JP5846466B1 - Surface modifier, coating composition and article - Google Patents
Surface modifier, coating composition and article Download PDFInfo
- Publication number
- JP5846466B1 JP5846466B1 JP2015525323A JP2015525323A JP5846466B1 JP 5846466 B1 JP5846466 B1 JP 5846466B1 JP 2015525323 A JP2015525323 A JP 2015525323A JP 2015525323 A JP2015525323 A JP 2015525323A JP 5846466 B1 JP5846466 B1 JP 5846466B1
- Authority
- JP
- Japan
- Prior art keywords
- group
- coating composition
- chain
- poly
- surface modifier
- 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.)
- Active
Links
- 239000003607 modifier Substances 0.000 title claims abstract description 66
- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 125000001033 ether group Chemical group 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 23
- 125000005647 linker group Chemical group 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- -1 perfluoromethylene group Chemical group 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 150000002009 diols Chemical class 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000002265 prevention Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003669 anti-smudge Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 description 1
- RBTROQHBNLSUTL-UHFFFAOYSA-N 1,1,2,2,3,4-hexafluoro-3,4-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C1(F)C(F)(F)F RBTROQHBNLSUTL-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004838 2-methylpentylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical group CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- 125000004820 3-methylbutylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004839 3-methylpentylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])C([H])([H])[*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000004840 4-methylpentylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 description 1
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical group CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
Abstract
本発明は、ガラス基材等の基材上に防汚性とすべり性に優れる被膜を形成することができる表面改質剤、該表面改質剤を含むコーティング組成物、及び該組成物を用いて得られる被膜を有する物品を提供することを目的として、下記一般式(1)〔式中、Aはそれぞれ加水分解性基または非加水分解性基であり、式中、二つある(A)3の各々において、少なくとも一つのAは加水分解性基である。X、Y1及びY2はそれぞれ2価の連結基である。PFPEは、ポリ(パーフルオロアルキレンエーテル)鎖を表す。〕で表される表面改質剤を提供する。The present invention uses a surface modifier capable of forming a film having excellent antifouling properties and slipperiness on a substrate such as a glass substrate, a coating composition containing the surface modifier, and the composition. For the purpose of providing an article having a coating obtained in the above manner, the following general formula (1): wherein A is a hydrolyzable group or a non-hydrolyzable group, In each of 3, at least one A is a hydrolyzable group. X, Y1 and Y2 are each a divalent linking group. PFPE represents a poly (perfluoroalkylene ether) chain. A surface modifier represented by the formula:
Description
本発明は、ガラス基材等の基材上に耐久性に優れる防汚性とすべり性に優れる被膜を形成することができる表面改質剤及び該表面改質剤を含むコーティング組成物に関する。また、本発明は、前記コーティング組成物を用いて得られる被膜を有する物品に関する。 The present invention relates to a surface modifier capable of forming a film having excellent durability and antislipping properties on a substrate such as a glass substrate, and a coating composition containing the surface modifier. The present invention also relates to an article having a film obtained by using the coating composition.
タッチパネルは、ガラスや合成樹脂等からなる2枚の透明基板が枠状のシール材を介して対向配置され、枠状の上記シール部材の内側に、透明導電膜または複数の電極からなる入力領域が設けられている。ここで、透明基材としてはプラスチックやガラス等が挙げられる。2枚の透明基板の組合せとしては、例えば、プラスチック(フィルム)/ガラスやガラス/ガラスが挙げられ、中でも、ガラス/ガラスの組合せを用いたタッチパネルは画面が非常にクリアで、なおかつ耐候性に優れる特徴を有する。その為、屋外で用いるスマートフォンやタブレットPC等の携帯機器や激しい温度差が発生する車載用途などに好適に使用できる。 In the touch panel, two transparent substrates made of glass, synthetic resin, or the like are arranged to face each other via a frame-shaped sealing material, and an input region composed of a transparent conductive film or a plurality of electrodes is placed inside the frame-shaped sealing member. Is provided. Here, examples of the transparent substrate include plastic and glass. Examples of the combination of the two transparent substrates include plastic (film) / glass and glass / glass. Among them, a touch panel using the glass / glass combination has a very clear screen and excellent weather resistance. Has characteristics. Therefore, it can be suitably used for portable devices such as smartphones and tablet PCs used outdoors and in-vehicle applications in which a severe temperature difference occurs.
前記タッチパネルは使用時に人間の指が触れるため、指紋、皮脂、汗等の人体由来の汚れが付着しやすい。これらの汚れは付着すると落ちにくく、また、光の加減等によっては目立つため、視認性や美観を損ねるという問題があった。 Since the touch panel is touched by human fingers during use, dirt derived from the human body such as fingerprints, sebum, and sweat tends to adhere to the touch panel. These stains are difficult to remove when attached, and they are conspicuous depending on the amount of light, etc., and thus there is a problem that visibility and aesthetics are impaired.
この問題の解決のために、撥水性と撥油性とを兼ね備える含フッ素化合物を人間の指が触れる最表面層にコーティングする手法が取られている。具体的には、例えば、加水分解性基を有する珪素原子を片方の末端に有し、且つ、もう片方の末端中にパーフルオロアルキレンエーテル鎖を有する化合物を含んでなる表面改質剤、及び該表面改質剤を含む有機溶剤溶液(コーティング組成物)が開示されている(例えば、特許文献1参照)。しかしながら、前記特許文献1で開示された表面改質剤では、前記汚れの付着に対する耐性(防汚性)が十分でない問題がある。 In order to solve this problem, a technique has been adopted in which a fluorine-containing compound having both water repellency and oil repellency is coated on the outermost surface layer touched by a human finger. Specifically, for example, a surface modifier containing a compound having a hydrolyzable silicon atom at one end and a perfluoroalkylene ether chain at the other end, and An organic solvent solution (coating composition) containing a surface modifier is disclosed (for example, see Patent Document 1). However, the surface modifier disclosed in Patent Document 1 has a problem that the resistance to dirt (antifouling property) is not sufficient.
また、前記タッチパネルの中でも例えば、スマートフォンやタブレットPCでは、タッチパネル上で指先やペン先をなぞる(スライドさせる)操作(スワイプ)を行う。近年、タッチパネル画面には、この操作の際に、指先やペン先に引っかかりを感じない滑らかさが求められている。しかしながら、前記特許文献1で開示された表面改質剤では、前記の滑らかさ(すべり性)も十分でない問題がある。 In addition, among the touch panels, for example, a smartphone or tablet PC performs an operation (swipe) for tracing (sliding) a fingertip or a pen tip on the touch panel. In recent years, the touch panel screen is required to be smooth so that the fingertip and the pen tip do not get caught during this operation. However, the surface modifier disclosed in Patent Document 1 has a problem that the smoothness (slidability) is not sufficient.
本発明の課題は、耐久性に優れ、且つ、防汚性とすべり性に優れる被膜が得られる表面改質剤とコーティング組成物を提供する事にある。また、本発明の課題は、防汚性とすべり性に優れる被膜を有する物品を提供することでもある。 An object of the present invention is to provide a surface modifier and a coating composition that can provide a film having excellent durability and antifouling properties and slipperiness. Moreover, the subject of this invention is also providing the articles | goods which have a film excellent in antifouling property and slipperiness.
