WO2021045209A1 - 含フッ素共重合体 - Google Patents
含フッ素共重合体 Download PDFInfo
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- WO2021045209A1 WO2021045209A1 PCT/JP2020/033655 JP2020033655W WO2021045209A1 WO 2021045209 A1 WO2021045209 A1 WO 2021045209A1 JP 2020033655 W JP2020033655 W JP 2020033655W WO 2021045209 A1 WO2021045209 A1 WO 2021045209A1
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- Prior art keywords
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- fluorine
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 100
- 239000011737 fluorine Substances 0.000 title claims abstract description 82
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005566 carbazolylene group Chemical group 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000007607 die coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- KWWOQRSLYPHAMK-UHFFFAOYSA-N ethyl 2-hydroxybutanoate Chemical compound CCOC(=O)C(O)CC KWWOQRSLYPHAMK-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
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- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
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- 230000005251 gamma ray Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000001620 monocyclic carbocycle group Chemical group 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
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- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 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
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001940 tetracyclic carbocycle group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000165 tricyclic carbocycle group Chemical group 0.000 description 1
- GJOGTGLNIWPDPF-UHFFFAOYSA-N trifluoromethyl hydrogen sulfite Chemical compound OS(=O)OC(F)(F)F GJOGTGLNIWPDPF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- 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
- C08G2150/00—Compositions for coatings
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- the present disclosure relates to a fluorinated copolymer and a surface treatment agent containing the fluorinated copolymer.
- Patent Document 1 describes a fluorine-containing polymer having a fluorine-containing group and a specific substituent (substituent group A in Patent Document 1) with respect to a base material of a resin material such as a transparent plastic such as acrylic resin or polycarbonate. It is disclosed to be used.
- the fluoropolymer described in Patent Document 1 described above can impart functions such as water repellency and oil repellency to the base material, but it may not be sufficiently soluble in a solvent and may cause a problem in the formation of the surface treatment layer. ..
- An object of the present disclosure is to provide a fluorine-containing copolymer having high water repellency, oil repellency and antifouling property as well as high solubility in a solvent for a base material made of various materials including a resin.
- R F1 is, Rf 1 -R F -O q - a and; R F2 is -R f 2 p -RF -O q- ; Rf 1 is a C 1-16 alkyl group that may be substituted with one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group that may be substituted with one or more fluorine atoms; R F is, independently, a divalent fluoropolyether group; p is 0 or 1; q is 0 or 1 independently of each other; R 4 is independently R 4a or R 4b at each appearance; R 4a is a divalent organic group having a functional group selected from the substituent group A independently at each appearance; R 4b is a divalent organic group having no functional group selected from the substituent group A independently at each appearance; The substituent group A contains a carbon-carbon double bond, a carbon-carbon triple bond,
- R F are each independently of the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 R Fa 6) d - (OC 2 F 4) e - (OCF 2) f - [In the formula, R Fa is a hydrogen atom, a fluorine atom or a chlorine atom independently at each appearance.
- a, b, c, d, e and f are independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b,
- the order of existence of each repeating unit in parentheses with c, d, e or f is arbitrary in the equation.
- [3] The fluorine-containing copolymer according to the above [2], wherein R Fa is a fluorine atom.
- RF is independently represented by the following equations (f1), (f2), (f3), (f4) or (f5): -(OC 3 F 6 ) d- (f1) [In the formula, d is an integer from 1 to 200. ], - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (f2) [In the equation, c and d are independently integers from 0 to 30; e and f are independently integers from 1 to 200; The sum of c, d, e and f is an integer from 10 to 200; The order of existence of each repeating unit with the subscripts c, d, e or f in parentheses is arbitrary in the equation.
- R 6 is OCF 2 or OC 2 F 4 ;
- R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or two or three selected from these groups.
- a combination of groups; g is an integer from 2 to 100.
- e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e.
- the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
- f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e.
- the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
- the functional group selected from the substituent group A in R 4a is a group having an epoxy group, a glycidyl group, an alicyclic epoxy group, an acryloyl group or a methacryloyl group, according to the above [1] to [6].
- the fluorine-containing copolymer according to any one of the items.
- [12] A film formed by the surface treatment agent according to the above [10] or the curable composition according to the above [11].
- [13] An article containing a base material and a layer formed on the surface of the base material by the surface treatment agent according to the above [10] or the curable composition according to the above [11].
- [18] The article according to the above [13], which is an automobile interior member.
- the fluorine-containing copolymer of the present disclosure has high solubility in a solvent and can be suitably used as a surface treatment agent.
- monovalent organic group means a carbon-containing monovalent group. Unless otherwise specified, the monovalent organic group may be a hydrocarbon group or a derivative thereof.
- a hydrocarbon group derivative is a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. in the terminal or molecular chain of the hydrocarbon group. Means. When simply referred to as “organic group”, it means a monovalent organic group.
- the "divalent organic group” means a divalent group containing carbon.
- the divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by desorbing one hydrogen atom from the organic group.
- hydrocarbon group means a group containing carbon and hydrogen, from which one hydrogen atom has been desorbed from the hydrocarbon.
- the hydrocarbon group is not particularly limited, but may be substituted with one or more substituents , such as a C 1-20 hydrocarbon group, for example, an aliphatic hydrocarbon group, an aromatic group. Hydrocarbon groups and the like can be mentioned.
- the "aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
- the hydrocarbon group may contain one or more ring structures.
- the substituent of the "hydrocarbon group” is not particularly limited, but may be substituted with, for example, a halogen atom, one or more halogen atoms, C 1-6 alkyl.
- Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl Groups include one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
- alkyl group is, for example, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3, still more preferably 1) unless otherwise specified. (Example, methyl group, ethyl group, propyl group, isopropyl group).
- the "alkyl group” may be linear or branched, but is preferably linear. Moreover, the said “alkyl group” may contain a functional group.
- R F1 is, Rf 1 -R F -O q - a and; R F2 is -R f 2 p -RF -O q- ; Rf 1 is a C 1-16 alkyl group that may be independently substituted with one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group that may be substituted with one or more fluorine atoms; R F is, independently, a divalent fluoropolyether group; p is 0 or 1; q is 0 or 1 independently of each other; R 4 is independently R 4a or R 4b at each appearance; R 4a is a divalent organic group having a functional group selected from the substituent group A independently at each appearance; R 4b is a divalent organic group having no functional group selected from the substituent group A independently at each appearance; The substituent group A contains a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic
- R F1 is, Rf 1 -R F -O q - is.
- R F2 is, -Rf 2 p -R F -O q - is.
- Rf 1 is a C 1-16 alkyl group which may be independently substituted with one or more fluorine atoms.
- the "C 1-16 alkyl group" in the C 1-16 alkyl group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a straight or branched C 1-6 alkyl group, particularly a C 1-3 alkyl group, more preferably a straight C 1-6 alkyl group, particularly a C 1-3 alkyl group.
- the Rf 1 is preferably a one or more C 1-16 alkyl group substituted by fluorine atoms, more preferably CF 2 H-C 1-15 perfluoroalkylene group, more preferably It is a C 1-16 perfluoroalkyl group.
- the C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, particularly C 1-3 perfluoro.
- Alkyl groups more preferably linear C 1-6 perfluoroalkyl groups, especially C 1-3 perfluoroalkyl groups, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 Is.
- Rf 2 is a C 1-6 alkylene group that may be substituted with one or more fluorine atoms.
- the "C 1-6 alkylene group" in the C 1-6 alkylene group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a straight chain or branched C 1-3 alkylene group, more preferably a straight chain C 1-3 alkylene group.
- the Rf 2 is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and even more preferably C 1-3. It is a perfluoroalkylene group.
- the C 1-6 perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched C 1-3 perfluoroalkylene group, and more preferably a straight chain.
- C 1-3 perfluoroalkyl group chain specifically -CF 2 -, - CF 2 CF 2 -, or -CF 2 CF 2 CF 2 - it is.
- p is 0 or 1. In one embodiment, p is 0. In another embodiment p is 1.
- q is 0 or 1 independently of each other. In one embodiment, q is 0. In another embodiment q is 1.
- RF is a divalent fluoropolyether group independently.
- RF is preferably the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 R Fa 6) d - (OC 2 F 4) e - (OCF 2) f -
- R Fa is a hydrogen atom, a fluorine atom or a chlorine atom independently at each appearance.
- a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more.
- the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ] It is a group represented by.
- R Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.
- A, b, c, d, e and f are preferably independent integers from 0 to 100.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
- the sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
- repeating units may be linear or branched.
- the repeating units are-(OC 6 F 12 )-,-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 ).
- -(OC 3 F 6 )-(that is, R Fa is a fluorine atom in the above formula) is-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-( It may be any of OCF 2 CF (CF 3))-.
- -(OC 2 F 4 )- may be either-(OCF 2 CF 2 )-and-(OCF (CF 3 ))-.
- the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, friction durability, etc. of the surface treatment layer can be improved.
- the repeating unit is branched chain. By forming the repeating unit into a branched chain shape, the coefficient of dynamic friction of the surface treatment layer can be increased.
- R F are each independently a group represented by any one of the following formulas (f1) ⁇ (f5). -(OC 3 F 6 ) d- (f1) [In the formula, d is an integer from 1 to 200. ]; - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (f2) [In the formula, c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
- e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e.
- the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
- f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e.
- the sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation.
- d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35.
- the above formula (f1) is preferably a group represented by ⁇ (OCF 2 CF 2 CF 2 ) d ⁇ or ⁇ (OCF (CF 3 ) CF 2 ) d ⁇ (OCF 2 CF 2).
- e and f are independently integers of preferably 5 or more and 200 or less, and more preferably 10 to 200.
- the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
- the above formula (f2) is preferably ⁇ (OCF 2 CF 2 CF 2 CF 2 ) c ⁇ (OCF 2 CF 2 CF 2 ) d ⁇ (OCF 2 CF 2 ) e ⁇ (OCF 2 ). It is a group represented by f ⁇ .
- the formula (f2) may be a group represented by ⁇ (OC 2 F 4 ) e ⁇ (OCF 2 ) f ⁇ .
- R 6 is preferably OC 2 F 4 .
