JPH11138011A - Photocatalytic hydrophilic composition - Google Patents
Photocatalytic hydrophilic compositionInfo
- Publication number
- JPH11138011A JPH11138011A JP9303959A JP30395997A JPH11138011A JP H11138011 A JPH11138011 A JP H11138011A JP 9303959 A JP9303959 A JP 9303959A JP 30395997 A JP30395997 A JP 30395997A JP H11138011 A JPH11138011 A JP H11138011A
- Authority
- JP
- Japan
- Prior art keywords
- water
- synthetic resin
- hydrophilic composition
- photocatalytic
- photocatalytic hydrophilic
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008119 colloidal silica Substances 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 64
- 229920003002 synthetic resin Polymers 0.000 abstract description 27
- 239000000057 synthetic resin Substances 0.000 abstract description 27
- 239000000243 solution Substances 0.000 abstract description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride 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
- 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
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (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】本発明は合成樹脂製品やガラ
ス製品等の物質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 substance such as a synthetic resin product or a glass product hydrophilic for a long period of time.
【０００２】[0002]
【従来の技術】ポリエチレン、ポリスチレン、ポリ塩化
ビニル、酢酸セルロース、ポリプロピレン等多くの合成
樹脂は表面エネルギーが比較的小さく、疎水性を呈す
る。このため、表面に結露や曇りが生じる。このため合
成樹脂表面にコロナ放電処理を行って親水性を付与する
物理的な手段も試みられているが、満足な親水性は得ら
れていない。2. Description of the Related Art Many synthetic resins such as polyethylene, polystyrene, polyvinyl chloride, cellulose acetate, and polypropylene have a relatively small surface energy and exhibit hydrophobicity. For this reason, dew condensation and fogging occur on the surface. For this reason, physical means for imparting hydrophilicity by performing corona discharge treatment on the surface of the synthetic resin has been attempted, but satisfactory hydrophilicity has not been obtained.
【０００３】そこで、一般的には界面活性剤に対し、シ
リカゾル、アルミナゾル或いは親水性ポリマーを１種以
上添加した水性液が提案されている。具体的には、特公
昭５０−１１３４８号公報、特公昭４９−３２６６８号
公報、特開昭５１−８１８７７号公報、特開昭５０−３
８３２号公報、特開昭５５−５６１７７号公報、特開昭
５４−２０９７９号公報等に記載されている。Therefore, an aqueous liquid in which one or more silica sol, alumina sol or hydrophilic polymer is added to a surfactant is generally proposed. Specifically, Japanese Patent Publication No. 50-11348, Japanese Patent Publication No. 49-32668, Japanese Patent Application Laid-Open No. 51-81877, Japanese Patent Application
No. 832, JP-A-55-56177, JP-A-54-20979 and the like.
【０００４】上述したように従来の親水性水性液には界
面活性剤が必ず添加されている。界面活性剤を添加する
ことで親水性水性液の表面張力が下がるので樹脂製品の
表面に塗布した場合に弾かれにくくなる。しかしなが
ら、界面活性剤が添加された親水性水性液にて形成され
た膜は、水と接触した場合には親水性を呈するが、水蒸
気と接した場合には小さな水滴を形成してしまう。[0004] As described above, a surfactant is always added to a conventional hydrophilic aqueous liquid. The addition of the surfactant lowers the surface tension of the hydrophilic aqueous liquid, so that it is less likely to be repelled when applied to the surface of a resin product. However, a film formed of a hydrophilic aqueous liquid to which a surfactant is added exhibits hydrophilicity when contacted with water, but forms small water droplets when contacted with water vapor.
【０００５】このため、特公平１−２１１７２号公報
に、界面活性剤を実質的に含まない水性液が提案されて
いる。この水性液はコロイダルシリカを０．０５〜２０
重量％、水溶性アルミニウム塩を１００ｍｌ当り０．０
００１〜０．１モル含み、その表面張力を３５〜７５ダ
インとしたものであり、この水性液を樹脂製品に塗布す
ることで、短時間のうちに樹脂製品表面に親水性に優れ
たシリカ粒子を沈着せしめるようにしたものである。[0005] For this reason, Japanese Patent Publication No. 1-21722 proposes an aqueous liquid substantially free of a surfactant. The aqueous liquid contains 0.05 to 20 colloidal silica.