本発明者らは、鋭意検討した結果、ポリ(パーフルオロアルキレンエーテル)鎖とウレタン結合と加水分解性シランを有する化合物であり、該ポリ(パーフルオロアルキレンエーテル)鎖の両末端にウレタン結合が配置し、更に該ウレタン結合と加水分解性シランが近傍した位置にあり、しかも該化合物の両末端に加水分解性シランを有する化合物が、防汚性とすべり性に優れる被膜が得られる表面改質剤として有用であること等を見出し、本発明を開発するに至った。 As a result of intensive studies, the present inventors have found that the compound has a poly (perfluoroalkylene ether) chain, a urethane bond, and a hydrolyzable silane, and urethane bonds are arranged at both ends of the poly (perfluoroalkylene ether) chain. Furthermore, the compound having the hydrolyzable silane at both ends of the compound, in which the urethane bond and the hydrolyzable silane are in the vicinity, is a surface modifier that provides a film having excellent antifouling properties and slipperiness. As a result, the present invention was developed.
即ち、本発明は、下記一般式(1) That is, the present invention provides the following general formula (1)
で表される表面改質剤と溶剤とを含有するコーティング組成物であり、該コーティング組成物中の該表面改質剤の含有率が0.05〜1質量%であることを特徴とするコーティング組成物を提供するものである。
A coating composition comprising a surface modifier represented by the formula (1) and a solvent, wherein the coating composition is characterized in that the content of the surface modifier in the coating composition is 0.05 to 1% by mass. A composition is provided.
更に、本発明は、基材上に前記コーティング組成物の被膜を有することを特徴とする物品を提供するものである。 Furthermore, this invention provides the article | item characterized by having a film of the said coating composition on a base material.
本発明の表面改質剤やコーティング組成物は、防汚性とすべり性に優れる被膜を好適に物品上に形成することができる。従って、タッチパネル等の防汚性とすべり性が要求される用途に特に有用である。 The surface modifier and the coating composition of the present invention can suitably form a film excellent in antifouling property and slipperiness on an article. Therefore, it is particularly useful for applications requiring antifouling properties and slipperiness such as touch panels.
本発明の表面改質剤は下記一般式(1) The surface modifier of the present invention is represented by the following general formula (1)
本発明の表面改質剤は前記一般式(1)で示される通り、二つのSi(A)3を有し、しかも、それぞれの(A)3中の少なくとも一つのAが加水分解性基である。このような珪素原子(反応性シリル基)を有することにより、本発明の表面改質剤は、以下のような反応により基材表面に共有結合すると発明者らは推測している。推測している反応の一つは、加水分解によりシラノール基を生成し、該シラノール基が各種基材、例えば、好ましくはガラス基材等の表面にある水酸基と脱水縮合し、基材表面に共有結合する反応である。推測しているもう一つの反応は、加水分解性基が基材の水酸基と直接縮合(加水分解性基がアルコキシ基の場合は脱アルコール縮合)し、基材表面に共有結合する反応である。本発明品は、片末端だけでなく両末端が基材と結合することができるため、これらの縮合反応により形成される共有結合により本発明の表面改質剤は従来発明品よりも基材表面に強固に固着し、表面改質剤が有するポリ(パーフルオロアルキレンエーテル)鎖が奏する防汚性とすべり性を兼ね備えながら、耐久性にも優れる被膜を形成することができる。The surface modifier of the present invention has two Si (A) 3 as shown by the general formula (1), and at least one A in each (A) 3 is a hydrolyzable group. is there. The inventors speculate that by having such a silicon atom (reactive silyl group), the surface modifier of the present invention is covalently bonded to the substrate surface by the following reaction. One of the presumed reactions is the generation of silanol groups by hydrolysis, which dehydrates and condenses with hydroxyl groups on the surface of various substrates, for example, preferably glass substrates, and is shared on the substrate surface. It is a reaction that binds. Another presumed reaction is a reaction in which the hydrolyzable group directly condenses with the hydroxyl group of the substrate (dealcoholization condensation when the hydrolyzable group is an alkoxy group) and is covalently bonded to the substrate surface. Since the product of the present invention can bond not only one end but also both ends to the base material, the surface modifier of the present invention is formed on the surface of the base material more than the conventional product due to the covalent bond formed by these condensation reactions. It is possible to form a film having excellent durability while having both the antifouling property and the slip property exhibited by the poly (perfluoroalkylene ether) chain of the surface modifier.
前記加水分解性基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基;メトキシエトキシ基等のアルコキシ基置換アルコキシ基;アセトキシ基、プロピオニルオキシ基、ベンゾイルオキシ基等のアシルオキシ基;イソプロペニルオキシ基、イソブテニルオキシ基等のアルケニルオキシ基;ジメチルケトキシム基、メチルエチルケトキシム基、ジエチルケトキシム基、シクロヘキサンオキシム基等のイミンオキシ基;メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等の置換アミノ基;N−メチルアセトアミド基、N−エチルアミド基等のアミド基;ジメチルアミノオキシ基、ジエチルアミノオキシ基等の置換アミノオキシ基;塩素等のハロゲン等が挙げられる。加水分解性基の中でも、加水分解の速度が早く、迅速に防汚性とすべり性を兼ね備えながら、耐久性にも優れる被膜を形成することができることからアルコキシ基が好ましく、炭素原子数1〜6のアルコキシ基がより好ましく、炭素原子数1〜3のアルコキシ基が更に好ましく、メトキシ基、エトキシ基が特に好ましい。 Examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; an alkoxy group-substituted alkoxy group such as a methoxyethoxy group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; Alkenyloxy groups such as propenyloxy group and isobutenyloxy group; Imineoxy groups such as dimethylketoxime group, methylethylketoxime group, diethylketoxime group and cyclohexaneoxime group; methylamino group, ethylamino group, dimethylamino group, diethylamino group A substituted amino group such as a group; an amide group such as an N-methylacetamide group and an N-ethylamide group; a substituted aminooxy group such as a dimethylaminooxy group and a diethylaminooxy group; and a halogen such as chlorine. Among the hydrolyzable groups, an alkoxy group is preferable because it has a high hydrolysis rate and can form a coating with excellent durability while having both antifouling properties and slipperiness, and has 1 to 6 carbon atoms. Are more preferable, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.
前記非加水分解性基としては、例えば、炭素原子数1〜20のアルキル基、炭素原子数2〜20のアルケニル基、炭素原子数6〜20のアリール基又は炭素原子数7〜20のアラルキル基等が挙げられる。中でも、立体障害を避けて加水分解速度を早くでき、その結果、迅速に防汚性とすべり性を兼ね備えながら、耐久性にも優れる被膜を形成することができることから炭素原子数1〜3のアルキル基が好ましく、メチル基がより好ましい。 Examples of the non-hydrolyzable group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Etc. Among these, the hydrolysis rate can be increased by avoiding steric hindrance, and as a result, it is possible to form a film having excellent durability while having both antifouling properties and slip properties, so that alkyl having 1 to 3 carbon atoms can be formed. Group is preferred, and a methyl group is more preferred.
前記(A)3中の加水分解性基の数は前記の通り少なくとも一つであるが、より耐久性に優れる被膜が形成できる表面改質剤が得られることから二つ以上が好ましく、前記二つある(A)3中のAはすべて加水分解性基であることがより好ましい。つまり、非加水分解性基がないものが最も好ましい。The number of hydrolyzable groups in the (A) 3 is at least one as described above, but two or more are preferable because a surface modifier capable of forming a film having more durability can be obtained. It is more preferable that all A in (A) 3 are hydrolyzable groups. That is, those having no non-hydrolyzable group are most preferable.
前記(A)3中の加水分解性基を複数有する場合、該加水分解性基は同一のものであっても良いし、異なっていても良い。また、非加水分解性基を複数有する場合も、該非加水分解性基は同一のものであっても良いし、異なっていても良い。In the case of having a plurality of hydrolyzable groups in (A) 3 , the hydrolyzable groups may be the same or different. Moreover, also when it has two or more non-hydrolyzable groups, this non-hydrolyzable group may be the same and may differ.
