JPH11156203A - Photocatalytic hydrophilic composition - Google Patents

Photocatalytic hydrophilic composition

Info

Publication number
JPH11156203A
JPH11156203A JP9321393A JP32139397A JPH11156203A JP H11156203 A JPH11156203 A JP H11156203A JP 9321393 A JP9321393 A JP 9321393A JP 32139397 A JP32139397 A JP 32139397A JP H11156203 A JPH11156203 A JP H11156203A
Authority
JP
Japan
Prior art keywords
photocatalytic
composition
hydrophilicity
polyvinyl alcohol
water
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
Application number
JP9321393A
Other languages
Japanese (ja)
Inventor
Makoto Hayakawa
信 早川
Mitsuhide Shimobukikoshi
光秀 下吹越
Masahiro Miyauchi
雅浩 宮内
Hirotaka Ishibashi
弘孝 石橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toto Ltd
Original Assignee
Toto Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP9321393A priority Critical patent/JPH11156203A/en
Publication of JPH11156203A publication Critical patent/JPH11156203A/en
Pending legal-status Critical Current

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  • Surface Treatment Of Glass (AREA)
  • Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalytic hydrophilic composition excellent in sticking property to the surface of a base material. SOLUTION: The photocatalytic hydrophilic composition gives hydrophilicity to the surface by dispersing a photocatalytic metal oxide particle such as a crystalline TiO2 and a polyvinyl alcohol having 50-90 mol.% saponification value in water to prepare a mixed solution and applying the mixed solution on the surface of the base material such as a glass plate and drying. The composition can be an aq. dispersion containing the photocatalytic metal oxide particle, the polyvinyl alcohol, and phosphoric acid and a silica particle or an alumina particle can be added.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は合成樹脂やガラス等
の基材表面に塗布することで表面を親水性にする光触媒
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 applying hydrophilicity to a surface of a base material such as synthetic resin or glass by applying the composition to the surface.

【0002】[0002]

【従来の技術】合成樹脂やガラス等の基材表面は表面エ
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。このため合成樹脂等の基材
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 The surface of a substrate such as a synthetic resin or glass has a relatively small surface energy and exhibits hydrophobicity. For this reason,
Condensation or fogging on the surface. For this reason, physical means for imparting hydrophilicity by performing corona discharge treatment on the surface of a base material such as a synthetic resin have 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】上述したように、従来
の親水性を付与する手段には種々の不具合があり、更に
従来の手段には共通して以下の課題がある。即ち、第1
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。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。
As described above, the conventional means for imparting hydrophilicity have various disadvantages, and the conventional means have the following problems in common. That is, the first
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, and once the hydrophilicity is lost, the hydrophilicity is maintained unless applied again. Does not recover. 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, the degree of hydrophilicity is only up to about 10 ° in terms of the contact angle with water,
Sufficient hydrophilicity cannot be exhibited.

【0005】[0005]

【課題を解決するための手段】上記課題を解決すべく本
発明に係る光触媒性親水性組成物は、基材の表面に親水
性を付与する組成物であって、光触媒性金属酸化物粒子
とポリビニルアルコールとを水に分散させて構成され
る。
Means for Solving the Problems To solve the above-mentioned problems, a photocatalytic hydrophilic composition according to the present invention is a composition for imparting hydrophilicity to the surface of a substrate, and comprises a photocatalytic metal oxide particle. It is constituted by dispersing polyvinyl alcohol in water.

【0006】尚、塗膜の強度を向上させるためリン酸を
添加することが可能である。リン酸の添加量はポリビニ
ルアルコールに対して重量比で、5〜50%とすること
が好ましい。5%未満では塗膜の強度が不足し、50%
を超えると塗膜に白い斑点が生じやすくなる。
[0006] Phosphoric acid can be added to improve the strength of the coating film. The amount of phosphoric acid to be added is preferably 5 to 50% by weight based on polyvinyl alcohol. If it is less than 5%, the strength of the coating film is insufficient, and 50%
When it exceeds, white spots tend to be formed on the coating film.