% By weight of water-soluble aluminum salt per 100 ml.
001-0.1 mol, the surface tension of which is 35-75 dynes. By applying this aqueous liquid to the resin product, the silica particles having excellent hydrophilicity on the surface of the resin product in a short time. Is to be deposited.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、特公平
１−２１１７２号公報の提案に係る組成物では、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１０
°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、合成樹脂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。However, in the composition disclosed in Japanese Patent Publication No. 1-21722, first, the degree of hydrophilicity is at most 10 in terms of the contact angle with water.
°, and sufficient hydrophilicity cannot be exhibited. 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 the synthetic resin, it is difficult to maintain the hydrophilicity for a long time. Once the hydrophilicity is lost, unless it is applied again, Hydrophilicity is not restored.
【０００７】[0007]
【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、光触媒性金属酸化
物粒子と、コロイダルシリカと、水溶性アルミニウム塩
とを水に分散させて構成される。Means for Solving the Problems To solve the above problems, a photocatalytic hydrophilic composition according to the present invention is obtained by dispersing photocatalytic metal oxide particles, colloidal silica, and a water-soluble aluminum salt in water. Be composed.
【０００８】ここで、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。Here, 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, tungsten trioxide,
And strontium titanate.
【０００９】前記コロイダルシリカとしては、市販のも
のを使用する。例えば、日産化学社製のスノーテックス
４０、スノーテックスＯ、スノーテックスＣ、触媒化成
工業社製カタロイドＳＨ−３０等が挙げられる。A commercially available colloidal silica is used. Examples include Snowtex 40, Snowtex O and Snowtex C manufactured by Nissan Chemical Co., Ltd., and Cataloid SH-30 manufactured by Catalysis Kasei Kogyo.
【００１０】水溶性アルミニウム塩としては、例えば、
硫酸アルミニウム、硝酸アルミニウム、塩化アルミニウ
ム、各種明ばん、酢酸アルミニウム等が挙げられる。As the water-soluble aluminum salt, for example,
Examples thereof include aluminum sulfate, aluminum nitrate, aluminum chloride, various alums, and aluminum acetate.
【００１１】また、前記光触媒性金属酸化物粒子の割合
は０．０１〜１０重量％、前記コロイダルシリカの割合
は０．０５〜２０重量％、前記水溶性アルミニウム塩の
割合は１００ｍｌ当り０．０００２〜０．１モルとする
のが好ましい。The ratio of the photocatalytic metal oxide particles is 0.01 to 10% by weight, the ratio of the colloidal silica is 0.05 to 20% by weight, and the ratio of the water-soluble aluminum salt is 0.0002 per 100 ml. It is preferable to set it to 0.1 mol.
【００１２】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
ダルシリカの割合が上記範囲よりも少ないと、樹脂製品
等の表面にコロイダルシリカを有効に沈着せしめること
ができず、上記範囲以上にすると処理後の製品表面の平
滑性が損われる。また、水溶性アルミニウム塩の割合が
上記範囲よりも少ないと、コロイダルシリカの沈着速度
が遅くなり、上記範囲以上にすると処理後の製品表面が
ザラつく。When the proportion of the photocatalytic metal oxide particles is less than the above range, the hydrophilicity of the photocatalyst becomes insufficient. 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 . On the other hand, if the proportion of colloidal silica is less than the above range, colloidal silica cannot be effectively deposited on the surface of a resin product or the like, and if it exceeds the above range, the smoothness of the product surface after treatment is impaired. On the other hand, if the proportion of the water-soluble aluminum salt is less than the above range, the deposition rate of the colloidal silica will be slow, and if it is more than the above range, the product surface after treatment will be rough.
【００１３】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.
