WO2023204024A1 - Fluoropolyether group-containing polymer composition, coating agent, article, and method for modifying surface of article - Google Patents
Fluoropolyether group-containing polymer composition, coating agent, article, and method for modifying surface of article Download PDFInfo
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- WO2023204024A1 WO2023204024A1 PCT/JP2023/014036 JP2023014036W WO2023204024A1 WO 2023204024 A1 WO2023204024 A1 WO 2023204024A1 JP 2023014036 W JP2023014036 W JP 2023014036W WO 2023204024 A1 WO2023204024 A1 WO 2023204024A1
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- containing polymer
- fluoropolyether
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- 229920000642 polymer Polymers 0.000 title claims abstract description 105
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 30
- 238000005299 abrasion Methods 0.000 claims description 29
- 125000002947 alkylene group Chemical group 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 210000002268 wool Anatomy 0.000 claims description 12
- 238000011156 evaluation Methods 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 5
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 21
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 230000001629 suppression Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 28
- -1 polysiloxane residue Polymers 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000003373 anti-fouling effect Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 125000000732 arylene group Chemical group 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 210000002374 sebum Anatomy 0.000 description 3
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000006116 anti-fingerprint coating Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 2
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 2
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 239000002939 oilproofing Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- AQZYBQIAUSKCCS-UHFFFAOYSA-N perfluorotripentylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AQZYBQIAUSKCCS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of 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
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Definitions
- the present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule), and in particular, to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule).
- a fluoropolyether group-containing polymer composition capable of forming an excellent cured film, a coating agent containing the composition, and an article having a layer consisting of a cured product of the coating agent, and further applying and curing the coating agent.
- the present invention relates to a method for modifying the surface of an article, including a step of forming a layer.
- fluoropolyether group-containing compounds have water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, etc. because their surface free energy is very small.
- it is widely used industrially as water-, oil-, and stain-proofing agents for paper and textiles, lubricants for magnetic recording media, oil-proofing agents for precision equipment, mold release agents, cosmetics, and protective films.
- its properties also mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of the substrate, it is difficult to make the film adhere to it. .
- silane coupling agents are well known as agents that bond organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for the surfaces of various substrates.
- a silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups cause a self-condensation reaction with moisture in the air to form a film. The coating becomes a durable and strong coating due to the hydrolyzable silyl group chemically and physically bonding to the surface of glass, metal, or the like.
- the antifouling thin film layer on the surface of a touch panel display has been given importance not only for its ability to prevent stains, but also for its usability (good slippage and smooth feel) when using a touch panel. Good feeling in use is related to a low coefficient of friction (Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906).
- the low coefficient of friction on the casing surface of a portable electronic device terminal may be disadvantageous.
- the coefficient of friction is low, there is a high possibility that the device will fall or vibrate during use. Therefore, it is important to control the coefficient of friction while maintaining antifouling performance and durability when applying antifouling coating thin film layers to various applications including portable electronic device terminals (Patent Document 7: JP 2019-131808A).
- the present invention was made in view of the above circumstances, and provides a fluoropolyether group-containing polymer composition capable of forming a cured film having excellent water and oil repellency and abrasion resistance and a high coefficient of friction, and the composition.
- An object of the present invention is to provide a coating agent containing the above-mentioned coating agent, an article having a layer made of a cured product of the coating agent, and a method for surface modification of an article, which further includes a step of applying and curing the coating agent to form a layer. .
- the present inventors have found that, in the fluoropolyether group-containing polymer composition, two specific types of fluoropolyether group-containing polymers described below are used in combination in a specific ratio.
- a fluoropolyether group-containing polymer composition (particularly a coating agent containing the composition) formed by using the polymer and/or its partial (hydrolyzed) condensate has excellent water and oil repellency and abrasion durability.
- the present invention has been completed based on the discovery that it is possible to form a cured film having anti-slip properties due to a high coefficient of friction.
- Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.)
- J is a single bond or a carbonyl group
- Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom
- L is independently is a single bond or a divalent heteroatom
- M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond
- X is independently a hydroxyl group or a hydrolyzable group
- R are independently an alkyl group or phenyl group having 1 to
- W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.
- [2] (II) component is represented by the following general formula (3)
- Rf2 contains a unit represented by -(C c F 2c O) -
- the C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching.
- R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
- X is independently a hydroxyl group or a hydrolyzable group
- n is bonded to a silicon atom.
- Each unit is independently an integer of 1 to 3
- Y is independently a divalent to hexavalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond.
- n is independently 1 It is an integer between ⁇ 5.
- A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is -CF 3 group, and b1 is an integer from 1 to 200.
- X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms.
- the fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
- each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.
- the above Rf2 is the following formula (In the formula, p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.
- each repeating unit shown in parentheses with p', q', r', s', t', and u' is random.
- X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms.
- a coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [9].
- a coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [9] is applied to the entire or part of the surface of the article by a dry method or a wet method and cured to form a layer.
- a method for surface modification of an article including a process.
- the fluoropolyether group-containing polymer composition of the present invention it is possible to provide a cured film that has excellent water and oil repellency and exhibits high abrasion durability despite having a high coefficient of friction.
- Articles for example, portable electronic device terminals, etc.
- having a layer made of a cured product of the composition particularly a coating agent containing the composition
- the "partial (hydrolyzed) condensate” refers to a partial condensate or a partially hydrolyzed condensate.
- the fluoropolyether group-containing polymer composition of the present invention contains two specific types of fluoropolyether group-containing polymers in a specific ratio, and for each of the fluoropolyether group-containing polymers, one of them contains One component (I) is a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, and the other component (II) has a fluorooxyalkylene group in the molecule. It is a polymer having reactive functional groups at both ends of the polymer.
- component (I) a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, is represented by the following general formula (1). fluoropolyether group-containing polymers and/or partial (hydrolyzed) condensates thereof.
- Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.)
- J is a single bond or a carbonyl group
- Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom
- L is independently is a single bond or a divalent heteroatom (preferably an oxygen atom in an ether bond)
- M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond
- X is independently is a hydroxyl group or a hydrolyzable group
- R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group
- n is an integer of 1 to 3 for each unit bonded to the silicon atom
- a is 2
- the component (II), a polymer having a fluorooxyalkylene group in the molecule and having reactive functional groups at both ends of the polymer has the following general formula (2 ) is a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof.
- W-O-CH 2 -Rf2-CH 2 -O-W (2) (In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching.
- W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
- the content of component (I) in the total of components (I) and (II) is 65 to 95% by mass, preferably 65 to 90% by mass.
- the content is preferably 65 to 85% by mass. If the content of component (I) in the total of components (I) and (II) is less than 65% by mass, the friction coefficient and wear durability of the cured film will decrease, and if it is more than 95% by mass, the friction coefficient will be high. The abrasion durability of the hardened coating on the product decreases.
- the fluoropolyether group-containing polymer of formula (1) has a structure in which a fluorooxyalkyl group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group. There are two or more hydrolyzable silyl groups or hydroxyl group-containing silyl groups in the molecule.
- the main chain structure is composed of a group represented by -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.) It is characterized by a high coefficient of friction (hard to slip).
- Rf1 is -(C 3 F 6 O) b - (the repeating unit C 3 F 6 O is a branched structure represented by -CF(CF 3 )CF 2 ⁇ - (i.e., hexafluoropropylene
- b is an integer of 2 to 200, preferably an integer of 3 to 100.
- A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is -CF 3 group, and b1 is an integer from 1 to 200.
- A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is a -CF 3 group
- the fluoroalkyl group whose terminal is a -CF 3 group is CF 3 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 -, CF 3 CF 2 -, CF 3 -, CF 3 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2
- Examples include CFH-, and CF 3 CF 2 CF 2 - is preferred.
- b1 is an integer of 1 to 200, preferably an integer of 3 to 100, more preferably an integer of 5 to 50. If b1 is smaller than the above upper limit, the adhesiveness and curability will be good, and it will be easy to handle, and if b1 is larger than the above lower limit, the characteristics of the fluorooxyalkyl group can be fully exhibited, which is preferable.
- Rf1 is an integer from 1 to 199, preferably from 3 to 100.
- Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, and specific examples of Q other than a single bond include The following groups may be mentioned. Note that it is preferable that the bond on the left side be bonded to J, and the bond on the right side be bonded to a carbon atom. (In the formula, e1 is an integer of 1 to 4, preferably 1 or 2, and e2 is an integer of 1 to 4, preferably 1, 2 or 3.)
- L is independently a single bond or a divalent heteroatom, and examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably an oxygen atom (in an ether bond) oxygen atom). L is preferably a single bond or an oxygen atom.
- M is independently a divalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, and specific examples of M include a propylene group, a butylene group, a hexamethylene group, etc.
- Alkylene groups having 3 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms such as phenylene groups (for example, alkylene/arylene groups having 8 to 16 carbon atoms), carbon atoms
- Examples include divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a polysiloxane residue, preferably alkylene groups having 3 to 10 carbon atoms, and phenylene groups containing 3 to 10 carbon atoms.
- an alkylene group with 3 to 10 carbon atoms a divalent group in which alkylene groups with 3 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and a bond of a divalent organopolysiloxane residue with 2 to 10 carbon atoms
- R 1 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group, and R 1 may be the same or different.
- R 2 is an alkylene group having 1 to 6 carbon atoms, such as a methylene group, ethylene group, or propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.
- linear divalent organopolysiloxane residue having 2 to 10 silicon atoms preferably 2 to 5 silicon atoms
- the following can be exemplified.
- R 1 is the same as above.
- g is an integer of 1 to 9, preferably an integer of 1 to 4.
- M examples include groups represented by the following formulas. (wherein, f1 is an integer of 3 to 10, preferably 3 to 6, f2 is an integer of 1 to 6, preferably 2 to 4, and f3 is an integer of 3 to 10, preferably g is an integer of 3 to 6, and g is an integer of 1 to 9, preferably 1 to 4.)
- M include the following groups. Note that it is preferable that the bond on the left side is bonded to L, and the bond on the right side is bonded to the silicon atom.
- X independently represents a hydroxyl group or a hydrolyzable group, specifically a group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc.
- R is independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a phenyl group, of which a methyl group is preferred.
- n is an integer of 1 to 3 independently for each unit bonded to a silicon atom, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.
- -SiX n (R) 3-n includes a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tri(isopropoxy)silyl group, a tributoxysilyl group, a tri(isobutoxysilyl group) ) silyl group, tri(sec-butoxy)silyl group, tri(tert-butoxy)silyl group, and other trialkoxysilyl groups are preferred.
- a is 2 or 3.
- all are single bonds, or one L is an oxygen atom, and the remaining one or two
- L is a single bond, particularly when a is 2, it is preferable that one of the two Ls present in one molecule is an oxygen atom and the other L is a single bond,
- a is 3, it is preferable that all three L's present in one molecule are single bonds.
- Examples of the fluoropolyether group-containing polymer represented by the formula (1) include those represented by the following formula.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- In the formula, b1' is an integer from 1 to 199.
- In the formula, b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- b1' is an integer from 1 to 199.
- the fluoropolyether group-containing polymer represented by the formula (1) is preferably one represented by the following formula. (In the formula, b1' is an integer from 1 to 199.)
- the fluoropolyether group-containing polymer of formula (2) is a polymer in which a fluorooxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group that does not have a polar group. structure, and one or more hydrolyzable silyl groups such as alkoxysilyl groups or hydroxyl group-containing silyl groups are present at each end, and two or more in total in the molecule, and the hydrolyzable silyl group or hydroxyl group-containing silyl group is present in the molecule.
- the silyl group there is no polar group in the molecule, specifically a carbonyl group, -NH- group, amide group, or hydroxyl group, resulting in a simpler bonding style.
- Rf2 is represented by the formula: -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6.) It is a linear fluorooxyalkylene group containing units and having no branching. By using a straight-chain fluorooxyalkylene group with no branching, high abrasion durability of the cured film can be obtained.
- the fluorooxyalkylene group for Rf2 is preferably one represented by the following formula (5).
- d is an integer from 0 to 5 independently for each unit
- p, q, r, s, t, and u are each an integer from 0 to 200
- p+q+r+s+t+u an integer from 10 to 250
- Each of these units is linear.
- each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.
- d is an integer of 0 to 5 independently for each unit, preferably an integer of 0 to 2, and more preferably 1 or 2.
- p, q, r, s, t, and u are each an integer of 0 to 200, preferably p is an integer of 10 to 150, q is an integer of 10 to 150, r is an integer of 0 to 20, and s is an integer of 0 to 20.
- t is an integer of 0 to 20
- u is an integer of 0 to 20
- p+q+r+s+t+u is an integer of 10 to 250, preferably an integer of 20 to 150.
- each of these units is linear. Further, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly combined.
- Such a fluorooxyalkylene group of Rf2 can be represented by the following structure, for example.
- p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.
- each repeating unit shown in parentheses with p', q', r', s', t', and u' is random.
- d' is an integer from 0 to 5 independently for each unit, and each of these units is linear.
- Rf2 preferably the following can be used.
- p" and q" are each an integer of 1 to 199, and the sum of p"+q" is an integer of 10 to 200, and the repeating unit (CF 2 CF 2 O) and (The arrangement of CF 2 O) is random.
- W is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal and having no polar group, preferably a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal.
- Examples of such W include groups represented by the following formulas (6a) to (6e).
- D is a divalent organic group having 1 to 20 carbon atoms and may be substituted with fluorine, v1 is an integer of 2 to 6, are independently integers from 2 to 10, and g1 is an integer from 1 to 9.
- D is an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, preferably 1 to 20 carbon atoms, More preferably, it is a divalent hydrocarbon group having 2 to 8 carbon atoms which may be substituted with fluorine, and examples of the divalent hydrocarbon group include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group.
- D is preferably an ethylene group, a propylene group, a butylene group, a hexamethylene group, or a phenylene group.
- v1 is an integer of 2 to 6, preferably an integer of 2 to 4
- v2 is independently an integer of 2 to 10, preferably an integer of 3 to 6
- g1 is an integer of 1 to 9, preferably an integer of 1 to 4.
- the fluoropolyether group-containing polymer of formula (2) is more preferably one represented by the following general formula (3).
- Rf2, R, X, and n are the same as above, and Y is independently a divalent to hexavalent hydrocarbon group and may have a silicon atom and/or a siloxane bond.m are independently integers from 1 to 5.
- Y is independently a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond, By not containing a polar group in the molecule, a coating film with excellent water and oil repellency can be provided.
