KR102615417B1 - Surface treatment liquid - Google Patents
Surface treatment liquid Download PDFInfo
- Publication number
- KR102615417B1 KR102615417B1 KR1020160121656A KR20160121656A KR102615417B1 KR 102615417 B1 KR102615417 B1 KR 102615417B1 KR 1020160121656 A KR1020160121656 A KR 1020160121656A KR 20160121656 A KR20160121656 A KR 20160121656A KR 102615417 B1 KR102615417 B1 KR 102615417B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- surface treatment
- resin
- treatment liquid
- functional
- Prior art date
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 86
- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 95
- 229920005989 resin Polymers 0.000 claims abstract description 95
- 239000002253 acid Substances 0.000 claims abstract description 65
- 125000000524 functional group Chemical group 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 19
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 125000003277 amino 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
- 125000000542 sulfonic acid group Chemical group 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
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- -1 polyoxyethylene groups Polymers 0.000 description 39
- 150000002430 hydrocarbons Chemical class 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229920002799 BoPET Polymers 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 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
- 238000000576 coating method Methods 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
- 238000002156 mixing Methods 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 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
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 238000006557 surface reaction Methods 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
- 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
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 238000001035 drying Methods 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
- 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
- 230000002209 hydrophobic effect Effects 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
- 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 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
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- GGTSAXBNFONRAB-UHFFFAOYSA-N (1-methyl-2-phenyl-4-propan-2-ylcyclohexyl)benzene Chemical compound C1C(C(C)C)CCC(C)(C=2C=CC=CC=2)C1C1=CC=CC=C1 GGTSAXBNFONRAB-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 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 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- AZLXQBNSOMJQEJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazolidin-2-one Chemical compound CC(C)N1CCN(C(C)C)C1=O AZLXQBNSOMJQEJ-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- 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
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- PJEXUIKBGBSHBS-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrolidin-2-one Chemical compound OCN1CCCC1=O PJEXUIKBGBSHBS-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- 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
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-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
- IEAJQNJSHYCMEK-UHFFFAOYSA-N 5-methoxy-2,5-dimethylhexanoic acid Chemical compound COC(C)(C)CCC(C)C(O)=O IEAJQNJSHYCMEK-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-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
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- 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
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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)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Laminated Bodies (AREA)
Abstract
본 발명은 피막 형성성의 수지를 포함하지 않아도, 피처리체의 표면의 양호한 친수화 또는 소수화를 실시할 수 있는 표면 처리액과, 상기 표면 처리액을 이용하는 표면 처리 방법을 제공하는 것이다.
(A) 수지와, (C) 용매를 포함하는 표면 처리액에서, (A) 수지로서 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I와, 상기 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 가지는 수지를 이용하고, 또한 표면 처리액에 pKa1 이하의 (B) 강산을 첨가한다.The present invention provides a surface treatment liquid that can satisfactorily hydrophilize or hydrophobize the surface of a treated object even without containing a film-forming resin, and a surface treatment method using the surface treatment liquid.
In a surface treatment solution containing (A) a resin and (C) a solvent, (A) the resin is a functional group I of one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a hydrophilic group other than the functional group I, or A resin having functional group II, which is a hydrophobic group, is used, and a strong acid (B) with a pKa 1 or lower is added to the surface treatment solution.
Description
본 발명은 표면 처리액, 및 상기 표면 처리액을 이용하는 표면 처리 방법에 관한 것이다.The present invention relates to a surface treatment liquid and a surface treatment method using the surface treatment liquid.
종래부터 여러 가지 물품의 표면 성질을 개질하기 위해서, 다양한 표면 처리액이 사용되고 있다. 표면 개질 중에서도, 물품의 표면의 친수화 또는 소수화에 대한 요구는 크고, 친수화용 또는 소수화용의 약제나 표면 처리액에 대해 다수 제안되고 있다.Conventionally, various surface treatment liquids have been used to modify the surface properties of various articles. Among surface modifications, there is a great demand for hydrophilization or hydrophobization of the surface of an article, and many hydrophilization or hydrophobization chemicals or surface treatment liquids have been proposed.
이러한 표면 처리용 약제에 관해서, 예를 들면 피막 표면에 친수성과 방오성을 부여할 수 있는 표면 조정제로서 적어도 아크릴아미드 모노머와, 특정한 골격의 실록시기 함유 모노(메타)아크릴레이트 모노머가 공중합된 중량 평균 분자량 1500~50000의 공중합물이 제안되어 있다(특허문헌 1).Regarding these surface treatment agents, for example, a weight average molecular weight copolymerization of at least an acrylamide monomer and a mono(meth)acrylate monomer containing a siloxy group of a specific skeleton is used as a surface conditioner capable of imparting hydrophilicity and antifouling properties to the film surface. A copolymer of 1500 to 50000 has been proposed (Patent Document 1).
그렇지만, 특허문헌 1에 기재된 표면 조정제를 이용해 친수화 처리를 실시하는 경우, 표면 조정제만을 포함하는 용액을 이용해 피처리체의 표면을 처리해도, 표면 조정제가 피처리체의 표면에 부착하기 어렵고 소망하는 친수화 효과를 얻기 어렵다.However, when hydrophilizing 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, it is difficult for the surface conditioner to adhere to the surface of the object to be treated and the desired hydrophilization is achieved. It is difficult to achieve effect.
이 때문에, 특허문헌 1에서는 표면 조정제의 용액에 아크릴 수지, 폴리에스테르 수지, 우레탄 수지, 알키드 수지, 에폭시 수지, 폴리아민 수지 등의 수지를 피막 형성 성분으로서 배합한 액을 표면 처리액으로서 이용하고 있다.For this reason, in Patent Document 1, a solution obtained by mixing a solution of a surface conditioner with a resin such as an acrylic resin, polyester resin, urethane resin, alkyd resin, epoxy resin, or polyamine resin as a film-forming component is used as a surface treatment solution.
그리고, 특허문헌 1에 기재의 표면 조정제와, 피막 형성 성분을 포함하는 표면 처리액을 이용하는 경우, 피처리체의 표면이 수지를 포함하는 피막에 의해 피복되어 버리기 때문에, 양호한 친수화는 할 수 있어도, 피처리체가 가지는 유용한 표면 특성까지 손상되어 버린다.In the case of using a surface treatment liquid containing the surface conditioner and a film-forming component described in Patent Document 1, the surface of the object to be treated is covered with a film containing a resin, so even if good hydrophilization can be achieved, Even the useful surface properties of the object to be processed are damaged.
본 발명은 상기의 과제를 감안하여 이루어진 것으로, 피막 형성성(形成性)의 수지를 포함하지 않아도, 피처리체의 표면의 양호한 친수화 또는 소수화를 실시할 수 있는 표면 처리액과, 상기 표면 처리액을 이용하는 표면 처리 방법을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above problems, and includes a surface treatment liquid capable of making the surface of a treated object well hydrophilic or hydrophobic even without containing a film-forming resin, and the surface treatment liquid. The purpose is to provide a surface treatment method using .
본 발명자들은 (A) 수지와, (C) 용매를 포함하는 표면 처리액에서, (A) 수지로서 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I와, 상기 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 가지는 수지를 이용하고, 또한 표면 처리액에 pKa1 이하의 (B) 강산을 첨가함으로써, 상기의 과제를 해결할 수 있는 것을 알아내어 본 발명을 완성하기에 이르렀다.The present inventors, in a surface treatment solution containing (A) a resin and (C) a solvent, (A) a functional group I of at least one group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group as the resin, and a functional group other than the functional group I It was found that the above problems could be solved by using a resin having functional group II, which is a hydrophilic or hydrophobic group, and adding a strong acid (B) of pKa 1 or less to the surface treatment solution, thereby completing the present invention.
본 발명의 제1 양태는 (A) 수지와, (B) 강산과, (C) 용매를 포함하고,A first aspect of the present invention includes (A) a resin, (B) a strong acid, and (C) a solvent,
(A) 수지가 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I와, 상기 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 가지고, (A) the resin 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 II which is a hydrophilic or hydrophobic group other than the functional group I,
다만 관능기 Ⅱ가 수산기, 시아노기, 및 카르복실기로부터 선택되는 1 이상의 기를 포함하는 경우, (A) 수지는 관능기 I를 가지지 않아도 되고, However, when functional group II contains one or more groups selected from hydroxyl group, cyano group, and carboxyl group, (A) the resin does not need to have functional group I,
(B) 강산의 pKa가 1 이하인 표면 처리액이다.(B) It is a surface treatment solution with a strong acid pKa of 1 or less.
본 발명의 제2 양태는 제1 양태에 이러한 표면 처리액의, 피처리체의 표면에 대한 도포를 포함하는 표면 처리 방법이다.The second aspect of the present invention is a surface treatment method in the first aspect that includes application of such a surface treatment liquid to the surface of an object to be treated.
본 발명에 의하면, 피막 형성성의 수지를 포함하지 않아도, 피처리체의 표면의 양호한 친수화 또는 소수화를 실시할 수 있는 표면 처리액과, 상기 표면 처리액을 이용하는 표면 처리 방법을 제공할 수 있다.According to the present invention, it is possible to provide a surface treatment liquid that can satisfactorily hydrophilize or hydrophobize the surface of an object to be treated even without containing a film-forming resin, and a surface treatment method using the surface treatment liquid.
≪표면 처리액≫≪Surface treatment liquid≫
표면 처리액(이하, 간단하게 처리액으로도 기재함)은 (A) 수지와, (B) 강산과, (C) 용매를 포함한다.The surface treatment liquid (hereinafter simply referred to as a treatment liquid) contains (A) a resin, (B) a strong acid, and (C) a solvent.
(A) 수지는 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I와, 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 갖는다. 또한 관능기 Ⅱ가 수산기, 시아노기, 및 카르복실기로부터 선택되는 1 이상의 기를 포함하는 경우에는 (A) 수지는 관능기 I를 가지지 않아도 된다.(A) The resin has functional group I, which is one or more groups selected from the group consisting of hydroxyl group, cyano group, and carboxyl group, and functional group II, which is a hydrophilic group or hydrophobic group other than functional group I. In addition, when functional group II contains one or more groups selected from hydroxyl group, cyano group, and carboxyl group, (A) resin does not need to have functional group I.
(B) 강산의 pKa는 1 이하이다.(B) The pKa of strong acids is 1 or less.