前記一般式(1)中のZは2価の連結基である。Y1及びY2は、それぞれ直接結合または2価の連結基である。2価の連結基としては、例えば、炭素原子数1〜22のアルキレン基等が挙げられる。前記アルキレン基としては、例えば、メチレン基、エチレン基、n−プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、sec−ブチレン基、tert−ブチレン基、2,2−ジメチルプロピレン基、2−メチルブチレン基、2−メチル−2−ブチレン基、3−メチルブチレン基、3−メチル−2−ブチレン基、ペンチレン基、2−ペンチレン基、3−ペンチレン基、3−ジメチル−2−ブチレン基、3,3−ジメチルブチレン基、3,3−ジメチル−2−ブチレン基、2−エチルブチレン基、ヘキシレン基、2−ヘキシレン基、3−ヘキシレン基、2−メチルペンチレン基、2−メチル−2−ペンチレン基、2−メチル−3−ペンチレン基、3−メチルペンチレン基、3−メチル−2−ペンチレン基、3−メチル−3−ペンチレン基、4−メチルペンチレン基、4−メチル−2−ペンチレン基、2,2−ジメチル−3−ペンチレン基、2,3−ジメチル−3−ペンチレン基、2,4−ジメチル−3−ペンチレン基、4,4−ジメチル−2−ペンチレン基、3−エチル−3−ペンチレン基、ヘプチレン基、2−ヘプチレン基、3−ヘプチレン基、2−メチル−2−ヘキシレン基、2−メチル−3−ヘキシレン基、5−メチルヘキシレン基、5−メチル−2−ヘキシレン基、2−エチルヘキシレン基、6−メチル−2−ヘプチレン基、4−メチル−3−ヘプチレン基、オクチレン基、2−オクチレン基、3−オクチレン基、2−プロピルペンチレン基、2,4,4−トリメチルペンチレン基、デカオクチレン基等のアルキレン基等が挙げられる。Z in the general formula (1) is a divalent linking group. Y 1 and Y 2 are each a direct bond or a divalent linking group. As a bivalent coupling group, a C1-C22 alkylene group etc. are mentioned, for example. Examples of the alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, and 2-methyl. Butylene group, 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3 , 3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2- Pentylene group, 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pen Len group, 4-methylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene Group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3- Hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene And alkylene groups such as a group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group and decaoctylene group.
前記Zとしては、合成が容易で、簡便に本発明の表面改質剤を得ることができることから炭素原子数1〜10のアルキレン基が好ましく、炭素原子数1〜6のアルキレン基がより好ましく、1〜3のアルキレン基がさらに好ましく、n−プロピレン基が特に好ましい。 Z is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, since synthesis is easy and the surface modifier of the present invention can be easily obtained. 1-3 alkylene groups are more preferred, and an n-propylene group is particularly preferred.
また、Y1、Y2としては、フッ素原子の含有率が高くなり、より防汚性に優れる被膜が得られる表面改質剤となることからそれぞれ炭素原子数1〜6のアルキレン基が好ましく、それぞれ炭素原子数1〜3のアルキレン基がより好ましく、防汚性に優れ、工業的に得られやすい点で、それぞれメチレン基が更に好ましい。In addition, as Y 1 and Y 2 , an alkylene group having 1 to 6 carbon atoms is preferable because the content of fluorine atoms is high, and a surface modifier that provides a film with more excellent antifouling properties is obtained. An alkylene group having 1 to 3 carbon atoms is more preferable, and a methylene group is more preferable because it is excellent in antifouling property and easily obtained industrially.
前記一般式(1)中で二つあるZは、同一のものであっても良いし、異なっていても良い。また、本発明の表面改質剤は、それぞれ異なるZを有する改質剤の混合物となっていても良い。 Two Zs in the general formula (1) may be the same or different. The surface modifier of the present invention may be a mixture of modifiers having different Zs.
前記一般式(1)中のY1とY2は、同一のものであっても良いし、異なっていても良い。また、本発明の表面改質剤は、それぞれ異なるY1とY2を有する改質剤の混合物となっていても良い。Y 1 and Y 2 in the general formula (1) may be the same or different. The surface modifier of the present invention may be a mixture of modifiers having different Y 1 and Y 2 .
本発明の表面改質剤は、骨格中にウレタン結合を有する。このウレタン結合を有することにより、本発明の表面改質剤は両末端にある加水分解性基の近傍の極性が向上する。その結果、後述する基材、好ましくはガラス基材との付着性が良好になり、効率的に基材表面との反応が進行する。その結果、耐久性を有し、且つ、防汚性とすべり性にも優れる被膜を好適に物品上に形成することができる。 The surface modifier of the present invention has a urethane bond in the skeleton. By having this urethane bond, the surface modifier of the present invention improves the polarity in the vicinity of the hydrolyzable groups at both ends. As a result, the adhesion to a substrate described later, preferably a glass substrate, is improved, and the reaction with the substrate surface proceeds efficiently. As a result, a film having durability and excellent antifouling properties and slipperiness can be suitably formed on the article.
以下に、本発明の表面改質剤の具体例を示す。式中、PFPEはポリ(パーフルオロアルキレンエーテル)鎖を表す。 Below, the specific example of the surface modifier of this invention is shown. In the formula, PFPE represents a poly (perfluoroalkylene ether) chain.
本発明の表面改質剤が有するPFPE〔ポリ(パーフルオロアルキレンエーテル)鎖〕としては、例えば、炭素原子数1〜3のパーフルオロアルキレン基と酸素原子が交互に連結した構造を有するものを好ましく挙げることができる。炭素原子数1〜3のパーフルオロアルキレン基は、一種類であっても良いし複数種の混合であっても良く、具体的には、下記構造式1で表されるものが挙げられる。 As the PFPE [poly (perfluoroalkylene ether) chain] of the surface modifier of the present invention, for example, those having a structure in which perfluoroalkylene groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected are preferable. Can be mentioned. The perfluoroalkylene group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specific examples include those represented by the following structural formula 1.
前記Xとしては、例えば、下記に示す構造等を例示できる Examples of X include the structures shown below.
これらのなかでも、ポリ(パーフルオロアルキレンエーテル)鎖は、すべり性を発現する屈曲点となる酸素原子が多く存在すること、鎖の屈曲運動を阻害する枝分かれ構造がないことから、Xはパーフルオロメチレン基とパーフルオロエチレン基が好ましく、工業的に得られやすい点も含めると、パーフルオロメチレン基とパーフルオロエチレン基とが共存するものがとりわけ好ましい。また、前記パーフルオロメチレン基(a)とパーフルオロエチレン基(b)とが共存する場合、その存在比(a/b)(個数の比)は1/10〜10/1が好ましい。 Among these, the poly (perfluoroalkylene ether) chain has a large number of oxygen atoms that serve as bending points that exhibit slipperiness, and there is no branched structure that inhibits the bending movement of the chain. A methylene group and a perfluoroethylene group are preferable, and a compound in which a perfluoromethylene group and a perfluoroethylene group coexist is particularly preferable, including a point that can be easily obtained industrially. When the perfluoromethylene group (a) and the perfluoroethylene group (b) coexist, the abundance ratio (a / b) (number ratio) is preferably 1/10 to 10/1.
前記炭素原子数1〜3のパーフルオロアルキレン基を有する表面改質剤としては、例えば、下記構造式で表されるものを好ましく例示できる。 Preferred examples of the surface modifier having a perfluoroalkylene group having 1 to 3 carbon atoms include those represented by the following structural formula.
