CN113717419B - 自清洁膜层及采用该自清洁膜层的接水盘、空调器 - Google Patents
自清洁膜层及采用该自清洁膜层的接水盘、空调器 Download PDFInfo
- Publication number
- CN113717419B CN113717419B CN202010448497.9A CN202010448497A CN113717419B CN 113717419 B CN113717419 B CN 113717419B CN 202010448497 A CN202010448497 A CN 202010448497A CN 113717419 B CN113717419 B CN 113717419B
- Authority
- CN
- China
- Prior art keywords
- film layer
- self
- hydrophobic
- air conditioner
- cleaning film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004140 cleaning Methods 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 34
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 229920003023 plastic Polymers 0.000 claims abstract description 11
- 239000004033 plastic Substances 0.000 claims abstract description 11
- -1 polypropylene Polymers 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical class CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- PJDOLCGOTSNFJM-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PJDOLCGOTSNFJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 claims description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- WZZRDRYYUVHLRD-UHFFFAOYSA-N 2-chloropentanoic acid Chemical compound CCCC(Cl)C(O)=O WZZRDRYYUVHLRD-UHFFFAOYSA-N 0.000 claims 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims 1
- 150000003626 triacylglycerols Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 229920013822 aminosilicone Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010288 cold spraying Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F13/00—Details common to, or for air-conditioning, air-humidification, ventilation or use of air currents for screening
- F24F13/22—Means for preventing condensation or evacuating condensate
- F24F13/222—Means for preventing condensation or evacuating condensate for evacuating condensate
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
Abstract