- Y is an alkylene group having 2 to 10 carbon atoms, including an alkylene group having 3 to 10 carbon atoms such as a propylene group, a butylene group, and a hexamethylene group, and an arylene group having 6 to 8 carbon atoms such as a phenylene group.
- alkylene/arylene groups having 8 to 16 carbon atoms divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and 2 to 16 silicon atoms.
- an alkylene group having 2 to 10 carbon atoms bonded to the bonds of the divalent to hexavalent organopolysiloxane residues.
- an alkylene group having 3 to 10 carbon atoms an alkylene group having 2 to 10 carbon atoms including a phenylene group, or an alkylene group having 2 to 10 carbon atoms connected to each other via a sylalkylene structure or a sylarylene structure.
- linear, branched, or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms include those shown below.
- R 1 is the same as above.
- g1 is an integer of 1 to 9, preferably an integer of 1 to 4
- h is an integer of 2 to 6, preferably 2 to 4
- j is an integer of 0 to 8.
- h+j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.
- Examples of Y include groups represented by the following formulas. (In the formula, v1, v2, and g1 are the same as above. v is an integer of 3 to 10, preferably an integer of 3 to 6, and v0 is an integer of 2 to 10, preferably an integer of 3 to 6. be.)
- Y include the following groups.
- n is independently an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate will decrease, and if it is 6 or more, the terminal alkoxy value will be too high, which will adversely affect the performance, so it is preferably 1 to 5. It is an integer of 3, and 1 is particularly preferred.
- fluoropolyether group-containing polymer represented by the above formula (3) examples include those represented by the following formula.
- p1 and q1 are each integers from 1 to 199, and the total of p1 and q1 is 10 to 200.
- the present invention provides a fluoropolyether group-containing polymer represented by the formula (1), a fluoropolyether group-containing polymer represented by the formula (2), and particularly a fluoropolyether group-containing polymer represented by the formula (3).
- a coating agent is provided that contains a fluoropolyether group-containing polymer composition in a specific proportion with a group-containing polymer.
- the hydroxyl group of the fluoropolyether group-containing polymer represented by the above formula (1) and the above formula (2), or the terminal hydrolyzable group of the fluoropolyether group-containing polymer is partially removed in advance by a known method. It may also contain a partial (hydrolysis) condensate obtained by condensing hydrolyzed hydroxyl groups.
- the coating agent may optionally contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methane, etc.). Sulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
- the amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight, based on 100 parts by weight of the fluoropolyether group-containing polymer composition.
- the coating agent may contain a suitable solvent.
- suitable solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), and fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane).
- Modified ether solvents methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.
- fluorine-modified alkylamine solvents perfluorotributylamine, perfluorotripentylamine, etc.
- hydrocarbon solvents petroleum benzine, toluene, xylene, etc.
- ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
- fluorine-modified solvents are preferable in terms of solubility and wettability, and in particular, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), and perfluorotrifluorinated solvents are preferred. Butylamine and ethyl perfluorobutyl ether are preferred.
- Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate.
- the optimum concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the treatment method, and may be in an amount that is easy to weigh.
- 0.01 to 10 parts by mass per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) In particular, it is preferably 0.05 to 5 parts by mass, and in the case of vapor deposition treatment, the amount of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) It is preferably 1 to 100 parts by weight, particularly 3 to 30 parts by weight, based on a total of 100 parts by weight.
- the coating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition.
- the heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited.
- the curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1. It is preferable to set the time period to 24 hours. Further, when applying by vapor deposition, it is desirable to apply at a temperature range of 20 to 200°C, particularly 25 to 80°C for 30 minutes to 36 hours, particularly 30 minutes to 24 hours.
- the thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.
- spray coating if the material is diluted with a fluorine-based solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.
- the film thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry, fluorescence X-ray measurement, or the like.
- the substrate treated with the coating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz.
- the coating agent of the present invention can impart water and oil repellency and steel wool abrasion resistance to the base material. In particular, it can be suitably used as a coating agent for SiO 2 -treated glass or film.
- Articles treated with the coating agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, and sunglasses. , medical equipment such as a gastrocamera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an antireflection film, and other optical articles. In addition, from the viewpoint of preventing slippage, it can also be applied to the cases of mobile phones, smartphones, PCs, etc.
- the coating agent of the present invention can prevent fingerprints and sebum from adhering to the article, and can also provide scratch resistance (wear resistance), so it can be used especially for mobile phones, smartphones, PC casings, etc. It is useful as a water- and oil-repellent layer.
- the coating agent of the present invention can be used as an antifouling coating for sanitary products such as bathtubs and washstands, as an antifouling coating for window glasses or tempered glass for automobiles, trains, and airplanes, for headlamp covers, and as a repellent for building materials for exterior walls.
- Water and oil repellent coating anti-oil coating for kitchen building materials, anti-fouling and anti-paper/graffiti coating for telephone booths, anti-fingerprint coating for works of art, anti-fingerprint coating for compact discs, DVDs, etc., gold It is also useful as a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersibility modifier for inorganic fillers, and a water and oil repellent for tapes, films, and the like. Furthermore, from the viewpoint of being non-slip, it is also useful as a stain-preventing coating for building materials, especially flooring and wall materials.
- a coating agent containing the fluoropolyether group-containing polymer composition of the present invention is applied to the entire or part of the surface of an article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.). By coating and curing to form a layer, the surface of an article can be modified.
- the coefficient of kinetic friction on the surface of the article is preferably 0.13 or more, more preferably 0.18 or more under the measurement conditions described below. preferable. If the coefficient of dynamic friction is less than 0.13, the surface of the cured coating may be too slippery, resulting in insufficient retention or fixation of the coated article.
- the fluoropolyether represented by the formula (1) is used in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention. This can be achieved by controlling the content of the group-containing polymer to 65% by mass or more.
- the abrasion durability on the surface of the article is preferably 5,000 times or more, and preferably 7,500 times or more under the test conditions described below. It is more preferable.
- the fluoropolymer represented by the above formula (2) is used in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention. This can be achieved by controlling the content of the ether group-containing polymer to 10% by mass or more.
- the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
- Examples 1 to 54, Comparative Examples 1 to 39 Preparation of coating agent and formation of cured film
- component (I) a fluoropolyether group-containing polymer having a structure represented by the following formula (A), (B), or (C);
- component (II) As a component, a fluoropolyether group-containing polymer having a structure represented by the following formula (D), (E), (F), (G), (H), or (I); were mixed in the proportions shown in Tables 1, 2, and 3 to obtain a fluoropolyether group-containing polymer composition.
- a coating agent was prepared by dissolving the polymer composition in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass. 6 ⁇ l of each coating agent was vacuum-deposited on glass (Gorilla, manufactured by Corning Inc.) whose outermost surface had been treated with 10 nm of SiO 2 (processing conditions: pressure: 3.0 ⁇ 10 ⁇ 3 Pa, heating temperature: 500° C.), After being left in an atmosphere of 80% relative humidity at 25°C for 30 minutes, it was cured for 12 hours or more in an atmosphere of 25°C and 50% relative humidity to form a cured film with a thickness of 13 nm.
- the dynamic friction coefficient is ⁇ (excellent) if it is 0.23 or more, ⁇ (good) if it is 0.18 or more and less than 0.23, ⁇ (fair) if it is 0.13 or more and less than 0.18, and less than 0.13. are marked as ⁇ (impossible) and are shown in Tables 1, 2, and 3.
- the test environmental conditions are 25° C. and 50% relative humidity.
- ⁇ (Excellent) is when the steel wool abrasion durability is 10,000 times or more, and ⁇ (Good) is 7,500 times or more but less than 10,000 times. ), 5,000 times or more but less than 7,500 times is ⁇ (acceptable), and less than 5,000 times is ⁇ (impossible), as shown in Tables 1, 2, and 3.
- the test environmental conditions are 25° C. and 50% relative humidity.
- the component (II) When the fluoropolyether group-containing polymer of component (I) was used alone, the coefficient of dynamic friction was good, but the wear resistance was insufficient.
- the component (II) also has a fluorooxyalkylene group in the molecule, a reactive functional group at both ends of the polymer, and a polar group.
- the fluoropolyether group-containing polymer was used in the proportions shown in the examples, both the coefficient of dynamic friction and the abrasion resistance were good. There was a tendency for the dynamic friction coefficient and wear resistance to decrease as the mixing ratio of component (II) to component (I) increased.
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Abstract
This fluoropolyether group-containing polymer composition, which contains, in a specific ratio, (I) a polymer of a specific structure having a fluorooxyalkyl group at one end and a reactive functional group at the other end and (II) a polymer of a specific structure having a fluorooxyalkylene group in a molecule and reactive functional groups at both ends, and not having a polar group, can form a cured coating film having excellent water repellency and oil repellency and wear durability, as well as slip suppression as a result of a high coefficient of friction.
Description
本発明は、フルオロポリエーテル基含有ポリマー（フルオロオキシアルキル基又はフルオロオキシアルキレン基を分子内に有する化合物）を含む組成物に関し、詳細には、撥水撥油性、耐摩耗性、滑り抑制性に優れた硬化被膜を形成することができるフルオロポリエーテル基含有ポリマー組成物、及び該組成物を含むコーティング剤、並びに該コーティング剤の硬化物からなる層を有する物品、更に該コーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法に関する。
The present invention relates to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule), and in particular, to a composition containing a fluoropolyether group-containing polymer (a compound having a fluorooxyalkyl group or a fluorooxyalkylene group in the molecule). A fluoropolyether group-containing polymer composition capable of forming an excellent cured film, a coating agent containing the composition, and an article having a layer consisting of a cured product of the coating agent, and further applying and curing the coating agent. The present invention relates to a method for modifying the surface of an article, including a step of forming a layer.
近年、携帯電話のディスプレイをはじめ、画面のタッチパネル化が加速している。しかし、タッチパネルは画面がむき出しの状態であり、指や頬などが直接接触する機会が多く、皮脂等の汚れが付きやすいことが問題となっている。そこで、外観や視認性をよくするためにディスプレイの表面に指紋を付きにくくする技術や、汚れを落としやすくする技術の要求が年々高まってきており、これらの要求に応えることのできる材料の開発が望まれている。最近ではディスプレイ表面だけではなく、筐体においても皮脂等の汚れが付着しやすいことが問題となっており、ディスプレイ、筐体共に撥水撥油層を設けることが望まれている。しかし、従来の撥水撥油層は撥水撥油性が高く、汚れ拭取り性に優れるが、使用中に防汚性能が劣化してしまうという問題点があった。
In recent years, the shift to touch panel screens, including mobile phone displays, has been accelerating. However, the screen of a touch panel is exposed, and there are many opportunities for direct contact with fingers, cheeks, etc., and this poses a problem in that it is easily contaminated with sebum and other dirt. Therefore, in order to improve the appearance and visibility, the demand for technology that prevents fingerprints from forming on the surface of the display and technology that makes it easier to remove dirt is increasing year by year, and it is necessary to develop materials that can meet these demands. desired. Recently, it has become a problem that dirt such as sebum easily adheres not only to the display surface but also to the casing, and it is desired to provide a water- and oil-repellent layer on both the display and the casing. However, although conventional water- and oil-repellent layers have high water- and oil-repellency and are excellent in dirt-wiping properties, they have a problem in that their anti-fouling performance deteriorates during use.
一般に、フルオロポリエーテル基含有化合物は、その表面自由エネルギーが非常に小さいために、撥水撥油性、耐薬品性、潤滑性、離型性、防汚性などを有する。その性質を利用して、工業的には紙・繊維などの撥水撥油防汚剤、磁気記録媒体の滑剤、精密機器の防油剤、離型剤、化粧料、保護膜など、幅広く利用されている。しかし、その性質は同時に他の基材に対する非粘着性、非密着性であることを意味しており、基材表面に塗布することはできても、その被膜を密着させることは困難であった。
In general, fluoropolyether group-containing compounds have water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, etc. because their surface free energy is very small. Utilizing its properties, it is widely used industrially as water-, oil-, and stain-proofing agents for paper and textiles, lubricants for magnetic recording media, oil-proofing agents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, its properties also mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of the substrate, it is difficult to make the film adhere to it. .
一方、ガラスや布などの基材表面と有機化合物とを結合させるものとして、シランカップリング剤がよく知られており、各種基材表面のコーティング剤として幅広く利用されている。シランカップリング剤は、１分子中に有機官能基と反応性シリル基（一般にはアルコキシシリル基等の加水分解性シリル基）を有する。加水分解性シリル基が、空気中の水分などによって自己縮合反応を起こして被膜を形成する。該被膜は、加水分解性シリル基がガラスや金属などの表面と化学的・物理的に結合することにより耐久性を有する強固な被膜となる。
On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for the surfaces of various substrates. A silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups cause a self-condensation reaction with moisture in the air to form a film. The coating becomes a durable and strong coating due to the hydrolyzable silyl group chemically and physically bonding to the surface of glass, metal, or the like.
そこで、フルオロポリエーテル基含有化合物に加水分解性シリル基を導入したフルオロポリエーテル基含有ポリマーを用いることによって、基材表面に密着しやすく、かつ基材表面に、撥水撥油性、耐薬品性、潤滑性、離型性、防汚性等を有する被膜を形成しうる組成物が開示されている（特許文献１～６：特表２００８－５３４６９６号公報、特表２００８－５３７５５７号公報、特開２０１２－０７２２７２号公報、特開２０１２－１５７８５６号公報、特開２０１３－１３６８３３号公報、特開２０１５－１９９９０６号公報）。
Therefore, by using a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, it is possible to easily adhere to the substrate surface, and the substrate surface has water and oil repellency and chemical resistance. , compositions capable of forming a film having lubricity, mold releasability, antifouling properties, etc. JP 2012-072272, JP 2012-157856, JP 2013-136833, JP 2015-199906).
該フルオロポリエーテル基含有化合物に加水分解性シリル基を導入したフルオロポリエーテル基含有ポリマーを含有する組成物で表面処理されたガラス基材表面等の硬化被膜（防汚コーティング薄膜層）は、スチールウールに対する摩耗耐久性に優れ、滑り性が高い。タッチパネルディスプレイ表面での防汚コーティング薄膜層は、汚れを防止する性能に加えて、タッチパネル使用時の使用感（滑りが良く、触感が滑らかなこと）も重要視されてきた。使用感の良さは摩擦係数の低さと関連する（特許文献６：特開２０１５－１９９９０６号公報）。
The cured film (antifouling coating thin film layer) on the surface of a glass substrate, etc., which has been surface-treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound, is coated on steel. Excellent abrasion resistance against wool and high slip properties. In addition to the ability to prevent stains, the antifouling thin film layer on the surface of a touch panel display has been given importance not only for its ability to prevent stains, but also for its usability (good slippage and smooth feel) when using a touch panel. Good feeling in use is related to a low coefficient of friction (Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906).
