JPH11140433A - Photocatalytic aqueous composition and formation of photocatalytic aqueous coat - Google Patents
Photocatalytic aqueous composition and formation of photocatalytic aqueous coatInfo
- Publication number
- JPH11140433A JPH11140433A JP9307239A JP30723997A JPH11140433A JP H11140433 A JPH11140433 A JP H11140433A JP 9307239 A JP9307239 A JP 9307239A JP 30723997 A JP30723997 A JP 30723997A JP H11140433 A JPH11140433 A JP H11140433A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytic
- water
- colloidal silica
- insulating board
- coat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000008119 colloidal silica Substances 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000003973 paint Substances 0.000 claims description 17
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 49
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000011787 zinc oxide Substances 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は無機質塗料からなる
塗膜の表面を長期間に亘って親水性に維持するための光
触媒性親水性組成物と、この組成物からなる光触媒性親
水性被膜を形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic hydrophilic composition for maintaining the surface of a coating film made of an inorganic coating material hydrophilic for a long period of time, and a photocatalytic hydrophilic film made of this composition. It relates to a method of forming.
【０００２】[0002]
【従来の技術】無機質充填剤とコロイダルシリカを水に
分散させた無機質塗料を、石膏ボード、パーライト板、
モルタル、珪酸カルシウム板等の無機基材の表面に塗布
した不燃性化粧建材が従来から提供されている。2. Description of the Related Art An inorganic paint in which an inorganic filler and colloidal silica are dispersed in water is used for a gypsum board, a pearlite board,
BACKGROUND ART Nonflammable decorative building materials applied to the surface of an inorganic base material such as a mortar or a calcium silicate plate have been conventionally provided.
【０００３】上記不燃性化粧建材の表面に形成される無
機質塗料からなる被膜は、耐水性と耐火性には優れる
も、表面硬度が低く汚れが付きやすいという欠点があ
る。そこで、特開昭５４−１３９９３８号公報には、無
機質塗料からなる被膜の上に更にコロイダルシリカとア
クリル系樹脂を含有する上塗り液を塗布する提案がなさ
れている。[0003] The coating made of an inorganic paint formed on the surface of the non-combustible decorative building material is excellent in water resistance and fire resistance, but has a drawback that it has low surface hardness and is easily stained. Therefore, Japanese Patent Application Laid-Open No. 54-139938 proposes to further apply an overcoating liquid containing colloidal silica and an acrylic resin on a coating made of an inorganic paint.
【０００４】[0004]
【発明が解決しようとする課題】ところで、従来から物
体の表面を親水性にして汚れを付着させない提案（特公
昭４６−１３２５２号公報など）がなされている。しか
しながら、特開昭５４−１３９９３８号公報に係る組成
物では、第１に親水性の度合いが水との接触角に換算し
てせいぜい３０°程度までしかならず、充分な親水性を
発揮することができない。第２に、数１０μｍ以上の厚
みで水性液を塗布しないと親水性を発揮しないため、そ
の厚みで塗布すると、光の乱反射による白濁が生じた
り、光の干渉による発色が生じる。第３に、従来の水性
液を塗布・乾燥せしめ、建材等の表面に親水性が付与さ
れても、長期間親水性を維持するのは困難で、一旦親水
性を失うと、再度塗布しない限り、親水性は回復しな
い。By the way, there has been conventionally proposed a method in which the surface of an object is made hydrophilic so that dirt does not adhere thereto (Japanese Patent Publication No. 46-13252). However, in the composition according to JP-A-54-139938, first, the degree of hydrophilicity is only up to about 30 ° in terms of a contact angle with water, and sufficient hydrophilicity can be exhibited. Can not. Secondly, since hydrophilicity is not exhibited unless the aqueous liquid is applied with a thickness of several tens of μm or more, if the aqueous liquid is applied with the thickness, white turbidity due to irregular reflection of light or color formation due to interference of light occurs. Third, even if a conventional aqueous liquid is applied and dried to impart hydrophilicity to the surface of a building material or the like, it is difficult to maintain the hydrophilicity for a long time, and once the hydrophilicity is lost, unless it is applied again. The hydrophilicity is not restored.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決すべく本
発明に係る光触媒性親水性組成物は、無機質塗料からな
る塗膜の表面に塗布する組成物であることを前提とし、
その組成は、光触媒性金属酸化物粒子と、コロイダルシ
リカと、アクリル系樹脂とを水に分散させた構成とし
た。Means for Solving the Problems In order to solve the above problems, the photocatalytic hydrophilic composition according to the present invention is premised on being a composition applied to the surface of a coating film made of an inorganic paint,
The composition was such that photocatalytic metal oxide particles, colloidal silica, and an acrylic resin were dispersed in water.
