CN113533381A - Method for evaluating weather resistance of coating film, method for forming coating film, and article having coating film - Google Patents
Method for evaluating weather resistance of coating film, method for forming coating film, and article having coating film Download PDFInfo
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- CN113533381A CN113533381A CN202110422474.5A CN202110422474A CN113533381A CN 113533381 A CN113533381 A CN 113533381A CN 202110422474 A CN202110422474 A CN 202110422474A CN 113533381 A CN113533381 A CN 113533381A
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- 238000000576 coating method Methods 0.000 title claims abstract description 112
- 239000011248 coating agent Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000000962 organic group Chemical group 0.000 claims description 31
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 238000011156 evaluation Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 1
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- 150000001875 compounds Chemical class 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 13
- -1 -CF2H radical Chemical class 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000005341 toughened glass Substances 0.000 description 11
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- 239000005871 repellent Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 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 4
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
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- 125000005647 linker group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910007161 Si(CH3)3 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 239000004210 ether based solvent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 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
- 239000006082 mold release agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 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
- 229920001690 polydopamine Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Polyethers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a method for evaluating weather resistance of a coating film, a method for forming the coating film and an article having the coating film. The invention provides a method for evaluating the weather resistance of a coating. The film is a film comprising a polymer having a perfluoropolyether group, and is excellent in water-and oil-repellency, weather resistance, and adhesion, and the film comprises a cured product of a polymer having a perfluoropolyether group, and has a film density of 1.40g/cm as measured by an X-ray reflectance method3Above and 2.50g/cm3The following. Said hasThe fluoropolyether-based polymer has a residue of a divalent perfluorooxyalkylene polymer, and has a perfluoropolyether group having at least one hydrolyzable group at least one terminal end in one molecule.
Description
Technical Field
The present invention relates to a method for evaluating weather resistance of a coating film, a method for forming the coating film, and an article having the coating film. More specifically, the present invention relates to a method for evaluating weather resistance of a coating film comprising a polymer having a perfluoropolyether group and having excellent water/oil repellency, weather resistance, and adhesion, a method for forming the coating film, and an article having the coating film.
Background
In general, a compound having a fluoropolyether group has water-and oil-repellency, chemical resistance, lubricity, releasability, antifouling property, and the like because the surface free energy thereof is very small. The compound having a fluoropolyether group is widely used in the fields of water-and oil-repellent antifouling agents for paper and fiber, lubricants for magnetic recording media, oil-repellent agents for precision machines, release agents, cosmetic materials, protective films, and the like in industrial production by utilizing its properties. However, the properties thereof mean both non-tackiness and non-tackiness to other substrates, and even if the fluoropolyether group-containing compound itself can be applied to the surface of the substrate, it is difficult to adhere the coating film containing the compound to the substrate.
On the other hand, silane coupling agents are widely known as materials for bonding organic compounds to the surface of a substrate such as glass or cloth, and are widely used as coating agents for the surface of various substrates. The 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. The hydrolyzable silyl group undergoes a self-condensation reaction due to moisture or the like in the air to form a coating film. The coating film is chemically and physically bonded to the surface of glass, metal, or the like via a hydrolyzable silyl group, and thus has durability.
Thus, a composition is disclosed (International publication WO2017/038832 (patent document 1), Japanese patent laid-open Nos. 2019-119747 (patent document 3), 2019-131807 (patent document 2)). The composition is easy to adhere to the surface of a base material by using a polymer having a perfluoropolyether group in which a hydrolyzable silyl group has been introduced into a compound having a perfluoropolyether group, and can form a coating film having water-and oil-repellency, chemical resistance, lubricity, releasability, antifouling property, and the like on the surface of a base material.
Cured coatings of lenses, antireflection films, and the like, which are surface-treated with a composition containing a polymer having a perfluoropolyether group in which a hydrolyzable silyl group is introduced into the compound having a perfluoropolyether group, have excellent slipperiness and water/oil repellency, but have not yet exhibited sufficient performance in terms of weather resistance.
Documents of the prior art
Patent document
[ patent document 1] International publication No. 2017/038832
[ patent document 2] Japanese patent application laid-open No. 2019-131807
[ patent document 3] Japanese patent application laid-open No. 2019-119747
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a method for evaluating weather resistance of a coating film, a method for forming the coating film, and an article having the coating film. The method is for providing a coating film comprising a polymer having a perfluoropolyether group, and is excellent in water-and oil-repellency, weather resistance, and adhesion.
Means for solving the problems
The present inventors have assiduously studied to achieve the above object and, as a result, have found that the weather resistance of a coating film can be improved by appropriately curing the coating film after the formation thereof and controlling the film density of the coating film within a predetermined range, thereby completing the present invention.
That is, the present invention provides a method for evaluating weather resistance of a coating film, a method for forming the coating film, and an article having the coating film.
[ 1] A method for evaluating the weather resistance of a coating film,
the evaluation method is a method for evaluating the weather resistance of a coating film comprising a cured product of a polymer having a perfluoropolyether group.