처리액이 관능기 I를 가지는 (A) 수지와, pKa1 이하의 (B) 강산을 포함함으로써, 표면 처리시에 (A) 수지가 피처리체의 표면에 양호하게 결합 내지 부착한다. 이 때문에, 피처리체의 표면에는 (A) 수지가 가지는 친수성 또는 소수성의 관능기 Ⅱ가 고효율로 도입된다. 그 결과, (A) 수지와, (B) 강산을 포함하는 처리액을 이용해 표면 처리를 실시하면, 피처리체의 표면이 고도로 친수화 또는 소수화된다.Since the treatment liquid contains resin (A) having a functional group I and a strong acid (B) with a pKa of 1 or less, the resin (A) binds or adheres well to the surface of the object to be treated during surface treatment. For this reason, the hydrophilic or hydrophobic functional group II of the resin (A) is introduced with high efficiency into the surface of the object to be treated. As a result, when surface treatment is performed using a treatment liquid containing (A) a resin and (B) a strong acid, the surface of the object to be treated becomes highly hydrophilic or hydrophobized.
이하, 처리액에 포함되는 필수 또는 임의의 성분에 대해 설명한다.Hereinafter, essential or optional components contained in the treatment liquid will be described.
＜(A) 수지＞＜(A) Resin＞
(A) 수지는 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I를 갖는다. (B) 강산이 관능기 I와 피처리체 표면의 반응 또는 상호작용을 높임으로써, (A) 수지가 기판 표면에 결합 내지 부착한다.(A) The resin has functional group I, which is one or more groups selected from the group consisting of hydroxyl group, cyano group, and carboxyl group. (B) The strong acid increases the reaction or interaction between the functional group I and the surface of the object to be processed, so that the resin (A) binds or adheres to the surface of the substrate.
(A) 수지는 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 갖는다. 친수성기를 가지는 (A) 수지를 포함하는 처리액을 이용하면 친수화 처리할 수 있고, 소수성기를 가지는 (A) 수지를 포함하는 처리액을 이용하면 소수화 처리할 수 있다.(A) The resin has functional group II, which is a hydrophilic or hydrophobic group other than functional group I. Hydrophilization treatment can be performed by using a treatment liquid containing (A) resin having a hydrophilic group, and hydrophobization treatment can be performed by using a treatment liquid containing (A) resin having a hydrophobic group.
친수성기 또는 소수성기는 종래부터 당업자에게 친수성기 또는 소수성기라고 인식되고 있는 관능기이면 특별히 한정되지 않고, 그 중에서 적절히 선택할 수 있다.The hydrophilic group or hydrophobic group is not particularly limited as long as it is a functional group conventionally recognized as a hydrophilic group or hydrophobic group by those skilled in the art, and can be appropriately selected from among them.
(A) 수지의 종류는 (A) 수지가 소정의 관능기를 가지고, 또한 (C) 용매에 가용인 한 특별히 한정되지 않는다. (A) 수지의 예로서는 (메타)아크릴 수지, 노볼락 수지, 폴리에스테르 수지, 폴리아미드 수지, 폴리이미드 수지, 폴리아미드이미드 수지, 및 실리콘 수지 등을 들 수 있다. 이들 수지 중에서는 관능기의 도입이나, 관능기를 가지는 단위의 함유 비율의 조정이 용이한 점에서 (메타)아크릴 수지가 바람직하다.The type of (A) resin is not particularly limited as long as (A) the resin has a predetermined functional group and (C) is soluble in the solvent. (A) Examples of the resin include (meth)acrylic resin, novolak resin, polyester resin, polyamide resin, polyimide resin, polyamidoimide resin, and silicone resin. Among these resins, (meth)acrylic resin is preferable because it is easy to introduce functional groups and adjust the content ratio of units having functional groups.
친수성기의 구체예로서는 폴리옥시알킬렌기(예를 들면, 폴리옥시에틸렌기, 폴리옥시프로필렌기, 옥시에틸렌기와 옥시프로필렌기가 블록 또는 랜덤 결합한 폴리옥시알킬렌기 등), 아미노기, 카르복실기, 수산기, 설폰산기 등을 들 수 있다. 또, 이들 기를 포함하는 유기기도 친수성기로서 바람직하다.Specific examples of hydrophilic groups include polyoxyalkylene groups (e.g., polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are block or randomly bonded, etc.), amino groups, carboxyl groups, hydroxyl groups, sulfonic acid groups, etc. I can hear it. Moreover, organic groups containing these groups are also preferable as hydrophilic groups.
(A) 수지가 관능기 Ⅱ로서 수산기, 시아노기, 및 카르복실기를 포함하는 친수성기 또는 소수성기를 가지는 경우, 상기 친수성기 또는 소수성기에 포함되는 수산기, 시아노기, 또는 카르복실기는 관능기 I로서의 역할도 나타낸다.(A) When the resin has a hydrophilic group or hydrophobic group including a hydroxyl group, a cyano group, and a carboxyl group as functional group II, the hydroxyl group, cyano group, or carboxyl group included in the hydrophilic group or hydrophobic group also plays a role as functional group I.
이 때문에, (A) 수지가 관능기 Ⅱ로서 수산기, 시아노기, 및 카르복실기를 포함하는 친수성기 또는 소수성기를 가지는 경우, (A) 수지는 관능기 I를 가지지 않아도 된다.For this reason, when the (A) resin has a hydrophilic group or hydrophobic group including a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, the (A) resin does not need to have the functional group I.
또한 수산기, 및 카르복실기를 포함하는 친수성기에는 수산기 그 자체, 및 카르복실기 그 자체가 포함된다.Additionally, hydrophilic groups containing hydroxyl groups and carboxyl groups include the hydroxyl groups themselves and the carboxyl groups themselves.
처리액의 친수화 효과가 뛰어난 점에서, 친수성기로서는 하기 식(A1):Since the treatment liquid has an excellent hydrophilic effect, the hydrophilic group is of the following formula (A1):
-NH-R1···(A1) -NH-R 1 ···(A1)
(식(A1) 중, R1은 아미노기, 설폰산기, 및 수산기로 이루어지는 군으로부터 선택되는 1 이상의 기로 치환된 탄소 원자수 1~4의 알킬기, 또는 수소 원자이다.)(In formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom.)
로 나타내는 기가 바람직하다.The group represented by is preferable.
식(A1)로 나타내는 친수성기의 구체예로서는 아미노기와, 하기 식으로 나타내는 기를 들 수 있다.Specific examples of the hydrophilic group represented by formula (A1) include an amino group and a group represented by the following formula.
[화 1][Tuesday 1]
[화 2][Tuesday 2]
[화 3][Tuesday 3]
상기 식(A1)로 나타내는 친수성기의 구체예 중, 보다 바람직한 기로서는 이하의 기를 들 수 있다.Among specific examples of the hydrophilic group represented by the above formula (A1), the following groups can be mentioned as more preferable groups.
[화 4][Tuesday 4]
상기 식(A1)로 나타내는 친수성기의 구체예 중, 특히 바람직한 기로서는 이하의 기를 들 수 있다.Among specific examples of the hydrophilic group represented by the above formula (A1), the following groups can be mentioned as particularly preferable groups.
[화 5][Tuesday 5]
소수성기의 구체예로서는, 예를 들면 불소화 탄화수소기, 실릴기, 실록산기, 탄소 원자수 6~20의 알킬기, 및 탄소 원자수 10~20의 방향족 탄화수소기 등을 들 수 있다.Specific examples of hydrophobic groups include fluorinated hydrocarbon groups, silyl groups, siloxane groups, alkyl groups with 6 to 20 carbon atoms, and aromatic hydrocarbon groups with 10 to 20 carbon atoms.
불소화 탄화수소기로서는 식(A3)에 대해 후술하는 기가 바람직하다.As the fluorinated hydrocarbon group, the group described later for formula (A3) is preferable.
실릴기의 적합한 예로서는 후술하는 식(A4)으로 나타내고, n이 0인 기를 들 수 있다. 실릴기의 구체예로서는, 예를 들면 트리메틸실릴기, 트리에틸실릴기, 트리프로필실릴기, 트리이소프로필실릴기, tert-부틸디메틸실릴기, 및 트리페닐실릴기 등을 들 수 있다.Suitable examples of the silyl group include a group represented by the formula (A4) described later and where n is 0. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group.
실록산기의 적합한 예로서는 후술하는 식(A4)으로 나타내고, n이 1 이상인 기를 들 수 있다.Suitable examples of the siloxane group include groups represented by the formula (A4) described later and where n is 1 or more.
(A) 수지로서는 여러 가지 관능기를 도입하기 쉽고, 관능기량의 조정이 용이한 점에서, 불포화 결합을 가지는 단량체의 중합체인 것이 바람직하다. 이러한 중합체는 호모폴리머여도, 코폴리머여도 된다.(A) The resin is preferably a polymer of a monomer having an unsaturated bond because it is easy to introduce various functional groups and the amount of functional groups can be easily adjusted. These polymers may be homopolymers or copolymers.
이 경우, (A) 수지가 가지는 관능기 I은 하기 식(A2):In this case, the functional group I of the resin (A) has the following formula (A2):
CH2=CR2-(R3)a-CO-R4···(A2) CH 2 =CR 2 -(R 3 ) a -CO-R 4 ···(A2)
(식(A2) 중, R2는 수소 원자 또는 메틸기이며, R3은 2가의 탄화수소기이며, a는 0 또는 1이며, R4는 -OH, -O-R5, 또는 -NH-R5이며, R5는 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 관능기로 치환된 탄화수소기이다.)(In formula (A2), R 2 is a hydrogen atom or a methyl group, R 3 is a divalent hydrocarbon group, a is 0 or 1, R 4 is -OH, -OR 5 , or -NH-R 5 , R 5 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of hydroxyl group, cyano group, and carboxyl group.)
로 나타내는 단량체로부터 유래하는 기인 것이 바람직하다.It is preferable that it is a group derived from the monomer represented by .
상기 식(A2) 중, R3은 2가의 탄화수소기이다. 2가의 탄화수소기의 탄소 원자수는 본 발명의 목적을 저해하지 않는 범위에서 특별히 한정되지 않는다. (A) 수지의 입수나 조제가 용이한 점에서, R3로서의 2가의 탄화수소기의 탄소 원자수는 1~20이 바람직하고, 1~12가 보다 바람직하며, 1~10이 특히 바람직하고, 1~6이 가장 바람직하다.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 it does not impair the purpose of the present invention. (A) Since the resin is easy to obtain and prepare, the number of carbon atoms of the divalent hydrocarbon group as R 3 is preferably 1 to 20, more preferably 1 to 12, especially preferably 1 to 10, and 1 to 12 carbon atoms. ~6 is most preferred.