一方で携帯用電子機器端末の筐体表面等においては、摩擦係数が低いということが不都合な場合もある。すなわち、摩擦係数が低いと、端末使用時に落下や振動などを生じる可能性が高くなる。そこで、汚れ防止性能や耐久性を保持しつつ、摩擦係数を制御することが、携帯用電子機器端末をはじめ様々な用途に防汚コーティング薄膜層を適用するうえで重要となる（特許文献７：特開２０１９－１３１８０８号公報）。
On the other hand, the low coefficient of friction on the casing surface of a portable electronic device terminal may be disadvantageous. In other words, if the coefficient of friction is low, there is a high possibility that the device will fall or vibrate during use. Therefore, it is important to control the coefficient of friction while maintaining antifouling performance and durability when applying antifouling coating thin film layers to various applications including portable electronic device terminals (Patent Document 7: JP 2019-131808A).
しかしながら、防汚コーティング薄膜層の摩擦係数を高く制御した場合、摩耗耐久性は不十分であった。
However, when the friction coefficient of the antifouling coating thin film layer was controlled to be high, the wear durability was insufficient.
本発明は、上記事情に鑑みなされたもので、撥水撥油性、耐摩耗性に優れ、高摩擦係数を有する硬化被膜を形成することができるフルオロポリエーテル基含有ポリマー組成物、及び該組成物を含むコーティング剤、並びに該コーティング剤の硬化物からなる層を有する物品、更に該コーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法を提供することを目的とする。
The present invention was made in view of the above circumstances, and provides a fluoropolyether group-containing polymer composition capable of forming a cured film having excellent water and oil repellency and abrasion resistance and a high coefficient of friction, and the composition. An object of the present invention is to provide a coating agent containing the above-mentioned coating agent, an article having a layer made of a cured product of the coating agent, and a method for surface modification of an article, which further includes a step of applying and curing the coating agent to form a layer. .
本発明者らは、上記目的を解決すべく鋭意検討した結果、上記フルオロポリエーテル基含有ポリマー組成物において、後述する特定の２種類のフルオロポリエーテル基含有ポリマー同士を特定割合で組み合わせて用いることにより、該ポリマー及び／又はその部分（加水分解）縮合物を併用してなるフルオロポリエーテル基含有ポリマー組成物（特に、該組成物を含むコーティング剤）が撥水撥油性、摩耗耐久性に優れ、かつ高い摩擦係数による滑り抑制性を有する硬化被膜を形成し得ることを見出し、本発明を完成した。
As a result of intensive studies to solve the above object, the present inventors have found that, in the fluoropolyether group-containing polymer composition, two specific types of fluoropolyether group-containing polymers described below are used in combination in a specific ratio. As a result, a fluoropolyether group-containing polymer composition (particularly a coating agent containing the composition) formed by using the polymer and/or its partial (hydrolyzed) condensate has excellent water and oil repellency and abrasion durability. The present invention has been completed based on the discovery that it is possible to form a cured film having anti-slip properties due to a high coefficient of friction.
従って、本発明は、下記のフルオロポリエーテル基含有ポリマー組成物、コーティング剤及び物品並びに物品の表面改質方法を提供するものである。
〔１〕
（Ｉ） 下記一般式（１）
（式中、Ｒｆ１は－（Ｃ3Ｆ6Ｏ）b－（繰り返し単位Ｃ3Ｆ6Ｏは分岐構造であり、ｂは２～２００の整数である。）の繰り返し単位を有するフルオロオキシアルキル基であり、Ｊは単結合又はカルボニル基であり、Ｑは単結合、又は－ＮＨ－基もしくは窒素原子を含む基を含有してもよい炭素数１～４のアルキレン基であり、Ｌは独立に単結合又は２価のヘテロ原子であり、Ｍは独立にケイ素原子及び／又はシロキサン結合を有してもよい２価炭化水素基であり、Ｘは独立に水酸基又は加水分解性基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、ｎはケイ素原子に結合する単位ごとに独立に１～３の整数であり、ａは２又は３である。）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物と、
（ＩＩ） 下記一般式（２）
Ｗ－Ｏ－ＣＨ2－Ｒｆ２－ＣＨ2－Ｏ－Ｗ （２）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基である。）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物を含むフルオロポリエーテル基含有ポリマー組成物であって、（Ｉ）成分と（ＩＩ）成分の合計における（Ｉ）成分の含有量が６５～９５質量％であるフルオロポリエーテル基含有ポリマー組成物。
〔２〕
（ＩＩ）成分が、下記一般式（３）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎはケイ素原子に結合する単位ごとに独立に１～３の整数であり、Ｙは独立に２～６価の炭化水素基であって、ケイ素原子及び／又はシロキサン結合を有していてもよい。ｍは独立に１～５の整数である。）
で表されるものである〔１〕に記載のフルオロポリエーテル基含有ポリマー組成物。
〔３〕
前記式（１）のＲｆ１が、下記一般式（４）で表されるフルオロオキシアルキル基である〔１〕又は〔２〕に記載のフルオロポリエーテル基含有ポリマー組成物。
（式中、Ａはフッ素原子、水素原子、又は末端が－ＣＦ3基であるフルオロアルキル基であり、ｂ１は１～２００の整数である。）
〔４〕
前記式（１）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である〔１〕～〔３〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔５〕
式（１）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである〔１〕～〔４〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
（式中、ｂ１’は１～１９９の整数である。）
〔６〕
前記Ｒｆ２が、下記式（５）で表されるものである〔１〕～〔５〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
（式中、ｄは単位毎に独立して０～５の整数であり、ｐ、ｑ、ｒ、ｓ、ｔ、ｕはそれぞれ０～２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＝１０～２５０の整数であり、これら各単位は直鎖状である。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
〔７〕
前記Ｒｆ２が、下記式
（式中、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’はそれぞれ１～２００の整数であり、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’の合計は１０～２５０であり、これら各単位は直鎖状である。また、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。ｄ’は単位毎に独立に０～５の整数であり、これら各単位は直鎖状である。）
で表されるポリマーから選ばれるものである〔１〕～〔６〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔８〕
前記式（３）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である〔２〕～〔７〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔９〕
前記式（３）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである〔２〕～〔８〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
（式中、ｐ１、ｑ１はそれぞれ１～１９９の整数で、ｐ１、ｑ１の合計は１０～２００である。）
〔１０〕
〔１〕～〔９〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤。
〔１１〕
〔１０〕に記載のコーティング剤の硬化物からなる層を有する物品。
〔１２〕
〔１１〕に記載の物品の表面における動摩擦係数が以下に記載の計測条件において０．１３以上であり、摩耗耐久回数が以下に記載の試験条件において５，０００回以上である物品。
［動摩擦係数計測条件］
ＡＳＴＭ Ｄ１８９４に準拠した手法による測定
荷重：１００ｇｆ
ストローク：１００ｍｍ
引張速度：５００ｍｍ／分
接触面積：１×３ｃｍ2
擦り材：不織布（ＢＥＭＣＯＴ（旭化成社製））
試験環境条件：２５℃、相対湿度５０％
［摩耗耐久試験条件］
往復摩耗試験機を用いたスチールウール摩耗耐久性の評価
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
試験環境条件：２５℃、相対湿度５０％
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測し、水接触角１００度以上を保つ摩耗往復回数を摩耗耐久回数とする。
〔１３〕
物品の表面全体又は一部に、乾式方法又は湿式方法により〔１〕～〔９〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法。 Accordingly, the present invention provides the following fluoropolyether group-containing polymer compositions, coating agents, articles, and methods for surface modification of articles.
[1]
(I) The following general formula (1)
(In the formula, Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.) , J is a single bond or a carbonyl group, Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, and L is independently is a single bond or a divalent heteroatom, M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond, X is independently a hydroxyl group or a hydrolyzable group, R are independently an alkyl group or phenyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3 independently for each unit bonded to a silicon atom, and a is 2 or 3.)
A fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof, represented by
(II) The following general formula (2)
W-O-CH 2 -Rf2-CH 2 -O-W (2)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
A fluoropolyether group-containing polymer composition containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof represented by: (I) in the total of components (I) and (II) A fluoropolyether group-containing polymer composition having a component content of 65 to 95% by mass.
[2]
(II) component is represented by the following general formula (3)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is bonded to a silicon atom. Each unit is independently an integer of 1 to 3, Y is independently a divalent to hexavalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond. m is independently 1 It is an integer between ~5.)
The fluoropolyether group-containing polymer composition according to [1], which is represented by:
[3]
The fluoropolyether group-containing polymer composition according to [1] or [2], wherein Rf1 in the formula (1) is a fluorooxyalkyl group represented by the following general formula (4).
(In the formula, A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is -CF 3 group, and b1 is an integer from 1 to 200.)
[4]
In the formula (1), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
[5]
The fluoropolyether group-containing polymer composition according to any one of [1] to [4], wherein the polymer represented by formula (1) is selected from polymers represented by the following formula.
(In the formula, b1' is an integer from 1 to 199.)
[6]
The fluoropolyether group-containing polymer composition according to any one of [1] to [5], wherein the Rf2 is represented by the following formula (5).
(In the formula, d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 200, p+q+r+s+t+u=an integer from 10 to 250, Each of these units is linear. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.)
[7]
The above Rf2 is the following formula
(In the formula, p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.In addition, each repeating unit shown in parentheses with p', q', r', s', t', and u' is random. (d' is an integer from 0 to 5 independently for each unit, and each of these units is linear.)
The fluoropolyether group-containing polymer composition according to any one of [1] to [6], which is selected from the polymers represented by:
[8]
In the formula (3), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to any one of [2] to [7], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
[9]
The fluoropolyether group-containing polymer composition according to any one of [2] to [8], wherein the polymer represented by formula (3) is selected from polymers represented by the following formula.
(In the formula, p1 and q1 are each integers from 1 to 199, and the total of p1 and q1 is 10 to 200.)
[10]
A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [9].
[11]
An article having a layer made of a cured product of the coating agent according to [10].
[12]
The article according to [11], wherein the coefficient of dynamic friction on the surface of the article is 0.13 or more under the measurement conditions described below, and the number of wear durability is 5,000 times or more under the test conditions described below.
[Dynamic friction coefficient measurement conditions]
Measured load according to ASTM D1894 method: 100gf
Stroke: 100mm
Pulling speed: 500mm/min Contact area: 1x3cm2
Rubbing material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei))
Test environment conditions: 25℃, relative humidity 50%
[Abrasion durability test conditions]
Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Test environmental conditions: 25℃, relative humidity 50%
The water contact angle of the friction-wearing part is measured every 2,500 frictional reciprocations, and the number of abrasion reciprocations that maintains the water contact angle of 100 degrees or more is defined as the wear durability number.
[13]
A coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [9] is applied to the entire or part of the surface of the article by a dry method or a wet method and cured to form a layer. A method for surface modification of an article including a process.
〔１〕
（Ｉ） 下記一般式（１）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物と、
（ＩＩ） 下記一般式（２）
Ｗ－Ｏ－ＣＨ2－Ｒｆ２－ＣＨ2－Ｏ－Ｗ （２）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基である。）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物を含むフルオロポリエーテル基含有ポリマー組成物であって、（Ｉ）成分と（ＩＩ）成分の合計における（Ｉ）成分の含有量が６５～９５質量％であるフルオロポリエーテル基含有ポリマー組成物。
〔２〕
（ＩＩ）成分が、下記一般式（３）
で表されるものである〔１〕に記載のフルオロポリエーテル基含有ポリマー組成物。
〔３〕
前記式（１）のＲｆ１が、下記一般式（４）で表されるフルオロオキシアルキル基である〔１〕又は〔２〕に記載のフルオロポリエーテル基含有ポリマー組成物。
〔４〕
前記式（１）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である〔１〕～〔３〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔５〕
式（１）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである〔１〕～〔４〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔６〕
前記Ｒｆ２が、下記式（５）で表されるものである〔１〕～〔５〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔７〕
前記Ｒｆ２が、下記式
で表されるポリマーから選ばれるものである〔１〕～〔６〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔８〕
前記式（３）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である〔２〕～〔７〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔９〕
前記式（３）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである〔２〕～〔８〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物。
〔１０〕
〔１〕～〔９〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤。
〔１１〕
〔１０〕に記載のコーティング剤の硬化物からなる層を有する物品。
〔１２〕
〔１１〕に記載の物品の表面における動摩擦係数が以下に記載の計測条件において０．１３以上であり、摩耗耐久回数が以下に記載の試験条件において５，０００回以上である物品。
［動摩擦係数計測条件］
ＡＳＴＭ Ｄ１８９４に準拠した手法による測定
荷重：１００ｇｆ
ストローク：１００ｍｍ
引張速度：５００ｍｍ／分
接触面積：１×３ｃｍ2
擦り材：不織布（ＢＥＭＣＯＴ（旭化成社製））
試験環境条件：２５℃、相対湿度５０％
［摩耗耐久試験条件］
往復摩耗試験機を用いたスチールウール摩耗耐久性の評価
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
試験環境条件：２５℃、相対湿度５０％
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測し、水接触角１００度以上を保つ摩耗往復回数を摩耗耐久回数とする。
〔１３〕
物品の表面全体又は一部に、乾式方法又は湿式方法により〔１〕～〔９〕のいずれかに記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法。 Accordingly, the present invention provides the following fluoropolyether group-containing polymer compositions, coating agents, articles, and methods for surface modification of articles.
[1]
(I) The following general formula (1)
A fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof, represented by
(II) The following general formula (2)
W-O-CH 2 -Rf2-CH 2 -O-W (2)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
A fluoropolyether group-containing polymer composition containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof represented by: (I) in the total of components (I) and (II) A fluoropolyether group-containing polymer composition having a component content of 65 to 95% by mass.
[2]
(II) component is represented by the following general formula (3)
The fluoropolyether group-containing polymer composition according to [1], which is represented by:
[3]
The fluoropolyether group-containing polymer composition according to [1] or [2], wherein Rf1 in the formula (1) is a fluorooxyalkyl group represented by the following general formula (4).
[4]
In the formula (1), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to any one of [1] to [3], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
[5]
The fluoropolyether group-containing polymer composition according to any one of [1] to [4], wherein the polymer represented by formula (1) is selected from polymers represented by the following formula.
[6]
The fluoropolyether group-containing polymer composition according to any one of [1] to [5], wherein the Rf2 is represented by the following formula (5).