【００１４】このように、本発明による親水性は、コロ
イダルシリカと水溶性アルミニウム塩を含む水性液に由
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、コロイダルシリ
カと水溶性アルミニウム塩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０．４
μｍ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。Thus, it is considered that the hydrophilicity according to the present invention is due to the hydrophilizing action of the photocatalyst, rather than to the aqueous solution containing colloidal silica and the water-soluble aluminum salt. This means that in order to exhibit hydrophilicity with an aqueous liquid containing colloidal silica and colloidal silica and a water-soluble aluminum salt, it had to be applied with a thickness of several tens of μm or more. 0.4
It can be confirmed from the fact that the particles exhibit hydrophilicity even at μm or less.
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.
【００１５】[0015]
【発明の実施の形態】（実施例１）シリカゾル（日産化
学社製：スノーテックス４０）を１重量％、ＡlＣl3・6
Ｈ2Ｏを水性液１００ｍｌ当り０．０００２モル、アナ
ターゼ型チタニアを１０重量％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）に合成樹脂製品を浸漬して塗布し、次いで乾
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、合成樹脂製品の表面の親水性は水との接触角に換
算してほぼ０°になった。また暗所にしばらく放置した
後、再び紫外線を照射すると水との接触角が０°に戻っ
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS (Example 1) silica sol (manufactured by Nissan Chemical Industries, Ltd. Snowtex 40) 1 wt%, AlCl 3 · 6
0.0002 mol of H 2 O and 100% by weight of anatase titania were weighed per 100 ml of the aqueous liquid, and these were 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. A synthetic resin product was immersed and applied to these photocatalytic hydrophilic composition liquids (A to C) and then dried to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the synthetic resin product was almost 0 ° in terms of the contact angle with water. Further, after being left in a dark place for a while, irradiation with ultraviolet light again returned the contact angle with water to 0 °.
【００１６】（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、この組成物液に合成樹
脂製品を浸漬して塗布した後に乾燥せしめて被膜を形成
した。その結果、合成樹脂製品の表面の親水性は水との
接触角に換算して約１０°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 solution was prepared by removing crystalline titania from Example 1 above, and a synthetic resin product was immersed in the composition solution, applied, and then dried to form a film. As a result, the hydrophilicity of the surface of the synthetic resin product was about 10 ° in terms of the contact angle with water. When the product was left for one month, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００１７】（実施例２）シリカゾル（日産化学社製：
スノーテックス４０）を２重量％、Ａl2（ＳＯ4）3を水
性液１００ｍｌ当り０．０２モル、アナターゼ型チタニ
アを１重量％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）は表面
張力が５３ダインと大きいため、スプレー塗布せずに合
成樹脂製品を上記組成物液中に浸漬して塗布し、次いで
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、合成樹脂製品の表面の親水性は水との接触角に
換算してほぼ０°になった。また暗所にしばらく放置し
た後、再び紫外線を照射すると水との接触角が０°に戻
った。(Example 2) Silica sol (manufactured by Nissan Chemical Industries, Ltd .:
2% by weight of Snowtex 40), 0.02 mol of Al 2 (SO 4 ) 3 per 100 ml of aqueous liquid and 1% by weight of anatase type titania were weighed, and these were dispersed in water to prepare a photocatalytic hydrophilic composition solution. (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. Since these photocatalytic hydrophilic composition liquids (A to C) have a large surface tension of 53 dynes, the synthetic resin product is dipped and applied in the above composition liquid without spray coating, and then dried to form a film. After formation, ultraviolet light was applied. As a result, the hydrophilicity of the surface of the synthetic resin product was almost 0 ° in terms of the contact angle with water. Further, after being left in a dark place for a while, irradiation with ultraviolet light again returned the contact angle with water to 0 °.