The evaluation method comprises measuring the film density of the coating layer of the polymer having a perfluoropolyether group applied to the surface of the substrate by X-ray reflectance method, and determining that the film density is 1.40g/cm3Above and 2.50g/cm3And a step of curing the film with a polymer having a perfluoropolyether group.
[ 2] the method for evaluating weather resistance of a coating film according to [ 1],
the polymer having a perfluoropolyether group is a polymer having a divalent perfluorooxyalkylene polymer residue in one molecule and having a perfluoropolyether group. The divalent perfluorooxyalkylene polymer residue is substituted with- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-represents that the polymer having a perfluoropolyether group has at least one hydrolysable group at least one terminal end in a molecule. In the above formula, p, q, r, s and t are each independently an integer of 0 to 200, and p + q + r + s + t is 3 to 500, each perfluoroalkoxyalkylene repeating unit shown in the parentheses may be randomly bonded, and d is independently an integer of 0 to 8. The unit may be linear or branched.
[ 3] the method for evaluating weather resistance of a coating film according to [ 1] or [ 2],
the polymer having a perfluoropolyether group is at least one selected from the group consisting of fluorine-containing hydrolyzable organosilicon compounds represented by the following general formulae (1) to (5),
(A-Rf)α-ZWβ (1)
Rf-(ZWβ)2 (2)
Z’-(Rf-ZWβ)γ (3)
in the formula, Rf is represented by- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-a divalent perfluorooxyalkylene polymer residue, p, q, r, s and t each independently being an integer of 0 to 200, and p + q + r + s + t being 3 to 500, each perfluorooxyalkylene repeating unit shown in the parentheses may be randomly bonded, d independently being an integer of 0 to 8, and the unit may be either a straight chain or a linearIs branched, A is a fluorine atom, a hydrogen atom or a terminal group is-CF3Group, -CF2H group or-CH2A monovalent fluorine-containing group of the group F, Z and Z' are independently a single bond or a 2 to 8-valent organic group which may include a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, or may be substituted with fluorine, W is a monovalent organic group having a hydrolyzable group at the terminal, α and β are independently integers of 1 to 7, α + β is an integer of 2 to 8, γ is an integer of 2 to 8,
A-Rf-Q-(Y)δ-B (4)
Rf-(Q-(Y)δ-B)2 (5)
wherein Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.
[ 4 ] the method for evaluating weather resistance of a coating film as described in [ 3],
wherein Z is an organic group having a silaphenylene or cyclic siloxane structure.
[ 5 ] the method for evaluating weather resistance of a coating film according to [ 3],
wherein Q is an organic group having a silaphenylene or cyclic siloxane structure.
[ 6 ] A method of,
the method is a method for producing a coating film which is used in any one of the methods for evaluating weather resistance of a coating film described in [ 1] to [ 5 ] and which comprises a cured product of a polymer having a perfluoropolyether group,
the method for producing a coating film comprises the steps of,
the film density measured by the X-ray reflectance method was 1.40g/cm3Above and 2.50g/cm3In the following manner, the polymer coating layer having a perfluoropolyether group applied to the surface of the substrate is cured and formed into a film.
[ 7 ] an article of manufacture,
having a coating film comprising a cured polymer having a perfluoropolyether groupAnd a film density of 1.40g/cm as measured by an X-ray reflectance method3Above and 2.50g/cm3The following.
ADVANTAGEOUS EFFECTS OF INVENTION
The film to be evaluated in the evaluation method of the present invention is excellent in water-and oil-repellency and weather resistance because it contains a polymer having a perfluoropolyether group and the film density of a cured product of the polymer is within a predetermined range.
Detailed Description
The present invention will be described in detail below.
The film to be evaluated in the evaluation method of the present invention is a film (cured product) comprising a polymer having a perfluoropolyether group, and has a film density of 1.40g/cm as measured by an X-ray reflectance method3Above and 2.50g/cm3The following coating film.
The film density of the film to be evaluated in the evaluation method of the present invention is from 1.40g/cm3To 2.50g/cm3Preferably from 1.45g/cm3To 2.30g/cm3More preferably from 1.50g/cm3To 2.00g/cm3. Film density lower than 1.40g/cm3The coating film of (2) does not exhibit sufficient water-and oil-repellency. In addition, the film density is higher than 2.50g/cm3The volume density of the film of (2) is greatly higher than that of the polymer having a perfluoropolyether group as a raw material, and therefore, it is difficult to produce such a film.
The film density of the coating film in the evaluation method of the present invention can be measured by an X-ray reflectance method. For example, the film density of the film can be calculated by measuring the reflectance of the film with X-rays under the following conditions and using the critical angle for total reflection thus obtained.
The measurement device: x-ray diffractometer ATX-G (manufactured by Rigaku corporation, Japan)
An X-ray generation device: rotary anticathode type Cu
Output: 50kV 300mA
Measurement range: 0.3-4.0 °
Stride: 0.001 °
Scanning speed: 0.2 degree/min
In the present invention, the film density can be regulated within the above-indicated range by curing the film by appropriately setting the curing conditions after the film comprising the polymer having a perfluoropolyether group is prepared.
