JP4060333B2 - Water repellent and its use - Google Patents
Water repellent and its use Download PDFInfo
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- JP4060333B2 JP4060333B2 JP2005516722A JP2005516722A JP4060333B2 JP 4060333 B2 JP4060333 B2 JP 4060333B2 JP 2005516722 A JP2005516722 A JP 2005516722A JP 2005516722 A JP2005516722 A JP 2005516722A JP 4060333 B2 JP4060333 B2 JP 4060333B2
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- water
- water repellent
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- fine particles
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 162
- 239000005871 repellent Substances 0.000 title claims description 117
- 230000002940 repellent Effects 0.000 title claims description 97
- 239000010419 fine particle Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 47
- 229920002545 silicone oil Polymers 0.000 claims description 37
- 239000007921 spray Substances 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- 239000012188 paraffin wax Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
- -1 polydimethylsiloxane Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001993 wax Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 125000005131 dialkylammonium group Chemical group 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000003075 superhydrophobic effect Effects 0.000 claims 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 8
- 229910002012 Aerosil® Inorganic materials 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000003380 quartz crystal microbalance Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000010919 Copernicia prunifera Nutrition 0.000 description 1
- 244000180278 Copernicia prunifera Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001553290 Euphorbia antisyphilitica Species 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Nanotechnology (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、固体物品の表面を撥水処理するために用いる撥水剤、撥水剤の使用方法、該撥水剤で処理されたコーティング物品、及び該撥水剤あるいは該コーティング物品の製造方法に関する。 The present invention relates to a water repellent used for water repellent treatment of the surface of a solid article, a method for using the water repellent, a coated article treated with the water repellent, and a method for producing the water repellent or the coated article. About.
シリコーンオイルは、金属、セラミック、プラスチック、あるいは繊維などからなる固体物品表面に撥水性を付与する材料として広く用いられている。例えば、自動車ボディーのコーティング用としてアミノ変性シリコーンオイル系の撥水剤が市販されているが、それをスプレーして得たコーティングでは、撥水性が低く、また、持続性が十分ではない。
そこで、シリコーンオイル中に無機または有機系微粒子を混ぜることによって、シリコーンオイルの撥水性をより向上させようとする試みがなされている。
例えば、特許文献１には、「塗膜表面の水接触角が９０度以上となるような樹脂溶液と、塗膜硬化後表面に微細凹凸を付与しうる無機または有機系微粒子とからなる撥水性コーティング用組成物」が記載され、この組成物を塗布した熱交換器では直径１ｍｍ程度の微細な水滴をフィン表面から落とすことができるという。
また、特許文献２では、「少なくとも表面が疎水性である平均粒径１ｎｍ〜１ｍｍの微粒子と樹脂塗膜からなり、該微粒子が該樹脂と膜表面積の２０％以上の領域に露出されて固着されていること特徴とする撥水性被膜」によって、いわゆる蓮の葉が水を弾くような撥水性を得ようとしている。そして、特許文献２には、微粒子の平均粒径について、小さくなると凹凸形状の効果が低下して接触角が小さくなり、大きくなると細かい水滴に対する撥水性が低下するので１ｎｍ〜１ｍｍに限定されると記載されている。
さらに、特許文献３には、「水の接触角が１２０°に満たない材料からなる表面上に形成した際、その被膜表面における水の接触角を１５０°以上とすることが可能な撥水性被膜であって、前記表面上に形成された、粘着性を有する撥水性高分子を含む層と、前記粘着性を有する撥水性高分子を含む層表面に固着された、撥水性シリカ粒子とからなる被膜であり、前記粘着性を有する撥水性高分子を含む層自体の表面における水の接触角は、１２０°以下であり、前記撥水性シリカ粒子の平均粒子径は、０．１〜１００μｍの範囲に選択され、対応させて、表面に固着された前記撥水性シリカ粒子の面密度は、１０２〜１０８個／ｍｍ２の範囲に選択されていることを特徴とする撥水性被膜」が記載され、得られる撥水性被膜は接触角が１５０°以上であること、「粘着性を有する撥水性高分子を含む層を構成する粘着性を有する撥水性高分子は、その表面に撥水性シリカ粒子を安定に固着する際、バインダーとして機能するものであり、上記の粘着性含フッ素高分子、あるいは、この粘着性含フッ素高分子と粘性シリコーン樹脂との混合物を利用することが一層好ましい」ことが記載されている。
さらにまた、特許文献４には、１ｎｍ〜１μｍの範囲内にある径を有するゲル粒子と疎水性ポリマー材料とからなる表面変性剤が記載され、それによって、少なくとも１５０°の接触角、さらには少なくとも１６０°の接触角を有するコーティングが形成されることが記載されている。
しかしながら、これらの従来技術は、いずれもコーティング表面における疎水性の向上を目的とするもので、接触角が１６０°を超えるような超撥水性の表面を提供できるというが、コーティングの透明性（光沢）や強度については不明である。
撥水剤を物品表面に適用する際、その物品自体の色、材質感などを損なわないために、コーティング膜は、透明で光沢を有することが要望される。また、一旦撥水剤コーティングを行った後は、物品表面から剥離することなく長時間撥水性を維持できることが望まれる。
特に、撥水剤を船舶、航空機、自動車などの車両、建造物に適用する際などにおいては、撥水性が高いのみでなく、撥水剤コーティングの透明性や光沢性が高いことがユーザーにとって関心が高い。また、撥水剤コーティング後、コーティング物品の洗浄や清拭によっても、あるいは物品が外気や光に暴露されても、撥水剤が剥離したり変質することなく、撥水性を長時間維持できることがユーザーの強い要望となる。
Therefore, attempts have been made to further improve the water repellency of silicone oil by mixing inorganic or organic fine particles in the silicone oil.
For example, Patent Document 1 states that “a water repellency comprising a resin solution having a water contact angle of 90 ° or more on the surface of the coating film and inorganic or organic fine particles capable of imparting fine irregularities to the surface after the coating film is cured. "Coating composition" is described, and it is said that fine water droplets having a diameter of about 1 mm can be dropped from the fin surface in a heat exchanger coated with this composition.
Further, in Patent Document 2, “it consists of fine particles having an average particle diameter of 1 nm to 1 mm having a hydrophobic surface at least and a resin coating film, and the fine particles are exposed and fixed in an area of 20% or more of the resin and the film surface area. With the water-repellent coating characterized by the fact that the so-called lotus leaf repels water, it is trying to obtain a water-repellent property. In Patent Document 2, when the average particle size of the fine particles is reduced, the effect of the uneven shape is reduced and the contact angle is reduced. When the average particle size is increased, the water repellency with respect to fine water droplets is reduced. Are listed.
Furthermore, Patent Document 3 states that “a water-repellent coating that can have a water contact angle of 150 ° or more when formed on a surface made of a material having a water contact angle of less than 120 °. And comprising a layer containing an adhesive water-repellent polymer formed on the surface and water-repellent silica particles fixed to the surface of the layer containing the adhesive water-repellent polymer. The contact angle of water on the surface of the layer itself comprising the water-repellent polymer having the adhesive property is 120 ° or less, and the average particle diameter of the water-repellent silica particles is in the range of 0.1 to 100 μm. The surface density of the water-repellent silica particles fixed to the surface in accordance with the above is selected in the range of 10 2 to 10 8 particles / mm 2. The resulting water repellent coating has a contact angle of 15 The adhesive water-repellent polymer constituting the layer containing the adhesive water-repellent polymer functions as a binder when the water-repellent silica particles are stably fixed to the surface. It is more preferable to use the above-mentioned adhesive fluorine-containing polymer or a mixture of this adhesive fluorine-containing polymer and a viscous silicone resin.
Furthermore,
However, all of these conventional techniques aim to improve the hydrophobicity on the coating surface and can provide a super water-repellent surface with a contact angle exceeding 160 °. ) And strength are unknown.
When a water repellent is applied to the surface of an article, the coating film is required to be transparent and glossy so as not to impair the color and texture of the article itself. In addition, it is desired that once the water repellent coating is performed, the water repellency can be maintained for a long time without peeling from the surface of the article.
In particular, when water repellent is applied to vehicles, buildings such as ships, airplanes, automobiles, etc., not only the water repellency is high, but also the water repellent coating is highly transparent and glossy for users. Is expensive. In addition, the water repellency can be maintained for a long time after the coating of the water repellent agent, even if the coated article is washed or wiped, or the article is exposed to the outside air or light, without causing the water repellent agent to peel off or deteriorate. This is a strong demand from users.
本発明の課題は、上記の従来技術の問題点を解決することであって、撥水性が高く、且つ、撥水剤のコーティング後において、高い透明性（光沢性）と強度を併せ持つ撥水剤を提供することにある。
さらに、本発明は、そのような撥水性、透明性、及び強度の高い撥水剤をコーティングした物品、及びその製造方法を提供することも課題とする。
本発明者らは、上記課題を鋭意研究した結果、シリコーンオイル、微粒子、及び溶剤を含む撥水剤において、微粒子同士、及び／または微粒子とシリコーンオイルとの結合性を増強できるような微粒子結合剤を添加することによって、撥水剤コーティング膜の強度を増強できることを見出し、本発明に至った。なお、本発明において膜の強度とは、撥水剤を固体表面にコーティングした際、長時間剥離することなく、また、水圧、布による摩擦などによっても剥離せず、あるいは外気や光に暴露されても、撥水剤が剥離したり変質することなく、長時間撥水性を維持することをいう。
また、本発明者らは、撥水剤コーティング後の撥水性膜の表面が、特定寸法の凹凸を有するときに高い撥水性を発揮できることを見出し、そのために撥水剤中の微粒子に好ましい粒子径があることを見出した。
さらに、本発明者らは、透明性を確保するために、表面凹凸による乱反射が可視光によって見えないことが必要であることを見出し、透明性のためにも、表面凹凸は特定寸法が好ましいことを見出した。
さらにまた、本発明者らは、上記の撥水剤に界面活性剤をさらに添加することで、撥水剤が長期にわたって保存性が良く、スプレーの際に目詰まりも少ないことを見出した。
本発明は、以上の知見によりなされたもので、以下に関する。
（１）シリコーンオイル、微粒子、微粒子の結合剤、水系溶剤及び水を含むことを特徴とする撥水剤。
（２）シリコーンオイルがポリジメチルシロキサンである上記（１）記載の撥水剤。
（３）微粒子の平均粒子径が１〜１００ｎｍである上記（１）または（２）に記載の撥水剤。
（４）微粒子の平均粒子径が５〜２０ｎｍである上記（３）記載の撥水剤。
（５）微粒子が金属酸化物からなる請求項１〜４のいずれかに記載の撥水剤。
（６）微粒子がシリカからなる上記（１）〜（４）のいずれかに記載の撥水剤。
（７）微粒子の結合剤がワックス及び／またはパラフィンである上記（１）〜（６）のいずれかに記載の撥水剤。
（８）シリコーンオイル、平均粒子径５〜２０ｎｍのシリカ微粒子、ワックス及び／またはパラフィン、水系溶剤及び水を含むことを特徴とする撥水剤。
（９）さらに界面活性剤を含む上記（１）〜（８）のいずれかに記載の撥水剤。
（１０）界面活性剤としてジアルキルアンモニウムクロライドを含む上記（９）に記載の撥水剤。
（１１）微粒子の結合剤を有機溶剤に混合して加熱溶解し、微粒子を添加混合することにより得た混合物を乾燥する工程、該乾燥物にシリコーンオイル、水系溶剤、及び水を添加攪拌する工程を含む上記（１）〜（８）のいずれかに記載の撥水剤の製造方法。
（１２）微粒子の結合剤を有機溶剤に混合して加熱溶解し、微粒子を添加混合することにより得た混合物を乾燥する工程、該乾燥物にシリコーンオイル、水系溶剤、及び水を添加攪拌する工程を含む撥水剤の製造方法において、微粒子の結合剤を有機溶剤に混合して加熱溶解する工程、あるいはシリコーンオイル、水系溶剤、及び水を添加攪拌する工程のいずれかの工程で、界面活性剤をさらに添加する上記（９）または（１０）に記載の撥水剤の製造方法。
（１３）上記（１）〜（１０）のいずれかに記載の撥水剤がコーティングされてなるコーティング物品。
（１４）コーティング量が単位表面積当たり３０〜５０ｎｇ／ｍｍ２である上記（１３）記載のコーティング物品。
（１５）コーティング量が単位表面積当たり３５〜４０ｎｇ／ｍｍ２である上記（１４）に記載のコーティング物品。
（１６）３０〜２００ｎｍの凹凸を表面に有する上記（１３）〜（１５）のいずれかに記載のコーティング物品。
（１７）上記（１）〜（１０）のいずれかに記載の撥水剤をスプレーしてコーティング物品を製造する方法。
（１８）スプレーした撥水剤をすばやく乾燥させながらスプレーすることを特徴とする上記（１７）記載のコーティング物品の製造方法。
（１９）撥水剤を間欠的にスプレーすることを特徴とする上記（１７）または（１８）記載のコーティング物品の製造方法。
（２０）スプレーノズルの径及び／又は噴射圧力を調整することによってコーティング量を調整することを特徴とする上記（１７）〜（１９）のいずれかに記載のコーティング物品の製造方法。
（２１）上記（１）〜（１０）のいずれかに記載の撥水剤を洗車機に用いる撥水剤の使用方法。
以上の構成により、本発明の撥水剤、及び本発明の撥水剤によりコーティングされた物品は、高い撥水性と透明性と強度とを併せ持つことができ、コーティング後１ヶ月たっても撥水性能が低下しない優れた効果を奏することができた。An object of the present invention is to solve the above-mentioned problems of the prior art, and has a high water repellency and has a high transparency (glossiness) and strength after coating with the water repellent. Is to provide.
Furthermore, another object of the present invention is to provide an article coated with such a water-repellent agent having high water repellency, transparency, and strength, and a method for producing the same.
As a result of intensive studies on the above problems, the present inventors have found that a fine particle binder that can enhance the bonding between fine particles and / or fine particles and silicone oil in a water repellent containing silicone oil, fine particles, and a solvent. It has been found that the strength of the water repellent coating film can be enhanced by adding, and the present invention has been achieved. In the present invention, the strength of the film means that when a water repellent is coated on a solid surface, it does not peel for a long time, does not peel due to water pressure, cloth friction, or is exposed to the outside air or light. However, it means that the water repellent is maintained for a long time without peeling off or deteriorating.
Further, the present inventors have found that the surface of the water-repellent film after coating with the water-repellent agent can exhibit high water repellency when having irregularities with specific dimensions. Found that there is.
Furthermore, the present inventors have found that in order to ensure transparency, it is necessary that the irregular reflection due to surface irregularities is not visible by visible light, and for the sake of transparency, the surface irregularities preferably have a specific dimension. I found.
Furthermore, the present inventors have found that by adding a surfactant to the above water repellent, the water repellent has good storage stability for a long period of time and is less clogged during spraying.
The present invention has been made based on the above findings and relates to the following.
(1) A water repellent comprising silicone oil, fine particles, a fine particle binder, an aqueous solvent and water.
(2) The water repellent according to (1) above, wherein the silicone oil is polydimethylsiloxane.
(3) The water repellent according to (1) or (2), wherein the average particle size of the fine particles is 1 to 100 nm.
(4) The water repellent according to (3) above, wherein the average particle size of the fine particles is 5 to 20 nm.
(5) The water repellent according to any one of claims 1 to 4, wherein the fine particles comprise a metal oxide.
(6) The water repellent according to any one of (1) to (4), wherein the fine particles are made of silica.
(7) The water repellent according to any one of (1) to (6), wherein the fine particle binder is wax and / or paraffin.
(8) A water repellent comprising silicone oil, silica fine particles having an average particle diameter of 5 to 20 nm, wax and / or paraffin, an aqueous solvent and water.
(9) The water repellent according to any one of (1) to (8), further comprising a surfactant.
(10) The water repellent according to (9) above, which contains dialkylammonium chloride as a surfactant.
(11) A step of mixing a fine particle binder in an organic solvent, dissolving by heating, and adding and mixing fine particles, and a step of adding and stirring silicone oil, an aqueous solvent, and water to the dried product The manufacturing method of the water repellent in any one of said (1)-(8) containing.
(12) A step of drying a mixture obtained by mixing a fine particle binder in an organic solvent, heating and dissolving, and adding and mixing the fine particles, and a step of adding and stirring silicone oil, an aqueous solvent, and water to the dried product In the method for producing a water repellent comprising the surfactant, the surfactant may be used in any of the steps of mixing the fine particle binder with an organic solvent and dissolving by heating, or adding and stirring silicone oil, an aqueous solvent, and water. The method for producing a water repellent as described in (9) or (10) above, wherein
(13) A coated article obtained by coating the water repellent according to any one of (1) to (10) above.
(14) The coated article according to the above (13), wherein the coating amount is 30 to 50 ng / mm 2 per unit surface area.
(15) The coated article according to (14), wherein the coating amount is 35 to 40 ng / mm 2 per unit surface area.
(16) The coated article according to any one of the above (13) to (15), which has irregularities of 30 to 200 nm on the surface.
(17) A method for producing a coated article by spraying the water repellent according to any one of (1) to (10) above.
(18) The method for producing a coated article according to (17), wherein the sprayed water repellent is sprayed while being quickly dried.
(19) The method for producing a coated article according to (17) or (18), wherein the water repellent is sprayed intermittently.
(20) The method for producing a coated article according to any one of (17) to (19), wherein the coating amount is adjusted by adjusting the diameter of the spray nozzle and / or the spray pressure.
(21) A method for using a water repellent, wherein the water repellent according to any one of (1) to (10) is used in a car wash machine.
With the above configuration, the water-repellent agent of the present invention and the article coated with the water-repellent agent of the present invention can have both high water repellency, transparency and strength, and water repellency even after one month after coating. It was possible to achieve an excellent effect that does not decrease.
図１は、本発明のコーティングに用いるスプレー装置の一例を示す。
図２は、本発明の撥水剤を洗車機に用いるための装置の一例を示す。
図３は、結合剤なしの比較例の顕微鏡写真を示す。
図４は、本発明の実施例の顕微鏡写真を示す。
［発明の実施における最良の形態］
以下に、本発明を具体的に説明するが、本発明はそれに限定されるわけではない。
本発明の撥水剤は、固体物品の表面を撥水処理するのに用いられる。固体物品は、金属、セラミック、ガラス、プラスチックなどの硬い素材でも、繊維などの柔らかい素材でもいずれでも適用できる。特に、船舶、航空機、自動車などの車両、建造物、ミラー、タイル、布帛の処理に好適に使用できる。
本発明の撥水剤に用いるシリコーンオイル（オルガノポリシロキサン）としては、微粒子と混合して粘性を有する液状物を形成できるものであればいずれでも良く、アミノ変性シリコーンオイル、高級脂肪酸変性シリコーンオイル、ジメチルシリコーンオイル、アルキル変性シリコーンオイル、アルキルアラキル変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシリル変性シリコーンオイルなどが用いられる。
好ましくはアミノ変性シリコーンオイル、ジメチルシリコーンオイル（ポリジメチルシロキサン）である。
シリコーンオイルの粘度は、５〜１００，０００ｃｔｓが好ましく、さらに好ましくは、５０〜５００ｃｔｓである。
本発明で用いる微粒子としては、無機物質でも有機物質でも構わないが、変質しない無機物質が好ましい。材質は問わないが、ｎｍオーダーの粒径の微粒子を得るためには、シリカ、アルミナ、チタニアなどの無機酸化物が好ましく、平均粒子径が５〜２０ｎｍの市販品がある点からシリカが最も好ましい。この微粒子シリカとして、日本アエロジル株式会社製、アエロジルＲ９７２、９７２Ｖ、Ｒ９７２ＣＦ、Ｒ９７４、Ｒ８１２、Ｒ８０５、ＲＸ２００、ＲＸ３００、ＲＹ２００（いずれも疎水性シリカ）などが挙げられ、中でもアエロジルＲ９７２、ＲＸ２００が好ましい。微粒子として、その他、日本アエロジル株式会社製、アエロジル５０、９０Ｇ、１３０、２００、２００Ｖ、２００ＣＦ、２００ＦＡＤ、３００、３００ＣＦ、３８０、Ｒ２０２、Ｒ８１２Ｓ、ＯＸ５０、ＴＴ６００、ＭＯＸ８０、ＭＯＸ１７０、ＣＯＫ８４、酸化アルミニウムＣ、二酸化チタンＴ８０５、二酸化チタンＰ２５等も用いることができる。これらの微粒子のうち親水性の微粒子は、あらかじめシランカップリング剤で疎水処理しておくことが好ましい。
微粒子の結合剤としては、樹脂類、界面活性剤類、油脂類などが用いられる。
樹脂類として、アクリル樹脂、エポキシ樹脂、シリコーン樹脂など；界面活性剤としては、モノアルキルアンモニウムクロライド、ジアルキルアンモニウムクロライド、エチレンオキサイド付加型アンモニウムクロライド、アミン酢酸塩類、アルキルアミン、アルキルジアミン、アルキルアミド、ビスアミド、アルキルアミンエチレンオキサイド付加物、脂肪酸エチレノキサイド付加物、脂肪塩類など；油脂類としては、脂肪酸、脂肪酸エステル、カルナバ、キャンデリラ、ラノリンなどの動植物油、ペトロール、イソパラフィン、ノルマルパラフィン、パラフィンワックス、マイクロクリスタルワックス、ペトロラタムなどの鉱物油類、モンタン酸やそのエステルワックス、ポリオレフィンワックス、ヒドロキシステアリン酸系エステルワックスなど合成ワックスが挙げられる。好ましくはワックス状（常温で固体、加熱時に比較的低粘度の液体になる有機物）を有するもが良い。さらに好ましくは融点１１５°Ｆ〜１５５°Ｆ（４６．１℃〜６３．９℃）のパラフィンワックスと１０〜１００ｃｔｓのノルマルパラフィンを混合したものが用いられる。
パラフィンは、古くから撥水剤として用いられるが（例えば、特開昭６２−２６３２７９号公報参照）、本発明では、パラフィンは、微粒子同士、及び／又は微粒子とシリコーンオイルとの結合性を増強するために添加するものである。パラフィンと微粒子のみ、あるいはシリコーンと微粒子のみからなる撥水剤では、所望の強度は得られない。
本発明において、撥水剤に界面活性剤を添加すると、微粒子の分散性がよくなり、長期間保存しても分離せず保存性が向上する。また、界面活性剤は、撥水剤をスプレーするときスプレーノズルを目詰まりさせないという効果を奏することもできる。用いられる界面活性剤としては、陽イオン界面活性剤が好ましく、中でも、モノアルキルアンモニウムクロライド、ジアルキルアンモニウムクロライドがさらに好ましい。
本発明における水系溶剤とは、水親和性を有する有機溶剤のことである。
水系溶剤として、アルコール、グリコール、エステル、ケトン、エーテルなど、撥水剤に通常用いられる溶剤をいずれも用いることが出来るが、沸点、引火点が高く、毒性が低いという安全性の面から、１，２−プロパンジオール（プロピレングリコール）、２−メチル−２，４−ペンタンジオール（ヘキシレングリコール）、ジエチレングリコールモノブチルエーテル（ブチルジグリコール）、１，５−ペンタンジオール（ペンタメチレングリコール）が好ましい。
本発明の撥水剤において、用いる微粒子の平均粒子径は１〜１００ｎｍが好ましく、撥水性と光沢と強度をバランスよく満足させるためには、５〜２０ｎｍであることがさらに好ましい。
本発明において、結合剤は、微粒子に対して重量比で０．０１〜２０％の範囲が好ましく、さらに０．１〜１０％が好ましい。結合剤が０．０１％以下の時は強度が得られず、２０％を超えると、光沢度が低下する。
本発明において、シリコーンオイルは、微粒子に対して重量比で０．１〜１００％の範囲が好ましく、さらに２〜３０％が好ましい。シリコーンオイルが０．１％以下の時は強度が得られず、１００％を超えると、光沢度が低下する。
水系溶剤の量は、微粒子が十分分散性を示す量であれば良く、微粒子１重量部に対して１〜１５重量部が好ましく、５〜１０重量部がより好ましい。水系溶剤が１重量部以下の時は十分な分散性を示さず、１５重量部を超えると、撥水剤としての付着効率が低下する。
本発明の撥水剤は、微粒子の結合剤を溶媒に混合して加熱溶解し、微粒子を添加混合して得た混合物を攪拌下で減圧乾燥する工程、該乾燥物にシリコーンオイル、水系溶剤、及び水を添加攪拌する工程によって製造することが出来る。
界面活性剤、特に陽イオン界面活性剤を添加するときには、微粒子の結合剤を溶媒に混合して加熱溶解工程、または、乾燥物にシリコーンオイル、水系溶剤、及び水を添加攪拌する工程添加することが出来る。
結合剤を溶解させる溶媒としては、結合剤が溶解性を示すものであれば良く、親油性溶剤や親水性と親油性を併せ持つ両親媒性溶剤がより好ましい。親油性溶剤として、ノルマルペンタン、ノルマルヘキサン、両親媒性溶剤としてエタノール、ヘキシルアルコールを例示することが出来る。
具体的には、結合剤を微粒子重量比０．０１〜２０％の範囲で計り取り、親油性溶剤と混合し、加熱溶解させる。このときの溶媒量は微粒子重量比で１５〜２０倍量とする。結合剤と親油性溶剤とを加熱溶解させた状態で、微粒子を加え攪拌しながら減圧乾燥させる。得られた乾燥物１重量部に水系溶剤を１〜１５重量部加え十分攪拌混合し、さらに攪拌下でシリコーンオイル０．００１〜１重量部、水５〜２０重量部を順次加え攪拌する。陽イオン界面活性剤を添加するときには、微粒子重量比で０．０１〜２０％添加する。得られた混合物１重量部に水１０〜８０重量部加えることによって撥水剤を製造する。
上記撥水剤は、金属、セラミック、布帛などの固体物質にスプレーコーティングなどすることによってコーティング物品を得る。
コーティング量によって、表面の凹凸の大きさが異なってきて、撥水性（接触角）や光沢に差が出てくるので、コーティング量を調節することが重要である。コーティング量は、単位表面積当たり３０〜５０ｎｇ／ｍｍ２、より好ましくは、単位表面積当たり３５〜４０ｎｇ／ｍｍ２である。
本発明でコーティング量は、ＱＣＭ（水晶振動子マイクロバランス：Ｑｕａｒｔｚ Ｃｒｙｓｔａｌ Ｍｉｃｒｏｂａｌａｎｃｅ）を用いて測定することができる。
表面の凹凸は、３０〜２００ｎｍが撥水性及び光沢の面から好ましい。
凹凸は、原子間力顕微鏡（ＡＦＭ）を用いて測定することができる。
コーティング方法は、ローラーコーティング、含浸、スプレーなど周知のいずれの手段でも使用できるが、スプレーが好ましい。
スプレーしてコーティング物品を製造するに際しては、通常にスプレーするだけでも良いが、スプレーした撥水剤をすばやく乾燥させながらスプレーすることが好ましい。スプレーした撥水剤をすばやく乾燥させながらスプレーを行うことで、乾燥して凹凸を形成した撥水剤コーティングの上にさらにスプレーするという状況が維持できるために、表面に好ましい凹凸を形成することができる。すばやく乾燥させながらスプレーを行うためには、撥水剤をスプレーすると同時に乾燥空気を吹き付けるなどの方法をとることができる。
また、スプレーを固体表面に対して間欠的に行うことによっても、すばやく乾燥させながらスプレーするという状況を実現できる。間欠的にスプレーするためには、ノズル位置を固定しておいて、噴射を間欠的に行っても良いし、スライダーなどを利用してノズルを移動させることによって行っても良い。具体的には、スライダーなどにスプレーノズルを載置し、スプレーノズルをスライダーにより往復移動させながら撥水剤をスプレーする。固体表面上のあるポイントに着目すれば、あるポイントに一定時間スプレーされたらスプレーノズルはそのポイントを通過してしまい、復路でスプレーされるまでの間に撥水剤は乾燥され、ある程度乾燥した撥水剤の上に再度撥水剤がスプレーされることになる。適当なコーティング量が得られるまで、スプレーノズルの往復を行う。また、スライダーを用いノズル位置を移動させながら、かつ、噴射も間欠的に行うこともできる。このような間欠的スプレーによって、より好ましい凹凸表面が形成される。
このような間欠スプレーを行うためのスプレー装置の一例を図１を参照しながら、以下に説明する。
図１において、（１）は、被コーティング物品であり、車のボディーを例示した。（２）がスプレーノズルであり、スプレーノズル（２）は、電動スライダー（３）上に固定されている。電動スライダー（３）は、モーター（４）により矢印方向に往復駆動される。電動スライダー（３）の往復動と共に往復するスプレーノズル（２）からは、撥水剤がスプレーされる。スプレーノズル（２）は、撥水剤貯槽（５）およびポンプ（６）と連結されており、撥水剤流量は、該ポンプ（６）の吐出量で制御することもできるし、該ポンプ（６）に設けた流量調節バルブ（図示せず）によって制御することもできる。
ノズル（２）における撥水剤の噴射圧力は、コンプレッサー（７）に設けられた電磁弁（図示せず）により制御される。一方、被コーティング物品には、撥水剤付着量を測定するためのＱＣＭ（水晶振動子マイクロバランス：Ｑｕａｒｔｚ Ｃｒｙｓｔａｌ Ｍｉｃｒｏｂａｌａｎｃｅ）（８）が取り付けられている。付着量はＱＣＭの周波数変動として周波数カウンタ（９）でカウントする。
周波数カウンタ（９）のカウントに基づきポンプ（６）の吐出量や流量調節バルブの開度、コンプレッサーの電磁弁をパソコン制御することによって、コーティング膜厚に応じた撥水剤流量を制御することができる。
図１において、（１０）は、スライダー（３）の駆動を制御するためのモーター制御装置、（１１）（１２）は、電源装置である。
また、本発明のスプレー装置は、ＱＣＭの周波数変動に応じて、乾燥を制御する制御手段、例えば間欠タイマーをさらに設けることができる（図示せず）。
このような装置によって、撥水剤の付着量をＱＣＭにより制御しながら、コーティング物品を製造することができる。
付着量は、スプレーノズルの径及び／又は噴射圧力を調整することによっても調整することができる。
本発明で、スプレーノズルから噴射される撥水剤ミストの粒径は８０μｍ以下が好ましく、６〜１４μｍに調整することがより好ましい。ミスト粒径をこの範囲に調整することで、望ましい凹凸を形成することができる。
また、本発明の撥水剤を洗車機に用いる場合の一例を図２に示した。
図２において（１３）〜（２４）は、スプレー用のノズルを示し、洗車される車体はノズル（１３）〜（２４）の下を徐々にくぐり移動することになる。撥水剤は、希釈水配管（２７）からの希釈水と共に撥水剤タンク（２５）からエジェクター（２８）によりノズルに送られ、ノズルから車体に向けてスプレーされる。このとき、希釈水吐出圧０〜５ｋｇ／ｃｍ２、原液使用量２０〜５００ｍｌ、希釈倍率０．１〜５％で、洗車機の移動速度０．５〜５０ｍｍ／ｓｅｃが好ましい。FIG. 1 shows an example of a spray device used for the coating of the present invention.
FIG. 2 shows an example of an apparatus for using the water repellent of the present invention in a car wash machine.
FIG. 3 shows a photomicrograph of a comparative example without binder.
FIG. 4 shows a photomicrograph of an example of the present invention.
[Best Mode for Carrying Out the Invention]
The present invention will be specifically described below, but the present invention is not limited thereto.
The water repellent of the present invention is used for water repellent treatment of the surface of a solid article. The solid article may be a hard material such as metal, ceramic, glass, or plastic, or a soft material such as fiber. In particular, it can be suitably used for the treatment of vehicles such as ships, airplanes and automobiles, buildings, mirrors, tiles and fabrics.
The silicone oil (organopolysiloxane) used in the water repellent of the present invention may be any silicone oil (organopolysiloxane) that can be mixed with fine particles to form a viscous liquid. Amino-modified silicone oil, higher fatty acid-modified silicone oil, Dimethyl silicone oil, alkyl-modified silicone oil, alkyl aralkyl-modified silicone oil, epoxy-modified silicone oil, carboxylyl-modified silicone oil, and the like are used.
Preferred are amino-modified silicone oil and dimethyl silicone oil (polydimethylsiloxane).
The viscosity of the silicone oil is preferably 5 to 100,000 cts, and more preferably 50 to 500 cts.
The fine particles used in the present invention may be an inorganic substance or an organic substance, but an inorganic substance that does not deteriorate is preferable. The material is not limited, but inorganic oxides such as silica, alumina, titania and the like are preferable in order to obtain fine particles having a particle size on the order of nm, and silica is most preferable because there is a commercial product having an average particle size of 5 to 20 nm. . Examples of the fine particle silica include Aerosil R972, 972V, R972CF, R974, R812, R805, RX200, RX300, and RY200 (all of which are hydrophobic silica) manufactured by Nippon Aerosil Co., Ltd. Among them, Aerosil R972 and RX200 are preferable. As other fine particles, Aerosil 50, 90G, 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, R202, R812S, OX50, TT600, MOX80, MOX170, COK84, aluminum oxide C, manufactured by Nippon Aerosil Co., Ltd. Titanium dioxide T805, titanium dioxide P25, etc. can also be used. Of these fine particles, the hydrophilic fine particles are preferably preliminarily treated with a silane coupling agent.
Resins, surfactants, oils and fats, etc. are used as the fine particle binder.
As resins, acrylic resin, epoxy resin, silicone resin, etc .; surfactants include monoalkyl ammonium chloride, dialkyl ammonium chloride, ethylene oxide addition type ammonium chloride, amine acetates, alkyl amine, alkyl diamine, alkyl amide, bisamide , Alkylamine ethylene oxide adducts, fatty acid ethylenoxide adducts, fatty salts, etc .; fats and oils include fatty acid, fatty acid ester, carnauba, candelilla, lanolin and other animal and vegetable oils, petrol, isoparaffin, normal paraffin, paraffin wax, micro Mineral oils such as crystal wax and petrolatum, montanic acid and its ester wax, polyolefin wax, hydroxystearic acid ester wax Such as synthetic wax box, and the like. Preferably, it may have a wax shape (an organic substance that is solid at room temperature and becomes a liquid having a relatively low viscosity when heated). More preferably, a mixture of paraffin wax having a melting point of 115 ° F. to 155 ° F. (46.1 ° C. to 63.9 ° C.) and normal paraffin of 10 to 100 cts is used.
Paraffin has long been used as a water repellent (see, for example, JP-A-62-263279). In the present invention, paraffin enhances the bonding between fine particles and / or fine particles and silicone oil. It is added for this purpose. A water repellent composed of only paraffin and fine particles or only silicone and fine particles cannot provide a desired strength.
In the present invention, when a surfactant is added to the water repellent, the dispersibility of the fine particles is improved, and the storability is improved without separation even after long-term storage. The surfactant can also have an effect of not clogging the spray nozzle when spraying the water repellent. As the surfactant used, a cationic surfactant is preferable, and among them, monoalkyl ammonium chloride and dialkyl ammonium chloride are more preferable.
The aqueous solvent in the present invention is an organic solvent having water affinity.
As the aqueous solvent, any solvent usually used for water repellents such as alcohol, glycol, ester, ketone, ether and the like can be used. However, from the viewpoint of safety that boiling point, flash point is high and toxicity is low, 1 , 2-propanediol (propylene glycol), 2-methyl-2,4-pentanediol (hexylene glycol), diethylene glycol monobutyl ether (butyl diglycol), and 1,5-pentanediol (pentamethylene glycol) are preferred.
In the water repellent of the present invention, the average particle size of the fine particles used is preferably 1 to 100 nm, and more preferably 5 to 20 nm in order to satisfy the water repellency, gloss and strength in a balanced manner.
In the present invention, the binder is preferably in the range of 0.01 to 20% by weight with respect to the fine particles, more preferably 0.1 to 10%. When the binder is 0.01% or less, the strength cannot be obtained, and when it exceeds 20%, the glossiness is lowered.
In the present invention, the silicone oil is preferably in the range of 0.1 to 100% by weight with respect to the fine particles, and more preferably 2 to 30%. When the silicone oil is 0.1% or less, strength is not obtained, and when it exceeds 100%, the glossiness is lowered.
The amount of the aqueous solvent is not particularly limited as long as the fine particles are sufficiently dispersible, and is preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight with respect to 1 part by weight of the fine particles. When the aqueous solvent is 1 part by weight or less, sufficient dispersibility is not exhibited, and when it exceeds 15 parts by weight, the adhesion efficiency as a water repellent is lowered.
The water repellent of the present invention is a step of mixing a fine particle binder in a solvent and dissolving by heating, and drying the mixture obtained by adding and mixing the fine particles under reduced pressure, with the silicone oil, an aqueous solvent, And it can manufacture by the process of adding and stirring water.
When adding a surfactant, especially a cationic surfactant, add a fine particle binder to a solvent and dissolve it by heating, or add a silicone oil, an aqueous solvent and water to the dried product and agitate it. I can do it.
The solvent for dissolving the binder is not particularly limited as long as the binder exhibits solubility, and an amphiphilic solvent having both hydrophilicity and lipophilicity is more preferable. Examples of the lipophilic solvent include normal pentane and normal hexane, and examples of the amphiphilic solvent include ethanol and hexyl alcohol.
Specifically, the binder is weighed in a fine particle weight ratio of 0.01 to 20%, mixed with an oleophilic solvent, and dissolved by heating. The amount of solvent at this time is 15 to 20 times the weight ratio of fine particles. In a state where the binder and the lipophilic solvent are dissolved by heating, fine particles are added and dried under reduced pressure while stirring. 1 to 15 parts by weight of an aqueous solvent is added to 1 part by weight of the obtained dried product, and the mixture is thoroughly stirred and mixed. Further, 0.001 to 1 part by weight of silicone oil and 5 to 20 parts by weight of water are sequentially added and stirred. When the cationic surfactant is added, 0.01 to 20% by weight of fine particles is added. A water repellent is produced by adding 10 to 80 parts by weight of water to 1 part by weight of the resulting mixture.
The water-repellent agent is used to obtain a coated article by spray coating or the like on a solid material such as metal, ceramic, or fabric.
Depending on the amount of coating, the size of the unevenness on the surface will vary, and the water repellency (contact angle) and gloss will differ, so it is important to adjust the coating amount. The coating amount is 30 to 50 ng / mm 2 per unit surface area, more preferably 35 to 40 ng / mm 2 per unit surface area.
In the present invention, the coating amount can be measured using a QCM (Quartz Crystal Microbalance).
The surface irregularities are preferably 30 to 200 nm in terms of water repellency and gloss.
The unevenness can be measured using an atomic force microscope (AFM).
The coating method can be any known means such as roller coating, impregnation, spraying, etc., but spraying is preferred.
When the coated article is produced by spraying, it may be sprayed normally, but it is preferable to spray the sprayed water repellent while quickly drying it. By spraying while quickly drying the sprayed water repellent, it is possible to maintain the condition of further spraying on the water repellent coating that has been dried to form irregularities, so that desirable irregularities can be formed on the surface it can. In order to perform spraying while quickly drying, it is possible to take a method such as spraying water repellent and blowing dry air at the same time.
Moreover, the situation of spraying while quickly drying can also be realized by intermittently spraying the solid surface. In order to spray intermittently, the nozzle position may be fixed and injection may be performed intermittently, or by moving the nozzle using a slider or the like. Specifically, the spray nozzle is placed on a slider or the like, and the water repellent is sprayed while the spray nozzle is reciprocated by the slider. Paying attention to a certain point on the solid surface, if sprayed at a certain point for a certain period of time, the spray nozzle will pass through that point, and the water repellent will be dried before spraying on the return path, and the water repellent will be dried to some extent. The water repellent is sprayed again on the liquid agent. The spray nozzle is reciprocated until an appropriate coating amount is obtained. Moreover, it is also possible to intermittently perform injection while moving the nozzle position using a slider. By such intermittent spraying, a more preferable uneven surface is formed.
An example of a spray device for performing such intermittent spraying will be described below with reference to FIG.
In FIG. 1, (1) is an article to be coated, which illustrates the body of a car. (2) is a spray nozzle, and the spray nozzle (2) is fixed on the electric slider (3). The electric slider (3) is reciprocated in the direction of the arrow by the motor (4). The water repellent is sprayed from the spray nozzle (2) that reciprocates with the reciprocating motion of the electric slider (3). The spray nozzle (2) is connected to the water repellent reservoir (5) and the pump (6), and the water repellent flow rate can be controlled by the discharge amount of the pump (6). It can also be controlled by a flow rate adjusting valve (not shown) provided in 6).
The spray pressure of the water repellent at the nozzle (2) is controlled by an electromagnetic valve (not shown) provided on the compressor (7). On the other hand, a QCM (Quartz Crystal Microbalance) (8) for measuring the water repellent adhesion amount is attached to the article to be coated. The amount of adhesion is counted by the frequency counter (9) as the frequency variation of the QCM.
Based on the count of the frequency counter (9), the flow rate of the water repellent according to the coating film thickness can be controlled by controlling the discharge amount of the pump (6), the opening of the flow rate adjusting valve, and the solenoid valve of the compressor. it can.
In FIG. 1, (10) is a motor control device for controlling the drive of the slider (3), and (11) and (12) are power supply devices.
In addition, the spray device of the present invention can further include a control means for controlling drying, for example, an intermittent timer (not shown) according to the frequency fluctuation of the QCM.
With such an apparatus, it is possible to manufacture a coated article while controlling the amount of water repellent attached by QCM.
The adhesion amount can also be adjusted by adjusting the diameter of the spray nozzle and / or the injection pressure.
In the present invention, the particle size of the water repellent mist sprayed from the spray nozzle is preferably 80 μm or less, and more preferably adjusted to 6 to 14 μm. Desirable irregularities can be formed by adjusting the mist particle diameter within this range.
An example of using the water repellent of the present invention in a car wash machine is shown in FIG.
In FIG. 2, (13) to (24) indicate spray nozzles, and the vehicle body to be washed gradually moves under the nozzles (13) to (24). The water repellent is sent from the water repellent tank (25) to the nozzle by the ejector (28) together with the dilution water from the dilution water pipe (27), and sprayed from the nozzle toward the vehicle body. At this time, it is preferable to use a dilution water discharge pressure of 0 to 5 kg / cm 2 , a stock solution usage of 20 to 500 ml, a dilution ratio of 0.1 to 5%, and a moving speed of the car wash machine of 0.5 to 50 mm / sec.
以下に、実施例を記載して、本発明をより詳細に説明するが、本発明はこれに限られるわけではない。
［実施例１］
（撥水剤の製造）
融点１１５°Ｆ（４６．１℃）パラフィンワックス０．１ｇ、７０ｃｔｓのノルマルパラフィン０．１ｇをノルマルヘキサン２００ｇに加え、６０℃に加熱溶解させる。さらに攪拌下で粒径１２ｎｍのシリカ微粒子（ＲＸ２００；日本アエロジル株式会社製）を１０．０ｇ加え、ロータリーエバポレーターで減圧乾燥させる。得られた乾燥物１．０ｇにジエチレングリコールモノブチルエーテル（ブチルジグリコール；ＢＤＧ）９．０ｇを加え攪拌し、さらにポリジメチルシロキサン（Ｇ．Ｅ．シリコーン製 ＴＳＦ４５１−３５０）０．１ｇ、水１５．０ｇ加え３時間攪拌する。得られた混合物１重量部に水２２重量部加えることによって撥水剤とする。
［実施例２］
実施例１の微粒子の粒径を７ｎｍ（ＲＸ３００：日本アエロジル株式会社製）に変えた以外は、同様にして撥水剤を製造した。
［実施例３］
実施例１〜２によって製造された撥水剤を金属基材からなる塗装被覆用テストピースに所定厚さが得られるまで乾燥させながら間欠スプレーした。得られたコーティングの特性を評価して表１にまとめた。
以下の表において、距離は、スプレーノズルからサンプルまでの距離、圧力は、スプレーノズルの噴射圧力である。
接触角は、Ｋｙｏｍａ Ｉｎｔｅｒｆａｃｅ Ｓｃｉｅｎｃｅ Ｃｏ．ＬＴＤ． Ｍｏｄｅｌ：ＣＡ−ＤＴ
光沢は、Ｈｏｒｉｂａ，Ｍｏｄｅｌ：ＩＧ−３３０
転落角は、Ｋｙｏｍａ Ｉｎｔｅｒｆａｃｅ Ｓｃｉｅｎｃｅ Ｃｏ．ＬＴＤ． Ｍｏｄｅｌ：ＣＡ−ＤＴ
ミスト径は、ＬＤＳＡ Ｗｉｎ ５．０４Ｌ
によって、測定した。接触角は、上記の接触角計に１０μｌの水滴を滴下することで測定した。なお、Ｈｏｒｉｂａ，Ｍｏｄｅｌ：ＩＧ−３３０の光沢計は、ＬＥＤからの８００ｎｍの光を表面に照射して反射率を測るものであり、コーティングなしの値を１００としたときのコーティング物品の反射率の値で示した。
接触角は１４５°以上、転落角は４０°以下であれば実用上十分であり、接触角１６０°以上、転落角２０°以下であればより優れた撥水性であることを示している。撥水性は滑水性ともいわれ、水滴が表面に付着せず、転がり落ち易くなる性質を示す。
結合剤量を変えた以外は、実施例１と同様に撥水剤を製造し、結合剤の有無あるいはその量が、撥水性、光沢、強度に与える影響を試験した。
結果を表２にまとめた。
ここで、Ｈ２Ｏ ｓｐｒａｙ １０ｍｉｎは、約２気圧の水圧を１０分間スプレーした後の、Ｈ２Ｏ ｓｐｒａｙ ２０ｍｉｎは、２０分スプレーした後の結果を示している。また、転落角×は基板を９０°傾斜させても水滴が転がらないことを示している。
結合剤量が１ｗｔ％のコーティングについて、原子間力顕微鏡（ＡＦＭ）を用いて表面の凹凸を測定したところ、平均９４ｎｍの凹凸であった。
また、結合剤なしの例と結合剤パラフィンを１ｗｔ％添加した例との電子顕微鏡（ＴＥＭ）写真を撮影した。図３が結合剤なし、図４が結合剤添加の例である。図３では、微粒子が凝集してしまっているが、図４では、微粒子がつながっているのが分かる。この微粒子のつながりが、コーティング物品表面に適度な凹凸を与えることになる。
［実施例５］
シリコーンオイル（ポリジメチルシロキサン）の量を種々に変更した以外は、実施例１と同様にして撥水剤を製造し、実施例３と同様にコーティングの特性を評価した。
［比較例１］
シリカ微粒子の粒径を３００ｎｍに変えた以外は実施例１と同様に撥水剤を製造して、撥水性を測定したところ、接触角６５°と撥水性が劣っていた。
［実施例６］
実施例１の撥水剤を金属基材からなる塗装被覆用テストピースにスプレーして得られたコーティングの耐久性を試験した。
結果を表４に示す。
また、目視観察を続けたところ、１ヵ月半後でも、超撥水性を維持し、光沢度においても十分な透明性を維持していた。
［実施例７］
（撥水剤の製造）
融点１１５°Ｆ（４６．１℃）パラフィンワックス０．０５ｇ、７０ｃｔｓのノルマルパラフィン０．０５ｇ、ジアルキルアンモニウムクロライド（商品名：アーカード、ライオンアクゾ（株））をノルマルヘキサン２００ｇに加え、６０℃に加熱溶解させる。さらに攪拌下で粒径１２ｎｍのシリカ微粒子（ＲＸ２００；日本アエロジル株式会社製）を１０．０ｇ加え、ロータリーエバポレーターで減圧乾燥させる。得られた乾燥物１．０ｇにジエチレングリコールモノブチルエーテル（ブチルジグリコール；ＢＤＧ）９．０ｇを加え攪拌し、さらにポリジメチルシロキサン（Ｇ．Ｅ．シリコーン製 ＴＳＦ４５１−３５０）０．１ｇ、水１５．０ｇ加え３時間攪拌する。得られた混合物１重量部に水２２重量部加えることによって撥水剤とする。
（コーティング）
撥水剤原液５０ｍｌを吐出圧３．０ｋｇ／ｃｍ２の希釈水で６０００ｍｌ（希釈倍率０．８３％）に希釈して、図２の洗車機ノズルよりスプレーした。洗車機の移動速度は１０ｍｍ／ｓｅｃで、３回繰り返しスプレーした。
上記の撥水剤の製造法でシリコーン０．０５ｇのもの、比較としてシリコーンなしのときのものも調製して同様にコーティングした。
実施例３と同様にコーティングの特性を評価して、結果を表５に示した。
[Example 1]
(Manufacture of water repellent)
Melting point 115 ° F. (46.1 ° C.) 0.1 g of paraffin wax and 0.1 g of 70 cts normal paraffin are added to 200 g of normal hexane, and heated and dissolved at 60 ° C. Furthermore, 10.0 g of silica fine particles having a particle size of 12 nm (RX200; manufactured by Nippon Aerosil Co., Ltd.) is added under stirring, and dried under reduced pressure using a rotary evaporator. To 1.0 g of the resulting dried product, 9.0 g of diethylene glycol monobutyl ether (butyl diglycol; BDG) was added and stirred, and 0.1 g of polydimethylsiloxane (GE Silicone TSF451-350) and 15.0 g of water were added. Add 3 hours stirring. A water repellent is obtained by adding 22 parts by weight of water to 1 part by weight of the obtained mixture.
[Example 2]
A water repellent was produced in the same manner except that the particle size of the fine particles of Example 1 was changed to 7 nm (RX300: manufactured by Nippon Aerosil Co., Ltd.).
[Example 3]
The water repellent produced in Examples 1 and 2 was intermittently sprayed on a paint coating test piece made of a metal substrate while being dried until a predetermined thickness was obtained. The properties of the resulting coating were evaluated and summarized in Table 1.
In the following table, the distance is the distance from the spray nozzle to the sample, and the pressure is the spray pressure of the spray nozzle.
The contact angle was measured using Kyoma Interface Science Co. LTD. Model: CA-DT
Gloss is Horiba, Model: IG-330
The sliding angle was measured by Kyoma Interface Science Co. LTD. Model: CA-DT
Mist diameter is LDSA Win 5.04L
Measured by The contact angle was measured by dropping a 10 μl water droplet on the contact angle meter. In addition, the gloss meter of Horiba, Model: IG-330 measures the reflectance by irradiating the surface with 800 nm light from the LED, and the reflectance of the coated article when the value without coating is 100 is used. Indicated by value.
A contact angle of 145 ° or more and a falling angle of 40 ° or less is practically sufficient, and a contact angle of 160 ° or more and a falling angle of 20 ° or less indicates better water repellency. Water repellency is also referred to as water slidability, and exhibits the property that water droplets do not adhere to the surface and are easy to roll off.
A water repellent was produced in the same manner as in Example 1 except that the amount of the binder was changed, and the effect of the presence or absence of the binder or the amount thereof on the water repellency, gloss and strength was tested.
The results are summarized in Table 2.
Here, H 2 O spray 10 min shows the result after spraying about 2 atmospheres of water pressure for 10 minutes, and H 2 O spray 20 min shows the result after spraying for 20 minutes. The falling angle x indicates that water droplets do not roll even when the substrate is inclined by 90 °.
When the surface roughness of the coating having a binder amount of 1 wt% was measured using an atomic force microscope (AFM), the average was 94 nm.
Moreover, the electron microscope (TEM) photograph of the example without a binder and the example which added 1 wt% of binder paraffin was image | photographed. FIG. 3 shows an example of no binder, and FIG. 4 shows an example of binder addition. In FIG. 3, the fine particles are aggregated, but in FIG. 4, it can be seen that the fine particles are connected. This connection of fine particles gives moderate unevenness to the surface of the coated article.
[Example 5]
A water repellent was produced in the same manner as in Example 1 except that the amount of silicone oil (polydimethylsiloxane) was variously changed, and the coating characteristics were evaluated in the same manner as in Example 3.
[Comparative Example 1]
A water repellent was produced in the same manner as in Example 1 except that the particle size of the silica fine particles was changed to 300 nm, and the water repellency was measured. As a result, the contact angle was 65 ° and the water repellency was poor.
[Example 6]
The durability of the coating obtained by spraying the water repellent of Example 1 onto a test piece for coating coating made of a metal substrate was tested.
The results are shown in Table 4.
Further, when visual observation was continued, the super water repellency was maintained even after one and a half months, and sufficient transparency was maintained in terms of glossiness.
[Example 7]
(Manufacture of water repellent)
Melting point 115 ° F (46.1 ° C) paraffin wax 0.05g, 70cts normal paraffin 0.05g, dialkylammonium chloride (trade name: Arcard, Lion Akzo Co., Ltd.) was added to normal hexane 200g and heated to 60 ° C. Dissolve. Furthermore, 10.0 g of silica fine particles having a particle size of 12 nm (RX200; manufactured by Nippon Aerosil Co., Ltd.) is added under stirring, and dried under reduced pressure using a rotary evaporator. To 1.0 g of the resulting dried product, 9.0 g of diethylene glycol monobutyl ether (butyl diglycol; BDG) was added and stirred, and 0.1 g of polydimethylsiloxane (GE Silicone TSF451-350) and 15.0 g of water were added. Add 3 hours stirring. A water repellent is obtained by adding 22 parts by weight of water to 1 part by weight of the obtained mixture.
(coating)
50 ml of the water repellent stock solution was diluted to 6000 ml (dilution ratio 0.83%) with diluted water having a discharge pressure of 3.0 kg / cm 2 and sprayed from the car wash machine nozzle of FIG. The moving speed of the car washer was 10 mm / sec and sprayed three times.
In the above water repellent production method, 0.05 g of silicone was prepared and, in comparison, the case without silicone, was coated in the same manner.
The properties of the coating were evaluated in the same manner as in Example 3, and the results are shown in Table 5.
本発明により、撥水性が良好で、光沢、強度も高い撥水剤及びコーティング物品が得られた。 According to the present invention, a water repellent and a coated article having good water repellency, high gloss and strength are obtained.
Claims (14)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003428546 | 2003-12-25 | ||
| JP2003428546 | 2003-12-25 | ||
| PCT/JP2004/019745 WO2005063903A1 (en) | 2003-12-25 | 2004-12-24 | Water repellent agent and use thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007277379A Division JP2008069365A (en) | 2003-12-25 | 2007-10-25 | Water repellent agent and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP4060333B2 true JP4060333B2 (en) | 2008-03-12 |
| JPWO2005063903A1 JPWO2005063903A1 (en) | 2009-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005516722A Expired - Lifetime JP4060333B2 (en) | 2003-12-25 | 2004-12-24 | Water repellent and its use |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4060333B2 (en) |
| KR (1) | KR20070015122A (en) |
| WO (1) | WO2005063903A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021017490A (en) * | 2019-07-19 | 2021-02-15 | 株式会社Ｓｎｔ | Polyester resin, water-repellent agent composition and water-repellent article |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4921766B2 (en) * | 2005-10-12 | 2012-04-25 | 株式会社パーカーコーポレーション | Coating composition for vehicle surface |
| JP4963896B2 (en) * | 2006-08-09 | 2012-06-27 | 株式会社ソフト９９コーポレーション | Water repellent treatment agent and water repellent treatment method |
| EP2229132B1 (en) | 2007-12-20 | 2019-02-27 | Avon Products, Inc. | Cosmetic compositions for imparting superhydrophobic films |
| JP4682213B2 (en) * | 2008-02-07 | 2011-05-11 | 株式会社ソフト９９コーポレーション | Water-repellent treatment composition for aerosol and aerosol-type water-repellent treatment agent |
| CA2717017C (en) * | 2008-03-04 | 2017-07-04 | Avon Products, Inc. | Cosmetic compositions for imparting superhydrophobic films |
| JP2009241943A (en) * | 2008-03-31 | 2009-10-22 | Snt Co | Coating agent and packaging material having dried coating film of the coating agent formed on surface thereof |
| JP6587823B2 (en) * | 2015-04-24 | 2019-10-09 | 東洋製罐株式会社 | Container with solid particles distributed on the surface |
| KR102171249B1 (en) * | 2018-11-27 | 2020-11-02 | 강남제비스코 주식회사 | Film with improved water repellency and oil elution properties and preparation method thereof |
| KR102744609B1 (en) * | 2022-01-06 | 2024-12-19 | 신상준 | Manufacturing method for anti-fouling coating for ship draft and composition using for the same |
| WO2023145932A1 (en) * | 2022-01-31 | 2023-08-03 | 国立研究開発法人物質・材料研究機構 | Coating composition, production method thereof, production method of coating film using same, lubricating article kit using same, and washer fluid using same |
| JP7578233B1 (en) | 2023-09-06 | 2024-11-06 | 吉川工業株式会社 | Super water repellent coating composition |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5387987A (en) * | 1977-01-12 | 1978-08-02 | Nitto Kagaku Kk | Aqueous washing water repellent composition |
| JP2799457B2 (en) * | 1988-12-17 | 1998-09-17 | 日東化学株式会社 | Antifouling agent for automotive coatings |
| JPH02232282A (en) * | 1989-03-06 | 1990-09-14 | Fuji Kasei Kk | Wax for automobile |
| JPH0673371A (en) * | 1992-08-25 | 1994-03-15 | Taiho Ind Co Ltd | Cleaning water repellent |
| JPH08199097A (en) * | 1995-01-28 | 1996-08-06 | Sofuto Kyukyu Corp:Kk | Automotive polish for repairing deteriorated coating film and small flaw |
| JP3924060B2 (en) * | 1997-03-10 | 2007-06-06 | インターセプト株式会社 | Ultraviolet-reducing super water repellent, modified cement-based molded body obtained by coating the same, and modified woven fabric formed by post-processing using the same |
| JPH11349929A (en) * | 1998-06-08 | 1999-12-21 | Taiho Ind Co Ltd | Water repellent and method for forming water repellent coating |
| JP4025892B2 (en) * | 1998-07-07 | 2007-12-26 | 株式会社ソフト９９コーポレーション | Water-repellent polish for gel-like painted surfaces |
| JP2000104047A (en) * | 1998-09-28 | 2000-04-11 | Soft 99 Corporation:Kk | Polishing water-repellent composition for automobile |
| JP4395628B2 (en) * | 1999-05-19 | 2010-01-13 | 株式会社ソフト９９コーポレーション | Treatment method of automobile paint surface |
| JP4169870B2 (en) * | 1999-06-29 | 2008-10-22 | 株式会社パーカーコーポレーション | Water repellent treatment |
| JP3888137B2 (en) * | 2001-11-16 | 2007-02-28 | 東陶機器株式会社 | Super water-repellent material and method for producing the same |
| JP2003147340A (en) * | 2001-11-16 | 2003-05-21 | Toto Ltd | Super water repellent and super water repellent produced using the same |
| JP2003147339A (en) * | 2001-11-16 | 2003-05-21 | Toto Ltd | Super water repellent material and method for producing the same |
| JP3927415B2 (en) * | 2002-01-15 | 2007-06-06 | 石原薬品株式会社 | Stabilized water-repellent coating agent for hard surface and water-repellent treatment method using the same |
| JP2004204131A (en) * | 2002-12-26 | 2004-07-22 | Kao Corp | Water repellent coating composition |
-
2004
- 2004-12-24 JP JP2005516722A patent/JP4060333B2/en not_active Expired - Lifetime
- 2004-12-24 WO PCT/JP2004/019745 patent/WO2005063903A1/en not_active Ceased
- 2004-12-24 KR KR1020067015005A patent/KR20070015122A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021017490A (en) * | 2019-07-19 | 2021-02-15 | 株式会社Ｓｎｔ | Polyester resin, water-repellent agent composition and water-repellent article |
| JP7281990B2 (en) | 2019-07-19 | 2023-05-26 | 株式会社Snt | Polyester resin, water repellent composition, and water repellent article |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005063903A1 (en) | 2005-07-14 |
| KR20070015122A (en) | 2007-02-01 |
| JPWO2005063903A1 (en) | 2009-05-07 |
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