JPH11156208A - Photocatalytic coating film forming surface treating agent and formation of photocatalytic coating film using the same - Google Patents
Photocatalytic coating film forming surface treating agent and formation of photocatalytic coating film using the sameInfo
- Publication number
- JPH11156208A JPH11156208A JP9327361A JP32736197A JPH11156208A JP H11156208 A JPH11156208 A JP H11156208A JP 9327361 A JP9327361 A JP 9327361A JP 32736197 A JP32736197 A JP 32736197A JP H11156208 A JPH11156208 A JP H11156208A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- water
- coating film
- treatment agent
- 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 22
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims description 32
- 239000012756 surface treatment agent Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 9
- 239000000057 synthetic resin Substances 0.000 abstract description 9
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000002689 soil Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- -1 amine salt Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 230000001443 photoexcitation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005357 flat glass Substances 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
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は既存の窓ガラス、窓
枠、外壁のように、既に表面に汚染物質が付着している
基材や合成樹脂等のように表面が塗料をハジく傾向のあ
る基材の表面に光触媒性親水性被膜を形成するための表
面処理剤と、この表面処理剤を用いた光触媒被膜の形成
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface of a substrate, such as a window glass, a window frame, and an outer wall, which has a contaminant already adhered thereto or a synthetic resin. The present invention relates to a surface treatment agent for forming a photocatalytic hydrophilic film on a surface of a substrate, and a method for forming a photocatalytic film using the surface treatment agent.
【０００２】[0002]
【従来の技術】本発明者らは、ＰＣＴ／ＷＯ９６／２９
３７５号に開示したように、基材表面に光触媒層を形成
すると、光触媒の光励起に応じて前記層表面が、水との
接触角に換算して１０°以下という高度の親水性を呈す
ることを見出し、さらにそれによりガラス、レンズ、鏡
等の透明部材の防曇・視界確保性向上、物品表面の水洗
浄性・降雨洗浄性向上などの効果が得られることを見出
した。2. Description of the Related Art The present inventors have proposed PCT / WO96 / 29.
As disclosed in Japanese Patent No. 375, when a photocatalyst layer is formed on a substrate surface, the layer surface exhibits a high degree of hydrophilicity of 10 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. Further, it has been found that effects such as improvement of anti-fog and improvement of visibility of transparent members such as glass, lens and mirror, and improvement of water washing property and rain washing property of an article surface can be obtained.
【０００３】また、光触媒層に紫外線を照射すると、価
電子帯にあった電子（ｅ-）が伝導帯に励起され、価電
子帯には正孔（ｈ+）が生じ、これら電子（ｅ-）及び正
孔（ｈ+）が酸化還元反応を促進することで、汚れ成分
を分解する作用があることは従来から知られている。When the photocatalyst layer is irradiated with ultraviolet light, electrons (e − ) in the valence band are excited to the conduction band, and holes (h + ) are generated in the valence band, and these electrons (e − ) are generated. ) And holes (h + ) have been known to promote the oxidation-reduction reaction, thereby decomposing dirt components.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、既存の
基材表面に光触媒層を形成しようとすると、既存の部材
表面には既に汚染物質が付着している場合が多く、その
汚染物質の影響で親水性を発揮する光触媒含有層を形成
するためのコーティング剤が弾かれたり、うまく固着し
なかったりして光触媒含有層の光励起による表面の親水
化機能や汚れ成分の分解機能が損なわれることがある。
また、表面に汚染物質が付着していなくとも合成樹脂の
表面等は表面エネルギーが低いためハジキ現象が起きて
しまい、薄く均一な光触媒被膜を形成することができな
い。However, when an attempt is made to form a photocatalyst layer on the surface of an existing substrate, there are many cases where a contaminant has already adhered to the surface of an existing member, and the surface of the existing member is hydrophilic. In some cases, the coating agent for forming the photocatalyst-containing layer exhibiting the property is repelled or does not adhere well, thereby impairing the function of hydrophilizing the surface by photoexcitation of the photocatalyst-containing layer and the function of decomposing dirt components.
Even if no contaminants are attached to the surface, the surface of the synthetic resin or the like has a low surface energy, so that a repelling phenomenon occurs, and a thin and uniform photocatalytic film cannot be formed.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記事情に鑑
みてなされたものであり、基材の表面に、光触媒含有層
を形成する前に、予め基材の表面に塗布され、基材の表
面を親水化して、最外側となる光触媒層の基材表面への
結合強度を向上させる表面処理剤を提供することを目的
とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is applied to a surface of a substrate in advance before forming a photocatalyst-containing layer on the surface of the substrate. It is an object of the present invention to provide a surface treatment agent that makes the surface of the surface of the photocatalyst hydrophilic so as to improve the bonding strength of the outermost photocatalytic layer to the substrate surface.
