WO2022224987A1 - 表面処理剤 - Google Patents
表面処理剤 Download PDFInfo
- Publication number
- WO2022224987A1 WO2022224987A1 PCT/JP2022/018281 JP2022018281W WO2022224987A1 WO 2022224987 A1 WO2022224987 A1 WO 2022224987A1 JP 2022018281 W JP2022018281 W JP 2022018281W WO 2022224987 A1 WO2022224987 A1 WO 2022224987A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- independently
- occurrence
- group
- integer
- formula
- Prior art date
Links
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 65
- -1 silane compound Chemical class 0.000 claims abstract description 72
- 229910000077 silane Inorganic materials 0.000 claims abstract description 58
- 125000000962 organic group Chemical group 0.000 claims description 211
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 106
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 79
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 54
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 44
- 125000002947 alkylene group Chemical group 0.000 claims description 42
- 125000001153 fluoro group Chemical group F* 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 229910052731 fluorine Inorganic materials 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 28
- 125000004429 atom Chemical group 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 15
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 12
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 10
- 230000003373 anti-fouling effect Effects 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 60
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 45
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 35
- 239000010410 layer Substances 0.000 description 34
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 34
- 239000002335 surface treatment layer Substances 0.000 description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 27
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 24
- 238000005299 abrasion Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 18
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 15
- 229920002545 silicone oil Polymers 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 125000003709 fluoroalkyl group Chemical group 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 9
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000005702 oxyalkylene group Chemical group 0.000 description 8
- 238000007637 random forest analysis Methods 0.000 description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 7
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 7
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 7
- 230000006750 UV protection Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000005871 repellent Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000547 substituted alkyl group Chemical group 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229910003849 O-Si Inorganic materials 0.000 description 4
- 229910003872 O—Si Inorganic materials 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002292 Radical scavenging effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000005345 chemically strengthened glass Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group 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
- 238000010884 ion-beam technique Methods 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 1
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000005566 carbazolylene group Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-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
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- 229950008618 perfluamine 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
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 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
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- 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
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- 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
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Definitions
- the present disclosure relates to surface treatment agents.
- a layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer”) can be used as a so-called functional thin film on various substrates such as glass, plastic, fiber, sanitary goods, and building materials. (Patent Document 1).
- An object of the present disclosure is to provide a surface treatment agent capable of forming a surface treatment layer with higher abrasion resistance.
- R F1 is independently at each occurrence Rf 1 -R FA -O q -;
- Rf 1 is independently at each occurrence a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
- RFA is independently at each occurrence a fluoropolyether group having a branched structure;
- q is independently 0 or 1 at each occurrence;
- R S1 is independently at each occurrence a group containing a Si atom having a hydroxyl group or a hydrolyzable group;
- each X A is independently a single bond or a divalent to decavalent organic group;
- ⁇ is an integer from 1 to 9;
- ⁇ is an integer of 1-9.
- R F2 is -Rf 2 p -R FB -O q -;
- Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms;
- R FB is independently at each occurrence a linear fluoropolyether group;
- p is 0 or 1;
- q is independently 0 or 1 at each occurrence;
- R S2 is independently at each occurrence a group containing a Si atom having a hydroxyl group or a hydrolyzable group;
- each X B is independently a single bond or a divalent to decavalent organic group;
- Each ⁇ is independently an integer of 1-9.
- a fluoropolyether group-containing silane compound (B) represented by A surface treatment agent comprising [2] R FA is independently at each occurrence of the formula: - (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 X F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - [In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f being at least 1; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula, X F is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.
- R FB is independently at each occurrence of the formula: - (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 X F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f -
- a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f being at least 1;
- the order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula
- X F is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.
- R FA is, at each occurrence independently, the following formula (f1), (f2), (f3), (f4), (f5) or (f6): -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1) [Wherein, d is an integer of 1 to 200, and e is 0 or 1.
- c and d are each independently an integer of 0 to 30; e and f are each independently an integer from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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 2 independently selected from these groups or a combination of three groups,
- R 6' is OCF 2 or OC 2 F 4 ;
- R 7′ 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 independently selected from these groups a combination of two or three groups,
- g is an integer from 2 to 100
- g' is an integer from 2 to 100
- Rr is (In the formula, * indicates the binding position.) is.
- f is an integer of 1 or more and 200 or less
- a, b, c, d and e are each independently an integer of 0 or more and 200 or less
- a, b, c, d, e or The order of existence of each repeating unit enclosed in parentheses with f is arbitrary in the formula.
- R FB is independently at each occurrence represented by the following formulas (f1), (f2), (f3), (f4), (f5) or (f6): -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1) [Wherein, d is an integer of 1 to 200, and e is 0 or 1.
- c and d are each independently an integer of 0 to 30; e and f are each independently an integer from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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 2 independently selected from these groups or a combination of three groups,
- R 6' is OCF 2 or OC 2 F 4 ;
- R 7′ 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 independently selected from these groups a combination of two or three groups,
- g is an integer from 2 to 100
- g' is an integer from 2 to 100
- Rr is (In the formula, * indicates the binding position.) is.
- f is an integer of 1 or more and 200 or less
- a, b, c, d and e are each independently an integer of 0 or more and 200 or less
- a, b, c, d, e or The order of existence of each repeating unit enclosed in parentheses with f is arbitrary in the formula.
- R FA is independently at each occurrence represented by the following formula (f1a): -(OCF(CF 3 )CF 2 ) d -(OCF(CF 3 )) e - (f1a) [Wherein, d is an integer of 1 to 200, and e is 0 or 1.
- R FB is independently at each occurrence represented by the following formula (f2b): - (OCF 2 CF 2 CF 2 CF 2 ) c - (OCF 2 CF 2 CF 2 ) d - (OCF 2 CF 2 ) e - (OCF 2 ) f - (f2b) [Wherein, c and d are each independently an integer of 0 to 30; e and f are each independently an integer from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
- R S1 and R S2 are each independently at each occurrence represented by the following formula (S1), (S2), (S3), (S4) or (S5):
- R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group
- R 12 is independently at each occurrence a hydrogen atom or a monovalent organic group
- n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit
- X 11 is independently at each occurrence a single bond or a divalent organic group
- R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group
- R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1
- each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene
- R S1 and R S2 are each independently at each occurrence represented by the following formula (S1), (S3), (S4) or (S5): [In the formula: R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently at each occurrence a hydrogen atom or a monovalent organic group; n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit; X 11 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 ; each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to
- X A and X B are each independently a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [In the formula: R 51 is a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, s5 is an integer from 1 to 20, X 51 is -(X 52 ) l5 -, X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -CO-, -C(O)O-, -Si(R 53 ) 2 from the group consisting of -, -(Si(R 53 ) 2 O
- the surface treatment agent according to any one of [1] to [9] above which is a group represented by [11]
- the content of the fluoropolyether group-containing silane compound (A) is 50 mol% with respect to the total of the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B).
- [12] The surface treatment agent according to any one of [1] to [11] above, which is used as an antifouling coating agent or a waterproof coating agent.
- An article comprising a substrate and a layer formed on the substrate from the surface treating agent according to any one of [1] to [13] above.
- a surface treatment agent that can form a surface treatment layer with higher abrasion resistance.
- a "monovalent organic group” means a monovalent group containing carbon.
- the monovalent organic group is not particularly limited, it may be a hydrocarbon group or a derivative thereof.
- a derivative of a hydrocarbon group is a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.
- organic group when it shows simply as an "organic group”, it means a monovalent organic group.
- the “divalent to decavalent organic group” means a divalent to decavalent group containing carbon.
- Such a divalent to decavalent organic group is not particularly limited, but includes a divalent to decavalent group in which 1 to 9 hydrogen atoms are further eliminated from an organic group.
- Examples of divalent organic groups include, but are not particularly limited to, divalent groups in which one hydrogen atom is further removed from an organic group.
- hydrocarbon group means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon.
- Such hydrocarbon groups include, but are not limited to, C 1-20 hydrocarbon groups optionally substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic A hydrocarbon group etc. are mentioned.
- 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.
- the substituent of the "hydrocarbon group” is not particularly limited, but for example, a halogen atom, 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.
- hydrolyzable group means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being detached from the backbone of a compound by a hydrolysis reaction.
- the surface treatment agent of the present disclosure includes a silane compound (A) containing a fluoropolyether group having a branched structure and a silane compound (B) containing a linear fluoropolyether group.
- the fluoropolyether group-containing silane compound (A) has the following formula (1): [In the formula: R F1 is independently at each occurrence Rf 1 -R FA -O q -; Rf 1 is independently at each occurrence a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; RFA is independently at each occurrence a fluoropolyether group having a branched structure; q is independently 0 or 1 at each occurrence; R S1 is independently at each occurrence a group containing a Si atom having a hydroxyl group or a hydrolyzable group; each X A is independently a single bond or a divalent to decavalent organic group; ⁇ is an integer from 1 to 9; ⁇ is an integer of 1-9. ] is represented by
- R F1 is preferably independently at each occurrence Rf 1 -R FA -O q -.
- Rf 1 at each occurrence is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms.
- the "C 1-16 alkyl group" in the C 1-16 alkyl group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a straight or branched C 1-6 alkyl group, especially a C 1-3 alkyl group, more preferably a straight chain C 1-6 alkyl group, especially a C 1-3 alkyl group.
- Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group, still more preferably It is a C 1-16 perfluoroalkyl group.
- the C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, especially C 1- 3 perfluoroalkyl group, more preferably a linear C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
- q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.
- RFA at each occurrence is independently a fluoropolyether group having a branched structure.
- a fluoropolyether group is typically represented by the following formula (f0): - ( OC6F12 ) a- ( OC5F10 ) b- ( OC4F8 ) c- ( OC3XF6 )d- ( OC2F4 ) e- ( OCF2 ) f- ( f0 )
- a, b, c, d, e, and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f being at least 1;
- the order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula,
- X F is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.
- X F is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom.
- X F is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
- a, b, c, d, e and f may preferably each independently be an integer of 0-100.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
- the sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
- the repeating unit may be linear or branched, and may contain a ring structure.
- - ( OC6F12 )- is - ( OCF2CF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2CF2 ) -, - ( OCF 2 CF (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 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 ))- and the like.
- - ( 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 ))- and the like.
- -( OC4F8 )- is - ( OCF2CF2CF2CF2 )-, - ( OCF ( CF3 ) CF2CF2 )-, - ( OCF2CF ( CF3 ) CF2 )- , -( OCF2CF2CF ( CF3 ))-, -(OC( CF3 ) 2CF2 )-, -( OCF2C (CF3)2 ) - , -(OCF ( CF3 )CF( CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-.
- -(OC 3 F 6 )- (that is, in the above formula, R 3 Fa is a fluorine atom) is represented by -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -( OCF 2 CF(CF 3 ))—.
- -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-.
- the ring structure may be the following three-membered ring, four-membered ring, five-membered ring, or six-membered ring. [In the formula, * indicates a binding position. ]
- the ring structure is preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.
- the repeating unit having a ring structure can preferably be the following units. [In the formula, * indicates a binding position. ]
- the formula (f0) is represented by any one of the following formulas (f1) to (f6). -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1, preferably 1.
- c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e and f is greater than or equal to 2;
- the order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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 2 independently selected from these groups or a combination of three groups, g is an integer from 2 to 100; ];
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 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 2 independently selected from these groups or a combination of three groups,
- R 6' is OCF 2 or OC 2 F 4 ;
- R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 ,
- f is an integer of 1 or more and 200 or less
- a, b, c, d and e are each independently an integer of 0 or more and 200 or less
- a, b, c, d , e or f in parentheses may be present in any order in the formula.
- d is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35.
- e is zero. In another aspect, e is 1.
- e and f are each independently an integer of preferably 5-200, more preferably 10-200. Also, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
- 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.
- 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 -.
- R 6 , R 7 and g have the same meanings as in formula (f3) above, and have the same aspects.
- R 6′ , R 7′ and g′ have the same meanings as R 6 , R 7 and g in formula (f3) above, respectively, and have the same aspects.
- R r is preferably [In the formula, * indicates a binding position. ] and more preferably [In the formula, * indicates a binding position. ] is.
- e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- the ratio of e to f (hereinafter, "e / f ratio ”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably is between 0.2 and 0.85.
- e/f ratio the ratio of e to f
- the slipperiness, wear resistance and chemical resistance (for example, durability against artificial perspiration) of the surface treatment layer obtained from this compound are further improved.
- the smaller the e/f ratio the more improved the sliding property and abrasion resistance of the surface treatment layer.
- the stability of the compound can be further enhanced. The higher the e/f ratio, the more stable the compound.
- the number average molecular weight of the fluoropolyether group is not particularly limited, it is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, the number average molecular weight of the fluoropolyether group is the value measured by 19 F-NMR.
- each occurrence of R FA is independently preferably a group represented by formula (f0) and having at least one branched structure.
- each occurrence of R FA is independently a group represented by formula (f0) in which all repeating units have a branched structure.
- Examples of the branched chain in the branched structure include CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 and the like, preferably CF 3 .
- repeating units having the branched structure include -(OC 6 F 12 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) CF2CF2CF2 )-,- ( OCF2CF2CF ( CF3 ) CF2CF2 )-,- ( OCF2CF2CF2CF ( CF3 ) CF2 ) - ,- ( OCF2CF 2 CF 2 CF(CF 3 ))— and the like.
- -(OC 5 F 10 )- includes -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF (CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))- and the like.
- -(OC 4 F 8 )- includes -(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 ))— may be mentioned.
- -(OC 3 F 6 )- (that is, X F is a fluorine atom in the above formula (f0)) includes -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ) )- can be mentioned.
- -(OC 2 F 4 )- includes -(OCF(CF 3 ))-.
- RFAs may contain linear repeating units in addition to repeating units having a branched structure.
- Linear repeating units include -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 )-.
- the number of repeating units having a branched structure in RFA is preferably at least 5, more preferably at least 10, still more preferably at least 20.
- the total number of repeating units (for example, the sum of a, b, c, d, e and f) is preferably 40 or more, more preferably 60 or more, more preferably 80 or more.
- the number of repeating units having a branched structure may be 100 or less, for example, 90 or less, with respect to the total number of repeating units of 100.