本发明提出一种自清洁膜层及采用该自清洁膜层的接水盘、空调器，属于高分子材料技术领域，能够解决现有空调接水盘上的冷凝水浸润在其表面，冷凝水及污物不能即时排出空调外、易滋生细菌等技术问题。该自清洁膜层由下至上依次为塑料基底层、底漆膜层和表面膜层，所述表面膜层由具有微/纳二元结构的超疏水颗粒形成得到，所述超疏水颗粒为利用疏水改性用材料改性粉末基材得到。本发明提供的自清洁膜层可应用于空调接水盘表面，可使污物随冷凝水及时排出空调器，起到良好的清洁效果。
Description
技术领域
本发明属于高分子材料技术领域，尤其涉及一种自清洁膜层及采用该自清洁膜层的接水盘、空调器。
背景技术
在空调组件中，接水盘用于承接换热器落下的冷凝水，并将冷凝水排出空调。行业现用的接水盘，其上的冷凝水浸润在表面难以流至出水口，因此不能即时排出空调外，极易造成灰尘的积累，并导致微生物的富集，影响生活环境质量，损害人体健康。
目前的空调清洁方案多为空调蒸发器、冷凝器的双清洁技术方案，针对接水盘的处理也主要集中在防漏水、降噪等方面，而对其清洁问题没有切实解决。
专利申请CN105386032A公开了一种利用冷喷涂技术制备耐磨超疏水涂层的方法及其产品，在对基材进行粗化处理后，通过冷喷涂微纳米金属及合金、陶瓷复合粉末制备涂层，经再次喷涂修饰有低表面能物质的粉末后，即制得耐磨超疏水涂层及产品。该方法制备的涂层虽具有耐磨疏水性，但在制备时基体表面必须经过粗化处理，且工艺对温度要求较高，预热温度为100-600℃。并且，上述疏水涂层的使用多集中在金属基材和玻璃基材上，相对来说对工艺要求也较高。
发明内容
本发明提出一种自清洁膜层及采用该自清洁膜层的接水盘、空调器，该自清洁膜层具有微/纳二元结构的超疏水膜层，应用于空调接水盘表面时，可使冷凝水不浸润停留在接水盘表面，可使污物随冷凝水及时排出空调器。
为了达到上述目的，本发明提供了一种自清洁膜层，所述自清洁膜层由下至上依次为塑料基底层、底漆膜层和表面膜层，所述表面膜层由具有微/纳二元结构的超疏水颗粒形成得到，所述超疏水颗粒为利用疏水改性用材料改性粉末基材得到。
作为优选，所述塑料基底层中的塑料选自ABS塑料、ASA塑料、AS塑料、聚苯乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚乙烯、聚甲醛、聚碳酸酯、聚对苯二甲酸丁二醇酯、聚氯乙烯和聚酰胺中的至少一种。
作为优选，所述底漆膜层中的底漆的主要成分选自环氧树脂类、聚酯树脂类、聚氨酯树脂类、、聚丙烯酸酯类、聚硅氧烷类、苯乙烯嵌段共聚物、不定型含氟聚合物和醇酸树脂混合物中的至少一种。
作为优选，所述底漆膜层中的底漆的主要成分可以为环氧树脂、聚氨酯、聚甲基丙烯酸甲酯、甲基硅树脂、甲基苯基硅树脂、氟硅树脂、聚苯乙烯、丙烯酸树脂、聚苯乙烯、聚丙烯酸酯、聚异丁烯、聚异戊二烯、聚乙烯吡咯烷酮、聚乙烯醇、氨基硅树脂中的至少一种。
作为优选，所述粉末基材选自二氧化硅、二氧化钛、氧化铝、氧化铁、氧化锌、硅酸铝、硅酸镁、氧化镁和疏水性硫化矿物中的至少一种。
作为优选，所述疏水改性用材料选自硅烷偶联剂、酸酯偶联剂、含氟化合物、饱和脂肪类化合物中的至少一种。
作为优选，所述疏水改性用材料选自氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷、异氰酸酯基硅烷、正十六烷基三甲氧基硅烷、单烷氧基酸型酯偶联剂、单烷氧基焦磷酸酯型酸酯偶联剂、螯合型酸酯偶联剂、配位体型酸酯偶联剂、聚偏氟乙烯、聚四氟乙烯、全氟辛醇、氟烷基有机硅、四氯邻苯二甲酸含氟酯、油酸、全氟丁酸、全氟辛酸、氟氯戊酸、含氟烷基磺酸钠、全氟氧杂酰胺季铵盐、含氟酸三甘油酯、饱和脂肪酸、含有巯基的高分子硫醇、异丁基三硅醇和笼状倍半硅氧烷中的至少一种。
作为优选，所述超疏水颗粒选自直径为10nm-20μm的纳米级-微米级颗粒。将颗粒直径限定在上述范围内原因在于：颗粒直径小于10nm时会对纳米级微观结构影响较小，而大于20μm则表面粗糙度过大，制成的材料表面疏液性差。
作为优选，利用疏水改性用材料改性粉末基材材料时，疏水改性用材料与粉末基材材料的物质的量比为1：(5-20)。
本发明提供了一种接水盘，所述接水盘表面涂覆有根据上述任一项技术方案所述的自清洁膜层。
本发明提供了一种空调器，包括上述技术方案所述的接水盘。
与现有技术相比，本发明的优点和积极效果在于：
本发明提供了一种基于高分子材料的自清洁膜层，该自清洁膜层的表面膜层为具有微/纳二元结构的超疏水膜层，由于纳/微二元结构可提高表面的空气接触面积，减少固液之间的接触面积且减少表面与污染物的接触面积，因此与膜层上的疏水基团共同作用，可起到良好的清洁效果。将该自清洁膜层应用于空调接水盘表面时，可使冷凝水不浸润停留在接水盘表面，从而可将污物随冷凝水及时排出空调器。
附图说明
图1为本发明实施例所提供的实施例1疏水粉末电镜图；