As the polymer having a perfluoropolyether group, a compound having a fluorinated oxyalkylene group (i.e., a monovalent or divalent perfluoropolyether residue) in one molecule is preferably cited. Said fluorinated oxyalkylene group is represented by the formula-CjF2jA compound having a structure of a (poly) fluoroalkyloxyalkylene group (a divalent perfluorooxyalkylene polymer residue) in which a plurality of repeating units represented by O-are bonded in a straight chain (in-line arrangement) (in the structure, j is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4). The polymer having a perfluoropolyether group is particularly a polymer having 3 to 500 repeating units, preferably 15 to 200 repeating units, more preferably 20 to 100 repeating units, and still more preferably 25 to 80 repeating units.
The above repeating unit-CjF2jO-itself may be either a straight chain or a branched chain. For example, the following units may be mentioned, and two or more of these repeating units may be bonded.
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2CF2O-
-CF2CF2CF2CF2CF2O-
-C(CF3)2O-
The above-mentioned (poly) fluoroalkyloxyalkylene structure (divalent perfluorooxyalkylene polymer residue), specifically- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-. Wherein p, q, r, s and t are respectively and independently integers of 0-200; preferably, p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, s is an integer of 0 to 50, and t is an integer of 0 to 100, and p + q + r + s + t is an integer of 3 to 500; preferably an integer of 10 to 105. In the above formula, the perfluoroalkylene unit (CF) is excluded from both terminals2)dIn addition, each of the perfluoroalkoxyalkylene repeating units shown in the parentheses may be randomly bonded. d is independently an integer of 0 to 8, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and the repeating unit may be a straight chain or a branched chain. In particular, the following structure can be used.
-(CF2)d′-O-(CF2CF2O)a′-(CF2)d′-
-(CF2)d′-O-(CF2CF2CF2O)r′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′(CF2CF2CF2CF2O)s′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′(CF2CF2CF2CF2O)s′-(CF2)d′-
(in the formula, p ', q', r ', s', t 'are each independently an integer of 1 to 200, and the sum of p', q ', r', s ', t' is 3 to 500.) in the above formula, excluding the perfluoroalkylene units (CF) at both ends2)d，In addition, each of the perfluoroalkoxyalkylene repeating units shown in the parentheses may be randomly bonded. d' is independently an integer of 0 to 5, and the repeating unit may be a straight chain or a branched chain. )
The polymer having a perfluoropolyether group according to the present invention is more preferably a fluorine-containing hydrolyzable organosilicon compound (fluorine-containing hydrolyzable organosilicon compound) represented by any one of the following general formulae (1) to (5). These may be used alone or in combination of two or more.
(A-Rf)α-ZWβ (1)
Rf-(ZWβ)2 (2)
Z’-(Rf-ZWβ)γ (3)
A-Rf-Q-(Y)δ-B (4)
Rf-(Q-(Y)δ-B)2 (5)
In the formulae (1) to (5), Rf is- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-a divalent perfluorooxyalkylene polymer residue. In Rf, p, q, r, s and t are each independently an integer of 0 to 200, and p + q + r + s + t is 3 to 500. In the above formula, the perfluoroalkylene unit (CF) excluding both terminals2)dIn addition, each of the perfluoroalkoxyalkylene repeating units shown in the parentheses may be randomly bonded. d is independently an integer of 0 to 8, and the unit may be a straight chain or a branched chain.
A is fluorine atom, hydrogen atom or terminal-CF3Radical, -CF2H radical or-CH2The monovalent fluorine of the F group contains a group. Z, Z' is independently a single bond or a 2-to 8-valent organic group which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom and may be substituted with fluorine, preferably a silaphenylene group or a cyclic siloxane structure, and W is a monovalent organic group having a hydrolytic group at the end. Alpha and beta are respectively independent integers of 1-7, wherein alpha is preferably an integer of 1-3, more preferably an integer of 1, beta is an integer of 1-3, and alpha + beta is an integer of 2-8, preferably an integer of 2-4. Gamma is an integer of 2 to 8, preferably 2 or 3.
Q is a single bond or a divalent organic group, and preferably includes a silylene group or a cyclic siloxane structure. δ is an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.
In the above formulas (1) to (5), Rf is- (CF) having the above (poly) fluoroalkyloxyalkylene structure (divalent perfluorooxyalkylene polymer residue)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)dThe same structure as described above can be exemplified.
In the above-mentioned formulae (1) and (4),a is fluorine atom, hydrogen atom or terminal-CF3Group, -CF2H group or-CH2The monovalent fluorine of the F group contains a group. As terminal is-CF3Radical, -CF2H radical or-CH2The monovalent fluorine-containing group of the F group may specifically be-CF3Group, -CF2CF3Group, -CF2CF2CF3Group, -CH2CF(CF3)-OC3F7Group, -CH2OCF2CFH-OC3F7Groups, and the like. Among them, preferred is-CF3Group, -CF2CF3Group, -CF2CF2CF3A group and-CH2OCF2CFH-OC3F7A group.