【０００６】また、本発明に係る光触媒性親水性被膜の
形成方法は、コロイダルシリカを含む水分散液からなる
無機質塗料を基材の表面に塗布して塗膜を形成し、次い
で、この塗膜の表面に、光触媒性金属酸化物粒子と、コ
ロイダルシリカと、アクリル系樹脂とを水に分散させて
なる光触媒性親水性組成物を塗布する。Further, the method for forming a photocatalytic hydrophilic coating according to the present invention is to form a coating by applying an inorganic coating comprising an aqueous dispersion containing colloidal silica to the surface of a substrate, and then forming the coating. Is coated with a photocatalytic hydrophilic composition obtained by dispersing photocatalytic metal oxide particles, colloidal silica, and an acrylic resin in water.
【０００７】ここで、前記無機質塗料としては、無機質
充填剤を含有するコロイダルシリカが挙げられ、無機質
充填剤には、酸化アルミニウム、水酸化アルミニウム、
珪酸アルミニウム、珪酸アルミニウムカルシウム、シリ
カ、炭酸カルシウム、ガラスタルク、クレー、ガラスバ
ルーン、シラスバルーン、アスベスト、マイカ等が挙げ
られる。Here, as the inorganic coating, colloidal silica containing an inorganic filler can be mentioned, and the inorganic filler includes aluminum oxide, aluminum hydroxide,
Examples include aluminum silicate, calcium aluminum silicate, silica, calcium carbonate, glass talc, clay, glass balloon, shirasu balloon, asbestos, mica, and the like.
【０００８】また、前記光触媒性金属酸化物粒子として
は、例えば、アナターゼ型酸化チタン、ルチル型酸化チ
タン、ブルカイト型酸化チタン、酸化亜鉛、酸化錫、酸
化第二鉄、三酸化二ビスマス、三酸化タングステン、チ
タン酸ストロンチウム等が挙げられる。The photocatalytic metal oxide particles include, for example, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, trioxide Examples include tungsten and strontium titanate.
【０００９】また、前記アクリル系樹脂としては、例え
ば、ポリアクリル酸エステル、ポリメタアクリル酸エス
テル、ポリアクリル酸エステル−メタアクリル酸エステ
ル共重合体、アクリル酸エステルまたはメタアクリル酸
エステルとスチレン、ブタジエン、アクリル酸、メタア
クリル酸、酢酸ビニル、塩化ビニル、ビニルトルエン等
との共重合体が挙げられる。The acrylic resin includes, for example, polyacrylate, polymethacrylate, polyacrylate-methacrylate copolymer, acrylate or methacrylate and styrene, butadiene. And acrylic acid, methacrylic acid, vinyl acetate, vinyl chloride, vinyl toluene and the like.
【００１０】また、前記光触媒性金属酸化物粒子の割合
は０．０１〜１０重量％とし、また前記コロイダルシリ
カとアクリル系樹脂の固形分重量比は１０：９０〜８
０：２０とすることが好ましい。The ratio of the photocatalytic metal oxide particles is 0.01 to 10% by weight, and the solid content ratio of the colloidal silica to the acrylic resin is 10:90 to 8%.
The ratio is preferably set to 0:20.
