JP6761713B2 - Surface treatment liquid - Google Patents
Surface treatment liquid Download PDFInfo
- Publication number
- JP6761713B2 JP6761713B2 JP2016183160A JP2016183160A JP6761713B2 JP 6761713 B2 JP6761713 B2 JP 6761713B2 JP 2016183160 A JP2016183160 A JP 2016183160A JP 2016183160 A JP2016183160 A JP 2016183160A JP 6761713 B2 JP6761713 B2 JP 6761713B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- surface treatment
- resin
- treatment liquid
- functional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004381 surface treatment Methods 0.000 title claims description 88
- 239000007788 liquid Substances 0.000 title claims description 82
- 239000011347 resin Substances 0.000 claims description 89
- 229920005989 resin Polymers 0.000 claims description 89
- 125000000524 functional group Chemical group 0.000 claims description 72
- 239000002253 acid Substances 0.000 claims description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000001165 hydrophobic group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 239000011147 inorganic material Substances 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical class 0.000 claims 5
- 101100116570 Caenorhabditis elegans cup-2 gene Proteins 0.000 claims 1
- 101100116572 Drosophila melanogaster Der-1 gene Proteins 0.000 claims 1
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- -1 polyoxyethylene group Polymers 0.000 description 42
- 150000002430 hydrocarbons Chemical class 0.000 description 27
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- 230000000052 comparative effect Effects 0.000 description 16
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- 125000001931 aliphatic group Chemical group 0.000 description 11
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- 125000003118 aryl group Chemical group 0.000 description 4
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 description 2
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
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- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- OWSKJORLRSWYGK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) propanoate Chemical compound CCC(=O)OCCC(C)(C)OC OWSKJORLRSWYGK-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
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- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
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- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- FMVOPJLFZGSYOS-UHFFFAOYSA-N 2-[2-(2-ethoxypropoxy)propoxy]propan-1-ol Chemical compound CCOC(C)COC(C)COC(C)CO FMVOPJLFZGSYOS-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-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
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- BEWYHVAWEKZDPP-UHFFFAOYSA-N bornane Chemical compound C1CC2(C)CCC1C2(C)C BEWYHVAWEKZDPP-UHFFFAOYSA-N 0.000 description 1
- 229930006742 bornane Natural products 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- FJAKCEHATXBFJT-UHFFFAOYSA-N ethyl 2-oxobutanoate Chemical compound CCOC(=O)C(=O)CC FJAKCEHATXBFJT-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229930004008 p-menthane Natural products 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- QZHDEAJFRJCDMF-UHFFFAOYSA-N perfluorohexanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-N 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
本発明は、表面処理液、及び当該表面処理液を用いる表面処理方法に関する。 The present invention relates to a surface treatment liquid and a surface treatment method using the surface treatment liquid.
従来より、種々の物品の表面の性質を改質するために、様々な表面処理液が使用されている。表面改質の中でも、物品の表面の親水化又は疎水化についての要求は大きく、親水化用又は疎水化用の薬剤や表面処理液について多数提案されている。 Conventionally, various surface treatment liquids have been used to modify the surface properties of various articles. Among the surface modifications, there is a great demand for hydrophilization or hydrophobization of the surface of articles, and many chemicals and surface treatment liquids for hydrophilization or hydrophobization have been proposed.
かかる表面処理用の薬剤に関して、例えば、被膜表面に親水性と防汚性とを付与できる表面調整剤として、少なくともアクリルアミドモノマーと、特定の骨格のシロキシ基含有モノ（メタ）アクリレートモノマーとが共重合された、重量平均分子量１５００〜５００００の共重合物が提案されている（特許文献１）。 Regarding such a chemical for surface treatment, for example, at least an acrylamide monomer and a siloxy group-containing mono (meth) acrylate monomer having a specific skeleton are copolymerized as a surface conditioner capable of imparting hydrophilicity and antifouling property to the film surface. A copolymer having a weight average molecular weight of 1500 to 50,000 has been proposed (Patent Document 1).
しかしながら、特許文献１に記載の表面調整剤を用いて親水化処理を行う場合、表面調整剤のみを含む溶液を用いて被処理体の表面を処理しても、表面調整剤が被処理体の表面に付着しにくく、所望する親水化効果を得にくい。
このため、特許文献１では、表面調整剤の溶液に、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、アルキッド樹脂、エポキシ樹脂、ポリアミン樹脂等の樹脂を被膜形成成分として配合した液を、表面処理液として用いている。
However, when the hydrophilization treatment is performed using the surface conditioner described in Patent Document 1, even if the surface of the object to be treated is treated with a solution containing only the surface conditioner, the surface conditioner is used as the surface conditioner. It is difficult to adhere to the surface and it is difficult to obtain the desired hydrophilic effect.
Therefore, in Patent Document 1, a liquid obtained by blending a solution of a surface conditioner with a resin such as an acrylic resin, a polyester resin, a urethane resin, an alkyd resin, an epoxy resin, or a polyamine resin as a film-forming component is used as a surface treatment liquid. ing.
そして、特許文献１に記載の表面調整剤と、被膜形成成分とを含む表面処理液を用いる場合、被処理体の表面が樹脂を含む被膜により被覆されてしまうため、良好な親水化はできても、被処理体が有する有用な表面特性まで損なわれてしまう。 When a surface treatment liquid containing the surface conditioner described in Patent Document 1 and a film-forming component is used, the surface of the object to be treated is covered with a film containing a resin, so that good hydrophilicity can be achieved. However, even the useful surface properties of the object to be treated are impaired.
本発明は、上記の課題に鑑みなされたものであって、被膜形成性の樹脂を含んでいなくても、被処理体の表面の良好な親水化又は疎水化を行うことができる表面処理液と、当該表面処理液を用いる表面処理方法とを提供することを目的とする。 The present invention has been made in view of the above problems, and is a surface treatment liquid capable of making the surface of the object to be treated good hydrophilic or hydrophobic even if it does not contain a film-forming resin. An object of the present invention is to provide a surface treatment method using the surface treatment liquid.
本発明者らは、（Ａ）樹脂と、（Ｃ）溶媒とを含む表面処理液において、（Ａ）樹脂として、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉと、前記官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩとを有する樹脂を用い、且つ、表面処理液にｐＫａ１以下の（Ｂ）強酸を添加することにより、上記の課題を解決できることを見出し、本発明を完成するに至った。 In a surface treatment liquid containing (A) resin and (C) solvent, the present inventors use one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group as the (A) resin. By using a resin having a certain functional group I and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I, and by adding a strong acid (B) of pKa1 or less to the surface treatment liquid, We have found that the above problems can be solved, and have completed the present invention.
本発明の第一の態様は、（Ａ）樹脂と、（Ｂ）強酸と、（Ｃ）溶媒とを含み、
（Ａ）樹脂が、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉと、前記官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩとを有し、
ただし、官能基ＩＩが水酸基、シアノ基、及びカルボキシル基から選択される１以上の基を含む場合、（Ａ）樹脂は官能基Ｉを有していなくてもよく、
（Ｂ）強酸のｐＫａが１以下である、表面処理液である。
A first aspect of the present invention comprises (A) a resin, (B) a strong acid, and (C) a solvent.
(A) A functional group I, which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II, which is a hydrophilic group or a hydrophobic group other than the functional group I. And have
However, when the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) does not have to have the functional group I.
(B) A surface treatment liquid having a strong acid pKa of 1 or less.
本発明の第二の態様は、第一の態様にかかる表面処理液の、被処理体の表面への塗布を含む、表面処理方法である。 A second aspect of the present invention is a surface treatment method including application of the surface treatment liquid according to the first aspect to the surface of an object to be treated.
本発明によれば、被膜形成性の樹脂を含んでいなくても、被処理体の表面の良好な親水化又は疎水化を行うことができる表面処理液と、当該表面処理液を用いる表面処理方法とを提供することができる。 According to the present invention, a surface treatment liquid capable of performing good hydrophilicity or hydrophobicity on the surface of the object to be treated without containing a film-forming resin, and a surface treatment using the surface treatment liquid. Methods and can be provided.
≪表面処理液≫
表面処理液（以下、単に処理液とも記す。）は、（Ａ）樹脂と、（Ｂ）強酸と、（Ｃ）溶媒とを含む。
（Ａ）樹脂は、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉと、官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩとを有する。なお、官能基ＩＩが水酸基、シアノ基、及びカルボキシル基から選択される１以上の基を含む場合には、（Ａ）樹脂は官能基Ｉを有していなくてもよい。
（Ｂ）強酸のｐＫａは１以下である。
≪Surface treatment liquid≫
The surface treatment liquid (hereinafter, also simply referred to as a treatment liquid) contains (A) a resin, (B) a strong acid, and (C) a solvent.
The resin (A) includes a functional group I, which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II, which is a hydrophilic group or a hydrophobic group other than the functional group I. Has. When the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) does not have to have the functional group I.
(B) The pKa of the strong acid is 1 or less.