- the number of repeating units having a branched structure is preferably 40 to 100, more preferably 60 to 100, still more preferably 80 to 100, relative to the total number of repeating units of 100 in the RFA .
- each occurrence of R FA is independently a group represented by the above formula (f1), (f2), (f3), (f4), (f5) or (f6), It is a group having at least one branched structure.
- R FA is each independently at each occurrence of formula (f1a): -(OCF(CF 3 )CF 2 ) d -(OCF(CF 3 )) e - (f1a) [Wherein, d is an integer of 1 to 200, and e is 0 or 1. ], is a group represented by
- R S1 is independently a hydroxyl group or a group containing a Si atom having a hydrolyzable group (hereinafter such a group may be simply referred to as a "hydrolyzable silane group").
- R S1 is preferably independently at each occurrence of formula (S1), (S2), (S3), (S4) or (S5): [In the formula: R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently at each occurrence a hydrogen atom or a monovalent organic group; n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit; X 11 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 ; each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; t is independently at each occurrence an
- each occurrence of R 11 is independently a hydroxyl group or a hydrolyzable group.
- R 11 is preferably independently at each occurrence a hydrolyzable group.
- R h include 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.
- R h is a methyl group, and in another aspect R h is an ethyl group.
- each occurrence of R 12 is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group is a monovalent organic group other than the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
- n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit.
- formula (S1) there is at least one (SiR 11 n1 R 12 3-n1 ) unit in which n1 is 1-3. That is, all n1s in equation (S1) cannot be 0 at the same time.
- formula (S1) there is at least one Si atom to which a hydroxyl group or hydrolyzable group is bonded.
- n1 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 11 n1 R 12 3-n1 ) unit.
- X 11 at each occurrence is independently a single bond or a divalent organic group.
- divalent organic groups are preferably —R 28 —O x —R 29 —, wherein R 28 and R 29 are each independently at each occurrence a single bond or a C 1-20 alkylene group. , x is 0 or 1.).
- Such C 1-20 alkylene groups may be straight chain or branched, but are preferably straight chain.
- Such C 1-20 alkylene groups are preferably C 1-10 alkylene groups, more preferably C 1-6 alkylene groups, still more preferably C 1-3 alkylene groups.
- X 11 is independently at each occurrence -C 1-6 alkylene-O-C 1-6 alkylene- or -O-C 1-6 alkylene-.
- each occurrence of X 11 is independently a single bond or a straight-chain C 1-6 alkylene group, preferably a single bond or a straight-chain C 1-3 alkylene group, more preferably a single It is a bond or straight chain C 1-2 alkylene group, more preferably a straight chain C 1-2 alkylene group.
- each occurrence of R 13 is independently a hydrogen atom or a monovalent organic group.
- Such monovalent organic groups are preferably C 1-20 alkyl groups.
- R 13 is independently at each occurrence a hydrogen atom or a linear C 1-6 alkyl group, preferably a hydrogen atom or a linear C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.
- t is an integer of 2 or more independently at each occurrence.
- t is independently an integer of 2-10, preferably an integer of 2-6 at each occurrence.
- each occurrence of R 14 is independently a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 .
- a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
- R 14 is a hydrogen atom.
- each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
- each occurrence of R 15 is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
- R 15 is a single bond.
- formula (S1) is the following formula (S1-a).
- R 11 , R 12 , R 13 , X 11 , and n1 have the same meanings as described in formula (S1) above;
- t1 and t2 are each independently at each occurrence an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, such as an integer of 1 to 5 or an integer of 2 to 5;
- the order of existence of each repeating unit bracketed with t1 and t2 is arbitrary in the formula.
- formula (S1) is the following formula (S1-b). [Wherein, R 11 , R 12 , R 13 , X 11 , n1 and t have the same meanings as described in formula (S1) above]
- each occurrence of R a1 is independently —Z 1 —SiR 21 p1 R 22 q1 R 23 r1 .
- Z 1 is independently an oxygen atom or a divalent organic group.
- the right side is bound to (SiR 21 p1 R 22 q1 R 23 r1 ).
- Z 1 is a divalent organic group.
- Z 1 does not include those that form a siloxane bond with the Si atom to which Z 1 is bonded.
- (Si—Z 1 —Si) in formula (S3) does not contain a siloxane bond.
- the above Z 1 is preferably a C 1-6 alkylene group, —(CH 2 ) z1 —O—(CH 2 ) z2 — (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6 and z2 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3 -phenylene- (CH 2 ) z4 -, wherein z3 is an integer of 0 to 6, For example, it is an integer from 1 to 6, and z4 is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
- 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. is preferably unsubstituted.
- Z 1 is a C 1-6 alkylene group or -(CH 2 ) z3 -phenylene- (CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -.
- Z 1 is such a group, higher light resistance, especially UV resistance, can be obtained.
- Z 1 above is a C 1-3 alkylene group.
- Z 1 can be -CH 2 CH 2 CH 2 -.
- Z 1 can be -CH 2 CH 2 -.
- R 21 above is independently at each occurrence —Z 1′ —SiR 21′ p1′ R 22′ q1′ R 23′ r1′ .
- Z 1′ is independently an oxygen atom or a divalent organic group.
- the right side is bound to (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ).
- Z 1' is a divalent organic group.
- Z 1' does not include those that form a siloxane bond with the Si atom to which Z 1' is bonded.
- (Si—Z 1′ —Si) in formula (S3) does not contain a siloxane bond.
- the above Z 1′ is preferably a C 1-6 alkylene group, —(CH 2 ) z1′ —O—(CH 2 ) z2′ — (wherein z1′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z2' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3' -phenylene- (CH 2 ) z4' - (wherein z3' is an integer from 0 to 6, such as an integer from 1 to 6, and z4' is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
- 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. is preferably unsubstituted.
- Z 1' is a C 1-6 alkylene group or -(CH 2 ) z3' -phenylene- (CH 2 ) z4' -, preferably -phenylene-(CH 2 ) z4' -.
- Z 1′ is such a group, it can have higher light resistance, especially UV resistance.
- Z 1′ above is a C 1-3 alkylene group.
- Z 1' can be -CH 2 CH 2 CH 2 -.
- Z 1' can be -CH 2 CH 2 -.
- R 21′ above is independently at each occurrence —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ .
- Each occurrence of Z 1′′ above is independently an oxygen atom or a divalent organic group . ).
- Z 1′′ is a divalent organic group.
- Z 1′′ does not include those that form a siloxane bond with the Si atom to which Z 1′′ is bonded.
- Si—Z 1′′ —Si does not contain a siloxane bond.
- Z 1′′ is preferably a C 1-6 alkylene group, —(CH 2 ) z1′′ —O—(CH 2 ) z2′′ — (wherein z1′′ is an integer of 0 to 6, for example 1 to is an integer of 6, and z2′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z3′′ —phenylene- (CH 2 ) z4′′ —, wherein z3′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z4′′ is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups are linear or branched, but preferably straight-chain, these groups are, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2- It may be substituted with one or more substituents selected from 6 alkynyl groups, but is preferably unsubstituted.
- Z 1′′ is a C 1-6 alkylene group or -(CH 2 ) z3′′ -phenylene- (CH 2 ) z4′′ -, preferably -phenylene-(CH 2 ) z4′′ -.
- Z 1′′ is such a group, it can be more light-resistant, especially UV-resistant.
- Z 1′′ is a C 1-3 alkylene group. In one aspect, Z 1′′ can be —CH 2 CH 2 CH 2 —. In another aspect, Z 1′′ can be —CH 2 CH 2 —.
- R 22′′ above is independently a hydroxyl group or a hydrolyzable group.
- R 22 ′′ above is preferably independently at each occurrence a hydrolyzable group.
- Each occurrence of R 23 ′′ above is independently a hydrogen atom or a monovalent organic group.
- Such monovalent organic groups are monovalent organic groups excluding the above hydrolyzable groups.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
- q1′′ is independently at each occurrence an integer from 0 to 3
- the at least one r1′′ is independently at each occurrence an integer from 0 to 3.
- the sum of q1′′ and r1′′ is 3 in units of (SiR 22′′ q1′′ R 23′′ r1′′ ).
- q1′′ is an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 22′′ q1′′ R 23′′ r1′′ ) unit.
- R 22′ is independently a hydroxyl group or a hydrolyzable group.
- R 22' is preferably independently at each occurrence a hydrolyzable group.
- R 22′ is preferably independently at each occurrence —OR h , —OCOR h , —ON ⁇ CR h 2 , —NR h 2 , —NHR h , or halogen (wherein R h represents a substituted or unsubstituted C 1-4 alkyl group), more preferably -OR h (ie, an alkoxy group).
- R h include 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.
- R h is a methyl group, and in another aspect R h is an ethyl group.
- Each occurrence of R 23′ above is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group is a monovalent organic group other than the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
- p1' is independently an integer of 0 to 3 at each occurrence
- q1' is independently an integer of 0 to 3 at each occurrence
- r1' is independently at each occurrence.
- the sum of p', q1' and r1' is 3 in the unit of (SiR 21' p1' R 22' q1' R 23' r1' ).
- p1' is 0.
- p1' is an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit. may In a preferred embodiment, p1' is 3.
- q1′ is an integer of 1 to 3, preferably an integer of 2 to 3, each independently for each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) unit, 3 is more preferable.
- p1' is 0 and q1' is an integer of 1 to 3 independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit, preferably is an integer of 2-3, more preferably 3.
- R 22 above is independently a hydroxyl group or a hydrolyzable group.
- R 22 is preferably independently at each occurrence a hydrolyzable group.
- R h include 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.
- R h is a methyl group, and in another aspect R h is an ethyl group.
- Each occurrence of R 23 above is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group is a monovalent organic group other than the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
- p1 above independently at each occurrence is an integer of 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.
- the sum of p1, q1 and r1 is 3 in units of (SiR 21 p1 R 22 q1 R 23 r1 ).
- p1 is 0.
- p1 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit. In a preferred embodiment, p1 is 3.
- q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
- p1 is 0 and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit. 3 is preferred.
- each occurrence of R b1 is independently a hydroxyl group or a hydrolyzable group.
- R b1 above is preferably independently at each occurrence a hydrolyzable group.
- R h include 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.
- R h is a methyl group, and in another aspect R h is an ethyl group.
- each occurrence of R c1 is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group is a monovalent organic group other than the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
- k1 above independently at each occurrence is an integer of 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.
- the sum of k1, l1 and m1 is 3 in units of (SiR a1 k1 R b1 l1 R c1 m1 ).
- k1 is independently an integer of 1 to 3, preferably 2 or 3, more preferably 3 for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit. In a preferred embodiment, k1 is 3.
- At least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded are present at the terminal portion of formula (S3).
- the group represented by formula (S3) is —Z 1 —SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 and r1 is an integer of 0 to 2.), —Z 1′ —SiR 22′ q1′ R 23′ r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer of 0 to 2), or —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ (wherein q1′′ is 1 to is an integer of 3, preferably 2 or 3, more preferably 3, and r1′′ is an integer of 0 to 2.) Z 1 , Z 1′ , Z 1′′ , R 22 , R 23 , R 22′ , R 23′ , R 22′′ , and R 23′′ are as defined above.
- R 21′ if R 21′ is present, at least one, preferably all R 21′ , q1′′ is an integer from 1 to 3, preferably 2 or 3, or more 3 is preferred.
- R 21 if R 21 is present, at least one, preferably all R 21 , p1′ is 0 and q1′ is an integer of 1 to 3, preferably is 2 or 3, more preferably 3.
- R a1 if R a1 is present, at least one, preferably all R a1 , p1 is 0, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
- k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3, in formula (S3).
- R d1 is independently at each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
- Z 2 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group.
- the right side is bound to (CR 31 p2 R 32 q2 R 33 r2 ).
- Z 2 is a divalent organic group.
- the above Z 2 is preferably a C 1-6 alkylene group, —(CH 2 ) z5 —O—(CH 2 ) z6 — (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6 and z6 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z7 -phenylene- (CH 2 ) z8 -, wherein z7 is an integer of 0 to 6, For example, an integer from 1 to 6, and z8 is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be straight chain or branched, but are preferably straight chain.
- 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. is preferably unsubstituted.
- Z 2 is a C 1-6 alkylene group or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene- (CH 2 ) z8 -.
- Z2 is such a group, it can be more light-resistant, especially UV-resistant.
- Z 2 above is a C 1-3 alkylene group.
- Z 2 can be -CH 2 CH 2 CH 2 -.
- Z 2 can be -CH 2 CH 2 -.
- R 31 is independently at each occurrence -Z 2' -CR 32' q2' R 33' r2' .
- Z 2' at each occurrence is independently a single bond, an oxygen atom or a divalent organic group.
- the right side is bound to (CR 32′ q2′ R 33′ r2′ ).
- the above Z 2′ is preferably a C 1-6 alkylene group, —(CH 2 ) z5′ —O—(CH 2 ) z6′ — (wherein z5′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z6' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z7' -phenylene- (CH 2 ) z8' - (wherein z7' is an integer from 0 to 6, such as an integer from 1 to 6, and z8' is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be straight chain or branched, but are preferably straight chain.
- 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. is preferably unsubstituted.
- Z 2' is a C 1-6 alkylene group or -(CH 2 ) z7' -phenylene- (CH 2 ) z8' -, preferably -phenylene-(CH 2 ) z8' -.
- Z 2′ is such a group, it can be more light-resistant, especially UV-resistant.
- Z 2′ above is a C 1-3 alkylene group.
- Z 2' can be -CH 2 CH 2 CH 2 -.
- Z 2' can be -CH 2 CH 2 -.
- R 32′ is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
- Z 3 is independently a single bond, an oxygen atom, or a divalent organic group.
- the right side is bound to (SiR 34 n2 R 35 3-n2 ).
- Z3 is an oxygen atom.
- Z 3 is a divalent organic group.
- the above Z 3 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as 1 to 6 and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z7′′ —phenylene- (CH 2 ) z8′′ — (wherein z7′′ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
- 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. is preferably unsubstituted.
- Z 3 is a C 1-6 alkylene group or —(CH 2 ) z7′′-phenylene- (CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8 ′′ -.
- a group higher light resistance, especially UV resistance, can be obtained.