【００１１】光触媒性金属酸化物粒子の割合が上記範囲
よりも少ないと、光触媒による親水性作用が不十分とな
り、上記範囲以上に添加しても添加による効果の向上は
なく、却って被膜の結合強度を低下せしめることにな
る。また、表面層中の光触媒性金属酸化物粒子の量とし
ては、１×１０-7〜１×１０-3ｇ／ｃｍ2、好ましくは
５×１０-7〜５×１０-4ｇ／ｃｍ2、更に好ましくは１
×１０-6〜１×１０-4ｇ／ｃｍ2である。また、コロイ
ダルシリカの使用量が上記の範囲よりも多量になると、
塗膜の光沢が悪くなり、逆に上記の範囲よりも少量にな
ると、表面硬度が低下する。If the proportion of the photocatalytic metal oxide particles is less than the above range, the hydrophilic effect of the photocatalyst becomes insufficient. Even if the content exceeds the above range, the effect is not improved by the addition, but rather the bonding strength of the coating film. Will be reduced. The amount of the photocatalytic metal oxide particles in the surface layer is 1 × 10 −7 to 1 × 10 −3 g / cm 2 , preferably 5 × 10 −7 to 5 × 10 −4 g / cm 2. , More preferably 1
× 10 -6 to 1 × 10 -4 g / cm 2 . Also, when the amount of colloidal silica used is larger than the above range,
If the gloss of the coating film is deteriorated, and if it is smaller than the above range, the surface hardness is reduced.
【００１２】尚、本発明による親水化現象は以下の機構
によってもたらされる。即ち、光触媒の価電子帯上端と
伝導帯下端とのエネルギーギャップ以上のエネルギーを
有する光が光触媒に照射されると、光触媒の価電子帯中
の電子が励起されて伝導電子と正孔とが生成する。そし
て、その結果、表面に極性（おそらくは電子吸引性）が
付与される。それにより、表面に雰囲気との平衡以上の
量の水が化学吸着する。すると、その表面の水素結合に
基づく表面自由エネルギーが増加し、その表面自由エネ
ルギーの増加に応じた量の水分子がさらに物理吸着し、
表面に固定される。ところで、表面自由エネルギーが近
い物質同士は互いに接着しやすいことから、水分子が物
理吸着した表面は水になじみやすいものとなる。即ち、
そのような表面は親水化されることになる。The hydrophilization phenomenon according to the present invention is brought about by the following mechanism. That is, when light having energy equal to or greater than the energy gap between the upper end of the valence band and the lower end of the conduction band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. I do. As a result, the surface is given a polarity (probably an electron-withdrawing property). As a result, an amount of water equal to or more than the equilibrium with the atmosphere is chemically adsorbed on the surface. Then, the surface free energy based on hydrogen bonding of the surface increases, and the amount of water molecules according to the increase in the surface free energy further physically adsorbs,
Fixed to the surface. By the way, substances having similar surface free energies are likely to adhere to each other, so that the surface on which water molecules are physically adsorbed is easily adapted to water. That is,
Such a surface will be hydrophilized.
【００１３】このように、本発明による親水性は、コロ
イダルシリカとアクリル系樹脂を含む水性液に由来する
よりも、光触媒の親水化作用によるものと考えられる。
このことは、コロイダルシリカとアクリル系樹脂を含む
水性液によって親水性を発揮するには数１０μｍ以上の
厚みで塗布しなければならなかったが、本発明による組
成物の場合には０．４μｍ以下でも親水性を発揮するこ
とからも首肯できる。ここで、０．４μｍ以下の厚みに
することで、光の乱反射による白濁を防止することがで
き、更に０．２μｍ以下の厚みにすることで、光の干渉
による表面相の発色を防止することができる。As described above, the hydrophilicity according to the present invention is considered to be due to the hydrophilizing action of the photocatalyst, rather than to the aqueous solution containing colloidal silica and acrylic resin.
This means that in order to exhibit hydrophilicity with an aqueous liquid containing colloidal silica and an acrylic resin, it had to be applied with a thickness of several tens of μm or more, but in the case of the composition according to the present invention, it was 0.4 μm or less. However, it can be confirmed because of its hydrophilicity. Here, by setting the thickness to 0.4 μm or less, it is possible to prevent white turbidity due to irregular reflection of light, and by setting the thickness to 0.2 μm or less, it is possible to prevent surface phase coloring due to light interference. Can be.