R3로서의 2가의 탄화수소기는 지방족기여도, 방향족기여도, 지방족 부분과 방향족 부분을 포함하는 탄화수소기여도 된다. 2가의 탄화수소기가 지방족기인 경우, 상기 지방족기는 포화 지방족기여도 불포화 지방족기여도 된다. 또, 상기 지방족기의 구조는 직쇄상이어도, 분기쇄상이어도, 환상이어도, 이들 구조의 조합이어도 된다.The divalent hydrocarbon group as R 3 may be an aliphatic group, an aromatic group, or a hydrocarbon group including an aliphatic moiety and an aromatic moiety. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. Additionally, the structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.
R3의 적합한 구체예로서는 메틸렌기, 에탄-1,2-디일기, 에탄-1,1-디일기, 프로판-1,3-디일기, 프로판-1,1-디일기, 프로판-2,2-디일기, n-부탄-1,4-디일기, n-펜탄-1,5-디일기, n-헥산-1,6-디일기, n-헵탄-1,7-디일기, n-옥탄-1,8-디일기, n-노난-1,9-디일기, n-데칸-1,10-디일기, o-페닐렌기, m-페닐렌기, p-페닐렌기, 나프탈렌-2,6-디일기, 나프탈렌-2,7-디일기, 나프탈렌-1,4-디일기, 비페닐-4,4'-디일기 등을 들 수 있다.Suitable 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-heptane-1,7-diyl group, n- Octane-1,8-diyl group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-2, Examples include 6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, and biphenyl-4,4'-diyl group.
R4는 -OH, -O-R5, 또는 -NH-R5이며, R5는 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 관능기로 치환된 탄화수소기이다. R 4 is -OH, -OR 5 , or -NH-R 5 , and R 5 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.
R5의 기의 주골격을 구성하는 탄화수소기는 직쇄상, 분기쇄상, 또는 환상의 지방족기여도 되고, 방향족 탄화수소기여도 된다. The hydrocarbon group constituting the main skeleton of the group of R 5 may be a linear, branched, or cyclic aliphatic group, or may be an aromatic hydrocarbon group.
직쇄상, 분기쇄상, 또는 환상의 지방족기의 탄소 원자수는 1~20이 바람직하고, 1~12가 보다 바람직하다.The number of carbon atoms in the linear, branched, or cyclic aliphatic group is preferably 1 to 20, and more preferably 1 to 12.
직쇄상, 또는 분기쇄상의 지방족기의 적합한 예로서는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기, n-펜틸기, 이소펜틸기, 네오펜틸기, sec-펜틸기, tert-펜틸기, n-헥실기, n-헵틸기, n-옥틸기, n-노닐기, n-데실기 등을 들 수 있다.Suitable examples of linear or branched aliphatic groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and iso. Pentyl group, neopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.
환상의 지방족기의 적합한 예로서는 시클로프로필기, 시클로부틸기, 시클로 펜틸기, 시클로헥실기, 시클로헵틸기, 및 시클로옥틸기 등의 시클로알킬기나, 아다만탄, 노르보르난, 이소보르난, 트리시클로데칸, 및 테트라시클로도데칸 등의 폴리시클로알칸으로부터 1개의 수소 원자를 제외한 기나, 이들 폴리시클로알칸의 C1-C4알킬 치환체로부터 1개의 수소 원자를 제외한 기를 들 수 있다.Suitable examples of cyclic aliphatic groups include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, adamantane, norbornane, isobornane, and tri. Examples include groups in which one hydrogen atom has been removed from polycycloalkanes such as cyclodecane and tetracyclododecane, and groups in which one hydrogen atom has been removed from the C1-C4 alkyl substituent of these polycycloalkanes.
방향족 탄화수소기의 적합한 예로서는 페닐기, 나프틸기, 안트라닐기, 페난트레닐기, 및 비페닐릴기 등을 들 수 있다. 방향족 탄화수소기는 메틸기, 에틸기 등의 C1-C4 알킬기로 치환되어 있어도 된다.Suitable examples of aromatic hydrocarbon groups include phenyl group, naphthyl group, anthranyl group, phenanthrenyl group, and biphenylyl group. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as a methyl group or ethyl group.
식(A2)로 나타내는 단량체로부터 유래하는 단위의 특히 바람직한 구체예로서는 하기 a2-1~a2-9의 단위를 들 수 있다. 하기 a2-1~a2-9의 단위 중에서는 a2-1~a2-4의 단위가 보다 바람직하다.Particularly preferable examples of units derived from the monomer represented by formula (A2) include the units a2-1 to a2-9 below. Among the units a2-1 to a2-9 below, the units a2-1 to a2-4 are more preferable.
[화 6][Tuesday 6]
(A) 수지가 관능기 Ⅱ로서 소수성기를 가지는 경우, 관능기 Ⅱ는 하기 식(A3):(A) When the resin has a hydrophobic group as functional group II, functional group II has the following formula (A3):
CH2=CR2-(CO-O)b-R6···(A3) CH 2 =CR 2 -(CO-O) b -R 6 ···(A3)
(식(A3) 중, R2는 수소 원자 또는 메틸기이며, b는 0 또는 1이며, R6은 불소화 탄화수소기, 또는 하기 식(A4):(In 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):
-SiR7R8-(-O-SiR7R8-)n-R9···(A4)-SiR 7 R 8 -(-O-SiR 7 R 8 -) n -R 9 ···(A4)
로 나타내는 기이며, R7, R8, 및 R9는 각각 독립적으로 탄소 원자수 1~6의 탄화수소기이며, n은 0 이상의 정수이다.)It is a group represented by , 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.)
로 나타내는 단량체로부터 유래하는 것이 바람직하다.It is preferable that it is derived from the monomer represented by .
식(A3) 중, R6이 불소화 탄화수소기인 경우, 상기 불소화 탄화수소기의 주골격을 구성하는 탄화수소기는 전술한 R5의 기의 주골격을 구성하는 탄화수소기와 동일하다. 상기 불소화 탄화수소기는 탄화수소기가 가지는 수소 원자의 모두가 불소 원자로 치환된 기여도 된다.In formula (A3), when R 6 is a fluorinated hydrocarbon group, the hydrocarbon group constituting the main skeleton of the fluorinated hydrocarbon group is the same as the hydrocarbon group constituting the main skeleton of the group of R 5 described above. The above-mentioned fluorinated hydrocarbon group is one in which all hydrogen atoms of the hydrocarbon group are replaced with fluorine atoms.
R6로서의 불소화 탄화수소기의 구체예로서는 -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, 및 -CH(CF3)2 등의 쇄상 불소화 알킬기; 펜타플루오로페닐기, o-트리플루오로메틸페닐기, m-트리플루오로메틸페닐기, p-트리플루오로메틸페닐기 등의 불소화 방향족 탄화수소기; 옥타플루오로아다만틸기 등의 불소화 지환식기를 들 수 있다.Specific examples of the fluorinated hydrocarbon group as R 6 are -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 chain fluorinated alkyl groups such as 3 , -CH 2 CH 2 (CF 2 ) 6 CF 3 , -CH 2 CH 2 (CF 2 ) 7 CF 3 , and -CH(CF 3 ) 2 ; Fluorinated aromatic hydrocarbon groups such as pentafluorophenyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, and p-trifluoromethylphenyl group; and fluorinated alicyclic groups such as octafluoroadamantyl group.
식(A3) 중, R6이 식(A4)로 나타내는 기인 경우, R7, R8, 및 R9는 각각 독립적으로 메틸기, 에틸기, 또는 페닐기인 것이 바람직하고, R7, R8, 및 R9가 모두 메틸기인 것이 보다 바람직하다. In formula (A3), when R 6 is a group represented by formula (A4), R 7 , R 8 , and R 9 are each independently preferably a methyl group, ethyl group, or phenyl group, and R 7 , R 8 , and R It is more preferable that all 9 's are methyl groups.
식(A4) 중, n의 상한은 본 발명의 목적을 저해하지 않는 범위에서 특별히 한정되지 않는다. n은 0 이상 35 이하의 정수인 것이 바람직하고, 0 이상 10 이하의 정수인 것이 보다 바람직하다.In formula (A4), the upper limit of n is not particularly limited as long as it does not impair the purpose of the present invention. It is preferable that n is an integer of 0 or more and 35 or less, and it is more preferable that it is an integer of 0 or more and 10 or less.
식(A3)로 나타내는 단량체로부터 유래하는 소수성기를 가지는 단위의 특히 바람직한 구체예로서는 하기 a3-1~a3-22의 단위를 들 수 있다. 하기의 단위 중에서는 a3-8, a3-18, a3-19, 및 a3-22의 단위가 보다 바람직하다.Particularly preferable examples of units having a hydrophobic group derived from the monomer represented by formula (A3) include the units a3-1 to a3-22 below. Among the units shown below, the units a3-8, a3-18, a3-19, and a3-22 are more preferable.
[화 7][Tuesday 7]
또, (A) 수지가 관능기 Ⅱ로서 친수성기를 가지는 경우, 관능기 Ⅱ는 하기 식(A5):Additionally, when (A) the resin has a hydrophilic group as functional group II, functional group II has the following formula (A5):
CH2=CR2-CO-NH-R1···(A5) CH 2 =CR 2 -CO-NH-R 1 ···(A5)
(식(A5) 중, R1은 아미노기, 설폰산기, 및 수산기로 이루어지는 군으로부터 선택되는 1 이상의 기로 치환된 탄소 원자수 1~4의 알킬기, 또는 수소 원자이며, R2는 수소 원자 또는 메틸기이다.)(In formula (A5), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom, and R 2 is a hydrogen atom or a methyl group. .)
로 나타내는 단량체로부터 유래하는 것이 바람직하다.It is preferable that it is derived from the monomer represented by .
식(A5) 중, R1에 대해서는 전술한 것과 같다.In equation (A5), R 1 is the same as described above.
식(A5)로 나타내는 단량체로부터 유래하는 친수성기를 가지는 단위의 특히 바람직한 구체예로서는 하기 a5-1~a5-5의 단위를 들 수 있다. 하기의 단위 중에서는 a5-1~a5-4의 단위가 보다 바람직하다.Particularly preferable examples of units having a hydrophilic group derived from the monomer represented by formula (A5) include the units a5-1 to a5-5 below. Among the units shown below, the units a5-1 to a5-4 are more preferable.
[화 8][Tuesday 8]
(A) 수지가 불포화 결합을 가지는 단량체의 중합체인 경우, 이러한 중합체는 본 발명의 목적을 저해하지 않는 범위에서, 전술한 식(A2)로 나타내는 단량체로부터 유래하는 단위, 식(A3)로 나타내는 단량체로부터 유래하는 단위, 및 식(A5)로 나타내는 단량체로부터 유래하는 단위 이외의 그 밖의 구성 단위를 포함하고 있어도 된다.(A) When the resin is a polymer of a monomer having an unsaturated bond, such polymer may be a unit derived from the monomer represented by the above-mentioned formula (A2), a monomer represented by the formula (A3), to the extent that it does not impair the purpose of the present invention. It may contain other structural units other than the unit derived from and the unit derived from the monomer represented by formula (A5).
그 밖의 구성 단위로서는, 예를 들면 (메타)아크릴산메틸, (메타)아크릴산에틸, (메타)아크릴산이소프로필, (메타)아크릴산-n-프로필, (메타)아크릴산-n-부틸, (메타)아크릴산이소부틸, (메타)아크릴산-tert-부틸, (메타)아크릴산-n-펜틸, (메타)아크릴산이소펜틸, (메타)아크릴산페닐, N-메틸(메타)아크릴아미드, N-에틸(메타)아크릴아미드, N-n-프로필(메타)아크릴아미드, N-이소프로필(메타)아크릴아미드, N-n-부틸(메타)아크릴아미드, N-n-펜틸(메타)아크릴아미드, N-이소펜틸(메타)아크릴아미드, N-페닐(메타)아크릴아미드, N,N-디메틸(메타)아크릴아미드, N,N-디에틸(메타)아크릴아미드, N,N-디-n-프로필(메타)아크릴아미드, N,N-디-n-부틸(메타)아크릴아미드, N,N-디-n-펜틸(메타)아크릴아미드, 스티렌, α-메틸스티렌, β-메틸스티렌, o-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 및 클로로스티렌 등의 단량체로부터 유래하는 구성 단위를 들 수 있다.Other structural units include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Isobutyl, (meth)acrylic acid-tert-butyl, (meth)acrylic acid-n-pentyl, isopentyl (meth)acrylate, phenyl (meth)acrylate, N-methyl(meth)acrylamide, N-ethyl(meth)acrylic Amide, N-n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-n-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- Structural units derived from monomers such as methylstyrene and chlorostyrene can be mentioned.
(A) 수지가 불포화 결합을 가지는 단량체의 중합체인 경우, 이러한 중합체에 포함되는 전체 구성 단위 중의 식(A2)로 나타내는 단량체로부터 유래하는 구성 단위의 몰 비율은 0.1~50몰%가 바람직하고, 1~20몰%가 보다 바람직하며, 1~15몰%가 특히 바람직하다.(A) When the resin 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) to the total structural units contained in this polymer is preferably 0.1 to 50 mol%, 1 ~20 mol% is more preferred, and 1-15 mol% is particularly preferred.
(A) 수지가 불포화 결합을 가지는 단량체의 중합체인 경우, 이러한 중합체에 포함되는 전체 구성 단위 중의 식(A3) 또는 (A5)으로 나타내는 단량체로부터 유래하는 구성 단위의 몰 비율은 50~99.9몰%가 바람직하고, 60~99몰%가 보다 바람직하며, 70~99몰%가 특히 바람직하다.(A) When the resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by formula (A3) or (A5) to the total structural units contained in this polymer is 50 to 99.9 mol%. It is preferable, 60 to 99 mol% is more preferable, and 70 to 99 mol% is particularly preferable.
다만, 식(A5)로 나타내는 단량체로부터 유래하는 구성 단위가 수산기, 시아노기, 카르복실기의 어느 하나의 기를 포함하는 경우, 중합체에 포함되는 전체 구성 단위 중의 식(A5)로 나타내는 단량체로부터 유래하는 구성 단위의 비율은 100%여도 된다.However, when the structural unit derived from the monomer represented by formula (A5) contains any of a hydroxyl group, a cyano group, or a carboxyl group, the structural unit derived from the monomer represented by formula (A5) among all structural units contained in the polymer. The ratio may be 100%.
처리액에 포함되는 (A) 수지의 양은 본 발명의 목적을 저해하지 않는 범위에서 특별히 한정되지 않고, 처리액의 도포성 등을 감안해 적절히 정해진다. 전형적으로는 처리액 중의 (A) 수지의 양은 처리액 중의 (A) 수지의 양과, 후술하는 (C) 용매의 양의 관계는 이하의 관계인 양이 바람직하다.The amount of resin (A) contained in the treatment liquid is not particularly limited as long as it does not impair the purpose of the present invention, and is appropriately determined in consideration of the applicability of the treatment liquid, etc. Typically, the amount of resin (A) in the treatment liquid is preferably such that the relationship between the amount of resin (A) in the treatment liquid and the amount of solvent (C), which will be described later, is as follows.
처리액 중의 수지의 질량을 100질량부로 하는 경우에, 후술하는 (C) 용매의 양이 100~10000질량부인 것이 바람직하고, 500~8000질량부인 것이 보다 바람직하며, 1000~6000질량부인 것이 특히 바람직하다.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 10,000 parts by mass, more preferably 500 to 8,000 parts by mass, and especially preferably 1,000 to 6,000 parts by mass. do.
＜(B) 강산＞＜(B) Strong acid＞
처리액은 (B) 강산을 포함한다. (B) 강산의 pKa는 1 이하이다. 또한 pKa는 수중에서의 값이다.The treatment liquid contains (B) a strong acid. (B) The pKa of strong acids is 1 or less. Also, pKa is the value in water.
(B) 강산은 (A) 수지가 가지는 관능기 I에 작용함으로써, (A) 수지의 피처리체의 표면에 대한 부착 또는 결합을 촉진시킨다.(B) The strong acid acts on the functional group I of the resin (A), thereby promoting attachment or bonding of the resin (A) to the surface of the object to be treated.
(B) 강산의 종류는 pKa가 1 이하인 한 특별히 한정되지 않는다. (B) 강산으로서는 pKa가 1 이하인 산을 2종 이상 조합하여 이용할 수 있다.(B) The type of strong acid is not particularly limited as long as the pKa is 1 or less. (B) As a strong acid, two or more acids with a pKa of 1 or less can be used in combination.
(B) 강산의 적합한 예로서는 불소화 지방족 카르복시산(예를 들면 트리플루오로아세트산 등), 플루오로설폰산, 탄소 원자수 1~30의 알칸설폰산(예를 들면 메탄설폰산, 도데칸설폰산 등), 아릴설폰산(예를 들면 벤젠설폰산, p-톨루엔설폰산 등), 탄소 원자수 1~30의 플루오로알칸설폰산(예를 들면 트리플루오로메탄설폰산, 펜타플루오로에탄설폰산, 헵타플루오로프로판설폰산, 노나플루오로부탄설폰산, 운데카플루오로펜탄설폰산 및 트리데카플루오로헥산설폰산), 비스설포닐이미드 화합물, 2개의 설포닐기가 플루오로알킬렌기로 연결된 환상 설포닐이미드 화합물, 및 N-아실플루오로알칸설폰산아미드 등을 들 수 있다.(B) Suitable examples of strong acids include fluorinated aliphatic carboxylic acids (e.g., trifluoroacetic acid, etc.), fluorosulfonic acids, alkanesulfonic acids with 1 to 30 carbon atoms (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), Arylsulfonic acid (e.g. benzenesulfonic acid, p-toluenesulfonic acid, etc.), fluoroalkanesulfonic acid with 1 to 30 carbon atoms (e.g. trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoroethylene sulfonic acid) Fluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), bissulfonylimide compound, cyclic sulfonate in which two sulfonyl groups are connected to a fluoroalkylene group Ponylimide compounds, N-acylfluoroalkane sulfonic acid amides, etc. can be mentioned.
이들 (B) 강산이 플루오로알킬기, 또는 플루오로알킬렌기를 포함하는 경우, 이들 기는 부분적으로 불소화된 플루오로알킬기, 또는 플루오로알킬렌기여도 되고, 완전히 불소화된 퍼플루오로알킬기, 또는 퍼플루오로알킬렌기여도 된다.When these (B) strong acids contain a fluoroalkyl group or a fluoroalkyl group, these groups may be a partially fluorinated fluoroalkyl group, or a fluoroalkyl group, or a fully fluorinated perfluoroalkyl group, or a perfluoroalkyl group. It may be an alkylene group.
이들 (B) 강산 중에서는 플루오로설폰산, 탄소 원자수 1~30의 알칸설폰산, 탄소 원자수 1~30의 플루오로알칸설폰산, 비스(플루오로알킬설포닐)이미드산, 2개의 설포닐기가 플루오로알킬렌기로 연결된 환상 설폰이미드산, 및 N-아실플루오로알칸설폰산아미드가 바람직하고, 탄소 원자수 1~30의 플루오로알칸설폰산, 비스설포닐이미드 화합물, 2개의 설포닐기가 플루오로알킬렌기로 연결된 환상 설포닐이미드 화합물, 및 N-아실플루오로알칸설폰산아미드가 바람직하다.Among these (B) strong acids, fluorosulfonic acid, alkanesulfonic acid with 1 to 30 carbon atoms, fluoroalkanesulfonic acid with 1 to 30 carbon atoms, bis(fluoroalkylsulfonyl)imidic acid, and two sulphonic acids. Cyclic sulfonimid acids in which a phenyl group is connected to a fluoroalkylene group, and N-acylfluoroalkanesulfonic acid amides are preferred, fluoroalkanesulfonic acids having 1 to 30 carbon atoms, bisulfonylimide compounds, and two Cyclic sulfonylimide compounds in which a sulfonyl group is linked to a fluoroalkylene group, and N-acylfluoroalkanesulfonic acid amides are preferred.
탄소 원자수 1~30의 플루오로알칸설폰산으로서는 트리플루오로메탄설폰산, 펜타플루오로에탄설폰산, 헵타플루오로프로판설폰산, 및 노나플루오로부탄설폰산 등이 바람직하다.Preferred fluoroalkanesulfonic acids having 1 to 30 carbon atoms include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, and nonafluorobutanesulfonic acid.
