JPH11106679A - Surface-treating agent for formation of photocatalyst coating film and formation of photocatalyst coating film using the same surface treating agent - Google Patents
Surface-treating agent for formation of photocatalyst coating film and formation of photocatalyst coating film using the same surface treating agentInfo
- Publication number
- JPH11106679A JPH11106679A JP9275588A JP27558897A JPH11106679A JP H11106679 A JPH11106679 A JP H11106679A JP 9275588 A JP9275588 A JP 9275588A JP 27558897 A JP27558897 A JP 27558897A JP H11106679 A JPH11106679 A JP H11106679A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- photocatalyst coating
- photocatalyst
- treating agent
- coating film
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 title abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000008119 colloidal silica Substances 0.000 claims abstract description 18
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 8
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 8
- 239000012756 surface treatment agent Substances 0.000 claims description 26
- 230000001699 photocatalysis Effects 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- -1 organo silica sol Chemical compound 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000001443 photoexcitation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PHFDTSRDEZEOHG-UHFFFAOYSA-N hydron;octan-1-amine;chloride Chemical compound Cl.CCCCCCCCN PHFDTSRDEZEOHG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 2
- VCOYQLVGJRYNFY-UHFFFAOYSA-M trimethyl(tridecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)C VCOYQLVGJRYNFY-UHFFFAOYSA-M 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- Catalysts (AREA)
- Paints Or Removers (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
部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。The present invention relates to a surface treating agent for forming a photocatalytic hydrophilic coating on the surface of a member having a contaminant already attached to the surface, such as an existing window glass, window frame, or outer wall. And a method for forming a photocatalytic film using the surface treating 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
部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。However, when an attempt is made to form a photocatalyst layer on the surface of an existing member, in many cases, a contaminant has already adhered to the surface of the existing member. In some cases, the coating agent for forming the photocatalyst-containing layer exhibiting the above-mentioned properties 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.
【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、既存の部材の表面に、光触媒
含有層を形成する前に、予め既存の部材の表面に塗布さ
れ、既存の部材の表面を親水化して、最外側となる光触
媒層の部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 the surface of an existing member in advance before forming a photocatalyst-containing layer on the surface of the existing member. It is an object of the present invention to provide a surface treatment agent that hydrophilizes the surface of an existing member and improves the bonding strength of the outermost photocatalytic layer to the member 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、コロイダルシリカを０．０５
重量％以上２０重量％以下、カチオン性界面活性剤及び
／又は両性界面活性剤を０．０００１重量％以上０．１
重量％以下の割合で含有する水溶液から構成される。[0006] In order to solve the above problems, the surface treatment agent for forming a photocatalytic film according to the present invention comprises colloidal silica at 0.05%.
Weight% or more and 20 weight% or less, and 0.0001 to 0.1 weight% of a cationic surfactant and / or an amphoteric surfactant.
It is composed of an aqueous solution containing at a ratio of not more than% by weight.
【０００７】光触媒被膜の形成方法としては、図１に示
すように、既存の部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、既存の部材
の表面にはシリカ粒子が沈着して親水化せしめられる。
そこで、この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、部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 an existing member, the surface treatment agent having the above-described structure is applied to the surface. Then, the silica particles are deposited on the surface of the existing member and are made hydrophilic.
Therefore, a photocatalyst coating liquid is applied to the surface that has been hydrophilized and dried to obtain a photocatalyst layer having excellent bonding strength to the member surface.
【０００８】ここで、コロイダルシリカの割合を０．０
５重量％以上２０重量％以下とするのは、０．０５重量
％未満であると部材表面にシリカ粒子が沈着しにくく、
２０重量％を超えると、表面処理剤の安定性が悪くなる
からであり、界面活性剤の割合を０．０００１重量％以
上０．１重量％以下とするのは、０．０００１重量％未
満であると部材表面にシリカ粒子が沈着しにくく、０．
１重量％を超えると、凝集が起こり保存性が悪くなるか
らであり、また、表面処理剤の表面張力は扱いやすさと
シリカ粒子の沈着を考慮すると、３５〜７０ダイン／ｃ
ｍが適当である。尚、表面張力の調整は界面活性剤の添
加量にて行う。Here, the ratio of colloidal silica is set to 0.0
When the content is 5% by weight or more and 20% by weight or less, if less than 0.05% by weight, silica particles are hardly deposited on the member surface,
If the content exceeds 20% by weight, the stability of the surface treatment agent deteriorates. The reason why the ratio of the surfactant is 0.0001% by weight or more and 0.1% by weight or less is less than 0.0001% by weight. If it is present, silica particles hardly deposit on the surface of the member.