【００１４】[0014]
【発明の実施の形態】（実施例１）４０％コロイダルシ
リカ（ルドックスＨＳ４０：デユポン製）１０００ｇに
アルミナ粉末１４００ｇ、酸化亜鉛５ｇを添加して無機
質塗料を調製し、この無機質塗料を断熱ボード表面に塗
布し、放置して無機質塗料からなる塗膜を形成した。一
方、４０％コロイダルシリカ（ルドックスＨＳ４０：デ
ユポン製）７５ｇ、４５％スチレン・２−エチルヘキシ
ルアクリレート共重合エマルジョン（ポリトロンＡ−４
５：旭化成製）１５５ｇ、アナターゼ型チタニアを３０
ｇを秤量し、これらを水に分散させて光触媒性親水性組
成物液（Ａ）を調製した。同様にして、アナターゼ型チ
タニアの代わりにルチル型チタニアを分散させた光触媒
性親水性組成物液（Ｂ）及びブルカイト型チタニアを分
散させた光触媒性親水性組成物液（Ｃ）を調製した。こ
れら光触媒性親水性組成物液（Ａ〜Ｃ）を断熱ボードの
表面に塗布し、室温で１日乾燥せしめて被膜を形成した
後、紫外線を照射した。その結果、断熱ボードの表面の
親水性は水との接触角に換算して１０°以下になった。
また、暗所に放置した後、再び紫外線を照射すると、水
との接触角は１０°以下に戻った。(Example 1) An inorganic paint is prepared by adding 1400 g of alumina powder and 5 g of zinc oxide to 1000 g of 40% colloidal silica (Ludox HS40: manufactured by DuPont), and the inorganic paint is coated on the surface of a heat insulating board. It was applied and left to form a coating film composed of an inorganic paint. On the other hand, 75 g of 40% colloidal silica (Ludox HS40: manufactured by DuPont) and 45% styrene / 2-ethylhexyl acrylate copolymer emulsion (Polytron A-4)
5: Asahi Kasei) 155 g, 30 anatase type titania
g were weighed and dispersed in water to prepare a photocatalytic hydrophilic composition liquid (A). In the same manner, a photocatalytic hydrophilic composition liquid (B) in which rutile-type titania was dispersed instead of anatase-type titania and a photocatalytic hydrophilic composition liquid (C) in which brookite-type titania were dispersed were prepared. These photocatalytic hydrophilic composition liquids (A to C) were applied to the surface of a heat insulating board, dried at room temperature for one day to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the heat insulating board became 10 ° or less in terms of the contact angle with water.
When the device was left in a dark place and irradiated again with ultraviolet rays, the contact angle with water returned to 10 ° or less.
【００１５】（比較例１）上記実施例１から結晶性チタ
ニアを除いた組成物液を調製し、これを断熱ボードの表
面に塗布し乾燥せしめた後、室温で１日かけて乾燥せし
めた。その結果、断熱ボードの表面の親水性は水との接
触角に換算して約３０°になった。また、当該製品を１
ヵ月放置したところ、水との接触角は約５０°になっ
た。これに紫外線を照射しても水との接触角に変化はな
かった。(Comparative Example 1) A composition liquid was prepared by removing crystalline titania from Example 1 described above, and this was applied to the surface of a heat insulating board, dried, and then dried at room temperature for one day. As a result, the hydrophilicity of the surface of the heat insulating board was about 30 ° in terms of the contact angle with water. In addition, 1
After standing for months, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００１６】（実施例２）４０％コロイダルシリカ（ル
ドックスＨＳ４０：デユポン製）１０００ｇにアルミナ
粉末１４００ｇ、酸化亜鉛５ｇを添加して無機質塗料を
調製し、この無機質塗料を断熱ボード表面に塗布し、放
置して無機質塗料からなる塗膜を形成した。一方、４０
％コロイダルシリカ（ルドックスＨＳ４０：デユポン
製）１２５ｇ、４５％エチルアクリレート・メチルメタ
アクリレート共重合エマルジョン（セビアンＡ４５００
０：ダイセル製）１１０ｇ、アナターゼ型チタニアを３
ｇを秤量し、これらを水に分散させて光触媒性親水性組
成物液（Ａ）を調製した。同様にして、アナターゼ型チ
タニアの代わりにルチル型チタニアを分散させた光触媒
性親水性組成物液（Ｂ）及びブルカイト型チタニアを分
散させた光触媒性親水性組成物液（Ｃ）を調製した。こ
れら光触媒性親水性組成物液（Ａ〜Ｃ）を断熱ボードの
表面に塗布し、室温で１日乾燥せしめて被膜を形成した
後、紫外線を照射した。その結果、断熱ボードの表面の
親水性は水との接触角に換算して１０°以下になった。
また、暗所に放置した後、再び紫外線を照射すると、水
との接触角は１０°以下に戻った。Example 2 1400 g of alumina powder and 5 g of zinc oxide were added to 1000 g of 40% colloidal silica (Ludox HS40, manufactured by DuPont) to prepare an inorganic paint, and the inorganic paint was applied to the surface of a heat insulating board and allowed to stand. Thus, a coating film composed of an inorganic paint was formed. On the other hand, 40
