JPH11140432A - Photocatalytic hydrophilic composition - Google Patents
Photocatalytic hydrophilic compositionInfo
- Publication number
- JPH11140432A JPH11140432A JP9307128A JP30712897A JPH11140432A JP H11140432 A JPH11140432 A JP H11140432A JP 9307128 A JP9307128 A JP 9307128A JP 30712897 A JP30712897 A JP 30712897A JP H11140432 A JPH11140432 A JP H11140432A
- Authority
- JP
- Japan
- Prior art keywords
- water
- photocatalytic
- weight
- surfactant
- 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 66
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 32
- 239000000057 synthetic resin Substances 0.000 claims abstract description 32
- 239000008119 colloidal silica Substances 0.000 claims abstract description 23
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-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
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000002563 ionic surfactant Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 66
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 26
- 239000010410 layer Substances 0.000 description 21
- 239000011941 photocatalyst Substances 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000011734 sodium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 102220559234 Voltage-dependent L-type calcium channel subunit alpha-1C_S30H_mutation Human genes 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000463 material Substances 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic 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
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (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
物理的な手段の試みもなされているが、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、一般的には以下のような手段にて
親水性を発揮するようにしている。 (1)熱可塑性合成樹脂材料で成形品を製造するにあた
り、界面活性剤のような親水性物質を練り込んでおく方
法。しかしながら、この方法では、親水性物質が水によ
って流されてしまい、短期間のうちに防曇性がなくなっ
てしまう。 (2)ポリビニルアルコール等の水溶性親水性物質を製品
表面に塗布する方法（特公昭４６−１３２５２号公
報）。アクリル酸ヒドロキシアルキルエステルを主成分
とする親水性ポリマーと界面活性剤とからなる組成物を
製品表面に塗布する方法（特公昭５０−６４３７号公
報）。しかしながら、これらの方法では、親水性物質が
加水分解を受けやすく耐水性に劣るため、充分な防曇効
果を発揮し得ない。 (3)ヒドロキシ基を有する親水性アクリル酸エステル系
重合体を架橋剤にて水不溶化する方法（特公昭５６−３
４２１９号公報）。しかしながら、この方法では、防曇
性自体が低下してしまう。 (4)アルミナゾルに界面活性剤を加えた組成物を成形品
表面に塗布する（特公昭４９−３２６６８号公報）。し
かしながら、この組成物は保存安定性に欠けるという欠
点がある。[0003] Therefore, in general, hydrophilicity is exerted by the following means. (1) A method in which a hydrophilic substance such as a surfactant is kneaded in producing a molded article from a thermoplastic synthetic resin material. However, in this method, the hydrophilic substance is washed away by the water, and the antifogging property is lost in a short time. (2) A method of applying a water-soluble hydrophilic substance such as polyvinyl alcohol to the product surface (Japanese Patent Publication No. 46-13252). A method comprising applying a composition comprising a hydrophilic polymer mainly composed of hydroxyalkyl acrylate and a surfactant to the product surface (Japanese Patent Publication No. 50-6437). However, in these methods, the hydrophilic substance is easily hydrolyzed and has poor water resistance, so that a sufficient antifogging effect cannot be exhibited. (3) A method of insolubilizing a hydrophilic acrylic acid ester-based polymer having a hydroxy group with a cross-linking agent (Japanese Patent Publication No. Sho 56-3)
No. 4219). However, in this method, the antifogging property itself is reduced. (4) A composition obtained by adding a surfactant to an alumina sol is applied to the surface of a molded article (Japanese Patent Publication No. 49-32668). However, this composition has the disadvantage of lacking storage stability.
【０００４】[0004]
【発明が解決しようとする課題】上述した従来技術の不
具合を改善するため、特公昭６３−４５４３２号公報
に、合成樹脂成形物やガラス等の表面の防曇剤として、
１価の陽イオンで安定化されたコロイダルシリカと、非
イオン性界面活性剤及び／又はアニオン性界面活性剤と
を含有する安定な水性分散液が提案されている。In order to improve the disadvantages of the prior art described above, Japanese Patent Publication No. 45432/1988 discloses an antifogging agent for the surface of synthetic resin molded articles, glass, etc.
Stable aqueous dispersions containing monovalent cation stabilized colloidal silica and nonionic and / or anionic surfactants have been proposed.
【０００５】しかしながら、こ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 according to this proposal, first, the degree of hydrophilicity is not more than about 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.