処理液が、官能基Ｉを有する（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸とを含むことにより、表面処理時に、（Ａ）樹脂が、被処理体の表面に良好に結合ないし付着する。このため、被処理体の表面には、（Ａ）樹脂が有する親水性又は疎水性の官能基ＩＩが高効率で導入される。その結果、（Ａ）樹脂と、（Ｂ）強酸とを含む処理液を用いて表面処理を行うと、被処理体の表面が高度に親水化又は疎水化される。 When the treatment liquid contains the resin (A) having a functional group I and the strong acid (B) having a pKa of 1 or less, the resin (A) is satisfactorily bonded or adhered to the surface of the object to be treated during the surface treatment. .. Therefore, the hydrophilic or hydrophobic functional group II of the resin (A) is introduced into the surface of the object to be treated with high efficiency. As a result, when surface treatment is performed using a treatment liquid containing (A) resin and (B) strong acid, the surface of the object to be treated is highly hydrophilic or hydrophobic.
以下、処理液に含まれる必須又は任意の成分について説明する。 Hereinafter, essential or arbitrary components contained in the treatment liquid will be described.
＜（Ａ）樹脂＞
（Ａ）樹脂は、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉを有する。（Ｂ）強酸が、官能基Ｉと非処理体表面との反応又は相互作用を高めることによって、（Ａ）樹脂が基板表面に結合ないし付着する。
<(A) Resin>
The resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The strong acid (B) enhances the reaction or interaction between the functional group I and the surface of the untreated body, so that the resin (A) is bonded or adhered to the surface of the substrate.
（Ａ）樹脂は、官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩを有する。親水性基を有する（Ａ）樹脂を含む処理液を用いると親水化処理でき、疎水性基を有する（Ａ）樹脂を含む処理液を用いると疎水化処理できる。
親水性基又は疎水性基は、従来から、当業者に親水性基又は疎水性基であると認識されている官能基であれば特に限定されず、その中から適宜選択できる。
The resin (A) has a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I. A treatment solution containing a resin (A) having a hydrophilic group can be used for a hydrophilic treatment, and a treatment solution containing a resin (A) having a hydrophobic group can be used for a hydrophobic treatment.
The hydrophilic group or hydrophobic group is not particularly limited as long as it is a functional group conventionally recognized by those skilled in the art as a hydrophilic group or a hydrophobic group, and can be appropriately selected from among them.
（Ａ）樹脂の種類は、（Ａ）樹脂が、所定の官能基を有し、且つ（Ｃ）溶媒に可溶である限り特に限定されない。（Ａ）樹脂の例としては、（メタ）アクリル樹脂、ノボラック樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、及びシリコーン樹脂等が挙げられる。これらの樹脂の中では、官能基の導入や、官能基を有する単位の含有比率の調整が容易である事から（メタ）アクリル樹脂が好ましい。 The type of the resin (A) is not particularly limited as long as the resin (A) has a predetermined functional group and is soluble in the solvent (C). Examples of the resin (A) include (meth) acrylic resin, novolak resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, silicone resin and the like. Among these resins, (meth) acrylic resin is preferable because it is easy to introduce a functional group and adjust the content ratio of a unit having a functional group.
親水性基の具体例としては、ポリオキシアルキレン基（例えば、ポリオキシエチレン基、ポリオキシプロピレン基、オキシエチレン基とオキシプロピレン基がブロック又はランダム結合したポリオキシアルキレン基等）、アミノ基、カルボキシル基、水酸基、スルホン酸基等があげられる。また、これらの基を含む有機基も親水性基として好ましい。 Specific examples of the hydrophilic group include a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded), an amino group, and a carboxyl group. Examples include groups, hydroxyl groups and sulfonic acid groups. Further, an organic group containing these groups is also preferable as a hydrophilic group.
（Ａ）樹脂が、官能基ＩＩとして、水酸基、シアノ基、及びカルボキシル基を含む親水性基又は疎水性基を有する場合、当該親水性基又は疎水性基に含まれる水酸基、シアノ基、又はカルボキシル基は、官能基Ｉとしての役割も果たす。
このため、（Ａ）樹脂が、官能基ＩＩとして、水酸基、シアノ基、及びカルボキシル基を含む親水性基又は疎水性基を有する場合、（Ａ）樹脂は、官能基Ｉを有していなくてもよい。
なお、水酸基、及びカルボキシル基を含む親水性基には、水酸基そのもの、及びカルボキシル基そのものが含まれる。
When the resin (A) has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group and a carboxyl group as the functional group II, the hydroxyl group, the cyano group or the carboxyl contained in the hydrophilic group or the hydrophobic group The group also serves as a functional group I.
Therefore, when the resin (A) has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, the resin (A) does not have the functional group I. May be good.
The hydroxyl group and the hydrophilic group containing the carboxyl group include the hydroxyl group itself and the carboxyl group itself.
処理液の親水化効果が優れる点で、親水性基としては、下記式（Ａ１）：
−ＮＨ−Ｒ１・・・（Ａ１）
（式（Ａ１）中、Ｒ１は、アミノ基、スルホン酸基、及び水酸基からなる群より選択される１以上の基で置換された炭素原子数１〜４のアルキル基、又は水素原子である。）
で表される基が好ましい。
In that the treatment liquid has an excellent hydrophilic effect, the hydrophilic group includes the following formula (A1):
-NH-R 1 ... (A1)
(In the formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group. .)
The group represented by is preferable.
式（Ａ１）で表される親水性基の具体例としては、アミノ基と、下記式で表される基と、が挙げられる。
上記の式（Ａ１）で表される親水性基の具体例のうち、より好ましい基としては、以下の基が挙げられる。
上記の式（Ａ１）で表される親水性基の具体例のうち、特に好ましい基としては、以下の基が挙げられる。
疎水性基の具体例としては、例えば、フッ素化炭化水素基、シリル基、シロキサン基、炭素原子数６〜２０のアルキル基、及び炭素原子数１０〜２０の芳香族炭化水素基等が挙げられる。
フッ素化炭化水素基としては、式（Ａ３）について後述する基が好ましい。
シリル基の好適な例としては、後述する式（Ａ４）で表され、ｎが０である基が挙げられる。シリル基の具体例としては、例えば、トリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、トリイソプロピルシリル基、ｔｅｒｔ−ブチルジメチルシリル基、及びトリフェニルシリル基等が挙げられる。
シロキサン基の好適な例としては、後述する式（Ａ４）で表され、ｎが１以上である基が挙げられる。
Specific examples of the hydrophobic group include a fluorinated hydrocarbon group, a silyl group, a siloxane group, an alkyl group having 6 to 20 carbon atoms, an aromatic hydrocarbon group having 10 to 20 carbon atoms, and the like. ..
As the fluorinated hydrocarbon group, a group described later in the formula (A3) is preferable.
Preferable examples of the silyl group include a group represented by the formula (A4) described later, in which n is 0. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group and the like.
Preferable examples of the siloxane group include a group represented by the formula (A4) described later and having n of 1 or more.
（Ａ）樹脂としては、種々の官能基を導入しやすく、官能基量の調整が容易である事から、不飽和結合を有する単量体の重合体であるのが好ましい。かかる重合体は、ホモポリマーであっても、コポリマーであってもよい。 The resin (A) is preferably a polymer of a monomer having an unsaturated bond because it is easy to introduce various functional groups and it is easy to adjust the amount of functional groups. Such a polymer may be a homopolymer or a copolymer.
この場合、（Ａ）樹脂が有する官能基Ｉは、下式（Ａ２）：
ＣＨ２＝ＣＲ２−（Ｒ３）ａ−ＣＯ−Ｒ４・・・（Ａ２）
（式（Ａ２）中、Ｒ２は水素原子又はメチル基であり、Ｒ３は２価の炭化水素基であり、ａは０又は１であり、Ｒ４は、−ＯＨ、−Ｏ−Ｒ５、又は−ＮＨ−Ｒ５であり、Ｒ５は、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の官能基で置換された炭化水素基である。）
で表される単量体に由来する基であるのが好ましい。
In this case, the functional group I contained in the resin (A) is the following formula (A2):
CH 2 = CR 2- (R 3 ) a- CO-R 4 ... (A2)
(In the formula (A2), R 2 is a hydrogen atom or a methyl group, R 3 is a divalent hydrocarbon group, a is 0 or 1, and R 4 is -OH, -O-R 5. , Or -NH-R 5 , where R 5 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of hydroxyl groups, cyano groups, and carboxyl groups.)
It is preferably a group derived from the monomer represented by.
上記式（Ａ２）中、Ｒ３は２価の炭化水素基である。２価の炭化水素基の炭素原子数は、本発明の目的を阻害しない範囲で特に限定されない。（Ａ）樹脂の入手や調製が容易である事から、Ｒ３としての２価の炭化水素基の炭素原子数は、１〜２０が好ましく、１〜１２がより好ましく、１〜１０が特に好ましく、１〜６が最も好ましい。 In the above formula (A2), R 3 is a divalent hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms of the divalent hydrocarbon group as R 3 is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 10 because the resin (A) can be easily obtained and prepared. , 1 to 6 are most preferable.
Ｒ３としての２価の炭化水素基は、脂肪族基でも、芳香族基でも、脂肪族部分と芳香族部分とを含む炭化水素基であってもよい。２価の炭化水素基が、脂肪族基である場合、当該脂肪族基は、飽和脂肪族基でも不飽和脂肪族基でもよい。また、当該脂肪族基の構造は、直鎖状でも、分岐鎖状でも、環状でも、これらの構造の組み合わせであってもよい。 The divalent hydrocarbon group as R 3 may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic portion and an aromatic portion. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. Further, the structure of the aliphatic group may be linear, branched chain, cyclic, or a combination of these structures.
