JP4608042B2 - Coating agent for forming inorganic film, method for producing the same, and method for forming the inorganic film - Google Patents
Coating agent for forming inorganic film, method for producing the same, and method for forming the inorganic film Download PDFInfo
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- JP4608042B2 JP4608042B2 JP26155299A JP26155299A JP4608042B2 JP 4608042 B2 JP4608042 B2 JP 4608042B2 JP 26155299 A JP26155299 A JP 26155299A JP 26155299 A JP26155299 A JP 26155299A JP 4608042 B2 JP4608042 B2 JP 4608042B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、光活性、抗菌性、親水性、耐汚染性、防曇性、ガス分解性、脱臭性、水処理性、エネルギー変換性、脱色性等の優れた酸化チタン膜を提供する無機膜形成用塗布剤、無機膜形成用塗布剤の製造方法及び無機膜形成方法に関する。
【０００２】
【従来の技術及びその課題】
従来、酸化チタン膜を形成する方法としては、（１）酸化チタンゾルを基材に塗布後、焼結する方法、（２）塩化チタンや硫酸チタンの水溶液を基材に塗布後、加熱処理する方法、（３）固体粒子を大気中で発生させたプラズマ中で溶融し基材表面にたたき付けるプラズマ溶射方法、（４）真空中で酸化物のタ−ゲットをスパッタリングし基材上に成膜するスパッタ法、（５）有機金属化合物等を揮発させ電気炉の中で分解して基材上に膜を形成させるＣＶＤ法、（６）金属アルコキシドの加水分解で得たゾルを基材に塗布後、焼結するゾルーゲル法等が挙げられる。
【０００３】
しかしながら、上記した方法においては、（１）は０．１μｍ以上の膜厚ではワレ、剥がれを生じるため造膜性が劣り、また数百度以上の温度で焼結する必要があり手間が掛かること、（２）は熱分解物による基材への悪影響や数百度以上の温度で焼結する必要があり手間が掛かること、（３）は緻密な膜が形成できないこと、基材に対する付着性が劣ること、（４）及び（５）は減圧下でなければ良好な膜が得られず、真空排気できる反応容器が必要であり、一般に成膜速度が遅く、緻密な膜を得るためには数百度以上に基体を加熱しなければならないこと、（６）のゾル中には酸やアルカリあるいは有機物が加えられており、被コーティング材の腐蝕の問題があり、有機物除去のための温度（４００℃以上）が必要あった。
【０００４】
また、上記した欠点である高温焼結する工程を含まない方法として、（７）酸化チタンの弗化物水溶液と硼酸から酸化チタン膜を形成すること、（８）塩化チタンや硫酸チタン水溶液とアンモニアや苛性ソーダ等のアルカリ溶液から水酸化チタンゲルを沈殿させ、次いでデカンテーションによって水酸化チタンゲル分離し、良く水洗し、さらに過酸化水素水を加え製造する方法（特開平9-71418号公報参照）等が知られている。
しかしながら、（７）は膜を形成するのに長時間必要とすること、弗化物の取り扱いが面倒であること、（８）は工程が複雑であること、アルカリ塩の除去が面倒であること、他金属が混入し易く純度の高いものを得ることは難しい、ＰＨのコントロールが難しくその変動によって得られるものが異なってしまう等の欠点がある。
【０００５】