% Colloidal silica (Ludox HS40: manufactured by DuPont) 125 g, 45% ethyl acrylate / methyl methacrylate copolymer emulsion (Sebian A4500)
0: made by Daicel) 110 g, 3 anatase type titania
g were weighed and dispersed in water to prepare a photocatalytic hydrophilic composition liquid (A). In the same manner, a photocatalytic hydrophilic composition liquid (B) in which rutile-type titania was dispersed instead of anatase-type titania and a photocatalytic hydrophilic composition liquid (C) in which brookite-type titania were dispersed were prepared. These photocatalytic hydrophilic composition liquids (A to C) were applied to the surface of a heat insulating board, dried at room temperature for one day to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the heat insulating board became 10 ° or less in terms of the contact angle with water.
When the device was left in a dark place and irradiated again with ultraviolet rays, the contact angle with water returned to 10 ° or less.
【００１７】（比較例２）上記実施例２から結晶性チタ
ニアを除いた組成物液を調製し、これを断熱ボードの表
面に塗布し乾燥せしめた後、室温で１日かけて乾燥せし
めた。その結果、断熱ボードの表面の親水性は水との接
触角に換算して約３０°になった。また、当該製品を１
ヵ月放置したところ、水との接触角は約５０°になっ
た。これに紫外線を照射しても水との接触角に変化はな
かった。(Comparative Example 2) A composition liquid prepared by removing crystalline titania from Example 2 was prepared, applied to the surface of a heat insulating board, dried, and then dried at room temperature for one day. As a result, the hydrophilicity of the surface of the heat insulating board was about 30 ° in terms of the contact angle with water. In addition, 1
After standing for months, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００１８】（実施例３）４０％コロイダルシリカ（ル
ドックスＨＳ４０：デユポン製）１０００ｇにアルミナ
粉末１４００ｇ、酸化亜鉛５ｇを添加して無機質塗料を
調製し、この無機質塗料を断熱ボード表面に塗布し、放
置して無機質塗料からなる塗膜を形成した。一方、４０
％コロイダルシリカ（ルドックスＨＳ４０：デユポン
製）１７５ｇ、５０％酢酸ビニル・アクリルエステル共
重合エマルジョン（ボンコート６１５０：大日本インキ
化学製）６０ｇ、アナターゼ型チタニアを０．３ｇを秤
量し、これらを水に分散させて光触媒性親水性組成物液
（Ａ）を調製した。同様にして、アナターゼ型チタニア
の代わりにルチル型チタニアを分散させた光触媒性親水
性組成物液（Ｂ）及びブルカイト型チタニアを分散させ
た光触媒性親水性組成物液（Ｃ）を調製した。これら光
触媒性親水性組成物液（Ａ〜Ｃ）を断熱ボードの表面に
塗布し、室温で１日乾燥せしめて被膜を形成した後、紫
外線を照射した。その結果、断熱ボードの表面の親水性
は水との接触角に換算して１０°以下になった。Example 3 1400 g of alumina powder and 5 g of zinc oxide were added to 1000 g of 40% colloidal silica (Ludox HS40: manufactured by DuPont) to prepare an inorganic paint, and the inorganic paint was applied to the surface of a heat insulating board and allowed to stand. Thus, a coating film composed of an inorganic paint was formed. On the other hand, 40
% Colloidal silica (Ludox HS40: manufactured by Du Pont), 175 g, 50% vinyl acetate / acrylic ester copolymer emulsion (Boncoat 6150: manufactured by Dainippon Ink and Chemicals), and 0.3 g of anatase titania were weighed and dispersed in water. Thus, a photocatalytic hydrophilic composition liquid (A) was prepared. In the same manner, a photocatalytic hydrophilic composition liquid (B) in which rutile-type titania was dispersed instead of anatase-type titania and a photocatalytic hydrophilic composition liquid (C) in which brookite-type titania were dispersed were prepared. These photocatalytic hydrophilic composition liquids (A to C) were applied to the surface of a heat insulating board, dried at room temperature for one day to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the heat insulating board became 10 ° or less in terms of the contact angle with water.