【０００６】[0006]
【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、合成樹脂等の表面
に親水性を付与する組成物であって、光触媒性金属酸化
物粒子と、１価の陽イオンで安定化されたコロイダルシ
リカと、非イオン性界面活性剤及び／又はアニオン性界
面活性剤とを水に分散させて構成される。Means for Solving the Problems In order to solve the above problems, a photocatalytic hydrophilic composition according to the present invention is a composition for imparting hydrophilicity to the surface of a synthetic resin or the like, and comprises a photocatalytic metal oxide particle. And colloidal silica stabilized with a monovalent cation, and a nonionic surfactant and / or an anionic surfactant dispersed in water.
【０００７】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, as the photocatalytic metal oxide particles, 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.
【０００８】本発明の表面処理剤を構成するコロイダル
シリカとしては、粒子径が１００μｍ以下、好ましくは
１０μｍ程度のもので、ナトリウムやアンモニウム等の
１価の陽イオンで安定化したものであり、例えば、スノ
ーテックス（日産化学製）、ルドックス（デュポン社
製）、カタロイド（触媒化成製）が挙げられる。The colloidal silica constituting the surface treatment agent of the present invention has a particle diameter of 100 μm or less, preferably about 10 μm, and is stabilized with a monovalent cation such as sodium or ammonium. , Snowtex (manufactured by Nissan Chemical), Ludox (manufactured by DuPont), and cataloid (manufactured by Catalysis Kasei).
【０００９】また、非イオン性界面活性剤としては、以
下に挙げるものを用いることができる。 （エーテル型）ポリオキシアルキレンアルキルフェニル
エーテル、ポリオキシアルキレンアルキルエーテルが挙
げられ、アルキルフェニル基またはアルキル基は炭素数
８〜２２のものが好ましい。また更されるアルキレンオ
キサイドは炭素数２〜４のもの、またその付加モル数は
２〜３０が好ましい。アルキレンオキサイドの付加は、
１種類の単独付加であってもよく、更に混合付加の場合
には、付加形態がブロック付加でもランダム付加でもよ
い。 （エステル型）ポリオキシアルキレンアルキルエステ
ル、ポリアルキレングリコールアルキルエステル、及び
ポリオキシアルキレン多価アルコールエステル挙げら
れ、この場合の付加モル数等は前記エーテル型と同様で
ある。また、アルキレングリコールは炭素数２〜４のも
ので、それぞれ１種類単独でも２種以上の混合でもよ
く、更に混合の場合には、ブロックでもランダムでもよ
い。また、多価アルコールとしては、グリセリン、ソル
ビトール、ペンタエリスリトール及びトリメチロールプ
ロパン等がある。 （ポリアルキレングリコール）前記エーテル型の非イオ
ン性界面活性剤の項で述べたアルキレンオキサイドの付
加重合物で、その付加モル数は２〜５００である。 （フッ素系非イオン性界面活性剤）フロロアルキル基含
有アルキレンオキサイド付加物、例えば、パーフロロア
ルキルエチレンオキサイド付加物等が挙げられる。フッ
素系非イオン性界面活性剤は、純分０．０１％水溶液で
の表面張力が６０ダイン／ｃｍ以下のもの、特に３０ダ
イン／ｃｍ以下のものが好ましい。表面張力が大きすぎ
るものは被塗布物表面の濡れ性を低下させるので好まし
くない。フッ素系非イオン性界面活性剤としては、ＨＬ
Ｂ値が５〜１５のものが望ましい。具体的には、ポリオ
キシエチレン（５モル）ノニルフェニルエーテル、ポリ
オキシエチレン（１０モル）ノニルフェニルエーテル、
ポリオキシエチレン（４モル）ラウリルエーテル、ポリ
オキシエチレン（１０モル）ラウリルエーテル、ポリオ
キシエチレン（４モル）ラウリルアミン等が挙げられ
る。 （シリコン系非イオン性界面活性剤）オルガノポリシロ
キサンを含む界面活性剤、例えばオルガノポリシロキサ
ンのアルキレンオキサイド付加物等が使用できる。The following nonionic surfactants can be used. (Ether type) polyoxyalkylene alkylphenyl ether and polyoxyalkylene alkyl ether are exemplified, and the alkylphenyl group or the alkyl group preferably has 8 to 22 carbon atoms. The alkylene oxide further has 2 to 4 carbon atoms, and the number of moles added is preferably 2 to 30. The addition of the alkylene oxide is
One type of single addition may be used, and in the case of mixed addition, the addition form may be block addition or random addition. (Ester type) Polyoxyalkylene alkyl ester, polyalkylene glycol alkyl ester, and polyoxyalkylene polyhydric alcohol ester are exemplified, and the number of moles added in this case is the same as that of the ether type. The alkylene glycol has 2 to 4 carbon atoms, and each may be a single type or a mixture of two or more types. In the case of a mixture, the alkylene glycol may be block or random. Examples of the polyhydric alcohol include glycerin, sorbitol, pentaerythritol and