本発明は上記した問題点を解消した無機膜形成用塗布剤、その製造方法及び無機膜形成方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者は、上記した目的を達成すべく鋭意研究を重ねた結果、特に酸化チタンゾルの存在下で、加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物を過酸化水素水と反応させて得られる無機膜形成用塗布剤及びその加熱変性による無機膜形成用塗布剤が、従来からの欠点を全て解消することを見出し、本発明を完成するに至った。即ち、本発明は、酸化チタンゾルの存在下で、加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物を過酸化水素水と反応させることを特徴とする無機膜形成用塗布剤の製造方法、上記製造方法において、加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物を過酸化水素水と反応温度１〜７０℃の範囲内で反応させることを特徴とする無機膜形成用塗布剤の製造方法、並びに該製造方法によって得られた無機膜形成用塗布剤を基材に塗布あるいは含浸させ、乾燥あるいは加熱処理して形成させて得られることを特徴とする無機膜形成方法に係わる。
【０００７】
【発明の実施の形態】
本発明の無機膜形成用塗布剤は、酸化チタンゾルの存在下で、加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物を過酸化水素水と反応させて得られるものである。
【０００８】
本発明で使用する酸化チタンゾルは、無定型チタニア、アナタース型チタニア微粒子が水（必要に応じて、例えば、アルコール系、アルコールエーテル系等の水性有機溶剤を含有しても構わない）に分散したゾルである。
【０００９】
上記した酸化チタンゾルとしては従来から公知のものを使用することができる。該酸化チタンゾルとしては、例えば、（１）硫酸チタンや硫酸チタニルなどの含チタン溶液を加水分解して得られるもの、（２）チタンアルコキシド等の有機チタン化合物を加水分解して得られるもの、（３）四塩化チタン等のハロゲン化チタン溶液を加水分解又は中和して得られるもの等の酸化チタン凝集物を水に分散した無定型チタニアゾルや該酸化チタン凝集物を焼成してアナタース型チタン微粒子としこのものを水に分散したものを使用することができる。無定形チタニアの焼成は少なくともアナターゼの結晶化温度以上の温度、例えば、４00℃〜500℃以上の温度で焼成すれば、無定形チタニアをアナターゼ型チタニアに変換させることができる。該酸化チタンの水性ゾルとして、例えば、ＴＫＳ−２０１（テイカ（株）社製、商品名、アナターズ型結晶形、平均粒子径６ｎｍ）、ＴＡ−１５（日産化学（株）社製、商品名、アナターズ型結晶形）、ＳＴＳ−１１（石原産業（株）社製、商品名、アナターズ型結晶形）等が挙げられる。
【００１０】
チタンモノマーやその縮合物と過酸化水素水とを反応させるために使用する際の上記酸化チタンゾルとチタン過酸化水素反応物との重量比率は１／９９〜９９／１、好ましくは約１０／９０〜９０／１０範囲である。重量比率が１／９９未満になると安定性、光反応性等酸化チタンゾルを添加した効果が見られず、９９／１を越えると造膜性が劣るので好ましくない。
【００１１】
該加水分解して水酸基になる基を含有するチタンモノマーとしては、特に一般式 Ｔｉ（ＯＲ）4 （式中、Ｒは同一もしくは異なって炭素数１〜５のアルキル基を示す）のテトラアルコキシチタンが好ましい。炭素数１〜５のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられる。
【００１２】
また、加水分解して水酸基になる基を含有するチタンモノマーの低縮合物としては、特に上記したＴｉ（ＯＲ）4 をお互いに縮合反応させてなる縮合度２〜３０の化合物が使用可能で、特に縮合度２〜１０の範囲内のものを使用することが好ましい。
加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物（以下、これらのものを単に「加水分解性チタン」と略す）と過酸化水素水との混合割合が、加水分解性チタン１０重量部に対して過酸化水素換算で０．１〜１００重量部、特に１〜２０重量部の範囲内が好ましい。過酸化水素換算で０．１重量部未満になるとキレート形成が十分でなく白濁沈殿してしまう。一方、１００重量部を超えると未反応の過酸化水素が残存し易く貯蔵中に危険な活性酸素を放出するので好ましくない。
【００１３】
過酸化水素水の過酸化水素濃度は特に限定されないが３〜３０重量範囲内であることが取り扱いやすさ、塗装作業性に関係する生成液の固形分の点で好ましい。
また、本発明の無機膜形成用塗布剤は、加水分解性チタンを過酸化水素水と反応温度１〜 ７０℃の範囲内で１０分〜２０時間反応させることにより製造できる。
【００１４】