【0007】ポリビニルアルコール(PVA)のケン化
度は50〜90モル%であることが好ましい。完全ケン
化型PVAとTiO2(光触媒性金属酸化物粒子)とを混
合する場合にはTiO2の比率が高い方が水との接触角が
小さくなり、部分ケン化型PVAとTiO2とを混合する
場合にはPVAの比率が高い方が水との接触角が小さく
なる傾向にあることが実験の結果判明した。そして、ケ
ン化度を上記の範囲にすることで、暗所や製造直後の水
との接触角が小さくなる。
The degree of saponification of polyvinyl alcohol (PVA) is preferably from 50 to 90 mol%. When fully saponified PVA and TiO 2 (photocatalytic metal oxide particles) are mixed, the higher the ratio of TiO 2 , the smaller the contact angle with water, and the more partially saponified PVA and TiO 2 are mixed. Experiments have shown that when mixing, the higher the ratio of PVA, the smaller the contact angle with water tends to be. By setting the degree of saponification in the above range, the contact angle with water in a dark place or immediately after production becomes small.

【0008】また、本発明に係る光触媒性親水性組成物
には、シリカ粒子やアルミナ粒子を添加することが可能
である、これらシリカ粒子やアルミナ粒子を添加するこ
とで、膜の強度が向上する。
Further, it is possible to add silica particles or alumina particles to the photocatalytic hydrophilic composition according to the present invention. By adding these silica particles or alumina particles, the strength of the film is improved. .

【0009】また、水性液中の光触媒性金属酸化物粒子
は0.01重量%以上〜10重量%以下とするのが好ま
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
って塗膜の結合強度を低下せしめることになる。また、
塗膜中の光触媒性金属酸化物粒子の量としては、1×1
-7〜1×10-3g/cm2、好ましくは5×10-7
5×10-4g/cm2、更に好ましくは1×10-6〜1
×10-4g/cm2である。
[0009] The content of the photocatalytic metal oxide particles in the aqueous liquid is preferably 0.01% by weight 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 it is added above the above range, the effect is not improved by the addition, but rather the bonding strength of the coating film is reduced. Will be. Also,
The amount of the photocatalytic metal oxide particles in the coating film was 1 × 1
0 -7 to 1 × 10 -3 g / cm 2 , preferably 5 × 10 -7 to
5 × 10 −4 g / cm 2 , more preferably 1 × 10 −6 to 1
× 10 −4 g / cm 2 .

【0010】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。
[0010] 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.

【0011】このように、本発明による親水性は、ポリ
ビニルアルコールに由来するよりも、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、ポリビニルア
ルコール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。
As described above, it is considered that the hydrophilicity according to the present invention is due to the hydrophilizing action of the photocatalyst, rather than being derived from polyvinyl alcohol. This means that in order to exhibit hydrophilicity by polyvinyl alcohol, it had to be applied with a thickness of several tens of μm or more, but in the case of the composition according to the present invention, hydrophilicity was exhibited even at 0.4 μm or less. I can also agree.

【0012】ここで、塗膜の厚みを0.4μm以下の厚
みにすることで、光の乱反射による白濁を防止すること
ができ、更に0.2μm以下の厚みにすることで、光の
干渉による表面相の発色を防止することができる。
Here, by setting the thickness of the coating film to 0.4 μm or less, it is possible to prevent white turbidity due to irregular reflection of light, and to further reduce the thickness to 0.2 μm or less to prevent interference by light. Coloring of the surface phase can be prevented.

【0013】[0013]

【発明の実施の形態】以下の(表1)に示す4種類のP
VA(日本合成化学工業社製)を用意した。尚、粘度は
4%水溶液のものである。
DESCRIPTION OF THE PREFERRED EMBODIMENTS Four types of P shown in the following (Table 1)
VA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was prepared. The viscosity is that of a 4% aqueous solution.

【0014】[0014]

【表1】 [Table 1]

【0015】上記の各PVAにチタニアゾル(昭和電工
製、pH4、固形分濃度10重量%)を以下の(表2)
に示す割合で混合し、この混合液を水に分散させて光触
媒性親水性組成物液を調製した。PVAとTiO2との比
率、水に分散させた場合の固形分比、液の安定性、ガラ
ス板にフローコーティング法にて塗布した場合の膜の外
観、製膜直後の水との接触角、耐消しゴム摺動回数(耐
摩耗性)を以下の(表2)に示す。
Titania sol (manufactured by Showa Denko, pH 4, solid content concentration 10% by weight) was added to each of the PVAs described above (Table 2).
And the mixture was dispersed in water to prepare a photocatalytic hydrophilic composition liquid. The ratio of PVA to TiO 2 , the solid content ratio when dispersed in water, the stability of the liquid, the appearance of the film when applied to a glass plate by the flow coating method, the contact angle with water immediately after film formation, The number of erase rubber sliding times (wear resistance) is shown in the following (Table 2).