비스설포닐이미드 화합물로서는 하기 식(B1)로 나타내는 화합물이 바람직하다.As the bissulfonylimide compound, a compound represented by the following formula (B1) is preferable.
[화 9][Tuesday 9]
식(B1) 중, X1 및 X2는 각각 독립적으로 적어도 1개의 전자 흡인성기로 치환된 탄화수소기를 나타낸다. 탄화수소기는 식(B1)로 나타내는 화합물의 강산성이 손상되지 않는 범위에서, 전자 흡인성기 이외의 여러 가지 기로 치환되어 있어도 된다. X1 및 X2의 탄소 원자수는 1~20이 바람직하고, 1~10이 보다 바람직하며, 1~7이 특히 바람직하다.In formula (B1), X 1 and X 2 each independently represent a hydrocarbon group substituted with at least one electron-withdrawing group. The hydrocarbon group may be substituted with various groups other than the electron-withdrawing group, as long as the strong acidity of the compound represented by formula (B1) is not impaired. The number of carbon atoms of X 1 and X 2 is preferably 1 to 20, more preferably 1 to 10, and especially preferably 1 to 7.
전자 흡인성기로 치환된 탄화수소기로서는 불소화 알킬기, 니트로기를 가지는 아릴기가 바람직하다. 불소화 알킬기는 직쇄상이어도, 분기쇄상이어도, 환상이어도 된다. 불소화 알킬기는 완전히 불소화된 퍼플루오로알킬기인 것이 바람직하다. 니트로기를 가지는 아릴기로서는 o-니트로페닐기, m-니트로페닐기, 및 p-니트로페닐기가 바람직하고, p-니트로페닐기가 보다 바람직하다.The hydrocarbon group substituted with an electron-withdrawing group is preferably a fluorinated alkyl group or an aryl group having a nitro group. The fluorinated alkyl group may be linear, branched, or cyclic. The fluorinated alkyl group is preferably a completely fluorinated perfluoroalkyl group. As an aryl group having a nitro group, o-nitrophenyl group, m-nitrophenyl group, and p-nitrophenyl group are preferable, and p-nitrophenyl group is more preferable.
식(B1)로 나타내는 화합물의 적합한 구체예로서는 하기 식의 화합물을 들 수 있다.Suitable specific examples of the compound represented by formula (B1) include compounds of the following formula.
[화 10][Tuesday 10]
2개의 설포닐기가 플루오로알킬렌기로 연결된 환상 설포닐이미드 화합물로서는 하기 식(B2)로 나타내는 화합물이 바람직하다.As a cyclic sulfonylimide compound in which two sulfonyl groups are linked to a fluoroalkylene group, a compound represented by the following formula (B2) is preferable.
[화 11][Tuesday 11]
식(B2) 중, X3은 적어도 1개의 수소 원자가 불소 원자로 치환된 직쇄상 또는 분기상의 알킬렌기를 나타낸다. X3의 탄소 원자수는 2~6이 바람직하고, 3~5가 보다 바람직하며, 3이 특히 바람직하다.In formula (B2), X 3 represents a linear or branched alkylene group in which at least one hydrogen atom is replaced with a fluorine atom. The number of carbon atoms of X 3 is preferably 2 to 6, more preferably 3 to 5, and especially preferably 3.
식(B2)로 나타내는 화합물의 적합한 구체예로서는 하기 식의 화합물을 들 수 있다.Suitable specific examples of the compound represented by formula (B2) include compounds of the following formula.
[화 12][Tuesday 12]
N-아실플루오로알칸설폰산아미드로서는 하기 식(B3)로 나타내는 화합물이 바람직하다.As the N-acylfluoroalkane sulfonic acid amide, a compound represented by the following formula (B3) is preferable.
[화 13][Tuesday 13]
식(B3) 중, X4는 적어도 1개의 수소 원자가 불소 원자로 치환된 직쇄상 또는 분기상의 알킬기를 나타낸다. X4의 탄소 원자수는 1~10이 바람직하고, 1~7이 보다 바람직하며, 1~3이 특히 바람직하다. In formula (B3), X 4 represents a linear or branched alkyl group in which at least one hydrogen atom is replaced with a fluorine atom. The number of carbon atoms for X 4 is preferably 1 to 10, more preferably 1 to 7, and especially preferably 1 to 3.
X5는 탄화수소기이다. 탄화수소기에 대해서, 전술한 R5의 기의 주골격을 구성하는 탄화수소기와 동일하다.X 5 is a hydrocarbon group. Regarding the hydrocarbon group, it is the same as the hydrocarbon group constituting the main skeleton of the group of R 5 described above.
식(B3)로 나타내는 화합물의 적합한 구체예로서는 하기 식의 화합물을 들 수 있다.Suitable specific examples of the compound represented by formula (B3) include compounds of the following formula.
[화 14][Tuesday 14]
처리액 중의 (B) 강산의 함유량은 처리액에 의한 표면 처리를 양호하게 실시하는 것이 가능한 한 특별히 한정되지 않는다. 처리액 중의 (B) 강산의 함유량은 (A) 수지 100질량에 대해서, 0.1~20질량부가 바람직하고, 0.1~10질량부가 보다 바람직하며, 0.1~5질량부가 특히 바람직하다.The content of the strong acid (B) in the treatment liquid is not particularly limited as long as it is possible to satisfactorily treat the surface with the treatment liquid. The content of the strong acid (B) in the treatment liquid is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and especially preferably 0.1 to 5 parts by mass, based on 100 masses of the (A) resin.
＜(C) 용매＞＜(C) Solvent＞
(C) 용매는 (A) 수지와, (B) 강산이 가용인 용매이면 특별히 한정되지 않는다. 처리액 중에, (A) 수지와, (B) 강산이 소정량 용해하고 있으면, 처리액은 용해하고 있지 않은 상태의 (A) 수지와, (B) 강산을 포함하고 있어도 된다. (A) 수지와, (B) 강산은 처리액에 완전히 용해하고 있는 것이 바람직하다.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 the resin (A) and the strong acid (B) are dissolved in a predetermined amount in the treatment liquid, the treatment liquid may contain the resin (A) and the strong acid (B) in an undissolved state. It is preferable that (A) the resin and (B) the strong acid are completely dissolved in the treatment liquid.
처리액이 불용물을 포함하는 경우, 표면 처리시에 피처리체의 표면에 불용물이 부착하는 경우가 있다. 이 경우, 표면 처리된 피처리체의 표면을 후술하는 방법으로 린스함으로써, 피처리체의 표면에 부착하는 불용물을 제거할 수 있다.When the treatment liquid contains insoluble matter, the insoluble matter may adhere to the surface of the object to be treated during surface treatment. In this case, insoluble substances adhering to the surface of the object to be treated can be removed by rinsing the surface of the object to be treated by the method described later.
(C) 용매는 물이어도, 유기용매여도, 유기용매의 수용액이어도 된다.(C) The solvent may be water, an organic solvent, or an aqueous solution of the organic solvent.
(C) 용매로서 사용되는 유기용매의 구체예로서는,(C) Specific examples of organic solvents used as solvents include:
디메틸설폭사이드 등의 설폭사이드류;Sulfoxides such as dimethyl sulfoxide;
디메틸설폰, 디에틸설폰, 비스(2-히드록시에틸)설폰, 테트라메틸렌설폰 등의 설폰류;Sulfones such as dimethylsulfone, diethylsulfone, bis(2-hydroxyethyl)sulfone, and tetramethylenesulfone;
N,N-디메틸포름아미드, N-메틸포름아미드, N,N-디메틸아세트아미드, N-메틸아세트아미드, N,N-디에틸아세트아미드 등의 아미드류;Amides such as N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide;
N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, N-프로필-2-피롤리돈, N-히드록시 메틸-2-피롤리돈, N-히드록시에틸-2-피롤리돈 등의 락탐류;N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxy methyl-2-pyrrolidone, N-hydroxyethyl-2- Lactams such as pyrrolidone;
1,3-디메틸-2-이미다졸리디논, 1,3-디에틸-2-이미다졸리디논, 1,3-디이소프로필-2-이미다졸리디논 등의 이미다졸리디논류; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone;
디메틸글리콜, 디메틸디글리콜, 디메틸트리글리콜, 메틸에틸디글리콜, 디에틸글리콜, 트리에틸렌글리콜 부틸메틸에테르 등의 디알킬글리콜에테르류;dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl glycol, and triethylene glycol butylmethyl ether;
에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노-n-프로필에테르, 에틸렌글리콜 모노-n-부틸에테르, 디에틸렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르, 디에틸렌글리콜 모노-n-프로필에테르, 디에틸렌글리콜 모노-n-부틸에테르, 트리에틸렌글리콜 모노메틸에테르, 트리에틸렌글리콜 모노에틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노-n-프로필에테르, 프로필렌글리콜 모노-n-부틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜 모노-n-프로필에테르, 디프로필렌글리콜 모노-n-부틸에테르, 트리프로필렌글리콜 모노메틸에테르, 트리프로필렌글리콜 모노에틸에테르 등의 (폴리)알킬렌글리콜 모노알킬에테르류;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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;
에틸렌글리콜 모노메틸에테르아세테이트, 에틸렌글리콜 모노에틸에테르아세테이트, 디에틸렌글리콜 모노메틸에테르아세테이트, 디에틸렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트 등의 (폴리)알킬렌글리콜 모노알킬에테르아세테이트류;(poly)alkylene 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, propylene glycol monoethyl ether acetate, etc. glycol monoalkyl ether acetates;
디메틸에테르, 디에틸에테르, 메틸에틸에테르, 디프로필에테르, 디이소프로필에테르, 디부틸에테르, 디이소아밀에테르, 디에틸렌글리콜 디메틸에테르, 디에틸렌글리콜 메틸에틸에테르, 디에틸렌글리콜 디에틸에테르, 테트라히드로푸란 등의 다른 에테르류;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, tetra other ethers such as hydrofuran;
메틸에틸케톤, 시클로헥사논, 2-헵타논, 3-헵타논 등의 케톤류;Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;
2-히드록시프로피온산메틸, 2-히드록시프로피온산에틸 등의 락트산알킬에스테르류; 2-히드록시-2-메틸프로피온산에틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 에톡시아세트산에틸, 히드록시아세트산에틸, 2-히드록시-3-메틸부탄산메틸, 3-메틸-3-메톡시부틸아세테이트, 3-메틸-3-메톡시부틸프로피오네이트, 아세트산에틸, 아세트산-n-프로필, 아세트산-i-프로필, 아세트산-n-부틸, 아세트산-i-부틸, 포름산-n-펜틸, 아세트산-i-펜틸, 프로피온산-n-부틸, 부티르산에틸, 부티르산-n-프로필, 부티르산-i-프로필, 부티르산-n-부틸, 피루브산메틸, 피루브산에틸, 피루브산-n-프로필, 아세토아세트산메틸, 아세토아세트산에틸, 2-옥소부탄산에틸 등의 다른 에스테르류;Alkyl lactic acid esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate methyl, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, acetic acid-n-propyl, acetic acid-i-propyl, -n-butyl acetate, -i-butyl acetate, -n-pentyl formate, -i-pentyl acetate, -n-butyl propionate, ethyl butyrate, -n-propyl butyrate, -i-propyl butyrate, -n-butyl butyrate , other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;
β-프로피오락톤, γ-부티로락톤, δ-펜티로락톤 등의 락톤류;Lactones such as β-propiolactone, γ-butyrolactone, and δ-pentyrolactone;
n-헥산, n-헵탄, n-옥탄, n-노난, 메틸옥탄, n-데칸, n-운데칸, n-도데칸, 2,2,4,6,6-펜타메틸헵탄, 2,2,4,4,6,8,8-헵타메틸노난, 시클로헥산, 메틸시클로헥산 등의 직쇄상, 분기쇄상, 또는 환상의 지방족 탄화수소류;n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptane, 2,2 straight-chain, branched-chain, or cyclic aliphatic hydrocarbons such as ,4,4,6,8,8-heptamethylnonane, cyclohexane, and methylcyclohexane;
벤젠, 톨루엔, 크실렌, 1,3,5-트리메틸벤젠, 나프탈렌 등의 방향족 탄화수소류;Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, and naphthalene;
p-멘탄, 디페닐멘탄, 리모넨, 테르피넨, 보르난, 노르보르난, 피난 등의 테르펜류; 등을 들 수 있다.Terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and finan; etc. can be mentioned.