本発明の無機膜形成用塗布剤は、加水分解性チタンを過酸化水素水と反応させることにより、加水分解性チタンが水で加水分解されて水酸基含有チタン化合物を生成し、次いで過酸化水素が生成した水酸基含有チタン化合物に配位するものと推察され、この加水分解反応及び過酸化水素による配位が同時近くに起こることにより得られたものであり、室温域で安定性が極めて高く長期の保存に耐えるキレート液を生成する。従来の製法で用いられる水酸化チタンゲルはＴｉ−Ｏ−Ｔｉ結合により部分的に三次元化しており、このゲルと過酸化水素水を反応させた物とは組成、安定性に関し本質的に異なる。又、酸化チタンゾルをあらかじめ添加しておくと、合成時に一部縮合反応が起きて増粘する事を防ぐようになる。その理由は縮合反応物が酸化チタンゾルの表面に吸着され、溶液状態での高分子化を防いでいるためと考えられる。
本発明の無機膜形成用塗布剤を基材上に塗布乾燥、または低温で加熱処理することにより付着性に優れた緻密な酸化チタン膜を形成できる。低い温度でも酸化チタン膜を形成できるが、密着性を良くするためには２００℃以上の処理温度が好ましい。また、１回の塗布で１μｍ以上の酸化チタン膜を剥離することなく付着性に優れた膜が形成できるが、膜厚としては通常、０．００１〜１０μｍ、特に０．１〜１μｍの範囲が好ましい。
本発明の無機膜形成用塗布剤は、２００℃未満では水酸基を若干含む非晶質の酸化チタンが含まれた膜を形成するが、２００℃以上では結晶性の緻密な酸化チタン膜を形成する。
【００１５】
酸化チタンゾルの量が多い場合は塗布するだけでも結晶性の酸化チタン膜が形成できるため、加熱処理をできない材料のコーティング材として有用である。このような方法において、上記した種々の用途に利用可能であり、しかも比較的密度が高く密着性の良いものを低温で得ることができる。
乾燥しただけの膜は耐水性があるが含侵性もあり、他の化合物溶液を含侵させその後加熱処理させることにより、酸化チタン膜の中に他の物質を担持あるいは分散した複合体を形成することも可能である。他の物質としては、例えば、他の金属化合物が使用可能である。
【００１６】
上記無機膜形成用塗布剤に後から他の顔料やゾルを添加分散する事も出来る。添加物としては、市販されている酸化チタンゾル、酸化チタン粉末等が一例として挙げることができる。
【００１７】
本発明で使用できる基材としては、例えば、金属、陶磁器、プラスチックス、繊維、ガラス、コンクリート等、用途に応じた加熱処理に耐え得る素材であればあらゆるものに塗布が可能であり、多孔体の内部や粉体の表面処理を行なうことも可能である。
本発明によって得られた酸化チタン膜の中には、光照射によって活性になる物が多い。例えば、窒素酸化物等を酸化して硝酸に変化させることができる。
また、本発明によって得られた酸化チタン膜は光活性の性質以外に耐熱性、防食性に優れた被膜を形成することができるので耐熱、防食塗膜として利用することもできる。
【００１８】
上記のような酸化チタンの光活性の性質を利用して、例えば、大気や水の環境汚染物質を分解除去、親水化処理、抗菌処理、消臭、防曇性、水処理、エネルギー変換性等の分野で利用できる。
【００１９】
【実施例】
次に実施例を挙げて本発明を詳細に説明する。本発明は下記した実施例に限定されるものではない。なお、実施例及び比較例に記載の「部」及び「％」は重量基準である。
実施例１
テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロパノール１０部の混合物をＴＫＳ−２０１（テイカ(株)製、酸化チタンゾル）を５部（固形分）、３０％過酸化水素水１０部、脱イオン水１００部の混合物中に１０℃で１時間かけて撹拌しながら滴下した。その後１０℃で２４時間熟成し黄色透明の少し粘性のある無機膜形成用塗布剤を得た。
【００２０】
実施例２
製造例１のテトラｉｓｏ−プロポキシチタンの代わりにテトラｎ−ブトキシチタンを使用して同様の製造条件で無機膜形成用塗布剤を得た。
【００２１】
実施例３
実施例１のテトラｉｓｏ−プロポキシチタンの代わりにテトラｉｓｏ−プロポキシチタンの３量体を使用して同様の製造条件で無機膜形成用塗布剤液を得た。
【００２２】
実施例４
実施例１において過酸化水素水を３倍量用い１０℃で１時間かけて滴下しさらに１０℃で３０時間熟成し無機膜形成用塗布剤を得た。
【００２３】
比較例１
テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロパノール１０部の混合物を３０％過酸化水素水１０部、脱イオン水１００部の混合物中に１０℃で１時間かけて撹拌しながら滴下した。その後１０℃で２４時間熟成し黄色透明の少し粘性のある無機膜形成用塗布剤を得た。
実施例１〜４と比較例１の無機膜形成用塗布液を酸化チタン濃度で５％まで濃縮すると比較例１はノリ状に固化したが、製造例１〜４は流動性のある液体であった。
【００２４】
塗膜形成方法は次の方法で形成した。
実施例１〜４の無機膜形成用塗布剤及び比較例１の無機膜形成用塗布剤をバーコーターで軟鋼板に乾燥膜厚が０．３μｍになるように塗装し、１００℃で３０分間焼付けた。
実施例１〜４の無機膜形成用塗布剤及び比較例１の無機膜形成用塗布剤の貯蔵安定性（１）及び上記条件で形成した塗板を使用して塗膜状態（２）、付着性（３）、鉛筆硬度（４）、耐水性（５）、水濡れ性（水接触角）（６）の試験を行ない、その結果をまとめて表１に示す。
【００２５】
【表１】
（１）貯蔵安定性：５０℃で１００時間貯蔵後の粘度変化や沈降性等を調べた（初期のものと比較）。
（２）塗膜状態：塗膜の平滑性、透明性、造膜性（ワレ等）などの塗膜異常の有無を観察した。
（３）付着性：ＪＩＳ Ｋ−５４００ ８．５．２（１９９０）碁盤目−テ−プ法に準じて、１ｍｍ×１ｍｍのマス目を１００個作成し、その表面にテ−プを密着させ剥離した際のマス目の残った数を調べた。
（４）鉛筆硬度：ＪＩＳ Ｋ−５４００ ８．４．２（１９９０）に規定する鉛筆引っかき試験を行ない、すり傷による評価を行なった。
（５）耐水性：２０℃の水に７日間浸漬した後、塗膜外観を目視で観察した。
（６）水濡れ性：塗膜表面の水接触角を測定した。４ＫＷ高圧水銀灯を塗膜表面からの距離３０ｃｍで１０分照射後、水接触角を測定した。水接触角は２０℃にて試験塗板上に０．０３ｃｃの脱イオン水の水滴を形成し、水滴の接触角を協和化学（株）製、コンタクタングルメ−タ−ＤＣＣＡ型にて測定した。
【００２７】
【発明の効果】
本発明の製造方法において、酸化チタンゾルの存在下で加水分解して水酸基になる基を含有するチタンモノマー及び／又はその低縮合物を過酸化水素水と反応させることにより、該チタンモノマー及び／又はその低縮合物の成分が酸化チタンゾルの酸化チタンゾル粒子に吸着され、この吸着されたチタンモノマー及び／又はその低縮合物が該粒子表面で縮合反応して粒子表面の水酸基と反応しチタンモノマー及び／又はその低縮合物と化学結合すると共に、該チタンモノマー及び／又はその低縮合物自体も粒子表面上で縮合反応して高分子化されるのでゲル化や増粘がなく安定かつ製造バラツキ無く塗膜性能に優れた塗布剤（チタンゾル液）が製造できる。当然、酸化チタンゾルだけでは造膜性に劣るし、後からチタン過酸化水素錯体を加えても相溶性が低く造膜性もそれほど向上しない。
また、本発明の製造方法において、チタンモノマー及び／又はその低縮合物と過酸化水素水と反応で形成されるチタン過酸化水素錯体だけでは低温で塗膜乾燥させると無定型の酸化チタンしか形成しないが、ゾルとしてアナターゼ型酸化チタンソルを使用した場合には低温で塗膜乾燥した場合でも光触媒としての機能を発揮する。 このものは防食性等の分野や該酸化チタン膜の光触媒活性を利用した分野などで使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention provides an inorganic film that provides a titanium oxide film having excellent photoactivity, antibacterial properties, hydrophilicity, stain resistance, antifogging properties, gas decomposability, deodorizing properties, water treatment properties, energy conversion properties, decolorizing properties, etc. The present invention relates to a forming coating agent, a method for producing an inorganic film forming coating agent, and an inorganic film forming method.