前記式(1−2−1)で表される表面改質剤は、炭素原子数1〜3のパーフルオロアルキレン基を有する。このように、短い鎖を有する事により、柔軟な骨格となり、その結果として、すべり性に優れる被膜を物品上に形成することができる。一般式(1)中のnは12〜200がより好ましく、30〜150がより好ましく、50〜120がさらに好ましい。 The surface modifier represented by the formula (1-2-1) has a perfluoroalkylene group having 1 to 3 carbon atoms. Thus, by having a short chain | strand, it becomes a flexible frame | skeleton, As a result, the film excellent in slip property can be formed on an article | item. As for n in General formula (1), 12-200 are more preferable, 30-150 are more preferable, and 50-120 are more preferable.
前記(1−2−1)で表される表面改質剤としては、例えば、下記式で表されるものを例示することができる。 As a surface modifier represented by said (1-2-1), what is represented by a following formula can be illustrated, for example.
前記ポリ(パーフルオロアルキレンエーテル)鎖は、汚れ拭き取り性とすべり性が優れる点からポリ(パーフルオロアルキレンエーテル)鎖1本に含まれるフッ素原子の合計が18〜600個の範囲であることが好ましく、90〜450個の範囲であることがさらに好ましく、150〜360個の範囲であることが特に好ましい。 The poly (perfluoroalkylene ether) chain preferably has a total of 18 to 600 fluorine atoms contained in one poly (perfluoroalkylene ether) chain from the viewpoint of excellent dirt wiping property and slipperiness. The range of 90 to 450 is more preferable, and the range of 150 to 360 is particularly preferable.
本発明の表面改質剤は、例えば、下記一般式(2) The surface modifier of the present invention is, for example, the following general formula (2)
前記一般式(2)中のY1、Y2、PFPE及び一般式(3)中のZ、Aは、前記一般式(1)中のものと同じである。Y 1 , Y 2 , PFPE in the general formula (2) and Z and A in the general formula (3) are the same as those in the general formula (1).
前記一般式(2)で表されるジオールとしては、例えば、下記に示すジオール等を例示する事ができる。 Examples of the diol represented by the general formula (2) include diols shown below.
前記一般式(2−1)、(2−2)の中でも、下記に示すジオールを好ましく例示できる。 Among the general formulas (2-1) and (2-2), diols shown below can be preferably exemplified.
前記一般式(3)で表されるイソシアネートとしては、例えば、下記に示すイソシアネート等を例示することができる。 As isocyanate represented by the said General formula (3), the isocyanate etc. which are shown below can be illustrated, for example.
前記式(3−1)〜(3−12)で表されるイソシアネート化合物中のZは、合成が容易で、簡便に本発明の表面改質剤を得ることができることから炭素原子数1〜10のアルキレン基が好ましく、炭素原子数1〜6のアルキレン基がより好ましく、1〜3のアルキレン基がさらに好ましく、n−プロピレン基が特に好ましい。 Z in the isocyanate compounds represented by the formulas (3-1) to (3-12) is easy to synthesize and can easily obtain the surface modifier of the present invention. An alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and an n-propylene group is particularly preferable.
前記一般式(2)であらわされるジオールと一般式(3)で表されるイソシアネートとを反応させる際には、前記一般式(2)に含まれるOH基1モルに対して、一般式(3)で表されるイソシアネートを、0.5〜1.5モルになるように仕込むのが好ましく、0.9〜1.1モルとなるように仕込むのがより好ましく、0.98〜1.02モルとなるように仕込むのが最も好ましい。 When the diol represented by the general formula (2) is reacted with the isocyanate represented by the general formula (3), the general formula (3) is added to 1 mol of the OH group contained in the general formula (2). ) Is preferably charged to 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol, and 0.98 to 1.02. Most preferably, it is charged so as to be a mole.
前記一般式(2)であらわされるジオールと一般式(3)で表されるイソシアネートとの反応(ウレタン化反応)においては、前記一般式(2)であらわされるジオールと一般式(3)で表されるイソシアネートとの反応を促進させるために、例えばトリエチルアミン、ベンジルジメチルアミン等の第3級アミン類、ジブチル錫ジラウリレート、ジオクチル錫ジラウリレート、2−エチルヘキサン酸錫等の錫化合物を触媒として用いて行うことができる。 In the reaction of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3) (urethanization reaction), the diol represented by the general formula (2) and the general formula (3) are used. In order to accelerate the reaction with the isocyanate produced, for example, a tertiary amine such as triethylamine or benzyldimethylamine, a tin compound such as dibutyltin dilaurate, dioctyltin dilaurate or tin 2-ethylhexanoate is used as a catalyst. be able to.
前記触媒の添加量は、反応混合物全体に対して0.001〜5.0質量%が好ましく、より好ましくは0.01〜1.0質量%で、更に好ましくは0.02〜0.2質量%である。反応時間は1〜10時間が好ましい。また反応温度は30〜120℃が好ましく、より好ましくは40〜90℃である。 The amount of the catalyst added is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.02 to 0.2% by mass with respect to the entire reaction mixture. %. The reaction time is preferably 1 to 10 hours. Moreover, 30-120 degreeC of reaction temperature is preferable, More preferably, it is 40-90 degreeC.
一般式(2)であらわされるジオールと一般式(3)で表されるイソシアネートとの反応(ウレタン化反応)を行う際は、反応系は無溶剤系であっても良いし、イソシアネート基に不活性なアセトン、メチルエチルケトン、トルエン、キシレン等の溶剤やフッ素系の溶剤を反応溶剤とした溶剤系であっても良い。 When the reaction of the diol represented by the general formula (2) and the isocyanate represented by the general formula (3) (urethanization reaction) is performed, the reaction system may be a solvent-free system, and the isocyanate group may not be used. A solvent system using a solvent such as active acetone, methyl ethyl ketone, toluene, xylene, or a fluorine-based solvent as a reaction solvent may be used.
本発明のコーティング組成物は、本発明の表面改質剤と溶剤とを含有することを特徴とする。前記溶剤としては、フッ素原子を含有する溶剤が、本発明の表面改質剤を良好に溶解できることから好ましく使用することができる。 The coating composition of the present invention contains the surface modifier of the present invention and a solvent. As the solvent, a solvent containing a fluorine atom can be preferably used because it can dissolve the surface modifier of the present invention well.
前記フッ素原子を含有する溶剤としては、例えば、ハイドロフルオロエーテル、ハイドロフルオロカーボン及びパーフルオロカーボン等が挙げられる。フッ素原子を含有する溶剤は直鎖状、分岐状、環状のいずれであってもよく、ヘテロ原子を含有してもよい。また、フッ素原子を含有する溶剤の炭素原子数は2〜12が好ましく、4〜10がより好ましい。 Examples of the solvent containing a fluorine atom include hydrofluoroether, hydrofluorocarbon, perfluorocarbon, and the like. The solvent containing a fluorine atom may be linear, branched or cyclic, and may contain a hetero atom. Moreover, 2-12 are preferable and, as for the carbon atom number of the solvent containing a fluorine atom, 4-10 are more preferable.