【0016】[0016]

【表2】 [Table 2]

【0017】上記の(表2)からも明らかなように、P
VAとチタニアゾルを含む水性液はpHを調製するまで
もなく安定しており、固形分比が8%のものを除いて膜
の外観も良好で、また製膜直後の親水性については、完
全ケン化型PVA(NL-05,NH-26)はTiO2の比率が高
い方が接触角が低く、部分ケン化型PVA(GL-03,GH-
23)はPVAの比率が高い方が接触角が低かった。更
に、PVAの重合度については、重合度が低い方が親水
性に優れ、また重合度が高い方が膜強度に優れることが
判明した。
As is clear from the above (Table 2), P
The aqueous liquid containing VA and titania sol is stable without adjusting the pH, the appearance of the film is good except for those having a solid content ratio of 8%, and the hydrophilicity immediately after film formation is completely As for the modified PVA (NL-05, NH-26), the higher the ratio of TiO 2 , the lower the contact angle, and the partially saponified PVA (GL-03, GH-26).
In 23), the higher the ratio of PVA, the lower the contact angle. Furthermore, as for the degree of polymerization of PVA, it was found that the lower the degree of polymerization, the better the hydrophilicity, and the higher the degree of polymerization, the better the film strength.

【0018】次に、上記の各膜に対して、0.5mW/
cm2の強度のBLBランプ(紫外線ランプ)を24時
間照射した結果、何れの膜も水との接触角は5°以下に
なった。この後、水との接触角が製膜直後の状態になる
まで暗所に放置し、この後再び0.5mW/cm2の強
度のBLBランプを照射すると、再び水との接触角が5
°以下に戻った。
Next, for each of the above films, 0.5 mW /
As a result of irradiating a BLB lamp (ultraviolet lamp) having an intensity of cm 2 for 24 hours, the contact angle of any of the films with water became 5 ° or less. Thereafter, the film was left in a dark place until the contact angle with water became a state immediately after film formation. Thereafter, irradiation with a BLB lamp having an intensity of 0.5 mW / cm 2 again caused the contact angle with water to become 5 again.
° returned to below.

【0019】これに対し、重合度1700のポリビニル
アルコールの5%水溶液50ccに85%リン酸0.5
ccを加えた溶液をガラス板にフローコーティング法に
て塗布した場合の膜については、紫外線を照射しても水
との接触角に変化は生じなかった。
On the other hand, 85% phosphoric acid 0.5
Regarding the film when the solution containing cc was applied to the glass plate by the flow coating method, the contact angle with water did not change even when the film was irradiated with ultraviolet rays.

【0020】更に、(表2)に示した各試料にシリカ粒
子を添加した。その結果、暗所での親水性維持効果が大
幅に向上した。また、シリカ粒子の代りにアルミナ粒子
を添加した場合にも暗所での親水性維持効果が向上し
た。
Further, silica particles were added to each sample shown in (Table 2). As a result, the effect of maintaining hydrophilicity in a dark place was greatly improved. Further, when alumina particles were added instead of silica particles, the effect of maintaining hydrophilicity in a dark place was improved.

【0021】また、(表2)に示した各試料にリン酸を
ポリビニルアルコールに対して重量比で5〜50%の範
囲で添加した結果、耐消しゴム摺動回数(耐摩耗性)に
おいて、向上がみられた。
Further, as a result of adding phosphoric acid to each of the samples shown in Table 2 in a weight ratio of 5 to 50% with respect to polyvinyl alcohol, the number of times of sliding of the eraser rubber (abrasion resistance) was improved. Was seen.

