount of 1-5 parts by weight.
また、別の観点から、含フッ素オイルは、一般式Rf’-F(式中、Rf’はC5-16パーフルオロアルキル基である。)で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Rf’-Fで表される化合物およびクロロトリフルオロエチレンオリゴマーは、RfがC1-16パーフルオロアルキル基である(A)PFPE含有シラン化合物と高い親和性が得られる点で好ましい。
From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf' is a C5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer. The compound represented by Rf'-F and the chlorotrifluoroethylene oligomer are preferable in that they have a high affinity with (A) the PFPE-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group.
含フッ素オイルを含むことにより、硬化性組成物は、より柔軟な硬化組成物を形成し得る。
By including a fluorine-containing oil, the curable composition can form a more flexible cured composition.
一の態様において、PFPE含有シラン化合物(a)(あるいは式(A)、(B)、(C)または(D)で表される化合物)の平均分子量よりも、含フッ素オイルの平均分子量を大きくしてもよい。このような平均分子量とすることにより、硬化性組成物を用いて形成された硬化物において、より優れた摩擦耐久性と表面滑り性を得ることができる。
In one aspect, the average molecular weight of the fluorine-containing oil is larger than the average molecular weight of the PFPE-containing silane compound (a) (or the compound represented by formula (A), (B), (C) or (D)). You may With such an average molecular weight, it is possible to obtain more excellent friction durability and surface slipperiness in a cured product formed using the curable composition.
一の態様において、PFPE含有シラン化合物(a)(あるいは式(A)、(B)、(C)または(D)で表される化合物)の平均分子量よりも、含フッ素オイルの平均分子量を小さくしてもよい。このような平均分子量とすることにより、硬化性組成物を用いて形成される硬化物の透明性の低下を抑制しつつ、高い摩擦耐久性および高い表面滑り性を有する硬化物の形成に寄与できる。
In one aspect, the average molecular weight of the fluorine-containing oil is smaller than the average molecular weight of the PFPE-containing silane compound (a) (or the compound represented by formula (A), (B), (C) or (D)). You may By setting such an average molecular weight, it is possible to contribute to the formation of a cured product having high friction durability and high surface slipperiness while suppressing deterioration in the transparency of the cured product formed using the curable composition. .
着色剤としては、顔料、染料等を挙げることができる。
Examples of coloring agents include pigments and dyes.
耐熱性向上剤としては、ベンガラ、酸化セリウム等を挙げることができる。
Examples of heat resistance improvers include red iron oxide and cerium oxide.
液状補強剤としては、トリオルガノシロキシ単位およびSiO2単位よりなる網状ポリシロキサン等を挙げることができる。
Examples of liquid reinforcing agents include network polysiloxanes composed of triorganosiloxy units and SiO2 units.
(硬化性組成物の製造方法)
硬化性組成物は、必須成分である(a)~(c)成分および任意成分である(d)以下の成分を、万能混練機、ニーダー等の混合手段によって均一に混練して製造することができる。各成分の添加順は、任意であるが、(a)成分並びに場合によりその他のシラン化合物の混合物中に任意成分である充填剤等を加えて分散させた後に、架橋剤、触媒等の残りの成分を加えて混合することが好ましい。 (Method for producing curable composition)
The curable composition can be produced by uniformly kneading the essential components (a) to (c) and the optional component (d) below using a mixing means such as a universal kneader or a kneader. can. The order of addition of each component is arbitrary, but after adding and dispersing an optional component such as a filler into the mixture of component (a) and optionally other silane compounds, the remaining components such as a cross-linking agent and a catalyst are added. It is preferred to add and mix the ingredients.
硬化性組成物は、必須成分である(a)~(c)成分および任意成分である(d)以下の成分を、万能混練機、ニーダー等の混合手段によって均一に混練して製造することができる。各成分の添加順は、任意であるが、(a)成分並びに場合によりその他のシラン化合物の混合物中に任意成分である充填剤等を加えて分散させた後に、架橋剤、触媒等の残りの成分を加えて混合することが好ましい。 (Method for producing curable composition)
The curable composition can be produced by uniformly kneading the essential components (a) to (c) and the optional component (d) below using a mixing means such as a universal kneader or a kneader. can. The order of addition of each component is arbitrary, but after adding and dispersing an optional component such as a filler into the mixture of component (a) and optionally other silane compounds, the remaining components such as a cross-linking agent and a catalyst are added. It is preferred to add and mix the ingredients.
このような硬化性組成物の構成に関しては、用途に応じていわゆる1液タイプとして構成してもよいし、あるいは、2液タイプとし、使用時に両者を混合するようにしてもよい。
Regarding the composition of such a curable composition, it may be configured as a so-called one-liquid type or as a two-liquid type, and the two may be mixed at the time of use, depending on the application.
(用途)
本発明の硬化性組成物の硬化物は、例えば、ポッティング材、シール材等に使用し得る。また、基材との高い密着性を奏するため、接着剤としても有用に使用し得る。本発明の硬化性組成物の硬化物は、例えば、電子部材の空隙(例えば、筐体とプリント基板の張り合わせ部、または樹脂モールドされた金属端子部とモールド樹脂の隙間等)に充填し、充填後、乾燥させることによって使用し得る。 (Application)
A cured product of the curable composition of the present invention can be used, for example, as a potting material, a sealing material, and the like. Moreover, since it exhibits high adhesion to the base material, it can be used effectively as an adhesive. The cured product of the curable composition of the present invention is filled, for example, in a gap of an electronic member (for example, a gap between a housing and a printed circuit board, or a gap between a resin-molded metal terminal and a mold resin). After drying, it can be used.
本発明の硬化性組成物の硬化物は、例えば、ポッティング材、シール材等に使用し得る。また、基材との高い密着性を奏するため、接着剤としても有用に使用し得る。本発明の硬化性組成物の硬化物は、例えば、電子部材の空隙(例えば、筐体とプリント基板の張り合わせ部、または樹脂モールドされた金属端子部とモールド樹脂の隙間等)に充填し、充填後、乾燥させることによって使用し得る。 (Application)
A cured product of the curable composition of the present invention can be used, for example, as a potting material, a sealing material, and the like. Moreover, since it exhibits high adhesion to the base material, it can be used effectively as an adhesive. The cured product of the curable composition of the present invention is filled, for example, in a gap of an electronic member (for example, a gap between a housing and a printed circuit board, or a gap between a resin-molded metal terminal and a mold resin). After drying, it can be used.
より高い耐摩耗性を有する硬化物(例えば、ポッティング材、シール材)を形成するためには、本発明の硬化性組成物による処理に先だって、空隙の壁面の油分を取り除くために、処理対象物をアセトン、ハイドロフルオロエーテル等で洗浄した後、乾燥することが好ましい。さらに、上記の洗浄に加えて、UVオゾン、酸素プラズマ等で、前処理することにより、硬化物の耐摩耗性をより向上させることができる。
In order to form a cured product (e.g., potting material, sealing material) having higher wear resistance, prior to treatment with the curable composition of the present invention, the object to be treated is is preferably washed with acetone, hydrofluoroether or the like and then dried. Furthermore, in addition to the above cleaning, pretreatment with UV ozone, oxygen plasma, or the like can further improve the abrasion resistance of the cured product.
本発明の硬化性組成物による処理に先立って、必要に応じて、空隙の壁面等に対してプライマー処理を施すことによって、硬化性組成物から形成されるポッティング材の接着性を向上させて、耐摩耗性をより向上させることができる。プライマー処理は、常法に従って、シランカップリング剤を用いる場合のプライマー処理と同様の条件で処理を行えばよい。基材としては、アルミニウム、銅、ニッケル、鉄、黄銅、ステンレス等の金属;エポキシ樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート樹脂等のポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリイミド樹脂、フェノール樹脂、ポリアミド樹脂、ポリフェニレンサルファイド樹脂等のエンジニアリングプラスチック;ガラス等を使用することができる。
Prior to the treatment with the curable composition of the present invention, if necessary, the walls of the voids, etc. are subjected to primer treatment to improve the adhesiveness of the potting material formed from the curable composition, Abrasion resistance can be further improved. The primer treatment may be performed according to a conventional method under the same conditions as those for the primer treatment when using a silane coupling agent. Examples of base materials include metals such as aluminum, copper, nickel, iron, brass, and stainless steel; polyester resins such as epoxy resins, polyethylene terephthalate and polybutylene terephthalate resins; Engineering plastics such as polyphenylene sulfide resin; glass and the like can be used.