图2为本发明实施例所提供的实施例1接触角测试结果图；
图3为本发明实施例所提供的实施例2接触角测试结果图。
具体实施方式
为了更清楚详细地介绍本发明实施例所提供的自清洁膜层及采用该自清洁膜层的接水盘、空调器，下面将结合具体实施例进行描述。
实施例1
在ABS塑料基底层上涂布一层氨基硅树脂，将超疏水颗粒分散喷涂在氨基硅树脂层上，形成自清洁膜层。其中，超疏水颗粒为疏水改性处理的二氧化硅颗粒，具体制备方法如下：
将20份去离子水、20份无水乙醇以及适量氨水混合均匀调节pH为8-10；将18份原硅酸四乙酯，缓慢滴入充分混合后的溶液中，在40℃恒温搅拌下；待反应完毕，将产物离心分离处理并清洗、干燥并制成疏水性粉末二氧化硅粉末，粉末粒径50nm-2.5μm，其电镜图如图1所示。
将20份无水乙醇和20份去离子水与乙酸调节pH为3-6，加入所得粉末混合均匀；随后缓慢滴加正十六烷基三甲氧基硅烷(正十六烷基三甲氧基硅烷的添加量为二氧化硅粉末物质的量的1/10)；反应结束后，清洗干燥得到疏水改性处理的纳米二氧化硅颗粒，粉末粒径50nm-2.5μm。
在上述制备过程中，具有大表面能的纳米粒径颗粒在水与乙醇的碱性溶液中易自发团聚降低表面能形成微米级的大颗粒，可以得到纳米级粗糙度、微米级粒径的特殊结构粉末。
实施例2
在基底材料聚苯乙烯塑料上涂布一层氨基硅树脂，将超疏水颗粒分散喷涂在氨基硅树脂层上，形成自清洁膜层。其中，超疏水颗粒为疏水改性处理的纳米二氧化硅和纳米二氧化钛的混合物，具体制备方法如下：
将8份水与32份乙醇混合均匀，滴加乙酸使pH在3-5；将1份钛酸四丁酯与4份乙醇混合(钛酸四丁酯与水的物质的量比为1：80)；加入油酸，保持油酸与钛酸四丁酯的物质的量比1：15，在60℃的搅拌条件下反应3h，清洗、干燥后得到粒径约为20nm疏水性的纳米二氧化钛粉体。
将粒径为0.5微米的二氧化硅用实施例1的方法进行疏水改性。
实施例3
在聚丙烯基底材料塑料上涂布一层丙烯酸树脂，将超疏水颗粒分散喷涂在氨基硅树脂层上，形成自清洁膜层。其中，超疏水颗粒为疏水改性处理的硅酸镁：
将粒径为0.4μm的硅酸镁浸渍在油酸中，浸渍1h后取出。
实施例4
在ABS塑料基底上涂布一层EP-12环氧树脂，将超疏水颗粒分散喷涂在氨基硅树脂层上，形成自清洁膜层。其中，超疏水颗粒为疏水改性处理的纳米二氧化钛与氧化铝的混合物，具体制备方法如下：
将粒径为70nm的二氧化钛颗粒与粒径200nm的氧化铝浸渍与异丙基二油酸酰氧基钛酸酯(一种酸酯偶联剂)混合，加入适量水，搅拌1h后，取出并干燥疏水颗粒。
性能测试
对实施例1和2所制备得到的自清洁膜层进行性能测试，测试方法如下：
如上表数据可见，在疏水材料和表面粗糙结构的双重效用下，制备得到的自清洁膜层均具有良好的疏水效果；脏污的水滴不易在膜层表面停留、附着，可以起到膜层表面的自清洁作用。应用此类膜层的空调器部件可有效降低表面污染物留存的概率，保持空调器清洁。
Claims (6)
1.自清洁膜层，其特征在于，所述自清洁膜层由下至上依次为塑料基底层、底漆膜层和表面膜层，所述表面膜层由具有微/纳二元结构的超疏水颗粒形成得到，所述超疏水颗粒为利用疏水改性用材料改性粉末基材得到；
利用疏水改性用材料改性粉末基材材料时，疏水改性用材料与粉末基材材料的物质的量比为1：(5-20)；
所述粉末基材选自二氧化硅、二氧化钛、氧化铝、氧化铁、氧化锌、硅酸铝、硅酸镁、氧化镁和疏水性硫化矿物中的至少一种；
所述疏水改性用材料选自硅烷偶联剂、酸酯偶联剂、含氟化合物、饱和脂肪类化合物和具有3D结构的低表面能高聚物中的至少一种；
所述超疏水颗粒选自直径为10nm-20μm的纳米级-微米级颗粒。
2.根据权利要求1所述的自清洁膜层，其特征在于，所述塑料基底层中的塑料选自ABS塑料、ASA塑料、AS塑料、聚苯乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚乙烯、聚甲醛、聚碳酸酯、聚对苯二甲酸丁二醇酯、聚氯乙烯和聚酰胺中的至少一种。
3.根据权利要求1所述的自清洁膜层，其特征在于，所述底漆膜层中的底漆的主要成分选自环氧树脂类、聚酯树脂类、聚氨酯树脂类、聚丙烯酸酯类、聚硅氧烷类、苯乙烯嵌段共聚物、不定型含氟聚合物和醇酸树脂混合物中的至少一种。
4.根据权利要求1所述的自清洁膜层，其特征在于，所述疏水改性用材料选自氨基硅烷、环氧基硅烷、硫基硅烷、甲基丙烯酰氧基硅烷、乙烯基硅烷、脲基硅烷、异氰酸酯基硅烷、正十六烷基三甲氧基硅烷、单烷氧基酸型酯偶联剂、单烷氧基焦磷酸酯型酸酯偶联剂、螯合型酸酯偶联剂、配位体型酸酯偶联剂、聚偏氟乙烯、聚四氟乙烯、全氟辛醇、氟烷基有机硅、四氯邻苯二甲酸含氟酯、油酸、全氟丁酸、全氟辛酸、氟氯戊酸、含氟烷基磺酸钠、全氟氧杂酰胺季铵盐、含氟酸三甘油酯、饱和脂肪酸、含有巯基的高分子硫醇、异丁基三硅醇和笼状倍半硅氧烷中的至少一种。