Ｒ３の好適な具体例としては、メチレン基、エタン−１，２−ジイル基、エタン−１，１−ジイル基、プロパン−１，３−ジイル基、プロパン−１，１−ジイル基、プロパン−２，２−ジイル基、ｎ−ブタン−１，４−ジイル基、ｎ−ペンタン−１，５−ジイル基、ｎ−ヘキサン−１，６−ジイル基、ｎ−ヘプタン−１，７−ジイル基、ｎ−オクタン−１，８−ジイル基、ｎ−ノナン−１，９−ジイル基、ｎ−デカン−１，１０−ジイル基、ｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基、ナフタレン−２，６−ジイル基、ナフタレン−２，７−ジイル基、ナフタレン−１，４−ジイル基、ビフェニル−４，４’−ジイル基等が挙げられる。 Preferable specific examples of R 3 include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,1-diyl group and propane. -2,2-diyl group, n-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptan-1,7-diyl group Group, n-octane-1,8-diyl group, n-nonan-1,9-diyl group, n-decane-1,10-diyl group, o-phenylene group, m-phenylene group, p-phenylene group, Examples thereof include naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, biphenyl-4,4'-diyl group and the like.
Ｒ４は、−ＯＨ、−Ｏ−Ｒ５、又は−ＮＨ−Ｒ５であり、Ｒ５は、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の官能基で置換された炭化水素基である。
Ｒ５の基の主骨格を構成する炭化水素基は、直鎖状、分岐鎖状、又は環状の脂肪族基であってもよく、芳香族炭化水素基であってもよい。
直鎖状、分岐鎖状、又は環状の脂肪族基の炭素原子数は１〜２０が好ましく、１〜１２がより好ましい。
直鎖状、又は分岐鎖状の脂肪族基の好適な例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｓｅｃ−ペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基等が挙げられる。
環状の脂肪族基の好適な例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、及びシクロオクチル基等のシクロアルキル基や、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、及びテトラシクロドデカン等のポリシクロアルカンから１個の水素原子を除いた基や、これらのポリシクロアルカンのＣ１−Ｃ４アルキル置換体から１個の水素原子を除いた基が挙げられる。
芳香族炭化水素基の好適な例としては、フェニル基、ナフチル基、アントラニル基、フェナントレニル基、及びビフェニリル基等が挙げられる。芳香族炭化水素基は、メチル基、エチル基等のＣ１−Ｃ４アルキル基で置換されていてもよい。
R 4 was -OH, -OR 5 or -NH-R 5 , where R 5 was substituted with one or more functional groups selected from the group consisting of hydroxyl groups, cyano groups, and carboxyl groups. It is a hydrocarbon group.
Hydrocarbon group constituting the main skeleton of group R 5 is a linear, branched, or may be a cyclic aliphatic group may be an aromatic hydrocarbon group.
The number of carbon atoms of the linear, branched, or cyclic aliphatic group is preferably 1 to 20, and more preferably 1 to 12.
Preferable examples of linear or branched aliphatic groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. , N-pentyl group, isopentyl group, neopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. ..
Preferable examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and adamantan, norbornan, isobornan, tricyclodecane, and the like. Examples thereof include a group obtained by removing one hydrogen atom from a polycycloalkane such as tetracyclododecane, and a group obtained by removing one hydrogen atom from a C1-C4 alkyl substituent of these polycycloalkanes.
Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranil group, a phenanthrenil group, a biphenylyl group and the like. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or an ethyl group.
式（Ａ２）で表される単量体に由来する単位の特に好ましい具体例としては、下記ａ２−１〜ａ２−９の単位が挙げられる。下記ａ２−１〜ａ２−９の単位の中では、ａ２−１〜ａ２−４の単位がより好ましい。
（Ａ）樹脂が、官能基ＩＩとして疎水性基を有する場合、官能基ＩＩは下式（Ａ３）：
ＣＨ２＝ＣＲ２−（ＣＯ−Ｏ）ｂ−Ｒ６・・・（Ａ３）
（式（Ａ３）中、Ｒ２は水素原子又はメチル基であり、ｂは０又は１であり、Ｒ６は、フッ素化炭化水素基、又は下式（Ａ４）：
−ＳｉＲ７Ｒ８−（−Ｏ−ＳｉＲ７Ｒ８−）ｎ−Ｒ９・・・（Ａ４）
で表される基であり、Ｒ７、Ｒ８、及びＲ９は、それぞれ独立に炭素原子数１〜６の炭化水素基であり、ｎは０以上の整数である。）
で表される単量体に由来するのが好ましい。
When the resin (A) has a hydrophobic group as the functional group II, the functional group II has the following formula (A3):
CH 2 = CR 2- (CO-O) b- R 6 ... (A3)
(In the formula (A3), R 2 is a hydrogen atom or a methyl group, b is 0 or 1, and R 6 is a fluorinated hydrocarbon group, or the following formula (A4):
-SiR 7 R 8 - (- O -SiR 7 R 8 -) n -R 9 ··· (A4)
R 7 , R 8 and R 9 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more. )
It is preferably derived from the monomer represented by.
式（Ａ３）中、Ｒ６がフッ素化炭化水素基である場合、当該フッ素化炭化水素基の主骨格を構成する炭化水素基は、前述のＲ５の基の主骨格を構成する炭化水素基と同様である。当該フッ素化炭化水素基は、炭化水素基が有する水素原子の全てがフッ素原子で置換された基でもよい。
Ｒ６としてのフッ素化炭化水素基の具体例としては、−ＣＦ３、−ＣＦ２ＣＦ３、−（ＣＦ２）２ＣＦ３、−（ＣＦ２）３ＣＦ３、−（ＣＦ２）４ＣＦ３、−（ＣＦ２）５ＣＦ３、−（ＣＦ２）６ＣＦ３、−（ＣＦ２）７ＣＦ３、−（ＣＦ２）８ＣＦ３、−（ＣＦ２）９ＣＦ３、−ＣＨ２ＣＦ３、−ＣＨ２ＣＦ２ＣＦ３、−ＣＨ２（ＣＦ２）２ＣＦ３、−ＣＨ２（ＣＦ２）３ＣＦ３、−ＣＨ２（ＣＦ２）４ＣＦ３、−ＣＨ２（ＣＦ２）５ＣＦ３、−ＣＨ２（ＣＦ２）６ＣＦ３、−ＣＨ２（ＣＦ２）７ＣＦ３、−ＣＨ２（ＣＦ２）８ＣＦ３、−ＣＨ２ＣＨ２ＣＦ３、−ＣＨ２ＣＨ２ＣＦ２ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）２ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）３ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）４ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）５ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）６ＣＦ３、−ＣＨ２ＣＨ２（ＣＦ２）７ＣＦ３、及び−ＣＨ（ＣＦ３）２等の鎖状フッ素化アルキル基；ペンタフルオロフェニル基、ｏ−トリフルオロメチルフェニル基、ｍ−トリフルオロメチルフェニル基、ｐ−トリフルオロメチルフェニル基等のフッ素化芳香族炭化水素基；オクタフルオロアダマンチル基等のフッ素化脂環式基が挙げられる。
In the formula (A3), when R 6 is a fluorinated hydrocarbon group, the hydrocarbon group constituting the main skeleton of the fluorinated hydrocarbon group is a hydrocarbon group constituting the main skeleton of the above-mentioned R 5 group. Is similar to. The fluorinated hydrocarbon group may be a group in which all the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms.
Specific examples of the fluorinated hydrocarbon group as R 6 include -CF 3 , -CF 2 CF 3 ,-(CF 2 ) 2 CF 3 ,-(CF 2 ) 3 CF 3 ,-(CF 2 ) 4 CF. 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 6 CF 3 ,-(CF 2 ) 7 CF 3 ,-(CF 2 ) 8 CF 3 ,-(CF 2 ) 9 CF 3 , -CH 2 CF 3 , -CH 2 CF 2 CF 3 , -CH 2 (CF 2 ) 2 CF 3 , -CH 2 (CF 2 ) 3 CF 3 , -CH 2 (CF 2 ) 4 CF 3 , -CH 2 (CF 2) ) 5 CF 3 , -CH 2 (CF 2 ) 6 CF 3 , -CH 2 (CF 2 ) 7 CF 3 , -CH 2 (CF 2 ) 8 CF 3 , -CH 2 CH 2 CF 3 , -CH 2 CH 2 CF 2 CF 3 , -CH 2 CH 2 (CF 2 ) 2 CF 3 , -CH 2 CH 2 (CF 2 ) 3 CF 3 , -CH 2 CH 2 (CF 2 ) 4 CF 3 , -CH 2 CH 2 (CF 2 ) 5 CF 3 , -CH 2 CH 2 (CF 2 ) 6 CF 3 , -CH 2 CH 2 (CF 2 ) 7 CF 3 , and -CH (CF 3 ) 2 and other chain fluorinated alkyl groups Fluorinated aromatic hydrocarbon groups such as pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl group; fluorinated alicyclic group such as octafluoroadamantyl group The group is mentioned.