(C) 용매가 물과 유기용매의 혼합 용매인 경우, (C) 용매 중의 유기용매의 함유량은 10질량% 이상이 바람직하고, 20질량% 이상이 보다 바람직하다.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, and more preferably 20% by mass or more.
＜그 밖의 성분＞＜Other ingredients＞
처리액은 본 발명의 목적을 저해하지 않는 범위에서, (A) 수지, (B) 강산, 및 (C) 용매 이외의 여러 가지 성분을 포함하고 있어도 된다. 그 밖의 성분으로서는, 예를 들면 착색제, 계면활성제, 소포제, 점도 조정제, 계면활성제 등을 들 수 있다.The treatment liquid may contain various components other than (A) resin, (B) strong acid, and (C) solvent, as long as they do not impair the purpose of the present invention. Other components include, for example, colorants, surfactants, anti-foaming agents, viscosity modifiers, and surfactants.
＜처리액의 조제 방법＞＜Preparation method of treatment solution＞
처리액을 조제하는 방법은 특별히 한정되지 않는다. 처리액은 전형적으로는 각각 소정량의 (A) 수지와, (B) 강산과, (C) 용매와, 필요에 따라 그 밖의 성분을 균일하게 혼합함으로써 조제된다.The method of 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 other components as needed.
이상 설명한 처리액은, 예를 들면 세포 배양 기구나, 세포 등의 생체 시료를 포함하는 액체를 유통시키는 마이크로 유로 디바이스 등의 세포 접착 방지용의 표면 처리, 여러 가지 물품에 대한 방오성이나 방담성(防曇性)의 부여 등의 목적에서의 표면 처리 등에 적합하게 사용된다.The treatment solution described above is, for example, a surface treatment for preventing cell adhesion to cell culture equipment and micro-channel devices that distribute liquids containing biological samples such as cells, and has antifouling and antifogging properties for various articles. It is suitably used for surface treatment for purposes such as imparting properties.
≪표면 처리 방법≫≪Surface treatment method≫
이상 설명한 표면 처리액을 이용하는 표면 처리 방법은 통상 피처리체의 표면에 대한 표면 처리액의 도포를 포함한다. 표면 처리액의 도포 방법은 특별히 한정되지 않는다. 도포 방법의 구체예로서는 스핀 코트법, 스프레이법, 롤러 코트법, 침지법 등을 들 수 있다. 피처리체가 기판인 경우, 표면 처리액을 균일하게 도포함으로써, 기판 표면을 균일하게 친수화 또는 소수화할 수 있는 점에서, 도포 방법으로서 스핀 코트법이 바람직하다.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 application method of the surface treatment liquid is not particularly limited. Specific examples of the application method include spin coating, spraying, roller coating, and dipping. When the object to be processed is a substrate, the spin coating method is preferable as an application method because the surface of the substrate can be uniformly hydrophilized or hydrophobized by uniformly applying the surface treatment liquid.
피처리체의 표면 처리액이 도포되는 면의 재질은 특별히 한정되지 않고, 유기 재료여도, 무기 재료여도 된다.The material of the surface of the object to be treated to which the surface treatment liquid is applied is not particularly limited, and may be an organic material or an inorganic material.
유기 재료로서는 PET 수지, PBT 수지 등의 폴리에스테르 수지, 각종 나일론, 폴리이미드 수지, 폴리아미드이미드 수지, 폴리에틸렌 및 폴리프로필렌 등의 폴리올레핀, 폴리스티렌, (메타)아크릴 수지 등, 여러 가지 수지 재료를 들 수 있다.Organic materials include various resin materials, such as polyester resins such as PET resin and PBT resin, various nylons, polyimide resins, polyamidoimide resins, polyolefins such as polyethylene and polypropylene, polystyrene, and (meth)acrylic resin. there is.
또, 여러 가지 레지스트 재료에 포함되는 감광성의 수지 성분이나, 알칼리 가용성의 수지 성분도 유기 재료로서 바람직하다.Additionally, photosensitive resin components and alkali-soluble resin components contained in various resist materials are also preferable as organic materials.
무기 재료로서는 유리, 실리콘이나, 구리, 알루미늄, 철, 텅스텐 등의 여러 가지 금속을 들 수 있다. 금속은 합금이어도 된다.Inorganic materials include glass, silicon, and various metals such as copper, aluminum, iron, and tungsten. The metal may be an alloy.
전술한 표면 처리액에 의해 표면 처리되는 면의 재질은 특별히 한정되지 않지만, 표면 처리액이 도포되는 면의 재질이 유기 재료인 경우에는 관능기 I로서 수산기 및/또는 카르복실기를 가지는 (A) 수지를 포함하는 표면 처리액을 이용하는 것이 바람직하다.The material of the surface to be treated with the above-mentioned surface treatment liquid is not particularly limited, but if the material of the surface to which the surface treatment liquid is applied is an organic material, it contains (A) resin having a hydroxyl group and/or a carboxyl group as the functional group I. It is preferable to use a surface treatment liquid that
표면 처리액이 도포되는 면의 재질이 무기 재료인 경우에는 관능기 I로서 수산기 및/또는 시아노기를 가지는 (A) 수지를 포함하는 표면 처리액을 이용하는 것이 바람직하다.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 having a hydroxyl group and/or a cyano group as the functional group I.
피처리체의 형상은 특별히 한정되지 않는다. 피처리체는 평탄한 기판이어도 되고, 예를 들면 구상이나, 주상 등의 입체 형상이어도 된다. 또, 피처리체의 표면은 평활해도, 규칙적 또는 불규칙한 요철을 가지고 있어도 된다.The shape of the object to be processed is not particularly limited. The object to be processed may be a flat substrate or, for example, may have a three-dimensional shape such as spherical or columnar. Additionally, the surface of the object to be processed may be smooth or may have regular or irregular irregularities.
표면 처리액을 피처리체의 표면에 도포한 후에는, 필요에 따라 도포막을 가열해 (C) 용매의 적어도 일부를 제거해도 된다.After applying the surface treatment liquid to the surface of the object to be treated, the coating film may be heated as needed to remove at least part of the solvent (C).
피처리체 위의 표면 처리액이 도포된 개소는 린스되는 것이 바람직하다. 상술한 바와 같이, 소정의 관능기를 가지는 (A) 수지와, (B) 강산을 포함하는 표면 처리액을 피처리체의 표면에 도포하면, 피처리체의 표면에 (A) 수지가 양호하게 부착 또는 결합한다. 그러나, 피처리체의 표면에는 상기 표면에 부착 또는 결합하고 있지 않는 (A) 수지도 어느 정도의 양으로 존재하고 있다. 따라서, (A) 수지의 피처리체의 표면 특성에 부여하는 영향을 최대한 저감시키기 위해서, 린스에 의해 피처리체의 표면에 부착 또는 결합하고 있지 않는 (A) 수지를 씻어 흘리는 것이 바람직하다.It is preferable that the area on the object to be treated where the surface treatment liquid is applied is rinsed. As described above, when a surface treatment liquid containing (A) a resin having a predetermined functional group and (B) a strong acid is applied to the surface of an object to be treated, the resin (A) adheres or bonds well to the surface of the object to be treated. do. However, a certain amount of resin (A) that is not attached or bonded to the surface of the object to be processed is present. Therefore, in order to minimize the influence of resin (A) on the surface properties of the object to be treated, it is preferable to wash away the resin (A) that is not attached or bonded to the surface of the object to be treated by rinsing.
표면 처리액이 (C) 용매로서 물을 포함하는 경우, 물에 의해 린스를 실시하는 것이 바람직하다. 또, 표면 처리액이 (C) 용매로서 유기용매를 포함하는 경우, 유기용매에 의해 린스를 실시하는 것도 바람직하다. 유기용매에 의해 린스를 실시하는 경우, 표면 처리액에 포함되는 유기용매와 동종의 유기용매를 이용하는 것이 바람직하다.When the surface treatment liquid contains water as the (C) solvent, it is preferable to rinse with water. Additionally, 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 is performed with an organic solvent, it is preferable to use the same organic solvent as the organic solvent contained in the surface treatment liquid.