5.接水盘，其特征在于，所述接水盘表面涂覆有根据权利要求1-4任一项所述的自清洁膜层。
6.空调器，其特征在于，包括权利要求5所述的接水盘。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010448497.9A CN113717419B (zh) | 2020-05-25 | 2020-05-25 | 自清洁膜层及采用该自清洁膜层的接水盘、空调器 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010448497.9A CN113717419B (zh) | 2020-05-25 | 2020-05-25 | 自清洁膜层及采用该自清洁膜层的接水盘、空调器 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113717419A CN113717419A (zh) | 2021-11-30 |
| CN113717419B true CN113717419B (zh) | 2024-01-26 |
Family
ID=78671557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010448497.9A Active CN113717419B (zh) | 2020-05-25 | 2020-05-25 | 自清洁膜层及采用该自清洁膜层的接水盘、空调器 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113717419B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231060B (zh) * | 2021-12-24 | 2023-01-17 | 中国船舶重工集团公司第七二五研究所 | 一种可按需去除的高耐久性超疏水涂层材料及其制备方法 |
| CN116285666A (zh) * | 2023-03-31 | 2023-06-23 | 华南理工大学 | 一种微纳结构超疏水涂层及其制备方法和应用 |
| CN116554522A (zh) * | 2023-04-28 | 2023-08-08 | 广东坚派新材料有限公司 | 一种低粘附力疏冰的风电叶片面漆涂层结构 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1024267A (ja) * | 1996-07-12 | 1998-01-27 | Mitsui Eng & Shipbuild Co Ltd | 撥水性表面の形成方法 |
| CN101722818A (zh) * | 2008-10-20 | 2010-06-09 | 法雷奥企业管理(北京)有限公司上海分公司 | 汽车空调系统 |
| KR20160067440A (ko) * | 2014-12-04 | 2016-06-14 | 한국전기연구원 | 결빙 억제용 초발수 용액, 용액 제조방법 및 이를 이용한 초발수 표면 제조방법 |
| CN110041741A (zh) * | 2019-04-04 | 2019-07-23 | 东南大学 | 一种高效集水自清洁超双疏涂层及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006023375A1 (de) * | 2006-05-17 | 2007-11-22 | Nano-X Gmbh | Beschichtungsmaterial |
-
2020
- 2020-05-25 CN CN202010448497.9A patent/CN113717419B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1024267A (ja) * | 1996-07-12 | 1998-01-27 | Mitsui Eng & Shipbuild Co Ltd | 撥水性表面の形成方法 |
| CN101722818A (zh) * | 2008-10-20 | 2010-06-09 | 法雷奥企业管理(北京)有限公司上海分公司 | 汽车空调系统 |
| KR20160067440A (ko) * | 2014-12-04 | 2016-06-14 | 한국전기연구원 | 결빙 억제용 초발수 용액, 용액 제조방법 및 이를 이용한 초발수 표면 제조방법 |