trimethylolpropane. (Polyalkylene glycol) An alkylene oxide addition polymer described in the section of the ether type nonionic surfactant, and the number of moles of the addition polymer is 2 to 500. (Fluorine nonionic surfactant) Fluoroalkyl group-containing alkylene oxide adducts, such as perfluoroalkyl ethylene oxide adducts. The fluorine-based nonionic surfactant preferably has a surface tension of 60 dynes / cm or less, particularly preferably 30 dynes / cm or less in a 0.01% aqueous solution of a pure component. If the surface tension is too high, the wettability of the surface of the object to be coated is reduced, so that it is not preferable. HL non-ionic surfactants include HL
Those having a B value of 5 to 15 are desirable. Specifically, polyoxyethylene (5 mol) nonyl phenyl ether, polyoxyethylene (10 mol) nonyl phenyl ether,
Examples thereof include polyoxyethylene (4 mol) lauryl ether, polyoxyethylene (10 mol) lauryl ether, and polyoxyethylene (4 mol) laurylamine. (Silicon Nonionic Surfactant) A surfactant containing an organopolysiloxane, for example, an alkylene oxide adduct of an organopolysiloxane can be used.
【００１０】また、アニオン性界面活性剤としては、以
下に挙げるものを用いることができる。 （硝酸エステル型界面活性剤）各種高級アルコール硝酸
エステル、各種の液体脂肪酸の硝酸エステルが挙げられ
る。 （スルホン酸塩型界面活性剤）各種のアルキルアリルス
ルホン酸塩、各種の脂肪族アマイドの硫酸塩等が挙げら
れる。 （リン酸エステル型界面活性剤）各種の脂肪族アルコー
ルのリン酸エステルが挙げられる。 （フッ素系アニオン性界面活性剤）フロロアルキル基含
有カルボン酸、同カルボン酸塩、フロロアルキル基含有
リン酸エステル等がある。例えば、パーフロロアルキル
カルボン酸、パーフロロアルキルカルボン酸塩及びパー
フロロアルキルリン酸エステルが挙げられる。フッ素系
アニオン性界面活性剤もフッ素系非イオン性界面活性剤
と同様に、純分０．０１％水溶液での表面張力が６０ダ
イン／ｃｍ以下のもの、特に３０ダイン／ｃｍ以下のも
のが好ましい。 （シリコン系アニオン性界面活性剤）オルガノポリシロ
キサン含有カルボン酸及びその塩が挙げられる。As the anionic surfactant, the following ones can be used. (Nitrate ester type surfactant) Examples include nitrates of various higher alcohols and nitrates of various liquid fatty acids. (Sulfonate type surfactant) Various alkyl allyl sulfonates, various aliphatic amide sulfates and the like can be mentioned. (Phosphate ester type surfactant) Phosphate esters of various aliphatic alcohols may be mentioned. (Fluorine-based anionic surfactant) Examples include fluoroalkyl group-containing carboxylic acids, carboxylic acid salts thereof, and fluoroalkyl group-containing phosphate esters. For example, perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylate, and perfluoroalkyl phosphate are mentioned. Like the fluorine-based nonionic surfactant, the fluorine-based anionic surfactant also preferably has a surface tension of 60 dyne / cm or less, particularly preferably 30 dyne / cm or less in a 0.01% pure aqueous solution. . (Silicon-based anionic surfactant) Organopolysiloxane-containing carboxylic acids and salts thereof.
【００１１】また、光触媒性金属酸化物粒子の割合は
０．０１〜１０重量％とするのが好ましい。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／ｃ
ｍ2である。The proportion of the photocatalytic metal oxide particles is preferably 0.01 to 10% by weight. When the proportion of the photocatalytic metal oxide particles is less than the above range, the hydrophilic action by the photocatalyst becomes insufficient, and even if added above the above range, the effect is not improved by the addition, but rather the bonding strength of the coating is reduced. become. 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
cm 2 , more preferably 1 × 10 −6 to 1 × 10 −4 g / c
m 2 .