[7]
The above Rf2 is the following formula
The fluoropolyether group-containing polymer composition according to any one of [1] to [6], which is selected from the polymers represented by:
[8]
In the formula (3), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to any one of [2] to [7], wherein the fluoropolyether group is a group selected from the group consisting of halogen groups and halogen groups.
[9]
The fluoropolyether group-containing polymer composition according to any one of [2] to [8], wherein the polymer represented by formula (3) is selected from polymers represented by the following formula.
[10]
A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of [1] to [9].
[11]
An article having a layer made of a cured product of the coating agent according to [10].
[12]
The article according to [11], wherein the coefficient of dynamic friction on the surface of the article is 0.13 or more under the measurement conditions described below, and the number of wear durability is 5,000 times or more under the test conditions described below.
[Dynamic friction coefficient measurement conditions]
Measured load according to ASTM D1894 method: 100gf
Stroke: 100mm
Pulling speed: 500mm/min Contact area: 1x3cm2
Rubbing material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei))
Test environment conditions: 25℃, relative humidity 50%
[Abrasion durability test conditions]
Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Test environmental conditions: 25℃, relative humidity 50%
The water contact angle of the friction-wearing part is measured every 2,500 frictional reciprocations, and the number of abrasion reciprocations that maintains the water contact angle of 100 degrees or more is defined as the wear durability number.
[13]
A coating agent containing the fluoropolyether group-containing polymer composition according to any one of [1] to [9] is applied to the entire or part of the surface of the article by a dry method or a wet method and cured to form a layer. A method for surface modification of an article including a process.
本発明のフルオロポリエーテル基含有ポリマー組成物によれば、撥水撥油性に優れ、摩擦係数が高いにもかかわらず、高い摩耗耐久性を示す硬化被膜を与えることができ、これにより本発明の組成物（特に、該組成物を含むコーティング剤）の硬化物からなる層を有する物品（例えば、携帯用電子機器端末等）は、撥水撥油性、摩耗耐久性に優れ、高い滑り抑制性を有する。
According to the fluoropolyether group-containing polymer composition of the present invention, it is possible to provide a cured film that has excellent water and oil repellency and exhibits high abrasion durability despite having a high coefficient of friction. Articles (for example, portable electronic device terminals, etc.) having a layer made of a cured product of the composition (particularly a coating agent containing the composition) have excellent water and oil repellency, abrasion durability, and high slip resistance. have
本発明において、「部分（加水分解）縮合物」とは、部分縮合物又は部分加水分解縮合物のことである。
In the present invention, the "partial (hydrolyzed) condensate" refers to a partial condensate or a partially hydrolyzed condensate.
本発明のフルオロポリエーテル基含有ポリマー組成物は、特定の２種類のフルオロポリエーテル基含有ポリマーを特定割合で含有してなるものであり、それぞれの該フルオロポリエーテル基含有ポリマーについて、その片方である（Ｉ）成分は、分子内にフルオロオキシアルキル基及び該ポリマーの片末端に反応性官能基を有するポリマーであり、別の片方である（ＩＩ）成分は、分子内にフルオロオキシアルキレン基を有し、該ポリマーの両末端に反応性官能基を有するポリマーである。
The fluoropolyether group-containing polymer composition of the present invention contains two specific types of fluoropolyether group-containing polymers in a specific ratio, and for each of the fluoropolyether group-containing polymers, one of them contains One component (I) is a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, and the other component (II) has a fluorooxyalkylene group in the molecule. It is a polymer having reactive functional groups at both ends of the polymer.
本発明のフルオロポリエーテル基含有ポリマー組成物において、（Ｉ）成分である分子内にフルオロオキシアルキル基及び該ポリマーの片末端に反応性官能基を有するポリマーは、下記一般式（１）で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物である。
（式中、Ｒｆ１は－（Ｃ3Ｆ6Ｏ）b－（繰り返し単位Ｃ3Ｆ6Ｏは分岐構造であり、ｂは２～２００の整数である。）の繰り返し単位を有するフルオロオキシアルキル基であり、Ｊは単結合又はカルボニル基であり、Ｑは単結合、又は－ＮＨ－基もしくは窒素原子を含む基を含有してもよい炭素数１～４のアルキレン基であり、Ｌは独立に単結合又は２価のヘテロ原子（好ましくはエーテル結合中の酸素原子）であり、Ｍは独立にケイ素原子及び／又はシロキサン結合を有してもよい２価炭化水素基であり、Ｘは独立に水酸基又は加水分解性基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、ｎはケイ素原子に結合する単位ごとに独立に１～３の整数であり、ａは２又は３である。）
In the fluoropolyether group-containing polymer composition of the present invention, component (I), a polymer having a fluorooxyalkyl group in the molecule and a reactive functional group at one end of the polymer, is represented by the following general formula (1). fluoropolyether group-containing polymers and/or partial (hydrolyzed) condensates thereof.
(In the formula, Rf1 is a fluorooxyalkyl group having a repeating unit of -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.) , J is a single bond or a carbonyl group, Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, and L is independently is a single bond or a divalent heteroatom (preferably an oxygen atom in an ether bond), M is independently a divalent hydrocarbon group that may have a silicon atom and/or a siloxane bond, and X is independently is a hydroxyl group or a hydrolyzable group, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 3 for each unit bonded to the silicon atom, and a is 2 or 3)
本発明のフルオロポリエーテル基含有ポリマー組成物において、（ＩＩ）成分である分子内にフルオロオキシアルキレン基を有し、該ポリマーの両末端に反応性官能基を有するポリマーは、下記一般式（２）で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物である。
Ｗ－Ｏ－ＣＨ2－Ｒｆ２－ＣＨ2－Ｏ－Ｗ （２）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基である。） In the fluoropolyether group-containing polymer composition of the present invention, the component (II), a polymer having a fluorooxyalkylene group in the molecule and having reactive functional groups at both ends of the polymer, has the following general formula (2 ) is a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof.
W-O-CH 2 -Rf2-CH 2 -O-W (2)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
Ｗ－Ｏ－ＣＨ2－Ｒｆ２－ＣＨ2－Ｏ－Ｗ （２）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基である。） In the fluoropolyether group-containing polymer composition of the present invention, the component (II), a polymer having a fluorooxyalkylene group in the molecule and having reactive functional groups at both ends of the polymer, has the following general formula (2 ) is a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof.
W-O-CH 2 -Rf2-CH 2 -O-W (2)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
本発明のフルオロポリエーテル基含有ポリマー組成物において、（Ｉ）成分と（ＩＩ）成分の合計における（Ｉ）成分の含有量は６５～９５質量％であり、６５～９０質量％であることが好ましく、６５～８５質量％であることがより好ましい。（Ｉ）成分と（ＩＩ）成分の合計における（Ｉ）成分の含有量が６５質量％未満であると硬化被膜の摩擦係数と摩耗耐久性が低下し、９５質量％より多いと摩擦係数は高いものの硬化被膜の摩耗耐久性が低下する。
In the fluoropolyether group-containing polymer composition of the present invention, the content of component (I) in the total of components (I) and (II) is 65 to 95% by mass, preferably 65 to 90% by mass. The content is preferably 65 to 85% by mass. If the content of component (I) in the total of components (I) and (II) is less than 65% by mass, the friction coefficient and wear durability of the cured film will decrease, and if it is more than 95% by mass, the friction coefficient will be high. The abrasion durability of the hardened coating on the product decreases.
前記式（１）のフルオロポリエーテル基含有ポリマーは、フルオロオキシアルキル基と、アルコキシシリル基等の加水分解性シリル基あるいは水酸基含有シリル基が、連結基を介して結合した構造であり、アルコキシシリル基等の加水分解性シリル基あるいは水酸基含有シリル基が分子内に２個以上存在している。また、主鎖構造が－（Ｃ3Ｆ6Ｏ）b－（繰り返し単位Ｃ3Ｆ6Ｏは分岐構造であり、ｂは２～２００の整数である。）で表される基から構成されることで摩擦係数が高い（滑りにくい）ことを特徴としている。
The fluoropolyether group-containing polymer of formula (1) has a structure in which a fluorooxyalkyl group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group. There are two or more hydrolyzable silyl groups or hydroxyl group-containing silyl groups in the molecule. In addition, the main chain structure is composed of a group represented by -(C 3 F 6 O) b - (The repeating unit C 3 F 6 O has a branched structure, and b is an integer from 2 to 200.) It is characterized by a high coefficient of friction (hard to slip).
前記式（１）において、Ｒｆ１は－（Ｃ3Ｆ6Ｏ）b－（繰り返し単位Ｃ3Ｆ6Ｏは、－ＣＦ（ＣＦ3）ＣＦ2О－で示される分岐構造（即ち、ヘキサフルオロプロピレンオキシドが開環した繰り返し単位構造）であり、ｂは２～２００の整数、好ましくは３～１００の整数である。）で表される基（ヘキサフルオロプロピレンオキシドの繰り返し構造）を主要構造として含む、フルオロオキシアルキル基であり、下記一般式（４）で表されるフルオロオキシアルキル基であることが好ましい。
In the formula (1), Rf1 is -(C 3 F 6 O) b - (the repeating unit C 3 F 6 O is a branched structure represented by -CF(CF 3 )CF 2 О- (i.e., hexafluoropropylene A repeating unit structure in which oxide is ring-opened, and b is an integer of 2 to 200, preferably an integer of 3 to 100. , is a fluorooxyalkyl group, and is preferably a fluorooxyalkyl group represented by the following general formula (4).
前記式（４）において、Ａはフッ素原子、水素原子、又は末端が－ＣＦ3基であるフルオロアルキル基であり、末端が－ＣＦ3基であるフルオロアルキル基としては、ＣＦ3ＣＦ2ＣＦ2ＣＦ2－、ＣＦ3ＣＦ2ＣＦ2－、ＣＦ3ＣＦ2－、ＣＦ3－、ＣＦ3ОＣＦ2ＣＦＨ－、ＣＦ3ＣＦ2ＣＦ2ОＣＦ2ＣＦＨ－、ＣＦ3ОＣＦ2ＣＦ2ＣＦ2ОＣＦ2ＣＦＨ－等が挙げられ、好ましくはＣＦ3ＣＦ2ＣＦ2－である。
In the above formula (4), A is a fluorine atom, a hydrogen atom, or a fluoroalkyl group whose terminal is a -CF 3 group, and the fluoroalkyl group whose terminal is a -CF 3 group is CF 3 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 -, CF 3 CF 2 -, CF 3 -, CF 3 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CFH-, CF 3 CF 2 CF 2 CF 2 CF 2 Examples include CFH-, and CF 3 CF 2 CF 2 - is preferred.
ｂ１は１～２００の整数であり、好ましくは３～１００の整数、より好ましくは５～５０の整数である。ｂ１が上記上限値より小さければ密着性や硬化性が良好であり、また、取り扱いやすく、上記下限値より大きければフルオロオキシアルキル基の特徴を十分に発揮することができるので好ましい。
b1 is an integer of 1 to 200, preferably an integer of 3 to 100, more preferably an integer of 5 to 50. If b1 is smaller than the above upper limit, the adhesiveness and curability will be good, and it will be easy to handle, and if b1 is larger than the above lower limit, the characteristics of the fluorooxyalkyl group can be fully exhibited, which is preferable.
Ｒｆ１として、具体的には、下記のものを例示することができる。
（式中、ｂ１’は１～１９９の整数、好ましくは３～１００の整数である。）
Specifically, the following can be exemplified as Rf1.
(In the formula, b1' is an integer from 1 to 199, preferably from 3 to 100.)
前記式（１）において、Ｊは単結合又はカルボニル基（－Ｃ（＝Ｏ）－）である。
In the above formula (1), J is a single bond or a carbonyl group (-C(=O)-).
前記式（１）において、Ｑは単結合、又は－ＮＨ－基もしくは窒素原子を含む基を含有してもよい炭素数１～４のアルキレン基であり、Ｑの単結合以外の具体例としては以下の基が挙げられる。なお、左側の結合手はＪと、右側の結合手は炭素原子と結合することが好ましい。
（式中、ｅ１は１～４の整数、好ましくは１又は２であり、ｅ２は１～４の整数、好ましくは１、２又は３である。）
In the above formula (1), Q is a single bond or an alkylene group having 1 to 4 carbon atoms which may contain an -NH- group or a group containing a nitrogen atom, and specific examples of Q other than a single bond include The following groups may be mentioned. Note that it is preferable that the bond on the left side be bonded to J, and the bond on the right side be bonded to a carbon atom.
(In the formula, e1 is an integer of 1 to 4, preferably 1 or 2, and e2 is an integer of 1 to 4, preferably 1, 2 or 3.)
前記式（１）において、Ｌは独立に単結合又は２価のヘテロ原子であり、２価のヘテロ原子としては酸素原子、窒素原子、硫黄原子が挙げられるが、好ましくは酸素原子（エーテル結合中の酸素原子）である。Ｌとしては単結合又は酸素原子であることが好ましい。
In the above formula (1), L is independently a single bond or a divalent heteroatom, and examples of the divalent heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably an oxygen atom (in an ether bond) oxygen atom). L is preferably a single bond or an oxygen atom.
前記式（１）において、Ｍは独立にケイ素原子及び／又はシロキサン結合を有してもよい２価炭化水素基であり、Ｍとして、具体的には、プロピレン基、ブチレン基、ヘキサメチレン基等の炭素数３～１０のアルキレン基、フェニレン基等の炭素数６～８のアリーレン基を含む炭素数３～１０のアルキレン基（例えば、炭素数８～１６のアルキレン・アリーレン基等）、炭素数３～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状の２価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２価の基などが挙げられ、好ましくは炭素数３～１０のアルキレン基、フェニレン基を含む炭素数３～１０のアルキレン基、炭素数３～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、２価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２価の基であり、更に好ましくは炭素数３～６のアルキレン基、炭素数３～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基である。
In the formula (1), M is independently a divalent hydrocarbon group which may have a silicon atom and/or a siloxane bond, and specific examples of M include a propylene group, a butylene group, a hexamethylene group, etc. Alkylene groups having 3 to 10 carbon atoms, including arylene groups having 6 to 8 carbon atoms such as phenylene groups (for example, alkylene/arylene groups having 8 to 16 carbon atoms), carbon atoms A divalent group in which 3 to 10 alkylene groups are bonded to each other via a sylalkylene structure or a sylarylene structure, a linear divalent organoleptic group having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms. Examples include divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a polysiloxane residue, preferably alkylene groups having 3 to 10 carbon atoms, and phenylene groups containing 3 to 10 carbon atoms. an alkylene group with 3 to 10 carbon atoms, a divalent group in which alkylene groups with 3 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and a bond of a divalent organopolysiloxane residue with 2 to 10 carbon atoms A divalent group in which alkylene groups of 3 to 6 carbon atoms are bonded, more preferably alkylene groups having 3 to 6 carbon atoms, and alkylene groups having 3 to 10 carbon atoms bonded to each other via a sylalkylene structure or a sylarylene structure. It is a divalent group.