[0002]
[Prior art and problems]
Conventionally, as a method for forming a titanium oxide film, (1) a method in which a titanium oxide sol is applied to a substrate and then sintered, and (2) a method in which an aqueous solution of titanium chloride or titanium sulfate is applied to the substrate and then heat-treated. (3) A plasma spraying method in which solid particles are melted in a plasma generated in the air and are applied to the surface of the substrate. (4) An oxide target is sputtered in vacuum to form a film on the substrate. (5) CVD method in which organometallic compounds are volatilized and decomposed in an electric furnace to form a film on the substrate, and (6) a sol obtained by hydrolysis of metal alkoxide is applied to the substrate. And a sol-gel method for sintering.
[0003]
However, in the above-described method, (1) causes cracking and peeling at a film thickness of 0.1 μm or more, so that the film forming property is inferior, and it is necessary to sinter at a temperature of several hundred degrees or more. (2) is an adverse effect on the base material due to the pyrolyzate, and it is necessary to sinter at a temperature of several hundred degrees or more, and (3) is incapable of forming a dense film, and has poor adhesion to the base material. In (4) and (5), a good film cannot be obtained unless the pressure is reduced, and a reaction vessel that can be evacuated is required. In general, the film forming speed is low, and in order to obtain a dense film, several hundred degrees The substrate must be heated as described above, and acid, alkali or organic matter is added to the sol of (6), and there is a problem of corrosion of the material to be coated. ) Was necessary.
[0004]
Further, as a method not including the above-mentioned disadvantageous high temperature sintering step, (7) forming a titanium oxide film from an aqueous fluoride solution of titanium oxide and boric acid, (8) an aqueous solution of titanium chloride or an aqueous titanium sulfate solution, ammonia, Known is a method in which titanium hydroxide gel is precipitated from an alkaline solution such as caustic soda, then separated by decantation, thoroughly washed with water, and further added with hydrogen peroxide (see JP-A-9-71418). It has been.
However, (7) requires a long time to form a film, the handling of fluoride is troublesome, (8) the process is complicated, the removal of alkali salts is troublesome, There are drawbacks such that it is difficult to obtain a high purity material that is easily mixed with other metals, and that it is difficult to control the pH and that the product obtained by the variation is different.
[0005]
An object of the present invention is to provide a coating agent for forming an inorganic film, a method for producing the same, and a method for forming an inorganic film, which have solved the above-mentioned problems.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the present inventor has peroxidized a titanium monomer and / or a low condensate thereof containing a group that hydrolyzes into a hydroxyl group, particularly in the presence of a titanium oxide sol. It has been found that an inorganic film-forming coating agent obtained by reacting with hydrogen water and an inorganic film-forming coating agent by heat modification thereof can eliminate all the conventional drawbacks, and have completed the present invention. That is, the present invention is for forming an inorganic film characterized by reacting a titanium monomer containing a group that hydrolyzes into a hydroxyl group and / or a low condensate thereof with hydrogen peroxide in the presence of a titanium oxide sol. In the production method of the coating agent and the production method described above, a titanium monomer containing a group that hydrolyzes to become a hydroxyl group and / or a low condensate thereof is reacted with hydrogen peroxide within a reaction temperature range of 1 to 70 ° C. A method for producing a coating agent for forming an inorganic film characterized by the above, and a coating agent for forming an inorganic film obtained by the production method applied to or impregnated on a base material, followed by drying or heat treatment. The present invention relates to a featured inorganic film forming method.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The coating agent for forming an inorganic film of the present invention is obtained by reacting a titanium monomer containing a group that hydrolyzes into a hydroxyl group and / or a low condensate thereof with hydrogen peroxide in the presence of a titanium oxide sol. It is.