【００１２】コロイダルシリカと界面活性剤の合計量に
対するコロイダルシリカの割合については、塗布面のベ
トつきを回避すべく４０重量％以上とすることが好まし
い。また、コロイダルシリカと界面活性剤の割合として
は、コロイダルシリカを７５〜９０重量％、界面活性剤
を２５〜１０重量％にするのが適当であり、更に、これ
ら光触媒性金属酸化物粒子、コロイダルシリカ及び界面
活性剤の水性液中での濃度は０．１〜５０重量％とする
のが均一な塗布膜を形成する上で好ましい。The ratio of the colloidal silica to the total amount of the colloidal silica and the surfactant is preferably at least 40% by weight in order to avoid stickiness of the coated surface. The ratio of the colloidal silica to the surfactant is suitably from 75 to 90% by weight of the colloidal silica and from 25 to 10% by weight of the surfactant. The concentration of silica and surfactant in the aqueous liquid is preferably 0.1 to 50% by weight in order to form a uniform coating film.
【００１３】また、界面活性剤としてエーテル型非イオ
ン性界面活性剤を用いる場合には、ＨＬＢ（親水性親油
性化指数：Hydrophile-Lipophile-Balance）が５〜１５
の界面活性剤が好ましい。When an ether type nonionic surfactant is used as the surfactant, the HLB (Hydrophilic-Lipophile-Balance) is 5 to 15.
Surfactants are preferred.
【００１４】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。Incidentally, 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.
【００１５】このように、本発明による親水性は、１価
の陽イオンで安定化されたコロイダルシリカと、非イオ
ン性界面活性剤及び／又はアニオン性界面活性剤とを含
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、１価の陽イオンで安定
化されたコロイダルシリカと、非イオン性界面活性剤及
び／又はアニオン性界面活性剤と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０．２
μｍ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 derived from an aqueous liquid containing colloidal silica stabilized with a monovalent cation and a nonionic surfactant and / or an anionic surfactant. Rather, it is thought to be due to the hydrophilizing action of the photocatalyst. This means that a thickness of several tens μm or more is required to exhibit hydrophilicity with an aqueous liquid containing colloidal silica stabilized with a monovalent cation and a nonionic surfactant and / or an anionic surfactant. However, in the case of the composition according to the present invention, it can be confirmed that the composition exhibits hydrophilicity even at 0.4 μm or less. Here, by setting the thickness to 0.4 μm or less, cloudiness due to irregular reflection of light can be prevented.
By setting the thickness to not more than μm, it is possible to prevent coloring of the surface phase due to light interference.
【００１６】[0016]
【発明の実施の形態】（実施例１）Ｎaで安定化せしめ
たコロイダルシリカ（デュポン社製：ルドックスＡＭ）
を８６重量部、フッ素系非イオン性界面活性剤（住友ス
リーエム社製：ＦＣ−１７６）を８重量部、フッ素系ア
ニオン性界面活性剤（住友スリーエム社製：ＦＣ−１２
８）を８重量部、アナターゼ型チタニアを１０重量％混
合し、更にこの混合液を３０重量％となるように水に混
合し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）を合成樹脂製品の表面にスポンジ拭きにより
塗布した後、２０℃で２０分乾燥させることにより、光
触媒層を硬化させて試料を得た。上記試料について、光
触媒層形成後、３時間太陽光に晒すことにより、紫外線
が照射されるようにした後、水を噴霧したところ、水滴
が形成されず、水が一様に広がる様子が観察された。ま
た、暗所に放置した後、再び紫外線を照射すると、水が
一様に広がる状態に戻った。(Example 1) Colloidal silica stabilized by Na (DuPont: Ludox AM)
86 parts by weight, 8 parts by weight of a fluorine-based nonionic surfactant (manufactured by Sumitomo 3M Ltd .: FC-176), and 8 parts by weight of a fluorine-based anionic surfactant (manufactured by Sumitomo 3M Limited: FC-12)
8) and 10% by weight of anatase titania were mixed with 8 parts by weight of 8), and this mixed solution was further mixed with water so as to be 30% by weight 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of the synthetic resin product by wiping with a sponge, the photocatalytic layer was cured by drying at 20 ° C. for 20 minutes to obtain a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being irradiated with ultraviolet light, and then sprayed with water. As a result, it was observed that no water droplets were formed and the water spread evenly. Was. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００１７】（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、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 liquid was prepared by removing crystalline titania from Example 1 above, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００１８】（実施例２）Ｎaで安定化せしめたコロイ
ダルシリカ（デュポン社製：ルドックスＳＭ−３０）を