【０００６】上記課題を解決すべく本発明に係る光触媒
被膜形成用表面処理剤は、基材の表面に光触媒被膜を形
成する前に、当該表面の前処理を行うために塗布する表
面処理剤であって、この表面処理剤は、無機質ゾルと、
スルホン酸塩基含有ポリエステルとを水に分散させて構
成される。[0006] In order to solve the above-mentioned problems, the surface treatment agent for forming a photocatalytic film according to the present invention is a surface treatment agent applied for performing a pretreatment of the surface before forming the photocatalytic film on the surface of the substrate. Then, this surface treatment agent, an inorganic sol,
A sulfonic acid group-containing polyester is dispersed in water.
【０００７】前記無機質ゾルとしては、例えば、シリ
カ、アルミナ、水不溶性リチウムシリケート、水酸化ア
ルミニウム、水酸化鉄、水酸化錫、硫酸バリウム等の無
機質水性コロイド粒子の１または２以上を水（媒体）中
に分散せしめた水性ゾルが挙げられる。As the inorganic sol, for example, one or two or more of inorganic aqueous colloidal particles such as silica, alumina, water-insoluble lithium silicate, aluminum hydroxide, iron hydroxide, tin hydroxide, barium sulfate and the like can be used as water (medium). Aqueous sol dispersed therein.
【０００８】前記スルホン酸塩基含有ポリエステルとし
ては、ジカルボン酸成分を縮重合して得られるポリエス
テルを無水硫酸、クロルスルホン酸、重亜硫酸ナトリウ
ムなどのスルホン化剤を反応させてスルホン化して得ら
れるものや、ジカルボン酸成分、ジオール成分、−ＳＯ
3Ｍ（Ｍはアンモニウム塩、アミン塩、水素または金属
イオン）を含有する二官能性単量体を縮重合させて得ら
れるものが挙げられる。Examples of the sulfonic acid group-containing polyester include those obtained by subjecting a polyester obtained by polycondensation of a dicarboxylic acid component to sulfonation by reacting with a sulfonating agent such as sulfuric anhydride, chlorosulfonic acid or sodium bisulfite. , Dicarboxylic acid component, diol component, -SO
Those obtained by condensation polymerization of a bifunctional monomer containing 3 M (M is an ammonium salt, an amine salt, hydrogen or a metal ion) are exemplified.
【０００９】前記無機質ゾル１００重量部に対するスル
ホン酸塩基含有ポリエステルの割合は５〜２００重量部
とするのが好ましい。スルホン酸塩基含有ポリエステル
の割合が５重量部未満であると、塗装性及び親水性の持
続性に劣り、２００重量部を超えると親水性が薄れる。The proportion of the sulfonic acid group-containing polyester to 100 parts by weight of the inorganic sol is preferably 5 to 200 parts by weight. If the proportion of the sulfonic acid group-containing polyester is less than 5 parts by weight, the coatability and the durability of the hydrophilicity are poor, and if it exceeds 200 parts by weight, the hydrophilicity is weakened.
【００１０】光触媒被膜の形成方法としては、図１に示
すように、基材の表面を洗浄した後、当該表面に上記構
成の表面処理剤を塗布する。すると、基材の表面がある
程度親水化せしめられる。そこで、このある程度親水化
された表面に光触媒コーティング液を塗布し乾燥せしめ
ることで、基材表面に対する結合力に優れた光触媒層が
得られる。As a method for forming a photocatalytic film, as shown in FIG. 1, after cleaning the surface of a substrate, the surface treatment agent having the above-mentioned structure is applied to the surface. Then, the surface of the base material is made hydrophilic to some extent. Then, a photocatalyst coating solution is applied to the surface which has been made hydrophilic to some extent and dried to obtain a photocatalyst layer having excellent bonding strength to the substrate surface.