なお、本発明の硬化性組成物から得られる硬化物を各種基材に接着させる場合、各種プライマーを併用することもできる。
When the cured product obtained from the curable composition of the present invention is adhered to various substrates, various primers can be used together.
処理時の温度については特に限定はなく、通常は、室温で処理を行えばよい。処理時間についても特に限定はないが、例えば、5分~1時間とすることができる。
There is no particular limitation on the temperature during the treatment, and usually the treatment should be performed at room temperature. The treatment time is also not particularly limited, but can be, for example, 5 minutes to 1 hour.
一の態様において、硬化性組成物は、室温で硬化し得る。このような硬化性組成物は、ポッティング材形成用の組成物として特に有用である。
In one aspect, the curable composition can be cured at room temperature. Such a curable composition is particularly useful as a composition for forming a potting material.
一の態様において、本発明の硬化性組成物を使用するに当たり、その用途、目的に応じて該組成物をさらに溶剤を用いて希釈して用いてもよい。希釈に用いる溶剤としては、上記に例示したフッ素型溶剤を用いることができる。例えば、溶剤として1,3-ビス(トリフルオロメチル)ベンゼン、フロリナート(3M社製)、パーフルオロブチルメチルエーテル、パーフルオロブチルエチルエーテル等に所望の濃度に溶解して使用してもよい。特に、薄膜コーティング用途においては上記溶剤を使用することが好ましい。
In one embodiment, when using the curable composition of the present invention, the composition may be diluted with a solvent depending on its use and purpose. As a solvent used for dilution, the above-exemplified fluorine type solvents can be used. For example, it may be dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutylmethylether, perfluorobutylethylether, etc. to a desired concentration. In particular, it is preferable to use the above solvents in thin film coating applications.
本発明の硬化性組成物は、金属またはプラスチック基材に対しての接着剤として使用するに際し、基材との高い密着性を奏することから、特に電気電子部品周辺や車載用部品周辺用途の接着剤として有用である。本発明の硬化性組成物の硬化物は、良好な弾性率、耐薬品性、耐酸性、耐塩基性を備えることができる。さらに、低いガラス転移温度を備えることができ低温での弾性率が大きくなることを抑制することができ、かつ分解温度が高い。このような本発明の硬化性組成物の硬化物は、自動車部材(例えば、シール材、具体的には、ガスケット)等、化学プラント、半導体製造装置等の電気電子部品、また寒冷地(例えば-50℃以下)や高温条件において使用可能な自動車部材等にも使用することができる。
When the curable composition of the present invention is used as an adhesive for metal or plastic substrates, it exhibits high adhesion to substrates, and is therefore particularly suitable for use around electrical and electronic components and vehicle-mounted components. useful as an agent. A cured product of the curable composition of the present invention can have good elastic modulus, chemical resistance, acid resistance, and base resistance. Furthermore, it has a low glass transition temperature, can suppress an increase in elastic modulus at low temperatures, and has a high decomposition temperature. The cured product of such a curable composition of the present invention can be used in automobile parts (e.g., sealing materials, specifically, gaskets), chemical plants, electrical and electronic parts such as semiconductor manufacturing equipment, and cold regions (e.g. - 50° C. or less) and automobile parts that can be used under high temperature conditions.
以下の実施例を通じてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、本実施例において、パーフルオロ(ポリ)エーテルを構成する繰り返し単位の存在順序は任意である。
Although more specific explanations will be given through the following examples, the present invention is not limited to these examples. In this example, the order of existence of the repeating units constituting the perfluoro(poly)ether is arbitrary.
(製造例1)
・PFPE含有シラン化合物(a)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1,3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、ビス(4-アミノシクロヘキシル)メタン40gを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルトリメトキシシラン67mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(a)を得た。得られたPFPE含有シラン化合物(a)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を97mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が87mol%、CH2CH3が13mol%であった。
PFPE含有シラン化合物(a)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)12-(OCF2CF2)12-OCF2-CONH-C6H10-CH2-C6H10-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 1)
- Preparation of PFPE-containing silane compound (a) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 40 g of bis(4-aminocyclohexyl)methane, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 67 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (a) represented by the following formula. The resulting PFPE-containing silane compound (a) was identified by 19 F-NMR analysis as containing -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 97 mol %. As for R′ in the following formula, 87 mol % of CH 3 and 13 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (a)
(R'O)3Si-CH2CH2CH2-NHCO - CF2- ( OCF2 ) 12- ( OCF2CF2 ) 12 - OCF2 - CONH - C6H10 - CH2 - C6H 10 -NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n -OCF2 - CONH - CH2CH2CH2 - Si(OR') 3
(m≈12, n≈12)
・PFPE含有シラン化合物(a)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1,3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、ビス(4-アミノシクロヘキシル)メタン40gを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルトリメトキシシラン67mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(a)を得た。得られたPFPE含有シラン化合物(a)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を97mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が87mol%、CH2CH3が13mol%であった。
PFPE含有シラン化合物(a)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)12-(OCF2CF2)12-OCF2-CONH-C6H10-CH2-C6H10-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 1)
- Preparation of PFPE-containing silane compound (a) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 40 g of bis(4-aminocyclohexyl)methane, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 67 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (a) represented by the following formula. The resulting PFPE-containing silane compound (a) was identified by 19 F-NMR analysis as containing -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 97 mol %. As for R′ in the following formula, 87 mol % of CH 3 and 13 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (a)
(R'O)3Si-CH2CH2CH2-NHCO - CF2- ( OCF2 ) 12- ( OCF2CF2 ) 12 - OCF2 - CONH - C6H10 - CH2 - C6H 10 -NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n -OCF2 - CONH - CH2CH2CH2 - Si(OR') 3
(m≈12, n≈12)
(製造例2)
・PFPE含有シラン化合物(b)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1,3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、ビス(4-アミノシクロヘキシル)メタン40gを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルメチルジメトキシシラン66mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(b)を得た。得られたPFPE含有シラン化合物(b)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)2(CH3)と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を97mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が85mol%、CH2CH3が15mol%であった。
PFPE含有シラン化合物(b)
(R’O)2(CH3)Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-C6H10-CH2-C6H10-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)2(CH3)
(m≒12、n≒12) (Production example 2)
- Preparation of PFPE-containing silane compound (b) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 40 g of bis(4-aminocyclohexyl)methane, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 66 mL of 3-aminopropylmethyldimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (b) represented by the following formula. The resulting PFPE-containing silane compound (b) was identified by 19 F-NMR analysis as —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 2 (CH 3 ) and the raw material —CF 2 — By comparing the integrated values of the COOCH 2 CH 3 peaks, the silane termination rate was calculated to be 97 mol %. As for R′ in the following formula, 85 mol % of CH 3 and 15 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (b)
(R'O) 2 ( CH3 )Si - CH2CH2CH2-NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - C6H10 - CH2 -C6H10 -NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n -OCF2 - CONH - CH2CH2CH2 - Si(OR') 2 ( CH3 )
(m≈12, n≈12)
・PFPE含有シラン化合物(b)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1,3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、ビス(4-アミノシクロヘキシル)メタン40gを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルメチルジメトキシシラン66mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(b)を得た。得られたPFPE含有シラン化合物(b)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)2(CH3)と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を97mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が85mol%、CH2CH3が15mol%であった。
PFPE含有シラン化合物(b)
(R’O)2(CH3)Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-C6H10-CH2-C6H10-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)2(CH3)
(m≒12、n≒12) (Production example 2)
- Preparation of PFPE-containing silane compound (b) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 40 g of bis(4-aminocyclohexyl)methane, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 66 mL of 3-aminopropylmethyldimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (b) represented by the following formula. The resulting PFPE-containing silane compound (b) was identified by 19 F-NMR analysis as —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 2 (CH 3 ) and the raw material —CF 2 — By comparing the integrated values of the COOCH 2 CH 3 peaks, the silane termination rate was calculated to be 97 mol %. As for R′ in the following formula, 85 mol % of CH 3 and 15 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (b)