- R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or 2 or independently selected from these groups. It is a combination of three groups, more preferably a group selected from OC 3 F 6 and OC 4 F 8.
- the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, but is, for example, -OC 2 F 4 OC 3 F 6- , -OC.
- g is preferably an integer of 3 or more, more preferably 5 or more.
- the above g is preferably an integer of 50 or less.
- OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably straight. It is a chain.
- the above formula (f3) is preferably ⁇ (OC 2 F 4 ⁇ OC 3 F 6 ) g ⁇ or ⁇ (OC 2 F 4 ⁇ OC 4 F 8 ) g ⁇ .
- e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- f is preferably an integer of 1 or more and 100 or less, and more preferably 5 or more and 100 or less.
- the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- the R F is a group represented by the formula (f1).
- the R F is a group represented by the formula (f2).
- the R F is a group represented by the formula (f3).
- the R F is a group represented by the above formula (f4).
- the R F is a group represented by the above formula (f5).
- the ratio of e for f (hereinafter, referred to as "e / f ratio”) is 0.1 to 10, preferably from 0.2 to 5, more preferably 0.2 to 2 Yes, more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
- e / f ratio the slipperiness, friction durability and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved.
- the smaller the e / f ratio the better the slipperiness and friction durability of the surface treatment layer.
- the stability of the compound can be further enhanced. The larger the e / f ratio, the better the stability of the compound.
- the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.
- the e / f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.
- a number average molecular weight of R F1 and R F2 portion is not particularly limited, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably It is 2,000 to 10,000.
- the number average molecular weight of R F1 and R F2 is a value measured by 19 F-NMR.
- the number average molecular weight of R F1 and R F2 portion 500 to 30,000, preferably more preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further 2, It can be between 000 and 10,000, for example 3,000 and 6,000.
- the number average molecular weight of R F1 and R F2 portion 4,000 to 30,000, preferably be 5,000 to 10,000, more preferably 6,000 to 10,000.
- R 4 is R 4a or R 4b independently at each appearance.
- the R 4a is a divalent organic group having a functional group selected from the substituent group A independently at each appearance.
- the substituent group A in the above "functional group selected from the substituent group A” is not particularly limited, but for example, a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, and a hydroxyl group.
- the substituent group A is a combination of an allyl group, a silicic acid group, a sorbic acid group, an epoxy group, a glycidyl group, an alicyclic epoxy group, an acryloyl group and a methacryloyl group (hereinafter, acryloyl group and a methacryloyl group).
- (Meta) acryloyl group "(Meta) acryloyl group”), halogen atom, vinyl ether (vinyloxy) group, hydroxyl group, oxetanyl group, catechol group, thiol group, amino group, alkylamino group, dialkylamino group, azide group, phosphoric acid It can be a group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a silane coupling group, or a precursor group thereof.
- the substituent group A is, for example, an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, an optionally substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group.
- the functional group selected from the preferred substituent group A depends on the material to be coated.
- the material is an amorphous synthetic resin (eg, acrylic resin)
- it is selected from the “substituent group A”.
- the alicyclic epoxy group preferably has the following formula: (In the formula, n is an integer from 1 to 5.) It is a group represented by.
- the alicyclic epoxy group is more preferable. Is.
- R 4a preferably has the following formula: It is a group represented by.
- R 31 independently represents a hydrogen atom or an alkyl group at each appearance.
- the R 31 is preferably a hydrogen atom.
- R 32 represents an alkyl group which may be independently substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or fluorine at each appearance.
- the R 32 is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom.
- R 33 represents a functional group selected from the substituent group A independently at each appearance.
- X 1 represents an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group) which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom or fluorine.
- R c represents an organic group, preferably an alkyl group.
- Y 2 represents a linker having a single bond or a main chain having 1 to 16 atoms (more preferably 2 to 12, still more preferably 2 to 10).
- Preferred Y 2 is-(CH 2- CH 2- O) p1- (p1 represents an integer of 1 to 10) or-(CHR d ) p2- O- (p2 is an integer of 1 to 40).
- R d represents hydrogen or a methyl group), and specific examples thereof include -CH 2 -CH 2 -O- are.
- R 4a is more preferably represented by the following formula: It is a group represented by.
- q1 is an integer of 1 to 10, preferably an integer of 1 to 5, for example 1.
- q2 is an integer of 1 to 10, preferably an integer of 1 to 5, for example 2.
- q3 is an integer of 1 to 10, preferably an integer of 1 to 5, for example 1.
- the R 4b is a divalent organic group having no functional group selected from the substituent group A independently at each appearance.
- R 4b is preferably ⁇ CHR 4c ⁇ CR 4d R 4e ⁇ .
- R 4c and R 4d independently represent a hydrogen atom or an alkyl group
- the R 4e group is ⁇ Y 3- R 4f .
- Y 3 has the same meaning as Y 1 described above
- R 4f is an organic group having no functional group selected from the substituent group A, and the group R 4 g described later is via a linker or directly. is a group bonded to Y 3.
- the linker is preferably (A) - (CH 2 -CH 2 -O) s1 -, (s1 represents an integer of 1-10.) (B)-(CHR 4h ) s2- O- (s2 represents the number of repetitions which is an integer of 1 to 40. R 4h represents a hydrogen or methyl group),. (C) - (CH 2 -CH 2 -O) s1 -CO-NH-CH 2 -CH 2 -O-, (s1 are as defined above.) (D) -CH 2 -CH 2 -O -CH 2 -CH 2 -, (E) - (CH 2) s3 - (.
- S3 represents an integer of 1-6), or (f) - (CH 2) s4 -O-CONH- (CH 2) s5 - (s4 1-8 integer, preferably, the .s5 representing two or four integer of 1-6, preferably a 3.), or (g) -O- (where, Y 3 is not -O-) Is.
- R 4g is preferably the following group.
- (I) Alkyl group Example: Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl
- the alkyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is preferable.
- R 11 is an n-butyl group having carbon atoms
- R 12 to R 17 is a methyl group.
- the aryl group is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms.
- the aryl group may contain two or more rings.
- a preferred aryl group is a phenyl group.
- the alkyl group and aryl group may contain a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom in the molecular chain or ring.
- alkyl and aryl groups are optionally substituted with halogen; one or more halogens, C 1-6 alkyl groups, C 2-6 alkenyl groups, C 2-6 alkynyl groups. , C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C 6-10 aryl group, 5-10 member hetero It may be substituted with one or more substituents selected from the aryl groups.
- R 18 represents a divalent organic group.
- R 18 is preferably ⁇ (CH 2 ) r ” ⁇ (in the equation, r” is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less), and more preferably ⁇ ( CH 2 ) r " -(in the formula, r" is an integer of 1 or more and 10 or less).
- n4 is an integer of 1 or more and 500 or less independently.
- the n4 is preferably 1 or more and 200 or less, and more preferably 10 or more and 200 or less.
- R 4g may be more preferably a hydrogen atom (excluding those bonded to O to form a hydroxyl group), or fluorinated, and may be bonded via an ethylene chain or an oxyethylene chain.
- an alkyl group more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group, or R 4i -CF 2, - (CF 2) s6 - (CH 2) s7 -O- (CH 2) 2 - (R 4i is It is a fluorine atom or a hydrogen atom, s6 is an integer of 0 to 6 and s7 is an integer of 1 to 6), more preferably a 3- (perfluoroethyl) propoxyethyl group [property formula: CF 3- (CF 2 )-(CH 2 ) 3- O- (CH 2 ) 2- ].
- the structural unit R 4a and the structural unit R 4b may each form a block or may be randomly connected.
- the structural unit R 4a and the structural unit R 4b each form a block.
- R 4 in R 4 , the structural unit R 4a and the structural unit R 4b are randomly combined.
- R 4 is R 4a . That is, R 4 is composed of a structural unit R 4a having a functional group selected from the substituent group A.
- the number of R4a (degree of polymerization) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, and even more preferably 2 to 30.
- R 4 is R 4b . That is, R 4 is composed of a structural unit R 4b that does not have a functional group selected from the substituent group A.
- the number of R 4b (degree of polymerization) is 1 to 100, preferably 2 to 70, more preferably 2 to 50, and even more preferably 2 to 30.
- n is an integer of 1 to 100, preferably an integer of 2 to 70, more preferably an integer of 2 to 50, and even more preferably an integer of 2 to 30.
- X a is a divalent organic group independently of each other.
- X b is a divalent organic group independently of each other.
- X a and X b may be any divalent organic group as long as the compounds represented by the formulas (1) and (2) can be stably present.
- each of Xa is independently expressed by the following equation: - (Q) e - (CFZ ) f - (CH 2) g - It is a group represented by.
- e, f and g are independently integers of 0 to 10
- the sum of e, f and g is 1 or more
- the order of existence of each repeating unit enclosed in parentheses is in the formula. Is optional.
- Q is an oxygen atom, phenylene, carbazolylene, -NR q- (in the formula, R q1 represents a hydrogen atom or an organic group) or a divalent polar group, respectively, at each appearance. ..
- R q1 represents a hydrogen atom or an organic group
- Q is an oxygen atom or a divalent polar group.
- the "lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.
- Z is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group at each appearance, and is preferably a fluorine atom.
- the "lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and more preferably a trifluoromethyl group or penta. It is a fluoroethyl group, more preferably a trifluoromethyl group.
- X a is preferably expressed by the following formula: -(O) e- (CF 2 ) f- (CH 2 ) g- [In the formula, e, f and g have the same meaning as above, and the order of existence of each repeating unit in parentheses is arbitrary in the formula]. It is a group represented by. These groups left end binds to R F1.
- X a is -(O) e1- (CH 2 ) g2- O-[(CH 2 ) g3- O-] g4 , -(O) e1- (CF 2 ) f2- (CH 2 ) g2- O-[(CH 2 ) g3- O-] g4
- e1 is 0 or 1
- f2 and g3 are independently integers of 1 to 10.
- g4 is 0 or 1] It can be a group represented by. These groups left end binds to R F1.
- X a is -(CH 2 ) g2- O- [In the formula, g2 is an integer from 1 to 10. ] It can be a group represented by. Incidentally, such a group is left to bind to R F1.
- X b is a divalent organic group independently of each other.