【0022】[0022]

【発明の効果】以上に説明した如く本発明によれば、光
触媒性金属酸化物粒子とポリビニルアルコールを水に分
散させて光触媒性親水性組成物を構成したので、基材に
対する塗膜の固着性が向上し、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。そして、特
にシリカ粒子やアルミナ粒子を添加することで、暗所で
の親水性維持効果が向上し、また膜の強度も向上する。
As described above, according to the present invention, since the photocatalytic hydrophilic composition is formed by dispersing the photocatalytic metal oxide particles and polyvinyl alcohol in water, the adhesion of the coating film to the substrate is improved. In addition, the photocatalytic hydrophilic coating once formed can maintain a highly hydrophilized surface for a long period of time and can reduce the thickness of the coating, so that there is no problem such as cloudiness or coloring. Furthermore, since it is an aqueous composition, it has no solvent odor and is excellent in handleability. In particular, by adding silica particles or alumina particles, the effect of maintaining hydrophilicity in a dark place is improved, and the strength of the film is also improved.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C08K 3/00 C08K 3/00 3/22 3/22 C08L 29/04 C08L 29/04 A //(C08K 3/00 3:22 3:32) (C08K 3/00 3:22 3:32 3:36) (72)発明者 宮内 雅浩 福岡県北九州市小倉北区中島2丁目1番1 号 東陶機器株式会社内 (72)発明者 石橋 弘孝 福岡県北九州市小倉北区中島2丁目1番1 号 東陶機器株式会社内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 3/00 C08K 3/00 3/22 3/22 C08L 29/04 C08L 29/04 A // (C08K 3/00 3: (22:32) (C08K 3/00 3:22 3:32 3:36) (72) Inventor Masahiro Miyauchi 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Totoki Kiki Co., Ltd. (72) Inventor Hirotaka Ishibashi 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 基材の表面に親水性を付与する組成物で
あって、この組成物は、光触媒性金属酸化物粒子と、ポ
リビニルアルコールとを含有する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 substrate, wherein the composition comprises an aqueous dispersion containing photocatalytic metal oxide particles and polyvinyl alcohol. Photocatalytic hydrophilic composition.
【請求項2】 基材の表面に親水性を付与する組成物で
あって、この組成物は、光触媒性金属酸化物粒子と、ポ
リビニルアルコールと、リン酸とを含有する水性分散液
からなることを特徴とする光触媒性親水性組成物。
2. A composition for imparting hydrophilicity to the surface of a substrate, wherein the composition comprises an aqueous dispersion containing photocatalytic metal oxide particles, polyvinyl alcohol, and phosphoric acid. A photocatalytic hydrophilic composition comprising:
【請求項3】 請求項1または請求項2に記載の光触媒
性親水性組成物において、この組成物にはシリカ粒子ま
たはアルミナ粒子が添加されている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, wherein silica or alumina particles are added to the composition.
【請求項4】 請求項1乃至請求項3に記載の光触媒性
親水性組成物において、前記ポリビニルアルコールのケ
ン化度は50〜90モル%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 polyvinyl alcohol has a saponification degree of 50 to 90 mol%.
JP9321393A 1997-11-21 1997-11-21 Photocatalytic hydrophilic composition Pending JPH11156203A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9321393A JPH11156203A (en) 1997-11-21 1997-11-21 Photocatalytic hydrophilic composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9321393A JPH11156203A (en) 1997-11-21 1997-11-21 Photocatalytic hydrophilic composition

Publications (1)

Publication Number Publication Date
JPH11156203A true JPH11156203A (en) 1999-06-15

Family

ID=18132056

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9321393A Pending JPH11156203A (en) 1997-11-21 1997-11-21 Photocatalytic hydrophilic composition

Country Status (1)

Country Link
JP (1) JPH11156203A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001080974A (en) * 1999-09-08 2001-03-27 Fuji Photo Film Co Ltd Composite base plate material and method for producing the same
WO2005014720A1 (en) * 2003-08-12 2005-02-17 Taiyo Kogyo Corporation Photocatalyst dispersion liquid and method for producing same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001080974A (en) * 1999-09-08 2001-03-27 Fuji Photo Film Co Ltd Composite base plate material and method for producing the same
WO2005014720A1 (en) * 2003-08-12 2005-02-17 Taiyo Kogyo Corporation Photocatalyst dispersion liquid and method for producing same

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