(R'O) 2 ( CH3 )Si - CH2CH2CH2-NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - C6H10 - CH2 -C6H10 -NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n -OCF2 - CONH - CH2CH2CH2 - Si(OR') 2 ( CH3 )
(m≈12, n≈12)
(製造例3)
・PFPE含有シラン化合物(c)の調製
還流冷却器、温度計および撹拌機を取り付けた1000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000gを仕込み、窒素気流下、3-アミノプロピルトリメトキシシラン143mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(c)を得た。得られたPFPE含有シラン化合物(c)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を99mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が91mol%、CH2CH3が9mol%であった。
PFPE含有シラン化合物(c)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 3)
- Preparation of PFPE-containing silane compound (c) Into a 1000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) was charged with 1000 g of a PFPE-modified ester, and 143 mL of 3-aminopropyltrimethoxysilane was added under a nitrogen stream. Stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (c) represented by the following formula. The resulting PFPE-containing silane compound (c) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 99 mol %. As for R′ in the following formula, 91 mol % of CH 3 and 9 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (c)
(R'O)3Si-CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2 - Si ( OR' ) 3
(m≈12, n≈12)
・PFPE含有シラン化合物(c)の調製
還流冷却器、温度計および撹拌機を取り付けた1000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000gを仕込み、窒素気流下、3-アミノプロピルトリメトキシシラン143mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(c)を得た。得られたPFPE含有シラン化合物(c)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を99mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が91mol%、CH2CH3が9mol%であった。
PFPE含有シラン化合物(c)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 3)
- Preparation of PFPE-containing silane compound (c) Into a 1000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) was charged with 1000 g of a PFPE-modified ester, and 143 mL of 3-aminopropyltrimethoxysilane was added under a nitrogen stream. Stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (c) represented by the following formula. The resulting PFPE-containing silane compound (c) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 3 and the raw material -CF 2 -COOCH 2 CH 3 were compared, and the silane termination rate was calculated to be 99 mol %. As for R′ in the following formula, 91 mol % of CH 3 and 9 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (c)
(R'O)3Si-CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2 - Si ( OR' ) 3
(m≈12, n≈12)
(製造例4)
・PFPE含有シラン化合物(d)の調製
還流冷却器、温度計および撹拌機を取り付けた1000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000gを仕込み、窒素気流下、3-アミノプロピルメチルジメトキシシラン131mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(d)を得た。得られたPFPE含有シラン化合物(d)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)2(CH3)と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を100mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が88mol%、CH2CH3が12mol%であった。
PFPE含有シラン化合物(d)
(R’O)2(CH3)Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)2(CH3)
(m≒12、n≒12) (Production example 4)
- Preparation of PFPE-containing silane compound (d) Into a 1000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) was charged with 1000 g of a PFPE-modified ester, and 131 mL of 3-aminopropylmethyldimethoxysilane was added under a nitrogen stream. Stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (d) represented by the following formula. The resulting PFPE-containing silane compound (d) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 2 (CH 3 ) and the raw material -CF 2 - By comparing the peak integral values of COOCH 2 CH 3 , the silane termination rate was calculated to be 100 mol %. As for R′ in the following formula, 88 mol % of CH 3 and 12 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (d)
(R'O) 2 ( CH3 )Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2- Si(OR') 2 ( CH3 )
(m≈12, n≈12)
・PFPE含有シラン化合物(d)の調製
還流冷却器、温度計および撹拌機を取り付けた1000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000gを仕込み、窒素気流下、3-アミノプロピルメチルジメトキシシラン131mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(d)を得た。得られたPFPE含有シラン化合物(d)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)2(CH3)と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を100mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が88mol%、CH2CH3が12mol%であった。
PFPE含有シラン化合物(d)
(R’O)2(CH3)Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)2(CH3)
(m≒12、n≒12) (Production example 4)
- Preparation of PFPE-containing silane compound (d) Into a 1000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH3CH2OCO - CF2- ( OCF2 ) m- ( OCF2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) was charged with 1000 g of a PFPE-modified ester, and 131 mL of 3-aminopropylmethyldimethoxysilane was added under a nitrogen stream. Stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (d) represented by the following formula. The resulting PFPE-containing silane compound (d) was identified by 19 F-NMR analysis as -CF 2 -CONH-CH 2 CH 2 CH 2 -Si(OR') 2 (CH 3 ) and the raw material -CF 2 - By comparing the peak integral values of COOCH 2 CH 3 , the silane termination rate was calculated to be 100 mol %. As for R′ in the following formula, 88 mol % of CH 3 and 12 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (d)
(R'O) 2 ( CH3 )Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2- Si(OR') 2 ( CH3 )
(m≈12, n≈12)
(製造例5)
・PFPE含有シラン化合物(e)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1、3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、滴下漏斗を用いてエチレンジアミン13mLを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルトリメトキシシラン67mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(e)を得た。得られたPFPE含有シラン化合物(e)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を99mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が89mol%、CH2CH3が11mol%であった。
PFPE含有シラン化合物(e)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONHCH2CH2NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 5)
Preparation of PFPE-containing silane compound (e) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH 3 CH 2 OCO—CF 2 —(OCF 2 ) m —(OCF 2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester represented by 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 13 mL of ethylenediamine using a dropping funnel, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 67 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (e) represented by the following formula. The resulting PFPE-containing silane compound (e) was identified by 19 F-NMR analysis as containing —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 3 and the starting material —CF 2 —COOCH 2 CH 3 . were compared, and the silane termination rate was calculated to be 99 mol %. As for R′ in the following formula, 89 mol % of CH 3 and 11 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (e)
(R'O)3Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONHCH2CH2NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2 - Si(OR') 3
(m≈12, n≈12)
・PFPE含有シラン化合物(e)の調製
還流冷却器、温度計および撹拌機を取り付けた2000mLの4つ口フラスコに、平均組成CH3CH2OCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-COOCH2CH3(m≒12、n≒12)で表されるPFPE変性エステル体1000g、1、3-ビス(トリフルオロメチル)ベンゼン500gを仕込み、窒素気流下、滴下漏斗を用いてエチレンジアミン13mLを加えた後、25℃にて1時間攪拌した。続いて、3-アミノプロピルトリメトキシシラン67mLを加えた後、25℃にて1時間攪拌した。その後減圧下で揮発分を留去することにより、下式で表されるPFPE含有シラン化合物(e)を得た。得られたPFPE含有シラン化合物(e)は、19F-NMR分析により、-CF 2 -CONH-CH2CH2CH2-Si(OR’)3と原料である-CF 2 -COOCH2CH3のピークの積分値を比較し、シラン末端化率を99mol%と算出した。なお、下式中のR’としては、1H-NMR分析により、CH3が89mol%、CH2CH3が11mol%であった。
PFPE含有シラン化合物(e)
(R’O)3Si-CH2CH2CH2-NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONHCH2CH2NHCO-CF2-(OCF2)m-(OCF2CF2)n-OCF2-CONH-CH2CH2CH2-Si(OR’)3
(m≒12、n≒12) (Production example 5)
Preparation of PFPE-containing silane compound (e) Into a 2000 mL 4-necked flask equipped with a reflux condenser, thermometer and stirrer was added the average composition CH 3 CH 2 OCO—CF 2 —(OCF 2 ) m —(OCF 2 ). CF 2 ) n -OCF 2 -COOCH 2 CH 3 (m≈12, n≈12) PFPE-modified ester represented by 1000 g and 1,3-bis(trifluoromethyl)benzene 500 g were charged, under a nitrogen stream, After adding 13 mL of ethylenediamine using a dropping funnel, the mixture was stirred at 25° C. for 1 hour. Subsequently, after adding 67 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, volatile matter was distilled off under reduced pressure to obtain a PFPE-containing silane compound (e) represented by the following formula. The resulting PFPE-containing silane compound (e) was identified by 19 F-NMR analysis as containing —CF 2 —CONH—CH 2 CH 2 CH 2 —Si(OR′) 3 and the starting material —CF 2 —COOCH 2 CH 3 . were compared, and the silane termination rate was calculated to be 99 mol %. As for R′ in the following formula, 89 mol % of CH 3 and 11 mol % of CH 2 CH 3 were found by 1 H-NMR analysis.