【００１９】（比較例３）上記実施例２から結晶性チタ
ニアを除いた組成物液を調製し、これを断熱ボードの表
面に塗布し乾燥せしめた後、室温で１日かけて乾燥せし
めた。その結果、断熱ボードの表面の親水性は水との接
触角に換算して約３０°になった。また、当該製品を１
ヵ月放置したところ、水との接触角は約５０°になっ
た。これに紫外線を照射しても水との接触角に変化はな
かった。(Comparative Example 3) A composition liquid was prepared by removing crystalline titania from Example 2 described above, applied to the surface of a heat insulating board, dried, and dried at room temperature for one day. As a result, the hydrophilicity of the surface of the heat insulating board was about 30 ° in terms of the contact angle with water. In addition, 1
After standing for months, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００２０】（実施例４）４０％コロイダルシリカ（ル
ドックスＨＳ４０：デユポン製）１０００ｇにアルミナ
粉末１４００ｇ、酸化亜鉛５ｇを添加して無機質塗料を
調製し、この無機質塗料を断熱ボード表面に塗布し、放
置して無機質塗料からなる塗膜を形成した。一方、４０
％コロイダルシリカ（ルドックスＨＳ４０：デユポン
製）７５ｇ、４５％スチレン・２−エチルヘキシルアク
リレート共重合エマルジョン（ポリトロンＡ−４５：旭
化成製）１５５ｇ、アナターゼ型チタニア、ルチル型チ
タニア及びブルカイト型チタニアの混合物を３０ｇを秤
量し、これらを水に分散させて光触媒性親水性組成物液
を調製した。この光触媒性親水性組成物液を断熱ボード
の表面に塗布し、室温で１日乾燥せしめて被膜を形成し
た後、紫外線を照射した。その結果、断熱ボードの表面
の親水性は水との接触角に換算して１０°以下になっ
た。Example 4 1400 g of alumina powder and 5 g of zinc oxide were added to 1000 g of 40% colloidal silica (Ludox HS40, manufactured by DuPont) to prepare an inorganic paint, and the inorganic paint was applied to the surface of a heat insulating board and allowed to stand. Thus, a coating film composed of an inorganic paint was formed. On the other hand, 40
% Colloidal silica (Rudox HS40: manufactured by DuPont), 75 g of 45% styrene / 2-ethylhexyl acrylate copolymer emulsion (Polytron A-45: manufactured by Asahi Kasei), 155 g, 30 g of a mixture of anatase-type titania, rutile-type titania and brookite-type titania They were weighed and dispersed in water to prepare a photocatalytic hydrophilic composition liquid. This photocatalytic hydrophilic composition solution was applied to the surface of a heat insulating board, dried at room temperature for one day to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the heat insulating board became 10 ° or less in terms of the contact angle with water.