In the formulae (1) to (3), Z, Z' is independently a single bond or a 2 to 8-valent organic group which may contain a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, or may be substituted with fluorine. The organic group may be represented by (L)e-M (e is an integer of 1 to 7, preferably an integer of 1 to 3).
Wherein L is a single bond or an oxygen atom, a sulfur atom or a divalent organic group, and in the above formulae (1) to (3), L of Z is a linking group of Rf and M (or W), and L of Z' is a linking group of M (or Rf) and Rf. The divalent organic group is preferably a diorganosilylene group which may include an amide bond, an ether bond, a carbonyl bond, an ester bond, a dimethylsilylene group or the like, -Si [ OH][(CH2)fSi(CH3)3]One or two or more kinds of divalent organic groups having 2 to 12 unsubstituted or substituted carbon atoms among the groups represented by the formula (f is an integer of 2 to 4), and more preferably divalent hydrocarbon groups having 2 to 12 unsubstituted or substituted carbon atoms in the structure.
Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include alkylene groups such as ethylene, propylene (trimethylene and methylethylene), butylene (tetramethylene and methylpropylene), hexamethylene and octamethylene, arylene groups such as phenylene, and combinations of two or more of these groups (alkylene and arylene groups). In addition, some or all of the hydrogen atoms bonded to carbon atoms of these groups may be substituted with a halogen atom such as fluorine or iodine. Among them, an unsubstituted or substituted alkylene group or phenylene group having 2 to 4 carbon atoms is preferable.
Examples of the divalent organic group of L include a group represented by the following structure and a group to which two or more of these organic groups have been bonded.
-(CH2)u-O-(CH2)v-
(in the formula, f is an integer of 2-4, b is an integer of 2-6, preferably an integer of 2-4, u and v are each an integer of 1-4, g is an integer of 2-4, and Me is methyl.)
In addition, in (L)eAnd M represents an organic group represented by (e) an integer of 1 to 7, preferably an integer of 1 to 3, wherein M is a single bond, a nitrogen atom, a silicon atom, a carbon atom, a phosphorus atom or a group containing these, or an organic group having a valence of 2 to 8 (the valence of (e + 1)). In particular, it is a single bond, selected from the group consisting of1 2A divalent group represented by C-R3 2Divalent group represented by Si-NR4A divalent group represented by the formula-R, a trivalent group represented by the formula-R, and a trivalent group represented by the formula-R1A trivalent group represented by-R3A trivalent group represented by Si ≡ or a tetravalent group represented by-C ≡ or a tetravalent group represented by-O-C ≡ or a tetravalent siloxane residue represented by-Si ≡ or 2 to 8. In the above formulae (1) to (3), M of Z is a linking group of L (or Rf) and W, and M of Z' is a group linking L and Rf (or each of Rf).
In the above, R1Independently of each other, a group having a repeating unit of an oxyalkylene group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, and optionally a diorganosiloxane structure having 2 to 51 silicon atoms, or R2 3Silyl ether group represented by SiO-. R2Independently of each other, a hydrogen atom, preferably an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, or an alkoxy group having 1 to 3 carbon atoms.
R3Independently of each other, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a chloro group is preferable.
R4An aryl group having 6 to 10 carbon atoms such as an alkyl group having 1 to 3 carbon atoms or a phenyl group.
When M is a siloxane residue, it preferably has a linear, branched or cyclic organopolysiloxane structure having 2 to 51 silicon atoms, preferably 2 to 13 silicon atoms, more preferably 2 to 11 silicon atoms, and still more preferably 2 to 5 silicon atoms. The organopolysiloxane may also have methyl, ethyl, propyl, butyl and C of 1-8 carbon atoms3F7-C3H6And the like are unsubstituted or fluorine-substituted alkyl groups or phenyl groups. In addition, it may also include a silylene structure in which two silicon atoms are bonded with an alkylene group, i.e., including Si- (CH)2)n-Si. In the formula, n is an integer of 2 to 6, preferably an integer of 2 to 4.
Examples of such M include the following groups.
(in the formula, i is an integer of 1-20, c is an integer of 1-50, and Me is methyl.)
In the formulae (1) to (3), W is a monovalent organic group having a hydrolyzable group at the end, and is preferably a group represented by the following formula.
(in the formula, R is alkyl or phenyl with 1-4 carbon atoms, X is a hydrolytic group, a is 2 or 3, and m is an integer of 0-10.)
In the above formula, examples of the hydrolyzable group of X include alkoxy groups having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy and butoxy groups; alkoxyalkoxy groups having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy; an acyloxy group having 1 to 10 carbon atoms such as an acetoxy group; an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenyloxy group; halogen groups such as chlorine, bromine, and iodine; amino groups, and the like. Among them, methoxy and ethoxy are preferable.