【００１１】[0011]
【発明の実施の形態】（実施例１）分子量２０，０００
のポリエステルを１，２−ジクロロエタンに溶解した液
に無水硫酸を滴下してスルホン化し、これにアンモニア
水を加えるとともに加熱して１，２−ジクロロエタンを
留出除去して、スルホン化ポリエステルのアンモニウム
塩水溶液（スルホン酸塩基含有量は３モル％）を得た。
上記のスルホン酸塩基含有ポリエステルを３０重量部、
シリカゾルを３０重量部及びアルミナゾルを３０重量部
秤量し、これらを水に分散させて表面処理剤を調製し
た。この表面処理剤を既に使用されている合成樹脂製品
の表面にスポンジ拭きにより塗布した後、石原産業製光
触媒コーティング液ＳＴＫ０１（酸化チタン粒子８重量
部とアルキルシリケート２重量部と硝酸水溶液５４．８
重量部とメタノール２８重量部とプロパノール７．２重
量部からなる組成物）を溶媒（２−プロパノール９重量
部とジアセトンアルコール１重量部との混合液）で１０
０倍に希釈して得た光触媒コーティング液を、直径８ｍ
ｍのエアガンを用いて１０５ｍ2／ｇスプレーコーティ
ング法により塗布後、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、上記試料を暗所に置いて水との接触角が
３０°になった後、再び紫外線を照射したところ、水と
の接触角は５°未満に回復した。(Example 1) Molecular weight of 20,000
Sulfuric anhydride was added dropwise to a solution of the above polyester dissolved in 1,2-dichloroethane to form a sulfonate. Ammonia water was added thereto, and the mixture was heated to distill and remove the 1,2-dichloroethane. An aqueous solution (sulfonate group content was 3 mol%) was obtained.
30 parts by weight of the above sulfonic acid group-containing polyester,
30 parts by weight of silica sol and 30 parts by weight of alumina sol were weighed and dispersed in water to prepare a surface treating agent. After applying this surface treating agent to the surface of the synthetic resin product already used by wiping with a sponge, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, and 54.8 parts of nitric acid aqueous solution)
Parts by weight of a solvent (composition comprising 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) in a solvent.
The photocatalyst coating solution obtained by diluting 0-fold was 8 m in diameter.
After applying by a spray coating method of 105 m 2 / g using an air gun of m, the photocatalyst 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 the sample was placed in a dark place and the contact angle with water became 30 °, and the sample was irradiated with ultraviolet rays again, the contact angle with water recovered to less than 5 °.
【００１２】（実施例２）実施例１と同様にして得たス
ルホン酸塩基含有ポリエステルを５０重量部、シリカゾ
ルを１０重量部、アルミナゾルを４０重量部秤量し、こ
れらを水に分散させて表面処理剤を調製した。この表面
処理剤を既に使用されている合成樹脂製品の表面にスポ
ンジ拭きにより塗布した後、石原産業製光触媒コーティ
ング液ＳＴＫ０１（酸化チタン粒子８重量部とアルキル
シリケート２重量部と硝酸水溶液５４．８重量部とメタ
ノール２８重量部とプロパノール７．２重量部からなる
組成物）を溶媒（２−プロパノール９重量部とジアセト
ンアルコール１重量部との混合液）で１００倍に希釈し
て得た光触媒コーティング液を、直径８ｍｍのエアガン
を用いて１０５ｍ2／ｇスプレーコーティング法により
塗布後、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、
上記試料を暗所に置いて水との接触角が３０°になった
後、再び紫外線を照射したところ、水との接触角は５°
未満に回復した。Example 2 50 parts by weight of a sulfonate group-containing polyester obtained in the same manner as in Example 1, 10 parts by weight of silica sol, and 40 parts by weight of alumina sol were weighed and dispersed in water to perform surface treatment. An agent was prepared. After applying this surface treatment agent to the surface of the synthetic resin product already used by wiping with a sponge, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate and 54.8 parts by weight of nitric acid aqueous solution) Photocatalyst coating obtained by diluting 100 parts by weight, a composition comprising 28 parts by weight of methanol and 7.2 parts by weight of propanol) with a solvent (a mixed solution of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol). The solution was applied by a spray coating method of 105 m 2 / g using an air gun having a diameter of 8 mm, and then dried at 20 ° C. for 20 minutes to cure the photocatalyst layer 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. Also,
After the sample was placed in a dark place and the contact angle with water became 30 °, the sample was irradiated with ultraviolet rays again, and the contact angle with water was 5 °.
Recovered to less than.