[0008]
The titanium oxide sol used in the present invention is a sol in which amorphous titania and anatase titania fine particles are dispersed in water (for example, an alcohol-based or alcohol-ether-based aqueous organic solvent may be contained if necessary). It is.
[0009]
A conventionally well-known thing can be used as said titanium oxide sol. Examples of the titanium oxide sol include (1) those obtained by hydrolyzing a titanium-containing solution such as titanium sulfate and titanyl sulfate, (2) those obtained by hydrolyzing an organic titanium compound such as titanium alkoxide, 3) Amorphous titania sol in which titanium oxide aggregates such as those obtained by hydrolyzing or neutralizing titanium halide solutions such as titanium tetrachloride are dispersed in water, and anatase titanium fine particles by firing the titanium oxide aggregates It is possible to use a product obtained by dispersing this in water. Amorphous titania can be converted into anatase titania by firing at least at a temperature higher than the crystallization temperature of anatase, for example, at a temperature of 400 ° C. to 500 ° C. or higher. As an aqueous sol of the titanium oxide, for example, TKS-201 (manufactured by Teika Co., Ltd., trade name, Anata's crystal form, average particle diameter 6 nm), TA-15 (manufactured by Nissan Chemical Co., Ltd., trade name, Anata's crystal form), STS-11 (Ishihara Sangyo Co., Ltd., trade name, Anata's crystal form) and the like.
[0010]
The weight ratio of the titanium oxide sol and titanium hydrogen peroxide reactant when used to react the titanium monomer or its condensate with hydrogen peroxide is 1/99 to 99/1, preferably about 10/90. ~ 90/10 range. When the weight ratio is less than 1/99, the effect of adding titanium oxide sol such as stability and photoreactivity is not observed, and when it exceeds 99/1, the film forming property is inferior, which is not preferable.
[0011]
As the titanium monomer containing a group which becomes a hydroxyl group upon hydrolysis, tetraalkoxy titanium of the general formula Ti (OR) 4 (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms) Is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group. Can be mentioned.
[0012]
In addition, as a low condensate of a titanium monomer containing a group that is hydrolyzed to become a hydroxyl group, a compound having a condensation degree of 2 to 30 obtained by condensation reaction of Ti (OR) 4 with each other can be used. In particular, it is preferable to use those having a condensation degree of 2 to 10.
The mixing ratio of titanium monomer and / or its low condensate (hereinafter simply referred to as “hydrolyzable titanium”) containing hydrolyzed hydroxyl groups and hydrogen peroxide solution The amount is preferably 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide, based on 10 parts by weight of titanium. If the amount is less than 0.1 parts by weight in terms of hydrogen peroxide, chelate formation is not sufficient and white turbid precipitation occurs. On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide tends to remain, and dangerous active oxygen is released during storage.
[0013]
The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but it is preferably within the range of 3 to 30 weights from the viewpoint of ease of handling and the solid content of the product liquid related to coating workability.
The coating agent for forming an inorganic film of the present invention can be produced by reacting hydrolyzable titanium with hydrogen peroxide within a reaction temperature range of 1 to 70 ° C. for 10 minutes to 20 hours.
[0014]
In the coating agent for forming an inorganic film of the present invention, hydrolyzable titanium is hydrolyzed with water by reacting hydrolyzable titanium with aqueous hydrogen peroxide to produce a hydroxyl group-containing titanium compound. It is presumed to coordinate with the hydroxyl group-containing titanium compound produced, and it was obtained by the simultaneous occurrence of this hydrolysis reaction and coordination with hydrogen peroxide. Produces a chelating solution that can withstand storage. The titanium hydroxide gel used in the conventional production method is partially three-dimensionalized by Ti—O—Ti bond, and the product obtained by reacting this gel with hydrogen peroxide is essentially different in terms of composition and stability. In addition, if a titanium oxide sol is added in advance, a partial condensation reaction occurs during synthesis to prevent thickening. The reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol and prevents polymerization in the solution state.