８６重量部、フッ素系非イオン性界面活性剤としてポリ
オキシエチレン（１０モル）ノニルフェニルエーテル
（ＨＬＢ：１３．３）を８重量部、フッ素系アニオン性
界面活性剤（旭硝子社製：サーフロンＳ−１１１）を８
重量部、アナターゼ型チタニアを１重量％混合し、更に
この混合液を３０重量％となるように水に混合して光触
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
合成樹脂製品の表面にスポンジ拭きにより塗布した後、
２０℃で２０分乾燥させることにより、光触媒層を硬化
させて試料を得た。上記試料について、光触媒層形成
後、３時間太陽光に晒すことにより、紫外線が照射され
るようにした後、水を噴霧したところ、水滴が形成され
ず、水が一様に広がる様子が観察された。また、暗所に
放置した後、再び紫外線を照射すると、水が一様に広が
る状態に戻った。Example 2 86 parts by weight of colloidal silica stabilized by Na (Ludox SM-30 manufactured by DuPont), and polyoxyethylene (10 mol) nonylphenyl ether as a fluorine-based nonionic surfactant (HLB: 13.3) in an amount of 8 parts by weight, and a fluorine-based anionic surfactant (Surflon S-111 manufactured by Asahi Glass Co., Ltd.) in an amount of 8 parts by weight.
1 part by weight of anatase titania and 1 part by weight of anatase type titania were further mixed with water so as to be 30% by weight 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of a synthetic resin product by sponge wiping,
By drying at 20 ° C. for 20 minutes, the photocatalyst layer was cured to obtain a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being irradiated with ultraviolet light, and then sprayed with water. As a result, it was observed that no water droplets were formed and the water spread evenly. Was. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００１９】（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、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 liquid prepared by removing crystalline titania from Example 2 was prepared, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００２０】（実施例３）Ｎaで安定化せしめたコロイ
ダルシリカ（触媒化成社製：カタロイドＳ３０Ｈ）を７
０重量部、フッ素系非イオン性界面活性剤としてポリオ
キシエチレン（５モル）ラウリルエーテル（ＨＬＢ：１
０．８）を３０重量部、アナターゼ型チタニアを１重量
％混合し、更にこの混合液を３０重量％となるように水
に混合し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）を合成樹脂製品の表面にスポンジ拭きによ
り塗布した後、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。上記試料について、
光触媒層形成後、３時間太陽光に晒すことにより、紫外
線が照射されるようにした後、水を噴霧したところ、水
滴が形成されず、水が一様に広がる様子が観察された。
また、暗所に放置した後、再び紫外線を照射すると、水
が一様に広がる状態に戻った。(Example 3) Colloidal silica stabilized by Na (catalyst S30H manufactured by Kasei Kasei Co., Ltd.) was mixed with 7
0 parts by weight, polyoxyethylene (5 mol) lauryl ether (HLB: 1) as a fluorine-based nonionic surfactant
0.8) was mixed with 1 part by weight of anatase-type titania, and the mixture was further mixed with water so as to be 30% by weight 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of a synthetic resin product by wiping with a sponge, drying at 20 ° C. for 20 minutes,
The sample was obtained by curing the photocatalyst layer. About the above sample,
After the photocatalytic layer was formed, the film was exposed to sunlight for 3 hours so as to be irradiated with ultraviolet rays, and then sprayed with water. As a result, a state in which water droplets were not formed and water spread uniformly was observed.
When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００２１】（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、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 liquid prepared by removing crystalline titania from Example 3 was prepared, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００２２】（実施例４）Ｎaで安定化せしめたコロイ
ダルシリカ（デュポン社製：ルドックスＡＭ）を８６重
量部、フッ素系非イオン性界面活性剤（住友スリーエム
社製：ＦＣ−１７６）を８重量部、ポリオキシエチレン
（５モル）ラウリルアミンを８重量部、アナターゼ型チ
タニアを１重量％混合し、更にこの混合液を４０重量％
となるように水に混合し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）を合成樹脂製品の表面
にスポンジ拭きにより塗布した後、２０℃で２０分乾燥
させることにより、光触媒層を硬化させて試料を得た。
上記試料について、光触媒層形成後、３時間太陽光に晒
すことにより、紫外線が照射されるようにした後、水を
噴霧したところ、水滴が形成されず、水が一様に広がる
様子が観察された。また、暗所に放置した後、再び紫外
線を照射すると、水が一様に広がる状態に戻った。Example 4 86 parts by weight of colloidal silica stabilized by Na (Ludox AM, manufactured by DuPont) and 8 parts by weight of a fluorine-based nonionic surfactant (FC-176, manufactured by Sumitomo 3M Limited) Parts, 8 parts by weight of polyoxyethylene (5 mol) laurylamine and 1% by weight of anatase-type titania, and further, the mixed solution was 40% by weight.