- X b is expressed by the following equation: -CO-R b3- CR b1 R b2-
- R b1 and R b2 are independently hydrogen atoms, C 1-3 alkyl groups, phenyl groups or -CN, respectively.
- R b3 is a C 1-6 alkylene group that may be single bonded or substituted. ] It can be a group represented by. Incidentally, such a group at the right end is bonded to R 4.
- the R b1 and R b2 are independently and preferably a C 1-3 alkyl group, a phenyl group or -CN, and more preferably a C 1-3 alkyl group or -CN.
- the C 1-3 alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.
- R b1 is a C 1-3 alkyl group, preferably a methyl group
- R b2 is a hydrogen atom or -CN.
- the substituent in the " optionally substituted C 1-6 alkylene group" in R b3 is preferably a C 1-3 alkyl group or a phenyl group, and preferably a C 1-3 alkyl group.
- the C 1-3 alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.
- the substituent may be one or two or more.
- the C 1-6 alkylene group in R b3 may be preferably a C 1-3 alkylene group, more preferably a C 2-3 alkylene group, for example a dimethylene group.
- R b3 is a single bond.
- R b3 is a optionally substituted C 1-6 alkylene group, preferably a C 1-6 alkylene group.
- Ra is alkyl, phenyl, -SR a1 , -OR a2 , -NR a3 2 , Is.
- R a may be part of a so-called RAFT agent.
- R a1 , R a2 , R a3 , R a4 , R a5 and R a6 are independently alkyl groups or phenyl groups, respectively.
- the Ra1 is preferably a C 1-20 alkyl group, more preferably a C 3-18 alkyl group, and even more preferably a C 4-12 alkyl group.
- the Ra2 is preferably a phenyl group or a C 1-20 alkyl group.
- the C 1-20 alkyl group is preferably a C 1-10 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a C 1-3 alkyl group.
- the Ra3 is preferably a C 1-20 alkyl group, more preferably a C 1-10 alkyl group, even more preferably a C 1-6 alkyl group, and even more preferably a C 1-3 alkyl group.
- the Ra4 is preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a methyl group.
- the R a5 are preferably C 1-6 alkyl groups, more preferably C 1-3 alkyl groups, more preferably methyl group.
- the Ra6 is preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a methyl group.
- the R a7 represents a hydrogen or halogen atom (e.g., fluorine, chlorine, bromine or iodine, preferably chlorine) is.
- halogen atom e.g., fluorine, chlorine, bromine or iodine, preferably chlorine
- Ra is -SR a1 or -OR a2 .
- the fluorine-containing copolymer of the present disclosure can be a fluorine-containing copolymer represented by the formula (1).
- the number average molecular weight of the fluorine-containing copolymer of the present disclosure is not particularly limited, but is 2 ⁇ 10 2 to 1 ⁇ 10 5 , preferably 1 ⁇ 10 3 to 5 ⁇ 10 4 , and more preferably 3 ⁇ . It can be 10 3 to 2 ⁇ 10 4 .
- the number average molecular weight can be determined by gel permeation chromatography (GPC).
- the multidispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the fluorine-containing copolymer of the present disclosure is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0. Hereinafter, it may be even more preferably 1.5 or less.
- the fluorine-containing polymer of the present disclosure can be synthesized by using, for example, so-called RAFT (Reversible addition-fragmentation chain transfer) type radical polymerization.
- RAFT Reversible addition-fragmentation chain transfer
- a RAFT agent having a perfluoropolyether group is prepared.
- compound (A) having a perfluoropolyester and compound (B1) or (B2) having a RAFT skeleton (-SC ( S)-):
- Ra , R F1 , R F2 , X a and X b have the same meaning as above; L 1 and L 2 are detached portions, respectively.
- R a , R F1 , R F2 , X a and X b have the same meaning as described above.
- the compound represented by the above formula (1) or (2) can be obtained by reacting the chain transfer agent (1a) or (2a) obtained above with a monomer having an unsaturated bond. it can.
- a reaction is so-called RAFT polymerization, and as the reaction conditions, conditions generally used in RAFT polymerization can be used.
- the fluorine-containing copolymer of the present disclosure is preferably used for treating the surface of a base material made of various materials including a resin. That is, the present disclosure provides one or more surface treatment agents containing a fluorine-containing copolymer represented by the above formulas (1) and (2).
- the surface treatment agent of the present disclosure further includes the following general formula (C): It may contain at least one kind of fluorine-containing oil represented by (hereinafter, also referred to as “fluorine-containing oil (C)").
- Rf 2 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms
- Rf 3 is a hydrogen atom, a fluorine atom, or one. It represents an alkyl group having 1 to 16 carbon atoms which may be substituted with an or more fluorine atom.
- Rf 2 and Rf 3 are alkyl groups having 1 to 3 carbon atoms which may be independently substituted with one or more fluorine atoms, and more preferably 1 to 3 carbon atoms. It is a perfluoroalkyl group.
- a', b', c'and d' represent the number of three types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and 0 or more and 300 independently of each other.
- the order of existence of each repeating unit in parentheses with the subscripts a', b', c'or d' is arbitrary in the equation.
- -(OC 3 F 6 )- is either-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Often, preferably-(OCF 2 CF 2 CF 2 )-.
- -(OC 2 F 4 )- may be any of-(OCF 2 CF 2 )-and-(OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
- Rf 2 and Rf 3 are as described above, b "is an integer from 0 to 300, and the order of existence of each repeating unit enclosed in parentheses with the subscript b" is in the formula. Is optional.
- the fluorine-containing oil (C) may have an average molecular weight of about 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
- the fluorine-containing oil (C) is, for example, 0 with respect to a total of 100 parts by mass of the above-mentioned fluorine-containing copolymer (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in an amount of about 80 parts by mass, preferably 0 to 40 parts by mass.
- the fluorine-containing oil (C) can be contained in an amount of preferably 40% by mass or less based on the total of the fluorine-containing copolymer and the fluorine-containing oil (C).
- the fluorine-containing oil (C) contributes to improving the surface slipperiness of the surface treatment layer.
- the surface treatment agent of the present disclosure may contain other components such as silicone oil, an active energy ray radical curing initiator, a thermoacid generator, an active energy ray cationic curing initiator and the like.
- the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
- the linear silicone oil may be a so-called straight silicone oil or a modified silicone oil.
- the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
- the modified silicone oil include those obtained by modifying straight silicone oil with polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
- Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
- such silicone oil is, for example, 0 to 50 parts by mass with respect to a total of 100 parts by mass of the above-mentioned fluorine-containing copolymer (in the case of two or more kinds, the total of these, the same applies hereinafter). It may be contained in an amount of 0 to 10 parts by mass, preferably 0 to 10 parts by mass.
- radicals are generated for the first time when an electromagnetic wave in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, ⁇ -rays, etc. are irradiated, and the substituent group A It acts as a catalyst for initiating the curing (crosslinking reaction) of the curable moiety (for example, carbon-carbon double bond) of a fluorine-containing copolymer having a curable moiety as a more selected functional group, and is usually ultraviolet. Use a light beam that generates radicals.
- the active energy ray radical curing initiator in the surface treatment agent of the present disclosure is appropriately selected depending on the type of curable site in the fluorine-containing copolymer, the type of active energy ray used (wavelength range, etc.), irradiation intensity, and the like.
- an initiator for curing a fluorine-containing copolymer having a radically reactive curable site (carbon-carbon double bond) using active energy rays in the ultraviolet region for example, the following can be exemplified. ..
- Acetophenone-based acetophenone chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, ⁇ -aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.
- Benzoin-based benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.
- Benzophenone-based benzophenone benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylicized benzophenone, Michler's ketone, etc.
- active energy ray curing initiators may be used alone or in combination of two or more.
- the active energy ray curing initiator is not particularly limited, but is 0.01 to 1000 with respect to a total of 100 parts by mass of the fluorine-containing copolymer and, if present, the fluorine-containing oil (C). It is contained in parts by mass, preferably 0.1 to 500 parts by mass.
- a decomposition reaction of a compound containing a cationic species occurs due to heat, and the curable site (for example, cyclic ether) of a fluorine-containing copolymer having a curable site is cured (crosslinking reaction). Let's get started.
- thermoacid generator examples include the following general formula (a): (R 1 a R 2 b R 3 c R 4 d Z) + m (AXn) -m (a)
- Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements.
- R 1 , R 2 , R 3 and R. 4 represents the same or different organic group.
- A, b, c and d are 0 or positive, and the sum of a, b, c and d is equal to the valence of Z.
- Cation (R 1). a R 2 b R 3 c R 4 d Z) + m represents an onium salt.
- A is a metal element or semi-metal element (metall) which is a central atom of the halide complex. represents oid) and is at least one selected from the group consisting of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co.
- X represents a halogen element.
- m is the net charge of the halide complex ion.
- n is the number of halogen elements in the halide complex ion. ) Is suitable.
- anion (AXn) -m of the general formula (a) tetrafluoroborate (BF 4 -), hexafluorophosphate (PF 6 -), hexafluoroantimonate (SbF 6 -), hexafluoro arsenates (AsF 6 -), hexachloroantimonate (SbCl 6 -), and the like.
- an anion represented by the general formula AXn (OH) ⁇ can also be used.
- thermoacid generator examples include, for example, diazonium salt type such as AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeca), WPAG series (manufactured by Wako Junyaku Co., Ltd.); UVE series. (General Electric), FC series (3M), UV9310C (GE Toshiba Silicone), Photoinitiator 2074 (Rhone Pulan), WPI series (Wako Junyaku), etc.
- diazonium salt type such as AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeca), WPAG series (manufactured by Wako Junyaku Co., Ltd.); UVE series. (General Electric), FC series (3M), UV9310C (GE Toshiba Silicone), Photoinitiator 2074 (Rhone Pulan), WPI series (Wako Junyaku), etc.
- Iodonium salt type CYRACURE Series (Union Carbide), UVI Series (General Electric), FC Series (3M), CD Series (Satomer), Optomer SP Series / Optomer CP Series (Adeca), Sun Aid SI Series Examples include sulfonium salt types such as (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Junyaku Co., Ltd.), and CPI series (manufactured by San Apro Co., Ltd.).
- thermal acid generators may be used alone or in combination of two or more.