By applying and drying the inorganic film-forming coating agent of the present invention on a substrate or heat-treating it at a low temperature, a dense titanium oxide film having excellent adhesion can be formed. Although the titanium oxide film can be formed at a low temperature, a treatment temperature of 200 ° C. or higher is preferable in order to improve adhesion. In addition, a film having excellent adhesion can be formed without peeling off a titanium oxide film having a thickness of 1 μm or more by one coating, but the film thickness is usually in the range of 0.001 to 10 μm, particularly 0.1 to 1 μm. preferable.
The coating agent for forming an inorganic film of the present invention forms a film containing amorphous titanium oxide containing some hydroxyl groups at less than 200 ° C., but forms a crystalline dense titanium oxide film at 200 ° C. or more. .
[0015]
When the amount of the titanium oxide sol is large, a crystalline titanium oxide film can be formed only by coating, so that it is useful as a coating material for a material that cannot be heat-treated. In such a method, a material having a relatively high density and good adhesion can be obtained at a low temperature.
A film that has only been dried is water-resistant but also impregnated, and impregnates other compound solutions and then heat-treated to form a composite in which other substances are supported or dispersed in the titanium oxide film. It is also possible to do. As other substances, for example, other metal compounds can be used.
[0016]
Other pigments and sols can be added and dispersed later in the coating agent for forming an inorganic film. Examples of the additive include commercially available titanium oxide sol, titanium oxide powder, and the like.
[0017]
As the base material that can be used in the present invention, for example, metals, ceramics, plastics, fibers, glass, concrete, and the like can be applied to any material as long as it can withstand heat treatment according to the application. It is also possible to perform surface treatment of the inside of the powder and powder.
Many of the titanium oxide films obtained by the present invention are activated by light irradiation. For example, nitrogen oxides can be oxidized and converted into nitric acid.
Moreover, since the titanium oxide film obtained by the present invention can form a film having excellent heat resistance and corrosion resistance in addition to the photoactive property, it can also be used as a heat resistant and anticorrosive coating film.
[0018]
Utilizing the photoactive properties of titanium oxide as described above, for example, decomposing and removing environmental pollutants in the atmosphere and water, hydrophilization treatment, antibacterial treatment, deodorization, anti-fogging property, water treatment, energy conversion, etc. Available in the field.
[0019]
【Example】
EXAMPLES Next, an Example is given and this invention is demonstrated in detail. The present invention is not limited to the examples described below. In the examples and comparative examples, “parts” and “%” are based on weight.
Example 1
A mixture of 10 parts of tetraiso-propoxytitanium and 10 parts of iso-propanol, 5 parts (solid content) of TKS-201 (manufactured by Teika Co., Ltd.), 10 parts of 30% hydrogen peroxide water, 100 parts of deionized water The mixture was added dropwise to 1 part of the mixture with stirring at 10 ° C. over 1 hour. Thereafter, it was aged at 10 ° C. for 24 hours to obtain a yellow transparent slightly viscous coating agent for forming an inorganic film.
[0020]
Example 2
A coating agent for forming an inorganic film was obtained under the same production conditions using tetra-n-butoxytitanium instead of tetraiso-propoxytitanium in Production Example 1.
[0021]
Example 3
A tetraiso-propoxytitanium trimer was used in place of the tetraiso-propoxytitanium of Example 1 to obtain a coating solution for forming an inorganic film under the same production conditions.
[0022]
Example 4
In Example 1, 3 times the amount of hydrogen peroxide solution was added dropwise at 10 ° C. over 1 hour and further aged at 10 ° C. for 30 hours to obtain an inorganic film forming coating agent.
[0023]
Comparative Example 1
A mixture of 10 parts of tetraiso-propoxytitanium and 10 parts of iso-propanol was dropped into a mixture of 10 parts of 30% hydrogen peroxide and 100 parts of deionized water with stirring at 10 ° C. over 1 hour. Thereafter, it was aged at 10 ° C. for 24 hours to obtain a yellow transparent slightly viscous coating agent for forming an inorganic film.