R is an alkyl group such as a methyl group or an ethyl group having 1 to 4 carbon atoms or a phenyl group. Among them, methyl is preferable.
a is 2 or 3, but a is preferably 3 from the viewpoint of reactivity and adhesion to a substrate. m is an integer of 0 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 or 3.
In the formulae (1) to (3), as represented by-ZWβThe structure shown may be as follows.
(in the formula, L, R, X, f, c and a are as described above, m1 is an integer of 0 to 10, preferably 2 to 8, m2 is an integer of 1 to 10, preferably 2 to 8, and Me is methyl.)
In the above formulae (4) and (5), Q is a single bond or a divalent organic group, and is a linking group of Rf and Y. The divalent organic group of Q preferably may include a diorganosilylene group selected from the group consisting of an amide bond, an ether bond, an ester bond, and a dimethylsilylene group, -Si [ OH ]][(CH2)fSi(CH3)3]One or two or more kinds of unsubstituted or substituted divalent organic groups having 2 to 12 carbon atoms in the group consisting of the groups represented by the formula (i) - (f is an integer of 2 to 4), and more preferably, the group may include an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms in the structure.
Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms include the same groups as those exemplified for the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms in the above-mentioned L.
Examples of the divalent organic group of Q include groups represented by the following structures.
-(CH2)u-O-(CH2)v-
(in the formula, f is an integer of 2 to 4, b is an integer of 2 to 6, preferably an integer of 2 to 4, u and v are each an integer of 1 to 4, g is an integer of 2 to 4, and Me is a methyl group.)
In the above formulae (4) and (5), Y is independently a divalent organic group having a hydrolyzable group, preferably a group having a structure represented by the following formula.
(in the formula, R, X and a is as described above, k is 0-10 integer, preferably 1-10 integer, more preferably 2-8 integer, h is 1-6 integer, preferably 1 or 2, M' is unsubstituted or substituted 3-8 valent, preferably trivalent or tetravalent hydrocarbon group, and the hydrocarbon group in part or all of the carbon atoms can be replaced by silicon atoms
M' is preferably a group represented by the following structure.
(in the above, M1A diorganosilylene group such as a single bond, an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, or a dimethylsilylene group. M2Is represented by-R1A trivalent group represented by C ═ or by-R3Si ═ represents a trivalent group. At M2In, R1、R3As described above. R5A monovalent hydrocarbon group such as a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group. )
As M1Examples thereof include a single bond, phenylene group, dimethylsilylene group, and tetrafluoroethylene group. In addition, as M2Examples thereof include the following groups.
(in the formula, Me is methyl.)
Examples of such Y include the following groups.
(in the formula, X is the same as above, k1 is an integer of 0 to 10, preferably 1 to 8, k2 is an integer of 2 to 10, preferably 2 to 8, and Me is methyl.)
In the above formulae (4) and (5), δ is an integer of 1 to 10, preferably an integer of 1 to 4, independently.
And B is independently a hydrogen atom, an alkyl group such as a methyl group, ethyl group, propyl group or butyl group having 1 to 4 carbon atoms, or a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom.
Examples of the polymer having a perfluoropolyether group (fluorohydrolyzable organosilicon compound) represented by the above formulae (1) to (5) include the following compounds.
(wherein Me is a methyl group, p1, q1, r1, s1 and t1 are each independently an integer of 1 to 200, and the total of p1, q1, r1, s1 and t1 is 3 to 500. the repeating units shown in parentheses may be randomly bonded.)
The polymer having a perfluoropolyether group (fluorohydrolyzable organosilicon compound) represented by the general formulae (1) to (5) of the present invention may include a compound (X is an OH group) obtained by hydrolyzing a part or all of the above-mentioned hydrolyzable group (X), or may include a compound obtained by condensing a part or all of the above-mentioned OH group.
The fluorine-containing hydrolyzable organosilicon compound is preferably diluted with a solvent in advance. Such a solvent is not particularly limited as long as it can uniformly dissolve the fluorine-containing hydrolyzable organosilicon compound. Examples thereof include fluorine-modified aliphatic hydrocarbon solvents (e.g., perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (e.g., 1, 3-trifluoromethylbenzene, etc.), fluorine-modified ether solvents (e.g., methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (e.g., perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (e.g., petroleum ether, toluene, xylene, etc.), and ketone solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these solvents, from the viewpoint of solubility, stability and the like, a fluorine-modified solvent is preferable, and a fluorine-modified ether-based solvent and a fluorine-modified aromatic hydrocarbon-based solvent are particularly preferable.
The solvent may be used alone or in combination of two or more. The solvent is preferably contained so that the content of the fluorine-containing hydrolyzable organosilicon compound in the water-and oil-repellent agent (solution containing the fluorine-containing hydrolyzable organosilicon compound and the solvent) is 0.01 to 50% by mass, preferably 0.03 to 10% by mass, and more preferably 0.05 to 1% by mass.
The water-and oil-repellent agent containing the fluorine-containing hydrolyzable organosilicon compound can be applied to the substrate by a known method such as a wet coating method (dipping method, brush coating, spin coating, spray coating, gravure coating, die coating, bar coating, slit coating), vapor deposition method, or the like.