【００１８】（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、この組成物液に合成樹
脂製品を浸漬して塗布した後に乾燥せしめて被膜を形成
した。その結果、合成樹脂製品の表面の親水性は水との
接触角に換算して約１０°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 solution was prepared by removing crystalline titania from Example 2, and a synthetic resin product was immersed in the composition solution, applied, and then dried to form a film. As a result, the hydrophilicity of the surface of the synthetic resin product was about 10 ° in terms of the contact angle with water. When the product was left for one month, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００１９】（実施例３）シリカゾル（日産化学社製：
スノーテックス４０）を５重量％、Ａl（ＮＯ2）3・9Ｈ2
Ｏを水性液１００ｍｌ当り０．０５モル、アナターゼ型
チタニアを０．１重量％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）は表面張力が５０ダインと大きいため、スプレー
塗布せずに合成樹脂製品を上記組成物液中に浸漬して塗
布し、次いで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、合成樹脂製品の表面の親水性は水
との接触角に換算してほぼ０°になった。また暗所にし
ばらく放置した後、再び紫外線を照射すると水との接触
角が０°に戻った。(Example 3) Silica sol (manufactured by Nissan Chemical Industries, Ltd .:
Snowtex 40) and 5 wt%, Al (NO 2) 3 · 9H 2
O was weighed at 0.05 mol per 100 ml of aqueous liquid, and 0.1% by weight of anatase titania, and these were 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
In Examples C to C, since the surface tension was as large as 50 dynes, the synthetic resin product was immersed and applied in the above-mentioned composition solution without spray coating, then dried to form a film, and then irradiated with ultraviolet rays. As a result, the hydrophilicity of the surface of the synthetic resin product was almost 0 ° in terms of the contact angle with water. Further, after being left in a dark place for a while, irradiation with ultraviolet light again returned the contact angle with water to 0 °.
【００２０】（比較例３）上記実施例３から結晶性チタ
ニアを除いた組成物液を調製し、この組成物液に合成樹
脂製品を浸漬して塗布した後に乾燥せしめて被膜を形成
した。その結果、合成樹脂製品の表面の親水性は水との
接触角に換算して約１０°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 solution was prepared by removing crystalline titania from Example 3 above, a synthetic resin product was immersed in the composition solution, applied, and then dried to form a film. As a result, the hydrophilicity of the surface of the synthetic resin product was about 10 ° in terms of the contact angle with water. When the product was left for one month, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００２１】（実施例４）シリカゾル（日産化学社製：
スノーテックス４０）を１重量％、Ａl2（ＣＨ3ＣＯ
Ｏ）4・4Ｈ2Ｏを水性液１００ｍｌ当り０．０２モル、ア
ナターゼ型チタニアを０．０１重量％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）は表面張力が５０ダインと大きい
ため、スプレー塗布せずに合成樹脂製品を上記組成物液
中に浸漬して塗布し、次いで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、合成樹脂製品の表
面の親水性は水との接触角に換算してほぼ０°になっ
た。また暗所にしばらく放置した後、再び紫外線を照射
すると水との接触角が０°に戻った。Example 4 Silica Sol (Nissan Chemical:
1% by weight of Snowtex 40), Al 2 (CH 3 CO
O) 4 · 4H the 2 O 0.02 moles per aqueous solution 100 ml, the anatase form of titania was weighed 0.01 wt%, these were prepared by dispersing in water photocatalytic hydrophilic composition solution (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. Since these photocatalytic hydrophilic composition liquids (A to C) have a large surface tension of 50 dynes, the synthetic resin product is immersed and applied in the above composition liquid without spray coating, and then dried to form a film. After formation, ultraviolet light was applied. As a result, the hydrophilicity of the surface of the synthetic resin product was almost 0 ° in terms of the contact angle with water. Further, after being left in a dark place for a while, irradiation with ultraviolet light again returned the contact angle with water to 0 °.