前記ハイドロフルオロエーテルとしては、例えば、C3F7OCH3、C4F9OCH3、C4F9OC2H5、C2F5CF(OCH3)C3F7、HCF2CF2OCH2CF3等が挙げられる。前記ハイドロフルオロカーボンとしては、例えば、C4F9C2H5、(CF3)2CFCHFCHFCF3、C6F13H、C6F13C2H5、C8F17C2H5、CF3(CF2)4CHF2、CF3CH2CF2CH3、CF3(CHF)2CF2CF3等が挙げられる。As the hydrofluoroether, for example, C 3 F 7 OCH 3, C 4 F 9 OCH 3, C 4 F 9 OC 2
前記パーフルオロカーボンとしては、例えば、C3F8、C4F10,C5F12、C6F14、C7F16,C8F18、C9F20,C10F22、C11F24、C12F26、(C4F9)3N、パーフルオロ(1,2−ジメチルシクロブタン)、パーフルオロ(メチルシクロヘキサン)、パーフルオロ(2−ブチルテトラヒドロフラン)等が挙げられる。 Examples of the perfluorocarbon include C 3 F 8 , C 4 F 10 , C 5 F 12 , C 6 F 14 , C 7 F 16 , C 8 F 18 , C 9 F 20 , C 10 F 22 , and C 11. Examples thereof include F 24 , C 12 F 26 , (C 4 F 9 ) 3 N, perfluoro (1,2-dimethylcyclobutane), perfluoro (methylcyclohexane), perfluoro (2-butyltetrahydrofuran) and the like.
前記フッ素原子を含有する溶剤の中でも、C4F9C2H5、(CF3)2CFCHFCHFCF3、C6F13H、C6F13C2H5、C4F9OCH3、C4F9OC2H5、C2F5CF(OCH3)C3F7及びHCF2CF2OCH2CF3からなる群から選ばれる1種以上であることが好ましい。Among the solvents containing fluorine atoms, C 4 F 9 C 2 H 5 , (CF 3 ) 2 CFCHFCHFCF 3 , C 6 F 13 H, C 6 F 13 C 2 H 5 , C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5, C 2
本発明のコーティング組成物中の表面改質剤の含有率としては、表面改質剤を含む被覆が均一に形成でき、且つ、該表面改質剤とガラス等の基材に良好に反応することにより、耐久性に優れる被膜が形成できることから0.01〜50質量%が好ましく、0.02〜10質量%がより好ましく、0.05〜1質量%がさらに好ましい。 As the content of the surface modifier in the coating composition of the present invention, a coating containing the surface modifier can be uniformly formed, and the surface modifier and the substrate such as glass react well. Therefore, 0.01 to 50% by mass is preferable, 0.02 to 10% by mass is more preferable, and 0.05 to 1% by mass is even more preferable.
本発明の物品は、基材上に本発明のコーティング組成物の被膜を有することを特徴とする。前記基材としては、ガラス等の無機基材;アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリブチレンテレフタレート樹脂、ポリプロピレン樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリ塩化ビニル樹脂、ポリフッ化ビニル樹脂等の有機基材等が挙げられる。 The article of the present invention is characterized by having a coating of the coating composition of the present invention on a substrate. Examples of the substrate include inorganic substrates such as glass; organic substrates such as acrylic resin, polycarbonate resin, polyester resin, polybutylene terephthalate resin, polypropylene resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, and polyvinyl fluoride resin. Etc.
本発明で用いる基材としては、本発明のコーティング組成物中の表面改質剤が良好に反応し、基材上に防汚性とすべり性に優れ、しかも耐久性を有する被膜を形成することができることから、ガラス基材が好ましい。 As the base material used in the present invention, the surface modifier in the coating composition of the present invention reacts satisfactorily to form a film having excellent antifouling property and slipperiness and durability on the base material. Therefore, a glass substrate is preferable.
本発明で用いる基材の形状としては、種々の形状のものを使用することが出来る。中でも、シート状のものが好適に使用することができる。シート状の基材の厚さは、例えば、5μm〜800μmの範囲のものを例示できる。 As the shape of the substrate used in the present invention, various shapes can be used. Especially, a sheet-like thing can be used conveniently. The thickness of a sheet-like base material can illustrate the thing of the range of 5 micrometers-800 micrometers, for example.
前記基材上に本発明のコーティング組成物の被膜を形成させる方法としては、種々の方法を用いることができる。具体的には、例えば、浸漬コーティング法、スピンコーティング法、フローコーティング法、スプレーコーティング法、ロールコーティング法、グラビアコーティング法、蒸着法等を例示できる。 Various methods can be used as a method of forming the coating composition of the present invention on the substrate. Specific examples include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and vapor deposition.
本発明の表面改質剤やコーティング組成物は、物品表面に防汚性とすべり性に優れる被膜を形成することができる。このような優れた効果を利用して、本発明の表面改質剤やコーティング組成物は指先が画面に直接接触し、しかも、指先やペン先で画面をなぞる(スライドさせる)操作(スワイプ)を行うスマートフォンやタブレットPCの画面の最表面の被膜形成に特に好ましく用いることができる。 The surface modifier and coating composition of the present invention can form a film having excellent antifouling properties and slipperiness on the surface of an article. Utilizing such excellent effects, the surface modifying agent or coating composition of the present invention allows the fingertip to directly touch the screen, and to perform an operation (swipe) for tracing (sliding) the screen with the fingertip or the pen tip. It can be particularly preferably used for film formation on the outermost surface of the screen of a smartphone or tablet PC to be performed.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。例中、断りのない限り、「部」、「%」は質量基準である。尚、得られた表面改質剤のIRスペクトル、1H−NMRスペクトル及び19F−NMRスペクトルの測定条件は下記の通りである。Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “part” and “%” are based on mass unless otherwise specified. In addition, the measurement conditions of IR spectrum of the obtained surface modifier, < 1 > H-NMR spectrum, and 19 F-NMR spectrum are as follows.
[IRスペクトル測定条件]
装置:日本分光株式会社製「FT/IR−6100」
測定方法:KBr法[IR spectrum measurement conditions]
Apparatus: “FT / IR-6100” manufactured by JASCO Corporation
Measuring method: KBr method
[1H−NMRスペクトル、19F−NMRスペクトルの測定条件]
装置:日本電子株式会社製「JNM−ECA500」
溶媒:重水素化クロロホルム[Measurement conditions for 1 H-NMR spectrum and 19 F-NMR spectrum]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: deuterated chloroform
実施例1(表面改質剤の調製)
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、下記式(2−1−1)で表されるポリ(パーフルオロアルキレンエーテル)鎖を有するジオール88.9gとウレタン化触媒としてオクチル酸スズ0.05gを仕込み、窒素気流下で攪拌を開始し、60℃を保ちながら3−イソシアナトプロピルトリエトキシシラン11.1gを15分間かけて滴下した。滴下終了後、60℃で1時間攪拌した後、更に80℃に昇温して2時間攪拌することにより前記ジオールと3−イソシアナトプロピルトリエトキシシランとを反応させ、反応物を得た。その後、この反応物についてIRスペクトル測定を行い、反応物中のイソシアネート基の消失を確認した。得られた反応物を孔径0.2μmのPTFEフィルターを使用してろ過精製し、一般式(1)で表される本発明の表面改質剤(1)を得た。ここで、表面改質剤(1)は、一般式(1)において、Aはエトキシ基であり、Zはn−プロピレン基であり、Y1、Y2はメチレン基である。Example 1 (Preparation of surface modifier)
As a urethanization catalyst and 88.9 g of a diol having a poly (perfluoroalkylene ether) chain represented by the following formula (2-1-1) in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. 0.05 g of tin octylate was charged, stirring was started under a nitrogen stream, and 11.1 g of 3-isocyanatopropyltriethoxysilane was added dropwise over 15 minutes while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, and further heated to 80 ° C. and stirred for 2 hours to react the diol with 3-isocyanatopropyltriethoxysilane to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain the surface modifier (1) of the present invention represented by the general formula (1). Here, in the general formula (1), the surface modifier (1) is an ethoxy group, Z is an n-propylene group, and Y 1 and Y 2 are methylene groups.