Before the water-and oil-repellent agent containing the fluorine-containing hydrolyzable organosilicon compound is applied, the surface of the primer layer on the substrate may be subjected to cleaning such as plasma treatment, UV treatment, or ozone treatment, or may be subjected to surface activation treatment.
The film thickness of the fluorine layer (water-and oil-repellent layer) of the water-and oil-repellent member formed from the coating film in the evaluation method of the present invention is preferably 0.5 to 30nm, and particularly preferably 1 to 20 nm.
If necessary, a hydrolysis condensation catalyst, for example, an organic tin compound (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), an organic titanium compound (e.g., tetra-n-butyl titanate), an organic acid (e.g., acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), and an inorganic acid (e.g., hydrochloric acid or sulfuric acid) may be added to the coating film of the present invention. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferable.
The addition amount of the hydrolytic condensation catalyst is a catalyst amount, and is usually 0.01 to 5 parts by mass, particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of the polymer having a fluoropolyether group and/or the partially hydrolyzed polymer thereof
The substrate to be treated with the coating film of the present invention is not particularly limited, and may be a substrate made of various materials such as paper, cloth, metal and oxides thereof, glass, plastic, ceramic, and quartz. The film of the present invention can impart water-and oil-repellency to the substrate. The coating film of the present invention is particularly suitable as a SiO coating film2The surface treatment material of the treated glass or film is used.
Examples of the article treated with the film of the present invention include medical instruments such as car navigation systems, mobile phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audios, game machines, spectacle lenses, camera lenses, lens filters, sunglasses, and gastroscopes, and optical articles such as copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The coating film of the present invention can prevent fingerprints and sebum from adhering to the article, and can further impart scratch resistance, and therefore, is useful particularly as a water-and oil-repellent layer for touch panel displays, antireflection films, and the like.
The film of the present invention is useful as an antifouling coating layer for sanitary goods such as bathtubs and wash tables; antifouling coatings for glass windows or tempered glass, head lamp covers, etc. of automobiles, electric cars, airplanes, etc.; the outer wall is coated with water-repellent and oil-repellent coating of building material; an oil-stain-proofing coating for a kitchen building material; antifouling and anti-post/anti-graffiti coatings for telephone kiosks; a coating for preventing adhesion of fingerprints to an art product or the like; fingerprint adhesion preventing coatings for optical disks, DVDs, and the like; mold release agents or coating additives for molds; a resin modifier, a fluidity modifier or a dispersibility modifier for an inorganic filler; lubricity improvers for tapes, films and the like are also useful.
Method for producing coating film
The film to be evaluated in the weather resistance evaluation method of the present invention is only required to have a film density of 1.40g/cm as obtained by the X-ray reflectance method3Above and 2.50g/cm3The following may be used. The method of applying (coating) or curing the surface of the base material of the polymer having a perfluoropolyether group for producing the film is not particularly limited, and conventional methods can be used. However, it is also possible to use a film having a film density of 1.40g/cm as measured by X-ray reflectance method according to the kind (molecular structure) of the polymer having a perfluoropolyether group applied3Above and 2.50g/cm3An application method (coating method) of applying a polymer having a perfluoropolyether group to the surface of a substrate and having a film density of 1.40g/cm as measured by an X-ray reflectance method3Above and 2.50g/cm3The coating applied to the evaluation method of the present invention can be produced by forming a coating layer by curing and film-forming with a curing method of the following embodiment (under conditions of temperature, humidity, time, and the like). The method for measuring the film density of the coating by the X-ray reflectance method is as described above.
[ examples ]
Formation and curing of coating film
[ coating method ]
(A) Vacuum evaporation
First, the surface of tempered glass (Gorilla 3 manufactured by Corning Incorporated) was cleaned by plasma treatment under the following conditions.
Next, each of the surface-treating agents was prepared by dissolving the polymer having a perfluoropolyether group obtained in examples 1 to 6, 9 to 11, 13, 14 and comparative examples 1 to 3 and 5 in Novec7200 (Ethyl perfluorobutyl ether manufactured by 3M) at a concentration of 20% by mass, and then 4. mu.L of each of the surface-treating agents obtained above was applied to each of the tempered glasses at a film thickness of about 10nm to obtain each coating film (treatment conditions were a pressure of 2.0X 10)-2Pa, heating temperature: 700 ℃; a vacuum deposition apparatus: the model is as follows: VTR-350M/ERH, manufactured by アルバック machinist).
[ conditions of plasma treatment ]
An apparatus: PDC210 plasma drying and cleaning device
Gas: oxygen 80cc, argon 10cc
Output: 250W
Time: 30 seconds
(B) Spraying of paint
First, the surface of tempered glass (gorella 3 manufactured by Corning Incorporated) was cleaned by plasma treatment under the same conditions as described above.