Was mixed with 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of the synthetic resin product by wiping with a sponge, the photocatalytic layer was cured by drying at 20 ° C. for 20 minutes to obtain a sample.
After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being irradiated with ultraviolet light, and then sprayed with water. As a result, it was observed that no water droplets were formed and the water spread evenly. Was. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００２３】（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、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 liquid prepared by removing crystalline titania from Example 4 was prepared, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００２４】（実施例５）Ｎaで安定化せしめたコロイ
ダルシリカ（デュポン社製：ルドックスＡＭ）を８６重
量部、ポリオキシエチレン（１０モル）ノニルフェニル
エーテル（ＨＬＢ：１３．３）を８重量部、フッ素系ア
ニオン性界面活性剤（住友スリーエム社製：ＦＣ−１２
８）を８重量部、アナターゼ型チタニアを０．１重量％
混合し、更にこの混合液を５０重量％となるように水に
混合し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）を合成樹脂製品の表面にスポンジ拭きにより
塗布した後、２０℃で２０分乾燥させることにより、光
触媒層を硬化させて試料を得た。上記試料について、光
触媒層形成後、３時間太陽光に晒すことにより、紫外線
が照射されるようにした後、水を噴霧したところ、水滴
が形成されず、水が一様に広がる様子が観察された。ま
た、暗所に放置した後、再び紫外線を照射すると、水が
一様に広がる状態に戻った。Example 5 86 parts by weight of colloidal silica stabilized by Na (Ludox AM manufactured by DuPont) and 8 parts by weight of polyoxyethylene (10 mol) nonylphenyl ether (HLB: 13.3) , A fluorine-based anionic surfactant (manufactured by Sumitomo 3M Limited: FC-12)
8) 8 parts by weight, 0.1% by weight of anatase titania
The resulting mixture was mixed with water so as to be 50% by weight 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of the synthetic resin product by wiping with a sponge, the photocatalytic layer was cured by drying at 20 ° C. for 20 minutes to obtain a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being irradiated with ultraviolet light, and then sprayed with water. As a result, it was observed that no water droplets were formed and the water spread evenly. Was. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００２５】（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、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 liquid composition was prepared by removing crystalline titania from Example 5 above, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００２６】（実施例６）Ｎaで安定化せしめたコロイ
ダルシリカ（デュポン社製：ルドックスＡＭ）を８６重
量部、ポリオキシエチレン（１０モル）ノニルフェニル
エーテル（ＨＬＢ：１３．３）を８重量部、フッ素系ア
ニオン性界面活性剤（東北肥料社製：エフトップＥＦ１
１２）を８重量部、アナターゼ型チタニアを０．０１重
量％混合し、更にこの混合液を３０重量％となるように
水に混合し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）を合成樹脂製品の表面にスポンジ
拭きにより塗布した後、２０℃で２０分乾燥させること
により、光触媒層を硬化させて試料を得た。上記試料に
ついて、光触媒層形成後、３時間太陽光に晒すことによ
り、紫外線が照射されるようにした後、水を噴霧したと
ころ、水滴が形成されず、水が一様に広がる様子が観察
された。また、暗所に放置した後、再び紫外線を照射す
ると、水が一様に広がる状態に戻った。(Example 6) 86 parts by weight of colloidal silica stabilized by Na (Ludox AM manufactured by DuPont) and 8 parts by weight of polyoxyethylene (10 mol) nonylphenyl ether (HLB: 13.3) , A fluorine-based anionic surfactant (manufactured by Tohoku Fertilizer: F-Top EF1)
8) and 0.01% by weight of anatase-type titania were mixed, and this mixed solution was further mixed with water so as to be 30% by weight 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. After applying these photocatalytic hydrophilic composition liquids (A to C) to the surface of the synthetic resin product by wiping with a sponge, the photocatalytic layer was cured by drying at 20 ° C. for 20 minutes to obtain a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being irradiated with ultraviolet light, and then sprayed with water. As a result, it was observed that no water droplets were formed and the water spread evenly. Was. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００２７】（比較例６）上記実施例６から結晶性チタ
ニアを除いた組成物液を調製し、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 6) A composition liquid was prepared by removing crystalline titania from Example 6 above, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００２８】（実施例７）Ｎaで安定化せしめたコロイ
ダルシリカ（触媒化成社製：カタロイドＳ３０Ｈ）を６
０重量部、ポリオキシエチレン（１０モル）ノニルフェ
ニルエーテル（ＨＬＢ：１３．３）を４０重量部、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
タニアの混合物を１０重量％混合し、更にこの混合液を
３０重量％となるように水に混合し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合成
樹脂製品の表面にスポンジ拭きにより塗布した後、２０
℃で２０分乾燥させることにより、光触媒層を硬化させ
て試料を得た。上記試料について、光触媒層形成後、３
時間太陽光に晒すことにより、紫外線が照射されるよう
にした後、水を噴霧したところ、水滴が形成されず、水
が一様に広がる様子が観察された。また、暗所に放置し
た後、再び紫外線を照射すると、水が一様に広がる状態
に戻った。Example 7 Colloidal silica stabilized by Na (catalyst S30H manufactured by Kasei Kasei Co., Ltd.) was mixed with 6
0 parts by weight, 40 parts by weight of polyoxyethylene (10 mol) nonylphenyl ether (HLB: 13.3), 10% by weight of a mixture of anatase-type titania, rutile-type titania, and brookite-type titania; Was mixed with water so as to be 30% by weight to prepare a photocatalytic hydrophilic composition liquid. After applying the photocatalytic hydrophilic composition solution to the surface of the synthetic resin product by wiping with a sponge,
The sample was obtained by drying at 20 ° C. for 20 minutes to cure the photocatalyst layer. For the above sample, after forming the photocatalyst layer, 3
After being irradiated with ultraviolet rays by exposing to sunlight for a time, when water was sprayed, it was observed that no water droplets were formed and the water spread evenly. When left in a dark place and then irradiated again with ultraviolet rays, the water returned to a state where it spread uniformly.
【００２９】（比較例７）上記実施例７から結晶性チタ
ニアを除いた組成物液を調製し、これを合成樹脂製品の
表面に塗布し、２０℃で２０分乾燥させることにより、
光触媒層を硬化させて試料を得た。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 7) A composition liquid prepared by removing crystalline titania from Example 7 was prepared, applied to the surface of a synthetic resin product, and dried at 20 ° C for 20 minutes.
The sample was obtained by curing the photocatalyst layer. As a result, the hydrophilicity of the surface of the synthetic resin product is approximately 10 ° in terms of the contact angle with water.
Became. 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.
【００３０】[0030]
【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、１価の陽イオンで安定化され
たコロイダルシリカと、非イオン性界面活性剤及び／又
はアニオン性界面活性剤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、塗布の際には、合成樹脂製
品等の被塗装物表面に弾かれることなく、均一に且つ薄
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, photocatalytic metal oxide particles, monovalent cation-stabilized colloidal silica, nonionic surfactant and / or anionic interface Since the activator and the activator are dispersed in water to constitute the photocatalytic hydrophilic composition, the photocatalytic hydrophilic coating is uniform and thin without being repelled on the surface of the object to be coated such as a synthetic resin product at the time of application. In addition, once 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, causing problems such as cloudiness and coloring. Absent. 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 Ｃ０９Ｋ 3/00 Ｃ０９Ｋ 3/00 Ｒ // Ｂ０５Ｄ 7/24 ３０３ Ｂ０５Ｄ 7/24 ３０３Ｂ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI C09K 3/00 C09K 3/00 R // B05D 7/24 303 B05D 7/24 303B
Claims (5)
成物であって、この組成物は、光触媒性金属酸化物粒子
と、１価の陽イオンで安定化されたコロイダルシリカ
と、非イオン性界面活性剤及び／又はアニオン性界面活
性剤とを含有する安定な水性分散液からなることを特徴
とする光触媒性親水性組成物。1. A composition for imparting hydrophilicity to the surface of a synthetic resin or the like, comprising a photocatalytic metal oxide particle, colloidal silica stabilized with a monovalent cation, A photocatalytic hydrophilic composition comprising a stable aqueous dispersion containing an ionic surfactant and / or an anionic surfactant.
において、前記コロイダルシリカが、コロイダルシリカ
と界面活性剤の合計量に対し、４０重量％以上であるこ
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 amount of the colloidal silica is at least 40% by weight based on the total amount of the colloidal silica and the surfactant. Composition.