ここで、シルアルキレン構造、シルアリーレン構造としては、下記に示すものが例示できる。
（式中、Ｒ1はメチル基、エチル基、プロピル基、ブチル基等の炭素数１～４のアルキル基、フェニル基等の炭素数６～１０のアリール基であり、Ｒ1は同一でも異なっていてもよい。Ｒ2はメチレン基、エチレン基、プロピレン基（トリメチレン基、メチルエチレン基）等の炭素数１～６のアルキレン基、フェニレン基等の炭素数６～１０のアリーレン基である。）
Here, as the sylalkylene structure and sylarylene structure, those shown below can be exemplified.
(In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group, and R 1 may be the same or different. R 2 is an alkylene group having 1 to 6 carbon atoms, such as a methylene group, ethylene group, or propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group. )
また、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状の２価のオルガノポリシロキサン残基としては、下記に示すものが例示できる。
（式中、Ｒ1は上記と同じである。ｇは１～９の整数、好ましくは１～４の整数である。）
Furthermore, as the linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms, the following can be exemplified.
(In the formula, R 1 is the same as above. g is an integer of 1 to 9, preferably an integer of 1 to 4.)
Ｍとしては、下記式で示される基が挙げられる。
（式中、ｆ１は３～１０の整数、好ましくは３～６の整数であり、ｆ２は１～６の整数、好ましくは２～４の整数であり、ｆ３は３～１０の整数、好ましくは３～６の整数であり、ｇは１～９の整数、好ましくは１～４の整数である。）
Examples of M include groups represented by the following formulas.
(wherein, f1 is an integer of 3 to 10, preferably 3 to 6, f2 is an integer of 1 to 6, preferably 2 to 4, and f3 is an integer of 3 to 10, preferably g is an integer of 3 to 6, and g is an integer of 1 to 9, preferably 1 to 4.)
Ｍの具体例としては、例えば、下記の基が挙げられる。なお、左側の結合手はＬと、右側の結合手はケイ素原子と結合することが好ましい。
Specific examples of M include the following groups. Note that it is preferable that the bond on the left side is bonded to L, and the bond on the right side is bonded to the silicon atom.
前記式（１）において、Ｘは独立に水酸基又は加水分解性基であり、具体的には、水酸基、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基などの炭素数１～１０のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基などの炭素数２～１０のアルコキシアルコキシ基、アセトキシ基などの炭素数１～１０のアシロキシ基、イソプロペノキシ基などの炭素数２～１０のアルケニルオキシ基、クロル基、ブロモ基、ヨード基などのハロゲン基などが挙げられる。中でもメトキシ基、エトキシ基、イソプロペノキシ基、クロル基が好適である。
また、Ｒは独立に炭素数１～４のメチル基、エチル基、プロピル基、ブチル基等のアルキル基、又はフェニル基であり、中でもメチル基が好適である。
ｎはケイ素原子に結合する単位ごとに独立に１～３の整数であり、好ましくは２又は３であり、反応性、基材に対する密着性の観点から３がより好ましい。 In the formula (1), X independently represents a hydroxyl group or a hydrolyzable group, specifically a group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc. Alkoxy group, alkoxyalkoxy group having 2 to 10 carbon atoms such as methoxymethoxy group, methoxyethoxy group, acyloxy group having 1 to 10 carbon atoms such as acetoxy group, alkenyloxy group having 2 to 10 carbon atoms such as isopropenoxy group, chloro group, bromo group, halogen group such as iodo group, and the like. Among these, methoxy, ethoxy, isopropenoxy, and chloro groups are preferred.
Further, R is independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a phenyl group, of which a methyl group is preferred.
n is an integer of 1 to 3 independently for each unit bonded to a silicon atom, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.
また、Ｒは独立に炭素数１～４のメチル基、エチル基、プロピル基、ブチル基等のアルキル基、又はフェニル基であり、中でもメチル基が好適である。
ｎはケイ素原子に結合する単位ごとに独立に１～３の整数であり、好ましくは２又は３であり、反応性、基材に対する密着性の観点から３がより好ましい。 In the formula (1), X independently represents a hydroxyl group or a hydrolyzable group, specifically a group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc. Alkoxy group, alkoxyalkoxy group having 2 to 10 carbon atoms such as methoxymethoxy group, methoxyethoxy group, acyloxy group having 1 to 10 carbon atoms such as acetoxy group, alkenyloxy group having 2 to 10 carbon atoms such as isopropenoxy group, chloro group, bromo group, halogen group such as iodo group, and the like. Among these, methoxy, ethoxy, isopropenoxy, and chloro groups are preferred.
Further, R is independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a phenyl group, of which a methyl group is preferred.
n is an integer of 1 to 3 independently for each unit bonded to a silicon atom, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.
前記式（１）において、－ＳｉＸn（Ｒ）3-nとしては、トリメトキシシリル基、トリエトキシシリル基、トリプロポキシシリル基、トリ（イソプロポキシ）シリル基、トリブトキシシリル基、トリ（イソブトキシ）シリル基、トリ（ｓｅｃ－ブトキシ）シリル基、トリ（ｔｅｒｔ－ブトキシ）シリル基等のトリアルコキシシリル基が好ましい。
In the formula (1), -SiX n (R) 3-n includes a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tri(isopropoxy)silyl group, a tributoxysilyl group, a tri(isobutoxysilyl group) ) silyl group, tri(sec-butoxy)silyl group, tri(tert-butoxy)silyl group, and other trialkoxysilyl groups are preferred.
前記式（１）において、ａは２又は３である。
なお、前記式（１）において、１分子中に２個又は３個存在するＬのうち、すべてが単結合である、又は１個のＬが酸素原子であり、残余の１個又は２個のＬが単結合であることが好ましく、特にはａが２のとき、１分子中に２個存在するＬのうち一方のＬが酸素原子であり、他方のＬが単結合であることが好ましく、ａが３のとき、１分子中に３個存在するＬのすべてが単結合であることが好ましい。 In the formula (1), a is 2 or 3.
In addition, in the above formula (1), out of two or three L present in one molecule, all are single bonds, or one L is an oxygen atom, and the remaining one or two It is preferable that L is a single bond, particularly when a is 2, it is preferable that one of the two Ls present in one molecule is an oxygen atom and the other L is a single bond, When a is 3, it is preferable that all three L's present in one molecule are single bonds.
なお、前記式（１）において、１分子中に２個又は３個存在するＬのうち、すべてが単結合である、又は１個のＬが酸素原子であり、残余の１個又は２個のＬが単結合であることが好ましく、特にはａが２のとき、１分子中に２個存在するＬのうち一方のＬが酸素原子であり、他方のＬが単結合であることが好ましく、ａが３のとき、１分子中に３個存在するＬのすべてが単結合であることが好ましい。 In the formula (1), a is 2 or 3.
In addition, in the above formula (1), out of two or three L present in one molecule, all are single bonds, or one L is an oxygen atom, and the remaining one or two It is preferable that L is a single bond, particularly when a is 2, it is preferable that one of the two Ls present in one molecule is an oxygen atom and the other L is a single bond, When a is 3, it is preferable that all three L's present in one molecule are single bonds.
前記式（１）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが例示できる。
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
（式中、ｂ１’は１～１９９の整数である。）
Examples of the fluoropolyether group-containing polymer represented by the formula (1) include those represented by the following formula.
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
(In the formula, b1' is an integer from 1 to 199.)
前記式（１）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが好ましい。
（式中、ｂ１’は１～１９９の整数である。）
The fluoropolyether group-containing polymer represented by the formula (1) is preferably one represented by the following formula.
(In the formula, b1' is an integer from 1 to 199.)
前記式（２）のフルオロポリエーテル基含有ポリマーは、フルオロオキシアルキレン基と、アルコキシシリル基等の加水分解性シリル基あるいは水酸基含有シリル基が、極性基を有さない連結基を介して結合した構造であり、アルコキシシリル基等の加水分解性シリル基あるいは水酸基含有シリル基が両末端にそれぞれ１個以上、分子内に合計で２個以上存在し、かつ、該加水分解性シリル基あるいは水酸基含有シリル基以外には分子内に極性基、具体的にはカルボニル基、－ＮＨ－基、アミド基や水酸基などがなく、より簡素な結合様式になっている。
The fluoropolyether group-containing polymer of formula (2) is a polymer in which a fluorooxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group are bonded via a linking group that does not have a polar group. structure, and one or more hydrolyzable silyl groups such as alkoxysilyl groups or hydroxyl group-containing silyl groups are present at each end, and two or more in total in the molecule, and the hydrolyzable silyl group or hydroxyl group-containing silyl group is present in the molecule. Other than the silyl group, there is no polar group in the molecule, specifically a carbonyl group, -NH- group, amide group, or hydroxyl group, resulting in a simpler bonding style.
前記式（２）において、Ｒｆ２は、式：－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基である。分岐を有しない直鎖状のフルオロオキシアルキレン基を用いることで硬化被膜の高い摩耗耐久性が得られる。
In the formula (2), Rf2 is represented by the formula: -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6.) It is a linear fluorooxyalkylene group containing units and having no branching. By using a straight-chain fluorooxyalkylene group with no branching, high abrasion durability of the cured film can be obtained.
Ｒｆ２のフルオロオキシアルキレン基としては、下記式（５）で表されるものが好ましい。
（式中、ｄは単位毎に独立して０～５の整数であり、ｐ、ｑ、ｒ、ｓ、ｔ、ｕはそれぞれ０～２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＝１０～２５０の整数であり、これら各単位は直鎖状である。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
The fluorooxyalkylene group for Rf2 is preferably one represented by the following formula (5).
(In the formula, d is an integer from 0 to 5 independently for each unit, p, q, r, s, t, and u are each an integer from 0 to 200, p+q+r+s+t+u=an integer from 10 to 250, Each of these units is linear. Also, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.)
上記式（５）において、ｄは単位毎に独立して０～５の整数であり、好ましくは０～２の整数であり、更に好ましくは１又は２である。
また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕはそれぞれ０～２００の整数、好ましくは、ｐは１０～１５０の整数、ｑは１０～１５０の整数、ｒは０～２０の整数、ｓは０～２０の整数、ｔは０～２０の整数、ｕは０～２０の整数であり、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕは１０～２５０の整数、好ましくは２０～１５０の整数である。ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕが上記上限値より小さければ基材と硬化被膜の密着性や、合成時の反応性が良好であり、上記下限値より大きければ硬化被膜の撥水撥油性や摩耗耐久性が良好である。これら各単位は直鎖状である。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。 In the above formula (5), d is an integer of 0 to 5 independently for each unit, preferably an integer of 0 to 2, and more preferably 1 or 2.
Further, p, q, r, s, t, and u are each an integer of 0 to 200, preferably p is an integer of 10 to 150, q is an integer of 10 to 150, r is an integer of 0 to 20, and s is an integer of 0 to 20. t is an integer of 0 to 20, u is an integer of 0 to 20, and p+q+r+s+t+u is an integer of 10 to 250, preferably an integer of 20 to 150. If p + q + r + s + t + u is smaller than the above upper limit, the adhesion between the base material and the cured film and the reactivity during synthesis are good, and if it is larger than the above lower limit, the water and oil repellency and abrasion durability of the cured film are good. Each of these units is linear. Further, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly combined.
また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕはそれぞれ０～２００の整数、好ましくは、ｐは１０～１５０の整数、ｑは１０～１５０の整数、ｒは０～２０の整数、ｓは０～２０の整数、ｔは０～２０の整数、ｕは０～２０の整数であり、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕは１０～２５０の整数、好ましくは２０～１５０の整数である。ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕが上記上限値より小さければ基材と硬化被膜の密着性や、合成時の反応性が良好であり、上記下限値より大きければ硬化被膜の撥水撥油性や摩耗耐久性が良好である。これら各単位は直鎖状である。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。 In the above formula (5), d is an integer of 0 to 5 independently for each unit, preferably an integer of 0 to 2, and more preferably 1 or 2.
Further, p, q, r, s, t, and u are each an integer of 0 to 200, preferably p is an integer of 10 to 150, q is an integer of 10 to 150, r is an integer of 0 to 20, and s is an integer of 0 to 20. t is an integer of 0 to 20, u is an integer of 0 to 20, and p+q+r+s+t+u is an integer of 10 to 250, preferably an integer of 20 to 150. If p + q + r + s + t + u is smaller than the above upper limit, the adhesion between the base material and the cured film and the reactivity during synthesis are good, and if it is larger than the above lower limit, the water and oil repellency and abrasion durability of the cured film are good. Each of these units is linear. Further, each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly combined.
このようなＲｆ２のフルオロオキシアルキレン基としては、例えば下記構造で示すことができる。
（式中、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’はそれぞれ１～２００の整数であり、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’の合計は１０～２５０であり、これら各単位は直鎖状である。また、ｐ’、ｑ’、ｒ’、ｓ’、ｔ’及びｕ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。ｄ’は単位毎に独立に０～５の整数であり、これら各単位は直鎖状である。）
Such a fluorooxyalkylene group of Rf2 can be represented by the following structure, for example.
(In the formula, p', q', r', s', t' and u' are each an integer from 1 to 200, and the sum of p', q', r', s', t' and u' is 10 to 250, and each of these units is linear.In addition, each repeating unit shown in parentheses with p', q', r', s', t', and u' is random. (d' is an integer from 0 to 5 independently for each unit, and each of these units is linear.)
Ｒｆ２として、好ましくは下記のものを用いることができる。
（式中、ｐ”及びｑ”は、それぞれ１～１９９の整数であり、かつｐ”＋ｑ”の和は、１０～２００の整数であり、式中の繰り返し単位（ＣＦ2ＣＦ2Ｏ）及び（ＣＦ2Ｏ）の配列はランダムである。）
As Rf2, preferably the following can be used.
(In the formula, p" and q" are each an integer of 1 to 199, and the sum of p"+q" is an integer of 10 to 200, and the repeating unit (CF 2 CF 2 O) and (The arrangement of CF 2 O) is random.)
前記式（２）において、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基であり、好ましくは、末端に水酸基含有シリル基又は加水分解性シリル基、及びこのシリル基とＯ基（エーテル結合酸素原子）とを連結する極性基（カルボニル基、－ＮＨ－基、アミド基や水酸基など）を有さない連結基からなる１価の基であり、このようなＷとしては、例えば、下記式（６ａ）～（６ｅ）で示される基が挙げられる。
（式中、Ｘ、Ｒ、ｎは上記と同じである。Ｄは炭素数１～２０のフッ素置換されていてもよい２価の有機基であり、ｖ１は２～６の整数であり、ｖ２は独立に２～１０の整数であり、ｇ１は１～９の整数である。）
In the formula (2), W is independently a monovalent group having a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal and having no polar group, preferably a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the terminal. A monovalent compound consisting of a hydrolyzable silyl group and a connecting group that does not have a polar group (carbonyl group, -NH- group, amide group, hydroxyl group, etc.) that connects this silyl group and an O group (ether-bonded oxygen atom). Examples of such W include groups represented by the following formulas (6a) to (6e).
(In the formula, X, R, and n are the same as above. D is a divalent organic group having 1 to 20 carbon atoms and may be substituted with fluorine, v1 is an integer of 2 to 6, are independently integers from 2 to 10, and g1 is an integer from 1 to 9.)
前記式（６ａ）～（６ｅ）において、Ｄは炭素数１～２０、好ましくは炭素数２～８のフッ素置換されていてもよい２価の有機基であり、好ましくは炭素数１～２０、より好ましくは炭素数２～８のフッ素置換されていてもよい２価炭化水素基であり、２価炭化水素基としては、メチレン基、エチレン基、プロピレン基（トリメチレン基、メチルエチレン基）、ブチレン基（テトラメチレン基、メチルプロピレン基）、ヘキサメチレン基、オクタメチレン基等のアルキレン基、フェニレン基等のアリーレン基、又はこれらの基の２種以上の組み合わせ（アルキレン・アリーレン基等）などや、これらの基の水素原子の一部又は全部がフッ素原子で置換されたもの等が挙げられる。Ｄとしては、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基、フェニレン基が好ましい。
In the formulas (6a) to (6e), D is an optionally fluorine-substituted divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, preferably 1 to 20 carbon atoms, More preferably, it is a divalent hydrocarbon group having 2 to 8 carbon atoms which may be substituted with fluorine, and examples of the divalent hydrocarbon group include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group. groups (tetramethylene group, methylpropylene group), alkylene groups such as hexamethylene group and octamethylene group, arylene groups such as phenylene group, or combinations of two or more of these groups (alkylene/arylene group, etc.), Examples include those in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms. D is preferably an ethylene group, a propylene group, a butylene group, a hexamethylene group, or a phenylene group.
前記式（６ａ）～（６ｅ）において、ｖ１は２～６の整数、好ましくは２～４の整数であり、ｖ２は独立に２～１０の整数、好ましくは３～６の整数であり、ｇ１は１～９の整数、好ましくは１～４の整数である。
In the formulas (6a) to (6e), v1 is an integer of 2 to 6, preferably an integer of 2 to 4, v2 is independently an integer of 2 to 10, preferably an integer of 3 to 6, and g1 is an integer of 1 to 9, preferably an integer of 1 to 4.
このようなＷとして、具体的には、下記に示すものが例示できる。
Specific examples of such W include those shown below.
前記式（２）のフルオロポリエーテル基含有ポリマーとして、更に好ましくは下記一般式（３）で表されるものである。
（式中、Ｒｆ２、Ｒ、Ｘ、ｎは上記と同じであり、Ｙは独立に２～６価の炭化水素基であって、ケイ素原子及び／又はシロキサン結合を有していてもよい。ｍは独立に１～５の整数である。）
The fluoropolyether group-containing polymer of formula (2) is more preferably one represented by the following general formula (3).
(In the formula, Rf2, R, X, and n are the same as above, and Y is independently a divalent to hexavalent hydrocarbon group and may have a silicon atom and/or a siloxane bond.m are independently integers from 1 to 5.)
前記式（３）において、Ｙは独立に２～６価、好ましくは２～４価、より好ましくは２価の炭化水素基であり、ケイ素原子及び／又はシロキサン結合を有していてもよく、分子中に極性基を含まないことで撥水撥油性に優れたコーティング膜を与えることができる。
In the formula (3), Y is independently a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, and may have a silicon atom and/or a siloxane bond, By not containing a polar group in the molecule, a coating film with excellent water and oil repellency can be provided.
Ｙとして、具体的には、プロピレン基、ブチレン基、ヘキサメチレン基等の炭素数３～１０のアルキレン基、フェニレン基等の炭素数６～８のアリーレン基を含む炭素数２～１０のアルキレン基（例えば、炭素数８～１６のアルキレン・アリーレン基等）、炭素数２～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状、分岐状又は環状の２～６価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２～６価の基などが挙げられ、好ましくは炭素数３～１０のアルキレン基、フェニレン基を含む炭素数２～１０のアルキレン基、炭素数２～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２～１０個の直鎖状又はケイ素原子数３～１０個の分岐状もしくは環状の２～４価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２～４価の基であり、更に好ましくは炭素数３～６のアルキレン基である。
Specifically, Y is an alkylene group having 2 to 10 carbon atoms, including an alkylene group having 3 to 10 carbon atoms such as a propylene group, a butylene group, and a hexamethylene group, and an arylene group having 6 to 8 carbon atoms such as a phenylene group. (for example, alkylene/arylene groups having 8 to 16 carbon atoms), divalent groups in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a sylalkylene structure or sylarylene structure, and 2 to 16 silicon atoms. 10, preferably 2 to 5 linear, branched or cyclic divalent to hexavalent organopolysiloxane residues, with an alkylene group having 2 to 10 carbon atoms bonded to the bonds of the divalent to hexavalent organopolysiloxane residues. Preferably, an alkylene group having 3 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms including a phenylene group, or an alkylene group having 2 to 10 carbon atoms connected to each other via a sylalkylene structure or a sylarylene structure. A divalent group bonded to a carbon bond in a linear chain having 2 to 10 silicon atoms, or a branched or cyclic divalent to 4-valent organopolysiloxane residue having 3 to 10 silicon atoms. It is a divalent to tetravalent group to which 2 to 10 alkylene groups are bonded, more preferably an alkylene group having 3 to 6 carbon atoms.
ここで、シルアルキレン構造、シルアリーレン構造としては、式（１）のＭにおいて例示したものと同様のものが例示できる。
Here, as the sylalkylene structure and sylarylene structure, the same structures as those exemplified for M in formula (1) can be exemplified.
また、ケイ素原子数２～１０個、好ましくは２～５個の直鎖状、分岐状又は環状の２～６価のオルガノポリシロキサン残基としては、下記に示すものが例示できる。
（式中、Ｒ1は上記と同じである。ｇ１は１～９の整数、好ましくは１～４の整数であり、ｈは２～６、好ましくは２～４の整数、ｊは０～８の整数、好ましくは０又は１で、ｈ＋ｊは３～１０の整数、好ましくは３～５の整数であり、ｋは１～３の整数、好ましくは２又は３である。）
Further, examples of linear, branched, or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms include those shown below.
(In the formula, R 1 is the same as above. g1 is an integer of 1 to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably 2 to 4, and j is an integer of 0 to 8. (h+j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.)
Ｙとしては、下記式で示される基が挙げられる。
（式中、ｖ１、ｖ２、ｇ１は上記と同じである。ｖは３～１０の整数、好ましくは３～６の整数であり、ｖ０は２～１０の整数、好ましくは３～６の整数である。）
Examples of Y include groups represented by the following formulas.
(In the formula, v1, v2, and g1 are the same as above. v is an integer of 3 to 10, preferably an integer of 3 to 6, and v0 is an integer of 2 to 10, preferably an integer of 3 to 6. be.)
Ｙの具体例としては、例えば、下記の基が挙げられる。
Specific examples of Y include the following groups.
ｍは独立に１～５の整数であり、１未満であると基材への密着性が低下し、６以上であると末端アルコキシ価が高すぎて性能に悪影響を与えるため、好ましくは１～３の整数であり、特に１が好ましい。
m is independently an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate will decrease, and if it is 6 or more, the terminal alkoxy value will be too high, which will adversely affect the performance, so it is preferably 1 to 5. It is an integer of 3, and 1 is particularly preferred.
前記式（３）で表されるフルオロポリエーテル基含有ポリマーとしては、下記式で表されるものが例示できる。
Examples of the fluoropolyether group-containing polymer represented by the above formula (3) include those represented by the following formula.
本発明は、前記式（１）で表されるフルオロポリエーテル基含有ポリマーと、前記式（２）で表されるフルオロポリエーテル基含有ポリマー、特には式（３）で表されるフルオロポリエーテル基含有ポリマーとの特定割合で構成されるフルオロポリエーテル基含有ポリマー組成物を含有するコーティング剤を提供する。該コーティング剤は、前記式（１）及び前記式（２）で表されるフルオロポリエーテル基含有ポリマーの水酸基、又は該フルオロポリエーテル基含有ポリマーの末端加水分解性基を予め公知の方法により部分的に加水分解した水酸基を縮合させて得られる部分（加水分解）縮合物を含んでいてもよい。
The present invention provides a fluoropolyether group-containing polymer represented by the formula (1), a fluoropolyether group-containing polymer represented by the formula (2), and particularly a fluoropolyether group-containing polymer represented by the formula (3). A coating agent is provided that contains a fluoropolyether group-containing polymer composition in a specific proportion with a group-containing polymer. In the coating agent, the hydroxyl group of the fluoropolyether group-containing polymer represented by the above formula (1) and the above formula (2), or the terminal hydrolyzable group of the fluoropolyether group-containing polymer is partially removed in advance by a known method. It may also contain a partial (hydrolysis) condensate obtained by condensing hydrolyzed hydroxyl groups.
コーティング剤には、必要に応じて、加水分解縮合触媒、例えば、有機錫化合物（ジブチル錫ジメトキシド、ジラウリン酸ジブチル錫など）、有機チタン化合物（テトラｎ－ブチルチタネートなど）、有機酸（酢酸、メタンスルホン酸、フッ素変性カルボン酸など）、無機酸（塩酸、硫酸など）を添加してもよい。これらの中では、特に酢酸、テトラｎ－ブチルチタネート、ジラウリン酸ジブチル錫、フッ素変性カルボン酸などが望ましい。
加水分解縮合触媒の添加量は触媒量であり、通常、フルオロポリエーテル基含有ポリマー組成物１００質量部に対して０．０１～５質量部、特に０．１～１質量部である。 The coating agent may optionally contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methane, etc.). Sulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight, based on 100 parts by weight of the fluoropolyether group-containing polymer composition.
加水分解縮合触媒の添加量は触媒量であり、通常、フルオロポリエーテル基含有ポリマー組成物１００質量部に対して０．０１～５質量部、特に０．１～１質量部である。 The coating agent may optionally contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methane, etc.). Sulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
The amount of the hydrolysis condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight, based on 100 parts by weight of the fluoropolyether group-containing polymer composition.
該コーティング剤は、適当な溶剤を含んでもよい。このような溶剤としては、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタンなど）、フッ素変性芳香族炭化水素系溶剤（１，３－ビス（トリフルオロメチル）ベンゼンなど）、フッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）など）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミンなど）、炭化水素系溶剤（石油ベンジン、トルエン、キシレンなど）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）を例示することができる。これらの中では、溶解性、濡れ性などの点で、フッ素変性された溶剤が望ましく、特には、１，３－ビス（トリフルオロメチル）ベンゼン、パーフルオロ（２－ブチルテトラヒドロフラン）、パーフルオロトリブチルアミン、エチルパーフルオロブチルエーテルが好ましい。
The coating agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), and fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane). Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferable in terms of solubility and wettability, and in particular, 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), and perfluorotrifluorinated solvents are preferred. Butylamine and ethyl perfluorobutyl ether are preferred.
上記溶剤はその２種以上を混合してもよく、フルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物を均一に溶解させることが好ましい。なお、溶剤に溶解させるフルオロポリエーテル基含有ポリマー組成物（フルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物）の最適濃度は、処理方法により異なり、秤量しやすい量であればよいが、直接塗工する場合は、溶剤及びフルオロポリエーテル基含有ポリマー組成物（フルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物）の合計１００質量部に対して０．０１～１０質量部、特に０．０５～５質量部であることが好ましく、蒸着処理をする場合は、溶剤及びフルオロポリエーテル基含有ポリマー組成物（フルオロポリエーテル基含有ポリマー及びその部分（加水分解）縮合物）の合計１００質量部に対して１～１００質量部、特に３～３０質量部であることが好ましい。
Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate. The optimum concentration of the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the treatment method, and may be in an amount that is easy to weigh. , in the case of direct coating, 0.01 to 10 parts by mass per 100 parts by mass of the total of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) In particular, it is preferably 0.05 to 5 parts by mass, and in the case of vapor deposition treatment, the amount of the solvent and the fluoropolyether group-containing polymer composition (fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate) It is preferably 1 to 100 parts by weight, particularly 3 to 30 parts by weight, based on a total of 100 parts by weight.
本発明のコーティング剤は、刷毛塗り、ディッピング、スプレー、蒸着処理など公知の方法で基材に施与することができる。蒸着処理時の加熱方法は、抵抗加熱方式でも、電子ビーム加熱方式のどちらでもよく、特に限定されるものではない。また、硬化温度は、硬化方法によって異なるが、例えば、直接塗工（刷毛塗り、ディッピング、スプレー等）の場合は、２５～２００℃、特に２５～８０℃にて３０分～３６時間、特に１～２４時間とすることが好ましい。また、蒸着処理で施与する場合は、２０～２００℃、特に２５～８０℃の温度範囲にて３０分～３６時間、特に３０分～２４時間とすることが望ましい。また、加湿下で硬化させてもよい。硬化被膜の膜厚は、基材の種類により適宜選定されるが、通常０．１～１００ｎｍ、特に１～２０ｎｍである。また、例えばスプレー塗工では予め水分を添加したフッ素系溶剤に希釈し、加水分解、つまりＳｉ－ＯＨを生成させた後にスプレー塗工すると塗工後の硬化が速い。
なお、膜厚は、例えば、分光反射率測定法、エックス線反射率測定法、分光エリプソメトリー測定法、蛍光エックス線測定法等の手段により測定できる。 The coating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1. It is preferable to set the time period to 24 hours. Further, when applying by vapor deposition, it is desirable to apply at a temperature range of 20 to 200°C, particularly 25 to 80°C for 30 minutes to 36 hours, particularly 30 minutes to 24 hours. Further, it may be cured under humidified conditions. The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spray coating, if the material is diluted with a fluorine-based solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.