- thermoacid generator is not particularly limited, but is 0.01 to 1,000 with respect to a total of 100 parts by mass of the fluorine-containing copolymer and, if present, the fluorine-containing oil (C). It is contained in parts by mass, preferably 0.1 to 500 parts by mass.
- a compound containing a cation species is excited by light to cause a photodecomposition reaction, and a curable moiety (for example, cyclic ether) of a fluorine-containing copolymer having a curable moiety occurs. Curing (crosslinking reaction) is started.
- Examples of the active energy ray cation curing initiator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, and p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate.
- Specific products of the active energy ray cation curing initiator include, for example, UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide); ADEKA PUTMER SP-150, SP-151.
- active energy ray cation curing initiators may be used alone or in combination of two or more.
- the active energy ray radical curing initiator is not particularly limited, but is 0.01 to 0.01 to 100 parts by mass of the total of 100 parts by mass of the fluorine-containing copolymer and, if present, the fluorine-containing oil (C). It is contained in an amount of 1,000 parts by mass, preferably 0.1 to 500 parts by mass.
- the surface treatment agent of the present disclosure may contain a solvent.
- the fluorine-containing copolymer contained in the surface treatment agent of the present disclosure exhibits high solubility not only in a fluorine-containing organic solvent but also in a fluorine-free organic solvent which is a general-purpose solvent.
- a containing organic solvent and a fluorine-free organic solvent can be used.
- fluorine-containing organic solvents examples include perfluorohexane, perfluorooctanoic acid, perfluorodimethylcyclohexane, perfluorodecanoic acid, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (florinate (trade name), etc.), and perfluoroalkyl ether.
- Perfluorobutyl tetrahydrofuran polyfluoroaliphatic hydrocarbon (Asahiclin AC6000 (trade name)), hydrochlorofluorocarbon (Asahiclin AK-225 (trade name), etc.), hydrofluoroether (Novec (trade name), HFE-7100) (Product name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluoroalcohol-containing alcohol, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Crytox (trade name), Demnum (trade name), vonbrin (trade name), etc.), 1,3-bistrifluoromethylbenzene, 2- (perfluoroalkyl) ethyl methacrylate, 2- (perfluoroalkyl) ethyl acrylate, perfluoroalkylethylene, Freon 134a , And hexafluoro
- fluorine-free organic solvent examples include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether.
- the solvent used in the surface treatment agent of the present disclosure is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol or 2-propanol. Is.
- solvents may be used alone or in combination of two or more.
- Such a solvent is contained in an amount of 5 to 100,000 parts by mass, preferably 5 to 50,000 parts by mass, based on a total of 100 parts by mass of the fluorine-containing copolymer and, if present, the fluorine-containing oil (C). Is done.
- the surface treatment agent of the present disclosure can be added to a composition forming a matrix to form a curable composition.
- the curable composition contains the fluorine-containing copolymer or surface treatment agent of the present disclosure in an amount of 0.01 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass. To do.
- the composition forming the matrix is a compound having at least one carbon-carbon double bond, for example, but not particularly limited, monofunctional and / or polyfunctional acrylate and methacrylate (hereinafter, acrylate and methacrylate). Together, they are also referred to as "(meth) acrylates"), meaning compositions containing compounds that are monofunctional and / or polyfunctional urethane (meth) acrylates, monofunctional and / or polyfunctional epoxy (meth) acrylates. ..
- the composition forming the matrix is not particularly limited, but is a composition generally regarded as a hard coating agent or an antireflection agent, for example, a hard coating agent containing a polyfunctional (meth) acrylate.
- an antireflection agent containing a fluorine-containing (meth) acrylate can be mentioned.
- the hard coating agent is, for example, beam set 502H, 504H, 505A-6, 550B, 575CB, 575, 1402 (trade name) from Arakawa Chemical Industry Co., Ltd., EBECRYL40 (trade name) from Daicel Cytec, HR300 series (trade name). It is commercially available from Yokohama Rubber as a product name).
- the antireflection agent is commercially available from Daikin Industries, Ltd., for example, as Optool AR-110 (trade name).
- composition forming the above matrix a composition containing a compound which is a monofunctional and / or polyfunctional epoxy is also preferable.
- a compound which is a monofunctional and / or polyfunctional epoxy is also preferable.
- a hydrogenated epoxy resin an alicyclic epoxy resin, or an epoxy resin containing an isocyanurate ring, or a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, Naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, hydrogenated epoxy resin obtained by hydrogenating the aromatic rings of the various epoxy resins, and dicyclopentadiene type epoxy resin can be used.
- the surface treatment agents and curable compositions of the present disclosure further include inorganic agents such as antioxidants, thickeners, leveling agents, antifoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, and silica. It may contain fine particles, aluminum paste, talc, glass frit, fillers such as metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).
- inorganic agents such as antioxidants, thickeners, leveling agents, antifoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, and silica. It may contain fine particles, aluminum paste, talc, glass frit, fillers such as metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).
- BHT butylated hydroxytoluene
- a base material and the surface treatment agent or curable composition of the present disclosure are combined with the surface of the base material are combined with each other to form a "surface treatment agent” or "surface treatment agent”.
- a surface treatment agent or “surface treatment agent”.
- an article containing a layer (surface treatment layer) formed of a “surface treatment composition” can be manufactured, for example, as follows.
- the substrates that can be used in the present disclosure include, for example, glass, resin (natural or synthetic resin, for example, general plastic material, preferably polycarbonate resin, poly (meth) acrylate resin, polyethylene terephthalate resin, triacetyl cellulose resin, etc. It may be a polyimide resin, a modified (transparent) polyimide resin, a polycycloolefin resin, a polyethylene naphthalate resin, a plate, a film, or any other form), a metal (a metal such as aluminum, copper, silver, iron, etc.). Any suitable material such as single substance or composite such as alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building material, etc. Can consist of.
- resin naturally or synthetic resin, for example, general plastic material, preferably polycarbonate resin, poly (meth) acrylate resin, polyethylene terephthalate resin, triacetyl cellulose resin
- the material constituting the surface of the base material may be a material for the optical member, for example, glass or transparent plastic.
- the base material may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a retardation film, etc., depending on the specific specifications thereof. It may have an organic EL display module, a liquid crystal display module, and the like.
- the material constituting the surface of the base material is an electronic or electrical material such as phenol resin, epoxy resin, polyimide, polyphenylene ether, liquid crystal polymer, or fluororesin.
- the composite material thereof may be, for example, paper phenol, glass cloth impregnated epoxy, or the like, a metal material such as copper or aluminum, or an inorganic material such as alumina or glass.
- the shape of the base material is not particularly limited. Further, the surface region of the base material on which the surface treatment layer should be formed may be at least a part of the surface of the base material, and may be appropriately determined according to the use of the article to be manufactured, specific specifications and the like.
- a film of the above-mentioned surface treatment agent of the present disclosure is formed on the surface of such a base material, and this film is post-treated as necessary to form a surface treatment layer from the surface treatment agent of the present disclosure. To do.
- the film formation of the surface treatment agent of the present disclosure can be carried out by applying the above surface treatment agent to the surface of the base material so as to cover the surface.
- the coating method is not particularly limited. For example, a wet coating method can be used.
- wet coating methods include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, microgravure coating, bar coating, die coating, screen printing and similar methods.
- the surface treatment agents of the present disclosure can be diluted with a solvent before being applied to the surface of the substrate.
- a solvent the above-mentioned fluorine-containing organic solvent and fluorine-free organic solvent can be used.
- the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5-12 carbon atoms (eg, perfluorohexane, perfluoromethylcyclohexane and perfluoro-.
- 1,3-dimethyl-cyclohexane polyfluoro aromatic hydrocarbons (e.g., bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbon; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3 ), Perfluorobutyl methyl ether (C 4 F 9 OCH 3 ), Perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), Perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) and other alkyl perfluoroalkyl ethers (perfluoroalkyl groups and alkyl groups may be linear or branched), hydrochlorofluorocarbons (Asahiclean AK-225 (trade name), etc.), methyl cellosolves, ethyl cellosolves, etc.
- HFE
- Methyl cellosolve acetate cellosolve solvent such as ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, lactic acid.
- cellosolve solvent such as ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, lactic acid.
- Ester solvents such as methyl, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Protinic glycol solvents such as glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino Ketone solvents such as ketone and 2-heptanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol and diacetone
- solvents can be used alone or as a mixture of two or more.
- hydrofluoro ethers, glycol solvents, ester solvents, ketone solvents, alcohol solvents are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and / or perfluoro butyl ethyl ether (C 4 F 9 OC). 2 H 5), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, butanol, diacetone alcohol are particularly preferred.
- the membrane is post-treated.
- This post-treatment is not particularly limited, but is performed by irradiating, for example, an active energy ray, for example, an electromagnetic wave in a wavelength region of 350 nm or less, that is, an ultraviolet ray, an electron beam, an X-ray, a ⁇ -ray, or the like. Alternatively, it is carried out by heating for a predetermined time.
- an active energy ray for example, an electromagnetic wave in a wavelength region of 350 nm or less, that is, an ultraviolet ray, an electron beam, an X-ray, a ⁇ -ray, or the like.
- it is carried out by heating for a predetermined time.
- a surface treatment layer derived from the surface treatment agent of the present disclosure is formed on the surface of the base material, and the article of the present disclosure is manufactured.
- the surface-treated layer thus obtained has both high surface slipperiness (or lubricity, such as wiping property of stains such as fingerprints and excellent tactile sensation to fingers) and high friction durability.
- this surface treatment layer has water repellency, oil repellency, and stain resistance (for example, adhesion of stains such as fingerprints), depending on the composition of the surface treatment agent used. (Prevent) and the like, and can be suitably used as a functional thin film.
- the present disclosure further relates to an optical material having the surface treatment layer as the outermost layer.
- optical material examples include optical materials related to displays and the like as exemplified below, as well as a wide variety of optical materials: for example, cathode ray tubes (CRTs; eg, TVs, personal computer monitors), liquid crystal displays, plasma displays, and the like.
- CTRs cathode ray tubes
- LCD liquid crystal display
- plasma displays plasma displays
- On displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, cathode ray tubes (VFD), electric field emission displays (FED; Field Mission Display), or protective plates, films or surfaces of those displays.
- Anti-reflection film treatment for example, cathode ray tubes (CRTs; eg, TVs, personal computer monitors), liquid crystal displays, plasma displays, and the like.
- On displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, cathode ray tubes (VFD), electric field emission displays (FED; Field Mission Display), or protective plates
- the article having the surface treatment layer obtained by the present disclosure is not particularly limited, but may be an optical member.
- optical components include: lenses such as optical discs; front protective plates for displays such as DVDs and LCDs, anti-scattering films, anti-reflection plates, polarizing plates, anti-glare plates; mobile phones, mobile information terminals.
- Touch panel sheets for devices such as; Blu-ray (registered trademark) discs, DVD discs, optical disc surfaces such as CD-Rs and MOs; optical discs, etc.
- examples of the article having the surface treatment layer obtained by the present disclosure include LiDAR (Light Detection and Ringing) cover member, sensor member, instrument panel cover member, automobile interior member, and the like, especially for automobiles. Members can be mentioned.
- LiDAR Light Detection and Ringing
- the thickness of the surface treatment layer is not particularly limited.
- the thickness of the surface treatment layer is in the range of 0.1 to 30 ⁇ m, preferably 0.5 to 20 ⁇ m, from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling property. preferable.
- the fluorine-containing copolymer of the present disclosure contains fluorine, it can also be used as an insulator or a dielectric having excellent electrical characteristics.
- the present disclosure further relates to insulators and dielectrics formed from curable compositions.
- the insulator and the dielectric may form a film. That is, the insulator and the dielectric are preferably used as an insulating film and a dielectric film.
- the insulating film is a gate insulating film, an interlayer insulating film, an insulating film for semiconductors such as an insulating film formed after resist peeling and cleaning, an insulating film laminated on a printed circuit board, an insulating film of a ceramic wiring board, a film condenser, and a signal line. (For example, electric wire) It can be used as an insulating film for a coating material.
- the insulating film or dielectric film can be used as a dielectric insulating layer in a high-frequency transmission line.
- An example of a high-frequency transmission line is a millimeter-wave radar board for automatic operation. Since the insulating film or the dielectric film contains fluorine, it has a low dielectric loss tangent tan ⁇ and a low dielectric constant, so that the sensitivity of the in-vehicle radar can be improved.
- the insulating film can be used as an insulator for a high-speed communication compatible substrate.
- the transmission loss can be reduced by reducing the dielectric constant or the dielectric loss tangent.
- the insulating film of the present disclosure has a low dielectric constant and dielectric loss tangent due to the effect of fluorine, and is therefore advantageous as an insulator for a high-speed compatible substrate.
- Examples of such a high-speed communication board include a base station antenna board, an antenna distribution board, a board for RRH (Remote Radio Head) which is a wireless part of a wireless base station, a control unit or a base band unit (BBU: Base) of a wireless base station.
- BandUnit) board high-speed communication transceiver board, RNC (RadioNetworkContoroler) board, high-speed transmitter board, high-speed receiver board, high-speed signal multiplexing circuit board, 60GHz band WiFig board, data center board Examples include data transfer boards used in servers.
- an antenna board for example, a board for a super multi-element antenna (Massive MIMO) for large-capacity communication required by a standard of 5G or later can be exemplified.
- Massive MIMO super multi-element antenna
- the above insulating film can be used not only as an insulator for a substrate but also as an insulator for a signal line coating material.
- insulating coating materials such as waveguides that transmit high-speed signals, QSFP cables for high-speed LAN, coaxial cables for high-speed communication (eg SFP + cables, QSFP + cables, etc.), coaxial cables for low loss, etc. Can be used as an insulating tube).
- the insulating film can also be used as an insulating material for such materials.
- the insulating film can also be used as an insulating material for connector printed wiring boards that require soldering. Since the insulator has excellent heat resistance, problems do not easily occur even at high temperatures during soldering.
- Dielectric waveguide In a dielectric waveguide, a material with low dielectric loss is required in order to transmit high frequency millimeter waves or submillimeter waves with low loss.
- the dielectric film can also be used as an insulating material for a dielectric waveguide that transmits millimeter waves, submillimeter waves, and the like.
- Dielectric waveguides include columnar dielectric lines, square dielectric lines, elliptical dielectric lines, tubular dielectric lines, image lines, insulator image lines, trapped image lines, rib guides, and strip dielectrics. Examples thereof include a body line, a reverse strip line, an H guide, and a non-radioelectric dielectric line (NRD guide).
- the component in which the insulating film or dielectric film of the present invention is used may be any component that requires insulation, and examples thereof include electronic components, touch panels, solar cell panels, and various display components. Specific examples of the components include semiconductors, printed circuit boards, element encapsulants, element protective films, and the like.
- Synthesis example 2 Synthesis of Chain Transfer Agent (A-2) 2-[(Dodecylsulfanylthiocarbonyl) Sulfanyl] Propionic Acid (Macromolecules, 2005, 38, 2191) instead of 0.505 g of 2-[(Butylsulfanylthiocarbonyl) Sulfanyl] Propionic Acid 4.28 g of the target product (A-2) was obtained in the same manner as in Synthesis Example 1 except that it was changed to 0.343 g (synthesized with reference to -2204).
- Synthesis example 3 Synthesis of Chain Transfer Agent (A-3) 2-[(Dodecylsulfanylthiocarbonyl) Sulfanyl] Propanoic Acid 0.505 g Instead of 4-Cyano-4-[(thioethoxyl) Sulfanyl] Pentanoic Acid (Tetrahedron Letters, 1999, (Synthesis with reference to 40,277-280) 4.20 g of the target product (A-3) was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 0.356 g.
- Synthesis example 4 Synthesis of chain transfer agent (A-4) CF 3 CF 2 CF 2 (OCF 2 CF 2 CF 2 ) n OCF 2 CF 2 CH 2 OH (mean value of n ⁇ 14) 3.1 g as an alcohol containing perfluoropolyester 2.59 g of the target product (A-4) was obtained in the same manner as in Synthesis Example 1 except that
- Synthesis example 6 Synthesis of Chain Transfer Agent (A-6) As an alcohol containing perfluoropolyester, CF 3 CF 2 CF 2 [OCF (CF 3 ) CF 2 ] n OCF (CF 3 ) CH 2 OH (n ⁇ 25) 5.0 g 4.68 g of the target product (A-6) was obtained in the same manner as in Synthesis Example 1 except that it was used.
- PFPE block polymer having epoxy group (1) Synthesis of PFPE block polymer (P-1) to (P-6) having epoxy group 1.0 g of chain transfer agent (A-1), 4 -Hydroxybutyl acrylate glycidyl ether (4HBAGE) (manufactured by Mitsubishi Chemical Industries, Ltd.) 0.92 g, N, N'-azobisisobutyronitrile (AIBN) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 12 mg, added 1,3- It was dissolved in 2.9 mL of bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.). The mixture was heated at 75 ° C.
- Synthetic chain transfer agent (A-1) 1.0 g of PFPE block polymer (P-11) having an epoxy group was changed to 1.0 g of chain transfer agent (A-6). Polymerization was carried out in the same manner as in the synthesis to obtain a block polymer (P-11) having a degree of polymerization of 20.
- block polymers (P-28) and (P-29) having a degree of polymerization of 10 and 7 were synthesized as shown in Table 1. ..
- Coating film preparation (1) Acrylic coating Acrylic hard coating agent Beam set 575CB (manufactured by Arakawa Chemical Industry Co., Ltd.) is dissolved in MIBK, and block polymers (P-1) to (P-12), (P) are further dissolved in the solution. -15) to (P-18) and (P-21) to (P-31) were added so as to be 1% in terms of solid content concentration with respect to the hard coating agent resin solid content, and 50% by mass of PFPE was added. A containing hard coat agent was obtained. A commercially available PET substrate (Toray Industries, Inc., Lumirror S10) was coated with the above-mentioned PFPE-containing hard coating agent with a bar coater, dried at 70 ° C.
- PET substrate Toray Industries, Inc., Lumirror S10
- a belt conveyor type ultraviolet irradiation device was used for ultraviolet irradiation, and the irradiation amount was 600 mJ / cm 2 .
- Epoxy-based coating Serokiside 2021P (manufactured by Daicel Co., Ltd.) is dissolved in MIBK, and the block polymers (P-1) to (P-12), (P-15) to (P-18), ( P-21) to (P-31) were added so as to be 1% in terms of solid content concentration with respect to the solid content of the epoxy compound to prepare a 50% by mass epoxy compound solution. Further, 3 wt% of Sun Aid SI-60L (manufactured by Sanshin Chemical Co., Ltd.), which is a thermoacid generator, was added to the epoxy compound to obtain a PFPE-containing treatment agent. The PET substrate was coated with a PFPE-containing treatment agent with a bar coater and heated at 90 ° C. for 2 hours to obtain a cured film.
- Sun Aid SI-60L manufactured by Sanshin Chemical Co., Ltd.
- Sun Aid SI-60L manufactured by Sanshin Chemical Co., Ltd.
- the PET substrate was coated with a PFPE-containing treatment agent with a bar coater and heated at 90 ° C. for 2 hours to obtain a cured film having a thickness of about 50 ⁇ m. Further, only the above-mentioned block polymer (P-1) is changed to the block polymers P-2, P-9, P-11, P-12, P-27 and P-30, and the thickness is similarly changed. A cured film of about 50 ⁇ m was obtained.
- the permittivity of 10 GHz and the dielectric loss tangent were determined by the split cylinder resonator method.
- a resonator manufactured by Kanto Denshi Applied Development Co., Ltd. was used as the split cylinder, and Keysight N5290A was used as the network spectrum analyzer.
- a sample to be measured a film having a thickness of 50 ⁇ m ⁇ a width of 62 mm ⁇ a length of 75 mm was used.
- the measurement temperature was 25 ° C.
- Table 2 The results are shown in Table 2.
- Comparative Example From the above Examples, only the block polymer (P-1) was removed, and then a cured film having a thickness of 50 ⁇ m (Comparative Example) was prepared in the same manner, and the dielectric constant and the dielectric loss tangent were measured in the same manner. The results are shown in Table 2.
- the surface treatment agent of the present disclosure can be suitably used for forming a surface treatment layer on a wide variety of base materials, particularly the surface of an optical member that is required to have transparency. It is also suitable as an insulator and a dielectric.
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Abstract
Description
[1] 下記式(1)または(2):
RF1は、Rf1-RF-Oq-であり;
RF2は、-Rf2 p-RF-Oq-であり;
Rf1は、1個またはそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
Rf2は、1個またはそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFは、それぞれ独立して、2価のフルオロポリエーテル基であり;
pは、0または1であり;
qは、それぞれ独立して、0または1であり;
R4は、各出現においてそれぞれ独立して、R4aまたはR4bであり;
R4aは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有する2価の有機基であり;
R4bは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有しない2価の有機基であり;
前記置換基群Aは、炭素-炭素二重結合、炭素-炭素三重結合、環状エーテル基、水酸基、チオール基、アミノ基、アジド基、含窒素複素環基、イソシアネート基、ハロゲン原子、リン酸含有基、又はシランカップリング基を含む基、あるいはこれらの前駆体基であり;
nは1~100の整数であり;
Xaは、それぞれ独立して、二価の有機基であり;
Xbは、それぞれ独立して、二価の有機基であり;
Raは、それぞれ独立して、アルキル、フェニル、-SRa1、-ORa2、-NRa3 2、
Ra1、Ra2、Ra3、Ra4、Ra5およびRa6は、それぞれ独立して、アルキル基またはフェニル基であり;
Ra7は、水素またはハロゲン原子である。]
で表される含フッ素共重合体。
[2] RFは、それぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3RFa 6)d-(OC2F4)e-(OCF2)f-
[式中、RFaは、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、
a、b、c、d、eおよびfは、それぞれ独立して、0~200の整数であって、a、b、c、d、eおよびfの和は1以上であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である、上記[1]に記載の含フッ素共重合体。
[3] RFaは、フッ素原子である、上記[2]に記載の含フッ素共重合体。
[4] RFは、それぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)または(f5):
-(OC3F6)d- (f1)
[式中、dは1~200の整数である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、cおよびdは、それぞれ独立して、0~30の整数であり;
eおよびfは、それぞれ独立して、1~200の整数であり;
c、d、eおよびfの和は、10~200の整数であり;
添字c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。]、
-(R6-R7)g- (f3)
[式中、R6は、OCF2またはOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から選択される2または3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f4)
[式中、eは、1以上200以下の整数であり、a、b、c、dおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、fは、1以上200以下の整数であり、a、b、c、dおよびeは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である、上記[1]~[3]のいずれか1項に記載の含フッ素共重合体。
[5] R4は、R4aである、上記[1]~[4]のいずれか1項に記載の含フッ素共重合体。
[6] R4aは、下記式:
R31は、各出現において、それぞれ独立して、水素原子、またはアルキル基であり;
R32は、各出現において、それぞれ独立して、水素原子、塩素原子、フッ素原子、またはフッ素により置換されていてもよいアルキル基でありであり;
R33は、各出現において、それぞれ独立して、置換基群Aより選択される官能基であり;
Y1は、単結合、-C(=O)O-、-C(=O)NH-、-OC(=O)-、-NHC(=O)-、-O-、-N(Rc)-、フェニレンまたはカルバゾリレンであり;
Rcは、有機基であり、
Y2は、単結合または主鎖の原子数が1~16であるリンカーである。]
で表される基である、上記[1]~[5]のいずれか1項に記載の含フッ素共重合体。
[7] R4aにおける置換基群Aより選択される官能基は、エポキシ基、グリシジル基、脂環式エポキシ基、アクリロイル基またはメタクリロイル基を有する基である、上記[1]~[6]のいずれか1項に記載の含フッ素共重合体。
[8] nは、2~50の整数である、上記[1]~[7]のいずれか1項に記載の含フッ素共重合体。
[9] nは、2~30の整数である、上記[1]~[8]のいずれか1項に記載の含フッ素共重合体。
[10] 1種またはそれ以上の上記[1]~[9]のいずれか1項に記載の含フッ素共重合体を含む、表面処理剤。
[11] 上記[1]~[9]のいずれか1項に記載の含フッ素共重合体または上記[10]に記載の表面処理剤;および
マトリックスを形成する組成物
を含む、硬化性組成物。
[12] 上記[10]に記載の表面処理剤あるいは上記[11]に記載の硬化性組成物により形成された膜。
[13] 基材と、該基材の表面に上記[10]に記載の表面処理剤あるいは上記[11]に記載の硬化性組成物により形成された層とを含む物品。
[14] 上記物品が光学部材である、上記[13]に記載の物品。
[15] LiDARカバー部材である、上記[13]に記載の物品。
[16] センサー部材である、上記[13]に記載の物品。
[17] インストルメントパネルカバー部材である、上記[13]に記載の物品。
[18] 自動車内装部材である、上記[13]に記載の物品。
[19] 上記物品が絶縁体、誘電体である、上記[13]に記載の物品。
RF1は、Rf1-RF-Oq-であり;
RF2は、-Rf2 p-RF-Oq-であり;
Rf1は、それぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
Rf2は、1個またはそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFは、それぞれ独立して、2価のフルオロポリエーテル基であり;
pは、0または1であり;
qは、それぞれ独立して、0または1であり;
R4は、各出現においてそれぞれ独立して、R4aまたはR4bであり;
R4aは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有する2価の有機基であり;
R4bは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有しない2価の有機基であり;
上記置換基群Aは、炭素-炭素二重結合、炭素-炭素三重結合、環状エーテル基、水酸基、チオール基、アミノ基、アジド基、含窒素複素環基、イソシアネート基、ハロゲン原子、リン酸含有基、又はシランカップリング基を含む基、あるいはこれらの前駆体基であり;
n1は1~100の整数であり;
Xaは、それぞれ独立して、二価の有機基であり;
Xbは、それぞれ独立して、二価の有機基であり;
Raは、それぞれ独立して、アルキル、フェニル、-SRa1、-ORa2、-NRa3 2、
Ra1、Ra2、Ra3、Ra4、Ra5およびRa6は、それぞれ独立して、アルキル基またはフェニル基であり;
Ra7は、水素またはハロゲン原子である。]
で表される含フッ素共重合体を提供する。
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3RFa 6)d-(OC2F4)e-(OCF2)f-
[式中:
RFaは、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、
a、b、c、d、eおよびfは、それぞれ独立して、0~200の整数であって、a、b、c、d、eおよびfの和は1以上である。a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である。
-(OC3F6)d- (f1)
[式中、dは、1~200の整数である。];
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、cおよびdは、それぞれ独立して0以上30以下の整数であり、eおよびfは、それぞれ独立して1以上200以下の整数であり、
c、d、eおよびfの和は2以上であり、
添字c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。];
-(R6-R7)g- (f3)
[式中、R6は、OCF2またはOC2F4であり、
R7は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から独立して選択される2または3つの基の組み合わせであり、
gは、2~100の整数である。];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f4)
[式中、eは、1以上200以下の整数であり、a、b、c、dおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、fは、1以上200以下の整数であり、a、b、c、dおよびeは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(CH2-CH2-O)p1-(p1は、1~10の整数を表す)、
-(CHRd)p2-O-(p2は、1~40の整数であり、Rdは、水素、またはメチル基を表す)、
-(CH2-CH2-O)p3-CO-NH-CH2-CH2-O-(p3は、1~10の整数を表す)、
-CH2-CH2-O-CH2-CH2-、
-(CH2)p4-(p4は1~6の整数を表す)、
-(CH2)p5-O-CONH-(CH2)p6-(p5は1~8の整数、好ましくは、2または4を表し、p6は1~6の整数、好ましくは3を表す)、
-(CH2)p7-NHC(=O)O-(CH2)p8-(p7は1~6の整数、好ましくは3を表し、p8は1~8の整数、好ましくは、2または4を表す)、または
-O-(但し、Y1は-O-ではない)が挙げられる。
(a)-(CH2-CH2-O)s1-(s1は、1~10の整数を表す。)、
(b)-(CHR4h)s2-O-(s2は、1~40の整数である繰り返し数を表す。R4hは、水素またはメチル基を表す。)、
(c)-(CH2-CH2-O)s1-CO-NH-CH2-CH2-O-(s1は、上記と同意義である。)、
(d)-CH2-CH2-O-CH2-CH2-、
(e)-(CH2)s3-(s3は1~6の整数を表す。)、または
(f)-(CH2)s4-O-CONH-(CH2)s5-(s4は1~8の整数、好ましくは、2または4を表す。s5は1~6の整数、好ましくは3を表す。)、または
(g)-O-(但し、Y3は-O-ではない)
である。
(i)アルキル基
例:メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、tert-ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ドデシル、オクタデシル