性親水性組成物において、この組成物中にはカチオン性
界面活性剤が含有されていないことを特徴とする光触媒
性親水性組成物。3. The photocatalytic hydrophilic composition according to claim 1 or 2, wherein the composition does not contain a cationic surfactant. .
親水性組成物において、前記界面活性剤が、エーテル型
非イオン性界面活性剤であり、且つそのＨＬＢが５〜１
５であることを特徴とする光触媒性親水性組成物。4. The photocatalytic hydrophilic composition according to claim 1, wherein the surfactant is an ether type nonionic surfactant, and the HLB thereof is 5 to 1.
5. A photocatalytic hydrophilic composition, which is 5.
親水性組成物において、この組成物は、光触媒性金属酸
化物粒子、コロイダルシリカ及び界面活性剤の割合が、
光触媒性金属酸化物粒子０．０１〜１０重量％、コロイ
ダルシリカ７５〜９０重量％、界面活性剤２５〜１０重
量％であり、且つこれらが水性液中に合計量で０．１〜
５０重量％の濃度で含有せしめられていることを特徴と
する光触媒性親水性組成物。5. The photocatalytic hydrophilic composition according to claim 1, wherein the composition comprises a photocatalytic metal oxide particle, colloidal silica, and a surfactant in a proportion of:
0.01 to 10% by weight of a photocatalytic metal oxide particle, 75 to 90% by weight of a colloidal silica, 25 to 10% by weight of a surfactant, and 0.1 to 10% by weight of these in an aqueous liquid.
A photocatalytic hydrophilic composition, which is contained at a concentration of 50% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9307128A JPH11140432A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic hydrophilic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9307128A JPH11140432A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic hydrophilic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11140432A true JPH11140432A (en) | 1999-05-25 |
Family
ID=17965375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9307128A Pending JPH11140432A (en) | 1997-11-10 | 1997-11-10 | Photocatalytic hydrophilic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11140432A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6425670B1 (en) * | 1999-11-12 | 2002-07-30 | Murakami Corporation | Colored anti-fog mirror |
| WO2008123278A1 (en) | 2007-03-26 | 2008-10-16 | Toto Ltd. | Photocatalyst-coated object and photocatalytic coating fluid therefor |
| JP2008307526A (en) * | 2007-03-30 | 2008-12-25 | Toto Ltd | Photocatalytic coated body and photocatalytic coating liquid for the same |
| US7749950B2 (en) | 2005-07-29 | 2010-07-06 | Nichiha Corporation | Stain-proofing agent and building board using same |
| US7919425B2 (en) | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP2013006131A (en) * | 2011-06-22 | 2013-01-10 | Toagosei Co Ltd | Photocatalyst solution composition |
-
1997
- 1997-11-10 JP JP9307128A patent/JPH11140432A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6425670B1 (en) * | 1999-11-12 | 2002-07-30 | Murakami Corporation | Colored anti-fog mirror |
| US7749950B2 (en) | 2005-07-29 | 2010-07-06 | Nichiha Corporation | Stain-proofing agent and building board using same |
| WO2008123278A1 (en) | 2007-03-26 | 2008-10-16 | Toto Ltd. | Photocatalyst-coated object and photocatalytic coating fluid therefor |
| CN101678398A (en) * | 2007-03-26 | 2010-03-24 | Toto株式会社 | Photocatalyst-coated object and photocatalytic coating fluid therefor |
| DE112008000793T5 (en) | 2007-03-26 | 2010-04-08 | Toto Ltd., Kitakyushu | Photocatalytically coated body and photocatalytic coating liquid therefor |
| US7977270B2 (en) | 2007-03-26 | 2011-07-12 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid therefor |
| US8207079B2 (en) | 2007-03-26 | 2012-06-26 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid therefor |
| US8216959B2 (en) | 2007-03-26 | 2012-07-10 | Toto Ltd. | Photocatalyst-coated body, coating composition for the same, and process for producing photocatalyst-coated body |
| US8372774B2 (en) | 2007-03-26 | 2013-02-12 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid therefor |
| JP2008307526A (en) * | 2007-03-30 | 2008-12-25 | Toto Ltd | Photocatalytic coated body and photocatalytic coating liquid for the same |
| US7919425B2 (en) | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP2013006131A (en) * | 2011-06-22 | 2013-01-10 | Toagosei Co Ltd | Photocatalyst solution composition |
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