PFPE-containing silane compound (e)
(R'O)3Si - CH2CH2CH2 - NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONHCH2CH2NHCO - CF2- ( OCF2 ) m- ( OCF2CF2 ) n - OCF2 - CONH - CH2CH2CH2 - Si(OR') 3
(m≈12, n≈12)
(実施例1)
・硬化性組成物の調製
PFPE含有シラン化合物(a)100質量部、架橋剤としてメチルトリメトキシシラン4質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 1)
Preparation of curable composition A plastic container for mixing 100 parts by mass of silane compound (a) containing PFPE, 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, and 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst. and stirred using a rotation/revolution mixer to prepare a curable composition.
・硬化性組成物の調製
PFPE含有シラン化合物(a)100質量部、架橋剤としてメチルトリメトキシシラン4質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 1)
Preparation of curable composition A plastic container for mixing 100 parts by mass of silane compound (a) containing PFPE, 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, and 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst. and stirred using a rotation/revolution mixer to prepare a curable composition.
(実施例2)
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(b)を用いた以外は実施例1と同様にして、硬化性組成物を調製した。 (Example 2)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (b) was used instead of the PFPE-containing silane compound (a).
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(b)を用いた以外は実施例1と同様にして、硬化性組成物を調製した。 (Example 2)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (b) was used instead of the PFPE-containing silane compound (a).
(実施例3)
触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)に代えてジブチルビス(トリエトキシシロキシ)スズ0.1質量部を用い、さらに3-アミノプロピルトリエトキシラン0.5質量部を加えた以外は、実施例1と同様に行い、硬化性組成物を調製した。 (Example 3)
Example except that 0.1 part by mass of dibutylbis(triethoxysiloxy)tin was used instead of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst, and 0.5 part by mass of 3-aminopropyltriethoxylan was added. 1 to prepare a curable composition.
触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)に代えてジブチルビス(トリエトキシシロキシ)スズ0.1質量部を用い、さらに3-アミノプロピルトリエトキシラン0.5質量部を加えた以外は、実施例1と同様に行い、硬化性組成物を調製した。 (Example 3)
Example except that 0.1 part by mass of dibutylbis(triethoxysiloxy)tin was used instead of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst, and 0.5 part by mass of 3-aminopropyltriethoxylan was added. 1 to prepare a curable composition.
(実施例4)
PFPE含有シラン化合物(a)80質量部、PFPE含有シラン化合物(c)20質量部、架橋剤としてメチルトリメトキシシラン4質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 4)
80 parts by mass of silane compound (a) containing PFPE, 20 parts by mass of silane compound (c) containing PFPE, 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, and 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst are mixed. A curable composition was prepared by weighing in a plastic container for the above and stirring using a rotation/revolution mixer.
PFPE含有シラン化合物(a)80質量部、PFPE含有シラン化合物(c)20質量部、架橋剤としてメチルトリメトキシシラン4質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 4)
80 parts by mass of silane compound (a) containing PFPE, 20 parts by mass of silane compound (c) containing PFPE, 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, and 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst are mixed. A curable composition was prepared by weighing in a plastic container for the above and stirring using a rotation/revolution mixer.
(実施例5)
実施例4の組成に加えて、さらにトリス(3-トリメトキシシリルプロピル)イソシアヌレート0.3質量部を加え、硬化性組成物を調製した。 (Example 5)
In addition to the composition of Example 4, 0.3 parts by mass of tris(3-trimethoxysilylpropyl)isocyanurate was further added to prepare a curable composition.
実施例4の組成に加えて、さらにトリス(3-トリメトキシシリルプロピル)イソシアヌレート0.3質量部を加え、硬化性組成物を調製した。 (Example 5)
In addition to the composition of Example 4, 0.3 parts by mass of tris(3-trimethoxysilylpropyl)isocyanurate was further added to prepare a curable composition.
(実施例6)
実施例5の組成に加えて、さらにヘキサメチルジシラザンで表面処理されたフュームドシリカ3.0質量部を加え、硬化性組成物を調製した。ここで、本実施例で用いたフュームドシリカのカーボン量は3.5質量%であった。 (Example 6)
In addition to the composition of Example 5, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition. Here, the amount of carbon in the fumed silica used in this example was 3.5% by mass.
実施例5の組成に加えて、さらにヘキサメチルジシラザンで表面処理されたフュームドシリカ3.0質量部を加え、硬化性組成物を調製した。ここで、本実施例で用いたフュームドシリカのカーボン量は3.5質量%であった。 (Example 6)
In addition to the composition of Example 5, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition. Here, the amount of carbon in the fumed silica used in this example was 3.5% by mass.
(実施例7)
PFPE含有シラン化合物(a)を60部、PFPE含有シラン化合物(d)を40部、架橋剤としてメチルトリメトキシシラン4質量部、トリス(3-トリメトキシシリルプロピル)イソシアヌレート0.3質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 7)
60 parts of PFPE-containing silane compound (a), 40 parts of PFPE-containing silane compound (d), 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, 0.3 parts by mass of tris(3-trimethoxysilylpropyl) isocyanurate, And 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst were weighed into a mixing plastic container and stirred using a rotation/revolution mixer to prepare a curable composition.
PFPE含有シラン化合物(a)を60部、PFPE含有シラン化合物(d)を40部、架橋剤としてメチルトリメトキシシラン4質量部、トリス(3-トリメトキシシリルプロピル)イソシアヌレート0.3質量部、および触媒としてジイソプロポキシチタンビス(エチルアセトアセテート)2質量部を混合用のプラスチック容器に秤量し、自転公転ミキサーを用いて撹拌を行い、硬化性組成物を調製した。 (Example 7)
60 parts of PFPE-containing silane compound (a), 40 parts of PFPE-containing silane compound (d), 4 parts by mass of methyltrimethoxysilane as a cross-linking agent, 0.3 parts by mass of tris(3-trimethoxysilylpropyl) isocyanurate, And 2 parts by mass of diisopropoxytitanium bis(ethylacetoacetate) as a catalyst were weighed into a mixing plastic container and stirred using a rotation/revolution mixer to prepare a curable composition.
(実施例8)
PFPE含有シラン化合物(a)をPFPE含有シラン化合物(d)の配合比を80:20に変更した以外は実施例7と同様にして、硬化性組成物を調製した。 (Example 8)
A curable composition was prepared in the same manner as in Example 7, except that the blending ratio of the PFPE-containing silane compound (a) to the PFPE-containing silane compound (d) was changed to 80:20.
PFPE含有シラン化合物(a)をPFPE含有シラン化合物(d)の配合比を80:20に変更した以外は実施例7と同様にして、硬化性組成物を調製した。 (Example 8)
A curable composition was prepared in the same manner as in Example 7, except that the blending ratio of the PFPE-containing silane compound (a) to the PFPE-containing silane compound (d) was changed to 80:20.
(実施例9)
実施例8の組成に加えて、さらにヘキサメチルジシラザンで表面処理されたフュームドシリカ3.0質量部を加え、硬化性組成物を調製した。 (Example 9)
In addition to the composition of Example 8, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition.
実施例8の組成に加えて、さらにヘキサメチルジシラザンで表面処理されたフュームドシリカ3.0質量部を加え、硬化性組成物を調製した。 (Example 9)
In addition to the composition of Example 8, 3.0 parts by mass of fumed silica surface-treated with hexamethyldisilazane was added to prepare a curable composition.
(比較例1)
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(c)を用いた以外は実施例1と同様にして、硬化性組成物を調製した。 (Comparative example 1)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (c) was used instead of the PFPE-containing silane compound (a).
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(c)を用いた以外は実施例1と同様にして、硬化性組成物を調製した。 (Comparative example 1)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (c) was used instead of the PFPE-containing silane compound (a).
(比較例2)
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(e)を用い、メチルトリメトキシシランの量を2質量部に変更した以外は実施例1と同様にして、硬化性組成物を調製した。 (Comparative example 2)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (e) was used instead of the PFPE-containing silane compound (a), and the amount of methyltrimethoxysilane was changed to 2 parts by mass. .