표면 처리액의 도포 후, 또는 린스 후에 피처리체의 표면을 건조시킴으로써, 양호하게 친수화 또는 소수화된 물품이 얻어진다.By drying the surface of the object to be treated after application of the surface treatment liquid or after rinsing, a well-hydrophilic or hydrophobized article can be obtained.
[[ 실시예Example ]]
이하, 본 발명을 실시예에 의해 더욱 상세하게 설명하지만, 본 발명은 이들 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
[실시예 1~16, 및 비교예 1~6][Examples 1 to 16, and Comparative Examples 1 to 6]
각 실시예 및 비교예에서, 표 1에 기재된 비율로 이하에 설명하는 구성 단위를 함유하는 수지를 (A) 수지로서 이용했다.In each Example and Comparative Example, a resin containing the structural units described below in the ratio shown in Table 1 was used as the (A) resin.
단위 A-1~A-7은 친수성기 또는 소수성기인 관능기 Ⅱ를 (A) 수지에 도입하는 구성 단위이다.Units A-1 to A-7 are structural units that introduce functional group II, which is a hydrophilic group or hydrophobic group, into (A) resin.
단위 B-1~B-4는 (A) 수지에 관능기 I를 도입하는 구성 단위이다.Units B-1 to B-4 are structural units that introduce functional group I into (A) resin.
단위 C-1~C-3은 관능기 I 및 관능기 Ⅱ 모두 갖지 않는 구성 단위이다.Units C-1 to C-3 are structural units that have neither functional group I nor functional group II.
[화 15][Tuesday 15]
[화 16][Tuesday 16]
[화 17][Tuesday 17]
실시예 및 비교예에 대해서, 산 성분으로서 이하의 Ac1~Ac4를 이용했다. Ac1(트리플루오로메탄설폰산)와, 하기 식의 화합물인 Ac2는 pKa1 이하의 강산이다. Ac3(인산)와 Ac4(아세트산)는 pKa1 초과의 산이다.For Examples and Comparative Examples, the following Ac1 to Ac4 were used as acid components. Ac1 (trifluoromethanesulfonic acid) and Ac2, a compound of the formula below, are strong acids with a pKa1 or less. Ac3 (phosphoric acid) and Ac4 (acetic acid) are acids above pKa1.
[화 18][Tuesday 18]
(Ac2) (Ac2)
실시예 및 비교예에 대해서, (C) 용매로서 S1: 순수, S2: 프로필렌글리콜 모노메틸에테르, 및 S3: 프로필렌글리콜 모노메틸에테르아세테이트를 이용했다.For Examples and Comparative Examples, (C) as solvents, S1: pure water, S2: propylene glycol monomethyl ether, and S3: propylene glycol monomethyl ether acetate were used.
(표면 처리액의 조제)(Preparation of surface treatment liquid)
표 1~3에 기재되는 종류 및 몰 비율의 구성 단위로 이루어지는 (A) 수지 100질량부와, 표 1~3에 기재되는 질량부의 산 성분과, 표 1~3에 기재되는 질량부의 용매를 균일하게 혼합하여 각 실시예 및 비교예의 표면 처리액을 얻었다. 100 parts by mass of resin (A) consisting of structural units of the type and molar ratio shown in Tables 1 to 3, an acid component by mass shown in Tables 1 to 3, and a solvent by mass shown in Tables 1 to 3 are uniformly mixed. By mixing thoroughly, surface treatment solutions for each Example and Comparative Example were obtained.
또한 비교예 1에서는 산 성분을 사용하지 않았다.Additionally, in Comparative Example 1, no acid component was used.
실시예 8에서는 단위 A-4만으로 이루어지는 수지를 이용하고 실시예 15에서는 단위 A-1과 단위 A-4만으로 이루어지는 수지를 이용했다. 단위 A-4에 포함되는 2-히드록시에틸아미노기는 친수성기인 것과 함께, 수산기 함유기이기도 하다. 이 때문에, 단위 A-4에 포함되는 수산기는 관능기 I로서의 역할도 나타낸다.In Example 8, a resin consisting of only unit A-4 was used, and in Example 15, a resin consisting of only units A-1 and A-4 was used. The 2-hydroxyethylamino group contained in unit A-4 is not only a hydrophilic group but also a hydroxyl group-containing group. For this reason, the hydroxyl group contained in unit A-4 also plays a role as functional group I.
(표면 처리 효과의 평가)(Evaluation of surface treatment effect)
이상의 방법에 의해 얻어진, 실시예 1~15, 및 비교예 1~5의 표면 처리액을 이용하고, 이하의 방법에 따라 PET 필름의 표면 처리를 실시했다.Using the surface treatment liquids of Examples 1 to 15 and Comparative Examples 1 to 5 obtained by the above method, the surface treatment of PET film was performed according to the following method.
우선, 스핀 코트법에 의해, PET 필름 위에 표면 처리액을 도포하여 막 두께 500nm의 도포막을 형성했다.First, the surface treatment liquid was applied on the PET film by spin coating to form a coating film with a thickness of 500 nm.
형성된 도포막을 40℃에서 60초간 가열한 후, PET 필름의 표면을 린스했다. 실시예 1~4, 실시예 8~13, 실시예 15, 및 비교예 1~4에 대해서는 순수로 린스를 실시했다. 실시예 5~7, 실시예 14, 및 비교예 5에 대해서는 프로필렌글리콜 모노메틸에테르를 이용한 린스를 실시했다.After heating the formed coating film at 40°C for 60 seconds, 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 using propylene glycol monomethyl ether was performed.
린스된 PET 필름을 건조시킨 후, PET 필름 표면의 물의 접촉각을 측정했다. 물의 접촉각의 측정은 Dropmaster700(쿄와 계면과학 주식회사 제)를 이용해 표면 처리된 기판의 표면에 순수 액적(2.0μL)을 적하하고, 적하 10초 후에서의 접촉각으로서 측정했다. 물의 접촉각의 측정 결과를 표 1~3에 기재한다.After drying the rinsed PET film, the contact angle of water on the PET film surface was measured. The contact angle of water was measured by dropping pure liquid droplets (2.0 μL) on the surface of the surface-treated substrate using Dropmaster700 (manufactured by Kyowa Interface Science Co., Ltd.) and measuring the contact angle 10 seconds after dropping. The measurement results of the water contact angle are listed in Tables 1 to 3.
또한 미처리의 PET 필름의 물의 접촉각은 70.6°이다.Additionally, the water contact angle of the untreated PET film is 70.6°.
구성 단위
(몰%）(A) Resin
constituent unit
(mole%)
pKa1 이하
(질량부）acid composition
Below pKa1
(Part by mass)
pKa1 초과
(질량부）
acid composition
exceeding pKa1
(Part by mass)
(질량부）(C) Solvent
(Part by mass)
구성 단위
(몰%）(A) Resin
constituent unit
(mole%)
pKa1 이하
(질량부）acid composition
Below pKa1
(Part by mass)
pKa1 초과
(질량부）acid composition
exceeding pKa1
(Part by mass)
(질량부）(C) Solvent
(Part by mass)
구성 단위
(몰%）(A) Resin
constituent unit
(mole%)
pKa1 이하
(질량부）acid composition
Below pKa1
(Part by mass)
pKa1 초과
(질량부）acid composition
exceeding pKa1
(Part by mass)
(질량부）(C) Solvent
(Part by mass)
실시예 1~16에 의하면, 소정의 관능기를 가지는 (A) 수지와 pKa1 이하의 (B) 강산과, (C) 용매를 포함하는 표면 처리액을 이용함으로써, PET 필름의 표면이 양호하게 친수화 또는 소수화되는 것을 알 수 있다.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 with a pKa 1 or less, and (C) a solvent, the surface of the PET film was made well hydrophilic. Alternatively, it can be seen that it is hydrophobized.
비교예 1에 의하면, 소정의 관능기를 가지는 (A) 수지와 (C) 용매를 포함하지만, 산 성분을 포함하지 않는 표면 처리액을 이용하는 경우, 양호한 표면 처리 효과를 얻을 수 없는 것을 알 수 있다.According to Comparative Example 1, it can be seen that a good surface treatment effect cannot be obtained when a surface treatment liquid containing (A) a resin having a predetermined functional group and a solvent (C) but not an acid component is used.
비교예 2 및 3에 의하면, 관능기 Ⅱ로서 친수성기 또는 소수성기를 갖지 않는 (A) 수지와, pKa1 이하의 (B) 강산과, (C) 용매를 포함하는 표면 처리액으로 PET 필름의 표면 처리를 실시해도 PET 필름의 물의 접촉각은 미처리된 상태로부터 크게 변하지 않는 것을 알 수 있다.According to Comparative Examples 2 and 3, the PET film was surface treated with a surface treatment solution containing (A) a resin having no hydrophilic group or hydrophobic group as functional group II, (B) a strong acid of pKa 1 or less, and (C) a solvent. It can be seen that the water contact angle of the PET film does not change significantly from the untreated state.
비교예 4 및 5에 의하면, 소정의 관능기를 가지는 (A) 수지와, 산 성분과, (C) 용매를 포함하지만, pKa1 이하의 (B) 강산을 포함하지 않는 표면 처리액으로, PET 필름의 표면 처리를 실시해도, PET 필름의 물의 접촉각은 미처리된 상태로부터 크게 변하지 않는 것을 알 수 있다.According to Comparative Examples 4 and 5, a surface treatment solution containing (A) a resin having a predetermined functional group, an acid component, and (C) a solvent, but not containing a strong acid (B) of pKa 1 or less, was used to prepare a PET film. It can be seen that even if surface treatment is performed, the water contact angle of the PET film does not change significantly from the untreated state.
비교예 6에 의하면, 관능기 I를 가지지 않는 (A) 수지와, pKa1 이하의 (B) 강산과, (C) 용매를 포함하는 표면 처리액으로, PET 필름의 표면 처리를 실시해도, PET 필름의 물의 접촉각은 미처리된 상태로부터 크게 변하지 않는 것을 알 수 있다.According to Comparative Example 6, even if the surface of the PET film is treated with a surface treatment liquid containing (A) a resin without functional group I, (B) a strong acid with a pKa 1 or less, and (C) a solvent, the PET film It can be seen that the contact angle of water does not change significantly from the untreated state.
[실시예 17, 실시예 18, 및 비교예 7][Example 17, Example 18, and Comparative Example 7]
표 4에 기재되는 종류 및 몰 비율의 구성 단위로 이루어지는 (A) 수지 100질량부와, 표 4에 기재되는 질량부의 산 성분과, 표 4에 기재되는 질량부의 용매를 균일하게 혼합하여 실시예 17, 실시예 18, 및 비교예 7의 표면 처리액을 얻었다.100 parts by mass of resin (A) consisting of structural units of the type and molar ratio shown in Table 4, the acid component shown in Table 4, and the solvent shown in Table 4 were uniformly mixed to obtain Example 17. , Example 18, and Comparative Example 7 were obtained.
얻어진 표면 처리액을 이용하고, PET 필름을 유리 기판으로 변경하는 것 외에는 실시예 1과 동일하게 하여 유리 기판의 표면 처리를 실시해, 표면 처리 후의 유리 기판의 물의 접촉각을 측정했다. 유리 기판의 물의 접촉각의 측정 결과를 표 4에 기재한다.Using the obtained surface treatment liquid, the surface treatment of the glass substrate was carried out in the same manner as in Example 1 except that the PET film was changed to a glass substrate, and the contact angle of water on the glass substrate after the surface treatment was measured. The measurement results of the contact angle of water on the glass substrate are listed in Table 4.
또한 미처리된 유리 기판의 물의 접촉각은 41.9°이다.Additionally, the contact angle of water on the untreated glass substrate is 41.9°.
구성 단위
(몰%）(A) Resin
constituent unit
(mole%)
pKa1 이하
(질량부）acid composition
Below pKa1
(Part by mass)
pKa1 초과
(질량부）acid composition
exceeding pKa1
(Part by mass)
(질량부）(C) Solvent
(Part by mass)
실시예 17 및 18에 의하면, 관능기 I로서 시아노기를 포함하는 단위 B-4, 및 친수성의 단위 A-1로 이루어지는 (A) 수지와, pKa1 이하의 (B) 강산과, (C) 용매를 포함하는 표면 처리액을 이용하는 경우, 무기 재료인 유리로 이루어지는 기판의 표면을 양호하게 친수화할 수 있는 것을 알 수 있다.According to Examples 17 and 18, (A) a resin consisting of unit B-4 containing a cyano group as the functional group I and a hydrophilic unit A-1, (B) a strong acid of pKa 1 or less, and (C) a solvent. It can be seen that the surface of a substrate made of glass, an inorganic material, can be satisfactorily made hydrophilic when using a surface treatment liquid containing
다른 한편, 비교예 7에서는 관능기 I를 포함하지 않는 (A) 수지와, pKa1 이하의 (B) 강산과, (C) 용매를 포함하는 표면 처리액을 이용해 유리 기판의 표면 처리를 실시해도, 유리 기판의 물의 접촉각은 미처리된 상태로부터 크게 변하지 않는 것을 알 수 있다.On the other hand, in Comparative Example 7, even if the surface treatment of the glass substrate was performed using a surface treatment solution containing (A) a resin not containing functional group I, (B) a strong acid of pKa 1 or less, and (C) a solvent, the glass substrate was It can be seen that the contact angle of water on the substrate does not change significantly from the untreated state.
[실시예 19][Example 19]
실시예 1의 표면 처리액을 이용하고, PET 필름을 유리 기판으로 변경하는 것 이외에는 실시예 1과 동일하게 하여 유리 기판의 표면 처리를 실시해 6장의 표면 처리된 유리 기판을 얻었다.Using the surface treatment solution of Example 1, the surface treatment of the glass substrate was carried out in the same manner as in Example 1 except that the PET film was changed to a glass substrate, and six surface-treated glass substrates were obtained.
얻어진 표면 처리된 유리 기판을 순수, 에탄올, 프로필렌글리콜 모노메틸에테르아세테이트(PGMEA), 생리 식염수, 1N NaOH 수용액에 실온에서 6개월 침지시킨 후 각각의 접촉각을 측정하였다.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 then each contact angle was measured.
또한 표면 처리된 유리 기판을 0.1M H2SO4 수용액에 100℃에서 100시간 침지시킨 후 접촉각을 측정했다.Additionally, the surface-treated glass substrate was immersed in a 0.1MH 2 SO 4 aqueous solution at 100°C for 100 hours, and then the contact angle was measured.
어떤 조건에서도 침지 전후에서 접촉각에 변화는 없고, 약액 내성이 우수한 것이 확인되었다.It was confirmed that there was no change in the contact angle before and after immersion under any conditions, and that the chemical resistance was excellent.
Claims (11)
상기 (A) 수지가 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 기인 관능기 I와, 상기 관능기 I 이외의 친수성기 또는 소수성기인 관능기 Ⅱ를 가지고,
상기 관능기 Ⅱ의 상기 친수성기가 하기 식(A1):
-NH-R1···(A1)
(식(A1) 중, R1은 아미노기, 설폰산기, 및 수산기로 이루어지는 군으로부터 선택되는 1 이상의 기로 치환된 탄소 원자수 1~4의 알킬기, 또는 수소 원자이다.)
로 나타내는 기이며,
다만 상기 관능기 Ⅱ가 수산기, 시아노기, 및 카르복실기로부터 선택되는 1 이상의 기를 포함하는 경우, 상기 (A) 수지는 상기 관능기 I를 가지지 않아도 되고,
상기 (B) 강산의 pKa가 1 이하인 표면 처리액.It includes (A) a resin, (B) a strong acid, and (C) a 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 II, which is a hydrophilic or hydrophobic group other than the functional group I,
The hydrophilic group of the functional group II has the following formula (A1):
-NH-R 1 ···(A1)
(In formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom.)
It is a group represented by,
However, when the functional group II includes one or more groups selected from hydroxyl groups, cyano groups, and carboxyl groups, the resin (A) does not need to have the functional group I,
(B) A surface treatment solution in which the strong acid has a pKa of 1 or less.
상기 관능기 I이 하기 식(A2):
CH2=CR2-(R3)a-CO-R4···(A2)
(식(A2) 중, R2는 수소 원자 또는 메틸기이며, R3은 2가의 탄화수소기이며, a는 0 또는 1이며, R4는 -OH, -O-R5, 또는 -NH-R5이며, R5는 수산기, 시아노기, 및 카르복실기로 이루어지는 군으로부터 선택되는 1 이상의 관능기로 치환된 탄화수소기이다.)
로 나타내는 단량체로부터 유래하는 표면 처리액.In claim 1,
The functional group I has the following formula (A2):
CH 2 =CR 2 -(R 3 ) a -CO-R 4 ···(A2)
(In formula (A2), R 2 is a hydrogen atom or a methyl group, R 3 is a divalent hydrocarbon group, a is 0 or 1, R 4 is -OH, -OR 5 , or -NH-R 5 , R 5 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of hydroxyl group, cyano group, and carboxyl group.)
A surface treatment solution derived from the monomer represented by .
상기 소수성기가 불소화 탄화수소기, 실릴기, 및 실록산기로 이루어지는 군으로부터 선택되는 1 이상의 기인 표면 처리액.In claim 1,
A surface treatment liquid wherein the hydrophobic group is one or more groups selected from the group consisting of a fluorinated hydrocarbon group, a silyl group, and a siloxane group.
상기 관능기 Ⅱ가 소수성기이며, 또한 하기 식(A3):
CH2=CR2-(CO-O)b-R6···(A3)
(식(A3) 중, R2는 수소 원자 또는 메틸기이며, b는 0 또는 1이며, R6은 불소화 탄화수소기, 또는 하기 식(A4):
-SiR7R8-(-O-SiR7R8-)n-R9···(A4)
로 나타내는 기이며, R7, R8, 및 R9는 각각 독립적으로 탄소 원자수 1~6의 탄화수소기이며, n은 0 이상의 정수이다.)
로 나타내는 단량체로부터 유래하는 표면 처리액.In claim 1,
The functional group II is a hydrophobic group, and has the following formula (A3):
CH 2 =CR 2 -(CO-O) b -R 6 ···(A3)
(In 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)
It is a group represented by , 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.)
A surface treatment solution derived from the monomer represented by .
상기 관능기 Ⅱ가 친수성기이며, 또한 하기 식(A5):
CH2=CR2-CO-NH-R1···(A5)
(식(A5) 중, R1은 아미노기, 설폰산기, 및 수산기로 이루어지는 군으로부터 선택되는 1 이상의 기로 치환된 탄소 원자수 1~4의 알킬기, 또는 수소 원자이며, R2는 수소 원자 또는 메틸기이다.)
로 나타내는 단량체로부터 유래하는 표면 처리액.In claim 1,
The functional group II is a hydrophilic group, and has the following formula (A5):
CH 2 =CR 2 -CO-NH-R 1 ···(A5)
(In formula (A5), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom, and R 2 is a hydrogen atom or a methyl group. .)
A surface treatment solution derived from the monomer represented by .
피처리체 위의 상기 표면 처리액이 도포된 개소의 린스를 포함하는 표면 처리 방법.In claim 6,
A surface treatment method comprising rinsing a location on an object to be treated where the surface treatment liquid is applied.
상기 피처리체가 기판이며, 상기 표면 처리액의 도포가 스핀 코트에 의해 실시되는 표면 처리 방법.In claim 6,
A surface treatment method in which the object to be treated is a substrate, and the surface treatment liquid is applied by spin coating.
상기 표면 처리액이 도포되는 면의 재질이 유기 재료이며, 상기 (A) 수지가 상기 관능기 I로서 수산기 및/또는 카르복실기를 가지는 표면 처리 방법.In claim 6,
A surface treatment method wherein the material of the surface to which the surface treatment liquid is applied is an organic material, and the resin (A) has a hydroxyl group and/or a carboxyl group as the functional group I.
상기 표면 처리액이 도포되는 면의 재질이 무기 재료이며, 상기 (A) 수지가 상기 관능기 I로서 수산기 및/또는 시아노기를 가지는 표면 처리 방법.In claim 6,
A surface treatment method in which the material of the surface to which the surface treatment liquid is applied is an inorganic material, and the resin (A) has a hydroxyl group and/or a cyano group as the functional group I.
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| JP7043222B2 (en) * | 2017-10-31 | 2022-03-29 | 東京応化工業株式会社 | Surface treatment liquid and surface treatment method |
| US20190127540A1 (en) * | 2017-10-31 | 2019-05-02 | Tokyo Ohka Kogyo Co., Ltd. | Surface treatment method, surface treatment liquid, and surface-treated article |
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