| CN110041741A (zh) * | 2019-04-04 | 2019-07-23 | 东南大学 | 一种高效集水自清洁超双疏涂层及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113717419A (zh) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113717419B (zh) | 自清洁膜层及采用该自清洁膜层的接水盘、空调器 | |
| CA2675408C (en) | Coating composition and its production, heat exchanger, and air conditioner | |
| JP4102583B2 (ja) | 自浄性表面、その製造方法、その使用及び表面の製造に適した粒子 | |
| Hsieh et al. | Super water-and oil-repellencies from silica-based nanocoatings | |
| JP2002346469A (ja) | 自浄性表面、その製造方法及びその使用 | |
| KR20110003535A (ko) | 초소수성 분체, 초소수성 표면을 갖는 구조체 및 그들의 제조 방법 | |
| JP2003238947A (ja) | 超撥水性膜、及び、超撥水性膜の製造方法 | |
| JP2011027039A (ja) | 送風装置及び空気調和機及びコーティング組成物 | |
| JP2022532828A (ja) | 超疎水性表面に関する改善 | |
| TW201609385A (zh) | 疏水物件 | |
| CN105164221B (zh) | 形成对附着污物的自清洁能力优异的皮膜的水系亲水性涂料组合物、以及形成有对附着污物的自清洁能力优异的皮膜的表面处理材料 | |
| CN112143332B (zh) | 一种超疏水涂层及制备方法 | |
| JP2011208937A (ja) | 空気調和機及びコーティング組成物 | |
| JP2017177683A (ja) | 撥水性被膜付基材およびその製造方法 | |
| CN108774447A (zh) | 一种碳-银微球/环氧树脂超疏水涂层制备方法 | |
| Xiao et al. | Dip-coating of superhydrophobic surface on irregular substrates for dropwise condensation | |
| KR102322390B1 (ko) | 초발수성 특성을 가진 플라스틱 표면 제조방법 | |
| Ullah et al. | Fabrication and characterization of functionalized nano-silica based transparent superhydrophobic surface | |
| JP2008105887A (ja) | 超撥水ガラス基板及びその製造方法 | |
| CN113770007A (zh) | 一种排水管及空调器 | |
| CN113845681B (zh) | 一种接水盘及空调器 | |
| JP2002176862A (ja) | 防滴性農園芸用フィルム、その製造方法および防滴剤組成物 | |
| JP2012189272A (ja) | 熱交換器及びその製造方法 | |
| CN117659752A (zh) | 一种超亲水增透防雾涂层及其制备方法 | |
| JPH10168381A (ja) | 高親水性塗料 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 266000 No. 151, Zhuzhou Road, Laoshan District, Shandong, Qingdao Applicant after: Hisense Air Conditioning Co.,Ltd. Address before: 266000 No. 151, Zhuzhou Road, Laoshan District, Shandong, Qingdao Applicant before: HISENSE (SHANDONG) AIR-CONDITIONING Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |