JP2004269898A - Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent - Google Patents
Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent Download PDFInfo
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- JP2004269898A JP2004269898A JP2004130037A JP2004130037A JP2004269898A JP 2004269898 A JP2004269898 A JP 2004269898A JP 2004130037 A JP2004130037 A JP 2004130037A JP 2004130037 A JP2004130037 A JP 2004130037A JP 2004269898 A JP2004269898 A JP 2004269898A
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- photocatalytic
- component
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- coating agent
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 6
- 239000002131 composite material Substances 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 95
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 17
- 229910000831 Steel Inorganic materials 0.000 abstract description 7
- 239000010959 steel Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 235000019645 odor Nutrition 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 39
- 239000003973 paint Substances 0.000 description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 22
- 239000008199 coating composition Substances 0.000 description 17
- 239000000049 pigment Substances 0.000 description 17
- -1 for example Substances 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
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- 238000000354 decomposition reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- 239000002987 primer (paints) Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 4
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 4
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- 238000009835 boiling Methods 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
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- 230000000007 visual effect Effects 0.000 description 4
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
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- 239000007789 gas Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
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- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- DIZPPYBTFPZSGK-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DIZPPYBTFPZSGK-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QBZIEGUIYWGBMY-FUZXWUMZSA-N (5Z)-5-hydroxyimino-6-oxonaphthalene-2-sulfonic acid iron Chemical compound [Fe].O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O QBZIEGUIYWGBMY-FUZXWUMZSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、光触媒性コーティング剤、及び光触媒性複合材並びにその製造方法に関する。 The present invention relates to a photocatalytic coating agent, a photocatalytic composite material, and a method for producing the same.
近年、光触媒材料が、建物外装に被覆することで、太陽光の照射により親水化して降雨によるセルフクリーニング機能を有する材料として注目されている。また、ＮＯｘ等の有害ガスを分解する環境上好ましい材料としても注目されている。
水溶性珪酸塩、硬化剤及び光触媒粉末（二酸化チタンまたは酸化亜鉛）を含む塗料を、トンネルやガードレールに塗布し、加熱処理することで、ＮＯxを分解することができる塗膜が形成されることが開示されている（例えば、特許文献１参照）。
また、珪酸リチウムと二酸化チタンを含有する塗料を塗布し、加熱処理することで、自浄効果に優れた建材が得られることが開示されている（例えば、特許文献２参照）。
In recent years, a photocatalyst material has attracted attention as a material having a self-cleaning function by rainfall by coating the building exterior with hydrophilicity by irradiation with sunlight. In addition, it is also attracting attention as an environmentally preferable material for decomposing harmful gases such as NOx.
A coating containing a water-soluble silicate, a curing agent, and a photocatalyst powder (titanium dioxide or zinc oxide) may be applied to a tunnel or a guardrail and heated to form a coating film capable of decomposing NOx. It is disclosed (for example, see Patent Document 1).
Further, it is disclosed that a building material having an excellent self-cleaning effect can be obtained by applying a paint containing lithium silicate and titanium dioxide and performing heat treatment (for example, see Patent Document 2).
作業環境、周辺への影響、臭いなどの観点から、最近では溶剤系塗料よりも水系塗料（水性塗料）を用いる傾向が高まりつつある。そのため、上記建物外装等の塗布するための光触媒の水性コート剤も提案されている。
光触媒とパーフルオロコポリマーをエマルジョンの状態で配合する塗料組成物が開示されている（例えば、特許文献３参照）。
また、光触媒とフルオロ基が含有されているシリコーンエマルジョンのコーティング組成物が提案されている（例えば、特許文献４参照）。
A coating composition in which a photocatalyst and a perfluoro copolymer are blended in an emulsion state is disclosed (for example, see Patent Document 3).
Also, a coating composition of a silicone emulsion containing a photocatalyst and a fluoro group has been proposed (for example, see Patent Document 4).
しかしながら、特許文献１や特許文献２に記載の水性塗料は、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に対する濡れ性が悪いため、使用の対象がガラス、木材、金属などに限定されてしまう。
また、特許文献３や特許文献４に記載の水性塗料は、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に対する濡れ性は改善されるものの屋外での使用を想定した場合、塗装直後の水との接触角が大きく、降雨によるセルフクリーニング機能を使用直後から享受することができなかった。
However, the water-based paints described in Patent Literature 1 and Patent Literature 2 have poor wettability to a substrate having a hydrophobic substance such as a plastic or a coated steel sheet on the surface thereof, and thus are limited to glass, wood, and metal. Will be done.
In addition, the water-based paints described in Patent Literature 3 and Patent Literature 4 have improved wettability to a base material having a hydrophobic substance such as plastic or coated steel sheet on the surface, but when used outdoors, immediately after coating, The contact angle with water was large, and the self-cleaning function by rainfall could not be enjoyed immediately after use.
本発明は、上記事情に鑑みてなされたもので、その目的は、作業環境、周辺への影響、臭いなどの観点から問題がなく、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に塗布可能であり、疎水性物質を表面に有する基材に被膜を形成した場合に、基材と被膜との密着性が強固であり、かつ被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性コーティング剤、及びそれを疎水性物質を表面に有する基材に被覆した光触媒性複合材並びにその製造方法を提供することにある。 The present invention has been made in view of the above circumstances, and its object is to provide a substrate having a hydrophobic material such as a plastic or a coated steel sheet on its surface without any problem in terms of working environment, influence on surroundings, odor, and the like. When a film is formed on a substrate having a hydrophobic substance on its surface, the adhesion between the substrate and the film is strong, and the surface of the film has a small contact angle with water immediately after painting. A photocatalytic coating agent capable of enjoying a self-cleaning function by rainfall immediately after use and maintaining the state for a long time by irradiating sunlight, and a photocatalytic coating agent having a hydrophobic substance on its surface. An object of the present invention is to provide a photocatalytic composite material coated on a material and a method for producing the same.
本発明では、上記課題を解決すべく、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水とを少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子の平均粒径は、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径よりも小さいことを特徴とする光触媒性コーティング剤を提供する。
このような構成にすることで、作業環境、周辺への影響、臭いなどの観点での問題がなく、疎水性物質を表面に有する基材に被膜を形成した場合に、基材と被膜との密着性が強固であり、かつ被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性コーティング剤が提供可能となる。
In order to solve the above problems, the present invention provides a photocatalytic coating agent containing at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, and (c) water, The photocatalytic coating agent is characterized in that the average particle size of the oxide particles is smaller than the average particle size of the particles dispersed in the hydrophobic resin emulsion.
By adopting such a configuration, there is no problem in terms of working environment, influence on the surroundings, odor, etc., and when a coating is formed on a substrate having a hydrophobic substance on its surface, the coating between the substrate and the coating is formed. Adhesion is strong, and the coating surface has a small contact angle with water immediately after painting, so that the self-cleaning function by rain can be enjoyed immediately after use, and the condition can be maintained for a long time by irradiating sunlight. It is possible to provide a photocatalytic coating agent that is maintained over a long period of time.
上記光触媒性コーティング剤を、疎水性物質を表面に有する基材に塗布すると、粒径の小さな光触媒性酸化物粒子が上方に移動する。それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。また、同時に、粒径の大きな疎水性樹脂エマルジョン中に分散した粒子が下方に移動し、疎水性物質を表面に有する基材との密着性が増すのである。 When the photocatalytic coating agent is applied to a substrate having a hydrophobic substance on its surface, the photocatalytic oxide particles having a small particle size move upward. As a result, the coating surface has a small contact angle with water immediately after painting, and can enjoy the self-cleaning function by rainfall immediately after use, and the state is maintained for a long time by irradiation of sunlight. Become like At the same time, the particles dispersed in the hydrophobic resin emulsion having a large particle size move downward, and the adhesion to the substrate having the hydrophobic substance on the surface increases.
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、（ｄ）シリカ粒子と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子及びシリカ粒子の平均粒径は、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径よりも小さいようにする。
シリカ粒子が加わることで、被膜表面の塗装直後における水との接触角がより小さくなり、降雨によるセルフクリーニング機能をより使用直後から享受しやすくなる。
In a preferred embodiment of the present invention, a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, (c) water, and (d) silica particles. The average particle size of the photocatalytic oxide particles and the silica particles is smaller than the average particle size of the particles dispersed in the hydrophobic resin emulsion.
By the addition of the silica particles, the contact angle with water immediately after the coating of the coating surface becomes smaller, and it becomes easier to enjoy the self-cleaning function by rainfall immediately after use.
上記光触媒性コーティング剤を、疎水性物質を表面に有する基材に塗布すると、粒径の小さな光触媒性酸化物粒子及びシリカ粒子が上方に移動する。それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。また、同時に、粒径の大きな疎水性樹脂エマルジョン中に分散した粒子が下方に移動し、疎水性物質を表面に有する基材との密着性が増すのである。 When the photocatalytic coating agent is applied to a substrate having a hydrophobic substance on its surface, the photocatalytic oxide particles and silica particles having a small particle size move upward. As a result, the coating surface has a small contact angle with water immediately after painting, and can enjoy the self-cleaning function by rainfall immediately after use, and the state is maintained for a long time by irradiation of sunlight. Become like At the same time, the particles dispersed in the hydrophobic resin emulsion having a large particle size move downward, and the adhesion to the substrate having the hydrophobic substance on the surface increases.
本発明の好ましい態様においては、光触媒性酸化物粒子の平均粒径は５〜５０ｎｍであり、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径は８０〜３００ｎｍであるようにする。
前記光触媒性酸化物粒子の平均粒径が５ｎｍ以上であれば、太陽光の照射による光触媒反応が充分に発揮されるようになり、長期に亘り親水性が維持されやすくなる。また、水との接触角が１０°以下の高度の親水状態が維持されやすくなる。
一方、前記光触媒性酸化物粒子の平均粒径が５０ｎｍ未満であり、かつ疎水性樹脂エマルジョン中に分散した粒子の平均粒径が８０ｎｍ以上であると、光触媒性酸化物粒子と疎水性樹脂エマルジョン中に分散した粒子との粒子径の大きさの差が充分に大きくなるために、粒径の小さな光触媒性酸化物粒子の上方への移動及び粒径の大きな疎水性樹脂エマルジョン中に分散した粒子の下方への移動が生じ易くなり、それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになると同時に、疎水性物質を表面に有する基材との密着性が増す。
また、疎水性樹脂エマルジョン中に分散した粒子の平均粒径が３００ｎｍ以上であると、エマルジョンとしての安定性が低下し、高粘度になるため塗料組成物として使用することが不可能となる。
In a preferred embodiment of the present invention, the photocatalytic oxide particles have an average particle size of 5 to 50 nm, and the particles dispersed in the hydrophobic resin emulsion have an average particle size of 80 to 300 nm.
When the average particle diameter of the photocatalytic oxide particles is 5 nm or more, the photocatalytic reaction by the irradiation of sunlight is sufficiently exerted, and the hydrophilicity is easily maintained for a long time. In addition, a highly hydrophilic state having a contact angle with water of 10 ° or less is easily maintained.
On the other hand, if the average particle size of the photocatalytic oxide particles is less than 50 nm and the average particle size of the particles dispersed in the hydrophobic resin emulsion is 80 nm or more, the photocatalytic oxide particles and the hydrophobic resin emulsion In order for the difference in particle size between the particles dispersed in the resin particles to be sufficiently large, the upward movement of the photocatalytic oxide particles having a small particle diameter and the dispersion of the particles dispersed in the hydrophobic resin emulsion having a large particle diameter are considered. Downward movement is likely to occur, so that the coating surface has a small contact angle with water immediately after painting, and can enjoy the self-cleaning function by rainfall immediately after use, and the state of sunlight At the same time as being maintained for a long time by irradiation, adhesion to a substrate having a hydrophobic substance on its surface is increased.
On the other hand, if the average particle size of the particles dispersed in the hydrophobic resin emulsion is 300 nm or more, the stability of the emulsion is reduced and the viscosity becomes high, so that it cannot be used as a coating composition.
本発明の好ましい態様においては、前記光触媒性酸化物粒子の平均粒径は５〜５０ｎｍであり、前記シリカ粒子の平均粒径は５〜１００ｎｍ、より好ましくは５〜５０ｎｍであり、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径は８０〜３００ｎｍ、より好ましくは１００〜３００ｎｍであるようにする。
シリカ粒子の平均粒径が５nmより小さい場合はシリカ同士の結合強度が大きくなるため、凝集しやすくなる。
光触媒性酸化物粒子の平均粒径は５０ｎｍ未満、前記シリカ粒子の平均粒径は１００ｎｍ未満、より好ましくは５０ｎｍ未満であり、かつ疎水性樹脂エマルジョン中に分散した粒子の平均粒径が８０ｎｍ以上、より好ましくは１００ｎｍ以上であると、光触媒性酸化物粒子及びシリカ粒子と疎水性樹脂エマルジョン中に分散した粒子との粒子径の大きさの差のために、粒径の小さな光触媒性酸化物粒子及びシリカ粒子の上方への移動及び粒径の大きな疎水性樹脂エマルジョン中に分散した粒子の下方への移動が生じ易くなり、それによって、被膜表面は塗装直後から水との接触角が非常に小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになると同時に、疎水性物質を表面に有する基材との密着性が増す。
In a preferred embodiment of the present invention, the photocatalytic oxide particles have an average particle size of 5 to 50 nm, the silica particles have an average particle size of 5 to 100 nm, more preferably 5 to 50 nm, and the hydrophobic resin The average particle size of the particles dispersed in the emulsion is from 80 to 300 nm, more preferably from 100 to 300 nm.
When the average particle size of the silica particles is smaller than 5 nm, the bonding strength between the silica particles is increased, so that the silica particles are easily aggregated.
The average particle size of the photocatalytic oxide particles is less than 50 nm, the average particle size of the silica particles is less than 100 nm, more preferably less than 50 nm, and the average particle size of the particles dispersed in the hydrophobic resin emulsion is 80 nm or more, More preferably 100 nm or more, due to the difference in particle size between the photocatalytic oxide particles and silica particles and the particles dispersed in the hydrophobic resin emulsion, photocatalytic oxide particles having a small particle size and The upward movement of the silica particles and the downward movement of the particles dispersed in the hydrophobic resin emulsion having a large particle diameter are likely to occur, whereby the coating surface has a very small contact angle with water immediately after coating, It is possible to enjoy the self-cleaning function by rainfall immediately after use, and to maintain that state for a long time by irradiating sunlight. Made at the same time, it increases the adhesion to a substrate having a hydrophobic substance on the surface.
本発明の好ましい態様においては、固形分中の配合割合が、前記光触媒性酸化物粒子が１〜２０重量％、より好ましくは１〜５重量％、前記疎水性樹脂エマルジョンが５〜９９重量％、より好ましくは１０〜９９重量％であり、前記水の配合割合が固形分１００重量部に対して１０〜５００重量部、より好ましくは１０〜１０９重量部であるようにする。
前記水の配合割合が１０〜５００重量部、より好ましくは１０〜１０９重量部であることで、膜厚１μｍ〜１ｍｍの塗料として適当な膜厚で塗膜が形成可能となる。
また、光触媒性酸化物粒子の配合割合が１重量％以上であることで、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。
また、光触媒性酸化物粒子の配合割合が固形分中２０重量％未満、より好ましくは５重量％未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーへの影響がなく、屋外の使用において長期に亘り、セルフクリーニング機能が維持される。
また、疎水性樹脂エマルジョンの配合割合が５重量％以上、より好ましくは１０重量％以上であることで、疎水性物質を表面に有する基材との密着性が増す。
In a preferred embodiment of the present invention, the proportion of the photocatalytic oxide particles in the solid content is 1 to 20% by weight, more preferably 1 to 5% by weight, and the hydrophobic resin emulsion is 5 to 99% by weight. It is more preferably 10 to 99% by weight, and the mixing ratio of the water is 10 to 500 parts by weight, more preferably 10 to 109 parts by weight, based on 100 parts by weight of the solid content.
When the mixing ratio of the water is 10 to 500 parts by weight, more preferably 10 to 109 parts by weight, a coating film having an appropriate thickness can be formed as a coating having a thickness of 1 μm to 1 mm.
Further, when the blending ratio of the photocatalytic oxide particles is 1% by weight or more, the surface of the coating has a small contact angle with water immediately after painting, and can enjoy the self-cleaning function by rainfall immediately after use. In addition, the state is maintained over a long period of time by irradiation of sunlight.
Further, when the compounding ratio of the photocatalytic oxide particles is less than 20% by weight, more preferably less than 5% by weight in the solid content, the hydrophobic resin emulsion is decomposed based on the redox power of the photocatalytic oxide. There is no effect on the binder obtained by curing, and the self-cleaning function is maintained for a long time in outdoor use.
When the blending ratio of the hydrophobic resin emulsion is 5% by weight or more, more preferably 10% by weight or more, the adhesion to a substrate having a hydrophobic substance on the surface is increased.
本発明の好ましい態様においては、固形分中の配合割合が、前記光触媒性酸化物粒子が１〜２０重量％、より好ましくは全固形分に対して１〜５重量％、前記シリカ粒子の配合割合が１〜９０重量％、前記疎水性樹脂エマルジョンの配合割合が５〜９８重量％、より好ましくは１０〜９８重量％、前記水の配合割合が固形分１００重量部に対して１０〜５００重量部、より好ましくは１０〜１０８重量部であるようにする。
シリカ粒子の配合割合が１重量％以上であることで、被膜表面は塗装直後から水との接触角がより小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。
In a preferred embodiment of the present invention, the mixing ratio in the solid content is such that the photocatalytic oxide particles are 1 to 20% by weight, more preferably 1 to 5% by weight based on the total solid content, and the mixing ratio of the silica particles is Is 1 to 90% by weight, the mixing ratio of the hydrophobic resin emulsion is 5 to 98% by weight, more preferably 10 to 98% by weight, and the mixing ratio of the water is 10 to 500 parts by weight with respect to 100 parts by weight of solids. And more preferably 10 to 108 parts by weight.
When the mixing ratio of the silica particles is 1% by weight or more, the coating surface has a smaller contact angle with water immediately after painting, and can enjoy the self-cleaning function by rainfall immediately after use, and in that state. Is maintained for a long time by the irradiation of sunlight.
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子は、全固形分に対して１〜５重量％であるようにする。
光触媒性酸化物粒子の配合割合が全固形分に対して５重量％未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーと光触媒性酸化物粒子のお互いの結合力及び基材との結合力への影響がなく、屋外の使用において長期に亘り、被膜の強度及び基材との密着性が維持される。
In a preferred aspect of the present invention, a photocatalytic coating agent containing at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, and (c) water, wherein the photocatalytic oxide The particles should be between 1 and 5% by weight relative to the total solids.
When the mixing ratio of the photocatalytic oxide particles is less than 5% by weight based on the total solid content, the binder and the photocatalyst obtained by curing the hydrophobic resin emulsion by the decomposition power based on the redox power of the photocatalytic oxide There is no effect on the mutual bonding force of the conductive oxide particles and the bonding force with the base material, and the strength of the coating film and the adhesion to the base material are maintained over a long period of time in outdoor use.
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、（ｄ）シリカ粒子と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子は、全固形分に対して１〜５重量％であるようにする。
光触媒性酸化物粒子の配合割合が全固形分に対して５重量部未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーと光触媒性酸化物粒子及びシリカ粒子のお互いの結合力及び基材との結合力への影響がなく、屋外の使用において長期に亘り、被膜の強度及び基材との密着性が維持される。
In a preferred embodiment of the present invention, a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, (c) water, and (d) silica particles. The photocatalytic oxide particles are contained in an amount of 1 to 5% by weight based on the total solid content.
When the blending ratio of the photocatalytic oxide particles is less than 5 parts by weight based on the total solid content, the binder obtained by curing the hydrophobic resin emulsion and the photocatalyst by the decomposition power based on the redox power of the photocatalytic oxide There is no effect on the mutual bonding force of the conductive oxide particles and the silica particles and the bonding force with the base material, and the strength of the coating film and the adhesion to the base material are maintained over a long period of time in outdoor use.
本発明の好ましい態様においては、前記疎水性樹脂エマルジョンは、フッ素樹脂エマルジョン、シリコーンエマルジョンのうちの１種以上であるようにする。
フッ素樹脂エマルジョン及び／又はシリコーンエマルジョンであることで、耐候性が良好になる。
In a preferred aspect of the present invention, the hydrophobic resin emulsion is at least one of a fluororesin emulsion and a silicone emulsion.
By being a fluororesin emulsion and / or a silicone emulsion, the weather resistance is improved.
以上に説明したように本発明によれば、光触媒を添加したことによる防汚、親水効果が発揮される。また、プラスチックなどの有機系基材表面に形成する塗膜の厚みを厚くしても、クラックが発生せず、しかも剥離強度に優れた塗膜となる水性塗料組成物が得られる。 As described above, according to the present invention, the addition of a photocatalyst exerts antifouling and hydrophilic effects. Further, even when the thickness of a coating film formed on the surface of an organic base material such as plastic is increased, a water-based coating composition which does not generate cracks and which becomes a coating film having excellent peel strength can be obtained.
以下に本発明の好ましい形態を説明する。
まず、以下に本発明で用いる語について説明する。
本発明において、「光触媒性酸化物粒子」には、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化鉄、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化ルテニウム、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化銅、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化マンガン、酸化ロジウム、酸化ニッケル、酸化レニウム、チタン酸ストロンチウム等の粒子が利用できる。
なお、酸化チタンを光触媒として用いる場合は、結晶型がアナターゼ型、またはブルッカイト型のものを用いることが、光触媒活性がもっとも強く、しかも長期間発現するので好ましい。
Hereinafter, preferred embodiments of the present invention will be described.
First, words used in the present invention will be described below.
In the present invention, the “photocatalytic oxide particles” include, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, oxide Particles such as cadmium, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, rhodium oxide, nickel oxide, rhenium oxide, and strontium titanate can be used.
When titanium oxide is used as the photocatalyst, it is preferable to use an anatase type or a brookite type as the crystal type, since the photocatalytic activity is the strongest and is exhibited for a long period of time.
「疎水性樹脂エマルジョン」としては、例えば、フッ素樹脂、シリコーン、アクリルシリコーン、酢酸ビニル、酢酸ビニルアクリル、アクリルウレタン、アクリル、エポキシ、塩化ビニル酢酸ビニル、塩化ビニリデン、ＳＢＲラテックス等のエマルジョンが利用できる。
フッ素樹脂エマルジョンとしては、例えばポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリクロロトリフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレンコポリマー、エチレン−テトラフルオロエチレンコポリマー、エチレン−クロロトリフルオロエチレンコポリマー、テトラフルオロエチレン−パーフルオロアルキルビニルエーテルコポリマー、パーフルオロシクロポリマー、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマー、テトラフルオロエチレン−ビニルエーテルコポリマー、クロロトリフルオロエチレン−ビニルエーテルコポリマー、テトラフルオロエチレンウレタン架橋体、テトラフルオロエチレンエポキシ架橋体、テトラフルオロエチレンアクリル架橋体、テトラフルオロエチレンメラミン架橋体等フルオロ基を含有するポリマーのエマルジョンが好適に利用できる。
また、シリコーンのエマルジョンとしては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロシラン、メチルトリブロムシラン、メチルトリイソプロポキシシラン、メチルトリｔ−ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリクロルシラン、エチルトリブロムシラン、エチルトリイソプロポキシシラン、エチルトリｔ−ブトキシシラン、ｎープロピルトリメトキシシラン、ｎープロピルトリエトキシシラン、ｎープロピルトリクロシラン、ｎープロピルトリブロムシラン、ｎープロピルトリイソプロポキシシラン、ｎープロピルトリｔ−ブトキシシラン、ｎーヘキシルトリメトキシシラン、ｎーヘキシルトリエトキシシラン、ｎーヘキシルトリクロシラン、ｎーヘキシルトリブロムシラン、ｎーヘキシルトリイソプロポキシシラン、ｎーヘキシルトリｔ−ブトキシシラン、ｎーデシルトリメトキシシラン、ｎーデシルトリエトキシシラン、ｎーデシルトリクロシラン、ｎーデシルトリブロムシラン、ｎーデシルトリイソプロポキシシラン、ｎーデシルトリｔ−ブトキシシラン、ｎーオクタトリメトキシシラン、ｎーオクタトリエトキシシラン、ｎーオクタトリクロシラン、ｎーオクタトリブロムシラン、ｎーオクタトリイソプロポキシシラン、ｎーオクタトリｔ−ブトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリクロシラン、フェニルトリブロムシラン、フェニルトリイソプロポキシシラン、フェニルトリｔ−ブトキシシラン、ジメチルジクロルシラン、ジメチルジブロムシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジクロルシラン、ジフェニルジブロムシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、フェニルメチルジクロルシラン、フェニルメチルジブロムシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、ビニルトリクロルシラン、ビニルトリブロムシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリｔ−ブトキシシラン、トリフルオロプロピルトリクロルシラン、トリフルオロプロピルトリジブロムシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、ビニルトリクロルシラン、トリフルオロプロピルトリイソプロポキシシラン、トリフルオロプロピルトリｔ−ブトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリイソプロポキシシラン、γ−グリシドキシプロピルトリｔ−ブトキシシラン、γ−メタアクリロキシプロピルメチルジメトキシシラン、γ−メタアクリロキシプロピルメチルジエトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリエトキシシラン、γ−メタアクリロキシプロピルトリイソプロポキシシラン、γ−メタアクリロキシプロピルトリｔ−ブトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノメタアクリロキシプロピルトリｔ−ブトキシシラン、γ−メチルカプトプロピルメチルジメトキシシラン、γ−メチルカプトプロピルメチルジエトキシシラン、γ−メチルカプトプロピルトリメトキシシラン、γ−メチルカプトプロピルトリエトキシシラン、γ−メチルカプトプロピルトリイソプロポキシシラン、γ−メチルカプトプロピルトリｔ−ブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシランの加水分解、脱水縮重合物などのエマルジョンが好適に利用できる。
As the "hydrophobic resin emulsion", for example, emulsions such as fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, and SBR latex can be used.
As the fluororesin emulsion, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-vinyl ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, tetrafluoroethylene urethane crosslinked product, Crosslinked tetrafluoroethylene epoxy, tetra Le Oro ethylene acrylic crosslinked emulsion polymers containing tetrafluoroethylene melamine crosslinked body and the like fluoro group can be suitably used.
Examples of the silicone emulsion include methyltrimethoxysilane, methyltriethoxysilane, methyltriclosilane, methyltribromosilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltriethoxysilane. Trichlorosilane, ethyltribromosilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyl Triisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltrichlorosilane, n-hexyltri Lomsilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltriisopropoxy Silane, n-decyltri-t-butoxysilane, n-octatrimethoxysilane, n-octatriethoxysilane, n-octatriclosilane, n-octatribromosilane, n-octatriisopropoxysilane, n-octatri-t-butoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethyldichlorosilane, dimethyldibro Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldisilane Ethoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltridibromosilane, trifluoropropyl Trimethoxysilane, trifluoropropyltriethoxysilane, vinyltrichlorosilane, trifluoropropyltriisoprop Ropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Roxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldi Toxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminomethacryloxypropyltri-t-butoxysilane, γ -Methylcaptopropylmethyldimethoxysilane, γ-methylcaptopropylmethyldiethoxysilane, γ-methylcaptopropyltrimethoxysilane, γ-methylcaptopropyltriethoxysilane, γ-methylcaptopropyltriisopropoxysilane, γ-methylcapto Propyl tri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Rujon can be suitably used.
「シリカ粒子」の好ましい具体例としては、無定型シリカ粒子が好ましい。無定型シリカでは、コロイダルシリカの形態が挙げられる。コロイダルシリカには、水に分散させたもの、あるいは、アルコールなどの非水系の有機溶媒に分散したものがあり、両方とも使用可能ではあるが、本発明では構成要素のエマルジョンの安定性を若干低下させるので、水に分散させたものを使用することが好ましい。また、有機溶剤に分散したコロイダルシリカは、前記水分散コロイダルシリカ中の水溶媒を有機溶媒に置換することで容易に調整することが可能である。 As a preferred specific example of “silica particles”, amorphous silica particles are preferable. The amorphous silica includes a form of colloidal silica. Colloidal silica may be dispersed in water or dispersed in a non-aqueous organic solvent such as alcohol, and both can be used, but in the present invention, the stability of the component emulsion is slightly reduced. Therefore, it is preferable to use one dispersed in water. Further, the colloidal silica dispersed in the organic solvent can be easily adjusted by replacing the aqueous solvent in the water-dispersed colloidal silica with an organic solvent.
光触媒性酸化物粒子及びシリカ粒子並びに疎水性樹脂エマルジョン中に分散した粒子の平均粒径は、レーザーを光源とした動的光散乱測定により測定した。測定装置は大塚電子株式会社製ＤＬＳ−６００を使用した。 The average particle size of the photocatalytic oxide particles, silica particles, and particles dispersed in the hydrophobic resin emulsion was measured by dynamic light scattering measurement using a laser as a light source. The measuring device used was DLS-600 manufactured by Otsuka Electronics Co., Ltd.
本発明のコーティング剤は、例えば、水分散性の光触媒性酸化物粒子のゾルに、必要に応じてコロイダルシリカを添加した後に、疎水性樹脂エマルジョンをさらに添加し、必要に応じて水で希釈することにより得ることが可能である。 The coating agent of the present invention, for example, after adding colloidal silica as necessary to the sol of water-dispersible photocatalytic oxide particles, further add a hydrophobic resin emulsion, and dilute with water as necessary It is possible to obtain by.
また、本発明のコーティング剤は、疎水性物質を表面に有する基材表面に被覆し、硬化せしめることで、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性複合材に改質できる。ここで、硬化は常温で行うのが、現場施工等には有利である。 In addition, the coating agent of the present invention can enjoy a self-cleaning function by rainfall immediately after use by coating and curing a base material surface having a hydrophobic substance on its surface, and the state can be improved by the sun. It can be modified into a photocatalytic composite material that is maintained for a long time by irradiation with light. Here, curing at room temperature is advantageous for on-site construction and the like.
「疎水性物質を表面に有する基材」は、例えば、プラスチック、有機物の繊維、有機物の布帛、塗装鋼板等の塗装体等が好適に利用できる。 As the “substrate having a hydrophobic substance on its surface”, for example, a plastic, an organic fiber, an organic cloth, a coated body such as a coated steel plate, or the like can be suitably used.
本発明のコーティング剤には、さらに、Ag、Cu、Znのような金属を添加することが好ましい。このような金属が添加された表面層は、表面に付着した細菌や黴や藻を暗所でも死滅させることができ、よって防汚性をより向上させることができる。 It is preferable to further add a metal such as Ag, Cu, and Zn to the coating agent of the present invention. The surface layer to which such a metal is added can kill bacteria, fungi, and algae adhering to the surface even in a dark place, and thus can further improve antifouling properties.
本発明のコーティング剤には、さらに、Pt、Pd、Ru、Rh、Ir、Osのような白金族金属を添加することができる。このような金属が添加された表面層は、光触媒の酸化還元活性を増強でき、有機物汚れの分解性、有害気体や悪臭の分解性を向上させることができる。 A platinum group metal such as Pt, Pd, Ru, Rh, Ir, and Os can be further added to the coating agent of the present invention. The surface layer to which such a metal is added can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.
本発明のコーティング剤には、さらに、疎水性樹脂エマルジョンの基材への造膜性を向上させるために造膜助剤を使用することが可能である。造膜助剤は、大部分の水分が気化した後も塗膜中に残存し、エマルション粒子どうしの融合を促進させる機能をもつものである。具体的には、沸点が１００℃以上の有機化合物が挙げられる。以下に具体例を示す。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、等のエチレン系グリコールエーテル類。
プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、
ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、ポリプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールジアセテート、プロピレングリコールフェニルエーテル、等のプロピレン系グリコールエーテル類。
２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、ｎ−ペンシルプロピオネ−ト（n-PENTYL PROPIONATE）、フタル酸ジブチル等のエステル類などが挙げられる。
そのうち、エステル類の一種である２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートは、フッ素樹脂エマルジョンへの浸透能力が高いこと、最低造膜温度（MFT）の低下効果が高いことから、その使用は好ましい。逆にエチレン系グリコールエーテル類は人体への毒性が強いので、その使用は好ましくない。
In the coating agent of the present invention, it is possible to further use a film forming aid for improving the film forming property of the hydrophobic resin emulsion on the substrate. The film-forming aid has a function of remaining in the coating film even after most of the water is vaporized, and promoting the fusion of the emulsion particles. Specifically, an organic compound having a boiling point of 100 ° C. or higher can be used. Specific examples are shown below.
Ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether,
Propylene glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, etc. Kind.
Esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, n-pentyl propionate (n-PENTYL PROPIONATE) and dibutyl phthalate are exemplified.
Among them, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, which is a kind of esters, has a high ability to penetrate into a fluororesin emulsion and has the effect of lowering the minimum film formation temperature (MFT). Due to its high cost, its use is preferred. Conversely, ethylene glycol ethers are highly toxic to the human body, so their use is not preferred.
本発明のコーティング剤には、さらに、着色料を添加することができる。着色料としては無機顔料、有機顔料、染料などから少なくとも１つを選ぶ。
無機顔料としては、酸化チタン、亜鉛華、ベンガラ、酸化クロム、コバルトブルー、鉄黒などの金属酸化物系、アルミナホワイト、黄色酸化鉄などの金属水酸化物系、紺青などのフェロシアン化合物系、黄鉛、ジンクロメート、モリブデンレッドなどのクロム酸鉛系、硫化亜鉛、朱、カドミウムイエロー、カドミウムレッドなどの硫化物、セレン化合物、バライト、沈降性硫酸バリウムなどの硫酸塩系、重質炭酸カルシウム、沈降性炭酸カルシウムなどの炭酸塩系、含水珪酸塩、クレイ、群青などの珪酸塩系、カーボンブラックなどの炭素系、アルミニウム粉、ブロンズ粉、亜鉛粉などの金属粉系、雲母・酸化チタン系などのパール顔料系などが挙げられる。
有機顔料としては、ナフトールグリーンＢなどのニトロソ系顔料、ナフトールＳなどのニトロ顔料系、リソールレッド、レーキレッドＣ、ファストエロー、ナフロールレッドなどのアゾ顔料系、アルカリブルーレッド、ローダミンキレート、キナクリドンレッド、ジオキサジンバイオレッド、イソインドリノンエローなどの縮合多環顔料系などが挙げられる。
染料としては、分散染料、塩基性染料、直接染料、酸性染料が挙げられる。
A coloring agent can be further added to the coating agent of the present invention. At least one colorant is selected from inorganic pigments, organic pigments, dyes, and the like.
As inorganic pigments, titanium oxide, zinc oxide, red iron oxide, chromium oxide, cobalt blue, metal oxides such as iron black, alumina white, metal hydroxides such as yellow iron oxide, ferrocyan compounds such as dark blue, Lead chromate such as graphite, zinc chromate, molybdenum red, sulfide such as zinc sulfide, vermilion, cadmium yellow, cadmium red, selenium compound, barite, sulfate such as precipitated barium sulfate, heavy calcium carbonate, Carbonates such as precipitated calcium carbonate, silicates such as hydrated silicates, clay and ultramarine, carbons such as carbon black, metal powders such as aluminum powder, bronze powder and zinc powder, mica / titanium oxide etc. Pearl pigments and the like.
Examples of organic pigments include nitroso pigments such as naphthol green B, nitro pigments such as naphthol S, azo pigments such as lithol red, lake red C, fast yellow and naflor red, alkali blue red, rhodamine chelate and quinacridone red. And condensed polycyclic pigments such as dioxazine violet and isoindolinone yellow.
Examples of the dye include a disperse dye, a basic dye, a direct dye, and an acid dye.
（塗料組成物の調製）
尚、本実施例、比較例の作成に用いた材料の固形分濃度、平均粒子径は表１の通り。
(Preparation of coating composition)
Table 1 shows the solid content concentration and the average particle size of the materials used in the preparation of this example and comparative examples.
実施例１
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）１０．２重量部、コロイダルシリカ（日本化学株式会社製、商品名シリカドール３０Ｂ）７９．６重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ３０００）１０．２重量部（以上固形分で表示）、造膜助剤（イーストマン・コダック社製、商品名テキサノール）２．１重量部を混合し、水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して４３３重量部であった。
Example 1
10.2 parts by weight of a photocatalyst oxide sol (manufactured by Nippon Parkerizing Co., Ltd., trade name: Pal titanium 5610), 79.6 parts by weight of colloidal silica (manufactured by Nippon Chemical Co., Ltd., trade name: Silica Doll 30B), fluororesin emulsion (Asahi Glass Co., Ltd.) Manufactured by Lumiflon FE3000) and 10.2 parts by weight of a film-forming aid (Texanol, trade name, manufactured by Eastman Kodak Co., Ltd.) to obtain an aqueous coating composition. It was adjusted. At this time, the water content was 433 parts by weight with respect to the total of 100 parts by weight of the solid content.
実施例２
光触媒酸化物ゾル（テイカ株式会社製、商品名ＴＫＳ−２０３）２０．１重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）１０．２重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）６９．７重量部（以上固形分で表示）、造膜助剤（イーストマン・コダック社製、商品名テキサノール）１５．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１５９重量部であった。
Example 2
20.1 parts by weight of photocatalytic oxide sol (manufactured by Teica Co., Ltd., trade name: TKS-203), 10.2 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), fluororesin emulsion (Asahi Glass Co., Ltd.) Aqueous coating composition comprising 69.7 parts by weight (manufactured by Lumiflon FE4300) and 15.7 parts by weight of a film-forming aid (Texanol, manufactured by Eastman Kodak Co.) was prepared. . The water content at this time was 159 parts by weight based on 100 parts by weight of the total of the solids.
実施例３
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）３．２重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）２５．９重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）３．２重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)３８．９重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）２８．８重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）０．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１３２重量部であった。
Example 3
3.2 parts by weight of photocatalyst oxide sol (manufactured by Nippon Parkerizing Co., Ltd., trade name: Pal titanium 5610), 25.9 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), fluororesin emulsion (Asahi Glass Co., Ltd.) 3.2 parts by weight, color pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF color MF5160) 38.9 parts by weight, extender pigment (manufactured by Otsuka Chemical Co., Ltd., trade name Tismo-N) ) 28.8 parts by weight (above indicated by solid content) and 0.7 parts by weight of a film-forming aid (trade name CS-12, manufactured by Chisso Corporation) were prepared. At this time, the water content was 132 parts by weight based on 100 parts by weight of the total solid content.
実施例４
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１．０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ）３８．８重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）２３．１重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２０．４重量部、体質顔料Ａ（大塚化学株式会社製、商品名ＨＴ−３００）４．７重量部、体質顔料Ｂ（日本タルク（株）製、ミクロエースＰ３）１２．０重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）７．８重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１５２重量部であった。
Example 4
1.0 parts by weight of photocatalytic oxide sol (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-21), 38.8 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL), fluororesin emulsion (Asahi Glass Co., Ltd.) 23.1 parts by weight, color pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF Color MF5160) 20.4 parts by weight, extender pigment A (manufactured by Otsuka Chemical Co., Ltd., trade name HT) -300) 4.7 parts by weight, extender pigment B (manufactured by Nippon Talc Co., Ltd., Microace P3) 12.0 parts by weight (above indicated by solid content), film forming aid (manufactured by Chisso Corporation, trade name CS) -12) 7.8 parts by weight of an aqueous coating composition was prepared. The water content at this time was 152 parts by weight with respect to the total of 100 parts by weight of the solid content.
実施例５
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１．４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ）５０．８重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）１５．０重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２６．７重量部、体質顔料（大塚化学株式会社製、商品名ＨＴ−３００）６．１重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）３．３重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１７５重量部であった。
Example 5
1.4 parts by weight of photocatalytic oxide sol (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-21), 50.8 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL), fluorine resin emulsion (Asahi Glass Co., Ltd.) 15.0 parts by weight, color pigment (manufactured by Dainichi Seika Industry Co., Ltd., trade name MF color MF5160) 26.7 parts by weight, extender pigment (manufactured by Otsuka Chemical Co., Ltd., trade name HT-) 300) 6.1 parts by weight (above indicated by solid content) and 3.3 parts by weight of a film forming aid (manufactured by Chisso Corporation, trade name CS-12) were prepared. At this time, the water content was 175 parts by weight based on 100 parts by weight of the total solid content.
実施例６
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１８．３重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）４４．３重量部、シリコーンエマルジョン（大日本インキ化学工業（株）製、商品名ボンコートＳＡ−５０８０）９．９重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)１５．２重量部、体質顔料（大塚化学株式会社製、商品名ＨＴ−３００）１２．３重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）２．４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して２９４重量部であった。
Example 6
18.3 parts by weight of a photocatalyst oxide sol (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-21), 44.3 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (Dainippon Ink) 9.9 parts by weight of a color pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name of MF Color MF5160) 15.2 parts by weight of an extender pigment (Otsuka Chemical Co., Ltd.) Co., Ltd., 12.3 parts by weight (brand name: HT-300) and 2.4 parts by weight of a film forming aid (Chisso Corporation, trade name CS-12). At this time, the water content was 294 parts by weight with respect to the total of 100 parts by weight of the solid content.
比較例１
フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）６７．８重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２６．７重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）５．５重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１４．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して８５重量部であった。
Comparative Example 1
67.8 parts by weight of a fluororesin emulsion (manufactured by Asahi Glass Co., Ltd., trade name: Lumiflon FE4300), 26.7 parts by weight of a coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF Color MF5160), extender pigment (Otsuka Chemical Co., Ltd.) Aqueous coating composition comprising 5.5 parts by weight (manufactured by Tismo-N) and 14.7 parts by weight of a film forming aid (trade name: CS-12, manufactured by Chisso Corporation) did. At this time, the water content was 85 parts by weight with respect to the total of 100 parts by weight of the solid content.
比較例２
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）２３．９重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)１１．４重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）５４．７重量部（以上固形分で表示）である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して２６９重量部であった。
Comparative Example 2
10 parts by weight of a photocatalyst oxide sol (manufactured by Nippon Parkerizing Co., Ltd., trade name: Pal titanium 5610), 23.9 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), coloring pigment (Dainichi Seika Kogyo Co., Ltd.) An aqueous coating composition was prepared which was 11.4 parts by weight (manufactured and trade name MF Color MF5160) and 54.7 parts by weight (solid content) of an extender pigment (trade name: Tismo-N manufactured by Otsuka Chemical Co., Ltd.) . At this time, the amount of water was 269 parts by weight based on 100 parts by weight of the total solid content.
比較例３
光触媒酸化物（日本パーカライジング株式会社製、商品名パルチタン５６１０）９．８重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）７９．３重量部、フッ素樹脂（旭硝子株式会社製、商品名ルミフロンＬＦ１００）１０．９重量部（以上固形分で表示）である塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して３２５重量部であった。塗布直前に硬化剤（日本ポリウレタン株式会社製、商品名コロネートＨＸ）を塗料組成物１００重量部に対して、０．４重量部添加した。
Comparative Example 3
9.8 parts by weight of a photocatalyst oxide (manufactured by Nippon Parkerizing Co., Ltd., trade name Pal Titanium 5610), 79.3 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), fluororesin (manufactured by Asahi Glass Co., Ltd.) A coating composition having a trade name of Lumiflon LF100 (10.9 parts by weight (indicated by solid content)) was prepared. At this time, the water content was 325 parts by weight with respect to the total of 100 parts by weight of the solid content. Immediately before coating, a curing agent (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate HX) was added in an amount of 0.4 part by weight based on 100 parts by weight of the coating composition.
（基材への塗布方法）
１５０ｍｍ×６５ｍｍに裁断した石綿セメント珪酸カルシウム板（ＪＩＳ Ａ５４１８に準拠したもの）にエポキシ樹脂系プライマー（エスケー化研、商品名 ＳＫサーフエポ）をスプレー塗装し、室温で２４時間乾燥させた。続いて、アクリルウレタン塗料（イサム塗料 商品名 ハイアート１０００）を、上記したプライマー塗装を行った石綿セメント珪酸カルシウム板上にスプレー塗装し、室温で２４時間乾燥させた。さらに続いて、前記で調製した実施例１、２、３及び比較例１、２、３の塗料組成物をプライマー塗装、アクリルウレタン塗装を行った石綿セメント珪酸カルシウム板上に刷毛塗りし、コーティング物を得た。
また、プライマー塗装を行った石綿セメント珪酸カルシウム板上にスズカファイン（株）製下地調整塗材（商品名「リメークプラ」）を刷毛塗し、室温で２４時間乾燥させたたものに、実施例４、５、６の塗料組成物の塗装を行ない、コーティング物を得た。
コーティングは試験片を垂直に立てた状態で行った。刷毛塗りした上記塗料組成物の重量は１５ｇ／ｍ2であった。最後に、上記コーティング物を室温で２４時間乾燥させて試験片１〜９を得た。
試験片１：実施例１の塗料を塗布
試験片２：実施例２の塗料を塗布
試験片３：実施例３の塗料を塗布
試験片４：実施例４の塗料を塗布
試験片５：実施例５の塗料を塗布
試験片６：実施例６の塗料を塗布
試験片７：比較例１の塗料を塗布
試験片８：比較例２の塗料を塗布
試験片９：比較例３の塗料を塗布
(Method of coating on substrate)
An asbestos cement calcium silicate plate (according to JIS A5418) cut to 150 mm x 65 mm was spray-coated with an epoxy resin-based primer (SK KAKEN, trade name: SK Surf Epo) and dried at room temperature for 24 hours. Subsequently, an acrylic urethane paint (trade name: Hi-Art 1000) was spray-coated on the asbestos-cemented calcium silicate plate on which the primer coating was performed, and dried at room temperature for 24 hours. Subsequently, the coating compositions of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 prepared as described above were brush-coated on an asbestos cement calcium silicate plate on which primer coating and acrylic urethane coating had been performed, and a coating material was obtained. Got.
Further, a primer coating material (trade name “Remakepla”) manufactured by Suzuka Fine Co., Ltd. was brush-coated on a primer-coated asbestos cement calcium silicate plate, and dried at room temperature for 24 hours. The coating compositions of Examples 5 and 6 were applied to obtain coatings.
The coating was performed with the test piece standing upright. The weight of the brush-coated coating composition was 15 g / m 2 . Finally, the coating was dried at room temperature for 24 hours to obtain test pieces 1 to 9.
Test piece 1: The paint of Example 1 was applied Test piece 2: The paint of Example 2 was applied Test piece 3: The paint of Example 3 was applied Test piece 4: The paint of Example 4 was applied Test piece 5: Example Test piece 6: The paint of Example 6 was applied Test piece 7: The paint of Comparative example 1 was applied Test piece 8: The paint of Comparative example 2 was applied Test piece 9: The paint of Comparative example 3 was applied
エリクセン評価、一酸化窒素分解性能評価用試験片の作成
１５０ｍｍ×６５ｍｍに裁断した亜鉛メッキ鋼板（ＪＩＳ Ａ５４００に準拠したもの）にエポキシ樹脂系プライマー（エスケー化研、商品名 ＳＫサーフエポ）をスプレー塗装し、室温で２４時間乾燥させた。続いて、前記で調製した実施例１、２、３、４、５、６及び比較例１、２、３の塗料組成物を、プライマー塗装を行った亜鉛メッキ鋼板上に刷毛塗りし、コーティング物を得た。
コーティングは試験片を垂直に立てた状態で行った。刷毛塗りした上記塗料組成物の重量は１５ｇ／ｍ2であった。最後に、上記コーティング物を室温で２４時間乾燥させて試験片１０〜１８を得た。
試験片１０：実施例１の塗料を塗布
試験片１１：実施例２の塗料を塗布
試験片１２：実施例３の塗料を塗布
試験片１３：実施例４の塗料を塗布
試験片１４：実施例５の塗料を塗布
試験片１５：実施例６の塗料を塗布
試験片１６：比較例１の塗料を塗布
試験片１７：比較例２の塗料を塗布
試験片１８：比較例３の塗料を塗布
Preparation of a test piece for Erichsen evaluation and nitric oxide decomposition performance evaluation A zinc-plated steel sheet (conforming to JIS A5400) cut to 150 mm x 65 mm was spray-coated with an epoxy resin-based primer (ESK Kaken, trade name: SK Surf Epo). And dried at room temperature for 24 hours. Subsequently, the coating compositions of Examples 1, 2, 3, 4, 5, 6 and Comparative Examples 1, 2, and 3 prepared as described above were brush-coated on a galvanized steel sheet that had been subjected to primer coating. Got.
The coating was performed with the test piece standing upright. The weight of the brush-coated coating composition was 15 g / m 2 . Finally, the coating was dried at room temperature for 24 hours to obtain test pieces 10 to 18.
Test piece 10: Apply the paint of Example 1 Test piece 11: Apply the paint of Example 2 Test piece 12: Apply the paint of Example 3 Test piece 13: Apply the paint of Example 4 Test piece 14: Example Test piece 15: The paint of Example 6 was applied Test piece 16: The paint of Comparative example 1 was applied Test piece 17: The paint of Comparative example 2 was applied Test piece 18: The paint of Comparative example 3 was applied
次に、上記各試験片について、膜厚、クラックの有無、密着性、エリクセン評価、光沢、耐アルカリ性、耐沸騰水性、熱冷サイクル試験、親水性（初期接触角と紫外線照射時の接触角を測定）を評価し、その結果を（表２）に示す。また、自己洗浄性評価についてはその結果を（表３）に示す。一酸化窒素分解性能についてはその結果を（図１〜５）に示す。 Next, for each of the above test pieces, film thickness, presence or absence of cracks, adhesion, Erichsen evaluation, gloss, alkali resistance, boiling water resistance, hot-cooling cycle test, hydrophilicity (initial contact angle and contact angle at the time of UV irradiation) Measurement) was evaluated, and the results are shown in (Table 2). The results of the self-cleaning evaluation are shown in (Table 3). The results of the nitric oxide decomposition performance are shown in FIGS.
評価方法は以下の通りである。
膜厚：走査型電子顕微鏡（日立製作所製Ｓ-4100）により試験片を断面方向から観察し、膜厚を測定した。
クラックの有無：光学顕微鏡（キーエンス製ＶＦ-7500）を用いて試験片表面を観察してクラックの有無を確認した。
密着性：ＪＩＳ Ｋ５４００ 碁盤目試験法により行った。即ち、作製した試験片の塗膜の上からカッターで２ｍｍ幅の碁盤目の切込みを入れる。大きさは１ｃｍ角にし、碁盤目の数を２５個とする。その後その碁盤目を完全に覆うようにセロハンテープを貼り付ける。その後、すばやく引き剥がして付着して残っている碁盤目の数を数える。
エリクセン評価：ＪＩＳ Ｂ７７２９に準拠したエリクセン試験機を用いて、金属板に塗布した試験片により裏面より鋼球を押し出し、試験片を変形させる。塗膜にクラック、割れ、剥がれ、を生じるまでの押し出し距離を調べる。
光沢：作製した試験片の光沢度を日本電色工業製ＶＧＳ-1Ｄを用いて測定した。
耐アルカリ性：水酸化カルシウム飽和水溶液に室温で７日間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
耐沸騰水性：９５℃以上の沸騰水中に２時間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
熱冷サイクル試験：５０℃の恒温槽に３時間、次いで、−２０℃の恒温槽に３時間、次いで２５℃の恒温水槽に１８時間を１サイクルとして１０サイクル繰り返す。取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
親水性（初期接触角）：試験片表面の水との接触角を、協和界面科学製ＣＸ-150を用いて測定した。
親水性（紫外線照射時）：作製した試験片にＢＬＢランプから発生した0.5ｍＷ／ｃｍ2の紫外線を７日間または殺菌灯ランプから発生した3.0ｍＷ／ｃｍ2の紫外線を3日間照射し、その後水との接触角を、協和界面科学製ＣＸ-150を用いて測定した。
自己洗浄性（屋外暴露）：作製した試験片を南側に向け、鉛直に対して４５°傾斜させたものを屋外に設置する。暴露する前、暴露1ヶ月後、暴露2ヶ月後の目視による外観評価及び接触角を測定した。
一酸化窒素分解性能評価：評価装置の模式図を図６に示す。入口側の一酸化窒素の濃度を空気と調整して０．２５ｐｐｍとする。流量を毎分１リットルに調整する。試験片を設置してから、３０分間流量が安定するまで気体を流す。その後紫外線をＢＬＢ灯にて０．５ｍＷ／ｃｍ2の強度にて照射する。一酸化窒素と二酸化窒素の濃度を記録する。
The evaluation method is as follows.
Film thickness: The test piece was observed from a cross-sectional direction with a scanning electron microscope (S-4100 manufactured by Hitachi, Ltd.), and the film thickness was measured.
Presence or absence of cracks: The presence or absence of cracks was confirmed by observing the surface of the test piece using an optical microscope (VF-7500 manufactured by Keyence).
Adhesion: Performed according to JIS K5400 grid test. That is, a 2 mm-width cross cut is made from above the coating film of the prepared test piece with a cutter. The size is 1 cm square, and the number of grids is 25. Thereafter, a cellophane tape is attached so as to completely cover the grid. After that, it is quickly peeled off and the number of grids remaining after being attached is counted.
Erichsen evaluation: Using an Erichsen testing machine based on JIS B7729, a steel ball is extruded from the back surface with a test piece applied to a metal plate to deform the test piece. Extrusion distance until cracks, cracks, and peeling occur in the coating film is examined.
Gloss: The gloss of the prepared test piece was measured using VGS-1D manufactured by Nippon Denshoku Industries.
Alkali resistance: dipped in a saturated aqueous solution of calcium hydroxide at room temperature for 7 days, taken out, washed with distilled water, dried sufficiently, and evaluated by visual appearance.
Boiling water resistance: Dipped in boiling water of 95 ° C. or more for 2 hours, taken out, washed with distilled water, dried sufficiently, and evaluated by visual appearance.
Heat-cooling cycle test: 10 cycles are repeated with 3 hours in a 50 ° C constant temperature bath, 3 hours in a -20 ° C constant temperature bath, and 18 hours in a 25 ° C constant temperature water bath. After taking out, it is washed with distilled water and dried sufficiently, and then evaluated by visual appearance.
Hydrophilicity (initial contact angle): The contact angle of the surface of the test piece with water was measured using CX-150 manufactured by Kyowa Interface Science.
Hydrophilic (during UV irradiation): the test piece was irradiated with ultraviolet rays of 3.0 mW / cm 2 that generates ultraviolet rays of 0.5 mW / cm 2 generated from 7 days or germicidal lamp lamp from BLB lamps 3 days was produced, then water Was measured using Kyowa Interface Science CX-150.
Self-cleaning property (outdoor exposure): The prepared test piece is directed to the south side, and a test piece inclined at 45 ° to the vertical is installed outdoors. Before the exposure, one month after the exposure, and two months after the exposure, the visual appearance and the contact angle were measured.
Evaluation of Nitric Oxide Decomposition Performance: FIG. 6 shows a schematic diagram of an evaluation device. The concentration of nitric oxide on the inlet side is adjusted to 0.25 ppm with air. Adjust the flow rate to 1 liter per minute. After installing the test piece, gas is flowed until the flow rate becomes stable for 30 minutes. Thereafter, ultraviolet light is irradiated at an intensity of 0.5 mW / cm 2 by a BLB lamp. Record the concentrations of nitric oxide and nitrogen dioxide.
Claims (12)
（ｂ）疎水性樹脂エマルジョンと、
（ｃ）水と、
を少なくとも含んだ光触媒性コーティング剤であって、
前記（ａ）成分の平均粒径は、前記（ｂ）成分中に分散した粒子の平均粒径よりも小さいことを特徴とする光触媒性コーティング剤。 (A) photocatalytic oxide particles,
(B) a hydrophobic resin emulsion;
(C) water;
A photocatalytic coating agent containing at least
The photocatalytic coating agent, wherein the average particle size of the component (a) is smaller than the average particle size of the particles dispersed in the component (b).
（ｂ）疎水性樹脂エマルジョンと、
（ｃ）水と、
（ｄ）シリカ粒子と、
を少なくとも含んだ光触媒性コーティング剤であって、
前記（ａ）成分及び（ｄ）成分の平均粒径は、前記（ｂ）成分中に分散した粒子の平均粒径よりも小さいことを特徴とする光触媒性コーティング剤。 (A) photocatalytic oxide particles,
(B) a hydrophobic resin emulsion;
(C) water;
(D) silica particles;
A photocatalytic coating agent containing at least
The photocatalytic coating agent, wherein the average particle size of the components (a) and (d) is smaller than the average particle size of the particles dispersed in the component (b).
A photocatalytic composite material obtained by the method for producing a photocatalytic composite material according to claim 10.
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