式（Ａ３）中、Ｒ６が式（Ａ４）で表される基である場合、Ｒ７、Ｒ８、及びＲ９は、それぞれ独立に、メチル基、エチル基、又はフェニル基であるのが好ましく、Ｒ７、Ｒ８、及びＲ９が全てメチル基であるのがより好ましい。
式（Ａ４）中、ｎの上限は、本発明の目的を阻害しない範囲で特に限定されない。ｎは、０以上３５以下の整数であるのが好ましく、０以上１０以下の整数であるのがより好ましい。
In formula (A3), when R 6 is a group represented by formula (A4), R 7 , R 8 and R 9 are independently methyl, ethyl, or phenyl groups, respectively. Preferably, R 7 , R 8 and R 9 are all methyl groups.
In the formula (A4), the upper limit of n is not particularly limited as long as it does not impair the object of the present invention. n is preferably an integer of 0 or more and 35 or less, and more preferably an integer of 0 or more and 10 or less.
式（Ａ３）で表される単量体に由来する、疎水性基を有する単位の特に好ましい具体例としては、下記ａ３−１〜ａ３−２２の単位が挙げられる。下記の単位の中では、ａ３−８、ａ３−１８、ａ３−１９、及びａ３−２２の単位がより好ましい。
また、（Ａ）樹脂が、官能基ＩＩとして親水性基を有する場合、官能基ＩＩは下式（Ａ５）：
ＣＨ２＝ＣＲ２−ＣＯ−ＮＨ−Ｒ１・・・（Ａ５）
（式（Ａ５）中、Ｒ１は、アミノ基、スルホン酸基、及び水酸基からなる群より選択される１以上の基で置換された炭素原子数１〜４のアルキル基、又は水素原子であり、Ｒ２は水素原子又はメチル基である。）
で表される単量体に由来するのが好ましい。
When the resin (A) has a hydrophilic group as the functional group II, the functional group II has the following formula (A5):
CH 2 = CR 2- CO-NH-R 1 ... (A5)
(In the formula (A5), R 1 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group. , R 2 is a hydrogen atom or a methyl group.)
It is preferably derived from the monomer represented by.
式（Ａ５）中、Ｒ１については、前述した通りである。 In the formula (A5), R 1 is as described above.
式（Ａ５）で表される単量体に由来する、親水性基を有する単位の特に好ましい具体例としては、下記ａ５−１〜ａ５−５の単位が挙げられる。下記の単位の中では、ａ５−１〜ａ５−４の単位がより好ましい。
（Ａ）樹脂が不飽和結合を有する単量体の重合体である場合、かかる重合体は、本発明の目的を阻害しない範囲で、前述の式（Ａ２）で表される単量体に由来する単位、式（Ａ３）で表される単量体に由来する単位、及び式（Ａ５）で表される単量体に由来する単位以外のその他の構成単位を含んでいてもよい。 When the resin (A) is a polymer of a monomer having an unsaturated bond, the polymer is derived from the monomer represented by the above formula (A2) as long as the object of the present invention is not impaired. It may contain a unit to be used, a unit derived from the monomer represented by the formula (A3), and other structural units other than the unit derived from the monomer represented by the formula (A5).
その他の構成単位としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸−ｎ−プロピル、（メタ）アクリル酸−ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸−ｔｅｒｔ−ブチル、（メタ）アクリル酸−ｎ−ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸フェニル、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ｎ−ブチル（メタ）アクリルアミド、Ｎ−ｎ−ペンチル（メタ）アクリルアミド、Ｎ−イソペンチル（メタ）アクリルアミド、Ｎ−フェニル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジ−ｎ−プロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジ−ｎ−ブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジ−ｎ−ペンチル（メタ）アクリルアミド、スチレン、α−メチルスチレン、β−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、及びクロルスチレン等の単量体に由来する構成単位が挙げられる。 Other constituent units include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, -n-propyl (meth) acrylate, -n-butyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n-pentyl (meth) acrylate, isopentyl (meth) acrylate, phenyl (meth) acrylate, N-methyl (meth) acrylamide, N -Ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn-pentyl (meth) acrylamide, N-isopentyl (meth) ) Acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-di -N-butyl (meth) acrylamide, N, N-di-n-pentyl (meth) acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, And structural units derived from monomers such as chlorostyrene.
（Ａ）樹脂が不飽和結合を有する単量体の重合体である場合、かかる重合体に含まれる全構成単位中の式（Ａ２）で表される単量体に由来する構成単位のモル比率は、０．１〜５０モル％が好ましく、１〜２０モル％がより好ましく、１〜１５モル％が特に好ましい。 When the resin (A) is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by the formula (A2) in all the structural units contained in the polymer. Is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, and particularly preferably 1 to 15 mol%.
（Ａ）樹脂が不飽和結合を有する単量体の重合体である場合、かかる重合体に含まれる全構成単位中の式（Ａ３）又は（Ａ５）で表される単量体に由来する構成単位のモル比率は、５０〜９９．９モル％が好ましく、６０〜９９モル％がより好ましく、７０〜９９モル％が特に好ましい。
ただし、式（Ａ５）で表される単量体に由来する構成単位が水酸基、シアノ基、カルボキシル基のいずれか１つの基を含む場合、重合体に含まれる全構成単位中の式（Ａ５）で表される単量体に由来する構成単位の比率は１００％であってもよい。
When the resin (A) is a polymer of a monomer having an unsaturated bond, a structure derived from the monomer represented by the formula (A3) or (A5) in all the structural units contained in the polymer. The molar ratio of the unit is preferably 50 to 99.9 mol%, more preferably 60 to 99 mol%, and particularly preferably 70 to 99 mol%.
However, when the structural unit derived from the monomer represented by the formula (A5) contains any one of a hydroxyl group, a cyano group and a carboxyl group, the formula (A5) in all the structural units contained in the polymer The ratio of the structural unit derived from the monomer represented by may be 100%.
処理液に含まれる（Ａ）樹脂の量は、本発明の目的を阻害しない範囲で特に限定されず、処理液の塗布性等を勘案して適宜定められる。典型的には、処理液中の（Ａ）樹脂の量は、処理液中の（Ａ）樹脂の量と、後述する（Ｃ）溶媒の量との関係は、以下の関係である量が好ましい。
処理液中の樹脂の質量を１００質量部とする場合に、後述する（Ｃ）溶媒の量が１００〜１００００質量部であるのが好ましく、５００〜８０００質量部であるのがより好ましく、１０００〜６０００質量部であるのが特に好ましい。
The amount of the resin (A) contained in the treatment liquid is not particularly limited as long as it does not impair the object of the present invention, and is appropriately determined in consideration of the coatability of the treatment liquid and the like. Typically, the amount of the (A) resin in the treatment liquid is preferably the amount having the following relationship between the amount of the (A) resin in the treatment liquid and the amount of the solvent (C) described later. ..
When the mass of the resin in the treatment liquid is 100 parts by mass, the amount of the solvent (C) described later is preferably 100 to 10000 parts by mass, more preferably 500 to 8000 parts by mass, and 1000 to 1000 parts by mass. It is particularly preferably 6000 parts by mass.
＜（Ｂ）強酸＞
処理液は、（Ｂ）強酸を含む。（Ｂ）強酸のｐＫａは１以下である。なお、ｐＫａは水中での値である。
（Ｂ）強酸は、（Ａ）樹脂が有する官能基Ｉに作用することで、（Ａ）樹脂の被処理体の表面への付着又は結合を促進させる。
（Ｂ）強酸の種類は、ｐＫａが１以下である限り特に限定されない。（Ｂ）強酸としては、ｐＫａが１以下である酸を２種以上組み合わせて用いることができる。
<(B) Strong acid>
The treatment liquid contains (B) a strong acid. (B) The pKa of the strong acid is 1 or less. In addition, pKa is a value in water.
The strong acid (B) acts on the functional group I of the resin (A) to promote the adhesion or bond of the resin (A) to the surface of the object to be treated.
(B) The type of strong acid is not particularly limited as long as pKa is 1 or less. As the strong acid (B), two or more kinds of acids having a pKa of 1 or less can be used in combination.
（Ｂ）強酸の好適な例としては、フッ素化脂肪族カルボン酸（例えばトリフルオロ酢酸等）、フルオロスルホン酸、炭素原子数１〜３０のアルカンスルホン酸（例えばメタンスルホン酸、ドデカンスルホン酸等）、アリールスルホン酸（例えばベンゼンスルホン酸、ｐ−トルエンスルホン酸等）、炭素原子数１〜３０のフルオロアルカンスルホン酸（例えばトリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸及びトリデカフルオロヘキサンスルホン酸）、ビススルホニルイミド化合物、２つのスルホニル基がフルオロアルキレン基で連結された環状スルホニルイミド化合物、及びＮ−アシルフルオロアルカンスルホン酸アミド等が挙げられる。 (B) Preferable examples of the strong acid are fluorinated aliphatic carboxylic acid (for example, trifluoroacetic acid), fluorosulfonic acid, alcan sulfonic acid having 1 to 30 carbon atoms (for example, methanesulfonic acid, dodecanesulfonic acid, etc.). , Aryl sulfonic acid (eg benzene sulfonic acid, p-toluene sulfonic acid, etc.), fluoroalcan sulfonic acid having 1 to 30 carbon atoms (eg trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane sulfonic acid, nonafluoro Butane sulfonic acid, undecafluoropentane sulfonic acid and tridecafluorohexane sulfonic acid), bissulfonylimide compound, cyclic sulfonylimide compound in which two sulfonyl groups are linked by a fluoroalkylene group, and N-acylfluoroalkanesulfonic acid amide. And so on.