【００２１】（比較例４）上記実施例４から結晶性チタ
ニアを除いた組成物液を調製し、これを断熱ボードの表
面に塗布し乾燥せしめた後、室温で１日かけて乾燥せし
めた。その結果、断熱ボードの表面の親水性は水との接
触角に換算して約３０°になった。また、当該製品を１
ヵ月放置したところ、水との接触角は約５０°になっ
た。これに紫外線を照射しても水との接触角に変化はな
かった。Comparative Example 4 A composition liquid was prepared by removing crystalline titania from Example 4 described above, applied to the surface of a heat insulating board, dried, and dried at room temperature for one day. As a result, the hydrophilicity of the surface of the heat insulating board was about 30 ° in terms of the contact angle with water. In addition, 1
After standing for months, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００２２】[0022]
【発明の効果】以上に説明した如く本発明によれば、光
触媒性金属酸化物粒子と、コロイダルシリカと、アクリ
ル系樹脂とを水に分散させて光触媒性親水性組成物を構
成したので、優れた表面光沢と強度が発揮されるだけで
なく、光触媒作用によって表面が親水性を呈するため、
汚れが付着しにくく、付着した場合でも雨水等によって
簡単に汚れが除去され、更に一旦形成された光触媒性親
水性被膜は高度に親水化した表面を長期に亘って維持で
き、しかも被膜の厚みを薄くできるので、白濁や発色な
どの問題も生じない。更に、水性組成物であるので、溶
剤臭がなく、取り扱い性にも優れる。As described above, according to the present invention, a photocatalytic hydrophilic composition is formed by dispersing photocatalytic metal oxide particles, colloidal silica, and an acrylic resin in water. Not only is the surface gloss and strength exhibited, but also the surface exhibits hydrophilicity due to photocatalysis,
Dirt is difficult to adhere, and even if it adheres, it is easily removed by rainwater etc., and once formed, the photocatalytic hydrophilic film can maintain a highly hydrophilic surface for a long period of time, and furthermore, the thickness of the film is reduced. Since it can be made thin, there is no problem such as cloudiness or coloring. Furthermore, since it is an aqueous composition, it has no solvent odor and is excellent in handleability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０４Ｂ 41/71 Ｃ０４Ｂ 41/71 Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｃ０９Ｋ 3/00 Ｃ０９Ｋ 3/00 Ｒ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C04B 41/71 C04B 41/71 C09D 5/00 C09D 5/00 C09K 3/00 C09K 3/00 R
Claims (3)
る組成物であって、この組成物は、光触媒性金属酸化物
粒子と、コロイダルシリカと、アクリル系樹脂とを水に
分散させてなることを特徴とする光触媒性親水性組成
物。1. A composition to be applied to the surface of a coating film made of an inorganic paint, wherein the composition is obtained by dispersing photocatalytic metal oxide particles, colloidal silica, and an acrylic resin in water. A photocatalytic hydrophilic composition, comprising:
において、前記光触媒性金属酸化物粒子の割合は０．０
１〜１０重量％であり、また前記コロイダルシリカとア
クリル系樹脂の固形分重量比は１０：９０〜８０：２０
であることを特徴とする光触媒性親水性組成物。2. The photocatalytic hydrophilic composition according to claim 1, wherein the ratio of the photocatalytic metal oxide particles is 0.0%.
The solid content ratio of the colloidal silica to the acrylic resin is 10:90 to 80:20.
A photocatalytic hydrophilic composition, characterized in that:
る無機質塗料を基材の表面に塗布して塗膜を形成し、次
いで、この塗膜の表面に、光触媒性金属酸化物粒子と、
コロイダルシリカと、アクリル系樹脂とを水に分散させ
てなる光触媒性親水性組成物を塗布することを特徴とす
る光触媒性親水性被膜の形成方法。3. An inorganic coating composed of an aqueous dispersion containing colloidal silica is applied to the surface of a substrate to form a coating film, and then, a photocatalytic metal oxide particle,
A method for forming a photocatalytic hydrophilic film, comprising applying a photocatalytic hydrophilic composition obtained by dispersing colloidal silica and an acrylic resin in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9307239A JPH11140433A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic aqueous composition and formation of photocatalytic aqueous coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9307239A JPH11140433A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic aqueous composition and formation of photocatalytic aqueous coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11140433A true JPH11140433A (en) | 1999-05-25 |
Family
ID=17966717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9307239A Pending JPH11140433A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic aqueous composition and formation of photocatalytic aqueous coat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11140433A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081394A (en) * | 1999-09-14 | 2001-03-27 | Titan Kogyo Kk | Primer composition and photocatalytic body |