例:
(v)イミダゾリウム塩を含有する基
例:
(vi)ケイ素を含有する基
上記式中、R11、R12、R13、R14、R15、R16およびR17は、それぞれ独立して、アルキル基またはアリール基を表す。
-(Q)e-(CFZ)f-(CH2)g-
で表される基である。式中、e、fおよびgは、それぞれ独立して、0~10の整数であり、e、fおよびgの和は1以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。
-(O)e-(CF2)f-(CH2)g-
[式中、e、fおよびgは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である]
で表される基である。なお、これらの基は左端がRF1に結合する。
-(O)e1-(CH2)g2-O-[(CH2)g3-O-]g4、
-(O)e1-(CF2)f2-(CH2)g2-O-[(CH2)g3-O-]g4
[式中、
e1は0または1であり、
f2、g2およびg3は、それぞれ独立して、1~10の整数であり、
g4は、0または1である]
で表される基であり得る。なお、これらの基は左端がRF1に結合する。
-(CH2)g2-O-
[式中、g2は、1~10の整数である。]
で表される基であり得る。なお、かかる基は左端がRF1に結合する。
-CO-Rb3-CRb1Rb2-
[式中:
Rb1およびRb2は、それぞれ独立して、水素原子、C1-3アルキル基、フェニル基または-CNであり、
Rb3は、単結合または置換されていてもよいC1-6アルキレン基である。]
で表される基であり得る。なお、かかる基は右端がR4に結合する。
L1およびL2は、それぞれ、脱離部分である。]
を反応させて、ペルフルオロポリエーテル基を有する連鎖移動剤(1a)または(2a):
を得ることができる。
Rf2-(OCF2CF2CF2)b”-Rf3 ・・・(C1)
[式中、Rf2およびRf3は上記の通りであり、b”は、0~300の整数であり、添字b”を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。]
Rf2-(OCF2CF2CF2CF2)a”-(OCF2CF2CF2)b”-(OCF2CF2)c”-(OCF2)d”-Rf3 ・・・(C2)
[式中、Rf2およびRf3は上記の通りであり、a”およびb”は、それぞれ独立して、0~30の整数であり、c”およびd”は、それぞれ独立して、0~300の整数であり、添字a”、b”、c”およびd”を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。]
で表される化合物(1種または2種以上の混合物であってよい)が挙げられる。
アセトフェノン、クロロアセトフェノン、ジエトキシアセトフェノン、ヒドロキシアセトフェノン、α-アミノアセトフェノン、ヒドロキシプロピオフェノン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパンー1-オンなど
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタールなど
ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、ヒドロキシベンゾフェノン、ヒドロキシ-プロピルベンゾフェノン、アクリル化ベンゾフェノン、ミヒラーズケトンなど
チオキサンソン、クロロチオキサンソン、メチルチオキサンソン、ジエチルチオキサンソン、ジメチルチオキサンソンなど
ベンジル、α-アシルオキシムエステル、アシルホスフィンオキサイド、グリオキシエステル、3-ケトクマリン、2-エチルアンスラキノン、カンファーキノン、アンスラキノンなど
(R1 aR2 bR3 cR4 dZ)+m(AXn)-m (a)
(式中、Zは、S、Se、Te、P、As、Sb、Bi、O、N及びハロゲン元素からなる群より選ばれる少なくとも一つの元素を表す。R1、R2、R3及びR4は、同一又は
異なって、有機基を表す。a、b、c及びdは、0又は正数であり、a、b、c及びdの合計はZの価数に等しい。カチオン(R1 aR2 bR3 cR4 dZ)+mはオニウム塩を表す。Aは、ハロゲン化物錯体の中心原子である金属元素又は半金属元素(metall
oid)を表し、B、P、As、Al、Ca、In、Ti、Zn、Sc、V、Cr、Mn、Coからなる群より選ばれる少なくとも一つである。Xは、ハロゲン元素を表す。mは、ハロゲン化物錯体イオンの正味の電荷である。nは、ハロゲン化物錯体イオン中のハロゲン元素の数である。)で表される化合物が好適である。
(BF4 -)、ヘキサフルオロホスフェート(PF6 -)、ヘキサフルオロアンチモネート(SbF6 -)、ヘキサフルオロアルセネート(AsF6 -)、ヘキサクロロアンチモネート(SbCl6 -)等が挙げられる。
更に一般式AXn(OH)-で表される陰イオンも用いることができる。また、その他の陰イオンとしては、過塩素酸イオン(ClO4 -)、トリフルオロメチル亜硫酸イオン(CF3SO3 -)、フルオロスルホン酸イオン(FSO3 -)、トルエンスルホン酸イオン、トリニトロベンゼンスルホン酸イオン等が挙げられる。
合成例1
連鎖移動剤(A-1)の合成
フラスコに2-[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸(富士フイルム和光純薬社製)0.505g、4-ジメチルアミノピリジン(DMAP)(東京化成工業社製)0.019g、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(EDCI)(東京化成工業社製)0.293g、CF3CF2CF2(OCF2CF2CF2)nOCF2CF2CH2OH(nの平均値≒25)で表されるペルフルオロポリエーテルを含有するアルコール(ダイキン工業社製)5.0gをとり、アサヒクリンAK-225(AGC社製)の13mLを加えて室温で撹拌し反応を行った。一晩撹拌後、反応液を飽和重曹水、食塩水で洗浄した。有機層を分離して濃縮し、メタノール中に滴下して、2-[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸とペルフルオロポリエーテルを含有するアルコールとの脱水縮合反応物である黄色油状の目的物(A-1)4.56gを得た。化合物の構造は1Hおよび19FNMR測定により確認した。
連鎖移動剤(A-2)の合成
2-[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸0.505gに替えて2-[(ブチルスルファニルチオカルボニル)スルファニル]プロパン酸(Macromolecules,2005,38,2191-2204を参照し合成)0.343gに変更した以外は合成例1と同様にして、目的物(A-2)4.28gを得た。
連鎖移動剤(A-3)の合成
2-[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸0.505gに替えて4-シアノ-4-[(チオエトキシル)スルファニル]ペンタン酸(Tetrahedron Letters,1999,40,277-280を参照し合成)0.356gに変更した以外は合成例1と同様にして、目的物(A-3)4.20gを得た。
連鎖移動剤(A-4)の合成
ペルフルオロポリエーテルを含むアルコールとしてCF3CF2CF2(OCF2CF2CF2)nOCF2CF2CH2OH(nの平均値≒14)3.1gを用いた以外は合成例1と同様にして、目的物(A-4)2.59gを得た。
連鎖移動剤(A-5)の合成
2-[(ドデシルスルファニルチオカルボニル)スルファニル]プロパン酸を0.421g、DMAPを0.015g、EDCIを0.230gに変更し、ペルフルオロポリエーテルを含有するアルコールとしてCF3CF2(OCF2)m(OCF2CF2)nOCF2CH2OH(数平均分子量4200、n/m=1.1)4.2gを用いたこと以外は合成例1と同様にして、目的物(A-5)4.27gを得た。
連鎖移動剤(A-6)の合成
ペルフルオロポリエーテルを含むアルコールとしてCF3CF2CF2[OCF(CF3)CF2]nOCF(CF3)CH2OH(n≒25)5.0gを用いた以外は合成例1と同様にして目的物(A-6)4.68gを得た。
ペルフルオロポリエーテルを含むアルコールとしてCF3CF2CF2(OCF2CF2CF2)nOCF2CF2CH2OH(nの平均値≒35)8.1gを用いた以外は合成例1と同様にして、目的物(A-7)7.70gを得た。
(1)エポキシ基を有するPFPEブロックポリマー(P-1)~(P-6)の合成
反応容器内に連鎖移動剤(A-1)の1.0g、4-ヒドロキシブチルアクリレートグリシジルエーテル(4HBAGE)(三菱ケミカル社製)0.92g、N,N’-アゾビスイソブチロニトリル(AIBN)(富士フイルム和光純薬社製)12mgを加え、1,3-ビス(トリフルオロメチル)ベンゼン(東京化成工業社製)2.9mLに溶解した。75℃で17時間加熱し、反応液をヘキサンに滴下してブロックポリマー(P-1)を沈殿させて回収した。1H-NMR測定より4HBAGEの重合度は20と算出された。
上記と同様にして、4HBAGEの仕込み量を0.46g、0.23g、1.40g、0.14g、4.83gに変えることにより表1に示すように重合度が10、5、30、3、105のブロックポリマー(P-2)~(P-6)を合成した。
連鎖移動剤(A-1)1.0gを連鎖移動剤(A-2)1.0gに変更したこと以外はP-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-7)を得た。
連鎖移動剤(A-1)1.0gを連鎖移動剤(A-3)1.0gに変更したこと以外はP-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-8)を得た。
連鎖移動剤(A-1)1.0gを連鎖移動剤(A-4)0.62gに、4HBAGEの仕込み量を0.46gに変更したこと以外はP-1の合成と同様に重合を行い、重合度10のブロックポリマー(P-9)を得た。
連鎖移動剤(A-1)1.0gを連鎖移動剤(A-5)1.0gに変更したこと以外はP-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-10)を得た。
連鎖移動剤(A-1)1.0gを連鎖移動剤(A-6)1.0gに変更したこと以外はP-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-11)を得た。
4HBAGEをアクリル酸-n-ブチル(nBA)0.59gに変更し、ポリマーを沈殿させる際にメタノールを用いたこと以外は、P-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-12)を得た。
(1)アクリル基を有するPFPEブロックポリマー(P-15),(P-16)の合成
反応容器内に連鎖移動剤(A-1)1.3g、2-ヒドロキシエチルアクリレート(HEA)(東京化成工業社製)0.18g、AIBN15.5mgを加え1,3-ビス(トリフルオロメチル)ベンゼン2.1mLに溶解した。70℃で22.5時間加熱し重合させ、ブロックポリマー(P-13)の溶液を得た。1H-NMR測定よりHEAの重合度は5と算出された。
同様にして、HEAの仕込み量を0.36gに変更し表に示すように重合度10のブロックポリマー(P-14)を合成した。
ブロックポリマー(P-14)についても同様の反応を行い、重合度の異なるブロックポリマー(P-16)を合成した。
カレンズAOIをカレンズMOI(昭和電工社製)に変更したこと以外はP-15およびP-16の合成と同様にして表に示すようにメタクリル基を有するブロックポリマー(P-17),(P-18)を合成した。
反応容器内に(A-1)1.2g、4-ヒドロキシブチルアクリレート(HBA)(東京化成工業社製)0.20g、AIBN14.0mgを加え1,3-ビス(トリフルオロメチル)ベンゼン2.1mLに溶解した。70℃で22.5時間加熱し重合させ、ブロックポリマー(P-19)の溶液を得た。1H-NMR測定よりHBAの重合度は5と算出された。
同様にして、HBAの仕込み量を0.40gに変更し表に示すように重合度10のブロックポリマー(P-20)を合成した。
ブロックポリマー(P-20)についても同様の反応を行い、重合度の異なるブロックポリマー(P-22)を合成した。
カレンズAOIをカレンズMOI(昭和電工社製)に変更したこと以外はP-19およびP-20と同様にして表に示すようにメタクリル基を有するブロックポリマー(P-23),(P-24)を合成した。
下図に示すブロックポリマー(P-26)を特許第5840236号実施例45の単量体2-(ビニロキシ)エトキシエチルメタクリレートを2-(ビニロキシ)エトキシエチルアクリレート(日本触媒社製)に変更することで合成した。
反応容器内に連鎖移動剤(A-7)0.9g、4HBAGE0.43g、AIBN7mgを加え、1,3-ビス(トリフルオロメチル)ベンゼン3.0mLに溶解した。75℃で17時間加熱し、反応液をヘキサンに滴下してブロックポリマー(P-27)を沈殿させて回収した。1H-NMR測定より4HBAGEの重合度は17と算出された。
4HBAGE0.92gを(3,4-エポキシシクロヘキシル)メチルアクリレート(ECHMA)(東京化成工業社製)0.76gに変更した以外はP-1の合成と同様に重合を行い、重合度20のブロックポリマー(P-30)を得た。また、ECHMAの仕込み量を0.38gに変更した以外はP-30の合成と同様に重合を行い、重合度10のブロックポリマー(P-31)を得た。
5.溶解性試験
上記で得られたポリマー(P-1)~(P-12)、(P-15)~(P-18)、および(P-21)~(P-31)を固形分濃度が20wt%となるようにメチルイソブチルケトン(MIBK)、またはメチルエチルケトン(MEK)中に加え、ミックスローターで2時間撹拌して溶解させ、溶液状態を目視で確認した。評価基準は以下の通りとした。結果を下記表1に示す。
G 透明かつ均一に溶解した。
NG 濁りが認められる。
(1)アクリル系コーティング
アクリル系ハードコート剤ビームセット575CB(荒川化学工業社製)をMIBKに溶解し、さらにその溶液にブロックポリマー(P-1)~(P-12)、(P-15)~(P-18)、(P-21)~(P-31)をハードコート剤樹脂固形分に対して固形分濃度換算で1%になるように添加し、50質量%のPFPE含有ハードコート剤を得た。
市販のPET基板(東レ社製、ルミラーS10)に前記のPFPE含有ハードコート剤をバーコーターで塗装し、70℃、10分間の条件で乾燥後、紫外線照射して硬化被膜を得た。紫外線照射はベルトコンベア式の紫外線照射装置を用い、照射量は600mJ/cm2とした。
セロキサイド2021P(ダイセル社製)をMIBKに溶解し、さらにその溶液にブロックポリマー(P-1)~(P-12)、(P-15)~(P-18)、(P-21)~(P-31)をエポキシ化合物固形分に対して固形分濃度換算で1%になるように添加し、50質量%のエポキシ化合物溶液を調製した。さらに熱酸発生剤であるサンエイドSI-60L(三新化学社製)をエポキシ化合物に対して3wt%添加してPFPE含有処理剤を得た。
PET基板にPFPE含有処理剤をバーコーターで塗装し、90℃、2時間の条件で加熱し、硬化被膜を得た。
上記塗膜作成工程で作製した硬化被膜について、水の静的接触角を接触角計(協和界面科学社製、「DropMaster」)を用いて、2μLの液量で測定した。結果を下記表1に示す。
実施例
ブロックポリマー(P-1)1重量部、セロキサイド2021P(ダイセル社製)10重量部を、MEK8重量部に均一溶解させた。さらに熱酸発生剤であるサンエイドSI-60L(三新化学社製)をエポキシ化合物に対して3wt%添加してコーティング剤を得た。
また、上記のブロックポリマー(P-1)のみを、ブロックポリマーP-2、P-9、P-11、P-12、P-27及びP-30に変えて、後は同様にして厚さ約50μmの硬化被膜を得た。
上記実施例から、ブロックポリマー(P-1)のみ除き、後は同様にして厚み50μmの硬化被膜(比較例)を作製し、同様に誘電率、誘電正接を測定した。結果を表2に示す。
Claims (19)
- 下記式(1)または(2):
RF1は、Rf1-RF-Oq-であり;
RF2は、-Rf2 p-RF-Oq-であり;
Rf1は、1個またはそれ以上のフッ素原子により置換されていてもよいC1-16アルキル基であり;
Rf2は、1個またはそれ以上のフッ素原子により置換されていてもよいC1-6アルキレン基であり;
RFは、それぞれ独立して、2価のフルオロポリエーテル基であり;
pは、0または1であり;
qは、それぞれ独立して、0または1であり;
R4は、各出現においてそれぞれ独立して、R4aまたはR4bであり;
R4aは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有する2価の有機基であり;
R4bは、各出現においてそれぞれ独立して、置換基群Aより選択される官能基を有しない2価の有機基であり;
前記置換基群Aは、炭素-炭素二重結合、炭素-炭素三重結合、環状エーテル基、水酸基、チオール基、アミノ基、アジド基、含窒素複素環基、イソシアネート基、ハロゲン原子、リン酸含有基、又はシランカップリング基を含む基、あるいはこれらの前駆体基であり;
nは1~100の整数であり;
Xaは、それぞれ独立して、二価の有機基であり;
Xbは、それぞれ独立して、二価の有機基であり;
Raは、それぞれ独立して、アルキル、フェニル、-SRa1、-ORa2、-NRa3 2、
Ra1、Ra2、Ra3、Ra4、Ra5およびRa6は、それぞれ独立して、アルキル基またはフェニル基であり;
Ra7は、水素またはハロゲン原子である。]
で表される含フッ素共重合体。 - RFは、それぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3RFa 6)d-(OC2F4)e-(OCF2)f-
[式中、RFaは、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、
a、b、c、d、eおよびfは、それぞれ独立して、0~200の整数であって、a、b、c、d、eおよびfの和は1以上であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である、請求項1に記載の含フッ素共重合体。 - RFaは、フッ素原子である、請求項2に記載の含フッ素共重合体。
- RFは、それぞれ独立して、下記式(f1)、(f2)、(f3)、(f4)または(f5):
-(OC3F6)d- (f1)
[式中、dは1~200の整数である。]、
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2)
[式中、cおよびdは、それぞれ独立して、0~30の整数であり;
eおよびfは、それぞれ独立して、1~200の整数であり;
c、d、eおよびfの和は、10~200の整数であり;
添字c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。]、
-(R6-R7)g- (f3)
[式中、R6は、OCF2またはOC2F4であり;
R7は、OC2F4、OC3F6、OC4F8、OC5F10およびOC6F12から選択される基であるか、あるいは、これらの基から選択される2または3つの基の組み合わせであり;
gは、2~100の整数である。]、
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f4)
[式中、eは、1以上200以下の整数であり、a、b、c、dおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5)
[式中、fは、1以上200以下の整数であり、a、b、c、dおよびeは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。]
で表される基である、請求項1~3のいずれか1項に記載の含フッ素共重合体。 - R4は、R4aである、請求項1~4のいずれか1項に記載の含フッ素共重合体。
- R4aは、下記式:
R31は、各出現において、それぞれ独立して、水素原子、またはアルキル基であり;
R32は、各出現において、それぞれ独立して、水素原子、塩素原子、フッ素原子、またはフッ素により置換されていてもよいアルキル基であり;
R33は、各出現において、それぞれ独立して、置換基群Aより選択される官能基であり;
Y1は、単結合、-C(=O)O-、-C(=O)NH-、-OC(=O)-、-NHC(=O)-、-O-、-N(Rc)-、フェニレンまたはカルバゾリレンであり;
Rcは、有機基であり、
Y2は、単結合または主鎖の原子数が1~16であるリンカーである。]
で表される基である、請求項1~5のいずれか1項に記載の含フッ素共重合体。 - R4aにおける置換基群Aより選択される官能基は、エポキシ基、グリシジル基、脂環式エポキシ基、アクリロイル基またはメタクリロイル基を有する基である、請求項1~6のいずれか1項に記載の含フッ素共重合体。
- nは、2~50の整数である、請求項1~7のいずれか1項に記載の含フッ素共重合体。
- nは、2~30の整数である、請求項1~8のいずれか1項に記載の含フッ素共重合体。
- 1種またはそれ以上の請求項1~9のいずれか1項に記載の含フッ素共重合体を含む、表面処理剤。
- 請求項1~9のいずれか1項に記載の含フッ素共重合体または請求項10に記載の表面処理剤;および
マトリックスを形成する組成物
を含む、硬化性組成物。 - 請求項10に記載の表面処理剤あるいは請求項11に記載の硬化性組成物により形成された膜。
- 基材と、該基材の表面に請求項10に記載の表面処理剤あるいは請求項11に記載の硬化性組成物により形成された層とを含む物品。
- 上記物品が光学部材である、請求項13に記載の物品。
- LiDARカバー部材である、請求項13に記載の物品。
- センサー部材である、請求項13に記載の物品。
- インストルメントパネルカバー部材である、請求項13に記載の物品。
- 自動車内装部材である、請求項13に記載の物品。
- 上記物品が絶縁体、誘電体である、請求項13に記載の物品。
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CN (1) | CN114174362A (ja) |
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WO2022050358A1 (ja) * | 2020-09-03 | 2022-03-10 | ダイキン工業株式会社 | シリコーン共重合体 |
WO2022050361A1 (ja) * | 2020-09-03 | 2022-03-10 | ダイキン工業株式会社 | 硬化性組成物 |
WO2022181795A1 (ja) * | 2021-02-26 | 2022-09-01 | ダイキン工業株式会社 | 表面処理剤 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2022050358A1 (ja) * | 2020-09-03 | 2022-03-10 | ダイキン工業株式会社 | シリコーン共重合体 |
WO2022050361A1 (ja) * | 2020-09-03 | 2022-03-10 | ダイキン工業株式会社 | 硬化性組成物 |
WO2022181795A1 (ja) * | 2021-02-26 | 2022-09-01 | ダイキン工業株式会社 | 表面処理剤 |
JP2022132171A (ja) * | 2021-02-26 | 2022-09-07 | ダイキン工業株式会社 | 表面処理剤 |
JP7425347B2 (ja) | 2021-02-26 | 2024-01-31 | ダイキン工業株式会社 | 表面処理剤 |
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EP4026694A4 (en) | 2023-08-30 |
CN114174362A (zh) | 2022-03-11 |
KR20220007664A (ko) | 2022-01-18 |
JPWO2021045209A1 (ja) | 2021-12-23 |
TWI827881B (zh) | 2024-01-01 |
US20220195115A1 (en) | 2022-06-23 |
JP7189476B2 (ja) | 2022-12-14 |
TW202120588A (zh) | 2021-06-01 |
EP4026694A1 (en) | 2022-07-13 |
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