これらの（Ｂ）強酸が、フルオロアルキル基、又はフルオロアルキレン基を含む場合、これらの基は、部分的にフッ素化されたフルオロアルキル基、又はフルオロアルキレン基であってもよく、完全にフッ素化されたパーフルオロアルキル基、又はパーフルオロアルキレン基であってもよい。 When these (B) strong acids contain a fluoroalkyl group or a fluoroalkylene group, these groups may be a partially fluorinated fluoroalkyl group or a fluoroalkylene group and are completely fluorinated. It may be a perfluoroalkyl group or a perfluoroalkylene group.
これらの（Ｂ）強酸の中では、フルオロスルホン酸、炭素原子数１〜３０のアルカンスルホン酸、炭素原子数１〜３０のフルオロアルカンスルホン酸、ビス（フルオロアルキルスルホニル）イミド酸、２つのスルホニル基がフルオロアルキレン基で連結された環状スルホンイミド酸、及びＮ−アシルフルオロアルカンスルホン酸アミドが好ましく、炭素原子数１〜３０のフルオロアルカンスルホン酸、ビススルホニルイミド化合物、２つのスルホニル基がフルオロアルキレン基で連結された環状スルホニルイミド化合物、及びＮ−アシルフルオロアルカンスルホン酸アミドが好ましい。 Among these (B) strong acids, fluorosulfonic acid, alkanesulfonic acid having 1 to 30 carbon atoms, fluoroalcansulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) imide acid, and two sulfonyl groups. Cyclic sulfonic acid, in which is linked with a fluoroalkylene group, and N-acylfluoroalcan sulfonic acid amide are preferable, and fluoroalcan sulfonic acid having 1 to 30 carbon atoms, a bissulfonylimide compound, and two sulfonyl groups are fluoroalkylene groups. Cyclic sulfonylimide compounds linked with, and N-acylfluoroalcan sulfonic acid amide are preferred.
炭素原子数１〜３０のフルオロアルカンスルホン酸としては、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、及びノナフルオロブタンスルホン酸等が好ましい。 As the fluoroalkane sulfonic acid having 1 to 30 carbon atoms, trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane sulfonic acid, nonafluorobutane sulfonic acid and the like are preferable.
ビススルホニルイミド化合物としては、下式（Ｂ１）で表される化合物が好ましい。
電子吸引性基で置換された炭化水素基としては、フッ素化アルキル基、ニトロ基を有するアリール基が好ましい。フッ素化アルキル基は、直鎖状でも、分岐鎖状でも、環状でもよい。フッ素化アルキル基は、完全にフッ素化されたパーフルオロアルキル基であるのが好ましい。ニトロ基を有するアリール基としては、ｏ−ニトロフェニル基、ｍ−ニトロフェニル基、及びｐ−ニトロフェニル基が好ましく、ｐ−ニトロフェニル基がより好ましい。
As the bissulfonylimide compound, the compound represented by the following formula (B1) is preferable.
As the hydrocarbon group substituted with the electron-withdrawing group, an alkyl fluorinated group and an aryl group having a nitro group are preferable. The alkyl fluorinated group may be linear, branched or cyclic. The fluorinated alkyl group is preferably a fully fluorinated perfluoroalkyl group. As the aryl group having a nitro group, an o-nitrophenyl group, an m-nitrophenyl group, and a p-nitrophenyl group are preferable, and a p-nitrophenyl group is more preferable.
式（Ｂ１）で表される化合物の好適な具体例としては、下式の化合物が挙げられる。
２つのスルホニル基がフルオロアルキレン基で連結された環状スルホニルイミド化合物としては、下式（Ｂ２）で表される化合物が好ましい。
式（Ｂ２）で表される化合物の好適な具体例としては、下式の化合物が挙げられる。
Ｎ−アシルフルオロアルカンスルホン酸アミドとしては、下式（Ｂ３）で表される化合物が好ましい。
Ｘ５は、炭化水素基である。炭化水素基について、前述のＲ５の基の主骨格を構成する炭化水素基と同様である
As the N-acylfluoroalkanesulfonic acid amide, a compound represented by the following formula (B3) is preferable.
X 5 is a hydrocarbon group. For the hydrocarbon group, the same as the hydrocarbon group constituting the main skeleton of the group described above for R 5
式（Ｂ３）で表される化合物の好適な具体例としては、下式の化合物が挙げられる。
処理液中の（Ｂ）強酸の含有量は、処理液による表面処理を良好に行うことが出来る限り特に限定されない。処理液中の（Ｂ）強酸の含有量は、（Ａ）樹脂１００質量に対して、０．１〜２０質量部が好ましく、０．１〜１０質量部がより好ましく、０．１〜５質量部が特に好ましい。 The content of the (B) strong acid in the treatment liquid is not particularly limited as long as the surface treatment with the treatment liquid can be performed satisfactorily. The content of (B) strong acid in the treatment liquid is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin (A). Part is particularly preferable.
＜（Ｃ）溶媒＞
（Ｃ）溶媒は、（Ａ）樹脂と、（Ｂ）強酸とが可溶である溶媒であれば特に限定されない。処理液中に、（Ａ）樹脂と、（Ｂ）強酸とが、所定量溶解していれば、処理液は、溶解していない状態の（Ａ）樹脂と、（Ｂ）強酸とを含んでいてもよい。（Ａ）樹脂と、（Ｂ）強酸とは、処理液に完全に溶解しているのが好ましい。
処理液が、不溶物を含む場合、表面処理時に、被処理体の表面に不溶物が付着する場合がある。この場合、表面処理された被処理体の表面を、後述するような方法でリンスすることにより、被処理体の表面に付着する不溶物を除去することができる。
<(C) Solvent>
The solvent (C) is not particularly limited as long as it is a solvent in which the resin (A) and the strong acid (B) are soluble. If a predetermined amount of the resin (A) and the strong acid (B) are dissolved in the treatment liquid, the treatment liquid contains the resin (A) in an undissolved state and the strong acid (B). You may. It is preferable that the resin (A) and the strong acid (B) are completely dissolved in the treatment liquid.
When the treatment liquid contains an insoluble matter, the insoluble matter may adhere to the surface of the object to be treated during the surface treatment. In this case, by rinsing the surface of the surface-treated object to be treated by a method as described later, insoluble matter adhering to the surface of the object to be treated can be removed.
（Ｃ）溶媒は、水であっても、有機溶媒であっても、有機溶媒の水溶液であってもよい。 The solvent (C) may be water, an organic solvent, or an aqueous solution of an organic solvent.
（Ｃ）溶媒として使用される有機溶媒の具体例としては、
ジメチルスルホキシド等のスルホキシド類；
ジメチルスルホン、ジエチルスルホン、ビス（２−ヒドロキシエチル）スルホン、テトラメチレンスルホン等のスルホン類；
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド等のアミド類；
Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、Ｎ−プロピル−２−ピロリドン、Ｎ−ヒドロキシメチル−２−ピロリドン、Ｎ−ヒドロキシエチル−２−ピロリドン等のラクタム類；
１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、１，３−ジイソプロピル−２−イミダゾリジノン等のイミダゾリジノン類；
ジメチルグリコール、ジメチルジグリコール、ジメチルトリグリコール、メチルエチルジグリコール、ジエチルグリコール、トリエチレングリコールブチルメチルエーテル等のジアルキルグリコールエーテル類；
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−ｎ−プロピルエーテル、エチレングリコールモノ−ｎ−ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ−ｎ−プロピルエーテル、ジエチレングリコールモノ−ｎ−ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ−ｎ−プロピルエーテル、プロピレングリコールモノ−ｎ−ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ−ｎ−プロピルエーテル、ジプロピレングリコールモノ−ｎ−ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等の（ポリ）アルキレングリコールモノアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；
ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジイソアミルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類；
メチルエチルケトン、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン等のケトン類；
２−ヒドロキシプロピオン酸メチル、２−ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類；２−ヒドロキシ−２−メチルプロピオン酸エチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メチル−３−メトキシブチルアセテート、３−メチル−３−メトキシブチルプロピオネート、酢酸エチル、酢酸−ｎ−プロピル、酢酸−ｉ−プロピル、酢酸−ｎ−ブチル、酢酸−ｉ−ブチル、ぎ酸−ｎ−ペンチル、酢酸−ｉ−ペンチル、プロピオン酸−ｎ−ブチル、酪酸エチル、酪酸−ｎ−プロピル、酪酸−ｉ−プロピル、酪酸−ｎ−ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸−ｎ−プロピル、アセト酢酸メチル、アセト酢酸エチル、２−オキソブタン酸エチル等の他のエステル類；
β−プロピロラクトン、γ−ブチロラクトン、δ−ペンチロラクトン等のラクトン類；
ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−ノナン、メチルオクタン、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカン、２，２，４，６，６−ペンタメチルヘプタン、２，２，４，４，６，８，８−ヘプタメチルノナン、シクロヘキサン、メチルシクロヘキサン等の直鎖状、分岐鎖状、又は環状の脂肪族炭化水素類；
ベンゼン、トルエン、キシレン、１，３，５−トリメチルベンゼン、ナフタレン等の芳香族炭化水素類；
ｐ−メンタン、ジフェニルメンタン、リモネン、テルピネン、ボルナン、ノルボルナン、ピナン等のテルペン類；等が挙げられる。
(C) Specific examples of the organic solvent used as the solvent include
Sulfoxides such as dimethyl sulfoxide;
Sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone;
Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide;
Lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone;
Imidazoridinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone;
Dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl glycol, triethylene glycol butyl methyl ether;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;
Other ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, acetic acid Ethyl, acetic acid-n-propyl, acetate-i-propyl, acetate-n-butyl, acetate-i-butyl, formate-n-pentyl, acetate-i-pentyl, propionate-n-butyl, ethyl butyrate, butyric acid Other esters such as -n-propyl, -i-propyl butyrate, -n-butyl butyrate, methyl pyruvate, ethyl pyruvate, -n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate Kind;
Lactones such as β-propyrolactone, γ-butyrolactone, and δ-pentilolactone;
n-Hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptan, 2,2,4 , 4,6,8,8-Heptamethylnonane, cyclohexane, methylcyclohexane and other linear, branched or cyclic aliphatic hydrocarbons;
Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene;
Terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, pinan;
（Ｃ）溶媒が、水と有機溶媒との混合溶媒である場合、（Ｃ）溶媒中の有機溶媒の含有量は１０質量％以上が好ましく、２０質量％以上がより好ましい。 When the solvent (C) is a mixed solvent of water and an organic solvent, the content of the organic solvent in the solvent (C) is preferably 10% by mass or more, more preferably 20% by mass or more.
＜その他の成分＞
処理液は、本発明の目的を阻害しない範囲で、（Ａ）樹脂、（Ｂ）強酸、及び（Ｃ）溶媒以外の種々の成分を含んでいてもよい。その他の成分としては、例えば、着色剤、界面活性剤、消泡剤、粘度調整剤、界面活性剤等が挙げられる。
<Other ingredients>
The treatment liquid may contain various components other than (A) resin, (B) strong acid, and (C) solvent as long as the object of the present invention is not impaired. Examples of other components include colorants, surfactants, defoamers, viscosity modifiers, surfactants and the like.
＜処理液の調製方法＞
処理液を調製する方法は特に限定されない。処理液は、典型的には、それぞれ所定量の（Ａ）樹脂と、（Ｂ）強酸と、（Ｃ）溶媒と、必要に応じてその他の成分を、均一に混合することにより調製される。
<Preparation method of treatment liquid>
The method for preparing the treatment liquid is not particularly limited. The treatment liquid is typically prepared by uniformly mixing a predetermined amount of (A) resin, (B) strong acid, (C) solvent, and if necessary, other components.
以上説明した処理液は、例えば、細胞培養器具や、細胞等の生体試料を含む液体を流通させるマイクロ流路デバイスの等の細胞接着防止用の表面処理、種々の物品への防汚性や防曇性の付与等の目的での表面処理等に好適に使用される。 The treatment liquid described above can be used for surface treatment for preventing cell adhesion such as cell culture equipment and microchannel devices for circulating a liquid containing a biological sample such as cells, and antifouling property and prevention for various articles. It is suitably used for surface treatment for the purpose of imparting cloudiness.
≪表面処理方法≫
以上説明した表面処理液を用いる表面処理方法は、通常、被処理体の表面への表面処理液の塗布を含む。表面処理液の塗布方法は特に限定されない。塗布方法の具体例としては、スピンコート法、スプレー法、ローラーコート法、浸漬法等が挙げられる。被処理体が基板である場合、表面処理液を均一に塗布することで、基板表面を均一に親水化又は疎水化できることから、塗布方法としてスピンコート法が好ましい。
≪Surface treatment method≫
The surface treatment method using the surface treatment liquid described above usually includes application of the surface treatment liquid to the surface of the object to be treated. The method of applying the surface treatment liquid is not particularly limited. Specific examples of the coating method include a spin coating method, a spray method, a roller coating method, a dipping method and the like. When the object to be treated is a substrate, the spin coating method is preferable as the coating method because the surface of the substrate can be uniformly made hydrophilic or hydrophobic by uniformly applying the surface treatment liquid.
被処理体の表面処理液が塗布される面の材質は特に限定されず、有機材料であっても、無機材料であってもよい。
有機材料としては、ＰＥＴ樹脂、ＰＢＴ樹脂等のポリエステル樹脂、各種ナイロン、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエチレン及びポリプリピレン等のポリオレフィン、ポリスチレン、（メタ）アクリル樹脂等、種々の樹脂材料が挙げられる。
また、種々のレジスト材料に含まれる感光性の樹脂成分や、アルカリ可溶性の樹脂成分も有機材料として好ましい。
無機材料としては、ガラス、シリコンや、銅、アルミニウム、鉄、タングステン等の種々の金属が挙げられる。金属は、合金であってもよい。
The material of the surface to which the surface treatment liquid of the object to be treated is applied is not particularly limited, and may be an organic material or an inorganic material.
Examples of the organic material include various resin materials such as PET resin, polyester resin such as PBT resin, various nylons, polyimide resins, polyamide-imide resins, polyolefins such as polyethylene and polyprepylene, polystyrene, and (meth) acrylic resin.
Further, a photosensitive resin component contained in various resist materials and an alkali-soluble resin component are also preferable as the organic material.
Examples of the inorganic material include glass, silicon, and various metals such as copper, aluminum, iron, and tungsten. The metal may be an alloy.
前述の表面処理液により表面処理される面の材質は特に限定されないが、表面処理液が塗布される面の材質が有機材料である場合は、官能基Ｉとして水酸基及び／又はカルボキシル基を有する（Ａ）樹脂を含む表面処理液を用いるのが好ましい。
表面処理液が塗布される面の材質が無機材料である場合は、官能基Ｉとして水酸基及び／又はシアノ基を有する（Ａ）樹脂を含む表面処理液を用いるのが好ましい。
The material of the surface to be surface-treated with the above-mentioned surface treatment liquid is not particularly limited, but when the material of the surface to which the surface treatment liquid is applied is an organic material, it has a hydroxyl group and / or a carboxyl group as the functional group I ( A) It is preferable to use a surface treatment liquid containing a resin.
When the material of the surface to which the surface treatment liquid is applied is an inorganic material, it is preferable to use a surface treatment liquid containing a resin (A) having a hydroxyl group and / or a cyano group as the functional group I.
被処理体の形状は特に限定されない。被処理体は平坦な基板であってもよく、例えば、球状や、柱状等の立体形状であってもよい。また、被処理体の表面は、平滑であっても、規則的又は不規則な凹凸を有していてもよい。 The shape of the object to be processed is not particularly limited. The object to be processed may be a flat substrate, and may have a three-dimensional shape such as a spherical shape or a columnar shape. Further, the surface of the object to be treated may be smooth or may have regular or irregular irregularities.
表面処理液を、被処理体の表面に塗布した後は、必要に応じて塗布膜を加熱して（Ｃ）溶媒の少なくとも一部を除去してもよい。 After the surface treatment liquid is applied to the surface of the object to be treated, at least a part of the solvent (C) may be removed by heating the coating film, if necessary.
被処理体上の表面処理液が塗布された箇所はリンスされるのが好ましい。前述の通り、所定の官能基を有する（Ａ）樹脂と、（Ｂ）強酸とを含む表面処理液を被処理体の表面に塗布すると、被処理体の表面に（Ａ）樹脂が良好に付着又は結合する。しかし、被処理体の表面には、当該表面に付着又は結合していない（Ａ）樹脂もある程度の量存在している。したがって、（Ａ）樹脂の、被処理体の表面特性に与える影響を極力低減させるために、リンスにより、被処理体の表面に付着又は結合していない（Ａ）樹脂を洗い流すのが好ましい。 It is preferable that the portion of the object to be treated to which the surface treatment liquid is applied is rinsed. As described above, when the surface treatment liquid containing the resin (A) having a predetermined functional group and the strong acid (B) is applied to the surface of the object to be treated, the resin (A) adheres well to the surface of the object to be treated. Or combine. However, on the surface of the object to be treated, a certain amount of the resin (A) that is not adhered to or bonded to the surface is also present. Therefore, in order to reduce the influence of the resin (A) on the surface characteristics of the object to be treated as much as possible, it is preferable to wash away the resin (A) which is not adhered to or bonded to the surface of the object to be treated by rinsing.
表面処理液が（Ｃ）溶媒として水を含む場合、水によりリンスを行うのが好ましい。また、表面処理液が（Ｃ）溶媒として有機溶媒を含む場合、有機溶媒によりリンスを行うのも好ましい。有機溶媒によりリンスを行う場合、表面処理液に含まれる有機溶媒と同種の有機溶媒を用いるのが好ましい。 When the surface treatment liquid contains water as the solvent (C), it is preferable to rinse with water. When the surface treatment liquid contains an organic solvent as the solvent (C), it is also preferable to rinse with the organic solvent. When rinsing with an organic solvent, it is preferable to use an organic solvent of the same type as the organic solvent contained in the surface treatment liquid.
表面処理液の塗布後、又はリンス後に、被処理体の表面を乾燥させることにより、良好に親水化又は疎水化された物品が得られる。 By drying the surface of the object to be treated after application of the surface treatment liquid or after rinsing, a well-hydrogenized or hydrophobic article can be obtained.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
〔実施例１〜１６、及び比較例１〜６〕
各実施例及び比較例において、表１に記載の比率で、以下に説明する構成単位を含有する樹脂を（Ａ）樹脂として用いた。
単位Ａ−１〜Ａ−７は、親水性基又は疎水性基である官能基ＩＩを（Ａ）樹脂に導入する構成単位である。
単位Ｂ−１〜Ｂ−４は、（Ａ）樹脂に官能基Ｉを導入する構成単位である。
単位Ｃ−１〜Ｃ−３は、官能基Ｉ及び官能基ＩＩのいずれも有さない構成単位である。
[Examples 1 to 16 and Comparative Examples 1 to 6]
In each of the Examples and Comparative Examples, the resin containing the structural unit described below was used as the resin (A) at the ratio shown in Table 1.
Units A-1 to A-7 are structural units for introducing a functional group II, which is a hydrophilic group or a hydrophobic group, into the resin (A).
Units B-1 to B-4 are structural units for introducing the functional group I into the resin (A).
Units C-1 to C-3 are structural units having neither functional group I nor functional group II.
実施例及び比較例について、酸成分として以下のＡｃ１〜Ａｃ４を用いた。Ａｃ１（トリフルオロメタンスルホン酸）と、下式の化合物であるＡｃ２とは、ｐＫａ１以下の強酸である。Ａｃ３（リン酸）と、Ａｃ４（酢酸）とは、ｐＫａ１超の酸である。
実施例及び比較例について、（Ｃ）溶媒としてＳ１：純水、Ｓ２：プロピレングリコールモノメチルエーテル、及びＳ３：プロピレングリコールモノメチルエーテルアセテートを用いた。 For Examples and Comparative Examples, S1: pure water, S2: propylene glycol monomethyl ether, and S3: propylene glycol monomethyl ether acetate were used as the solvent (C).
（表面処理液の調製）
表１〜３に記載される種類及びモル比率の構成単位からなる（Ａ）樹脂１００質量部と、表１〜３に記載される質量部の酸成分と、表１〜３に記載される質量部の溶媒とを均一に混合して、各実施例及び比較例の表面処理液を得た。
なお、比較例１では酸成分を使用しなかった。
(Preparation of surface treatment liquid)
100 parts by mass of the resin (A) consisting of the structural units of the types and molar ratios shown in Tables 1 to 3, the acid components of the parts by mass shown in Tables 1 to 3, and the masses shown in Tables 1 to 3. The solvent of each part was uniformly mixed to obtain the surface treatment liquids of each Example and Comparative Example.
In Comparative Example 1, the acid component was not used.
実施例８では、単位Ａ−４のみからなる樹脂を用い、実施例１５では、単位Ａ−１と単位Ａ−４とだけからなる樹脂を用いた。単位Ａ−４に含まれる２−ヒドロキシエチルアミノ基は、親水性基であるとともに、水酸基含有基でもある。このため、単位Ａ−４に含まれる水酸基は、官能基Ｉとしての役割も果たす。 In Example 8, a resin consisting only of the unit A-4 was used, and in Example 15, a resin consisting only of the unit A-1 and the unit A-4 was used. The 2-hydroxyethylamino group contained in the unit A-4 is not only a hydrophilic group but also a hydroxyl group-containing group. Therefore, the hydroxyl group contained in the unit A-4 also serves as a functional group I.
（表面処理効果の評価）
以上の方法により得られた、実施例１〜１５、及び比較例１〜５の表面処理液を用いて、以下の方法にしたがってＰＥＴフィルムの表面処理を行った。
まず、スピンコート法により、ＰＥＴフィルム上に表面処理液を塗布し、膜厚５００ｎｍの塗布膜を形成した。
形成された塗布膜を４０℃で６０秒間加熱した後、ＰＥＴフィルムの表面をリンスした。実施例１〜４、実施例８〜１３、実施例１５、及び比較例１〜４については、純水でリンスを行った。実施例５〜７、実施例１４、及び比較例５については、プロピレングリコールモノメチルエーテルを用いたリンスを行った。
リンスされたＰＥＴフィルムを乾燥させた後、ＰＥＴフィルム表面の水の接触角を測定した。水の接触角の測定は、Ｄｒｏｐｍａｓｔｅｒ７００（協和界面科学株式会社製）を用い表面処理された基板の表面に純水液滴（２．０μＬ）を滴下して、滴下１０秒後における接触角として測定した。水の接触角の測定結果を表１〜３に記す。
なお未処理のＰＥＴフィルムの水の接触角は７０．６°である。
(Evaluation of surface treatment effect)
Using the surface treatment solutions of Examples 1 to 15 and Comparative Examples 1 to 5 obtained by the above method, the surface treatment of the PET film was performed according to the following method.
First, a surface treatment liquid was applied onto the PET film by a spin coating method to form a coating film having a film thickness of 500 nm.
The formed coating film was heated at 40 ° C. for 60 seconds, and then the surface of the PET film was rinsed. Examples 1 to 4, Examples 8 to 13, Example 15, and Comparative Examples 1 to 4 were rinsed with pure water. For Examples 5 to 7, Example 14, and Comparative Example 5, rinsing with propylene glycol monomethyl ether was performed.
After the rinsed PET film was dried, the contact angle of water on the surface of the PET film was measured. The contact angle of water is measured by dropping a pure water droplet (2.0 μL) on the surface of a substrate surface-treated using a Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) and measuring it as the contact angle 10 seconds after the drop. did. The measurement results of the contact angle of water are shown in Tables 1 to 3.
The contact angle of water in the untreated PET film is 70.6 °.
実施例１〜１６によれば、所定の官能基を有する（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸と、（Ｃ）溶媒とを含む表面処理液を用いることにより、ＰＥＴフィルムの表面が良好に親水化又は疎水化されることが分かる。 According to Examples 1 to 16, by using a surface treatment liquid containing (A) a resin having a predetermined functional group, (B) a strong acid having a pKa of 1 or less, and (C) a solvent, the surface of the PET film can be prepared. It can be seen that it is well hydrophilic or hydrophobic.
比較例１によれば、所定の官能基を有する（Ａ）樹脂と（Ｃ）溶媒とを含むが、酸成分を含まない表面処理液を用いる場合、良好な表面処理効果が得られないことが分かる。
比較例２及び３によれば、官能基ＩＩとして親水性基又は疎水性基を有さない（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸と、（Ｃ）溶媒とを含む表面処理液で、ＰＥＴフィルムの表面処理を行っても、ＰＥＴフィルムの水の接触角は未処理の状態から大きく変わらないことが分かる。
比較例４及び５によれば、所定の官能基を有する（Ａ）樹脂と、酸成分と、（Ｃ）溶媒とを含むが、ｐＫａ１以下の（Ｂ）強酸を含まない表面処理液で、ＰＥＴフィルムの表面処理を行っても、ＰＥＴフィルムの水の接触角は未処理の状態から大きく変わらないことが分かる。
比較例６によれば、官能基Ｉを有しない（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸と、（Ｃ）溶媒とを含む表面処理液で、ＰＥＴフィルムの表面処理を行っても、ＰＥＴフィルムの水の接触角は未処理の状態から大きく変わらないことが分かる。
According to Comparative Example 1, when a surface treatment solution containing (A) resin having a predetermined functional group and (C) solvent but not containing an acid component is used, a good surface treatment effect may not be obtained. I understand.
According to Comparative Examples 2 and 3, a surface treatment solution containing (A) a resin having no hydrophilic group or a hydrophobic group as a functional group II, (B) a strong acid having a pKa of 1 or less, and (C) a solvent. It can be seen that even if the surface treatment of the PET film is performed, the contact angle of water of the PET film does not change significantly from the untreated state.
According to Comparative Examples 4 and 5, PET is a surface treatment liquid containing (A) a resin having a predetermined functional group, an acid component, and (C) a solvent, but not containing (B) a strong acid having a pKa of 1 or less. It can be seen that even if the surface treatment of the film is performed, the contact angle of water in the PET film does not change significantly from the untreated state.
According to Comparative Example 6, even if the surface treatment of the PET film is performed with a surface treatment liquid containing (A) resin having no functional group I, (B) strong acid having pKa1 or less, and (C) solvent. It can be seen that the contact angle of water in the PET film does not change significantly from the untreated state.
〔実施例１７、実施例１８、及び比較例７〕
表４に記載される種類及びモル比率の構成単位からなる（Ａ）樹脂１００質量部と、表４に記載される質量部の酸成分と、表４に記載される質量部の溶媒とを均一に混合して、実施例１７、実施例１８、及び比較例７の表面処理液を得た。
得られた表面処理液を用いて、ＰＥＴフィルムをガラス基板に変更することの他は、実施例１と同様にしてガラス基板の表面処理を行い、表面処理後のガラス基板の水の接触角を測定した。ガラス基板の水の接触角の測定結果を表４に記す。
なお未処理のガラス基板の水の接触角は４１．９°である。
[Example 17, Example 18, and Comparative Example 7]
100 parts by mass of the resin (A) composed of the structural units of the types and molar ratios shown in Table 4, the acid component by mass shown in Table 4, and the solvent by mass by mass shown in Table 4 are uniformly used. The surface treatment liquids of Example 17, Example 18, and Comparative Example 7 were obtained.
Except for changing the PET film to a glass substrate using the obtained surface treatment liquid, the surface treatment of the glass substrate is performed in the same manner as in Example 1, and the contact angle of water on the glass substrate after the surface treatment is adjusted. It was measured. Table 4 shows the measurement results of the contact angle of water on the glass substrate.
The contact angle of water on the untreated glass substrate is 41.9 °.
実施例１７及び１８によれば、官能基Ｉとしてシアノ基を含む単位Ｂ−４、及び親水性の単位Ａ−１からなる（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸と、（Ｃ）溶媒とを含む表面処理液を用いる場合、無機材料であるガラスからなる基板の表面を良好に親水化できることが分かる。
他方、比較例７からは、官能基Ｉを含まない（Ａ）樹脂と、ｐＫａ１以下の（Ｂ）強酸と、（Ｃ）溶媒とを含む表面処理液を用いてガラス基板の表面処理を行っても、ガラス基板の水の接触角は未処理の状態から大きく変わらないことが分かる。
According to Examples 17 and 18, a resin (A) consisting of a unit B-4 containing a cyano group as a functional group I and a hydrophilic unit A-1, a (B) strong acid having a pKa of 1 or less, and (C) It can be seen that when a surface treatment liquid containing a solvent is used, the surface of a substrate made of glass, which is an inorganic material, can be satisfactorily hydrophilized.
On the other hand, from Comparative Example 7, the surface treatment of the glass substrate was performed using a surface treatment liquid containing (A) a resin containing no functional group I, (B) a strong acid having a pKa of 1 or less, and (C) a solvent. However, it can be seen that the contact angle of water on the glass substrate does not change significantly from the untreated state.
〔実施例１９〕
実施例１の表面処理液を用いて、ＰＥＴフィルムをガラス基板に変更することの他は、実施例１と同様にしてガラス基板の表面処理を行い、６枚の表面処理されたガラス基板を得た。
得られた表面処理されたガラス基板を、純水、エタノール、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、生理食塩水、１Ｎ ＮａＯＨ水溶液に、室温で６ヶ月浸漬させた後、それぞれの接触角を測定した。
また、表面処理されたガラス基板を０．１Ｍ Ｈ２ＳＯ４水溶液に１００℃で１００時間浸漬させた後に、接触角を測定した。
いずれの条件においても、浸漬前後で接触角に変化は無く、薬液耐性に優れることが確認された。
[Example 19]
Except for changing the PET film to a glass substrate by using the surface treatment liquid of Example 1, the surface treatment of the glass substrate was performed in the same manner as in Example 1 to obtain 6 surface-treated glass substrates. It was.
The obtained surface-treated glass substrate was immersed in pure water, ethanol, propylene glycol monomethyl ether acetate (PGMEA), physiological saline, and 1N NaOH aqueous solution for 6 months at room temperature, and the contact angles of each were measured. ..
Further, the contact angle was measured after immersing the surface-treated glass substrate in a 0.1 MH 2 SO 4 aqueous solution at 100 ° C. for 100 hours.
Under all conditions, there was no change in the contact angle before and after immersion, and it was confirmed that the chemical resistance was excellent.
Claims (12)
前記（Ａ）樹脂が、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉと、前記官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩとを有し、
前記官能基ＩＩの前記親水性基が、下記式（Ａ１）：
−ＮＨ−Ｒ １ ・・・（Ａ１）
（式（Ａ１）中、Ｒ １ は、アミノ基、スルホン酸基、及び水酸基からなる群より選択される１以上の基で置換された炭素原子数２〜４のアルキル基、又は水素原子である。）
で表される基であり、
前記官能基ＩＩの前記疎水性基が下記式（Ａ３）：
ＣＨ ２ ＝ＣＲ ２ −（ＣＯ−Ｏ） ｂ −Ｒ ６ ・・・（Ａ３）
（式（Ａ３）中、Ｒ ２ は水素原子又はメチル基であり、ｂは０又は１であり、Ｒ ６ は、フッ素化芳香族炭化水素基、又はフッ素化脂環式基である。）
で表される単量体に由来する基を含み、
ただし、前記官能基ＩＩが水酸基を含む場合、前記（Ａ）樹脂は前記官能基Ｉを有していなくてもよく、
前記（Ｂ）強酸のｐＫａが１以下である、表面処理液。 It contains (A) resin, (B) strong acid, and (C) solvent.
The resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group which is a hydrophilic group or a hydrophobic group other than the functional group I. Has II and
The hydrophilic group of the functional group II has the following formula (A1):
-NH-R 1 ... (A1)
(In the formula (A1), R 1 is an alkyl group having 2 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group. .)
It is a group represented by
The hydrophobic group of the functional group II has the following formula (A3):
CH 2 = CR 2- (CO-O) b- R 6 ... (A3)
(In the formula (A3), R 2 is a hydrogen atom or a methyl group, b is 0 or 1, and R 6 is a fluorinated aromatic hydrocarbon group or a fluorinated alicyclic group.)
Contains a group derived from the monomer represented by
However, if the functional group II comprises a hydroxyl group, the resin (A) may not have the functional group I,
A surface treatment liquid having a pKa of the strong acid (B) of 1 or less.
前記（Ａ）樹脂が、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の基である官能基Ｉと、前記官能基Ｉ以外の親水性基又は疎水性基である官能基ＩＩとを有し、
前記官能基ＩＩの前記親水性基が、下記式（Ａ１）：
−ＮＨ−Ｒ １ ・・・（Ａ１）
（式（Ａ１）中、Ｒ １ は、アミノ基、スルホン酸基、及び水酸基からなる群より選択される１以上の基で置換された炭素原子数１〜４のアルキル基、又は水素原子である。）
で表される基であり、
ただし、前記官能基ＩＩが水酸基を含む場合、前記（Ａ）樹脂は前記官能基Ｉを有していなくてもよく、
前記（Ｂ）強酸のｐＫａが１以下であり、２つのスルホニル基がフルオロアルキレン基で連結された環状スルホンイミド酸を含む、表面処理液。 It contains (A) resin, (B) strong acid, and (C) solvent.
The resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group which is a hydrophilic group or a hydrophobic group other than the functional group I. Has II and
The hydrophilic group of the functional group II has the following formula (A1):
-NH-R 1 ... (A1)
(In the formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group. .)
It is a group represented by
However, if the functional group II comprises a hydroxyl group, the resin (A) may not have the functional group I,
Wherein (B) pKa of the strong acid is Ri der 1 below, two sulfonyl groups including cyclic sulfonimide acid linked by fluoroalkylene group, a surface treatment liquid.
ＣＨ２＝ＣＲ２−（ＣＯ−Ｏ）ｂ−Ｒ６・・・（Ａ３）
（式（Ａ３）中、Ｒ２は水素原子又はメチル基であり、ｂは０又は１であり、Ｒ６は、フッ素化炭化水素基、又は下式（Ａ４）：
−ＳｉＲ７Ｒ８−（−Ｏ−ＳｉＲ７Ｒ８−）ｎ−Ｒ９・・・（Ａ４）
で表される基であり、Ｒ７、Ｒ８、及びＲ９は、それぞれ独立に炭素原子数１〜６の炭化水素基であり、ｎは０以上の整数である。）
で表される単量体に由来する、請求項２又は３に記載の表面処理液。 The functional group II is a hydrophobic group, and the following formula (A3):
CH 2 = CR 2- (CO-O) b- R 6 ... (A3)
(In the formula (A3), R 2 is a hydrogen atom or a methyl group, b is 0 or 1, and R 6 is a fluorinated hydrocarbon group, or the following formula (A4):
-SiR 7 R 8 - (- O -SiR 7 R 8 -) n -R 9 ··· (A4)
R 7 , R 8 and R 9 are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more. )
The surface treatment liquid according to claim 2 or 3 , which is derived from the monomer represented by.
ＣＨ２＝ＣＲ２−ＣＯ−ＮＨ−Ｒ１・・・（Ａ５）
（式（Ａ５）中、Ｒ１は、アミノ基、スルホン酸基、及び水酸基からなる群より選択される１以上の基で置換された炭素原子数１〜４のアルキル基、又は水素原子であり、Ｒ２は水素原子又はメチル基である。）
で表される単量体に由来する、請求項１又は２に記載の表面処理液。 The functional group II is a hydrophilic group, and the following formula (A5):
CH 2 = CR 2- CO-NH-R 1 ... (A5)
(In the formula (A5), R 1 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group. , R 2 is a hydrogen atom or a methyl group.)
The surface treatment liquid according to claim 1 or 2 , which is derived from the monomer represented by.
ＣＨ２＝ＣＲ２−（Ｒ３）ａ−ＣＯ−Ｒ４・・・（Ａ２）
（式（Ａ２）中、Ｒ２は水素原子又はメチル基であり、Ｒ３は２価の炭化水素基であり、ａは０又は１であり、Ｒ４は、−ＯＨ、−Ｏ−Ｒ５、又は−ＮＨ−Ｒ５であり、Ｒ５は、水酸基、シアノ基、及びカルボキシル基からなる群より選択される１以上の官能基で置換された炭化水素基である。）
で表される単量体に由来する、請求項１〜６のいずれか１項に記載の表面処理液。 The functional group I is the following formula (A2):
CH 2 = CR 2- (R 3 ) a- CO-R 4 ... (A2)
(In the formula (A2), R 2 is a hydrogen atom or a methyl group, R 3 is a divalent hydrocarbon group, a is 0 or 1, and R 4 is -OH, -O-R 5. , Or -NH-R 5 , where R 5 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of hydroxyl groups, cyano groups, and carboxyl groups.)
The surface treatment liquid according to any one of claims 1 to 6 , which is derived from the monomer represented by.
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