The film thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry, fluorescence X-ray measurement, or the like.
なお、膜厚は、例えば、分光反射率測定法、エックス線反射率測定法、分光エリプソメトリー測定法、蛍光エックス線測定法等の手段により測定できる。 The coating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), the curing temperature is 25 to 200°C, especially 25 to 80°C for 30 minutes to 36 hours, especially 1. It is preferable to set the time period to 24 hours. Further, when applying by vapor deposition, it is desirable to apply at a temperature range of 20 to 200°C, particularly 25 to 80°C for 30 minutes to 36 hours, particularly 30 minutes to 24 hours. Further, it may be cured under humidified conditions. The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. In addition, for example, in spray coating, if the material is diluted with a fluorine-based solvent to which water has been added in advance and subjected to hydrolysis, that is, to generate Si--OH, then spray coating is performed, resulting in faster curing after coating.
The film thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry, fluorescence X-ray measurement, or the like.
本発明のコーティング剤で処理される基材は特に制限されず、紙、布、金属及びその酸化物、ガラス、プラスチック、セラミック、石英など各種材質のものであってよい。本発明のコーティング剤は、前記基材に撥水撥油性、耐スチールウール摩耗性を付与することができる。特に、ＳｉＯ2処理されたガラスやフイルムのコーティング剤として好適に使用することができる。
The substrate treated with the coating agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The coating agent of the present invention can impart water and oil repellency and steel wool abrasion resistance to the base material. In particular, it can be suitably used as a coating agent for SiO 2 -treated glass or film.
本発明のコーティング剤で処理される物品としては、カーナビゲーション、携帯電話、スマートフォン、デジタルカメラ、デジタルビデオカメラ、ＰＤＡ、ポータブルオーディオプレーヤー、カーオーディオ、ゲーム機器、眼鏡レンズ、カメラレンズ、レンズフィルター、サングラス、胃カメラ等の医療用器機、複写機、ＰＣ、液晶ディスプレイ、有機ＥＬディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ、保護フイルム、反射防止フイルムなどの光学物品が挙げられる。また、滑りにくい観点から携帯電話、スマートフォン、ＰＣなどの筐体にも処理することができる。本発明のコーティング剤は、前記物品に指紋及び皮脂が付着するのを防止し、更に傷つき防止性（耐摩耗性）を付与することができるため、特に携帯電話、スマートフォン、ＰＣの筐体などの撥水撥油層として有用である。
Articles treated with the coating agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, and sunglasses. , medical equipment such as a gastrocamera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, an antireflection film, and other optical articles. In addition, from the viewpoint of preventing slippage, it can also be applied to the cases of mobile phones, smartphones, PCs, etc. The coating agent of the present invention can prevent fingerprints and sebum from adhering to the article, and can also provide scratch resistance (wear resistance), so it can be used especially for mobile phones, smartphones, PC casings, etc. It is useful as a water- and oil-repellent layer.
また、本発明のコーティング剤は、浴槽、洗面台のようなサニタリー製品の防汚コーティング、自動車、電車、航空機などの窓ガラス又は強化ガラス、ヘッドランプカバー等の防汚コーティング、外壁用建材の撥水撥油コーティング、台所用建材の油汚れ防止用コーティング、電話ボックスの防汚及び貼り紙・落書き防止コーティング、美術品などの指紋付着防止付与のコーティング、コンパクトディスク、ＤＶＤなどの指紋付着防止コーティング、金型用に離型剤あるいは塗料添加剤、樹脂改質剤、無機質充填剤の流動性改質剤又は分散性改質剤、テープ、フイルムなどの撥水撥油剤としても有用である。更に滑りにくい観点より建築資材、特に床材や壁材の汚れ防止コーティングにも有用である。
In addition, the coating agent of the present invention can be used as an antifouling coating for sanitary products such as bathtubs and washstands, as an antifouling coating for window glasses or tempered glass for automobiles, trains, and airplanes, for headlamp covers, and as a repellent for building materials for exterior walls. Water and oil repellent coating, anti-oil coating for kitchen building materials, anti-fouling and anti-paper/graffiti coating for telephone booths, anti-fingerprint coating for works of art, anti-fingerprint coating for compact discs, DVDs, etc., gold It is also useful as a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersibility modifier for inorganic fillers, and a water and oil repellent for tapes, films, and the like. Furthermore, from the viewpoint of being non-slip, it is also useful as a stain-preventing coating for building materials, especially flooring and wall materials.
本発明によれば、物品の表面全体又は一部に、乾式方法（蒸着処理）又は湿式方法（刷毛塗り、ディッピング、スプレー等）により、本発明のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤を塗布、硬化して層を形成することにより、物品の表面を改質することができる。
According to the present invention, a coating agent containing the fluoropolyether group-containing polymer composition of the present invention is applied to the entire or part of the surface of an article by a dry method (vapor deposition treatment) or a wet method (brushing, dipping, spraying, etc.). By coating and curing to form a layer, the surface of an article can be modified.
本発明のコーティング剤の硬化物からなる層を有する物品において、物品の表面における動摩擦係数が、以下に記載の計測条件において０．１３以上であることが好ましく、０．１８以上であることがより好ましい。動摩擦係数が０．１３未満では硬化被膜の表面が滑りすぎるためコーティングされた物品の保持や固定が不十分になる場合がある。なお、本発明において、物品の表面における動摩擦係数を上記の値以上とするためには本発明のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤において、前記式（１）に示されるフルオロポリエーテル基含有ポリマーを６５質量％以上とすることにより達成できる。
［動摩擦係数計測条件］
ＡＳＴＭ Ｄ１８９４に準拠した手法による測定
荷重：１００ｇｆ
ストローク：１００ｍｍ
引張速度：５００ｍｍ／分
接触面積：１×３ｃｍ2
擦り材：不織布（ＢＥＭＣＯＴ（旭化成社製））
試験環境条件：２５℃、相対湿度５０％ In an article having a layer made of a cured product of the coating agent of the present invention, the coefficient of kinetic friction on the surface of the article is preferably 0.13 or more, more preferably 0.18 or more under the measurement conditions described below. preferable. If the coefficient of dynamic friction is less than 0.13, the surface of the cured coating may be too slippery, resulting in insufficient retention or fixation of the coated article. In the present invention, in order to make the coefficient of dynamic friction on the surface of the article greater than or equal to the above value, in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention, the fluoropolyether represented by the formula (1) is used. This can be achieved by controlling the content of the group-containing polymer to 65% by mass or more.
[Dynamic friction coefficient measurement conditions]
Measured load according to ASTM D1894 method: 100gf
Stroke: 100mm
Pulling speed: 500mm/min Contact area: 1x3cm2
Rubbing material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei))
Test environment conditions: 25℃, relative humidity 50%
［動摩擦係数計測条件］
ＡＳＴＭ Ｄ１８９４に準拠した手法による測定
荷重：１００ｇｆ
ストローク：１００ｍｍ
引張速度：５００ｍｍ／分
接触面積：１×３ｃｍ2
擦り材：不織布（ＢＥＭＣＯＴ（旭化成社製））
試験環境条件：２５℃、相対湿度５０％ In an article having a layer made of a cured product of the coating agent of the present invention, the coefficient of kinetic friction on the surface of the article is preferably 0.13 or more, more preferably 0.18 or more under the measurement conditions described below. preferable. If the coefficient of dynamic friction is less than 0.13, the surface of the cured coating may be too slippery, resulting in insufficient retention or fixation of the coated article. In the present invention, in order to make the coefficient of dynamic friction on the surface of the article greater than or equal to the above value, in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention, the fluoropolyether represented by the formula (1) is used. This can be achieved by controlling the content of the group-containing polymer to 65% by mass or more.
[Dynamic friction coefficient measurement conditions]
Measured load according to ASTM D1894 method: 100gf
Stroke: 100mm
Pulling speed: 500mm/min Contact area: 1x3cm2
Rubbing material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei))
Test environment conditions: 25℃, relative humidity 50%
本発明のコーティング剤の硬化物からなる層を有する物品において、物品の表面における摩耗耐久回数が、以下に記載の試験条件において５，０００回以上であることが好ましく、７，５００回以上であることがより好ましい。なお、本発明において、物品の表面における摩耗耐久回数を上記の値以上とするためには本発明のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤において、前記式（２）に示されるフルオロポリエーテル基含有ポリマーを１０質量％以上とすることにより達成できる。
［摩耗耐久試験条件］
往復摩耗試験機を用いたスチールウール摩耗耐久性の評価
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
試験環境条件：２５℃、相対湿度５０％
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測し、水接触角１００度以上を保つ摩耗往復回数を摩耗耐久回数とする。 In an article having a layer made of a cured product of the coating agent of the present invention, the abrasion durability on the surface of the article is preferably 5,000 times or more, and preferably 7,500 times or more under the test conditions described below. It is more preferable. In addition, in the present invention, in order to make the number of abrasion durability on the surface of the article equal to or higher than the above value, in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention, the fluoropolymer represented by the above formula (2) is used. This can be achieved by controlling the content of the ether group-containing polymer to 10% by mass or more.
[Abrasion durability test conditions]
Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Test environmental conditions: 25℃, relative humidity 50%
The water contact angle of the friction-wearing part is measured every 2,500 frictional reciprocations, and the number of abrasion reciprocations that maintains the water contact angle of 100 degrees or more is defined as the wear durability number.
［摩耗耐久試験条件］
往復摩耗試験機を用いたスチールウール摩耗耐久性の評価
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
試験環境条件：２５℃、相対湿度５０％
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測し、水接触角１００度以上を保つ摩耗往復回数を摩耗耐久回数とする。 In an article having a layer made of a cured product of the coating agent of the present invention, the abrasion durability on the surface of the article is preferably 5,000 times or more, and preferably 7,500 times or more under the test conditions described below. It is more preferable. In addition, in the present invention, in order to make the number of abrasion durability on the surface of the article equal to or higher than the above value, in the coating agent containing the fluoropolyether group-containing polymer composition of the present invention, the fluoropolymer represented by the above formula (2) is used. This can be achieved by controlling the content of the ether group-containing polymer to 10% by mass or more.
[Abrasion durability test conditions]
Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Test environmental conditions: 25℃, relative humidity 50%
The water contact angle of the friction-wearing part is measured every 2,500 frictional reciprocations, and the number of abrasion reciprocations that maintains the water contact angle of 100 degrees or more is defined as the wear durability number.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記実施例によって限定されるものではない。なお、下記式において、膜厚は分光エリプソメーターを用いた分光エリプソメトリー測定法により測定した値である。
Hereinafter, the present invention will be explained in more detail by showing Examples and Comparative Examples, but the present invention is not limited by the Examples below. In addition, in the following formula, the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.
［実施例１～５４、比較例１～３９］
コーティング剤の調製及び硬化被膜の形成
（Ｉ）成分として、下記式（Ａ）、（Ｂ）、（Ｃ）で表される構造のフルオロポリエーテル基含有ポリマーと、
（ＩＩ）成分として、下記式（Ｄ）、（Ｅ）、（Ｆ）、（Ｇ）、（Ｈ）、（Ｉ）で表される構造のフルオロポリエーテル基含有ポリマーと
を表１、２、３に示す割合で混合し、フルオロポリエーテル基含有ポリマー組成物を得た。該ポリマー組成物を、濃度２０質量％になるようにＮｏｖｅｃ ７２００（３Ｍ社製、エチルパーフルオロブチルエーテル）に溶解させてコーティング剤を調製した。最表面にＳｉＯ2を１０ｎｍ処理したガラス（コーニング社製 Ｇｏｒｉｌｌａ）に、各コーティング剤６μｌを真空蒸着し（処理条件は、圧力：３．０×１０-3Ｐａ、加熱温度：５００℃）、８０℃、相対湿度８０％の雰囲気下で３０分放置後、２５℃、相対湿度５０％の雰囲気下で１２時間以上硬化させて膜厚１３ｎｍの硬化被膜を形成した。
[Examples 1 to 54, Comparative Examples 1 to 39]
Preparation of coating agent and formation of cured film As component (I), a fluoropolyether group-containing polymer having a structure represented by the following formula (A), (B), or (C);
(II) As a component, a fluoropolyether group-containing polymer having a structure represented by the following formula (D), (E), (F), (G), (H), or (I);
were mixed in the proportions shown in Tables 1, 2, and 3 to obtain a fluoropolyether group-containing polymer composition. A coating agent was prepared by dissolving the polymer composition in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass. 6 μl of each coating agent was vacuum-deposited on glass (Gorilla, manufactured by Corning Inc.) whose outermost surface had been treated with 10 nm of SiO 2 (processing conditions: pressure: 3.0×10 −3 Pa, heating temperature: 500° C.), After being left in an atmosphere of 80% relative humidity at 25°C for 30 minutes, it was cured for 12 hours or more in an atmosphere of 25°C and 50% relative humidity to form a cured film with a thickness of 13 nm.
コーティング剤の調製及び硬化被膜の形成
（Ｉ）成分として、下記式（Ａ）、（Ｂ）、（Ｃ）で表される構造のフルオロポリエーテル基含有ポリマーと、
Preparation of coating agent and formation of cured film As component (I), a fluoropolyether group-containing polymer having a structure represented by the following formula (A), (B), or (C);
［初期撥水性の評価］
上記にて作製した硬化被膜を形成したガラスについて、接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）を測定した（液滴：２μｌ、温度：２５℃、相対湿度：５０％）。結果（初期水接触角）を表１、２、３に示す。
初期においては、実施例、比較例共に１１０°以上の良好な撥水性を示した。 [Evaluation of initial water repellency]
The contact angle (water repellency) of the cured film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) on the glass on which the cured film was formed (droplet: 2 μl, temperature :25°C, relative humidity: 50%). The results (initial water contact angle) are shown in Tables 1, 2, and 3.
In the initial stage, both Examples and Comparative Examples showed good water repellency of 110° or more.
上記にて作製した硬化被膜を形成したガラスについて、接触角計Ｄｒｏｐ Ｍａｓｔｅｒ（協和界面科学社製）を用いて、硬化被膜の水に対する接触角（撥水性）を測定した（液滴：２μｌ、温度：２５℃、相対湿度：５０％）。結果（初期水接触角）を表１、２、３に示す。
初期においては、実施例、比較例共に１１０°以上の良好な撥水性を示した。 [Evaluation of initial water repellency]
The contact angle (water repellency) of the cured film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) on the glass on which the cured film was formed (droplet: 2 μl, temperature :25°C, relative humidity: 50%). The results (initial water contact angle) are shown in Tables 1, 2, and 3.