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(e)を用い、メチルトリメトキシシランの量を2質量部に変更した以外は実施例1と同様にして、硬化性組成物を調製した。 (Comparative example 2)
A curable composition was prepared in the same manner as in Example 1, except that the PFPE-containing silane compound (e) was used instead of the PFPE-containing silane compound (a), and the amount of methyltrimethoxysilane was changed to 2 parts by mass. .
(比較例3)
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(e)を用いた以外は実施例3と同様にして、硬化性組成物を調製した。 (Comparative Example 3)
A curable composition was prepared in the same manner as in Example 3, except that the PFPE-containing silane compound (e) was used instead of the PFPE-containing silane compound (a).
PFPE含有シラン化合物(a)の代わりにPFPE含有シラン化合物(e)を用いた以外は実施例3と同様にして、硬化性組成物を調製した。 (Comparative Example 3)
A curable composition was prepared in the same manner as in Example 3, except that the PFPE-containing silane compound (e) was used instead of the PFPE-containing silane compound (a).
(密着性試験)
実施例および比較例の各硬化性組成物を、基材であるエポキシガラス板(新神戸電機株式会社製、KEL-GEF)に、スキージングにて20mm×20mm、厚み500μmとなるように塗布し、23℃/50%RH環境下で7日間硬化させた。このようにして得た硬化物にカッターで20mmの長さの切れ目を入れ、切れ目より指で硬化物をゆっくりと剥がした。剥がした後の硬化物の凝集破壊率を目視で判定し、以下の基準で基材との密着性を評価した。 (Adhesion test)
Each curable composition of Examples and Comparative Examples was applied to an epoxy glass plate (manufactured by Shin-Kobe Electric Machinery Co., Ltd., KEL-GEF) as a base material by squeegeeing so as to have a thickness of 20 mm × 20 mm and a thickness of 500 μm. It was cured for 7 days under an environment of 23°C/50% RH. A cut of 20 mm was made in the cured product thus obtained with a cutter, and the cured product was slowly peeled off from the cut with a finger. The cohesive failure rate of the cured product after peeling was visually determined, and the adhesion to the substrate was evaluated according to the following criteria.
実施例および比較例の各硬化性組成物を、基材であるエポキシガラス板(新神戸電機株式会社製、KEL-GEF)に、スキージングにて20mm×20mm、厚み500μmとなるように塗布し、23℃/50%RH環境下で7日間硬化させた。このようにして得た硬化物にカッターで20mmの長さの切れ目を入れ、切れ目より指で硬化物をゆっくりと剥がした。剥がした後の硬化物の凝集破壊率を目視で判定し、以下の基準で基材との密着性を評価した。 (Adhesion test)
Each curable composition of Examples and Comparative Examples was applied to an epoxy glass plate (manufactured by Shin-Kobe Electric Machinery Co., Ltd., KEL-GEF) as a base material by squeegeeing so as to have a thickness of 20 mm × 20 mm and a thickness of 500 μm. It was cured for 7 days under an environment of 23°C/50% RH. A cut of 20 mm was made in the cured product thus obtained with a cutter, and the cured product was slowly peeled off from the cut with a finger. The cohesive failure rate of the cured product after peeling was visually determined, and the adhesion to the substrate was evaluated according to the following criteria.
凝集破壊率の評価:
4:凝集破壊率80%以上
3:凝集破壊率60%以上80%未満
2:凝集破壊率30%以上60%未満
1:凝集破壊率30%未満 Evaluation of cohesive failure rate:
4: Cohesive failure rate 80% or more 3: Cohesive failure rate 60% or more and less than 80% 2: Cohesive failure rate 30% or more and less than 60% 1: Cohesive failure rate less than 30%
4:凝集破壊率80%以上
3:凝集破壊率60%以上80%未満
2:凝集破壊率30%以上60%未満
1:凝集破壊率30%未満 Evaluation of cohesive failure rate:
4: Cohesive failure rate 80% or more 3: Cohesive failure rate 60% or more and less than 80% 2: Cohesive failure rate 30% or more and less than 60% 1: Cohesive failure rate less than 30%
表1に示されるように、実施例、すなわち一般式(I)において環状炭化水素基を有するPFPE含有シラン化合物を用いた硬化性組成物は、凝集破壊率が高く、密着性に優れることがわかった。一方で比較例、すなわち一般式(I)において環状炭化水素基を有さない化合物を用いた場合は、硬化性組成物と基材との間で剥離が生じた。すなわち、接着剤としての有効性において、実施例の硬化性組成物の方が優れていた。
As shown in Table 1, the curable compositions of Examples, that is, the curable compositions using the PFPE-containing silane compound having a cyclic hydrocarbon group in the general formula (I) had a high cohesive failure rate and excellent adhesion. rice field. On the other hand, in a comparative example, that is, when a compound having no cyclic hydrocarbon group in general formula (I) was used, peeling occurred between the curable composition and the substrate. That is, the curable compositions of Examples were superior in terms of effectiveness as adhesives.
(流動性試験)
実施例6および9で調製した硬化性組成物0.1gを、45度に傾斜させたアルミニウム板(JIS H 4000 A1050Pに準拠)にシリンジを用いて円状に塗布し、10秒後に流れた距離(mm)を測定し、流動性値とした。流動性値は、15mm以下の範囲であると、組成物の流動性が抑えられ、安定な硬化物の形成性に優れている。流動性値は、より好ましくは10mm以下、特に好ましくは5mm以下の範囲である。実施例6および9の組成物は、いずれも流動性値が3mmであり、組成物の流動性が抑えられていることが示された。 (fluidity test)
0.1 g of the curable composition prepared in Examples 6 and 9 was applied in a circle using a syringe to an aluminum plate (in accordance with JIS H 4000 A1050P) inclined at 45 degrees, and the distance flowed after 10 seconds (mm) was measured and taken as the fluidity value. When the fluidity value is in the range of 15 mm or less, the fluidity of the composition is suppressed and the formation of a stable cured product is excellent. The fluidity value is more preferably in the range of 10 mm or less, particularly preferably 5 mm or less. The compositions of Examples 6 and 9 both had a fluidity value of 3 mm, indicating that the fluidity of the composition was suppressed.
実施例6および9で調製した硬化性組成物0.1gを、45度に傾斜させたアルミニウム板(JIS H 4000 A1050Pに準拠)にシリンジを用いて円状に塗布し、10秒後に流れた距離(mm)を測定し、流動性値とした。流動性値は、15mm以下の範囲であると、組成物の流動性が抑えられ、安定な硬化物の形成性に優れている。流動性値は、より好ましくは10mm以下、特に好ましくは5mm以下の範囲である。実施例6および9の組成物は、いずれも流動性値が3mmであり、組成物の流動性が抑えられていることが示された。 (fluidity test)
0.1 g of the curable composition prepared in Examples 6 and 9 was applied in a circle using a syringe to an aluminum plate (in accordance with JIS H 4000 A1050P) inclined at 45 degrees, and the distance flowed after 10 seconds (mm) was measured and taken as the fluidity value. When the fluidity value is in the range of 15 mm or less, the fluidity of the composition is suppressed and the formation of a stable cured product is excellent. The fluidity value is more preferably in the range of 10 mm or less, particularly preferably 5 mm or less. The compositions of Examples 6 and 9 both had a fluidity value of 3 mm, indicating that the fluidity of the composition was suppressed.
本発明は、室温で湿気により硬化が可能であり、基材との密着性に優れた硬化性組成物を提供する。密着性が良好であるため優れた接着性をもたらすので、本発明の硬化性組成物は接着における信頼性が高く、電気電子部品周辺や車載用部品周辺用途において好適に使用され得る。
The present invention provides a curable composition that can be cured by humidity at room temperature and has excellent adhesion to substrates. Since the curable composition of the present invention has excellent adhesiveness due to its good adhesion, the curable composition of the present invention has high reliability in adhesion and can be suitably used around electric and electronic parts and parts for vehicles.
Claims (16)
- (a)下記式(I):
[式中:
R3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
R4は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
pは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 pR4 3-p)jにおいて少なくとも1つのSiR3 pR4 3-pは、pが0~2の整数であり、
qは、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiR3 qR4 3-q)jにおいて少なくとも1つのSiR3 qR4 3-qは、qが0~2の整数であり、
R5は、各出現においてそれぞれ独立して、j+1価の有機基であり、
R6は、各出現においてそれぞれ独立して、-R22-R21-R23-であり、
R21は、各出現においてそれぞれ独立して、シクロアルキレン含有基であり、
R22は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R23は、各出現においてそれぞれ独立して、単結合または二価の有機基であり、
R7は、各出現においてそれぞれ独立して、水素原子またはC1-20アルキル基であり、
PFPE1は、各出現においてそれぞれ独立して、-RF-RFE-であり、
RFは、-(CfF2f)-であり(ここで、fは1~10の整数である)、
RFEは、式:
-(OCF2)a1-(OC2F4)a2-(OC3X10 6)a3-(OC4F8)a4-(OC5F10)a5-(OC6F12)a6-(OC7F14)a7-(OC8F16)a8-
(式中:
a1、a2、a3、a4、a5、a6、a7およびa8は、それぞれ独立して0~200の整数であり、a1、a2、a3、a4、a5、a6、a7およびa8の和は、少なくとも5であり、添字a1、a2、a3、a4、a5、a6、a7またはa8を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意であり、
X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、ただし、全てのX10が水素原子または塩素原子であるとき、a1、a2、a4、a5、a6、a7およびa8の少なくとも1つは、1以上の整数である)
で表される2価のフルオロポリエーテル基であり、
jは、各出現において独立して、1~9の整数であり、
kは、1以上の整数である]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物;
(b)Si原子と結合したOR2基を少なくとも2個有する化合物(ここで、R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基である)(ただし、前記(a)に該当するものを除く)またはその部分加水分解縮合物;並びに
(c)縮合触媒
を含む、硬化性組成物。 (a) the following formula (I):
[In the formula:
each occurrence of R 3 is independently a hydrogen atom or a monovalent organic group;
R 4 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
p is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 p R 4 3-p in (SiR 3 p R 4 3-p ) j is an integer of 0 to 2;
q is independently at each occurrence an integer from 0 to 3;
provided that at least one SiR 3 q R 4 3-q in (SiR 3 q R 4 3-q ) j is an integer of 0 to 2;
R 5 is independently at each occurrence a j+1 valent organic group;
R 6 is independently at each occurrence -R 22 -R 21 -R 23 -;
R 21 is independently at each occurrence a cycloalkylene-containing group;
R 22 is independently at each occurrence a single bond or a divalent organic group;
R 23 is independently at each occurrence a single bond or a divalent organic group;
R 7 is independently at each occurrence a hydrogen atom or a C 1-20 alkyl group;
PFPE 1 is independently at each occurrence -R F -R FE -;
R F is -(C f F 2f )-, where f is an integer from 1 to 10;
RFE has the formula:
-( OCF2 ) a1- ( OC2F4 ) a2- ( OC3X106 ) a3- (OC4F8 ) a4- ( OC5F10 ) a5- ( OC6F12 ) a6- ( OC 7 F 14 ) a7 - (OC 8 F 16 ) a8 -
(in the formula:
a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer from 0 to 200, and the sum of a1, a2, a3, a4, a5, a6, a7 and a8 is at least 5 and the order of existence of each repeating unit enclosed in parentheses with subscripts a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula,
X 10 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom, with the proviso that when all X 10 are hydrogen atoms or chlorine atoms, a1, a2, a4, a5, a6, a7 and at least one of a8 is an integer of 1 or more)
A divalent fluoropolyether group represented by
j is independently at each occurrence an integer from 1 to 9;
k is an integer of 1 or more]
A perfluoro (poly) ether group-containing silane compound represented by;
(b) a compound having at least two OR 2 groups bonded to a Si atom (wherein each occurrence of R 2 is independently a hydrogen atom or a monovalent organic group) (with the proviso that the above (a ) or a partial hydrolytic condensate thereof; and (c) a condensation catalyst. - 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、
R21が、各出現においてそれぞれ独立して、炭素数5~12の単環式、二環式または三環式シクロアルキレン基を含有する基であり、
R22が、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、
R23が、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基である、請求項1に記載の硬化性組成物。 (a) in the perfluoro(poly)ether group-containing silane compound represented by formula (I),
R 21 is independently at each occurrence a group containing a monocyclic, bicyclic or tricyclic cycloalkylene group having 5 to 12 carbon atoms;
R 22 is independently at each occurrence a single bond or a C 1-6 alkylene group;
The curable composition of claim 1, wherein R 23 is independently at each occurrence a single bond or a C 1-6 alkylene group. - 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、
R6が、環の水素原子が置換されていてもよい下記式:
[式中、
R22は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、
R23は、各出現においてそれぞれ独立して、単結合またはC1-6アルキレン基であり、
R24は、各出現においてそれぞれ独立して、C1-6アルキレン基である。]
から選択される基である、請求項1に記載の硬化性組成物。 (a) in the perfluoro(poly)ether group-containing silane compound represented by formula (I),
R 6 is represented by the following formula in which a ring hydrogen atom may be substituted:
[In the formula,
R 22 at each occurrence is independently a single bond or a C 1-6 alkylene group;
each occurrence of R 23 is independently a single bond or a C 1-6 alkylene group;
R 24 is independently at each occurrence a C 1-6 alkylene group. ]
2. The curable composition of claim 1, which is a group selected from - 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、X10が、全てフッ素原子である、請求項1に記載の硬化性組成物。 2. The curable composition according to claim 1, wherein in (a) the perfluoro(poly)ether group-containing silane compound represented by formula (I), all X 10 are fluorine atoms.
- 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、
RFEが、各出現においてそれぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)または(f5):
-(OC3F6)a3- (f1)
[式中、a3は5~200の整数である。]
-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f2)
[式中、a3およびa4は、それぞれ独立して、0~30の整数であり;
a1およびa2は、それぞれ独立して、1~200の整数であり;
a1、a2、a3およびa4の和は、10~200の整数であり;
添字a1、a2、a3またはa4を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。]
-(R16-R17)g- (f3)
[式中、R16は、OCF2またはOC2F4であり;
R17は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から選択される2または3つの基の組み合わせであり;
gは、2~100の整数である。]
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f4)
[式中、a2は、1~200の整数であり、a1、a3、a4、a5およびa6は、それぞれ独立して0~200の整数であって、a1、a2、a3、a4、a5およびa6の和は少なくとも5であり、また、a1、a2、a3、a4、a5またはa6を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a6-(OC5F10)a5-(OC4F8)a4-(OC3F6)a3-(OC2F4)a2-(OCF2)a1- (f5)
[式中、a1は、1~200の整数であり、a2、a3、a4、a5およびa6は、それぞれ独立して0~200の整数であって、a1、a2、a3、a4、a5およびa6の和は少なくとも5であり、また、a1、a2、a3、a4、a5またはa6を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である、請求項1に記載の硬化性組成物。 (a) in the perfluoro(poly)ether group-containing silane compound represented by formula (I),
R FE is independently at each occurrence of formula (f1), (f2), (f3), (f4) or (f5):
- (OC 3 F 6 ) a3 - (f1)
[In the formula, a3 is an integer of 5 to 200. ]
- (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f2)
[Wherein, a3 and a4 are each independently an integer of 0 to 30;
a1 and a2 are each independently an integer from 1 to 200;
the sum of a1, a2, a3 and a4 is an integer from 10 to 200;
The order of existence of each repeating unit enclosed in parentheses with subscript a1, a2, a3 or a4 is arbitrary in the formula. ]
-(R 16 -R 17 ) g - (f3)
[wherein R 16 is OCF 2 or OC 2 F 4 ;
R 17 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or two or three groups selected from these groups. is a combination of groups;
g is an integer from 2 to 100; ]
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f4)
[wherein a2 is an integer of 1 to 200, a1, a3, a4, a5 and a6 are each independently an integer of 0 to 200, a1, a2, a3, a4, a5 and a6 is at least 5, and the order of existence of each repeating unit bracketed with a1, a2, a3, a4, a5 or a6 is arbitrary in the formula. ]
- (OC 6 F 12 ) a6 - (OC 5 F 10 ) a5 - (OC 4 F 8 ) a4 - (OC 3 F 6 ) a3 - (OC 2 F 4 ) a2 - (OCF 2 ) a1 - (f5)
[Wherein, a1 is an integer of 1 to 200, a2, a3, a4, a5 and a6 are each independently an integer of 0 to 200, and a1, a2, a3, a4, a5 and a6 is at least 5, and the order of existence of each repeating unit bracketed with a1, a2, a3, a4, a5 or a6 is arbitrary in the formula. ]
The curable composition according to claim 1, which is a group represented by: - 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、R7が全て水素原子である、請求項1に記載の硬化性組成物。 2. The curable composition according to claim 1, wherein in (a) the perfluoro(poly)ether group-containing silane compound represented by formula (I), all R7 are hydrogen atoms.