If the content exceeds 1% by weight, cohesion occurs and the preservability deteriorates, and the surface tension of the surface treatment agent is 35 to 70 dynes / c in consideration of ease of handling and deposition of silica particles.
m is appropriate. The surface tension is adjusted by the amount of the surfactant added.
【０００９】因みに、特公平１−２１１７３号公報に
は、合成樹脂成形物の表面にコロイド状シリカ粒子を沈
着せしめて水滴が付着しないようにするための水溶液と
して、コロイダルシリカを０．０５重量％以上２０重量
％以下、カチオン性界面活性剤及び／又は両性界面活性
剤を０．０００１重量％以上０．１重量％以下の割合で
含有し、表面張力が３５〜７０ダイン／ｃｍの水溶液が
提案されているが、光触媒層を形成するための前処理剤
としては何ら示唆されていない。Japanese Patent Publication No. 1-21733 discloses that 0.05% by weight of colloidal silica is used as an aqueous solution for depositing colloidal silica particles on the surface of a synthetic resin molded article to prevent water droplets from adhering. An aqueous solution containing a cationic surfactant and / or an amphoteric surfactant in a proportion of 0.0001% to 0.1% by weight and a surface tension of 35 to 70 dynes / cm is proposed. However, there is no suggestion as a pretreatment agent for forming a photocatalytic layer.
【００１０】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、（オルガノシリカゾル、ＩＰＡ−Ｓ
Ｔ：日産化学製）、（スノーテックス４０：日産化学
製）、（スノーテックスＯ：日産化学製）、（スノーテ
ックスＣ：日産化学製）、（ルドックスＨＳ−４０：デ
ュポン社製）が挙げられる。The colloidal silica constituting the surface treating agent of the present invention includes (organo silica sol, IPA-S
T: Nissan Chemical), (Snowtex 40: Nissan Chemical), (Snowtex O: Nissan Chemical), (Snowtex C: Nissan Chemical), (Ludox HS-40: DuPont) .
【００１１】一般に、シリカゾルにカチオン性界面活性
剤や両性界面活性剤を加えると、シリカの電荷が中和さ
れて沈殿を生じたり、ゲル化するが、界面活性剤濃度を
比較的低濃度で添加することで、沈殿が生じないように
することが可能になる。また、カチオン性界面活性剤と
しては、例えばアルキルアミン塩、アルキルアンモニウ
ム塩、アルキルピリジニウム塩などが挙げられ、両性界
面活性剤としては、例えばぺタイン型のもの、グリシン
型のもの、硫酸エステル塩型のもの、スルホン酸型のも
の、リン酸エステル型のもの等が挙げられる。これらの
界面活性剤は２種以上の併用を妨げない。In general, when a cationic surfactant or an amphoteric surfactant is added to a silica sol, the charge of the silica is neutralized to cause precipitation or gelation. By doing so, it is possible to prevent precipitation. Examples of the cationic surfactant include an alkylamine salt, an alkylammonium salt, and an alkylpyridinium salt. Examples of the amphoteric surfactant include a petaine-type surfactant, a glycine-type surfactant, and a sulfate ester-type surfactant. , Sulfonic acid type, phosphoric acid ester type and the like. These surfactants do not prevent a combination of two or more.
【００１２】カチオン性界面活性剤及び両性界面活性剤
の具体的な名称を挙げると、ドデシルトリメチルアンモ
ニウムクロライド、オクタデシルトリメチルアンモニウ
ムブロマイド、ドデシルピリジニウムクロライド、塩化
オクチルアミン、トリデシルトリメチルアンモニウムク
ロライド、アノンＬＧ（日本油脂社製）等が適当であ
る。Specific names of the cationic surfactant and the amphoteric surfactant include dodecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, dodecylpyridinium chloride, octylamine chloride, tridecyltrimethylammonium chloride, Anone LG (Japan). And the like are suitable.