Next, the polymers having a perfluoropolyether group obtained in examples 7, 8, 12, 15 and comparative examples 4 and 6 were dissolved in Novec7200 (ethyl perfluorobutyl ether, manufactured by 3M) so that the concentration thereof was 0.1 mass%, and the respective surface-treating agents were applied to respective tempered glasses so that the film thickness thereof was about 10nm using a spray coating apparatus (NST-51, manufactured by T & K, ltd.) so as to prepare respective surface-treating agents.
(C) Impregnation
First, the surface of tempered glass (gorella 3 manufactured by Corning Incorporated) was subjected to plasma treatment cleaning under the same conditions as described above.
Next, the compound obtained in comparative example 7 was dissolved in Novec7200 (ethyl perfluorobutyl ether, manufactured by 3M) so that the concentration was 0.1 mass%, thereby preparing a surface treatment agent. After the tempered glass was immersed in the surface treatment agent for 30 seconds, the tempered glass was pulled up from the surface treatment agent at a speed of 150 mm/min, thereby obtaining a coating film.
[ curing method ]
Any of the curing methods of the coating film described below was selected and the coating film was cured.
(a) Temperature: humidity at 40 ℃: 80% curing time: 12 hours
(b) Temperature: 150 ℃ curing time: 5 hours
(c) Temperature: curing time at 200 ℃: 1 hour
(d) Temperature: humidity at 25 ℃: 50% curing time: 12 hours
(e) Temperature: curing time at 120 ℃: 30 minutes
(f) Temperature: curing time at 200 ℃: 30 minutes
(g) Temperature: curing time at 25 ℃: 1 hour
Example 1
A coating film was obtained by applying a compound (I) shown below to a tempered glass by the application method (a) and curing the compound by the selective curing method (a).
Example 2
A coating was obtained in the same manner as in example 1, except that the curing method was changed to the curing method (d).
Example 3
A coating film was obtained in the same manner as in example 2, except that the compound was changed to the compound (II) shown below.
Example 4
A coating was obtained in the same manner as in example 3, except that the curing method was changed to the curing method (a).
Example 5
A coating film was obtained in the same manner as in example 1, except that the compound was changed to the compound (III) shown below.
Example 6
A coating film was obtained in the same manner as in example 1, except that the compound was changed to the compound (IV) shown below.
Example 7
The compound (IV) is coated on the tempered glass by the coating method (B), and the obtained coating film is cured by the curing method (B).
Example 8
A coating film was obtained in the same manner as in example 7, except that the curing method was changed to the curing method (e).
Example 9
A coating film was obtained in the same manner as in example 1, except that the compound was changed to the compound (V) shown below.
Example 10
A coating was obtained in the same manner as in example 9, except that the curing method was changed to the curing method (d).
Example 11
A coating film was obtained in the same manner as in example 1, except that the compound was changed to the compound (VI) shown below synthesized according to the method described in international publication No. 2017/038832.
CF3-O-(CF2CF2O-CF2CF2CF2CF2O)X(CF2CF2O)-CF2CF2CF2-CONHCH2CH2CH2-Si(OCH3)3
(x＝13)
(VI)
Example 12
A coating film was obtained in the same manner as in example 11, except that the coating method was changed to the coating method (B) and the curing method was changed to the curing method (c).
Example 13
A coating was obtained in the same manner as in example 1, except that the compound was changed to the compound (VII) described in jp 2019-131807 a.
CF3CF2CF2-O-(CF2CF2CF2O)X-CF2CF2-CONHCH2C[CH2CH2CH2Si(OCH3)3]3
(x＝30)
(VII)
Example 14
A coating was obtained in the same manner as in example 13, except that the curing method was changed to the curing method (c).
Example 15
A coating film was obtained in the same manner as in example 14, except that the coating method was changed to the coating method (B).
Comparative example 1
A coating was obtained in the same manner as in example 6, except that the curing method was changed to the curing method (d).
Comparative example 2
A coating was obtained in the same manner as in example 5, except that the curing method was changed to the curing method (d).
Comparative example 3
A coating was obtained in the same manner as in example 11, except that the curing method was changed to the curing method (d).
Comparative example 4
A coating film was obtained in the same manner as in example 12, except that the curing method was changed to the curing method (e).
Comparative example 5
A coating was obtained in the same manner as in example 13, except that the curing method was changed to the curing method (d).
Comparative example 6
A coating was obtained in the same manner as in example 15, except that the curing method was changed to the curing method (f).
Comparative example 7
A coating film was obtained by applying a compound (VIII) shown below to tempered glass by the application method (C) and curing by the curing method (g).
C6F12SiNH1.5
(VIII)
Evaluation of cured coating
[ measurement of film Density ]
The film density (g/cm) of each cured film prepared in examples and comparative examples was calculated from the reflectance of X-rays measured under the following conditions and the critical angle of total reflection determined from the reflectance of X-rays measured above3). The results are shown in table 1.