なお、表面改質剤(1)のIRスペクトルのチャート図を図1に、1H−NMRスペクトルのチャート図を図2に、19F−NMRスペクトルのチャート図を図3に示す。In addition, the chart of the IR spectrum of the surface modifier (1) is shown in FIG. 1, the chart of the 1 H-NMR spectrum is shown in FIG. 2, and the chart of the 19 F-NMR spectrum is shown in FIG.
実施例2(同上)
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、上記式(2−1−1)で表されるポリ(パーフルオロアルキレンエーテル)鎖を有するジオール45.3gとウレタン化触媒としてオクチル酸スズ0.025gを仕込み、窒素気流下で攪拌を開始し、60℃を保ちながら3−イソシアナトプロピルトリメトキシシラン4.7gを15分間かけて滴下した。滴下終了後、60℃で1時間攪拌した後、更に80℃に昇温して2時間攪拌することにより前記ジオールと3−イソシアナトプロピルトリメトキシシランとを反応させ、反応物を得た。その後、この反応物についてIRスペクトル測定を行い、反応物中のイソシアネート基の消失を確認した。得られた反応物を孔径0.2μmのPTFEフィルターを使用してろ過精製し、一般式(1)で表される本発明の表面改質剤(2)を得た。ここで、表面改質剤(2)は、一般式(1)において、Aはメトキシ基であり、Zはn−プロピレン基であり、Y1、Y2はメチレン基である。式(2−1−1)中のXはパーフルオロメチレン基及びパーフルオロエチレン基であり、1分子あたり、パーフルオロメチレン基が平均21個、パーフルオロエチレン基が平均21個存在するものであり、フッ素原子の数が平均126である。Example 2 (same as above)
As a urethanization catalyst and 45.3 g of a diol having a poly (perfluoroalkylene ether) chain represented by the above formula (2-1-1) in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. Stirring under a nitrogen stream was started with 0.025 g of tin octylate, and 4.7 g of 3-isocyanatopropyltrimethoxysilane was added dropwise over 15 minutes while maintaining 60 ° C. After completion of the dropping, the mixture was stirred at 60 ° C. for 1 hour, further heated to 80 ° C. and stirred for 2 hours to react the diol with 3-isocyanatopropyltrimethoxysilane to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain the surface modifier (2) of the present invention represented by the general formula (1). Here, in the general formula (1), the surface modifier (2) is A is a methoxy group, Z is an n-propylene group, and Y 1 and Y 2 are methylene groups. X in the formula (2-1-1) represents a perfluoromethylene group and a perfluoroethylene group, and an average of 21 perfluoromethylene groups and an average of 21 perfluoroethylene groups exist per molecule. The average number of fluorine atoms is 126.
実施例3(同上)
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、上記式(2−1−1)で表されるポリ(パーフルオロアルキレンエーテル)鎖を有するジオール54.99gと含フッ素溶剤C4F9OC2H540gとウレタン化触媒としてオクチル酸スズ0.03gを仕込み、窒素気流下で攪拌を開始し、50℃を保ちながら3−イソシアナトプロピルトリエトキシシラン5.01gを15分間かけて滴下した。滴下終了後、50℃で18時間攪拌することにより前記ジオールと3−イソシアナトプロピルトリエトキシシランとを反応させ、反応物を得た。その後、この反応物についてIRスペクトル測定を行い、反応物中のイソシアネート基の消失を確認した。得られた反応物を孔径0.2μmのPTFEフィルターを使用してろ過精製し、一般式(1)で表される本発明の表面改質剤(3)の含フッ素溶剤溶液を得た。ここで、表面改質剤(3)は、一般式(1)において、Aはエトキシ基であり、Zはn−プロピレン基であり、Y1、Y2はメチレン基である。式(2−1−1)中のXはパーフルオロメチレン基及びパーフルオロエチレン基であり、1分子あたり、パーフルオロメチレン基が平均30個、パーフルオロエチレン基が平均30個存在するものであり、フッ素原子の数が平均180である。Example 3 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 54.99 g of a diol having a poly (perfluoroalkylene ether) chain represented by the above formula (2-1-1) and a fluorinated solvent C 4 F 9 OC 2 H 5 40 g and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and 5.01 g of 3-isocyanatopropyltriethoxysilane was maintained for 15 minutes while maintaining 50 ° C. It was dripped over. After completion of the dropping, the diol and 3-isocyanatopropyltriethoxysilane were reacted by stirring at 50 ° C. for 18 hours to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was filtered and purified using a PTFE filter having a pore size of 0.2 μm to obtain a fluorine-containing solvent solution of the surface modifier (3) of the present invention represented by the general formula (1). Here, in the general formula (1), the surface modifier (3) is an ethoxy group, Z is an n-propylene group, and Y 1 and Y 2 are methylene groups. X in formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and an average of 30 perfluoromethylene groups and an average of 30 perfluoroethylene groups are present per molecule. The average number of fluorine atoms is 180.
実施例4(同上)
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、上記式(2−1−1)で表されるポリ(パーフルオロアルキレンエーテル)鎖を有するジオール55.79gと含フッ素溶剤C4F9OC2H540gとウレタン化触媒としてオクチル酸スズ0.03gを仕込み、窒素気流下で攪拌を開始し、50℃を保ちながら3−イソシアナトプロピルトリメトキシシラン4.12gを15分間かけて滴下した。滴下終了後、50℃で18時間攪拌することにより前記ジオールと3−イソシアナトプロピルトリメトキシシランとを反応させ、反応物を得た。その後、この反応物についてIRスペクトル測定を行い、反応物中のイソシアネート基の消失を確認した。得られた反応物を孔径0.2μmのPTFEフィルターを使用してろ過精製し、一般式(1)で表される本発明の表面改質剤(4)の含フッ素溶剤溶液を得た。ここで、表面改質剤(4)は、一般式(1)において、Aはメトキシ基であり、Zはn−プロピレン基であり、Y1、Y2はメチレン基である。式(2−1−1)中のXはパーフルオロメチレン基及びパーフルオロエチレン基であり、1分子あたり、パーフルオロメチレン基が平均30個、パーフルオロエチレン基が平均30個存在するものであり、フッ素原子の数が平均180である。Example 4 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 55.79 g of a diol having a poly (perfluoroalkylene ether) chain represented by the above formula (2-1-1) and a fluorinated solvent C 40 F of 4 F 9 OC 2 H 5 and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and 4.12 g of 3-isocyanatopropyltrimethoxysilane was maintained for 15 minutes while maintaining 50 ° C. It was dripped over. After completion of the dropwise addition, the diol was reacted with 3-isocyanatopropyltrimethoxysilane by stirring at 50 ° C. for 18 hours to obtain a reaction product. Then, IR spectrum measurement was performed about this reaction material, and the loss | disappearance of the isocyanate group in a reaction material was confirmed. The obtained reaction product was purified by filtration using a PTFE filter having a pore size of 0.2 μm to obtain a fluorine-containing solvent solution of the surface modifier (4) of the present invention represented by the general formula (1). Here, in the general formula (1), the surface modifier (4) is A is a methoxy group, Z is an n-propylene group, and Y 1 and Y 2 are methylene groups. X in formula (2-1-1) is a perfluoromethylene group and a perfluoroethylene group, and an average of 30 perfluoromethylene groups and an average of 30 perfluoroethylene groups are present per molecule. The average number of fluorine atoms is 180.