【００１３】光触媒コーティング液を構成する光触媒粒
子としては、アナターゼ型酸化チタン、ルチル型酸化チ
タン、酸化亜鉛、酸化錫、酸化第二鉄、三酸化二ビスマ
ス、三酸化タングステン、チタン酸ストロンチウム等が
挙げられる。The photocatalyst particles constituting the photocatalyst coating liquid include anatase type titanium oxide, rutile type titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide, strontium titanate and the like. Can be
【００１４】[0014]
（実施例１）コロイダルシリカを２．０重量％、ドデシ
ルトリメチルアンモニウムクロライドを０．０２重量％
含有し、表面張力が４２ダイン／ｃｍの表面処理剤を調
製した。この表面処理剤を既に使用されている窓ガラス
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。(Example 1) 2.0% by weight of colloidal silica and 0.02% by weight of dodecyltrimethylammonium chloride
A surface treatment agent having a surface tension of 42 dynes / cm was prepared. This surface treatment agent is applied to a window glass that has already been used by wiping with a sponge. Then, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, and methanol A photocatalyst coating liquid obtained by diluting 28 parts by weight and 7.2 parts by weight of propanol) with a solvent (a mixture of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) 100 times, After applying by a spray coating method of 105 m 2 / g using an air gun having a diameter of 8 mm, and 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.
【００１５】（実施例２）コロイダルシリカを２．０重
量％、ドデシルトリメチルアンモニウムクロライドを
０．０５重量％含有し、表面張力が３５ダイン／ｃｍの
表面処理剤を調製した。この表面処理剤を既に使用され
ている窓ガラスに塗布した後、前記実施例１と同様に光
触媒コーティング液を塗布・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、前
記実施例１と同様に、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。(Example 2) A surface treatment agent containing 2.0% by weight of colloidal silica and 0.05% by weight of dodecyltrimethylammonium chloride and having a surface tension of 35 dynes / cm was prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. By exposing the sample to sunlight for 3 hours as in Example 1,
When the water was sprayed after the irradiation with the ultraviolet rays, water droplets were not formed, and it was observed that the water spread uniformly.
【００１６】（実施例３）コロイダルシリカを２．０重
量％、オクタデシルトリメチルアンモニウムブロマイド
を０．００１重量％含有し、表面張力が６８ダイン／ｃ
ｍの表面処理剤を調製した。この表面処理剤を既に使用
されている窓ガラスに塗布した後、前記実施例１と同様
に光触媒コーティング液を塗布・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、前記実施例１と同様に、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。EXAMPLE 3 Colloidal silica (2.0% by weight), octadecyltrimethylammonium bromide (0.001% by weight), surface tension 68 dyne / c
m of surface treatment agents were prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００１７】（実施例４）コロイダルシリカを２．０重
量％、ドデシルピリジニウムクロライドを０．０５重量
％含有し、表面張力が４３ダイン／ｃｍの表面処理剤を
調製した。この表面処理剤を既に使用されている窓ガラ
スに塗布した後、前記実施例１と同様に光触媒コーティ
ング液を塗布・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、前記実施例１と
同様に、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。Example 4 A surface treatment agent containing 2.0% by weight of colloidal silica and 0.05% by weight of dodecylpyridinium chloride and having a surface tension of 43 dynes / cm was prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００１８】（実施例５）コロイダルシリカを２．０重
量％、塩化オクチルアミンを０．０１重量％含有し、表
面張力が５１ダイン／ｃｍの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窓ガラスに塗布した
後、前記実施例１と同様に光触媒コーティング液を塗布
・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、前記実施例１と同様に、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。Example 5 A surface treatment agent containing 2.0% by weight of colloidal silica and 0.01% by weight of octylamine chloride and having a surface tension of 51 dynes / cm was prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００１９】（実施例６）コロイダルシリカを２．０重
量％、アノンＬＧ（日本油脂社製）を０．０１重量％含
有し、表面張力が４５ダイン／ｃｍの表面処理剤を調製
した。この表面処理剤を既に使用されている窓ガラスに
塗布した後、前記実施例１と同様に光触媒コーティング
液を塗布・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、前記実施例１と同様
に、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。Example 6 A surface treatment agent containing 2.0% by weight of colloidal silica and 0.01% by weight of Anon LG (manufactured by NOF Corporation) and having a surface tension of 45 dynes / cm was prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００２０】（実施例７）コロイダルシリカを２．０重
量％、トリデシルトリメチルアンモニウムクロライドを
０．０１重量％、アノンＬＧ（日本油脂社製）を０．０
１重量％含有し、表面張力が４３ダイン／ｃｍの表面処
理剤を調製した。この表面処理剤を既に使用されている
窓ガラスに塗布した後、前記実施例１と同様に光触媒コ
ーティング液を塗布・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、前記実施
例１と同様に、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。Example 7 2.0% by weight of colloidal silica, 0.01% by weight of tridecyltrimethylammonium chloride, and 0.0% of Anone LG (manufactured by NOF Corporation)
A surface treatment agent containing 1% by weight and having a surface tension of 43 dynes / cm was prepared. After applying this surface treatment agent to the window glass already used, the photocatalyst layer was hardened by applying and drying the photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００２１】（比較例１）既に使用されている窓ガラス
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 1) 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) was applied to a window glass already used without washing treatment. Photocatalyst obtained by diluting 100 parts by weight of a solvent (a mixture of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) with 100 parts by weight of methanol, 28 parts by weight of methanol and 7.2 parts by weight of propanol. The coating 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 to harden the photocatalyst layer to obtain 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.
【００２２】（比較例２）コロイダルシリカを２２重量
％、ドデシルトリメチルアンモニウムクロライドを０．
０２重量％含有する表面処理剤を調製したが、凝集が起
こり表面処理剤としては不安定であることが確認され
た。Comparative Example 2 22% by weight of colloidal silica and 0.2% of dodecyltrimethylammonium chloride were used.
Although a surface treatment agent containing 02% by weight was prepared, it was confirmed that aggregation occurred and the surface treatment agent was unstable.
【００２３】（比較例３）コロイダルシリカを２．０重
量％、ドデシルトリメチルアンモニウムクロライドを
０．２重量％含有する表面処理剤を調製したが、凝集が
起こり保存性が悪く、表面処理剤としては使用できない
ことが判明した。(Comparative Example 3) A surface treatment agent containing 2.0% by weight of colloidal silica and 0.2% by weight of dodecyltrimethylammonium chloride was prepared. However, aggregation occurred and storage stability was poor. It turned out to be unusable.
【００２４】以上の実施例及び比較例より、コロイダル
シリカと界面活性剤を所定の割合で含有する表面処理剤
を既存の部材に塗布してから、光触媒性親水性被膜を形
成すると、親水性が発現しやすいことが確認された。From the above Examples and Comparative Examples, when a surface treatment agent containing a predetermined ratio of colloidal silica and a surfactant is applied to an existing member and then a photocatalytic hydrophilic film is formed, the hydrophilicity is reduced. It was confirmed that expression was easy.
【００２５】[0025]
【発明の効果】以上に説明した如く、本発明の表面処理
剤を用いることにより、既存の部材に光触媒性親水性被
膜を形成した場合に、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, by using the surface treatment agent of the present invention, when a photocatalytic hydrophilic film is formed on an existing member, the hydrophilicity effect according to the photoexcitation of the photocatalyst can be stably obtained. Will be expressed.
【図１】既存の部材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 showing an example of a method for forming a photocatalytic film on an existing member.
Claims (3)
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、この表面処理剤はコロイダルシリカを
０．０５重量％以上２０重量％以下、カチオン性界面活
性剤及び／又は両性界面活性剤を０．０００１重量％以
上０．１重量％以下の割合で含有する水溶液からなるこ
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 of an existing member before forming a photocatalytic film on the surface of the member, the surface treatment agent comprising 0.05% by weight of colloidal silica. A surface treatment for forming a photocatalytic film, comprising an aqueous solution containing a cationic surfactant and / or an amphoteric surfactant in a proportion of 0.0001% to 0.1% by weight. Agent.
処理剤において、前記水溶液は表面張力が３５〜７０ダ
イン／ｃｍ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 aqueous solution has a surface tension of 35 to 70 dynes / cm.
２０重量％以下、カチオン性界面活性剤及び／又は両性
界面活性剤を０．０００１重量％以上０．１重量％以下
の割合で含有する水溶液を既存の部材の表面に塗布し、
既存の部材の表面を親水化した後に、当該既存の部材の
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。3. An aqueous solution containing colloidal silica in a proportion of 0.05 to 20% by weight and a cationic surfactant and / or an amphoteric surfactant in a proportion of 0.0001 to 0.1% by weight. Is applied to the surface of the existing member,
A method for forming a photocatalytic film, wherein a photocatalytic coating solution is applied to the surface of an existing member after the surface of the existing member is hydrophilized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9275588A JPH11106679A (en) | 1997-10-08 | 1997-10-08 | Surface-treating agent for formation of photocatalyst coating film and formation of photocatalyst coating film using the same surface treating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9275588A JPH11106679A (en) | 1997-10-08 | 1997-10-08 | Surface-treating agent for formation of photocatalyst coating film and formation of photocatalyst coating film using the same surface treating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11106679A true JPH11106679A (en) | 1999-04-20 |
Family
ID=17557556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9275588A Pending JPH11106679A (en) | 1997-10-08 | 1997-10-08 | Surface-treating agent for formation of photocatalyst coating film and formation of photocatalyst coating film using the same surface treating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11106679A (en) |
-
1997
- 1997-10-08 JP JP9275588A patent/JPH11106679A/en active Pending
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