【００１３】（実施例３）実施例１と同様にして得たス
ルホン酸塩基含有ポリエステルを８０重量部、シリカゾ
ルを４０重量部、アルミナゾルを１０重量部秤量し、こ
れらを水に分散させて表面処理剤を調製した。この表面
処理剤を既に使用されている合成樹脂製品の表面にスポ
ンジ拭きにより塗布した後、石原産業製光触媒コーティ
ング液ＳＴＫ０１（酸化チタン粒子８重量部とアルキル
シリケート２重量部と硝酸水溶液５４．８重量部とメタ
ノール２８重量部とプロパノール７．２重量部からなる
組成物）を溶媒（２−プロパノール９重量部とジアセト
ンアルコール１重量部との混合液）で１００倍に希釈し
て得た光触媒コーティング液を、直径８ｍｍのエアガン
を用いて１０５ｍ2／ｇスプレーコーティング法により
塗布後、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、
上記試料を暗所に置いて水との接触角が３０°になった
後、再び紫外線を照射したところ、水との接触角は５°
未満に回復した。Example 3 80 parts by weight of a sulfonate group-containing polyester obtained in the same manner as in Example 1, 40 parts by weight of silica sol, and 10 parts by weight of alumina sol were weighed and dispersed in water to perform surface treatment. An agent was prepared. After applying this surface treatment agent to the surface of the synthetic resin product already used by wiping with a sponge, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate and 54.8 parts by weight of nitric acid aqueous solution) Photocatalyst coating obtained by diluting 100 parts by weight, a composition comprising 28 parts by weight of methanol and 7.2 parts by weight of propanol) with a solvent (a mixed solution of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol). The solution was applied by a spray coating method of 105 m 2 / g using an air gun having a diameter of 8 mm, and then dried at 20 ° C. for 20 minutes to cure the photocatalyst layer 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. Also,
After the sample was placed in a dark place and the contact angle with water became 30 °, the sample was irradiated with ultraviolet rays again, and the contact angle with water was 5 °.
Recovered to less than.
【００１４】（実施例４）分子量１２，０００のポリエ
ステルを１００℃で攪拌しながらメタ重亜硫酸ナトリウ
ムを添加し、スルホン化ポリエステルのナトリウム塩水
溶液（スルホン酸塩基含有量は８モル％）を得た。上記
のスルホン酸塩基含有ポリエステルを４０重量部、シリ
カゾルを３０重量部、アルミナゾルを３０重量部秤量
し、これらを水に分散させて表面処理剤を調製した。こ
の表面処理剤を既に使用されている合成樹脂製品の表面
にスポンジ拭きにより塗布した後、石原産業製光触媒コ
ーティング液ＳＴＫ０１（酸化チタン粒子８重量部とア
ルキルシリケート２重量部と硝酸水溶液５４．８重量部
とメタノール２８重量部とプロパノール７．２重量部か
らなる組成物）を溶媒（２−プロパノール９重量部とジ
アセトンアルコール１重量部との混合液）で１００倍に
希釈して得た光触媒コーティング液を、直径８ｍｍのエ
アガンを用いて１０５ｍ2／ｇスプレーコーティング法
により塗布後、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、上記試料を暗所に置いて水との接触角が３０°に
なった後、再び紫外線を照射したところ、水との接触角
は５°未満に回復した。EXAMPLE 4 Sodium metabisulfite was added to a polyester having a molecular weight of 12,000 while stirring at 100 ° C. to obtain an aqueous solution of a sodium salt of a sulfonated polyester (sulfonate group content: 8 mol%). . 40 parts by weight of the above-mentioned sulfonic acid group-containing polyester, 30 parts by weight of silica sol and 30 parts by weight of alumina sol were weighed and dispersed in water to prepare a surface treating agent. After applying this surface treatment agent to the surface of the synthetic resin product already used by wiping with a sponge, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate and 54.8 parts by weight of nitric acid aqueous solution) Photocatalyst coating obtained by diluting 100 parts by weight, a composition comprising 28 parts by weight of methanol and 7.2 parts by weight of propanol) with a solvent (a mixed solution of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol). The liquid was applied by a spray coating method of 105 m 2 / g using an air gun having a diameter of 8 mm, and then dried 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 the sample was placed in a dark place and the contact angle with water became 30 °, and the sample was irradiated with ultraviolet rays again, the contact angle with water recovered to less than 5 °.