実施例5(コーティング組成物及び物品の調製)
表面改質剤(1)をフッ素原子含有溶剤であるC4F9OC2H5に0.1%の濃度となるように添加し、本発明のコーティング組成物(1)を得た。コーティング組成物(1)に、洗浄したガラス基板を1分間浸漬した。1分後、ガラス板をコーティング組成物(1)から取り出し、ガラス板を湿度90%、60℃で1時間乾燥させてガラス板表面にコーティング組成物の被膜を有する物品(1)を得た。Example 5 (Preparation of coating compositions and articles)
The surface modifier (1) was added to C 4 F 9 OC 2 H 5 which is a fluorine atom-containing solvent so as to have a concentration of 0.1% to obtain a coating composition (1) of the present invention. The washed glass substrate was immersed in the coating composition (1) for 1 minute. After 1 minute, the glass plate was taken out of the coating composition (1), and the glass plate was dried at 90% humidity and 60 ° C. for 1 hour to obtain an article (1) having a coating composition coating on the glass plate surface.
得られた物品(1)を用いて、下記方法に従って物品表面の撥水撥油性、すべり性、汚れ付着防止性及び汚れ付着防止性の耐久性の評価を行った。評価結果を第1表に示す。 Using the obtained article (1), durability of water / oil repellency, slipperiness, dirt adhesion prevention and dirt adhesion prevention on the article surface was evaluated according to the following method. The evaluation results are shown in Table 1.
<物品表面の撥水撥油性の評価方法>
水及びn−ドデカンの接触角を測定することにより評価した。接触角の測定は、接触角測定装置(協和界面科学株式会社製「MODEL CA−W150」)を用いた。接触角が高いほど、撥水撥油性に優れる。<Evaluation method of water and oil repellency on article surface>
Evaluation was made by measuring the contact angles of water and n-dodecane. The contact angle was measured using a contact angle measuring device (“MODEL CA-W150” manufactured by Kyowa Interface Science Co., Ltd.). The higher the contact angle, the better the water and oil repellency.
<物品表面のすべり性の評価方法>
表面性測定機(新東科学株式会社製「HEIDON−14D」を用いて、サンプル台に物品(1)を固定して水平を確認後、サンプル上にプローブをセットし、100g荷重にて、引張り速度0.3m/分の条件で測定を行い、動摩擦係数を求めた。動摩擦係数が低いほど、すべり性に優れる。<Evaluation method of slipperiness of article surface>
Using a surface property measuring instrument ("HEIDON-14D" manufactured by Shinto Kagaku Co., Ltd.), fix the article (1) on the sample table and check the level, then set the probe on the sample and pull it with 100g load. The dynamic friction coefficient was determined by measuring at a speed of 0.3 m / min, and the lower the dynamic friction coefficient, the better the sliding property.
<物品表面の汚れ付着防止性の評価方法>
物品(1)の表面に、油性フェルトペン(寺西化学工業株式会社製マジックインキ大型黒色)で線を描き、その黒色インクの付着状態を目視で観察した。なお、評価基準は下記の通りである。評価結果はA>B>C>Dの順で良好である。
A:黒色インクが玉状にはじく。
B:インクが玉状にはじかず、線状のはじきが生じ、かつ、線幅がフェルトペンのペン先の幅の50%未満。
C:インクが玉状にはじかず、線状のはじきが生じ、かつ、線幅がフェルトペンのペン先の幅の50%以上100%未満であったもの。
D:インクがまったくはじかずに表面にきれいに描けてしまうもの。<Evaluation method of antifouling property on article surface>
A line was drawn on the surface of the article (1) with an oil-based felt pen (Magic ink large black, manufactured by Teranishi Chemical Co., Ltd.), and the adhesion state of the black ink was visually observed. The evaluation criteria are as follows. The evaluation results are good in the order of A>B>C> D.
A: Black ink repels.
B: The ink does not repel, the linear repelling occurs, and the line width is less than 50% of the width of the pen tip of the felt pen.
C: The ink did not repel, the line repelled, and the line width was 50% or more and less than 100% of the width of the pen tip of the felt pen.
D: The ink can be drawn cleanly on the surface without repelling at all.
<汚れ付着防止性の耐久性の評価方法>
上記「物品表面の汚れ付着防止性の評価方法」において、マジックをふき取り後、再度物品表面の汚れ付着防止性の評価試験をして、はじかなくなるまで(上記評価で「D」と評価されるまで)何回物品表面の汚れ付着防止性の試験ができるか評価した。評価結果はA>B>C>Dの順で良好である。
A:汚れ付着防止性の試験を10回以上繰り返しできる。
B:汚れ付着防止性の試験を5〜9回繰り返しできる。
C:汚れ付着防止性の試験を1〜4回繰り返しできる。
D:汚れ付着防止性の試験を1も繰り返しできない。<Durability evaluation method for dirt adhesion prevention>
In the above “evaluation method of anti-smudge property on article surface”, after wiping off the magic, the evaluation test for anti-smudge property on the article surface is performed again until it does not repel (until it is evaluated as “D” in the above evaluation). ) It was evaluated how many times the surface of the article could be tested to prevent soil adhesion. The evaluation results are good in the order of A>B>C> D.
A: The soil adhesion prevention test can be repeated 10 times or more.
B: The soil adhesion prevention test can be repeated 5 to 9 times.
C: The soil adhesion prevention test can be repeated 1 to 4 times.
D: The soil adhesion prevention test cannot be repeated by one.
実施例6〜8(同上)
第1表に示す表面改質剤を用いた以外は実施例5と同様にしてコーティング組成物(2)〜(4)及び物品(2)〜(4)を得た。実施例5と同様にして撥水撥油性、すべり性及び汚れ付着防止性を評価した。評価結果を第1表に示す。Examples 6 to 8 (same as above)
Coating compositions (2) to (4) and articles (2) to (4) were obtained in the same manner as in Example 5 except that the surface modifier shown in Table 1 was used. In the same manner as in Example 5, the water and oil repellency, the slip property, and the antifouling property were evaluated. The evaluation results are shown in Table 1.
比較例1(比較対照用コーティング組成物及び比較対照用物品の調製)
表面改質剤(1)の代わりに特開2012−037896の合成例1に記載の表面改質剤〔CF3CF2CF2(OCF2CF2CF2)11OCF2CF2CH2OCH2CH2CH2Si(OCH3)3〕〔比較対照用表面改質剤(1´)〕を用いた以外は実施例5と同様にして比較対照用コーティング組成物(1´)及び比較対照用物品(1´)を得た。実施例5と同様にして撥水撥油性、すべり性、汚れ付着防止性及び汚れ付着防止性の耐久性の評価を評価した。評価結果を第1表に示す。Comparative Example 1 (Preparation of Comparative Coating Composition and Comparative Article)
Instead of the surface modifier (1), the surface modifier [CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) 11 OCF 2 CF 2 CH 2 OCH 2 described in Synthesis Example 1 of JP2012-037896A CH 2 CH 2 Si (OCH 3 ) 3 ] [surface modifier for comparison control (1 ′)], except that a comparative coating composition (1 ′) and comparison control were used in the same manner as in Example 5. Article (1 ') was obtained. In the same manner as in Example 5, evaluation of durability of water / oil repellency, slipperiness, stain adhesion prevention property and stain adhesion prevention property was evaluated. The evaluation results are shown in Table 1.
Claims (13)
で表される表面改質剤と溶剤とを含有するコーティング組成物であり、該コーティング組成物中の該表面改質剤の含有率が0.05〜1質量%であることを特徴とするコーティング組成物。 The following general formula (1)
A coating composition comprising a surface modifier represented by the formula (1) and a solvent, wherein the coating composition is characterized in that the content of the surface modifier in the coating composition is 0.05 to 1% by mass. Composition.
で表されるものである請求項1記載のコーティング組成物。 The surface modifier is represented by the following general formula (1-2-1)
The coating composition according to claim 1, which is represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015525323A JP5846466B1 (en) | 2014-01-31 | 2015-01-29 | Surface modifier, coating composition and article |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014017058 | 2014-01-31 | ||
JP2014017058 | 2014-01-31 | ||
PCT/JP2015/052464 WO2015115522A1 (en) | 2014-01-31 | 2015-01-29 | Surface modifier, coating composition, and article |
JP2015525323A JP5846466B1 (en) | 2014-01-31 | 2015-01-29 | Surface modifier, coating composition and article |
Publications (2)
Publication Number | Publication Date |
---|---|
JP5846466B1 true JP5846466B1 (en) | 2016-01-20 |
JPWO2015115522A1 JPWO2015115522A1 (en) | 2017-03-23 |
Family
ID=53757094
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015525323A Active JP5846466B1 (en) | 2014-01-31 | 2015-01-29 | Surface modifier, coating composition and article |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5846466B1 (en) |
KR (1) | KR102338699B1 (en) |
CN (1) | CN105940077B (en) |
TW (1) | TWI655226B (en) |
WO (1) | WO2015115522A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6780224B2 (en) * | 2015-07-28 | 2020-11-04 | Dic株式会社 | Coating compositions and articles |
US10544260B2 (en) | 2017-08-30 | 2020-01-28 | Ppg Industries Ohio, Inc. | Fluoropolymers, methods of preparing fluoropolymers, and coating compositions containing fluoropolymers |
CN112578054B (en) * | 2020-12-28 | 2022-10-25 | 四川微谱检测技术有限公司 | Method for detecting dioxin in medical waste incineration waste gas |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05279499A (en) * | 1991-11-20 | 1993-10-26 | Asahi Glass Co Ltd | Surface treated substrate |
JP2003238577A (en) * | 2001-10-05 | 2003-08-27 | Shin Etsu Chem Co Ltd | Perfluoropolyether-modified silane, surface treating agent and antireflection filter |
JP2004330664A (en) * | 2003-05-09 | 2004-11-25 | Hitachi Ltd | Article with water-repellent film and its manufacturing method |
WO2009101986A1 (en) * | 2008-02-12 | 2009-08-20 | Fujifilm Corporation | Fluorine-containing polyfunctional silicon compound and method for producing fluorine-containing polyfunctional silicon compound |
JP2011528663A (en) * | 2008-07-18 | 2011-11-24 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated ether silane and method of using the same |
JP2012037896A (en) * | 2005-04-01 | 2012-02-23 | Daikin Ind Ltd | Surface modifier |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000282009A (en) * | 1999-04-01 | 2000-10-10 | Toray Ind Inc | Antistaining composition and optical article having antistaining property |
US6716534B2 (en) * | 2001-11-08 | 2004-04-06 | 3M Innovative Properties Company | Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof |
US7803894B2 (en) * | 2003-12-05 | 2010-09-28 | 3M Innovatie Properties Company | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
US7652117B2 (en) * | 2007-06-20 | 2010-01-26 | 3M Innovative Properties Company | Fluorochemical urethane compounds and aqueous compositions thereof |
US7897678B2 (en) * | 2007-07-26 | 2011-03-01 | 3M Innovative Properties Company | Fluorochemical urethane compounds having pendent silyl groups |
EP2203516B1 (en) * | 2007-10-01 | 2013-10-23 | 3M Innovative Properties Company | Compositions comprising cationic fluorinated ether-silanes, and related methods |
-
2015
- 2015-01-29 TW TW104102949A patent/TWI655226B/en active
- 2015-01-29 CN CN201580006609.2A patent/CN105940077B/en active Active
- 2015-01-29 KR KR1020167018375A patent/KR102338699B1/en active IP Right Grant
- 2015-01-29 JP JP2015525323A patent/JP5846466B1/en active Active
- 2015-01-29 WO PCT/JP2015/052464 patent/WO2015115522A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05279499A (en) * | 1991-11-20 | 1993-10-26 | Asahi Glass Co Ltd | Surface treated substrate |
JP2003238577A (en) * | 2001-10-05 | 2003-08-27 | Shin Etsu Chem Co Ltd | Perfluoropolyether-modified silane, surface treating agent and antireflection filter |
JP2004330664A (en) * | 2003-05-09 | 2004-11-25 | Hitachi Ltd | Article with water-repellent film and its manufacturing method |
JP2012037896A (en) * | 2005-04-01 | 2012-02-23 | Daikin Ind Ltd | Surface modifier |
WO2009101986A1 (en) * | 2008-02-12 | 2009-08-20 | Fujifilm Corporation | Fluorine-containing polyfunctional silicon compound and method for producing fluorine-containing polyfunctional silicon compound |
JP2011528663A (en) * | 2008-07-18 | 2011-11-24 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated ether silane and method of using the same |
Also Published As
Publication number | Publication date |
---|---|
KR102338699B1 (en) | 2021-12-14 |
CN105940077A (en) | 2016-09-14 |
TWI655226B (en) | 2019-04-01 |
TW201538566A (en) | 2015-10-16 |
WO2015115522A1 (en) | 2015-08-06 |
KR20160114583A (en) | 2016-10-05 |
JPWO2015115522A1 (en) | 2017-03-23 |
CN105940077B (en) | 2018-05-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6524955B2 (en) | Fluoropolyether group-containing polymer modified silane, surface treating agent and article | |
TWI656145B (en) | Fluorinated polyether-containing polymer denatured decane, surface treatment agent and articles | |
JP6274083B2 (en) | Water- and oil-repellent treatment agent having heat resistance, method for producing the same, and article | |
JP6319143B2 (en) | Fluorine-containing coating agent and article treated with the coating agent | |
KR20120120012A (en) | Polymer composition containing fluoroxyalkylene group, surface treatment agent comprising said composition, and articles treated with said surface treatment agent | |
JP6544570B2 (en) | Surface modifier, coating composition and article | |
CN108699237B (en) | Polymer-modified silane containing fluoropolyether group, surface treatment agent and article | |
JPWO2017212850A1 (en) | Fluoropolyether group-containing polymer, surface treatment agent and article | |
KR102601067B1 (en) | Fluorine-containing coating composition and surface treatment agent and article containing the composition | |
KR20160030445A (en) | Fluorinated coating composition and article treated with said coating composition | |
JP5846466B1 (en) | Surface modifier, coating composition and article | |
JP6808913B2 (en) | Coating compositions and articles | |
KR20220163441A (en) | Surface treatment agents and articles containing fluoropolyether group-containing polymers and/or partial (hydrolysis) condensates thereof | |
KR20150130237A (en) | Fluorinated coating composition and article treated with said coating composition | |
JP7318735B2 (en) | Fluoropolyether group-containing polymer, surface treatment agent and article | |
KR20140045885A (en) | Surface treatment method and surface-treated article | |
JP6780224B2 (en) | Coating compositions and articles | |
JP2017008261A (en) | Surface modifier, coating composition and article | |
JP2017008240A (en) | Surface modifier, coating composition and article | |
JP6926659B2 (en) | Fluorine compounds, surface modifiers, coating compositions and articles | |
JP2017031348A (en) | Coating composition and article | |
KR20220019104A (en) | Fluoropolyether group-containing polymer and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20151029 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151111 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 5846466 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |