JP7408250B2 - Fluoropolyether group-containing polymer compositions, coating agents and articles - Google Patents
Fluoropolyether group-containing polymer compositions, coating agents and articles Download PDFInfo
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- JP7408250B2 JP7408250B2 JP2020167157A JP2020167157A JP7408250B2 JP 7408250 B2 JP7408250 B2 JP 7408250B2 JP 2020167157 A JP2020167157 A JP 2020167157A JP 2020167157 A JP2020167157 A JP 2020167157A JP 7408250 B2 JP7408250 B2 JP 7408250B2
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- 229920000642 polymer Polymers 0.000 title claims description 102
- 239000000203 mixture Substances 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title claims description 38
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- -1 hydroxysilyl group Chemical group 0.000 claims description 22
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 15
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000010408 film Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 238000005299 abrasion Methods 0.000 description 16
- 230000003373 anti-fouling effect Effects 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 3
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical group FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000006116 anti-fingerprint coating Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 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 2
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 2
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- AQZYBQIAUSKCCS-UHFFFAOYSA-N perfluorotripentylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AQZYBQIAUSKCCS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyethers (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、フルオロポリエーテル基含有ポリマー（１価のフルオロオキシアルキレン基含有ポリマー残基を分子内に有する化合物）組成物に関し、詳細には、撥水撥油性、摩耗耐久性に優れ、適度なすべり性を有する被膜を形成するフルオロポリエーテル基含有ポリマー組成物、及びコーティング剤、並びに該コーティング剤により形成される層を有する物品に関する。 The present invention relates to a fluoropolyether group-containing polymer (a compound having a monovalent fluorooxyalkylene group-containing polymer residue in the molecule) composition, and in particular, it has excellent water and oil repellency, wear resistance, and moderate The present invention relates to a fluoropolyether group-containing polymer composition that forms a film having slipperiness, a coating agent, and an article having a layer formed from the coating agent.
フルオロポリエーテル基含有ポリマーは、金属、磁器、ガラス、プラスチック等の基材の表面に塗布・硬化されると、該基材の表面に撥水撥油層（防汚コーティング薄膜層）を形成して、油脂汚れ、指紋汚れ、その他の汚れを防止する性能を該基材に付加する。すなわち、該フルオロポリエーテル基含有ポリマーは、携帯用電子機器端末のタッチパネルディスプレイ表面や、端末の筐体表面等に防汚コーティング薄膜層を形成するために使用されている（特許文献１～６）。 When a fluoropolyether group-containing polymer is applied and cured on the surface of a base material such as metal, porcelain, glass, or plastic, it forms a water- and oil-repellent layer (a thin antifouling coating layer) on the surface of the base material. , oil stains, fingerprint stains, and other stains are added to the base material. That is, the fluoropolyether group-containing polymer is used to form an antifouling coating thin film layer on the touch panel display surface of a portable electronic device terminal, the terminal housing surface, etc. (Patent Documents 1 to 6). .
また、タッチパネルディスプレイ表面での防汚コーティング薄膜層は、汚れを防止する性能に加えて、タッチパネル使用時の使用感（すべりが良く、触感が滑らかなこと）も重要視されてきた。使用感の良さは摩擦係数の低さと関連する（特許文献４）。 In addition to the antifouling coating thin film layer on the surface of a touch panel display, in addition to its ability to prevent dirt, importance has also been placed on the usability of the touch panel (good sliding and smooth feel). A good feeling in use is related to a low coefficient of friction (Patent Document 4).
しかしながら、携帯用電子機器端末の筐体表面等においては、摩擦係数が低いということが不都合な場合もある。すなわち、摩擦係数が低いと、端末使用時に落下や振動などを生じる可能性が高くなる。そこで、汚れ防止性能や耐久性を保持しつつ、摩擦係数を制御することが、携帯用電子機器端末をはじめ様々な用途に防汚コーティング薄膜層を適用するうえで、重要とある（特許文献７）。 However, the low coefficient of friction on the surface of the casing of a portable electronic device terminal may be disadvantageous in some cases. In other words, if the coefficient of friction is low, there is a high possibility that the device will fall or vibrate during use. Therefore, it is important to control the coefficient of friction while maintaining antifouling performance and durability when applying antifouling coating thin film layers to various applications including portable electronic device terminals (Patent Document 7). ).
したがって、本発明は、撥水撥油性、摩耗耐久性に優れ、適度なすべり性を有する硬化被膜を形成することができるフルオロポリエーテル基含有ポリマー組成物、及びコーティング剤、並びに該コーティング剤により形成される層を有する物品を提供することを目的とする。 Therefore, the present invention provides a fluoropolyether group-containing polymer composition and a coating agent that can form a cured film having excellent water and oil repellency, abrasion durability, and appropriate slip properties, and a coating agent formed using the coating agent. The object of the present invention is to provide an article having a layer of
本発明者らは、上記目的を解決すべく鋭意研究した結果、フルオロポリエーテル基含有ポリマー組成物において、ヒドロキシシリル基又は加水分解性シリル基を有する２種類の特定のフルオロポリエーテル基含有ポリマー同士を組み合わせて用いることにより、該ポリマー及び／又はその部分（加水分解）縮合物を併用してなるフルオロポリエーテル基含有ポリマー組成物（特に、コーティング剤）が撥水撥油性、摩耗耐久性に優れ、かつ適度なすべり性（適度な摩擦係数）を有する硬化被膜を形成し得ることを見出し、本発明を完成した。 As a result of intensive research to solve the above object, the present inventors have found that two specific fluoropolyether group-containing polymers having a hydroxysilyl group or a hydrolyzable silyl group can be used in a fluoropolyether group-containing polymer composition. By using the polymer and/or its partial (hydrolyzed) condensate in combination, a fluoropolyether group-containing polymer composition (particularly a coating agent) has excellent water and oil repellency and wear resistance. The present invention was completed based on the discovery that it is possible to form a cured film having a suitable slipperiness (appropriate coefficient of friction).
即ち、本発明は下記のフルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品等を提供するものである。 That is, the present invention provides the following fluoropolyether group-containing polymer compositions, coating agents, articles, and the like.
［１］
（Ａ）下記一般式（１）
又は、下記一般式（２）
で表されるフルオロポリエーテル基含有ポリマー、及び／又はその部分（加水分解）縮合物と、
（Ｂ）下記一般式（３）
で表されるフルオロポリエーテル基含有ポリマー、及び／又はその部分（加水分解）縮合物とを含むフルオロポリエーテル基含有ポリマー組成物であって、（Ａ）成分と（Ｂ）成分の合計における（Ａ）成分の含有量が６５～９５質量％であるフルオロポリエーテル基含有ポリマー組成物。
［２］
式（２）において、αが２であり、Ｌが単結合又は酸素原子であるか、又は、式（２）において、αが３であり、Ｌが単結合若しくは酸素原子であって、かつ、式（１）、（２）及び（３）において、Ｘがトリアルコキシシリル基である、［１］に記載のフルオロポリエーテル基含有ポリマー組成物。
［３］
式（１）及び（２）において、Ｒｆ１が下記一般式（４）で表される１価のフルオロオキシアルキレン基含有ポリマー残基であり、式（３）においてＲｆ２が下記一般式（５）で表される１価のフルオロオキシアルキレン基含有ポリマー残基である、［１］又は［２］に記載のフルオロポリエーテル基含有ポリマー組成物。
［４］
式（２）において、Ｑはイミノ基又は炭素数１～４のイミノ基含有アルキレン基であり、式（３）において、βは２又は３であり、かつ、式（２）及び／又は式（３）において、１分子中に２個又は３個存在するＬのうち１個のＬが酸素原子であり、残余の１個又は２個のＬが単結合である、［１］～［３］のいずれか１つに記載のフルオロポリエーテル基含有ポリマー組成物。
［５］
式（１）で表されるフルオロポリエーテル基含有ポリマーが、下記式
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上であり、
式（２）で表されるフルオロポリエーテル基含有ポリマーが下記式
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上であり、
式（３）で表されるフルオロポリエーテル基含有ポリマーが下記式
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上である、［１］～［３］のいずれか１つに記載のフルオロポリエーテル基含有ポリマー組成物。
［６］
［１］～［５］のいずれか１つに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤。
［７］
［６］に記載のコーティング剤の硬化物からなる層を有する物品。
［８］
物品の表面全体又は一部に、乾式方法又は湿式方法により［１］～［５］のいずれか１つに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法。
[1]
(A) General formula (1) below
Or the following general formula (2)
A fluoropolyether group-containing polymer represented by and/or a partial (hydrolyzed) condensate thereof,
(B) General formula (3) below
A fluoropolyether group-containing polymer composition containing a fluoropolyether group-containing polymer represented by: A) A fluoropolyether group-containing polymer composition in which the content of component is 65 to 95% by mass.
[2]
In formula (2), α is 2 and L is a single bond or an oxygen atom, or in formula (2), α is 3 and L is a single bond or an oxygen atom, and The fluoropolyether group-containing polymer composition according to [1], wherein in formulas (1), (2) and (3), X is a trialkoxysilyl group.
[3]
In formulas (1) and (2), Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (4), and in formula (3), Rf2 is the following general formula (5). The fluoropolyether group-containing polymer composition according to [1] or [2], which is a monovalent fluorooxyalkylene group-containing polymer residue.
[4]
In formula (2), Q is an imino group or an imino group-containing alkylene group having 1 to 4 carbon atoms, and in formula (3), β is 2 or 3, and In 3), one L among the two or three L present in one molecule is an oxygen atom, and the remaining one or two L are single bonds, [1] to [3] The fluoropolyether group-containing polymer composition according to any one of .
[5]
The fluoropolyether group-containing polymer represented by formula (1) has the following formula:
One or more types selected from fluoropolyether group-containing polymers represented by
The fluoropolyether group-containing polymer represented by formula (2) has the following formula:
One or more types selected from fluoropolyether group-containing polymers represented by
The fluoropolyether group-containing polymer represented by formula (3) has the following formula:
The fluoropolyether group-containing polymer composition according to any one of [1] to [3], which is one or more selected from the fluoropolyether group-containing polymers represented by:
[6]
A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [5].
[7]
An article having a layer made of a cured product of the coating agent according to [6].
[8]
A coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [5] is applied to the entire surface or a part of the surface of the article by a dry method or a wet method and cured to form a layer. A method of surface modification of an article, comprising the step of forming.
本発明のフルオロポリエーテル基含有ポリマー組成物によれば、撥水撥油性、摩耗耐久性に優れると同時に、従来より摩擦係数が増加した適度なすべり性（適度な摩擦係数）を発現することができ、これにより本発明の組成物（特に、コーティング剤）にて表面処理された物品（例えば、携帯用電子機器端末等）は、撥水撥油性、摩耗耐久性に優れ、適度なすべり性を有し、有用である。 According to the fluoropolyether group-containing polymer composition of the present invention, it has excellent water and oil repellency and abrasion durability, and at the same time exhibits appropriate slipperiness (appropriate friction coefficient) with an increased friction coefficient compared to conventional ones. As a result, articles (for example, portable electronic device terminals, etc.) whose surfaces have been treated with the composition of the present invention (particularly the coating agent) have excellent water and oil repellency, abrasion durability, and appropriate slipperiness. It has and is useful.
本発明のフルオロポリエーテル基含有ポリマー組成物は、特定の２種類のフルオロポリエーテル基含有ポリマーを含有してなるものであり、それぞれの該フルオロポリエーテル基含有ポリマーは、いずれも分子内にフルオロポリエーテル基及び反応性官能基を有するものであり、上記式（１）、（２）又は（３）で表されるものである。 The fluoropolyether group-containing polymer composition of the present invention contains two specific types of fluoropolyether group-containing polymers, and each of the fluoropolyether group-containing polymers has fluorine in the molecule. It has a polyether group and a reactive functional group, and is represented by the above formula (1), (2) or (3).
本発明のフルオロポリエーテル基含有ポリマー組成物は、上記式（１）又は（２）で示されるポリマー（具体的には、上記式（４）で示されるフルオロオキシアルキレン基を含むポリマー）と、上記式（３）で示されるポリマー（具体的には、上記式（５）で示されるフルオロオキシアルキレン基を含むポリマー）との混合組成物であり、撥水撥油性、摩耗耐久性に優れ、適度なすべり性を有する。 The fluoropolyether group-containing polymer composition of the present invention comprises a polymer represented by the above formula (1) or (2) (specifically, a polymer containing a fluorooxyalkylene group represented by the above formula (4)), It is a mixed composition with a polymer represented by the above formula (3) (specifically, a polymer containing a fluorooxyalkylene group represented by the above formula (5)), and has excellent water and oil repellency and abrasion durability. Has moderate slipperiness.
（Ａ）成分
フルオロポリエーテル基含有ポリマー（Ａ１）
本発明で用いられる（Ａ）成分のフルオロポリエーテル基含有ポリマーは下記式（１）又は（２）で示されるものであり、例えば、特許第５０６４０１２号等に記載の方法で合成されるものである。
下記式（１）において、Ｒｆ１は１価のフルオロオキシアルキレン基含有ポリマー残基であり、Ｚは単結合又は、ケイ素原子及び／又はシロキサン結合を有してもよい２価の炭化水素基からなる連結基であり、Ｘはヒドロキシシリル基（水酸基含有シリル基）又は加水分解性シリル基である。
The fluoropolyether group-containing polymer as component (A) used in the present invention is represented by the following formula (1) or (2), and is synthesized by the method described in, for example, Japanese Patent No. 5064012. be.
In the following formula (1), Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue, and Z is a single bond or a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond. It is a linking group, and X is a hydroxysilyl group (hydroxyl group-containing silyl group) or a hydrolyzable silyl group.
上記式（１）において、Ｒｆ１は１価のフルオロオキシアルキレン基含有ポリマー残基であり、このＲｆ１としては下記一般式（４）で表される１価のフルオロオキシアルキレン基含有ポリマー残基（ヘキサフルオロプロピレンオキシド繰り返し単位含有ポリマー残基）であることが好ましい。
ここで、ｎはフルオロオキシアルキレン単位（ヘキサフルオロプロピレンオキシド単位）の繰り返し数（又は重合度）であり、通常、１～２００の整数、好ましくは５～１００の整数、より好ましくは１０～６０の整数である。
In the above formula (1), Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue, and this Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue (hexane) represented by the following general formula (4). fluoropropylene oxide repeating unit-containing polymer residue).
Here, n is the repeating number (or degree of polymerization) of fluorooxyalkylene units (hexafluoropropylene oxide units), and is usually an integer of 1 to 200, preferably an integer of 5 to 100, more preferably 10 to 60. is an integer.
Ｚは、単結合又は、ケイ素原子及び／又はシロキサン結合を有してもよい２価の炭化水素基からなる連結基であり、該連結基Ｚ中に極性基を含まないことで撥水撥油性に優れた硬化被膜を与えることができる。Ｚとしては、具体的には、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基等の炭素数２～１０のアルキレン基、フェニレン基等の炭素数６～８のアリーレン基を有するアルキレン基（例えば、炭素数８～１６のアルキレン－アリーレン基等）、アルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状又は環状の２価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２価の基などが挙げられる。これらのなかでも、炭素数２～１０のアルキレン基、フェニレン基を含むアルキレン基、アルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２～１０個の直鎖状又はケイ素原子数３～１０個の環状の２価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２価の基が好ましく、炭素数２～６のアルキレン基が更に好ましい。 Z is a linking group consisting of a single bond or a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond, and since the linking group Z does not contain a polar group, it has water and oil repellency. can provide an excellent cured film. Specifically, Z is an alkylene group having 2 to 10 carbon atoms such as ethylene group, propylene group, butylene group, hexamethylene group, and an alkylene group having arylene group having 6 to 8 carbon atoms such as phenylene group (for example, , an alkylene-arylene group having 8 to 16 carbon atoms, etc.), a divalent group in which alkylene groups are bonded to each other via a sylalkylene structure or a sylarylene structure, and 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. Examples include divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to the bonds of linear or cyclic divalent organopolysiloxane residues. Among these, alkylene groups having 2 to 10 carbon atoms, alkylene groups including phenylene groups, divalent groups in which alkylene groups are bonded to each other via a sylalkylene structure or sylarylene structure, and 2 to 10 silicon atoms. A divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a linear or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms is preferable; More preferred are 2 to 6 alkylene groups.
シルアルキレン構造、シルアリーレン構造としては、下記に示すものが例示できる。
また、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状又は環状の２価のオルガノポリシロキサン残基としては、下記に示すものが例示できる。
Further, as the linear or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, the following can be exemplified.
Ｚとしては、下記式で示される基が挙げられる。
Ｚの具体例としては、例えば、下記の基が挙げられる。
（Ａ１）成分の前記式（１）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが例示できる。
フルオロポリエーテル基含有ポリマー（Ａ２）
また、本発明で用いられる（Ａ）成分のフルオロポリエーテル基含有ポリマーである下記式（２）：
Ｒｆ１－ＣＦ（ＣＦ3）－Ｊ－Ｑ－Ｃ（Ｈ）3-α（－Ｌ－Ｒ－Ｘ）α （２）
において、
Ｒｆ１は１価のフルオロオキシアルキレン基含有ポリマー残基であり、Ｊは単結合又はカルボニル基であり、Ｑは単結合、イミノ基又はイミノ基を含有してもよい炭素数１～４のアルキレン基であり、Ｌはそれぞれ独立に単結合又は２価のヘテロ原子（好ましくはエーテル結合中の酸素原子）であり、Ｒは独立に炭素数１～６のアルキレン基であり、Ｘはヒドロキシシリル基（水酸基含有シリル基）又は加水分解性シリル基であり、αは２又は３である。
上記式（２）において、Ｒｆ１は上記式（１）におけるＲｆ１と同様に、１価のフルオロオキシアルキレン基含有ポリマー残基であり、このＲｆ１としては下記一般式（４）で表される１価のフルオロオキシアルキレン基含有ポリマー残基（ヘキサフルオロプロピレンオキシド繰り返し単位含有ポリマー残基）であることが好ましい。
ここで、ｎはフルオロオキシアルキレン単位（ヘキサフルオロプロピレンオキシド単位）の繰り返し数（又は重合度）であり、通常、１～２００の整数、好ましくは５～１００の整数、より好ましくは１０～６０の整数である。
Fluoropolyether group-containing polymer (A2)
Further, the fluoropolyether group-containing polymer of component (A) used in the present invention has the following formula (2):
Rf1-CF(CF 3 )-JQ-C(H) 3- α(-LRX)α (2)
In,
Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue, J is a single bond or a carbonyl group, and Q is a single bond, an imino group, or an alkylene group having 1 to 4 carbon atoms that may contain an imino group. , L is each independently a single bond or a divalent heteroatom (preferably an oxygen atom in an ether bond), R is independently an alkylene group having 1 to 6 carbon atoms, and X is a hydroxysilyl group ( hydroxyl group-containing silyl group) or a hydrolyzable silyl group, and α is 2 or 3.
In the above formula (2), Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue similar to Rf1 in the above formula (1), and this Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (4). The fluorooxyalkylene group-containing polymer residue (hexafluoropropylene oxide repeating unit-containing polymer residue) is preferable.
Here, n is the repeating number (or degree of polymerization) of fluorooxyalkylene units (hexafluoropropylene oxide units), and is usually an integer of 1 to 200, preferably an integer of 5 to 100, more preferably 10 to 60. is an integer.
Ｊは単結合又はカルボニル基であり、Ｊの具体例としては以下の結合又は基が挙げられる。
Ｑは単結合、イミノ基又はイミノ基を含有してもよい炭素数１～４のアルキレン基であり、Ｑの具体例として以下の結合又は基が挙げられる。
Ｌはそれぞれ独立に単結合又は２価のヘテロ原子であり、２価のヘテロ原子としては酸素原子、窒素原子、硫黄原子が挙げられるが、好ましくは酸素原子（エーテル結合中の酸素原子）である。
Ｒは独立に炭素数１～６のアルキレン基であり、該アルキレン基としては、例えば、－（ＣＨ2）ｍ－（ｍは１～６の整数、好ましくは２～４の整数）等の直鎖状のアルキレン基が挙げられる。
Ｘはヒドロキシシリル基（水酸基含有シリル基）又は加水分解性シリル基であり、トリメトキシシリル基、トリエトキシシリル基、トリプロポキシシリル基、トリ（イソプロポキシ）シリル基、トリブトキシシリル基、トリ（イソブトキシ）シリル基、トリ（ｓｅｃ－ブトキシ）シリル基、トリ（ｔｅｒｔ－ブトキシ）シリル基等のトリアルコキシシリル基が好ましい。
αは２又は３である。
なお、上記式（２）において、１分子中に２個又は３個存在するＬのうち１個のＬが酸素原子であり、残余の１個又は２個のＬが単結合であることが好ましい。
L is each independently a single bond or a divalent heteroatom, and examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably an oxygen atom (an oxygen atom in an ether bond) .
R is independently an alkylene group having 1 to 6 carbon atoms, and the alkylene group is, for example, a straight group such as -(CH 2 )m- (m is an integer of 1 to 6, preferably an integer of 2 to 4). Examples include chain alkylene groups.
X is a hydroxysilyl group (hydroxyl group-containing silyl group) or a hydrolyzable silyl group; Trialkoxysilyl groups such as isobutoxy)silyl group, tri(sec-butoxy)silyl group, and tri(tert-butoxy)silyl group are preferred.
α is 2 or 3.
In addition, in the above formula (2), it is preferable that one L among the two or three L present in one molecule is an oxygen atom, and the remaining one or two L are single bonds. .
（Ａ２）成分の前記式（２）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが例示できる。
（Ｂ）成分
フルオロポリエーテル基含有ポリマー（Ｂ１）
本発明で用いられる（Ｂ）成分のフルオロポリエーテル基含有ポリマーは、下記式（３）で示されるものであり、例えば、特許第６２６０５７９号、特許第６４５１２７９号、特許第６５２４９５５号等に記載の方法で合成されるものである。
下記式（３）において、Ｇは単結合又はパーフルオロメチレン基であり、Ｌはそれぞれ独立に単結合又は２価のヘテロ原子であり、Ｒは独立に炭素数１～６のアルキレン基であり、Ｘはヒドロキシシリル基又は加水分解性シリル基であり、βは１～３の整数である。
The fluoropolyether group-containing polymer as component (B) used in the present invention is represented by the following formula (3), and is, for example, the polymer described in Japanese Patent No. 6260579, Japanese Patent No. 6451279, Japanese Patent No. 6524955, etc. It is synthesized by a method.
In the following formula (3), G is a single bond or a perfluoromethylene group, L is each independently a single bond or a divalent heteroatom, R is independently an alkylene group having 1 to 6 carbon atoms, X is a hydroxysilyl group or a hydrolyzable silyl group, and β is an integer from 1 to 3.
上記式（３）において、Ｒｆ２は１価のフルオロオキシアルキレン基含有ポリマー残基であり、このＲｆ２としては下記一般式（５）で表される１価のフルオロオキシアルキレン基含有ポリマー残基（ヘキサフルオロプロピレンオキシド繰り返し単位含有ポリマー残基）であることが好ましい。
上記式（５）において、ｐ、ｑはそれぞれ独立に、１～１００の整数、好ましくは５～５０の整数、より好ましくは１０～３０の整数であり、ｐ＋ｑ＝２～２００、好ましくは１０～１００、より好ましくは２０～６０である。なお、上記式（５）において、（ＣＦ2Ｏ）単位の繰り返し数ｐと（Ｃ2Ｆ4Ｏ）単位の繰り返し数ｑとの比率；ｐ／ｑは、特に制限されるものではないが、通常、ｐ／ｑは０．５～２、好ましくは０．６７～１．５、より好ましくは０．８～１．２５、更に好ましくは０．９～１．１程度であればよい。
In the above formula (3), Rf2 is a monovalent fluorooxyalkylene group-containing polymer residue, and this Rf2 is a monovalent fluorooxyalkylene group-containing polymer residue (hexane) represented by the following general formula (5). fluoropropylene oxide repeating unit-containing polymer residue).
In the above formula (5), p and q are each independently an integer of 1 to 100, preferably an integer of 5 to 50, more preferably an integer of 10 to 30, and p+q=2 to 200, preferably 10 to 30. 100, more preferably 20-60. In addition, in the above formula (5), the ratio between the number of repetitions p of (CF 2 O) units and the number of repetitions q of (C 2 F 4 O) units; p/q is not particularly limited; Usually, p/q may be about 0.5 to 2, preferably 0.67 to 1.5, more preferably 0.8 to 1.25, and still more preferably about 0.9 to 1.1.
Ｇは単結合又はパーフルオロメチレン基であり、Ｇの具体例としては以下の結合又は基が挙げられる。
Ｌはそれぞれ独立に単結合又は２価のヘテロ原子であり、２価のヘテロ原子としては酸素原子、窒素原子、硫黄原子が挙げられるが、好ましくは酸素原子（エーテル結合中の酸素原子）である。
Ｒは独立に炭素数１～６のアルキレン基であり、該アルキレン基としては、例えば、－（ＣＨ2）ｍ－（ｍは１～６の整数、好ましくは２～４の整数）等の直鎖状のアルキレン基が挙げられる。
Ｘはヒドロキシシリル基（水酸基含有シリル基）又は加水分解性シリル基であり、トリメトキシシリル基、トリエトキシシリル基、トリプロポキシシリル基、トリ（イソプロポキシ）シリル基、トリブトキシシリル基、トリ（イソブトキシ）シリル基、トリ（ｓｅｃ－ブトキシ）シリル基、トリ（ｔｅｒｔ－ブトキシ）シリル基等のトリアルコキシシリル基が好ましい。
βは１～３の整数である。
なお、上記式（３）において、βが２又は３の場合、１分子中に２個又は３個存在するＬのうち１個のＬが酸素原子であり、残余の１個又は２個のＬが単結合であることが好ましい。
βが１の場合、Ｌは好適には単結合である。
L is each independently a single bond or a divalent heteroatom, and examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably an oxygen atom (an oxygen atom in an ether bond) .
R is independently an alkylene group having 1 to 6 carbon atoms, and the alkylene group is, for example, a straight group such as -(CH 2 )m- (m is an integer of 1 to 6, preferably an integer of 2 to 4). Examples include chain alkylene groups.
X is a hydroxysilyl group (hydroxyl group-containing silyl group) or a hydrolyzable silyl group; Trialkoxysilyl groups such as isobutoxy)silyl group, tri(sec-butoxy)silyl group, and tri(tert-butoxy)silyl group are preferred.
β is an integer from 1 to 3.
In addition, in the above formula (3), when β is 2 or 3, one L among the two or three L present in one molecule is an oxygen atom, and the remaining one or two L is preferably a single bond.
When β is 1, L is preferably a single bond.
（Ｂ１）成分の前記式（３）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが例示できる。
本発明の組成物では、（Ａ）成分［Ａ１又はＡ２］と（Ｂ）成分［Ｂ１］の合計における（Ａ）成分の含有量が６５～９５質量％であり、好適には７０～９０質量％である。 In the composition of the present invention, the content of component (A) in the total of component (A) [A1 or A2] and component (B) [B1] is 65 to 95% by mass, preferably 70 to 90% by mass. %.
本発明の組成物は、上述のフルオロポリエーテル基含有ポリマー［（Ａ）成分及び（Ｂ）成分］のヒドロキシシリル基、又は該フルオロポリエーテル基含有ポリマーの末端加水分解性シリル基を予め公知の方法により部分的に加水分解した水酸基を縮合させて得られる部分（加水分解）縮合物を含んでいてもよい。 In the composition of the present invention, the hydroxysilyl group of the above-mentioned fluoropolyether group-containing polymer [component (A) and component (B)] or the terminal hydrolyzable silyl group of the fluoropolyether group-containing polymer is preliminarily converted to It may also contain a partial (hydrolysis) condensate obtained by condensing hydroxyl groups partially hydrolyzed by a method.
本発明の組成物には、必要に応じて、加水分解縮合触媒、例えば、有機錫化合物（ジブチル錫ジメトキシド、ジラウリン酸ジブチル錫など）、有機チタン化合物（テトラｎ－ブチルチタネートなど）、有機酸（酢酸、メタンスルホン酸、フッ素変性カルボン酸など）、無機酸（塩酸、硫酸など）を添加してもよい。これらの中では、特に酢酸、テトラｎ－ブチルチタネート、ジラウリン酸ジブチル錫、フッ素変性カルボン酸などが好ましい。
加水分解縮合触媒の添加量は触媒量であり、フルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物１００質量部に対して０．０１～５質量部が好ましく、特に０．１～１質量部が好ましい。
The composition of the present invention may optionally contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid ( Acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is preferably 0.01 to 5 parts by mass, particularly 0.1 to 100 parts by mass of the fluoropolyether group-containing polymer and/or its partial (hydrolyzed) condensate. ~1 part by mass is preferred.
本発明の組成物は、適当な溶剤を含んでもよい。このような溶剤としては、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタンなど）、フッ素変性芳香族炭化水素系溶剤（１，３－ビス（トリフルオロメチル）ベンゼンなど）、フッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）など）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミンなど）、炭化水素系溶剤（石油ベンジン、トルエン、キシレンなど）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）を例示することができる。これらの中では、溶解性、濡れ性などの点で、フッ素変性された溶剤（フッ素変性脂肪族炭化水素系溶剤、フッ素変性芳香族炭化水素系溶剤、フッ素変性エーテル系溶剤又はフッ素変性アルキルアミン系溶剤）が好ましく、特には、１，３－ビス（トリフルオロメチル）ベンゼン、エチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）、パーフルオロトリブチルアミンが好ましい。 The composition of the invention may also include a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), and fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane). Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, in terms of solubility and wettability, fluorine-modified solvents (fluorine-modified aliphatic hydrocarbon solvents, fluorine-modified aromatic hydrocarbon solvents, fluorine-modified ether solvents, or fluorine-modified alkylamine solvents) 1,3-bis(trifluoromethyl)benzene, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), and perfluorotributylamine are particularly preferred.
上記溶剤は一種単独で使用してもよく、２種以上を併用してもよく、フルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物を均一に溶解させ得るものが好ましい。なお、溶剤に溶解させるフルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物の最適量は、処理方法により異なり、秤量し易い量であればよいが、直接塗工する場合は、溶剤及びフルオロポリエーテル基含有ポリマー（及びその部分（加水分解）縮合物）の合計１００質量部に対して０．０１～１０質量部が好ましく、特に０．０５～５質量部であることが好ましく、蒸着処理をする場合は、溶剤及びフルオロポリエーテル基含有ポリマー（及びその部分（加水分解）縮合物）の合計１００質量部に対して１～１００質量部が好ましく、特に３～３０質量部であることが好ましい。 The above-mentioned solvents may be used alone or in combination of two or more, and those capable of uniformly dissolving the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate are preferred. The optimal amount of the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate to be dissolved in the solvent varies depending on the treatment method, and may be an amount that is easy to weigh. The amount is preferably from 0.01 to 10 parts by weight, particularly preferably from 0.05 to 5 parts by weight, based on a total of 100 parts by weight of the fluoropolyether group-containing polymer (and its partial (hydrolyzed) condensate). In the case of treatment, the amount is preferably 1 to 100 parts by weight, particularly 3 to 30 parts by weight, based on the total of 100 parts by weight of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolyzed) condensate). is preferred.
本発明の組成物は、刷毛塗り、ディッピング、スプレー、蒸着処理など公知の方法で基材に施与することができる。蒸着処理時の加熱方法は、抵抗加熱方式でも、電子ビーム加熱方式のどちらでもよく、特に限定されるものではない。また、硬化温度は、硬化方法によって異なるが、例えば、直接塗工（刷毛塗り、ディッピング、スプレー等）の場合は、２５～２００℃、特に２５～８０℃にて３０分～３６時間、特に１～２４時間とすることが好ましい。また、蒸着処理で施与する場合は、２０～２００℃の範囲が好ましい。また、加湿下で硬化させてもよい。硬化被膜の膜厚は、基材の種類により適宜選定されるが、通常０．１～１００ｎｍ、特に１～２０ｎｍである。また、例えばスプレー塗工では予め水分を添加したフッ素系溶剤に希釈し、加水分解、つまりＳｉ－ＯＨを生成させた後にスプレー塗工すると塗工後の硬化が速い。 The composition of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1. It is preferable to set the time period to 24 hours. Furthermore, when applying by vapor deposition, the temperature is preferably in the range of 20 to 200°C. Further, it may be cured under humidified conditions. The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spray coating, if the material is diluted with a fluorine-based solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.
本発明の組成物で処理される基材は特に制限されず、紙、布、金属及びその酸化物、ガラス、プラスチック、セラミック、石英など各種材質のものであってよい。本発明の組成物は、前記基材に撥水撥油性、摩耗耐久性及び適度なすべり性を付与することができる。特に、ＳｉＯ2処理されたガラスやフイルムのコーティング剤として好適に使用することができる。 The substrate treated with the composition of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The composition of the present invention can impart water and oil repellency, abrasion durability, and appropriate slipperiness to the base material. In particular, it can be suitably used as a coating agent for SiO 2 -treated glass or film.
本発明の組成物で処理される物品としては、カーナビゲーション、携帯電話、スマートフォン、デジタルカメラ、デジタルビデオカメラ、ＰＤＡ、ポータブルオーディオプレーヤー、カーオーディオ、ゲーム機器、眼鏡レンズ、カメラレンズ、レンズフィルター、サングラス、胃カメラ等の医療用器機、複写機、ＰＣ、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ、保護フイルム、反射防止フイルムなどの光学物品が挙げられる。本発明の組成物は、前記物品への指紋及び皮脂の付着防止、傷つき防止が期待でき、表面のすべり性を制御できる。そのため特にこれらの端末の筐体表面の撥水撥油層として有用である。 Articles treated with the composition of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, and sunglasses. , medical equipment such as a gastrocamera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an antireflection film, and other optical articles. The composition of the present invention can be expected to prevent fingerprints and sebum from adhering to the article and prevent scratches, and can control the slipperiness of the surface. Therefore, it is particularly useful as a water- and oil-repellent layer on the casing surface of these terminals.
また、本発明の組成物は、浴槽、洗面台のようなサニタリー製品の防汚コーティング、自動車、電車、航空機などの窓ガラス又は強化ガラス、ヘッドランプカバー等の防汚コーティング、外壁用建材の撥水撥油コーティング、台所用建材の油汚れ防止用コーティング、電話ボックスの防汚及び貼り紙・落書き防止コーティング、美術品などの指紋付着防止コーティング、コンパクトディスク、ＤＶＤなどの指紋付着防止コーティング、金型用に離型剤あるいは塗料添加剤、樹脂改質剤、無機質充填剤の流動性改質剤又は分散性改質剤、テープ、フイルムなどの潤滑性向上剤としても有用である。 In addition, the composition of the present invention can be used as an antifouling coating for sanitary products such as bathtubs and washstands, as an antifouling coating for window glass or tempered glass for automobiles, trains, and aircraft, for headlamp covers, and as a repellent for building materials for exterior walls. Water and oil repellent coating, anti-oil coating for kitchen building materials, antifouling and anti-paper/graffiti coating for telephone booths, anti-fingerprint coating for works of art, anti-fingerprint coating for compact discs, DVDs, etc., for molds. It is also useful as a mold release agent, paint additive, resin modifier, fluidity modifier or dispersion modifier for inorganic fillers, and lubricity improver for tapes, films, etc.
本発明の組成物の製造方法
本発明の組成物は、次に示されるような方法で製造することができる。
例えば、適当な溶剤に溶解された（Ａ）成分と、（Ｂ）成分とを、同時に又は別々に、混合することにより、本発明の組成物を得ることができる。また、使用用途によって、該組成物に、添加物を添加して混合してもよい。各成分は一種単独で使用してもよく、２種以上を併用してもよい。
この製造方法では、混合を行う装置について、特に限定されない。具体的には、例えば、撹拌機、振とう器、スターラー等を用いることができ、これらの装置を適宜組み合わせて使用してもよい。
Method for producing the composition of the present invention The composition of the present invention can be produced by the method shown below.
For example, the composition of the present invention can be obtained by simultaneously or separately mixing component (A) and component (B) dissolved in a suitable solvent. Furthermore, additives may be added and mixed into the composition depending on the intended use. Each component may be used alone or in combination of two or more.
In this manufacturing method, there are no particular limitations on the mixing device. Specifically, for example, a stirrer, a shaker, a stirrer, etc. can be used, and these devices may be used in an appropriate combination.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記実施例によって限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail by showing Examples and Comparative Examples, but the present invention is not limited by the Examples below.
［実施例１］
（Ａ）成分のフルオロポリエーテル基含有ポリマーとして、下記式で表す化合物（Ａ）９．０ｇと、（Ｂ）成分のフルオロポリエーテル基含有ポリマーとして、下記式で表す化合物（Ｂ）１．０ｇを、エチルパーフルオロブチルエーテル（Ｎｏｖｅｃ ７２００、３Ｍ社製）４０．０ｇに溶解し、フルオロポリエーテル基含有ポリマーの濃度が２０質量％のフルオロポリエーテル基含有ポリマー組成物を調製した。
9.0 g of the compound (A) represented by the following formula as the fluoropolyether group-containing polymer as the component (A), and 1.0 g of the compound (B) represented by the following formula as the fluoropolyether group-containing polymer as the component (B) was dissolved in 40.0 g of ethyl perfluorobutyl ether (Novec 7200, manufactured by 3M) to prepare a fluoropolyether group-containing polymer composition in which the concentration of the fluoropolyether group-containing polymer was 20% by mass.
抵抗加熱型真空蒸着装置（ＶＴＲ－３５０Ｍ、アルバック機工製）に、ＳｉＯ2が１０ｎｍの膜厚で成膜されている化学強化ガラス基材（ＧＯＲＩＬＬＡ、Ｃｏｒｎｉｎｇ社製）をセットし、抵抗加熱部に、上記で調製した組成物を４μＬ滴下し、減圧した。容器内圧力が３×１０-3Ｐａ以下にまで減圧されたら、抵抗加熱を開始した。抵抗加熱部から約２０ｃｍ離れた位置に設置された水晶振動子膜厚計における最大蒸発速度が１．０ｎｍ／秒になるように抵抗加熱の電力を調整した。水晶振動子膜厚計における蒸発速度が０．１ｎｍ／秒まで減少してから１００秒間は抵抗加熱を継続した。装置冷却のため、５分間待機後、大気開放を行い、フルオロポリエーテル基含有ポリマーの塗膜を有する基材を得た。 A chemically strengthened glass substrate (GORILLA, manufactured by Corning) on which SiO 2 is deposited to a thickness of 10 nm is set in a resistance heating vacuum evaporation device (VTR-350M, manufactured by ULVAC Kikou), and the substrate is placed in the resistance heating section. , 4 μL of the composition prepared above was added dropwise, and the pressure was reduced. When the pressure inside the container was reduced to 3×10 −3 Pa or less, resistance heating was started. The electric power for resistance heating was adjusted so that the maximum evaporation rate on a crystal resonator film thickness gauge installed at a position approximately 20 cm away from the resistance heating section was 1.0 nm/sec. Resistance heating was continued for 100 seconds after the evaporation rate measured by the quartz crystal film thickness meter decreased to 0.1 nm/sec. After waiting for 5 minutes to cool the device, it was opened to the atmosphere to obtain a substrate having a coating film of a fluoropolyether group-containing polymer.
前記の塗膜を有する基材を２５℃、相対湿度５０％の環境下で１２時間以上インキュベーションし、塗膜を硬化し、フルオロポリエーテル基含有ポリマーによる硬化被膜（防汚コーティング薄膜層）を有する基材を得た。 The substrate having the coating film described above is incubated at 25° C. and an environment of 50% relative humidity for 12 hours or more to cure the coating film, and a cured film (antifouling coating thin film layer) made of a fluoropolyether group-containing polymer is formed. A base material was obtained.
［実施例２～１０、比較例１～５］
上記の化合物（Ａ）及び化合物（Ｂ）に加えて、（Ａ）成分のフルオロポリエーテル基含有ポリマーとして、下記式で表す化合物（Ｄ）及び化合物（Ｅ）と、（Ｂ）成分のフルオロポリエーテル基含有ポリマーとして、下記式で表す化合物（Ｃ）とを用いて、表１に示す化合物の組み合せで、それぞれの添加量で調製した以外は、実施例１と同様の手順で防汚コーティング薄膜層を有する基材を得た。
In addition to the above compound (A) and compound (B), as the fluoropolyether group-containing polymer of component (A), compound (D) and compound (E) represented by the following formula, and fluoropolyether group-containing polymer of component (B) are used. An antifouling coating thin film was prepared in the same manner as in Example 1, except that the compound (C) represented by the following formula was used as the ether group-containing polymer, and the compound combinations shown in Table 1 were prepared in the amounts added. A substrate having layers was obtained.
耐すべり性の評価
［不織布による動摩擦係数の評価］
表面性測定機（ＴＹＰＥ１４ＦＷ、新東科学製）を用いて、上記で得られた防汚コーティング薄膜層を有する基材の表面の動摩擦係数を計測した。擦り材は不織布（ベンコットＭ－３ＩＩ、旭化成製）、荷重は１００ｇ／ｃｍ2、擦りスピードは５００ｍｍ／分とした。耐すべり性（すべりにくさ）評価の指標として、動摩擦係数が０．４以上で◎（優）、０．２以上０．４未満で〇（良）、０．１以上０．２未満で△（可）、０．１未満を×（不可）とし、表１に示す。
Evaluation of slip resistance [Evaluation of coefficient of dynamic friction using nonwoven fabric]
Using a surface property measuring device (TYPE 14FW, manufactured by Shinto Kagaku), the coefficient of dynamic friction of the surface of the base material having the antifouling coating thin film layer obtained above was measured. The rubbing material was a nonwoven fabric (Bemcot M-3II, manufactured by Asahi Kasei), the load was 100 g/cm 2 , and the rubbing speed was 500 mm/min. As an index for evaluating slip resistance (slip resistance), a dynamic friction coefficient of 0.4 or more is ◎ (excellent), 0.2 or more and less than 0.4 is 0 (good), and 0.1 or more and less than 0.2 is △. (Acceptable), less than 0.1 is indicated as × (Unacceptable), and is shown in Table 1.
［紙による動摩擦係数の評価］
表面性測定機（ＴＹＰＥ１４ＦＷ、新東科学製）を用いて、上記で得られた防汚コーティング薄膜層を有する基材の表面の動摩擦係数を計測した。擦り材は紙、荷重は１００ｇ／ｃｍ2、擦りスピードは５００ｍｍ／分とした。耐すべり性評価の指標として、動摩擦係数が０．２以上で◎（優）、０．１以上０．２未満で〇（良）、０．０５以上０．１未満で△（可）、０．０５未満を×（不可）とし、表１に示す。
[Evaluation of dynamic friction coefficient using paper]
Using a surface property measuring device (TYPE 14FW, manufactured by Shinto Kagaku), the coefficient of dynamic friction of the surface of the base material having the antifouling coating thin film layer obtained above was measured. The rubbing material was paper, the load was 100 g/cm 2 , and the rubbing speed was 500 mm/min. As an index of slip resistance evaluation, the coefficient of dynamic friction is 0.2 or more: ◎ (excellent), 0.1 or more and less than 0.2: 0 (good), 0.05 or more and less than 0.1: △ (fair), 0 If it is less than .05, it is marked as × (impossible) and is shown in Table 1.
［人工皮膚による動摩擦係数の評価］
表面性測定機（ＴＹＰＥ１４ＦＷ、新東科学製）を用いて、上記で得られた防汚コーティング薄膜層を有する基材の表面の動摩擦係数を計測した。擦り材は人工皮膚（サプラーレ、出光テクノファイン製）、荷重は１００ｇ／３×３ｃｍ2、擦りスピードは５００ｍｍ／分とした。耐すべり性評価の指標として、動摩擦係数が１．５以上で◎（優）、１．０以上１．５未満で〇（良）、０．５以上１．０未満で△（可）、０．５未満を×（不可）とし、表１に示す。
[Evaluation of dynamic friction coefficient using artificial skin]
Using a surface property measuring device (TYPE 14FW, manufactured by Shinto Kagaku), the coefficient of dynamic friction of the surface of the base material having the antifouling coating thin film layer obtained above was measured. The rubbing material was artificial skin (Sapure, manufactured by Idemitsu Technofine), the load was 100 g/3×3 cm 2 , and the rubbing speed was 500 mm/min. As an index of slip resistance evaluation, the dynamic friction coefficient is ◎ (excellent) when it is 1.5 or more, 〇 (good) when it is 1.0 or more and less than 1.5, △ (fair) when it is 0.5 or more and less than 1.0, and 0. If it is less than .5, it is marked as × (impossible) and is shown in Table 1.
撥水撥油性の評価
［初期撥水性の評価］
上記で得られた防汚コーティング薄膜層（硬化被膜）を有する基材について、接触角計（Ｄｒｏｐ Ｍａｓｔｅｒ、協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）を測定した（液滴：２μｌ、温度：２５℃、湿度：４０％）。結果（初期水接触角）を表１に示す。
初期においては、実施例、比較例共に１１０度以上の接触角が得られ、良好な撥水性を示した。
Evaluation of water and oil repellency [Evaluation of initial water repellency]
Regarding the base material having the antifouling coating thin film layer (cured film) obtained above, the contact angle (water repellency) of the cured film with respect to water was measured using a contact angle meter (Drop Master, manufactured by Kyowa Interface Science Co., Ltd.) (Droplet: 2 μl, Temperature: 25° C., Humidity: 40%). The results (initial water contact angle) are shown in Table 1.
In the initial stage, a contact angle of 110 degrees or more was obtained in both Examples and Comparative Examples, indicating good water repellency.
摩耗耐久性の評価
［スチールウール摩耗耐久性の評価］
上記で得られた防汚コーティング薄膜層（硬化被膜）を有する基材について、往復摩耗試験機（Ｔｙｐｅ４０、新東科学製）を用いて、以下の条件で試験した。
擦り材：スチールウール（Ｂｏｎｓｔａｒ＃００００）
荷重：１ｋｇ
往復距離：４０ｍｍ
往復速度：６０往復毎分
総摩擦往復回数：３０００回
摩擦往復回数５００回毎に摩擦摩耗部分の水接触角を計測した。水接触角１００度以上を保つ摩耗往復回数をスチールウール摩耗耐久回数とし、スチールウール摩耗耐久回数が３０００回以上を◎（優）、１５００回以上３０００回未満を〇（良）、５００回以上１５００回未満を△（可）、５００回未満を×（不可）とし、表１に示す。試験環境条件は２５℃、湿度４０％である。
Evaluation of abrasion durability [Evaluation of steel wool abrasion durability]
The base material having the antifouling coating thin film layer (cured film) obtained above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku).
Rubbing material: Steel wool (Bonstar #0000)
Load: 1kg
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Total number of frictional reciprocations: 3000 times The water contact angle of the frictionally worn portion was measured every 500 frictional reciprocations. The number of abrasion cycles that maintain a water contact angle of 100 degrees or more is defined as the steel wool abrasion durability number. ◎ (Excellent) if the steel wool abrasion durability number is 3000 times or more, 〇 (Good) if it is 1500 times or more and less than 3000 times, and 500 times or more and 1500 times. Less than 500 times is marked as △ (acceptable), and less than 500 times is marked as × (not acceptable), as shown in Table 1. The test environmental conditions were 25° C. and 40% humidity.
［消しゴム摩耗耐久性の評価］
上記で得られた防汚コーティング薄膜層（硬化被膜）を有する基材について、往復摩耗試験機（Ｔｙｐｅ４０、新東科学製）を用いて、以下の条件で試験した。
擦り材：消しゴム（Ｍｉｎｏａｎ社製、６ｍｍ直径）
荷重：１ｋｇ
往復距離：４０ｍｍ
往復速度：１５往復毎分
総摩擦往復回数：１００００回
摩擦往復回数１０００回毎に摩擦摩耗部分の水接触角を計測した。水接触角１００度以上を保つ摩耗往復回数を消しゴム摩耗耐久回数とし、消しゴム摩耗耐久回数が１００００回以上を◎（優）、５０００回以上１００００回未満を〇（良）、２０００回以上５０００回未満を△（可）、２０００回未満を×（不可）とし、表１に示す。試験環境条件は２５℃、湿度４０％である。
[Eraser abrasion durability evaluation]
The base material having the antifouling coating thin film layer (cured film) obtained above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku).
Rubbing material: Eraser (manufactured by Minoan, 6mm diameter)
Load: 1kg
Round trip distance: 40mm
Reciprocation speed: 15 reciprocations per minute Total number of friction reciprocations: 10,000 times The water contact angle of the frictionally worn portion was measured every 1,000 friction reciprocations. The number of abrasion cycles that maintain a water contact angle of 100 degrees or more is defined as the eraser abrasion durability number. ◎ (Excellent) if the eraser abrasion durability number is 10,000 times or more, ○ (Good) if it is 5,000 times or more and less than 10,000 times, and 2,000 times or more and less than 5,000 times. The results are shown in Table 1. The test environmental conditions were 25° C. and 40% humidity.
Claims (7)
又は、下記一般式（２）
で表されるフルオロポリエーテル基含有ポリマー、及び／又はその部分（加水分解）縮合物と、
（Ｂ）下記一般式（３）
で表されるフルオロポリエーテル基含有ポリマー、及び／又はその部分（加水分解）縮合物とを含むフルオロポリエーテル基含有ポリマー組成物であって、
式（１）及び（２）において、Ｒｆ１が下記一般式（４）で表される１価のフルオロオキシアルキレン基含有ポリマー残基であり、式（３）においてＲｆ２が下記一般式（５）で表される１価のフルオロオキシアルキレン基含有ポリマー残基であり、
（Ａ）成分と（Ｂ）成分の合計における（Ａ）成分の含有量が６５～９５質量％であるフルオロポリエーテル基含有ポリマー組成物。 (A) General formula (1) below
Or the following general formula (2)
A fluoropolyether group-containing polymer represented by and/or a partial (hydrolyzed) condensate thereof,
(B) General formula (3) below
A fluoropolyether group-containing polymer composition comprising a fluoropolyether group-containing polymer represented by and/or a partial (hydrolyzed) condensate thereof,
In formulas (1) and (2), Rf1 is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (4), and in formula (3), Rf2 is the following general formula (5). A monovalent fluorooxyalkylene group-containing polymer residue represented by
A fluoropolyether group-containing polymer composition in which the content of component (A) in the total of components (A) and (B) is 65 to 95% by mass.
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上であり、
式（２）で表されるフルオロポリエーテル基含有ポリマーが下記式
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上であり、
式（３）で表されるフルオロポリエーテル基含有ポリマーが下記式
で表されるフルオロポリエーテル基含有ポリマーから選ばれる１種又は２種以上である、請求項１又は２に記載のフルオロポリエーテル基含有ポリマー組成物。 The fluoropolyether group-containing polymer represented by formula (1) has the following formula:
One or more types selected from fluoropolyether group-containing polymers represented by
The fluoropolyether group-containing polymer represented by formula (2) has the following formula:
One or more types selected from fluoropolyether group-containing polymers represented by
The fluoropolyether group-containing polymer represented by formula (3) has the following formula:
The fluoropolyether group-containing polymer composition according to claim 1 or 2 , which is one or more selected from the fluoropolyether group-containing polymers represented by:
A coating agent containing the fluoropolyether group-containing polymer composition according to any one of claims 1 to 4 is applied to the whole or part of the surface of the article by a dry method or a wet method and cured to form a layer. A method for surface modification of an article including a process.
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