| JP2002338375A (en) * | 2001-05-23 | 2002-11-27 | Touso Sangyo Kk | Surface strengthening material |
| KR100391062B1 (en) * | 2000-03-17 | 2003-09-17 | 가부시기가이샤 이낙스 | Structure having hydrophilic fine porous antifouling layer and coating solution for forming said antifouling layer, and method for manufacturing said structure |
| WO2003102091A1 (en) | 2002-05-30 | 2003-12-11 | Toto Ltd. | Photocatalytic coating material, photocatalytic composite material and process for producing the same, self-cleaning water-based coating compositions, and self-cleaning member |
| JP2004051644A (en) * | 2001-08-30 | 2004-02-19 | Toto Ltd | Photocatalytic coating agent, photocatalytic composite material and method for producing the same |
| EP1415713A1 (en) * | 2001-07-10 | 2004-05-06 | Yoshiyuki Nagae | Coating material, paint, and process for producing coating material |
| JP2004269898A (en) * | 2001-08-30 | 2004-09-30 | Toto Ltd | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent |
| JP2009067871A (en) * | 2007-09-12 | 2009-04-02 | Kansai Paint Co Ltd | Aqueous coating composition |
| JP2010005613A (en) * | 2008-05-26 | 2010-01-14 | Asahi Kasei Chemicals Corp | Complex, functional structure and coating agent |
| JP2012086104A (en) * | 2010-10-15 | 2012-05-10 | Asahi Kasei Chemicals Corp | Photocatalyst composition |
| CN102796407A (en) * | 2011-05-23 | 2012-11-28 | 河源海川科技有限公司 | Organic-inorganic hybrid photocatalytic coating and preparation method thereof |
| JP2013129818A (en) * | 2011-11-24 | 2013-07-04 | Hoei Sangyo Kk | Emulsion-type paint |
-
1997
- 1997-11-10 JP JP9307239A patent/JPH11140433A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081394A (en) * | 1999-09-14 | 2001-03-27 | Titan Kogyo Kk | Primer composition and photocatalytic body |
| KR100391062B1 (en) * | 2000-03-17 | 2003-09-17 | 가부시기가이샤 이낙스 | Structure having hydrophilic fine porous antifouling layer and coating solution for forming said antifouling layer, and method for manufacturing said structure |
| JP2002338375A (en) * | 2001-05-23 | 2002-11-27 | Touso Sangyo Kk | Surface strengthening material |
| JPWO2003006159A1 (en) * | 2001-07-10 | 2004-10-28 | 永江 良行 | Coating agent, paint and method for producing coating agent |
| EP1415713A4 (en) * | 2001-07-10 | 2006-02-01 | Yoshiyuki Nagae | Coating material, paint, and process for producing coating material |
| EP1415713A1 (en) * | 2001-07-10 | 2004-05-06 | Yoshiyuki Nagae | Coating material, paint, and process for producing coating material |
| JP2004051644A (en) * | 2001-08-30 | 2004-02-19 | Toto Ltd | Photocatalytic coating agent, photocatalytic composite material and method for producing the same |
| JP2004269898A (en) * | 2001-08-30 | 2004-09-30 | Toto Ltd | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent |
| WO2003102091A1 (en) | 2002-05-30 | 2003-12-11 | Toto Ltd. | Photocatalytic coating material, photocatalytic composite material and process for producing the same, self-cleaning water-based coating compositions, and self-cleaning member |
| US7572486B2 (en) | 2002-05-30 | 2009-08-11 | Toto Ltd. | Photocatalytic coating material, photocatalytic composite material and method for producing the same, and self-cleaning water-based coating composition and self-cleaning member |
| US8524325B2 (en) | 2002-05-30 | 2013-09-03 | Toto Ltd. | Method for producing photocatalytic coating material |
| JP2009067871A (en) * | 2007-09-12 | 2009-04-02 | Kansai Paint Co Ltd | Aqueous coating composition |
| JP2010005613A (en) * | 2008-05-26 | 2010-01-14 | Asahi Kasei Chemicals Corp | Complex, functional structure and coating agent |
| JP2012086104A (en) * | 2010-10-15 | 2012-05-10 | Asahi Kasei Chemicals Corp | Photocatalyst composition |
| CN102796407A (en) * | 2011-05-23 | 2012-11-28 | 河源海川科技有限公司 | Organic-inorganic hybrid photocatalytic coating and preparation method thereof |
| JP2013129818A (en) * | 2011-11-24 | 2013-07-04 | Hoei Sangyo Kk | Emulsion-type paint |
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