- Z 3 above is a C 1-3 alkylene group.
- Z 3 can be -CH 2 CH 2 CH 2 -.
- Z 3 can be -CH 2 CH 2 -.
- R 34 above is independently a hydroxyl group or a hydrolyzable group.
- R 34 is preferably independently at each occurrence a hydrolyzable group.
- R h include 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.
- R h is a methyl group, and in another aspect R h is an ethyl group.
- Each occurrence of R 35 above is independently a hydrogen atom or a monovalent organic group.
- a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
- n2 is an integer of 0 to 3 independently for each (SiR 34 n2 R 35 3-n2 ) unit. However, at least one (SiR 34 n2 R 35 3-n2 ) unit having n2 of 1 to 3 is present at the terminal portion of formula (S4). That is, not all n2 are 0 at the same time. In other words, there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is attached at the terminal portion of formula (S4).
- n2 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
- Each occurrence of R 33′ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
- a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 , preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
- R 33' is a hydroxyl group.
- R 33' is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
- Each occurrence of q2' is independently an integer from 0 to 3, and each occurrence of r2' is independently an integer from 0 to 3.
- the sum of q2' and r2' is 3 in the unit of (CR 32' q2' R 33' r2' ).
- q2' is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
- R 32 is independently at each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 .
- Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
- Each occurrence of R 33 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
- a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
- R 33 is a hydroxyl group.
- R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
- p2 above independently at each occurrence is an integer of 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.
- the sum of p2, q2 and r2 is 3 in the unit of (CR 31 p2 R 32 q2 R 33 r2 ).
- p2 is 0.
- p2 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. In preferred embodiments, p2 is three.
- q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
- p2 is 0 and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. 3 is preferred.
- R e1 above is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
- Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
- Each occurrence of R f1 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
- a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
- the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is 1 to 6 an integer, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
- R f1 is a hydroxyl group.
- R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
- k2 above independently at each occurrence is an integer of 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.
- the sum of k2, l2 and m2 is 3 in units of (CR d1 k2 R e1 l2 R f1 m2 ).
- n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 ) units are each terminal moiety of formula (S4) 2 or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3, particularly preferably 3.
- n2 is an integer from 1 to 3, preferably 2 or 3, more preferably is 3.
- n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.
- R e1 if R e1 is present, at least one, preferably all R a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.
- k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3, in formula (S4).
- R g1 and R h1 are each independently at each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 .
- R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as above.
- R g1 and R h1 are each independently —Z 4 —SiR 11 n1 R 12 3-n1 .
- Z 4 is independently a single bond, an oxygen atom, or a divalent organic group.
- the right side is bound to (SiR 11 n1 R 12 3-n1 ).
- Z 4 is an oxygen atom.
- Z 4 is a divalent organic group.
- the above Z 4 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as 1 to 6 and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH 2 ) z7′′ —phenylene- (CH 2 ) z8′′ — (wherein z7′′ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
- Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
- 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. is preferably unsubstituted.
- Z 4 is a C 1-6 alkylene group or —(CH 2 ) z7′′-phenylene- (CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ -.
- Z 3 When is such a group, higher light resistance, especially UV resistance, can be obtained.
- Z 4 above is a C 1-3 alkylene group.
- Z 4 can be -CH 2 CH 2 CH 2 -.
- Z 4 can be -CH 2 CH 2 -.
- R S1 is a group represented by formula (S1), (S3), (S4) or (S5). These compounds can form a surface treatment layer with high abrasion resistance.
- R S1 is a group represented by formula (S3), (S4) or (S5). These compounds can form a surface treatment layer with high abrasion resistance.
- R S1 is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, they can form a surface treatment layer with even higher abrasion resistance.
- R S1 is a group represented by formula (S1).
- formula (S1) is a group represented by formula (S1-b).
- R 13 is a hydrogen atom and X 11 is a single bond or -R 28 -O x -R 29 - (wherein R 28 and R 29 are independently is a single bond or a C 1-20 alkylene group, x is 0 or 1), n1 is 1-3, preferably 2-3, more preferably 3.
- R S1 is a group represented by formula (S2).
- n1 is 1-3, preferably 2-3, more preferably 3.
- R S1 is a group represented by formula (S3).
- formula (S3) is -SiR a1 2 R c1 or -SiR a1 3
- R a1 is -Z 1 -SiR 22 q1 R 23 r1
- Z 1 is C 1-6
- R S1 is a group represented by formula (S4).
- formula (S4) is —CR e1 2 R f1 or —CR e1 3
- R e1 is —Z 3 —SiR 34 n2 R 35 3-n2
- Z 3 is C 1 —6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ —, wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is 0 -(CH 2 ) z7′′ -phenylene-(CH 2 ) z8 ′′ - (wherein z7′′ is an integer of 0 to 6, such as 1 to is an integer of 6, z8′′ is an integer of 0 to 6, such as an integer of 1 to 6), preferably a C 1-6 alkylene group, n2 is 1 to 3, preferably 2 to 3, and further 3 is preferred.
- R S1 is a group represented by formula (S5).
- R g1 and R h1 are —Z 4 —SiR 11 n1 R 12 3-n1
- Z 4 is a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ - (wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is an integer from 0 to 6, such as an integer from 1 to 6) or –( CH 2 ) z7′′ -phenylene- (CH 2 ) z8′′ —, wherein z7′′ is an integer from 0 to 6, such as an integer from 1 to 6, z8′′ is an integer from 0 to 6, such as 1 6), preferably a C 1-6 alkylene group, n1 is 1-3, preferably 2-3, more preferably 3.
- X A is understood as a linker that connects the fluoropolyether portion (R F1 ) that mainly provides water repellency, surface slipperiness, etc., and the portion (R S1 ) that provides bonding ability to the substrate. Therefore, XA may be a single bond or any group as long as the compound represented by formula (1) can exist stably.
- ⁇ is an integer of 1-9
- ⁇ is an integer of 1-9.
- ⁇ and ⁇ can vary depending on the valence of XA .
- the sum of ⁇ and ⁇ is the same as the valence of XA .
- X A is a decavalent organic group
- the sum of ⁇ and ⁇ is 10, such as ⁇ being 9 and ⁇ being 1, ⁇ being 5 and ⁇ being 5, or ⁇ being 1 and ⁇ being 9. obtain.
- ⁇ and ⁇ are 1 when X A is a divalent organic group.
- each X A is independently a single bond or a divalent to decavalent organic group
- the divalent to decavalent organic group in X A above is preferably a divalent to octavalent organic group.
- such divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups.
- such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.
- X A is a single bond or a divalent organic group, ⁇ is 1 and ⁇ is 1.
- X A is a tri- to hexavalent organic group, ⁇ is 1 and ⁇ is 2-5.
- X A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
- formula (1) is represented by formula (1′) below.
- X A is a single bond.
- X A is a divalent organic group.
- X A is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 -
- R 51 is a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s5 —, s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, even more preferably 1 or 2;
- X 51 is -(X 52 ) l5 -, X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -CO-, -C(O)O-, -Si(R 53 ) 2 from the group consisting of -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -CONR 54
- X A (typically the hydrogen atom of X A ) 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 be In preferred embodiments, X A is not substituted by these groups.
- the oxyalkylene-containing group having 1 to 10 carbon atoms is a group containing —O—C 1-10 alkylene—, for example, —R 55 —(—O—C 1-10 alkylene) n —R 56 (the formula wherein R 55 is a single bond or a divalent organic group, preferably a C 1-6 alkylene group, n is any integer, preferably an integer from 2 to 10, R 56 is a hydrogen atom or 1 a valent organic group, preferably a C 1-6 alkyl group).
- the above alkylene group may be linear or branched.
- each X A above is independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -.
- R 52 is a single bond, -(CH 2 ) t5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t5 -.
- t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3.
- R 52 (typically the hydrogen atom of R 52 ) 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 be In preferred embodiments, R 56 is unsubstituted by these groups.
- X A are each independently single bond, a C 1-20 alkylene group, —R 51 —X 53 —R 52 —, or [wherein R 51 and R 52 have the same meanings as above, X53 is -O-, -S-, -CO-, -C(O)O-, -CONR 54- , -O-CONR 54- , —O—(CH 2 ) u5 —CONR 54 —, —O—(CH 2 ) u5 —CO—, —Si(R 53 ) 2 —, —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —(Si(R 53 ) 2 O) m5 —Si(R 53 )
- the above X A are each independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 —, or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 — [In the formula, X 53 , s5 and t5 have the same meanings as above. ] is.
- each of the above X A is independently a single bond C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 — or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 —
- X 53 is -O-, -CO-, -CONR 54 -, -O-CONR 54 -, -O-(CH 2 ) u5 -CONR 54 -, or -O-(CH 2 ) u5 -CO- can be
- each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms
- s5 is an integer from 1 to 20
- t5 is an integer from 1 to 20
- u5 is an integer from 1 to 20
- s5
- each of the above X A is independently —(CH 2 ) s5 —O—(CH 2 ) t5 —, -CONR54- ( CH2 ) t5- , -(CH 2 ) s5 -O-(CH 2 ) u5 -CO-, or -(CH 2 ) s5 -O-(CH 2 ) u5 -CONR 54 -(CH 2 ) t5 -
- each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20; u5 is an integer from 1 to 20; ] can be
- X A is each independently one or more 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). It may be substituted by a substituent. In one aspect, X A is unsubstituted.
- each X A can independently be a -O-C 1-6 alkylene group, a C 1-6 alkylene group other than a -O-C 1-6 alkylene group.
- X A includes, for example, the following 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 -, —CONH—(CH 2 ) 3 —, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-(CH 2 ) 3 -, where Ph means phenyl, and (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
- X A 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 ) 4 —, —CH 2 O(CH 2 ) 5 —, —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) 2 Si(CH 3 ) 2 (CH
- each X A is independently a group of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH 2 ) z1 -.
- x1, y1 and z1 are each independently an integer of 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of existence of each parenthesized repeating unit is 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 18 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, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.
- 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 a trifluoromethyl group, It is a pentafluoroethyl group, more preferably a trifluoromethyl group.
- examples of X A include the 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 A group any one of the T's are attached to R F1 or R F2 of the molecular backbone: —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 -, —CONH—(CH 2 ) 3 —, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-(CH 2 ) 3 - (where Ph means phenyl), or [In the formula, each R 42 independently represents a hydrogen atom, a C
- T's are attached to R Si of the molecular backbone and, if present, the remaining T's are each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group group or UV-absorbing group.
- 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 ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
- preferred radical-scavenging groups or UV-absorbing groups include: is mentioned.
- each X A can independently be a trivalent to decavalent organic group.
- examples of X A include the groups: [wherein R 25 , R 26 and R 27 are each independently a divalent to hexavalent organic group, R 25 is bound to at least one R 2 F1 and R 26 and R 27 are each bound to at least one R 2 Si . ]
- R 25 above is a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, a C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 - R 59 -, or -R 57 -X 58 -.
- R 57 and R 59 above are each independently a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, or a C 5-20 arylene group.
- X 58 above is -O-, -S-, -CO-, -O-CO- or -COO-.
- R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, Preferred are C 1-6 alkyl group, —R 36 —R 37 —R 36 —, —R 36 —CHR 38 2 — and the like.
- each R 36 is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
- R 37 is N, O or S, preferably N or O.
- R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -.
- each R 45 is independently an alkyl group having 1 to 6 carbon atoms.
- R 46 is N, O or S, preferably O.
- each X A can independently be a trivalent to decavalent organic group.
- the fluoropolyether group-containing compound represented by the formula (1) is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Among these ranges, a number average molecular weight of 1,000 to 30,000, more preferably 1,500 to 10,000 is preferable from the viewpoint of abrasion resistance.
- the "number average molecular weight" is a value measured by 19 F-NMR.
- the fluoropolyether group-containing silane compound (A) can be synthesized by a known method.
- the fluoropolyether group-containing silane compound (B) has the following formula (2): [In the formula: R F2 is -Rf 2 p -R FB -O q -; Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; R FB is independently at each occurrence a linear fluoropolyether group; p is 0 or 1; q is independently 0 or 1 at each occurrence; R S2 is independently at each occurrence a group containing a Si atom having a hydroxyl group or a hydrolyzable group; each X B is independently a single bond or a divalent to decavalent organic group; Each ⁇ is independently an integer of 1-9. ] represented by
- R F2 is -Rf 2 p -R FB -O q -.
- Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms.
- C 1-6 alkylene group in the C 1-6 alkylene group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.
- Rf 2 above is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, still more preferably C 1- 3 is a perfluoroalkylene group.
- the C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably is a linear C 1-3 perfluoroalkyl group, specifically -CF 2 -, -CF 2 CF 2 -, or -CF 2 CF 2 CF 2 -.
- p is 0 or 1. In one aspect, p is zero. In another aspect, p is 1.
- q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.
- RFB is a linear fluoropolyether group.
- the fluoropolyether group is typically a group represented by the formula (f0).
- each occurrence of RFB is each independently preferably a group represented by formula (f0) in which all repeating units are linear.
- each occurrence of R FB is independently a group represented by the above formula (f1), (f2), (f3), (f4), (f5) or (f6), It is a straight chain group.
- R FB is independently at each occurrence of formula (f2b): - (OCF 2 CF 2 CF 2 CF 2 ) c - (OCF 2 CF 2 CF 2 ) d - (OCF 2 CF 2 ) e - (OCF 2 ) f - (f2b)
- c and d are each independently an integer of 0 to 30
- e and f are each independently an integer from 1 to 200
- the sum of c, d, e and f is an integer from 10 to 200
- the order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
- R S2 is independently at each occurrence a group containing a Si atom having a hydroxyl group or a hydrolyzable group.
- R S2 may have the same meaning as the group described for R S1 above, and includes the same aspects.
- R S2 is preferably a group represented by the above formula (S1), (S2), (S3), (S4) or (S5) independently at each occurrence.
- R S2 is a group represented by formula (S1), (S3), (S4) or (S5). These compounds can form a surface treatment layer with high abrasion resistance.
- R S2 is a group represented by formula (S3), (S4) or (S5). These compounds can form a surface treatment layer with high abrasion resistance.
- R S2 is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, they can form a surface treatment layer with even higher abrasion resistance.
- R S2 is a group represented by formula (S1).
- formula (S1) is a group represented by formula (S1-b).
- R 13 is a hydrogen atom and X 11 is a single bond or -R 28 -O x -R 29 - (wherein R 28 and R 29 are independently is a single bond or a C 1-20 alkylene group, x is 0 or 1), n1 is 1-3, preferably 2-3, more preferably 3.
- R S2 is a group represented by formula (S2).
- n1 is 1-3, preferably 2-3, more preferably 3.
- R S2 is a group represented by formula (S3).
- formula (S3) is -SiR a1 2 R c1 or -SiR a1 3
- R a1 is -Z 1 -SiR 22 q1 R 23 r1
- Z 1 is C 1-6
- R S2 is a group represented by formula (S4).
- formula (S4) is —CR e1 2 R f1 or —CR e1 3
- R e1 is —Z 3 —SiR 34 n2 R 35 3-n2
- Z 3 is C 1 —6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ —, wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is 0 -(CH 2 ) z7′′ -phenylene-(CH 2 ) z8 ′′ - (wherein z7′′ is an integer of 0 to 6, such as 1 to is an integer of 6, z8′′ is an integer of 0 to 6, such as an integer of 1 to 6), preferably a C 1-6 alkylene group, n2 is 1 to 3, preferably 2 to 3, and further 3 is preferred.
- R S2 is a group represented by formula (S5).
- R g1 and R h1 are —Z 4 —SiR 11 n1 R 12 3-n1
- Z 4 is a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ - (wherein z5′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z6′′ is an integer from 0 to 6, such as an integer from 1 to 6) or –( CH 2 ) z7′′ -phenylene- (CH 2 ) z8′′ —, wherein z7′′ is an integer from 0 to 6, such as an integer from 1 to 6, z8′′ is an integer from 0 to 6, such as 1 6), preferably a C 1-6 alkylene group, n1 is 1-3, preferably 2-3, more preferably 3.
- X B is understood to be a linker that connects the fluoropolyether portion (R F2 ) that mainly provides water repellency and surface slipperiness, etc., and the portion (R S2 ) that provides the ability to bond to a substrate. Therefore, X B may be a single bond or any group as long as the compound represented by formula (2) can exist stably.
- ⁇ is an integer of 1-9. ⁇ can vary depending on the valence of XB . That is, ⁇ is the value obtained by subtracting 1 from the valence of XB .
- Each X B is independently a single bond or a divalent to decavalent organic group.
- the divalent to decavalent organic group in X B above is preferably a divalent to octavalent organic group.
- such divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups.
- such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.
- X B is a single bond or a divalent organic group, ⁇ is 1 and ⁇ is 1.
- X B is a single bond or a divalent organic group and ⁇ is one.
- X B is a tri- to hexavalent organic group and ⁇ is 2-5.
- X B is a trivalent organic group and ⁇ is two.
- formula (2) is represented by formula (2′) below.
- X B can have the same meaning as the group described above for X A and includes similar aspects.
- the left side is bonded to R 2 F2 of formula (2), and the right side is bonded to R 2 S2 of formula (2).
- X B is a single bond.
- X B is a divalent organic group.
- X B is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 -
- R 51 is a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s5 —, s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, even more preferably 1 or 2;
- X 51 is -(X 52 ) l5 -, X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -CO-, -C(O)O-, -Si(R 53 ) 2 from the group consisting of -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -CONR 54
- X B (typically the hydrogen atom of X B ) 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 be In preferred embodiments, XB is not substituted by these groups.
- the oxyalkylene-containing group having 1 to 10 carbon atoms is a group containing —O—C 1-10 alkylene—, for example, —R 55 —(—O—C 1-10 alkylene) n —R 56 (the formula wherein R 55 is a single bond or a divalent organic group, preferably a C 1-6 alkylene group, n is any integer, preferably an integer of 2 to 10, R 56 is a monovalent organic group, preferably a C 1-6 alkyl group).
- the above alkylene group may be linear or branched.
- each X B above is independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -.
- R 52 is a single bond, -(CH 2 ) t5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t5 -.
- t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3.
- R 52 (typically the hydrogen atom of R 52 ) 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 be In preferred embodiments, R 56 is unsubstituted by these groups.
- X B are each independently single bond, a C 1-20 alkylene group, —R 51 —X 53 —R 52 —, or [wherein R 51 and R 52 have the same meanings as above, X53 is -O-, -S-, -CO-, -C(O)O-, -CONR 54- , -O-CONR 54- , —O—(CH 2 ) u5 —CONR 54 —, —O—(CH 2 ) u5 —CO—, —Si(R 53 ) 2 —, —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —(Si(R 53 ) 2 O) m5 —Si(R 53 )
- the above X B are each independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 —, or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 — [In the formula, X 53 , s5 and t5 have the same meanings as above. ] is.
- each of X B above is independently a single bond C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —X 53 —(CH 2 ) t5 — or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 —
- X 53 is -O-, -CO-, -CONR 54 -, -O-CONR 54 -, -O-(CH 2 ) u5 -CONR 54 -, or -O-(CH 2 ) u5 -CO-
- each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms
- s5 is an integer from 1 to 20
- t5 is an integer from 1 to 20
- u5 is an integer from 1 to 20;
- each of X B above is independently —(CH 2 ) s5 —O—(CH 2 ) t5 —, -CONR54- ( CH2 ) t5- , -(CH 2 ) s5 -O-(CH 2 ) u5 -CO-, or -(CH 2 ) s5 -O-(CH 2 ) u5 -CONR 54 -(CH 2 ) t5 -
- each occurrence of R 54 is independently a hydrogen atom, a phenyl group, a C 1-6 alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20; u5 is an integer from 1 to 20; ] can be
- Each of X B above is independently one or more 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). It may be substituted by a substituent. In one aspect, X B is unsubstituted.
- the above XB is coupled to R F1 on the left side of each formula and to R S1 on the right side.
- each X B may independently be a -O-C 1-6 alkylene group, a C 1-6 alkylene group other than a -O-C 1-6 alkylene group.
- X and B 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 ) 4 —, —CH 2 O(CH 2 ) 5 —, —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) 2 Si(CH 3 ) 2 (
- the fluoropolyether group-containing compound represented by formula (2) is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Among these ranges, a number average molecular weight of 1,000 to 30,000, more preferably 1,500 to 10,000 is preferable from the viewpoint of abrasion resistance.
- the "number average molecular weight" is a value measured by 19 F-NMR.
- the fluoropolyether group-containing silane compound (B) can be synthesized by a known method.
- R FA is a group represented by formula (f1a)
- R FB is a group represented by formula (f2b).
- f1a the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B) have the fluoropolyether group, the surface treatment layer formed has high abrasion resistance and UV resistance. .
- R FA is a group represented by formula (f1a)
- R S1 is represented by formula (S3), (S4) or (S5)
- R FB is a group represented by formula (f2b)
- R S2 is represented by formula (S3), (S4) or (S5) It is a group represented.
- the content of the fluoropolyether group-containing silane compound (A) with respect to the total of the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B) is It is preferably 50 mol % or more, more preferably 60 mol % or more, still more preferably 70 mol % or more.
- the content of the fluoropolyether group-containing silane compound (A) with respect to the total of the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B) is It is preferably 95 mol % or less, more preferably 90 mol % or less, for example 80 mol % or more.
- the content of the fluoropolyether group-containing silane compound (A) is preferably from 50 to the total of the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B). 95 mol %, more preferably 60 to 90 mol %, still more preferably 70 to 90 mol %.
- the surface treatment agent includes the fluoropolyether group-containing silane compound (A) and the fluoropolyether group-containing silane compound (B) (hereinafter collectively referred to as "fluoropolyether group-containing silane compound of the present disclosure"), It may contain other ingredients.
- Such other components include, but are not particularly limited to, for example, a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound (hereinafter referred to as "containing (hereinafter referred to as "silicone oil”), (non-reactive) silicone compounds that can be understood as silicone oils (hereinafter referred to as “silicone oils”), catalysts, lower alcohols, transition metals, halide ions, non-covalent in the molecular structure Examples include compounds containing atoms having electron pairs.
- fluorine-containing oil examples include, but are not limited to, compounds represented by the following general formula (1) (perfluoro(poly)ether compounds).
- Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted with one or more fluorine atoms
- Rf 6 is represents a C 1-16 alkyl group optionally substituted with one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom
- Rf 5 and Rf 6 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. It has at least one branched structure in the repeating unit.
- the repeating unit has at least one CF 3 terminal (specifically, -CF 3 , -C 2 F 5 , etc., more specifically -CF 3 ).
- Examples of repeating units having a branched structure include -(OC 4 F 8 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -( OCF2CF2CF ( CF3 ))-,-(OC(CF3) 2CF2 )-,-( OCF2C (CF3)2 ) - ,-(OCF ( CF3 )CF ( CF3 ) )-, -( OCF ( C 2 F 5 )CF 2 )- and -(OCF 2 CF ( C 2 F 5 ))-; 2 )- and -(OCF 2 CF(CF 3 ))-; -(OC 2 F 4 )- includes -(OCF(CF 3 ))-.
- Examples of perfluoro (poly) ether compounds represented by the general formula (1) include compounds represented by any of the following general formulas (1a) and (1b) (one or a mixture of two or more) may be used).
- Rf 5 and Rf 6 are as described above; in formula (1a), b'' is an integer of 1 or more and 100 or less; Each is independently an integer of 1 or more and 30 or less, and each of c'' and d'' is 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 (1a) preferably has a number average molecular weight of 2,000 to 8,000. Good friction durability can be obtained by having such a number average molecular weight.
- the compound represented by formula (1b) has a number average molecular weight of 3,000 to 8,000. In another aspect, the compound represented by formula (1b) 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 fluoropolyether group-containing silane compound. More preferably, it can be contained in an amount of 1 to 5 parts by mass.
- the fluorine-containing oil is, for example, 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0 to 10%, based on the total amount of the fluoropolyether group-containing silane compound and the fluorine-containing oil. may be included in mol %.
- 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 a chlorotrifluoroethylene oligomer are preferable in that they have a high affinity with the perfluoro(poly)ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group. .
- the fluorine-containing oil contributes to improving the abrasion resistance of the surface treatment layer.
- silicone oil for example, linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used.
- Linear silicone oils may be so-called straight silicone oils and modified silicone oils.
- straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
- Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
- Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.
- the silicone oil in the surface treatment agent is, for example, 0 to 50 parts by mass, preferably 0 to 50 parts by mass, based on 100 parts by mass of the fluoropolyether group-containing silane compound (the sum of these when two or more types are used, the same applies hereinafter). may be included at 0 to 5 parts by weight.
- Silicone oil contributes to improving the abrasion resistance of the surface treatment layer.
- the catalyst examples include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
- acids eg, acetic acid, trifluoroacetic acid, etc.
- bases eg, ammonia, triethylamine, diethylamine, etc.
- transition metals eg, Ti, Ni, Sn, etc.
- the catalyst promotes hydrolysis and dehydration condensation of the fluorine-containing silane compound and promotes formation of the surface treatment layer.
- lower alcohols examples include alcohol compounds having 1 to 6 carbon atoms.
- halide ions examples include chloride ions.
- Compounds containing atoms having a lone pair in the molecular structure include diethylamine, triethylamine, aniline, pyridine, hexamethylphosphoramide, N,N-diethylacetamide, N,N-diethylformamide, N,N -dimethylacetamide, N-methylformamide, N,N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide (DMSO), tetramethylenesulfoxide, methylphenylsulfoxide, diphenylsulfoxide and the like.
- DMSO dimethylsulfoxide
- tetramethylenesulfoxide methylphenylsulfoxide
- diphenylsulfoxide and the like is preferably used.
- Other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
- the surface treatment agent is a compound containing an atom having an unshared electron pair in its molecular structure, a fluorine-containing oil, a silicone oil, a catalyst, a lower alcohol, a transition metal, a halide ion, and a molecular structure, which are the other components. does not include
- the composition (for example, surface treatment agent) of this aspect can contribute to the formation of a cured layer having good friction durability. Furthermore, the cured layer formed using the composition of the present embodiment has good friction durability and good lubricity on the surface of the cured layer.
- the secondary structure of the RF portion tends to take a helical structure, and the polymer density per unit area and the cross-linking density of the silane coupling agent increase, so it is believed that the strength of the cured layer increases. be done.
- the surface treatment agent of the present disclosure contains the fluoropolyether group-containing silane compound of the present disclosure and a fluorine-containing oil.
- the surface treatment agent of the present disclosure contains the fluoropolyether group-containing silane compound of the present disclosure and does not contain the fluorine-containing oil, which is the other component (for example, the content of the fluorine-containing oil is It is 1 part by mass or less, more specifically, 0 part by mass with respect to 100 parts by mass of the surface treatment agent).
- the surface treatment agent of the present disclosure may optionally further include a hydrolysis condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), Organic acids (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acids, and the like are particularly desirable.
- a hydrolysis condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), Organic acids (acetic acid, me
- the amount of the hydrolytic condensation catalyst added is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0 .1 to 1 part by mass.
- the surface treatment agent of the present disclosure can be made into pellets by impregnating a porous material, such as a porous ceramic material, metal fiber, such as steel wool, into a flocculated material.
- a porous material such as a porous ceramic material, metal fiber, such as steel wool
- the pellet can be used, for example, for vacuum deposition.
- the surface treatment agent of the present disclosure is used as an antifouling coating agent or a waterproof coating agent.
- the coating agent (hereinafter also referred to as “coating agent of the present disclosure”) includes the composition of the present disclosure and a liquid medium.
- the coating agent of the present disclosure may be in liquid form, may be a solution, or may be a dispersion.
- the coating agent of the present disclosure only needs to contain the composition of the present disclosure, and may contain impurities such as by-products generated in the manufacturing process of compound (A), compound (B), and the like.
- the concentration of the composition of the present disclosure is preferably 0.001 to 50% by mass, more preferably 0.05 to 30% by mass, even more preferably 0.05 to 10% by mass, in the coating agent of the present disclosure. 1 to 1% by weight is particularly preferred.
- the organic solvent may be a fluorinated organic solvent, may be a non-fluorinated organic solvent, or may contain both solvents.
- Fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.
- fluorinated alkane compounds having 4 to 8 carbon atoms are preferred.
- Commercially available products include, for example, C 6 F 13 H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-2000) and C 6 F 13 C 2 H 5 (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-6000).
- C 2 F 5 CHFCHFCF 3 (Bertrell (registered trademark) XF, manufactured by Chemours) and the like.
- fluorinated aromatic compounds examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene and the like.
- fluoroalkyl ether compounds having 4 to 12 carbon atoms are preferred.
- Commercially available products include CF 3 CH 2 OCF 2 CF 2 H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C 4 F 9 OCH 3 (manufactured by 3M, Novec (registered trademark) 7100), C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec (registered trademark) 7200), C 2 F 5 CF(OCH 3 )C 3 F 7 (manufactured by 3M, Novec (registered trademark) 7300), etc. .
- fluorinated alkylamines examples include perfluorotripropylamine and perfluorotributylamine.
- fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
- the non-fluorine organic solvent is preferably a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms.
- the coating agent of the present disclosure preferably contains 50 to 99.999% by mass of the liquid medium, more preferably 70 to 99.5% by mass, even more preferably 90 to 99.5% by mass. It is particularly preferable to contain 99.9% by mass.
- the coating agent of the present disclosure may contain other components in addition to the composition and medium of the present disclosure within the range that does not impair the effects of the present invention.
- Other components include, for example, known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups.
- the content of other components in the coating agent of the present disclosure is preferably 10% by mass or less, particularly preferably 1% by mass or less.
- the solid content concentration of the coating agent of the present disclosure is preferably 0.001 to 50% by mass, more preferably 0.05 to 30% by mass, even more preferably 0.05 to 10% by mass, and 0.01 to 1% by mass. is particularly preferred.
- the solid content concentration of the coating agent is a value calculated from the mass of the coating agent before heating and the mass after heating for 4 hours in a 120°C convection dryer.
- the concentration of the composition of the present disclosure can be calculated from the solid content concentration and the charged amounts of the composition of the present disclosure, solvent, and the like.
- the surface treatment agent of the present disclosure is particularly suitable for coating display input devices such as touch panels; surface protective coatings for transparent glass or transparent plastic members, antifouling coatings for kitchens; electronic devices, heat exchangers, batteries, etc.
- Display input devices such as touch panels
- Water-repellent, moisture-proof and antifouling coatings for toiletries
- Coatings for components that require liquid repellency while conducting Water-repellent, waterproof, and water-sliding coatings for heat exchangers; It can be used for coats and the like. More specific examples of use include front protective plates for displays, anti-reflection plates, polarizing plates, anti-glare plates, or those with anti-reflection coatings on their surfaces, mobile phones (e.g., smart phones), and personal digital assistants.
- the article of the present disclosure includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present disclosure.
- Substrates that can be used in the present disclosure include, for example, glass, resins (natural or synthetic resins, such as common plastic materials), metals, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, non-woven fabrics etc.), fur, leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.
- resins natural or synthetic resins, such as common plastic materials
- metals such as common plastic materials
- ceramics such as common plastic materials
- semiconductors silicon, germanium, etc.
- fibers woven fabrics, non-woven fabrics etc.
- fur leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.
- the material forming the surface of the substrate may be a material for optical members, such as glass or transparent plastic.
- some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
- the antireflection layer may be either a single antireflection layer or a multi-layer antireflection layer. Examples of inorganic materials that can be used for the antireflection layer include SiO2 , SiO, ZrO2 , TiO2 , TiO , Ti2O3 , Ti2O5 , Al2O3 , Ta2O5 , Ta3O5 .
- the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on part of the surface of the substrate (glass).
- a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on part of the surface of the substrate (glass).
- the substrate may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase retardation film, and a liquid crystal display module.
- I-CON decorative frame layer
- the shape of the base material is not particularly limited, and may be, for example, plate-like, film, or other forms.
- the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.
- At least the surface portion of such a substrate may consist of a material that originally has hydroxyl groups.
- materials include glass, metals (particularly base metals), ceramics, and semiconductors on which a natural oxide film or thermal oxide film is formed.
- hydroxyl groups are introduced onto the surface of the base material by subjecting the base material to some pretreatment. can be increased or increased.
- pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter and the like).
- an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method), a chemical adsorption method, or the like.
- LB method Liuir-Blodgett method
- a chemical adsorption method or the like.
- such a substrate may comprise, at least a portion of its surface, another reactive group, such as a silicone compound having one or more Si—H groups, or a material comprising an alkoxysilane. .
- the substrate is glass.
- glass sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glasses are particularly preferred.
- the article of the present disclosure is produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure. It can be manufactured by forming.
- the layer formation of the surface treatment agent of the present disclosure can be carried out by applying the surface treatment agent to the surface of the substrate so as to coat the surface.
- a coating method is not particularly limited. For example, wet and dry coating methods can be used, preferably wet coating methods are used.
- wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
- Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods.
- vapor deposition methods usually vacuum vapor deposition methods
- Specific examples of vapor deposition methods include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods.
- Examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
- the layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with the catalyst for hydrolysis and dehydration condensation.
- the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure after the surface treatment agent of the present disclosure has been diluted with a solvent, just prior to application to the substrate surface.
- the surface treatment agent of the present disclosure to which the catalyst has been added is vapor-deposited (usually, vacuum deposition) as it is, or the surface treatment agent of the present disclosure to which the catalyst is added is applied to a metal porous body such as iron or copper.
- a vapor deposition (usually vacuum vapor deposition) process may be performed using a pellet-shaped material impregnated with .
- Any suitable acid or base can be used as the catalyst.
- acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid.
- a basic catalyst for example, ammonia, organic amines, and the like can be used.
- the surface treatment layer formed using the surface treatment agent of the present disclosure does not substantially contain the fluoropolyether group-containing compound contained in the surface treatment agent of the present disclosure.
- the present disclosure provides an article including a substrate and a surface-treated layer formed on the substrate, wherein the surface-treated layer is formed from a fluoropolyether group-containing silane compound and An article is provided that is substantially free of inclusion compounds.
- the surface treatment layer included in the article of the present disclosure has high abrasion resistance.
- the surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, it prevents the adhesion of stains such as fingerprints), depending on the composition of the surface treatment agent used.
- Waterproofness prevents water from penetrating into electronic parts, etc.
- surface slipperiness or lubricity, such as wiping off of fingerprints and other stains, excellent touch feeling on fingers
- chemical resistance etc. It can be suitably used as a functional thin film.
- the present disclosure also relates to an optical material having the surface treatment layer as the outermost layer.
- optical materials in addition to optical materials related to displays and the like as exemplified later, a wide variety of optical materials are preferably exemplified: for example, cathode ray tubes (CRT; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic EL. Displays such as displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), protective plates for these displays, or antireflection films on their surfaces processed.
- CTR cathode ray tubes
- LCD liquid crystal displays
- plasma displays organic EL.
- Displays such as displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), protective plates for these displays, or antireflection films on their surfaces processed.
- VFD fluorescent display tubes
- FED Field Emission Display
- optical members include the following: lenses for eyeglasses; front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; touch panel sheets; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers;
- the articles of the present disclosure may be medical devices or medical materials.
- the thickness of the layer is not particularly limited. In the case of optical members, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, abrasion resistance and antifouling properties.
- Polyether group-containing compound (b5') (m ⁇ 20, n ⁇ 33)
- Polyether group-containing compound (b5) (m ⁇ 20, n ⁇ 33, k ⁇ 3)
- a surface treatment agent was prepared by combining the above compounds and dissolving them in Novec 7200 (manufactured by 3M) to a total concentration of 20 wt %.
- the prepared surface treatment agent was vacuum-deposited on a chemically strengthened glass (“Gorilla” glass manufactured by Corning, thickness 0.7 mm).
- the conditions of the vacuum deposition method were a resistance heating deposition machine (manufactured by Syncron), chamber size 1,900 mm ⁇ , degree of vacuum 5.0E-05, current value 240 A, voltage 10 V, substrate temperature 40°C.
- the vapor-deposited chemically strengthened glass was allowed to stand in an atmosphere at a temperature of 150° C.
- UV durability test For the surface treatment layer formed above, the static contact angle of water after UV irradiation for 48 hours was measured.
- a UVB-313 lamp manufactured by Q-Lab, irradiance of 0.63 W/m 2 at 310 nm
- the black panel temperature of the substrate is 63 degrees
- the distance between the lamp and the surface treatment layer is 5 cm.
- the surface treatment agent of the present disclosure can be suitably used for various applications.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
Abstract
Description
[1] 下記式(1):
RF1は、各出現においてそれぞれ独立して、Rf1-RFA-Oq-であり;
Rf1は、各出現においてそれぞれ独立して、1個又はそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
RFAは、各出現においてそれぞれ独立して、分岐構造を有するフルオロポリエーテル基であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XAは、それぞれ独立して、単結合又は2~10価の有機基であり;
αは、1~9の整数であり;
βは、1~9の整数である。]
で表されるフルオロポリエーテル基含有シラン化合物(A)、及び
下記式(2):
RF2は、-Rf2 p-RFB-Oq-であり;
Rf2は、1個又はそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFBは、各出現においてそれぞれ独立して、直鎖のフルオロポリエーテル基であり;
pは、0又は1であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS2は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XBは、それぞれ独立して、単結合又は2~10価の有機基であり;
γは、それぞれ独立して、1~9の整数である。]
で表されるフルオロポリエーテル基含有シラン化合物(B)
を含む、表面処理剤。
[2] RFAは、各出現においてそれぞれ独立して、下記式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3XF 6)d-(OC2F4)e-(OCF2)f-
[式中、
a、b、c、d、e及びfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、e及びfの和は少なくとも1であり、a、b、c、d、e又はf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、
XFは、各出現においてそれぞれ独立して、水素原子、フッ素原子又は塩素原子である。]
で表される基であって、少なくとも1つの分岐構造を有する基であり、
RFBは、各出現においてそれぞれ独立して、下記式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3XF 6)d-(OC2F4)e-(OCF2)f-
[式中、
a、b、c、d、e及びfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、e及びfの和は少なくとも1であり、a、b、c、d、e又はf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、
XFは、各出現においてそれぞれ独立して、水素原子、フッ素原子又は塩素原子である。]
で表される基であって、直鎖の基である
上記[1]に記載の表面処理剤。
[3] RFAは、各出現においてそれぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)、(f5)又は(f6):
-(OC3F6)d-(OC2F4)e- (f1)
[式中、dは1~200の整数であり、eは0又は1である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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又はOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(R6-R7)g-Rr-(R7’-R6’)g’- (f4)
[式中、R6は、OCF2又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
R6’は、OCF2又はOC2F4であり、
R7’は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数であり、
g’は、2~100の整数であり、
Rrは、
である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、eは、1以上200以下の整数であり、a、b、c、d及びfは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f6)
[式中、fは、1以上200以下の整数であり、a、b、c、d及びeは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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。]
で表される基であって、少なくとも1つの分岐構造を有する基である、上記[1]又は[2]に記載の表面処理剤。
[4] RFBは、各出現においてそれぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)、(f5)または(f6):
-(OC3F6)d-(OC2F4)e- (f1)
[式中、dは1~200の整数であり、eは0又は1である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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又はOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(R6-R7)g-Rr-(R7’-R6’)g’- (f4)
[式中、R6は、OCF2又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
R6’は、OCF2又はOC2F4であり、
R7’は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数であり、
g’は、2~100の整数であり、
Rrは、
である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、eは、1以上200以下の整数であり、a、b、c、d及びfは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f6)
[式中、fは、1以上200以下の整数であり、a、b、c、d及びeは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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。]
で表される基であって、直鎖の基である、上記[1]~[3]のいずれか1項に記載の表面処理剤。
[5] RFAは、各出現においてそれぞれ独立して、下記式(f1a):
-(OCF(CF3)CF2)d-(OCF(CF3))e- (f1a)
[式中、dは1~200の整数であり、eは0又は1である。]、
で表される基である、上記[1]~[4]のいずれか1項に記載の表面処理剤。
[6] RFBは、各出現においてそれぞれ独立して、下記式(f2b):
-(OCF2CF2CF2CF2)c-(OCF2CF2CF2)d-(OCF2CF2)e-(OCF2)f- (f2b)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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、上記[1]~[5]のいずれか1項に記載の表面処理剤。
[7] RS1及びRS2は、各出現においてそれぞれ独立して、下記式(S1)、(S2)、(S3)、(S4)又は(S5):
R11は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R12は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n1は、(SiR11 n1R12 3-n1)単位毎にそれぞれ独立して、0~3の整数であり;
X11は、各出現においてそれぞれ独立して、単結合又は二価の有機基であり;
R13は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
R14は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子又は-X11-SiR11 n1R12 3-n1であり;
R15は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数1~6のアルキレン基又は炭素数1~6のアルキレンオキシ基であり;
tは、各出現においてそれぞれ独立して、2以上の整数であり;
Ra1は、各出現においてそれぞれ独立して、-Z1-SiR21 p1R22 q1R23 r1であり;
Z1は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21は、各出現においてそれぞれ独立して、-Z1’-SiR21’ p1’R22’ q1’R23’ r1’であり;
R22は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1、q1、及びr1の合計は、SiR21 p1R22 q1R23 r1単位において、3であり;
Z1’は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21’は、各出現においてそれぞれ独立して、-Z1”-SiR22” q1”R23” r1”であり;
R22’は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23’は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1’、q1’、及びr1’の合計は、SiR21’ p1’R22’ q1’R23’ r1’単位において、3であり;
Z1”は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R22”は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23”は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
q1”及びr1”の合計は、SiR22” q1”R23” r1”単位において、3であり;
Rb1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
Rc1は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
k1、l1及びm1の合計は、SiRa1 k1Rb1 l1Rc1 m1単位において、3であり;
Rd1は、各出現においてそれぞれ独立して、-Z2-CR31 p2R32 q2R33 r2であり;
Z2は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R31は、各出現においてそれぞれ独立して、-Z2’-CR32’ q2’R33’ r2’であり;
R32は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
p2、q2、及びr2の合計は、SiR31 p2R32 q2R33 r2単位において、3であり;
Z2’は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R32’は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33’は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
q2’、及びr2’の合計は、SiR32’ q2’R33’ r2’単位において、3であり;
Z3は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R34は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R35は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n2は、各出現においてそれぞれ独立して、0~3の整数であり;
Re1は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
Rf1は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
k2、l2及びm2の合計は、CRd1 k2Re1 l2Rf1 m2単位において、3であり;
Rg1及びRh1は、各出現においてそれぞれ独立して、-Z4-SiR11 n1R12 3-n1、-Z4-SiRa1 k1Rb1 l1Rc1 m1、又は-Z4-CRd1 k2Re1 l2Rf1 m2であり;
Z4は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
ただし、式(S1)、(S2)、(S3)、(S4)及び(S5)中、水酸基又は加水分解性基が結合したSi原子が少なくとも1つ存在する。]
で表される基である、上記[1]~[6]のいずれか1項に記載の表面処理剤。
[8] RS1及びRS2は、各出現においてそれぞれ独立して、下記式(S1)、(S3)、(S4)又は(S5):
R11は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R12は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n1は、(SiR11 n1R12 3-n1)単位毎にそれぞれ独立して、0~3の整数であり;
X11は、各出現においてそれぞれ独立して、単結合又は二価の有機基であり;
R13は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
R14は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子又は-X11-SiR11 n1R12 3-n1であり;
R15は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数1~6のアルキレン基又は炭素数1~6のアルキレンオキシ基であり;
tは、各出現においてそれぞれ独立して、2以上の整数であり;
Ra1は、各出現においてそれぞれ独立して、-Z1-SiR21 p1R22 q1R23 r1であり;
Z1は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21は、各出現においてそれぞれ独立して、-Z1’-SiR21’ p1’R22’ q1’R23’ r1’であり;
R22は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1、q1、及びr1の合計は、SiR21 p1R22 q1R23 r1単位において、3であり;
Z1’は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21’は、各出現においてそれぞれ独立して、-Z1”-SiR22” q1”R23” r1”であり;
R22’は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23’は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1’、q1’、及びr1’の合計は、SiR21’ p1’R22’ q1’R23’ r1’単位において、3であり;
Z1”は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R22”は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23”は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
q1”及びr1”の合計は、SiR22” q1”R23” r1”単位において、3であり;
Rb1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
Rc1は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
k1、l1及びm1の合計は、SiRa1 k1Rb1 l1Rc1 m1単位において、3であり;
Rd1は、各出現においてそれぞれ独立して、-Z2-CR31 p2R32 q2R33 r2であり;
Z2は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R31は、各出現においてそれぞれ独立して、-Z2’-CR32’ q2’R33’ r2’であり;
R32は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
p2、q2、及びr2の合計は、SiR31 p2R32 q2R33 r2単位において、3であり;
Z2’は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R32’は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33’は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
q2’、及びr2’の合計は、SiR32’ q2’R33’ r2’単位において、3であり;
Z3は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R34は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R35は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n2は、各出現においてそれぞれ独立して、0~3の整数であり;
Re1は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
Rf1は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
k2、l2及びm2の合計は、CRd1 k2Re1 l2Rf1 m2単位において、3であり;
Rg1及びRh1は、各出現においてそれぞれ独立して、-Z4-SiR11 n1R12 3-n1、-Z4-SiRa1 k1Rb1 l1Rc1 m1、又は-Z4-CRd1 k2Re1 l2Rf1 m2であり;
Z4は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
ただし、式(S1)、(S3)、(S4)及び(S5)中、水酸基又は加水分解性基が結合したSi原子が少なくとも2つ存在する。]
で表される基である、上記[1]~[7]のいずれか1項に記載の表面処理剤。
[9] α、β、及びγは、1である、上記[1]~[8]のいずれか1項に記載の表面処理剤。
[10] XA及びXBは、それぞれ独立して、単結合又は下記式:
-(R51)p5-(X51)q5-
[式中:
R51は、単結合、-(CH2)s5-又はo-、m-もしくはp-フェニレン基であり、
s5は、1~20の整数であり、
X51は、-(X52)l5-であり、
X52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、-CO-、-C(O)O-、-Si(R53)2-、-(Si(R53)2O)m5-Si(R53)2-、-CONR54-、-O-CONR54-、-NR54-及び-(CH2)n5-からなる群から選択される基であり、
R53は、各出現においてそれぞれ独立して、一価の有機基であり、
R54は、各出現においてそれぞれ独立して、水素原子、又は一価の有機基であり、
m5は、各出現においてそれぞれ独立して、1~100の整数であり、
n5は、各出現においてそれぞれ独立して、1~20の整数であり、
l5は、1~10の整数であり、
p5は、0又は1であり、
q5は、0又は1であり、
ここに、p5及びq5の少なくとも一方は1であり、p5又はq5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。]
で表される基である、上記[1]~[9]のいずれか1項に記載の表面処理剤。
[11] 前記フルオロポリエーテル基含有シラン化合物(A)と前記フルオロポリエーテル基含有シラン化合物(B)の合計に対して、前記フルオロポリエーテル基含有シラン化合物(A)の含有量は、50mol%以上である、上記[1]~[10]のいずれか1項に記載の表面処理剤。
[12] 防汚性コーティング剤又は防水性コーティング剤として使用される、上記[1]~[11]のいずれか1項に記載の表面処理剤。
[13] 湿潤被覆用である、上記[1]~[12]のいずれか1項に記載の表面処理剤。
[14] 基材と、該基材上に、上記[1]~[13]のいずれか1項に記載の表面処理剤より形成された層とを含む物品。
[15] 光学部材である、上記[14]に記載の物品。
フルオロポリエーテル基含有シラン化合物(A)は、下記式(1):
RF1は、各出現においてそれぞれ独立して、Rf1-RFA-Oq-であり;
Rf1は、各出現においてそれぞれ独立して、1個又はそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
RFAは、各出現においてそれぞれ独立して、分岐構造を有するフルオロポリエーテル基であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XAは、それぞれ独立して、単結合又は2~10価の有機基であり;
αは、1~9の整数であり;
βは、1~9の整数である。]
で表される。
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3XF 6)d-(OC2F4)e-(OCF2)f- (f0)
[式中、
a、b、c、d、e及びfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、e及びfの和は少なくとも1であり、a、b、c、d、e又はf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、
XFは、各出現においてそれぞれ独立して、水素原子、フッ素原子又は塩素原子である。]
で表される。
-(OC3F6)d-(OC2F4)e- (f1)
[式中、dは、1~200の整数であり、eは、0又は1、好ましくは1である。]
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、c及びdは、それぞれ独立して0以上30以下の整数であり、e及びfは、それぞれ独立して1以上200以下の整数であり、
c、d、e及びfの和は2以上であり、
添字c、d、e又はf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又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数である。];
-(R6-R7)g-Rr-(R7’-R6’)g’- (f4)
[式中、R6は、OCF2又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
R6’は、OCF2又はOC2F4であり、
R7’は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数であり、
g’は、2~100の整数であり、
Rrは、
である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、eは、1以上200以下の整数であり、a、b、c、d及びfは、それぞれ独立して0以上200以下の整数であって、また、a、b、c、d、e又はf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)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f6)
[式中、fは、1以上200以下の整数であり、a、b、c、d及びeは、それぞれ独立して0以上200以下の整数であって、また、a、b、c、d、e又はf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。]
であり、より好ましくは
である。
-(OCF(CF3)CF2)d-(OCF(CF3))e- (f1a)
[式中、dは1~200の整数であり、eは0又は1である。]、
で表される基である。
R11は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R12は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n1は、(SiR11 n1R12 3-n1)単位毎にそれぞれ独立して、0~3の整数であり;
X11は、各出現においてそれぞれ独立して、単結合又は二価の有機基であり;
R13は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
R14は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子又は-X11-SiR11 n1R12 3-n1であり;
R15は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数1~6のアルキレン基又は炭素数1~6のアルキレンオキシ基であり;
tは、各出現においてそれぞれ独立して、2以上の整数であり;
Ra1は、各出現においてそれぞれ独立して、-Z1-SiR21 p1R22 q1R23 r1であり;
Z1は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21は、各出現においてそれぞれ独立して、-Z1’-SiR21’ p1’R22’ q1’R23’ r1’であり;
R22は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
Z1’は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21’は、各出現においてそれぞれ独立して、-Z1”-SiR22” q1”R23” r1”であり;
R22’は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23’は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
Z1”は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R22”は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23”は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
Rb1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
Rc1は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
Rd1は、各出現においてそれぞれ独立して、-Z2-CR31 p2R32 q2R33 r2であり;
Z2は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R31は、各出現においてそれぞれ独立して、-Z2’-CR32’ q2’R33’ r2’であり;
R32は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
Z2’は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R32’は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33’は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
Z3は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R34は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R35は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n2は、各出現においてそれぞれ独立して、0~3の整数であり;
Re1は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
Rf1は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
Rg1及びRh1は、各出現においてそれぞれ独立して、-Z4-SiR11 n1R12 3-n1、-Z4-SiRa1 k1Rb1 l1Rc1 m1、又は-Z4-CRd1 k2Re1 l2Rf1 m2であり;
Z4は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
ただし、式(S1)、(S2)、(S3)、(S4)及び(S5)中、水酸基又は加水分解性基が結合したSi原子が少なくとも1つ存在する。]
で表される基である。
R11、R12、R13、X11、及びn1は、上記式(S1)の記載と同意義であり;
t1及びt2は、各出現においてそれぞれ独立して、1以上の整数、好ましくは1~10の整数、より好ましくは2~10の整数、例えば1~5の整数又は2~5の整数であり;
t1及びt2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。]
-(R51)p5-(X51)q5-
[式中:
R51は、単結合、-(CH2)s5-又はo-、m-もしくはp-フェニレン基であり、好ましくは-(CH2)s5-であり、
s5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又は2であり、
X51は、-(X52)l5-であり、
X52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、-CO-、-C(O)O-、-Si(R53)2-、-(Si(R53)2O)m5-Si(R53)2-、-CONR54-、-O-CONR54-、-NR54-及び-(CH2)n5-からなる群から選択される基であり、
R53は、各出現においてそれぞれ独立して、一価の有機基であり、好ましくはフェニル基、C1-6アルキル基又はC1-6アルコキシ基、より好ましくはフェニル基又はC1-6アルキル基、より好ましくはメチル基であり、
R54は、各出現においてそれぞれ独立して、水素原子、又は一価の有機基であり、好ましくは水素原子、フェニル基、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
m5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、
n5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、
l5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、
p5は、0又は1であり、
q5は、0又は1であり、
ここに、p5及びq5の少なくとも一方は1であり、p5又はq5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]
で表される二価の有機基が挙げられる。ここに、XA(典型的にはXAの水素原子)は、フッ素原子、C1-3アルキル基及びC1-3フルオロアルキル基から選択される1個又はそれ以上の置換基により置換されていてもよい。好ましい態様において、XAは、これらの基により置換されていない。
単結合、
C1-20アルキレン基、
-R51-X53-R52-、又は
[式中、R51及びR52は、上記と同意義であり、
X53は、
-O-、
-S-、
-CO-、
-C(O)O-、
-CONR54-、
-O-CONR54-、
-O-(CH2)u5-CONR54-、
-O-(CH2)u5-CO-、
-Si(R53)2-、
-(Si(R53)2O)m5-Si(R53)2-、
-O-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-、
-O-(CH2)u5-Si(R53)2-O-Si(R53)2-CH2CH2-Si(R53)2-O-Si(R53)2-、
-O-(CH2)u5-Si(OCH3)2OSi(OCH3)2-、
-CONR54-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-、
-CONR54-(CH2)u5-N(R54)-、又は
-CONR54-(o-、m-又はp-フェニレン)-Si(R53)2-
(式中、R53、R54及びm5は、上記と同意義であり、
u5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。]
であり得る。
単結合、
C1-20アルキレン基、
-(CH2)s5-X53-、
-X53-(CH2)t5-、又は
-(CH2)s5-X53-(CH2)t5-
[式中、X53、s5及びt5は、上記と同意義である。]
である。
単結合
C1-20アルキレン基、
-(CH2)s5-X53-、
-X53-(CH2)t5-又は
-(CH2)s5-X53-(CH2)t5-
[式中、
X53は、-O-、-CO-、-CONR54-、-O-CONR54-、-O-(CH2)u5-CONR54-、又は-O-(CH2)u5-CO-であり、
R54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、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
s5は、1~20の整数であり、
t5は、1~20の整数であり、
u5は1~20の整数である。]
であり得る。
-(CH2)s5-O-(CH2)t5-、
-CONR54-(CH2)t5-、
-(CH2)s5-O-(CH2)u5-CO-、又は
-(CH2)s5-O-(CH2)u5-CONR54-(CH2)t5-
[式中、
R54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、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
s5は、1~20の整数であり、
t5は、1~20の整数であり、
u5は1~20の整数である。]
であり得る。
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、及び
から選択される基であり、
Eは、-(CH2)n-(nは2~6の整数)であり、
Dは、分子主鎖のRF1に結合し、Eは、RS1に結合する。]
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)4-、
-CH2O(CH2)5-、
-CH2O(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-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)4-、
-CONH-(CH2)5-、
-CONH-(CH2)6-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CON(CH3)-(CH2)4-、
-CON(CH3)-(CH2)5-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-CH2-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)2-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)4-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)5-(式中、Phはフェニルを意味する)、
-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-、
-CH2OCH2-CONH-CH2-、
-CH2OCH2-CONH-(CH2)2-、
-CH2OCH2-CONH-(CH2)3-、
-CH2OCH2-CONH-(CH2)4-、
-CH2OCH2-CONH-(CH2)5-、
-CH2OCH2-CONH-(CH2)6-、
-CH2OCH2-CO-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(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-、
R41は、それぞれ独立して、水素原子、フェニル基、炭素数1~6のアルキル基、又はC1-6アルコキシ基好ましくはメチル基であり;
各XA基において、Tのうち任意のいくつかは、分子主鎖のRF1又はRF2に結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、又は
であり、別のTのいくつかは、分子主鎖のRSiに結合し、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アルコキシ基又はラジカル捕捉基又は紫外線吸収基である。
R25は、少なくとも1つのRF1に結合し、R26及びR27は、それぞれ、少なくとも1つのRSiに結合する。]
フルオロポリエーテル基含有シラン化合物(B)は、下記式(2):
RF2は、-Rf2 p-RFB-Oq-であり;
Rf2は、1個又はそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFBは、各出現においてそれぞれ独立して、直鎖のフルオロポリエーテル基であり;
pは、0又は1であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS2は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XBは、それぞれ独立して、単結合又は2~10価の有機基であり;
γは、それぞれ独立して、1~9の整数である。]
で表される
-(OCF2CF2CF2CF2)c-(OCF2CF2CF2)d-(OCF2CF2)e-(OCF2)f- (f2b)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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。
-(R51)p5-(X51)q5-
[式中:
R51は、単結合、-(CH2)s5-又はo-、m-もしくはp-フェニレン基であり、好ましくは-(CH2)s5-であり、
s5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又は2であり、
X51は、-(X52)l5-であり、
X52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、-CO-、-C(O)O-、-Si(R53)2-、-(Si(R53)2O)m5-Si(R53)2-、-CONR54-、-O-CONR54-、-NR54-及び-(CH2)n5-からなる群から選択される基であり、
R53は、各出現においてそれぞれ独立して、一価の有機基であり、好ましくはフェニル基、C1-6アルキル基又はC1-6アルコキシ基、より好ましくはフェニル基又はC1-6アルキル基、より好ましくはメチル基であり、
R54は、各出現においてそれぞれ独立して、水素原子、又は一価の有機基であり、好ましくは水素原子、フェニル基、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
m5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、
n5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、
l5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、
p5は、0又は1であり、
q5は、0又は1であり、
ここに、p5及びq5の少なくとも一方は1であり、p5又はq5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]
で表される二価の有機基が挙げられる。ここに、XB(典型的にはXBの水素原子)は、フッ素原子、C1-3アルキル基及びC1-3フルオロアルキル基から選択される1個又はそれ以上の置換基により置換されていてもよい。好ましい態様において、XBは、これらの基により置換されていない。
単結合、
C1-20アルキレン基、
-R51-X53-R52-、又は
[式中、R51及びR52は、上記と同意義であり、
X53は、
-O-、
-S-、
-CO-、
-C(O)O-、
-CONR54-、
-O-CONR54-、
-O-(CH2)u5-CONR54-、
-O-(CH2)u5-CO-、
-Si(R53)2-、
-(Si(R53)2O)m5-Si(R53)2-、
-O-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-、
-O-(CH2)u5-Si(R53)2-O-Si(R53)2-CH2CH2-Si(R53)2-O-Si(R53)2-、
-O-(CH2)u5-Si(OCH3)2OSi(OCH3)2-、
-CONR54-(CH2)u5-(Si(R53)2O)m5-Si(R53)2-、
-CONR54-(CH2)u5-N(R54)-、又は
-CONR54-(o-、m-又はp-フェニレン)-Si(R53)2-
(式中、R53、R54及びm5は、上記と同意義であり、
u5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。]
であり得る。
単結合、
C1-20アルキレン基、
-(CH2)s5-X53-、
-X53-(CH2)t5-、又は
-(CH2)s5-X53-(CH2)t5-
[式中、X53、s5及びt5は、上記と同意義である。]
である。
単結合
C1-20アルキレン基、
-(CH2)s5-X53-、
-X53-(CH2)t5-又は
-(CH2)s5-X53-(CH2)t5-
[式中、
X53は、-O-、-CO-、-CONR54-、-O-CONR54-、-O-(CH2)u5-CONR54-、又は-O-(CH2)u5-CO-、
であり、
R54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、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
s5は、1~20の整数であり、
t5は、1~20の整数であり、
u5は1~20の整数である。]
であり得る。
-(CH2)s5-O-(CH2)t5-、
-CONR54-(CH2)t5-、
-(CH2)s5-O-(CH2)u5-CO-、又は
-(CH2)s5-O-(CH2)u5-CONR54-(CH2)t5-
[式中、
R54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、C1-6アルキル基(好ましくはメチル基)又は炭素数1~10のオキシアルキレン含有基であり、
s5は、1~20の整数であり、
t5は、1~20の整数であり、
u5は1~20の整数である。]
であり得る。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)4-、
-CH2O(CH2)5-、
-CH2O(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-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)4-、
-CONH-(CH2)5-、
-CONH-(CH2)6-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CON(CH3)-(CH2)4-、
-CON(CH3)-(CH2)5-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-CH2-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)2-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)4-(式中、Phはフェニルを意味する)、
-CON(Ph)-(CH2)5-(式中、Phはフェニルを意味する)、
-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-、
-CH2OCH2-CONH-CH2-、
-CH2OCH2-CONH-(CH2)2-、
-CH2OCH2-CONH-(CH2)3-、
-CH2OCH2-CONH-(CH2)4-、
-CH2OCH2-CONH-(CH2)5-、
-CH2OCH2-CONH-(CH2)6-、
-CH2OCH2-CO-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(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-、
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 ・・・(1)
式中、Rf5は、1個又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個又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)、フッ素原子又は水素原子を表し、Rf5及び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’及び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’及び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’又は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。上記繰り返し単位中に少なくとも1の分岐構造を有する。すなわち、上記繰り返し単位は、少なくとも1のCF3末端(具体的には、-CF3、-C2F5等、より具体的には-CF3)を有する。分岐構造を有する繰り返し単位としては、-(OC4F8)-としては、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-及び-(OCF2CF(C2F5))-;-(OC3F6)-としては、-(OCF(CF3)CF2)-及び-(OCF2CF(CF3))-;-(OC2F4)-としては、-(OCF(CF3))-を挙げることができる。
Rf5-(OCF(CF3)CF2)b’’-Rf6 ・・・(1a)
Rf5-(OC4F8)a’’-(OC3F6)b’’-(OCF(CF3))c’’-(OCF2)d’’-Rf6 ・・・(1b)
これら式中、Rf5及びRf6は上記の通りであり;式(1a)において、b’’は1以上100以下の整数であり;式(1b)において、a’’及びb’’は、それぞれ独立して1以上30以下の整数であり、c’’及び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。-(OC4F8)-、-(OC3F6)-は分岐構造を有する。
・化合物(a1)及び(a2)
CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)CONHCH2C[CH2CH2CH2Si(OCH3)3]3
(化合物(a1):n=12;化合物(a2):n=24)
・化合物(b1)
[(CH3O)3SiCH2CH2CH2]3CCH2NHCOCF2O(CF2CF2O)m(CF2O)nCF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3
(m=18、n=29)
・化合物(b2)
[(CH3O)3SiCH2CH2CH2]2NCOCF2O(CF2CF2O)m(CF2O)nCF2CON[CH2CH2CH2Si(OCH3)3]2
(m=18、n=29)
・化合物(b3)
[(CH3O)3SiCH2CH2CH2]2NCOCH2OCH2CF2O(CF2CF2O)m(CF2O)nCF2CH2OCH2CON[CH2CH2CH2Si(OCH3)3]2
(m=18、n=29)
・化合物(b4)
[(CH3O)3SiCH2CH2CH2]3CCH2NHCOCH2OCH2CF2O(CF2CF2O)m(CF2O)nCF2CH2OCH2CONHCH2C[CH2CH2CH2Si(OCH3)3]3
(m=18、n=29)
HOOCCF2-(CF2CF2O)m-(CF2O)n-CF2COOH(m≒20、n≒33)を2.0g、トルエンを15g、m-ヘキサフルオロキシレンを15g、N,N-ジメチルホルムアミドを0.23mL、それぞれ加えた後、塩化チオニル0.65mLを仕込み、60℃に加熱し5時間攪拌した。その後、減圧下で揮発分を留去し、ヨウ化リチウム4.0gを加え、220℃に加熱し12時間攪拌した。その後、精製を行うことにより、下記のポリエーテル基含有化合物(b5’)10.5gを得た。
合成例1で得られたポリエーテル基含有化合物(b5’)ICF2-(CF2CF2O)m-(CF2O)n-CF2I(m≒20、n≒33)を5.0g、m-ヘキサフルオロキシレンを5.0g、トリクロロビニルシランを1.3mL、tert-ブチルペルオキシドを0.40mL、それぞれ加えた後、130℃に加熱し10時間撹拌した。その後、減圧下で揮発分を留去し、亜鉛0.8g及びテトラデカフルオロヘキサン5.0gを加え、氷浴で冷却し、メタノール6.3mLを加えた後、45℃で8時間攪拌した。その後、精製を行うことにより、下記のポリエーテル基含有化合物(b5)3.6gを得た。
・化合物(c1)
CF3O(CF2CF2O)m(CF2O)nCF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3
(m=18、n=29)
上記化合物を組み合わせ、ノベック7200(スリーエム社製)に溶解させて、合計濃度20wt%になるように、表面処理剤を調製した。調製した表面処理剤を、化学強化ガラス(コーニング社製、「ゴリラ」ガラス、厚さ0.7mm)上に真空蒸着した。真空蒸着法の条件は、抵抗加熱式蒸着機(シンクロン製)、チャンバーサイズ1,900mmφ、真空度5.0E-05、電流値240A、電圧10V、基材温度40℃であった。次に、蒸着した化学強化ガラスを、温度150℃の雰囲気下で30分静置し、その後室温まで放冷させ、ガラス基材上に表面処理層を形成した。化合物の組み合わせとその組成は、下記表に示す。なお、化合物(a1)と(b2)、化合物(a2)と(b2)、化合物(a1)と(b1)、化合物(a1)と(b3)、化合物(a1)と(b4)、及び化合物(a1)と(b5)の組み合わせは実施例であり、化合物(c1)と(b2)の組み合わせは比較例である。
(静的接触角の測定)
静的接触角は、水平に置いた基板にマイクロシリンジから水を2μL滴下し、滴下1秒後の静止画をビデオマイクロスコープで撮影することにより求めた。測定は、全自動接触角計DropMaster700(協和界面科学社製)を用いて行った。
まず、初期評価として、表面処理層を形成後、その表面に未だ何も触れていない状態で、水の静的接触角を測定した。
上記で形成された表面処理層について、ラビングテスター(新東科学社製)を用いて、下記条件で往復回数1000回後に水の静的接触角を測定した。
消しゴム:Raber Eraser(Minoan社製)
接地面積:6mmφ
移動距離(片道):40mm
移動速度:3,600mm/分
荷重:1kg/6mmφ
温度:25℃
湿度:40%RH
上記で形成された表面処理層について、48時間UV照射後の水の静的接触角を測定した。UV照射は、UVB-313ランプ(Q-Lab社製、310nmにおいて放射照度0.63W/m2)を用い、基材のブラックパネル温度は、63度で、ランプと表面処理層との距離を5cmとして行った。
Claims (15)
- 下記式(1):
RF1は、各出現においてそれぞれ独立して、Rf1-RFA-Oq-であり;
Rf1は、各出現においてそれぞれ独立して、1個又はそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
RFAは、各出現においてそれぞれ独立して、分岐構造を有するフルオロポリエーテル基であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XAは、それぞれ独立して、単結合又は2~10価の有機基であり;
αは、1~9の整数であり;
βは、1~9の整数である。]
で表されるフルオロポリエーテル基含有シラン化合物(A)、及び
下記式(2):
RF2は、-Rf2 p-RFB-Oq-であり;
Rf2は、1個又はそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFBは、各出現においてそれぞれ独立して、直鎖のフルオロポリエーテル基であり;
pは、0又は1であり;
qは、各出現においてそれぞれ独立して、0又は1であり;
RS2は、各出現においてそれぞれ独立して、水酸基又は加水分解性基を有するSi原子を含む基であり;
XBは、それぞれ独立して、単結合又は2~10価の有機基であり;
γは、それぞれ独立して、1~9の整数である。]
で表されるフルオロポリエーテル基含有シラン化合物(B)
を含む、表面処理剤。 - RFAは、各出現においてそれぞれ独立して、下記式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3XF 6)d-(OC2F4)e-(OCF2)f-
[式中、
a、b、c、d、e及びfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、e及びfの和は少なくとも1であり、a、b、c、d、e又はf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、
XFは、各出現においてそれぞれ独立して、水素原子、フッ素原子又は塩素原子である。]
で表される基であって、少なくとも1つの分岐構造を有する基であり、
RFBは、各出現においてそれぞれ独立して、下記式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3XF 6)d-(OC2F4)e-(OCF2)f-
[式中、
a、b、c、d、e及びfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、e及びfの和は少なくとも1であり、a、b、c、d、e又はf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、
XFは、各出現においてそれぞれ独立して、水素原子、フッ素原子又は塩素原子である。]
で表される基であって、直鎖の基である
請求項1に記載の表面処理剤。 - RFAは、各出現においてそれぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)、(f5)又は(f6):
-(OC3F6)d-(OC2F4)e- (f1)
[式中、dは1~200の整数であり、eは0又は1である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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又はOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(R6-R7)g-Rr-(R7’-R6’)g’- (f4)
[式中、R6は、OCF2又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
R6’は、OCF2又はOC2F4であり、
R7’は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数であり、
g’は、2~100の整数であり、
Rrは、
である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、eは、1以上200以下の整数であり、a、b、c、d及びfは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f6)
[式中、fは、1以上200以下の整数であり、a、b、c、d及びeは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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。]
で表される基であって、少なくとも1つの分岐構造を有する基である、請求項1又は2に記載の表面処理剤。 - RFBは、各出現においてそれぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)、(f5)又は(f6):
-(OC3F6)d-(OC2F4)e- (f1)
[式中、dは1~200の整数であり、eは0又は1である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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又はOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(R6-R7)g-Rr-(R7’-R6’)g’- (f4)
[式中、R6は、OCF2又はOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
R6’は、OCF2又はOC2F4であり、
R7’は、OC2F4、OC3F6、OC4F8、OC5F10及び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又は3つの基の組み合わせであり、
gは、2~100の整数であり、
g’は、2~100の整数であり、
Rrは、
である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、eは、1以上200以下の整数であり、a、b、c、d及びfは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f6)
[式中、fは、1以上200以下の整数であり、a、b、c、d及びeは、それぞれ独立して0以上200以下の整数であり、a、b、c、d、e又はf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。]
で表される基であって、直鎖の基である、請求項1~3のいずれか1項に記載の表面処理剤。 - RFAは、各出現においてそれぞれ独立して、下記式(f1a):
-(OCF(CF3)CF2)d-(OCF(CF3))e- (f1a)
[式中、dは1~200の整数であり、eは0又は1である。]、
で表される基である、請求項1~4のいずれか1項に記載の表面処理剤。 - RFBは、各出現においてそれぞれ独立して、下記式(f2b):
-(OCF2CF2CF2CF2)c-(OCF2CF2CF2)d-(OCF2CF2)e-(OCF2)f- (f2b)
[式中、c及びdは、それぞれ独立して、0~30の整数であり;
e及びfは、それぞれ独立して、1~200の整数であり;
c、d、e及びfの和は、10~200の整数であり;
添字c、d、e又はf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1~5のいずれか1項に記載の表面処理剤。 - RS1及びRS2は、各出現においてそれぞれ独立して、下記式(S1)、(S2)、(S3)、(S4)又は(S5):
R11は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R12は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n1は、(SiR11 n1R12 3-n1)単位毎にそれぞれ独立して、0~3の整数であり;
X11は、各出現においてそれぞれ独立して、単結合又は二価の有機基であり;
R13は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
R14は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子又は-X11-SiR11 n1R12 3-n1であり;
R15は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数1~6のアルキレン基又は炭素数1~6のアルキレンオキシ基であり;
tは、各出現においてそれぞれ独立して、2以上の整数であり;
Ra1は、各出現においてそれぞれ独立して、-Z1-SiR21 p1R22 q1R23 r1であり;
Z1は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21は、各出現においてそれぞれ独立して、-Z1’-SiR21’ p1’R22’ q1’R23’ r1’であり;
R22は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1、q1、及びr1の合計は、SiR21 p1R22 q1R23 r1単位において、3であり;
Z1’は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21’は、各出現においてそれぞれ独立して、-Z1”-SiR22” q1”R23” r1”であり;
R22’は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23’は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1’、q1’、及びr1’の合計は、SiR21’ p1’R22’ q1’R23’ r1’単位において、3であり;
Z1”は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R22”は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23”は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
q1”及びr1”の合計は、SiR22” q1”R23” r1”単位において、3であり;
Rb1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
Rc1は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
k1、l1及びm1の合計は、SiRa1 k1Rb1 l1Rc1 m1単位において、3であり;
Rd1は、各出現においてそれぞれ独立して、-Z2-CR31 p2R32 q2R33 r2であり;
Z2は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R31は、各出現においてそれぞれ独立して、-Z2’-CR32’ q2’R33’ r2’であり;
R32は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
p2、q2、及びr2の合計は、SiR31 p2R32 q2R33 r2単位において、3であり;
Z2’は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R32’は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33’は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
q2’、及びr2’の合計は、SiR32’ q2’R33’ r2’単位において、3であり;
Z3は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R34は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R35は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n2は、各出現においてそれぞれ独立して、0~3の整数であり;
Re1は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
Rf1は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
k2、l2及びm2の合計は、CRd1 k2Re1 l2Rf1 m2単位において、3であり;
Rg1及びRh1は、各出現においてそれぞれ独立して、-Z4-SiR11 n1R12 3-n1、-Z4-SiRa1 k1Rb1 l1Rc1 m1、又は-Z4-CRd1 k2Re1 l2Rf1 m2であり;
Z4は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
ただし、式(S1)、(S2)、(S3)、(S4)及び(S5)中、水酸基又は加水分解性基が結合したSi原子が少なくとも1つ存在する。]
で表される基である、請求項1~6のいずれか1項に記載の表面処理剤。 - RS1及びRS2は、各出現においてそれぞれ独立して、下記式(S1)、(S3)、(S4)又は(S5):
R11は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R12は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n1は、(SiR11 n1R12 3-n1)単位毎にそれぞれ独立して、0~3の整数であり;
X11は、各出現においてそれぞれ独立して、単結合又は二価の有機基であり;
R13は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
R14は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子又は-X11-SiR11 n1R12 3-n1であり;
R15は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数1~6のアルキレン基又は炭素数1~6のアルキレンオキシ基であり;
tは、各出現においてそれぞれ独立して、2以上の整数であり;
Ra1は、各出現においてそれぞれ独立して、-Z1-SiR21 p1R22 q1R23 r1であり;
Z1は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21は、各出現においてそれぞれ独立して、-Z1’-SiR21’ p1’R22’ q1’R23’ r1’であり;
R22は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1、q1、及びr1の合計は、SiR21 p1R22 q1R23 r1単位において、3であり;
Z1’は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R21’は、各出現においてそれぞれ独立して、-Z1”-SiR22” q1”R23” r1”であり;
R22’は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23’は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
p1’、q1’、及びr1’の合計は、SiR21’ p1’R22’ q1’R23’ r1’単位において、3であり;
Z1”は、各出現においてそれぞれ独立して、酸素原子又は二価の有機基であり;
R22”は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R23”は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
q1”及びr1”の合計は、SiR22” q1”R23” r1”単位において、3であり;
Rb1は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
Rc1は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
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;
k1、l1及びm1の合計は、SiRa1 k1Rb1 l1Rc1 m1単位において、3であり;
Rd1は、各出現においてそれぞれ独立して、-Z2-CR31 p2R32 q2R33 r2であり;
Z2は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R31は、各出現においてそれぞれ独立して、-Z2’-CR32’ q2’R33’ r2’であり;
R32は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
p2、q2、及びr2の合計は、SiR31 p2R32 q2R33 r2単位において、3であり;
Z2’は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R32’は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
R33’は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
q2’、及びr2’の合計は、SiR32’ q2’R33’ r2’単位において、3であり;
Z3は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
R34は、各出現においてそれぞれ独立して、水酸基又は加水分解性基であり;
R35は、各出現においてそれぞれ独立して、水素原子又は1価の有機基であり;
n2は、各出現においてそれぞれ独立して、0~3の整数であり;
Re1は、各出現においてそれぞれ独立して、-Z3-SiR34 n2R35 3-n2であり;
Rf1は、各出現においてそれぞれ独立して、水素原子、水酸基又は1価の有機基であり;
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;
k2、l2及びm2の合計は、CRd1 k2Re1 l2Rf1 m2単位において、3であり;
Rg1及びRh1は、各出現においてそれぞれ独立して、-Z4-SiR11 n1R12 3-n1、-Z4-SiRa1 k1Rb1 l1Rc1 m1、又は-Z4-CRd1 k2Re1 l2Rf1 m2であり;
Z4は、各出現においてそれぞれ独立して、単結合、酸素原子又は二価の有機基であり;
ただし、式(S1)、(S3)、(S4)及び(S5)中、水酸基又は加水分解性基が結合したSi原子が少なくとも2つ存在する。]
で表される基である、請求項1~7のいずれか1項に記載の表面処理剤。 - α、β、及びγは、1である、請求項1~8のいずれか1項に記載の表面処理剤。
- XA及びXBは、それぞれ独立して、単結合又は下記式:
-(R51)p5-(X51)q5-
[式中:
R51は、単結合、-(CH2)s5-又はo-、m-もしくはp-フェニレン基であり、
s5は、1~20の整数であり、
X51は、-(X52)l5-であり、
X52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、-CO-、-C(O)O-、-Si(R53)2-、-(Si(R53)2O)m5-Si(R53)2-、-CONR54-、-O-CONR54-、-NR54-及び-(CH2)n5-からなる群から選択される基であり、
R53は、各出現においてそれぞれ独立して、一価の有機基であり、
R54は、各出現においてそれぞれ独立して、水素原子、又は一価の有機基であり、
m5は、各出現においてそれぞれ独立して、1~100の整数であり、
n5は、各出現においてそれぞれ独立して、1~20の整数であり、
l5は、1~10の整数であり、
p5は、0又は1であり、
q5は、0又は1であり、
ここに、p5及びq5の少なくとも一方は1であり、p5又はq5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。]
で表される基である、請求項1~9のいずれか1項に記載の表面処理剤。 - 前記フルオロポリエーテル基含有シラン化合物(A)と前記フルオロポリエーテル基含有シラン化合物(B)の合計に対して、前記フルオロポリエーテル基含有シラン化合物(A)の含有量は、50mol%以上である、請求項1~10のいずれか1項に記載の表面処理剤。
- 防汚性コーティング剤又は防水性コーティング剤として使用される、請求項1~11のいずれか1項に記載の表面処理剤。
- 湿潤被覆用である、請求項1~12のいずれか1項に記載の表面処理剤。
- 基材と、該基材上に、請求項1~13のいずれか1項に記載の表面処理剤より形成された層とを含む物品。
- 光学部材である、請求項14に記載の物品。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22791758.0A EP4321590A1 (en) | 2021-04-20 | 2022-04-20 | Surface treatment agent |
KR1020237039685A KR20230170779A (ko) | 2021-04-20 | 2022-04-20 | 표면 처리제 |
CN202280029700.6A CN117396578A (zh) | 2021-04-20 | 2022-04-20 | 表面处理剂 |
US18/490,296 US20240052180A1 (en) | 2021-04-20 | 2023-10-19 | Surface treatment agent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-071009 | 2021-04-20 | ||
JP2021071009 | 2021-04-20 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/490,296 Continuation US20240052180A1 (en) | 2021-04-20 | 2023-10-19 | Surface treatment agent |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022224987A1 true WO2022224987A1 (ja) | 2022-10-27 |
Family
ID=83722321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/018281 WO2022224987A1 (ja) | 2021-04-20 | 2022-04-20 | 表面処理剤 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20240052180A1 (ja) |
EP (1) | EP4321590A1 (ja) |
JP (1) | JP7265212B2 (ja) |
KR (1) | KR20230170779A (ja) |
CN (1) | CN117396578A (ja) |
TW (1) | TW202307075A (ja) |
WO (1) | WO2022224987A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023204024A1 (ja) * | 2022-04-19 | 2023-10-26 | 信越化学工業株式会社 | フルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品、並びに物品の表面改質方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005290323A (ja) * | 2004-04-05 | 2005-10-20 | Shin Etsu Chem Co Ltd | 表面処理剤組成物 |
JP2007197425A (ja) * | 2005-12-26 | 2007-08-09 | Shin Etsu Chem Co Ltd | フッ素含有オルガノポリシロキサン及びこれを含む表面処理剤並びに該表面処理剤で表面処理された物品 |
JP2014218639A (ja) | 2012-11-05 | 2014-11-20 | ダイキン工業株式会社 | パーフルオロ(ポリ)エーテル基含有シラン化合物 |
JP2019070098A (ja) * | 2017-02-03 | 2019-05-09 | ダイキン工業株式会社 | パーフルオロ(ポリ)エーテル基含有化合物、これを含む表面処理剤、および物品 |
JP2019131808A (ja) * | 2018-02-02 | 2019-08-08 | ダイキン工業株式会社 | 電子機器 |
-
2022
- 2022-04-20 TW TW111115058A patent/TW202307075A/zh unknown
- 2022-04-20 JP JP2022069179A patent/JP7265212B2/ja active Active
- 2022-04-20 KR KR1020237039685A patent/KR20230170779A/ko active Search and Examination
- 2022-04-20 CN CN202280029700.6A patent/CN117396578A/zh active Pending
- 2022-04-20 EP EP22791758.0A patent/EP4321590A1/en active Pending
- 2022-04-20 WO PCT/JP2022/018281 patent/WO2022224987A1/ja active Application Filing
-
2023
- 2023-10-19 US US18/490,296 patent/US20240052180A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005290323A (ja) * | 2004-04-05 | 2005-10-20 | Shin Etsu Chem Co Ltd | 表面処理剤組成物 |
JP2007197425A (ja) * | 2005-12-26 | 2007-08-09 | Shin Etsu Chem Co Ltd | フッ素含有オルガノポリシロキサン及びこれを含む表面処理剤並びに該表面処理剤で表面処理された物品 |
JP2014218639A (ja) | 2012-11-05 | 2014-11-20 | ダイキン工業株式会社 | パーフルオロ(ポリ)エーテル基含有シラン化合物 |
JP2019070098A (ja) * | 2017-02-03 | 2019-05-09 | ダイキン工業株式会社 | パーフルオロ(ポリ)エーテル基含有化合物、これを含む表面処理剤、および物品 |
JP2019131808A (ja) * | 2018-02-02 | 2019-08-08 | ダイキン工業株式会社 | 電子機器 |
Also Published As
Publication number | Publication date |
---|---|
US20240052180A1 (en) | 2024-02-15 |
CN117396578A (zh) | 2024-01-12 |
EP4321590A1 (en) | 2024-02-14 |
JP2022165943A (ja) | 2022-11-01 |
TW202307075A (zh) | 2023-02-16 |
KR20230170779A (ko) | 2023-12-19 |
JP7265212B2 (ja) | 2023-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7425351B2 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物 | |
JP6332358B2 (ja) | フルオロオキシメチレン基含有パーフルオロポリエーテル変性体 | |
TWI605053B (zh) | 表面處理劑 | |
CN108495907B (zh) | 表面处理剂 | |
JP7339555B2 (ja) | 表面処理組成物 | |
EP3858943B1 (en) | Surface treatment agent | |
JP6435871B2 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物を含む表面処理剤 | |
WO2018169002A1 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物 | |
JP7299546B2 (ja) | 表面処理剤 | |
TW201936708A (zh) | 基材 | |
WO2018047695A1 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物を含む組成物 | |
JP7265212B2 (ja) | 表面処理剤 | |
WO2018168973A1 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物を含む表面処理剤、それを用いたペレットおよび物品 | |
WO2018168972A1 (ja) | パーフルオロ(ポリ)エーテル基含有シラン化合物を含む表面処理剤、それを用いたペレットおよび物品 | |
JP7116352B1 (ja) | 表面処理剤 | |
JP7252500B2 (ja) | 表面処理剤 | |
WO2023026876A1 (ja) | 表面処理剤 | |
WO2022163320A1 (ja) | 表面処理用液状組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22791758 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280029700.6 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022791758 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20237039685 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020237039685 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022791758 Country of ref document: EP Effective date: 20231109 |