- 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、R5がともに二価の有機基であり、jが1である、請求項1に記載の硬化性組成物。 2. Curability according to claim 1, wherein in the (a) perfluoro(poly)ether group-containing silane compound represented by formula (I), both R 5 are divalent organic groups and j is 1. Composition.
- 前記(a)式(I)で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物において、R5がともにC1-6アルキレン基であり、jが1である、請求項7に記載の硬化性組成物。 Curing according to claim 7, wherein (a) in the perfluoro(poly)ether group-containing silane compound represented by formula (I), both R 5 are C 1-6 alkylene groups and j is 1. sex composition.
- 前記(a)式(I)で表されるフパーフルオロ(ポリ)エーテル基含有シラン化合物が、下記式(A)、(B)、(C)、または(D):
[式中:
R11およびR11”は、各出現において、それぞれ独立して、水素原子またはハロゲン原子であり、
R12およびR12”は、各出現において、それぞれ独立して、水素原子または低級アルキル基であり、
R13およびR13”は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
R14およびR14”は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基であり、
X2は、各出現においてそれぞれ独立して、単結合または2価の有機基であり、
n1は、(-SiR13 n1R14 3-n1)単位毎、または(-SiR13” n1R14” 3-n1)単位毎に独立して、0~3の整数であり、
X1は、それぞれ独立して、アミド結合に連結する単結合または2~10価の有機基であり、
tは、それぞれ独立して、1~10の整数であり、
α1は、1~9の整数であり、
X3は、それぞれ独立して、2~10価の有機基であり、
β1は、1~9の整数であり、
X5は、それぞれ独立して、2~10価の有機基であり、
γ1は、1~9の整数であり、
Raは、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72 q1R73 r1であり、
Z3は、各出現においてそれぞれ独立して、酸素原子または2価の有機基であり、
R71は、各出現においてそれぞれ独立して、Ra’であり、
Ra’は、Raと同意義であり、
Ra中、Z3基を介して直鎖状に連結されるSiは最大で5個であり、
R72は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基であり、
p1は、各出現においてそれぞれ独立して、0~3の整数であり、
q1は、各出現においてそれぞれ独立して、0~3の整数であり、
r1は、各出現においてそれぞれ独立して、0~3の整数であり、
ただし、(-Z3-SiR71 p1R72 q1R73 r1)毎において、p1、q1およびr1の和は3であり、
RbおよびRb”は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
RcおよびRc”は、各出現においてそれぞれ独立して、水素原子または低級アルキル基であり、
Ra”は、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72” q1R73 r1であり、
Z3、R71、R73、p1、q1、およびr1は、上記と同意義であり、
R72”は、R72と同意義であり、
k1は、各出現においてそれぞれ独立して、0~3の整数であり、
l1は、各出現においてそれぞれ独立して、0~3の整数であり、
m1は、各出現においてそれぞれ独立して、0~3の整数であり、
ただし、(SiRa k1Rb l1Rc m1)毎または(SiRa” k1Rb” l1Rc” m1)毎において、k1、l1およびm1の和は、3であり、
X7は、それぞれ独立して、2~10価の有機基であり、
δ1は、1~9の整数であり、
Rdは、各出現においてそれぞれ独立して、-Z4-CR81 p2R82 q2R83 r2であり、
Rd”は、各出現においてそれぞれ独立して、-Z4-CR81 p2R82” q2R83 r2であり、
Z4は、各出現においてそれぞれ独立して、酸素原子または2価の有機基であり、
R81は、各出現においてそれぞれ独立して、Rd’であり、
Rd’は、Rdと同意義であり、
R82は、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2であり、
Yは、各出現においてそれぞれ独立して、2価の有機基であり、
R85は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、
R86は、各出現においてそれぞれ独立して、水素原子または低級アルキル基であり、
R82”は、各出現においてそれぞれ独立して、-Y-SiR85” n2R86” 3-n2であり、
R85”およびR86”は、それぞれ、R85およびR86と同意義であり、
R83は、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基であり、
n2は、(-Y-SiR85 n2R86 3-n2)単位毎、または(-Y-SiR85” n2R86” 3-n2)単位毎に独立して、0~3の整数であり、
p2は、各出現においてそれぞれ独立して、0~3の整数であり、
q2は、各出現においてそれぞれ独立して、0~3の整数であり、
r2は、各出現においてそれぞれ独立して、0~3の整数であり、
ただし、(-Z4-CR81 p2R82 q2R83 r2)毎、または(-Z4-CR81 p2R82” q2R83 r2)毎において、p2、q2およびr2の和は3であり、
Reは、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2であり、
Re”は、各出現においてそれぞれ独立して、-Y-SiR85” n2R86” 3-n2であり、
Rfは、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基であり、
Rf”は、Rfと同意義であり、
k2は、各出現においてそれぞれ独立して、0~3の整数であり、
l2は、各出現においてそれぞれ独立して、0~3の整数であり、
m2は、各出現においてそれぞれ独立して、0~3の整数であり、
ただし、k2、l2およびm2の和は3であり、
R6、R7、PFPE1、rは、請求項1に定義されたとおりである]
で表される、請求項1に記載の硬化性組成物。 The hupperfluoro(poly)ether group-containing silane compound (a) represented by formula (I) is represented by the following formula (A), (B), (C), or (D):
[In the formula:
R 11 and R 11″ at each occurrence are each independently a hydrogen atom or a halogen atom;
R 12 and R 12″ at each occurrence are each independently a hydrogen atom or a lower alkyl group;
R 13 and R 13″ are each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R 14 and R 14″ at each occurrence are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
X 2 is independently at each occurrence a single bond or a divalent organic group;
n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n1 ) unit or each (-SiR 13″ n1 R 14″ 3-n1 ) unit;
each X 1 is independently a single bond or a divalent to decavalent organic group linked to an amide bond;
t is each independently an integer from 1 to 10,
α1 is an integer from 1 to 9,
each X 3 is independently a divalent to decavalent organic group,
β1 is an integer from 1 to 9,
each X 5 is independently a divalent to decavalent organic group,
γ1 is an integer from 1 to 9,
R a is independently at each occurrence -Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ;
Z 3 is independently at each occurrence an oxygen atom or a divalent organic group,
R 71 is independently R a′ at each occurrence;
R a' has the same meaning as R a ,
In Ra, the maximum number of Si linked in a straight chain via 3 Z groups is 5,
R 72 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
each occurrence of R 73 is independently a hydrogen atom or a lower alkyl group;
p1 is independently at each occurrence an integer from 0 to 3;
q1 is independently at each occurrence an integer from 0 to 3;
r1 is independently at each occurrence an integer from 0 to 3;
provided that for each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ), the sum of p1, q1 and r1 is 3;
R b and R b″ are each independently at each occurrence a hydroxyl group or a hydrolyzable group;
R c and R c″ at each occurrence are each independently a hydrogen atom or a lower alkyl group;
R a″ at each occurrence is independently —Z 3 —SiR 71 p1 R 72″ q1 R 73 r1 ;
Z 3 , R 71 , R 73 , p1, q1, and r1 are as defined above;
R 72″ has the same meaning as R 72 ,
k1 is independently at each occurrence an integer from 0 to 3;
l1 is independently at each occurrence an integer from 0 to 3;
m1 is independently at each occurrence an integer from 0 to 3;
provided that for each (SiR a k1 R b l1 R c m1 ) or each (SiR a″ k1 R b″ l1 R c″ m1 ), the sum of k1, l1 and m1 is 3;
each X 7 is independently a divalent to decavalent organic group,
δ1 is an integer from 1 to 9,
R d is independently at each occurrence -Z 4 -CR 81 p2 R 82 q2 R 83 r2 ;
R d″ is independently at each occurrence -Z 4 -CR 81 p2 R 82″ q2 R 83 r2 ;
Z 4 is independently at each occurrence an oxygen atom or a divalent organic group,
R 81 is independently at each occurrence R d' ;
R d' has the same meaning as R d ;
R 82 is independently at each occurrence -Y-SiR 85 n2 R 86 3-n2 ;
Y is independently at each occurrence a divalent organic group;
R 85 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
each occurrence of R 86 is independently a hydrogen atom or a lower alkyl group;
R 82″ is independently at each occurrence —Y—SiR 85″ n2 R 86″ 3-n2 ;
R 85″ and R 86″ are synonymous with R 85 and R 86 respectively;
each occurrence of R 83 is independently a hydrogen atom, a hydroxyl group, or a lower alkyl group;
n2 is an integer of 0 to 3 independently for each (-Y-SiR 85 n2 R 86 3-n2 ) unit or each (-Y-SiR 85″ n2 R 86″ 3-n2 ) unit;
p2 is independently at each occurrence an integer from 0 to 3;
q2 is independently at each occurrence an integer from 0 to 3;
r2 is independently at each occurrence an integer from 0 to 3;
provided that the sum of p2, q2 and r2 is 3 for each (-Z 4 -CR 81 p2 R 82 q2 R 83 r2 ) or (-Z 4 -CR 81 p2 R 82″ q2 R 83 r2 ) ,
R e is independently at each occurrence -Y-SiR 85 n2 R 86 3-n2 ;
R e″ is independently at each occurrence —Y—SiR 85″ n2 R 86″ 3-n2 ;
each occurrence of R f is independently a hydrogen atom, a hydroxyl group, or a lower alkyl group;
R f ″ has the same meaning as R f,
k2 is independently at each occurrence an integer from 0 to 3;
l2 is independently at each occurrence an integer from 0 to 3;
m2 is independently at each occurrence an integer from 0 to 3;
where the sum of k2, l2 and m2 is 3,
R6, R7 , PFPE1 , r are as defined in claim 1 ]
The curable composition according to claim 1, represented by: - (b)成分が、下記式:
R1 nSi(OR2)4-n
(式中、
R1は、各出現においてそれぞれ独立して、置換または非置換の1価の炭化水素基であり、
R2は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
nは、0、1または2である)
で示される化合物またはその部分加水分解縮合物を含む、請求項1記載の硬化性組成物。 (b) component is represented by the following formula:
R 1 n Si(OR 2 ) 4-n
(In the formula,
R 1 is independently at each occurrence a substituted or unsubstituted monovalent hydrocarbon group,
R 2 is independently at each occurrence a hydrogen atom or a monovalent organic group;
n is 0, 1 or 2)
The curable composition according to claim 1, comprising a compound represented by or a partial hydrolysis condensate thereof. - (b)成分がさらに、下記式(B2):
(式中、
Rg3は、各出現においてそれぞれ独立して、水素原子または1価の有機基であり、
Rg4は、置換または非置換の1価の炭化水素基であり、
Rg6は、各出現においてそれぞれ独立して、Rg8-Rg7-であり、
Rg7は、各出現においてそれぞれ独立して、炭素原子数1~10のアルキレン基、または、炭素原子数1~10であり主鎖中に窒素原子もしくは酸素原子を含む基であり、
Rg8は、各出現においてそれぞれ独立して、第1級アミノ基、エポキシ基、(メタ)アクリロイル基、(メタ)アクリロキシ基、メルカプト基またはイソシアナト基であり、
ε4は、2または3であり、
ε5は、0または1であり、
ε6は、1または2であるが、ただし、ε4、ε5およびε6の和は4である)
で示される化合物またはその部分加水分解縮合物を含む、請求項10に記載の硬化性組成物。 The component (b) further has the following formula (B2):
(In the formula,
each occurrence of R g3 is independently a hydrogen atom or a monovalent organic group;
R g4 is a substituted or unsubstituted monovalent hydrocarbon group,
R g6 is independently at each occurrence R g8 -R g7 -;
each occurrence of R g7 is independently an alkylene group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain;
R g8 is independently at each occurrence a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group or an isocyanato group;
ε4 is 2 or 3;
ε5 is 0 or 1;
ε6 is 1 or 2, provided that the sum of ε4, ε5 and ε6 is 4)
The curable composition according to claim 10, comprising a compound represented by or a partial hydrolysis condensate thereof. - さらに、
(d)1分子中に2個以上のアルコキシシリル基を含有し、かつ、アルコキシシリル基間を連結する基が-O-基;およびシロキサン結合を有する基以外の基である化合物、またはその部分加水分解縮合物(ただし、前記(a)で表される化合物を除く)
を含む、請求項1記載の硬化性組成物。 moreover,
(d) a compound, or a portion thereof, containing two or more alkoxysilyl groups in one molecule and wherein the group connecting the alkoxysilyl groups is an —O— group; and a group other than a group having a siloxane bond; Hydrolytic condensate (excluding the compound represented by (a) above)
The curable composition of claim 1, comprising: - 前記(d)成分が、アルコキシシリル基含有イソシアヌレート化合物、アルコキシシリル基含有カルバシラトラン化合物、アルコキシシリル基含有フマル酸エステル化合物およびアルコキシシリル基含有アミン化合物からなる群より選択される、請求項12記載の硬化性組成物。 12. The component (d) is selected from the group consisting of an alkoxysilyl group-containing isocyanurate compound, an alkoxysilyl group-containing carbasilatrane compound, an alkoxysilyl group-containing fumarate compound, and an alkoxysilyl group-containing amine compound. A curable composition as described.
- さらに、
(a2)下記一般式(II):
[式中、R3、R4、R5、R6、R7、PFPE1、p、q、jは、請求項1に定義したとおりである]
で表されるパーフルオロ(ポリ)エーテル基含有シラン化合物
を含む、請求項1記載の硬化性組成物。 moreover,
(a2) the following general formula (II):
[wherein R 3 , R 4 , R 5 , R 6 , R 7 , PFPE 1 , p, q, j are as defined in claim 1]
2. The curable composition according to claim 1, comprising a perfluoro(poly)ether group-containing silane compound represented by: - 前記パーフルオロ(ポリ)エーテル基含有シラン化合物(a)と(a2)の質量比が、10:90~90:10の範囲である、請求項14記載の硬化性組成物。 The curable composition according to claim 14, wherein the mass ratio of said perfluoro(poly)ether group-containing silane compounds (a) and (a2) is in the range of 10:90 to 90:10.
- 接着剤として用いるための、請求項1~15のいずれか一項記載の硬化性組成物。 The curable composition according to any one of claims 1 to 15, for use as an adhesive.
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WO2016199909A1 (en) * | 2015-06-12 | 2016-12-15 | ダイキン工業株式会社 | Surface treatment agent |
WO2021125059A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125062A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125061A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125060A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125058A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
-
2022
- 2022-06-08 TW TW111121284A patent/TW202313774A/en unknown
- 2022-06-08 JP JP2022537198A patent/JP7326626B2/en active Active
- 2022-06-08 WO PCT/JP2022/023045 patent/WO2022260057A1/en active Application Filing
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JPH09137027A (en) * | 1995-05-29 | 1997-05-27 | Shin Etsu Chem Co Ltd | Room temperature-curable fluoropolymer composition |
JP2007126496A (en) * | 2005-11-01 | 2007-05-24 | Shin Etsu Chem Co Ltd | Adhesive composition |
US20140302267A1 (en) * | 2011-07-26 | 2014-10-09 | Virginia Commonwealth University | Abhesive coatings |
WO2016199909A1 (en) * | 2015-06-12 | 2016-12-15 | ダイキン工業株式会社 | Surface treatment agent |
WO2021125059A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125062A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125061A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125060A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
WO2021125058A1 (en) * | 2019-12-19 | 2021-06-24 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Curable composition |
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JP7326626B2 (en) | 2023-08-15 |
JPWO2022260057A1 (en) | 2022-12-15 |
TW202313774A (en) | 2023-04-01 |
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