The measurement device: x-ray diffractometer ATX-G (manufactured by Rigaku corporation)
An X-ray generation device: rotary anticathode type Cu
Output: 50kV 300mA
Measurement range: 0.3-4.0 °
Stride: 0.001 °
Scanning speed: 0.2 DEG/min
[ evaluation of Water repellency ]
The contact angle with water (water repellency) of each cured film prepared in examples and comparative examples was measured using a contact angle meter DropMaster (manufactured by nippon scientific corporation). The results are shown in table 1.
[ evaluation of weather resistance (UV test) ]
Each of the cured films prepared in examples and comparative examples was irradiated with UV light under the conditions shown below. Then, the contact angle (water repellency) with water of each cured film was measured by the same method as described above. The results are shown in table 1.
An apparatus: WEATHER-OMETER Ci4400(ATLAS Co., Ltd.)
Light source: metal halide lamp
Irradiance: 770W/m2
Wavelength range: 300-400nm
Blackboard temperature: 63 deg.C
Irradiation time: 180 hours
[ TABLE 1]
As is clear from Table 1, the film densities measured by the X-ray reflectance method in examples 1 to 15 were 1.40g/cm3Above and 2.50g/cm3The following coating film exhibited good weather resistance. And the coating film has good adhesion to the substrate.
Claims (7)
1. A method for evaluating the weather resistance of a coating film,
the evaluation method is a method for evaluating the weather resistance of a coating film of a cured product of a polymer having a perfluoropolyether group,
the evaluation method comprises measuring the film density of a polymer coating layer having a perfluoropolyether group applied to the surface of a substrate by X-ray reflectance method, and determining that the film density is 1.40g/cm3Above and 2.50g/cm3And a step of curing the film with a polymer having a perfluoropolyether group.
2. The method for evaluating the weather resistance of a coating film according to claim 1,
the polymer having a perfluoropolyether group is a polymer having a divalent perfluorooxyalkylene polymer residue in one molecule represented by- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)dThe polymer having a perfluoropolyether group has at least one hydrolyzable group at least one terminal end in a molecule, and in the formula, p, q, r, s, and t are each independently an integer of 0 to 200, and p + q + r + s + t is 3 to 500, each perfluoroalkoxyalkylene repeating unit shown in parentheses may be randomly bonded, and d is independently an integer of 0 to 8, and the unit may be linear or branched.
3. The method for evaluating the weather resistance of a coating film according to claim 1 or claim 2,
the polymer having a perfluoropolyether group is at least one selected from the group consisting of fluorine-containing hydrolyzable organosilicon compounds represented by the following general formulae (1) to (5),
(A-Rf)α-ZWβ (1)
Rf-(ZWβ)2 (2)
Z’-(Rf-ZWβ)γ (3)
in the formula, Rf is represented by- (CF)2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-a divalent perfluorooxyalkylene polymer residue, p, q, r, s and t are each independently an integer of 0 to 200, and p + q + r + s + t is 3 to 500, each perfluorooxyalkylene repeating unit shown in parentheses may be randomly bonded, d is independently an integer of 0 to 8, and the unit may be either a straight chain or a branched chain, a is a fluorine atom, a hydrogen atom or a terminal-CF3Group, -CF2H group or-CH2A monovalent fluorine-containing group of the group F, Z and Z' are independently a single bond or a 2 to 8-valent organic group which may include a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, or may be substituted with fluorine, W is a monovalent organic group having a hydrolyzable group at the terminal, α and β are independently integers of 1 to 7, α + β is an integer of 2 to 8, γ is an integer of 2 to 8,
A-Rf-Q-(Y)δ-B (4)
Rf-(Q-(Y)δ-B)2 (5)
wherein Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is an integer of 1 to 10, Y is a divalent organic group having a hydrolyzable group, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.
4. The method for evaluating the weather resistance of a coating film according to claim 3,
wherein Z is an organic group having a silaphenylene or cyclic siloxane structure.
5. The method for evaluating the weather resistance of a coating film according to claim 3,
wherein Q is an organic group having a silaphenylene or cyclic siloxane structure.
6. In a method for preparing a composite material by using a chemical reaction,
the method is a method for producing a coating film which is used in the method for evaluating weather resistance of a coating film according to claim 1 and which comprises a cured product of a polymer having a perfluoropolyether group,
the method for producing a coating film comprises the steps of,
the film density measured by the X-ray reflectance method was 1.40g/cm3Above and 2.50g/cm3In the following manner, the polymer coating layer having a perfluoropolyether group applied to the surface of the substrate is cured and formed into a film.
7. An article of manufacture, which is provided with a cover,
it has a coating film comprising a cured product of a polymer having a perfluoropolyether group and having a film density of 1.40g/cm as measured by the X-ray reflectance method3Above and 2.50g/cm3The following.
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| JP2020075510A JP7321655B2 (en) | 2020-04-21 | 2020-04-21 | METHOD FOR EVALUATING THE WEATHER RESISTANCE OF A COATING, METHOD FOR FORMING THE COATING, AND ARTICLES HAVING THE SAME COATING |
| JP2020-075510 | 2020-04-21 |
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