When the coating solutions for forming an inorganic film of Examples 1 to 4 and Comparative Example 1 were concentrated to 5% in terms of titanium oxide concentration, Comparative Example 1 solidified into a paste, but Production Examples 1 to 4 were fluid liquids. It was.
[0024]
The coating film forming method was formed by the following method.
The coating agent for forming an inorganic film of Examples 1 to 4 and the coating agent for forming an inorganic film of Comparative Example 1 were coated on a mild steel plate to a dry film thickness of 0.3 μm with a bar coater and baked at 100 ° C. for 30 minutes. It was.
Storage stability (1) of the coating agent for forming an inorganic film of Examples 1 to 4 and the coating agent for forming an inorganic film of Comparative Example 1 and the coating state (2) and adhesion using the coated plate formed under the above conditions Tests of (3), pencil hardness (4), water resistance (5), water wettability (water contact angle) (6) were conducted, and the results are shown in Table 1.
[0025]
[Table 1]
(1) Storage stability: Viscosity change and sedimentation after storage at 50 ° C. for 100 hours were examined (compared with the initial one).
(2) Coating film state: The presence or absence of coating film abnormalities such as coating film smoothness, transparency, film-forming property (cracking, etc.) was observed.
(3) Adhesion: According to JIS K-5400 8.5.2 (1990) grid-tape method, 100 squares of 1 mm × 1 mm are prepared, and the tape is adhered to the surface. The number of cells remaining when peeling was examined.
(4) Pencil hardness: A pencil scratch test specified in JIS K-5400 8.4.2 (1990) was performed, and evaluation by scratches was performed.
(5) Water resistance: After dipping in 20 ° C. water for 7 days, the appearance of the coating film was visually observed.
(6) Water wettability: The water contact angle on the coating film surface was measured. After irradiating a 4 KW high-pressure mercury lamp at a distance of 30 cm from the coating surface for 10 minutes, the water contact angle was measured. The water contact angle was 0.03 cc of deionized water droplets formed on the test coating plate at 20 ° C., and the contact angle of the water droplets was measured with a contactor gourmet-DCCA type manufactured by Kyowa Chemical Co., Ltd.
[0027]
【The invention's effect】
In the production method of the present invention, the titanium monomer and / or the low condensate thereof containing a group that hydrolyzes into a hydroxyl group in the presence of a titanium oxide sol is reacted with hydrogen peroxide solution, thereby reacting the titanium monomer and / or The component of the low condensate is adsorbed on the titanium oxide sol particles of the titanium oxide sol, and the adsorbed titanium monomer and / or the low condensate undergoes a condensation reaction on the particle surface to react with the hydroxyl group on the particle surface to react with the titanium monomer and / or In addition, the titanium monomer and / or the low condensate itself is polymerized by a condensation reaction on the particle surface, so that the polymer is polymerized, and there is no gelation or thickening. A coating agent (titanium sol liquid) excellent in film performance can be produced. Naturally, the titanium oxide sol alone is inferior in film forming property, and even if a titanium hydrogen peroxide complex is added later, the compatibility is low and the film forming property is not improved so much.
Further, in the production method of the present invention, only the titanium hydrogen peroxide complex formed by the reaction of the titanium monomer and / or its low condensate and hydrogen peroxide solution forms only amorphous titanium oxide when the coating film is dried at a low temperature. However, when anatase-type titanium oxide sol is used as the sol, it functions as a photocatalyst even when the coating film is dried at a low temperature. This material can be used in fields such as anticorrosion properties and fields utilizing the photocatalytic activity of the titanium oxide film.
Claims (6)
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| JP2006182791A (en) * | 2003-02-10 | 2006-07-13 | Kansai Paint Co Ltd | Coating material for forming photocatalyst film |
| TW200837156A (en) * | 2007-02-22 | 2008-09-16 | Kansai Paint Co Ltd | Coating agent for forming titanium/zirconium film, method for forming titanium/zirconium film and metal substrate coated with titanium/zirconium film |
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