【００２２】（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、この組成物液に合成樹
脂製品を浸漬して塗布した後に乾燥せしめて被膜を形成
した。その結果、合成樹脂製品の表面の親水性は水との
接触角に換算して約１０°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 solution was prepared by removing crystalline titania from Example 4 above, a synthetic resin product was immersed in the composition solution, applied, and then dried to form a film. As a result, the hydrophilicity of the surface of the synthetic resin product was about 10 ° in terms of the contact angle with water. When the product was left for one month, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００２３】（実施例５）シリカゾル（日産化学社製：
スノーテックス４０）を１重量％、Ａl2（ＣＨ3ＣＯ
Ｏ）4・4Ｈ2Ｏを水性液１００ｍｌ当り０．０２モル、ア
ナターゼ型チタニアとルチル型チタニアとブルカイト型
チタニアの混合物１０重量％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。これら光触
媒性親水性組成物液は表面張力が７０ダインと大きいた
め、スプレー塗布せずに合成樹脂製品を上記組成物液中
に浸漬して塗布し、次いで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、合成樹脂製品の表面
の親水性は水との接触角に換算してほぼ０°になった。
また暗所にしばらく放置した後、再び紫外線を照射する
と水との接触角が０°に戻った。(Example 5) Silica sol (manufactured by Nissan Chemical Industries, Ltd .:
1% by weight of Snowtex 40), Al 2 (CH 3 CO
O) 4 · 4H 2 O aqueous solution 100ml per 0.02 mole, mixture weighed 10 weight% of anatase type titania and rutile type titania and brookite type titania, these are dispersed in water photocatalytic hydrophilic composition solution Was prepared. Since these photocatalytic hydrophilic composition liquids have a large surface tension of 70 dynes, the synthetic resin product is immersed and applied in the above composition liquid without spray coating, and then dried to form a coating, Was irradiated. As a result, the hydrophilicity of the surface of the synthetic resin product was almost 0 ° in terms of the contact angle with water.
Further, after being left in a dark place for a while, irradiation with ultraviolet light again returned the contact angle with water to 0 °.
【００２４】（比較例５）上記実施例５から結晶性チタ
ニアを除いた組成物液を調製し、この組成物液に合成樹
脂製品を浸漬して塗布した後に乾燥せしめて被膜を形成
した。その結果、合成樹脂製品の表面の親水性は水との
接触角に換算して約１０°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 5 A composition solution was prepared by removing crystalline titania from Example 5 described above. A synthetic resin product was immersed in the composition solution, applied, and then dried to form a film. As a result, the hydrophilicity of the surface of the synthetic resin product was about 10 ° in terms of the contact angle with water. When the product was left for one month, the contact angle with water became about 50 °. Irradiation with ultraviolet light did not change the contact angle with water.
【００２５】[0025]
【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、水溶性
アルミニウム塩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、短時間のうちに、合成樹脂製品等の
被塗装物表面に光触媒性金属酸化物粒子とコロイダルシ
リカを沈着して、均一且つ薄い光触媒性親水性被膜を形
成することができ、また、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 constituted by dispersing photocatalytic metal oxide particles, colloidal silica, and a water-soluble aluminum salt in water. Within a short time, photocatalytic metal oxide particles and colloidal silica can be deposited on the surface of an object to be coated such as a synthetic resin product, and a uniform and thin photocatalytic hydrophilic coating can be formed. The photocatalytic hydrophilic coating can maintain a highly hydrophilic surface for a long period of time and can reduce the thickness of the coating, so that 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.
Claims (2)
シリカと、水溶性アルミニウム塩とを水に分散させてな
る光触媒性親水性組成物。1. A photocatalytic hydrophilic composition obtained by dispersing photocatalytic metal oxide particles, colloidal silica, and a water-soluble aluminum salt in water.
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％、前記コロイダルシリカの割合は０．０
５〜２０重量％、前記水溶性アルミニウム塩の割合は１
００ｍｌ当り０．０００２〜０．１モルであることを特
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%.
1 to 10% by weight, and the ratio of the colloidal silica is 0.0
5 to 20% by weight, the ratio of the water-soluble aluminum salt is 1
A photocatalytic hydrophilic composition, wherein the amount is 0.0002 to 0.1 mol per 00 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9303959A JPH11138011A (en) | 1997-11-06 | 1997-11-06 | Photocatalytic hydrophilic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9303959A JPH11138011A (en) | 1997-11-06 | 1997-11-06 | Photocatalytic hydrophilic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11138011A true JPH11138011A (en) | 1999-05-25 |
Family
ID=17927338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9303959A Pending JPH11138011A (en) | 1997-11-06 | 1997-11-06 | Photocatalytic hydrophilic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11138011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235511B2 (en) | 2003-09-30 | 2007-06-26 | Tokyo Roki Co., Ltd. | Exhaust gas purifying catalyst |
-
1997
- 1997-11-06 JP JP9303959A patent/JPH11138011A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235511B2 (en) | 2003-09-30 | 2007-06-26 | Tokyo Roki Co., Ltd. | Exhaust gas purifying catalyst |
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