In the initial stage, both Examples and Comparative Examples showed good water repellency of 110° or more.
［滑り性の評価］
上記にて作製した硬化被膜を形成したガラスについて、滑り性の評価として、下記に示す方法で不織布に対する動摩擦係数を評価した。硬化被膜を形成したガラスの不織布に対する動摩擦係数は、ＡＳＴＭ Ｄ１８９４に準拠して、表面性測定機ＴＹＰＥ：１４ＦＷ（新東科学社製）を用い、荷重１００ｇｆ、引張速度５００ｍｍ／分の条件で測定した。評価の指標として、動摩擦係数が０．２３以上で◎（優）、０．１８以上０．２３未満で○（良）、０．１３以上０．１８未満で△（可）、０．１３未満を×（不可）とし、表１、２、３に示す。試験環境条件は２５℃、相対湿度５０％である。
滑り性
荷重：１００ｇｆ
ストローク：１００ｍｍ
接触面積：１×３ｃｍ2
不織布：ＢＥＭＣＯＴ（旭化成社製） [Evaluation of slipperiness]
Regarding the glass on which the cured film produced above was formed, the coefficient of dynamic friction with respect to the nonwoven fabric was evaluated by the method shown below as an evaluation of slipperiness. The coefficient of dynamic friction of the glass on which the cured film was formed was measured in accordance with ASTM D1894 using a surface property measuring machine TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm/min. . As evaluation indicators, the dynamic friction coefficient is ◎ (excellent) if it is 0.23 or more, ○ (good) if it is 0.18 or more and less than 0.23, △ (fair) if it is 0.13 or more and less than 0.18, and less than 0.13. are marked as × (impossible) and are shown in Tables 1, 2, and 3. The test environmental conditions are 25° C. and 50% relative humidity.
Slipperiness <br/> Load: 100gf
Stroke: 100mm
Contact area: 1 x 3 cm 2
Non-woven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)
上記にて作製した硬化被膜を形成したガラスについて、滑り性の評価として、下記に示す方法で不織布に対する動摩擦係数を評価した。硬化被膜を形成したガラスの不織布に対する動摩擦係数は、ＡＳＴＭ Ｄ１８９４に準拠して、表面性測定機ＴＹＰＥ：１４ＦＷ（新東科学社製）を用い、荷重１００ｇｆ、引張速度５００ｍｍ／分の条件で測定した。評価の指標として、動摩擦係数が０．２３以上で◎（優）、０．１８以上０．２３未満で○（良）、０．１３以上０．１８未満で△（可）、０．１３未満を×（不可）とし、表１、２、３に示す。試験環境条件は２５℃、相対湿度５０％である。
滑り性
荷重：１００ｇｆ
ストローク：１００ｍｍ
接触面積：１×３ｃｍ2
不織布：ＢＥＭＣＯＴ（旭化成社製） [Evaluation of slipperiness]
Regarding the glass on which the cured film produced above was formed, the coefficient of dynamic friction with respect to the nonwoven fabric was evaluated by the method shown below as an evaluation of slipperiness. The coefficient of dynamic friction of the glass on which the cured film was formed was measured in accordance with ASTM D1894 using a surface property measuring machine TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm/min. . As evaluation indicators, the dynamic friction coefficient is ◎ (excellent) if it is 0.23 or more, ○ (good) if it is 0.18 or more and less than 0.23, △ (fair) if it is 0.13 or more and less than 0.18, and less than 0.13. are marked as × (impossible) and are shown in Tables 1, 2, and 3. The test environmental conditions are 25° C. and 50% relative humidity.
Slipperiness <br/> Load: 100gf
Stroke: 100mm
Contact area: 1 x 3 cm 2
Non-woven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)
［耐摩耗性の評価］
スチールウール摩耗耐久性の評価
上記で得られた防汚コーティング薄膜層（硬化被膜）を有する基材について、往復摩耗試験機（Ｔｙｐｅ４０、新東科学社製）を用いて、以下の条件で試験した。
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
総摩擦往復回数：１０，０００回
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測した。水接触角１００°以上を保つ摩耗往復回数をスチールウール摩耗耐久回数とし、スチールウール摩耗耐久回数が１０，０００回以上を◎（優）、７，５００回以上１０，０００回未満を○（良）、５，０００回以上７，５００回未満を△（可）、５，０００回未満を×（不可）とし、表１、２、３に示す。試験環境条件は２５℃、相対湿度５０％である。 [Evaluation of wear resistance]
Evaluation of steel wool abrasion durability The base material having the antifouling coating thin film layer (cured film) obtained above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagakusha). .
Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Total number of friction reciprocations: 10,000 times The water contact angle of the frictionally worn portion was measured every 2,500 friction reciprocations. The number of abrasion cycles that maintain a water contact angle of 100° or more is defined as the steel wool abrasion durability number. ◎ (Excellent) is when the steel wool abrasion durability is 10,000 times or more, and ○ (Good) is 7,500 times or more but less than 10,000 times. ), 5,000 times or more but less than 7,500 times is Δ (acceptable), and less than 5,000 times is × (impossible), as shown in Tables 1, 2, and 3. The test environmental conditions are 25° C. and 50% relative humidity.
スチールウール摩耗耐久性の評価
上記で得られた防汚コーティング薄膜層（硬化被膜）を有する基材について、往復摩耗試験機（Ｔｙｐｅ４０、新東科学社製）を用いて、以下の条件で試験した。
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
総摩擦往復回数：１０，０００回
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測した。水接触角１００°以上を保つ摩耗往復回数をスチールウール摩耗耐久回数とし、スチールウール摩耗耐久回数が１０，０００回以上を◎（優）、７，５００回以上１０，０００回未満を○（良）、５，０００回以上７，５００回未満を△（可）、５，０００回未満を×（不可）とし、表１、２、３に示す。試験環境条件は２５℃、相対湿度５０％である。 [Evaluation of wear resistance]
Evaluation of steel wool abrasion durability The base material having the antifouling coating thin film layer (cured film) obtained above was tested under the following conditions using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagakusha). .
Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Total number of friction reciprocations: 10,000 times The water contact angle of the frictionally worn portion was measured every 2,500 friction reciprocations. The number of abrasion cycles that maintain a water contact angle of 100° or more is defined as the steel wool abrasion durability number. ◎ (Excellent) is when the steel wool abrasion durability is 10,000 times or more, and ○ (Good) is 7,500 times or more but less than 10,000 times. ), 5,000 times or more but less than 7,500 times is Δ (acceptable), and less than 5,000 times is × (impossible), as shown in Tables 1, 2, and 3. The test environmental conditions are 25° C. and 50% relative humidity.
（Ｉ）成分のフルオロポリエーテル基含有ポリマーを単独で用いた場合、動摩擦係数は良好であるものの、耐摩耗性が不十分であった。（Ｉ）成分のフルオロポリエーテル基含有ポリマーに加えて、更に（ＩＩ）成分として、分子内にフルオロオキシアルキレン基を有し、該ポリマーの両末端に反応性官能基を有し、極性基を有さないフルオロポリエーテル基含有ポリマーを実施例で示す割合で用いた場合、動摩擦係数、耐摩耗性ともに良好であった。（Ｉ）成分に対する（ＩＩ）成分の混合比率が高くなると動摩擦係数と耐摩耗性が低下する傾向が見られた。
When the fluoropolyether group-containing polymer of component (I) was used alone, the coefficient of dynamic friction was good, but the wear resistance was insufficient. In addition to the fluoropolyether group-containing polymer as the component (I), the component (II) also has a fluorooxyalkylene group in the molecule, a reactive functional group at both ends of the polymer, and a polar group. When the fluoropolyether group-containing polymer was used in the proportions shown in the examples, both the coefficient of dynamic friction and the abrasion resistance were good. There was a tendency for the dynamic friction coefficient and wear resistance to decrease as the mixing ratio of component (II) to component (I) increased.
Claims (13)
- （Ｉ） 下記一般式（１）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物と、
（ＩＩ） 下記一般式（２）
Ｗ－Ｏ－ＣＨ2－Ｒｆ２－ＣＨ2－Ｏ－Ｗ （２）
（式中、Ｒｆ２は－（ＣcＦ2cＯ）－（ＣcＦ2cＯ単位は直鎖構造であり、ｃは１～６の整数である。）で表される単位を含み、分岐を有しない直鎖状のフルオロオキシアルキレン基であり、Ｗは独立に末端に水酸基含有シリル基又は加水分解性シリル基を有し、極性基を有さない１価の基である。）
で表されるフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物
を含むフルオロポリエーテル基含有ポリマー組成物であって、（Ｉ）成分と（ＩＩ）成分の合計における（Ｉ）成分の含有量が６５～９５質量％であるフルオロポリエーテル基含有ポリマー組成物。 (I) The following general formula (1)
A fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof, represented by
(II) The following general formula (2)
W-O-CH 2 -Rf2-CH 2 -O-W (2)
(In the formula, Rf2 contains a unit represented by -(C c F 2c O) - (The C c F 2c O unit has a linear structure, and c is an integer from 1 to 6), and has no branching. W is a monovalent group that independently has a hydroxyl group-containing silyl group or a hydrolyzable silyl group at the end and has no polar group.)
A fluoropolyether group-containing polymer composition containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof represented by: (I) in the total of components (I) and (II) A fluoropolyether group-containing polymer composition having a component content of 65 to 95% by mass. - （ＩＩ）成分が、下記一般式（３）
で表されるものである請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。 (II) component is represented by the following general formula (3)
The fluoropolyether group-containing polymer composition according to claim 1, which is represented by: - 前記式（１）のＲｆ１が、下記一般式（４）で表されるフルオロオキシアルキル基である請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。
- 前記式（１）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。 In the formula (1), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to claim 1, wherein the group is selected from the group consisting of groups and halogen groups.
- 式（１）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。
- 前記式（２）のＲｆ２が、下記式（５）で表されるものである請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。
- 前記式（２）のＲｆ２が、下記式
で表されるポリマーから選ばれるものである請求項１に記載のフルオロポリエーテル基含有ポリマー組成物。 Rf2 in the above formula (2) is the following formula
The fluoropolyether group-containing polymer composition according to claim 1, which is selected from the polymers represented by: - 前記式（３）において、Ｘが独立に、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数１～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれる基である請求項２に記載のフルオロポリエーテル基含有ポリマー組成物。 In the formula (3), X independently represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer composition according to claim 2, wherein the group is selected from the group consisting of groups and halogen groups.
- 前記式（３）で表されるポリマーが、下記式で表されるポリマーから選ばれるものである請求項２に記載のフルオロポリエーテル基含有ポリマー組成物。
- 請求項１～９のいずれか１項に記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤。 A coating agent comprising the fluoropolyether group-containing polymer composition according to any one of claims 1 to 9.
- 請求項１０に記載のコーティング剤の硬化物からなる層を有する物品。 An article having a layer made of a cured product of the coating agent according to claim 10.
- 請求項１１に記載の物品の表面における動摩擦係数が以下に記載の計測条件において０．１３以上であり、摩耗耐久回数が以下に記載の試験条件において５，０００回以上である物品。
［動摩擦係数計測条件］
ＡＳＴＭ Ｄ１８９４に準拠した手法による測定
荷重：１００ｇｆ
ストローク：１００ｍｍ
引張速度：５００ｍｍ／分
接触面積：１×３ｃｍ2
擦り材：不織布（ＢＥＭＣＯＴ（旭化成社製））
試験環境条件：２５℃、相対湿度５０％
［摩耗耐久試験条件］
往復摩耗試験機を用いたスチールウール摩耗耐久性の評価
擦り材：スチールウール＃００００（Ｂｏｎｓｔａｒ）
荷重：１ｋｇｆ
往復距離：４０ｍｍ
往復速度：６０往復毎分
試験環境条件：２５℃、相対湿度５０％
摩擦往復回数２，５００回毎に摩擦摩耗部分の水接触角を計測し、水接触角１００度以上を保つ摩耗往復回数を摩耗耐久回数とする。 The article according to claim 11, wherein the coefficient of dynamic friction on the surface of the article is 0.13 or more under the measurement conditions described below, and the number of wear durability is 5,000 times or more under the test conditions described below.
[Dynamic friction coefficient measurement conditions]
Measured load according to ASTM D1894 method: 100gf
Stroke: 100mm
Pulling speed: 500mm/min Contact area: 1x3cm2
Rubbing material: Non-woven fabric (BEMCOT (manufactured by Asahi Kasei))
Test environment conditions: 25℃, relative humidity 50%
[Abrasion durability test conditions]
Evaluation of steel wool abrasion durability using a reciprocating abrasion tester Rubbing material: Steel wool #0000 (Bonstar)
Load: 1kgf
Round trip distance: 40mm
Reciprocation speed: 60 reciprocations per minute Test environmental conditions: 25℃, relative humidity 50%
The water contact angle of the friction-wearing part is measured every 2,500 frictional reciprocations, and the number of abrasion reciprocations that maintains the water contact angle of 100 degrees or more is defined as the wear durability number. - 物品の表面全体又は一部に、乾式方法又は湿式方法により請求項１～９のいずれか１項に記載のフルオロポリエーテル基含有ポリマー組成物を含むコーティング剤を塗布、硬化して層を形成する工程を含む物品の表面改質方法。 A coating agent containing the fluoropolyether group-containing polymer composition according to any one of claims 1 to 9 is applied to the entire surface or a part of the surface of the article by a dry method or a wet method and cured to form a layer. A method for surface modification of an article including a process.
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| JP2019131808A (en) * | 2018-02-02 | 2019-08-08 | ダイキン工業株式会社 | Electronic device |
| JP2022059417A (en) * | 2020-10-01 | 2022-04-13 | 信越化学工業株式会社 | Fluoropolyether group-containing polymer composition, coating agent and article |
| JP2022165943A (en) * | 2021-04-20 | 2022-11-01 | ダイキン工業株式会社 | Surface treatment agent |
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| JP2005290323A (en) * | 2004-04-05 | 2005-10-20 | Shin Etsu Chem Co Ltd | Surface treatment agent composition |
| JP2011116947A (en) * | 2009-10-27 | 2011-06-16 | Shin-Etsu Chemical Co Ltd | Fluorooxyalkylene group-containing polymer composition, surface treatment agent comprising the composition and article surface-treated with the surface treatment agent |
| JP2012072272A (en) * | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article subjected to surface treatment using the surface treatment agent |
| JP2019131808A (en) * | 2018-02-02 | 2019-08-08 | ダイキン工業株式会社 | Electronic device |
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