【００１５】（比較例）既に使用されている合成樹脂製
品の表面に、洗浄処理をせずに、石原産業製光触媒コー
ティング液ＳＴＫ０１（酸化チタン粒子８重量部とアル
キルシリケート２重量部と硝酸水溶液５４．８重量部と
メタノール２８重量部とプロパノール７．２重量部から
なる組成物）を溶媒（２−プロパノール９重量部とジア
セトンアルコール１重量部との混合液）で１００倍に希
釈して得た光触媒コーティング液を、直径８ｍｍのエア
ガンを用いて１０５ｍ2／ｇスプレーコーティング法に
より塗布後、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、水を噴霧してみたが、所々
水滴が弾かれたり付着してしまい、充分に親水化されて
いない様子が観察された。これは、光触媒が均一に塗布
されていないためと考えられる。Comparative Example A photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate and 54 parts of nitric acid aqueous solution) was applied to the surface of a synthetic resin product already used without washing. 2.8 parts by weight, 28 parts by weight of methanol and 7.2 parts by weight of propanol) diluted 100-fold with a solvent (a mixed solution of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol). The photocatalyst coating solution was applied by a spray coating method of 105 m 2 / g using an air gun having a diameter of 8 mm, and then dried at 20 ° C. for 20 minutes to cure the photocatalyst layer, thereby obtaining a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being exposed to ultraviolet light, and then sprayed with water. An unconverted state was observed. This is probably because the photocatalyst was not uniformly applied.
【００１６】[0016]
【発明の効果】以上に説明した如く、本発明によれば、
無機質ゾルとスルホン酸塩基含有ポリエステルとを水に
分散させた表面処理剤を用いることにより、既存の基材
や合成樹脂からなる基材の表面に光触媒性親水性被膜を
形成する場合に、安定的に光触媒の光励起に応じた親水
化効果が発現されるようになる。As described above, according to the present invention,
By using a surface treatment agent in which an inorganic sol and a sulfonic acid group-containing polyester are dispersed in water, when a photocatalytic hydrophilic film is formed on the surface of an existing substrate or a substrate made of synthetic resin, it is stable. Thus, a hydrophilic effect corresponding to the photoexcitation of the photocatalyst is developed.
【図１】基材表面に光触媒被膜を形成する方法の一例を
示すブロック図FIG. 1 is a block diagram illustrating an example of a method for forming a photocatalytic film on a substrate surface.
Claims (5)
に、当該表面の前処理を行うために塗布する表面処理剤
であって、この表面処理剤は、無機質ゾルと、スルホン
酸塩基含有ポリエステルとを水に分散させてなることを
特徴とする光触媒被膜形成用表面処理剤。1. A surface treatment agent applied to perform a pretreatment of a surface before forming a photocatalytic film on a surface of a substrate, the surface treatment agent comprising an inorganic sol, a sulfonate-containing A surface treating agent for forming a photocatalytic film, comprising a polyester and water dispersed in water.
処理剤において、前記無機質ゾルは、シリカゾル及び／
又はアルミナゾルであることを特徴とする光触媒被膜形
成用表面処理剤。2. The surface treating agent for forming a photocatalytic film according to claim 1, wherein the inorganic sol is a silica sol and / or a silica sol.
Or a surface treatment agent for forming a photocatalytic film, which is an alumina sol.
処理剤において、前記スルホン酸塩基含有ポリエステル
のスルホン酸塩基含有量は０．５〜５０モル％であるこ
とを特徴とする光触媒被膜形成用表面処理剤。3. The photocatalytic film-forming surface treatment agent according to claim 1, wherein the sulfonic acid group-containing polyester has a sulfonic acid group content of 0.5 to 50 mol%. Surface treatment agent.
処理剤において、前記無機質ゾル１００重量部に対して
スルホン酸塩基含有ポリエステルが５〜２００重量部で
あることを特徴とする光触媒被膜形成用表面処理剤。4. The photocatalytic film forming surface treating agent according to claim 1, wherein the sulfonic acid group-containing polyester is 5-200 parts by weight based on 100 parts by weight of the inorganic sol. Surface treatment agent.
剤を基材の表面に塗布し、基材の表面を親水化した後
に、当該基材の表面に光触媒コーティング液を塗布する
ようにしたことを特徴とする光触媒被膜の形成方法。5. A photocatalyst coating liquid is applied to the surface of a substrate after applying the surface treatment agent according to claim 1 to the surface of the substrate and hydrophilizing the surface of the substrate. A method for forming a photocatalytic film, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9327361A JPH11156208A (en) | 1997-11-28 | 1997-11-28 | Photocatalytic coating film forming surface treating agent and formation of photocatalytic coating film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9327361A JPH11156208A (en) | 1997-11-28 | 1997-11-28 | Photocatalytic coating film forming surface treating agent and formation of photocatalytic coating film using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11156208A true JPH11156208A (en) | 1999-06-15 |
Family
ID=18198295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9327361A Pending JPH11156208A (en) | 1997-11-28 | 1997-11-28 | Photocatalytic coating film forming surface treating agent and formation of photocatalytic coating film using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11156208A (en) |
-
1997
- 1997-11-28 JP JP9327361A patent/JPH11156208A/en active Pending
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