JP2002088500A - Method for preparing crystal oriented laminar compound film by elecrophoresis method - Google Patents
Method for preparing crystal oriented laminar compound film by elecrophoresis methodInfo
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- JP2002088500A JP2002088500A JP2000282064A JP2000282064A JP2002088500A JP 2002088500 A JP2002088500 A JP 2002088500A JP 2000282064 A JP2000282064 A JP 2000282064A JP 2000282064 A JP2000282064 A JP 2000282064A JP 2002088500 A JP2002088500 A JP 2002088500A
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- layered
- thin film
- layered compound
- laminar compound
- compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電池の電極、触媒，光
触媒や光反応を利用する電池等、表面技術産業分野に応
用可能で、層間に種々のイオンや分子をインターカレー
トできる機能材料である層状化合物からなる薄膜を電気
泳動法で作製する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applicable to the surface technology industry, such as a battery electrode, a catalyst, a battery utilizing a photocatalyst or a photoreaction, and a functional material capable of intercalating various ions and molecules between layers. The present invention relates to a method for producing a thin film comprising a layered compound by electrophoresis.
【０００２】[0002]
【従来技術及び問題点】層状化合物、特に層状酸化物
は、層間に種々のイオンや分子をインターカレートでき
る興味ある機能材料として研究が進められている。電池
の電極や光触媒等の機能材料として利用する場合には、
層状化合物を基板に固定する必要がある。層状化合物の
固定化には、スピンコート法やＬＢ法が従来から採用さ
れている。しかし、スピンコート法やＬＢ法では、基板
に対する層状化合物の密着性が悪く、或いは結晶配向性
を保った膜として作製することが困難なこともある。2. Description of the Related Art Layered compounds, particularly layered oxides, have been studied as interesting functional materials capable of intercalating various ions and molecules between layers. When used as functional materials such as battery electrodes and photocatalysts,
It is necessary to fix the layered compound to the substrate. For immobilization of the layered compound, a spin coating method and an LB method have conventionally been employed. However, in the spin coating method or the LB method, the adhesion of the layered compound to the substrate may be poor, or it may be difficult to produce a film having a crystalline orientation.
【０００３】[0003]
【課題を解決するための手段】本発明者等は、スピンコ
ート法やＬＢ法に代わる方法として電気泳動法による固
定化を検討した。電気泳動法による成膜自体は従来から
知られている技術であるが、層状化合物の成膜に適用し
た例はこれまでのところ報告されていない。本発明者等
による調査・研究の結果、電気泳動法で固定した層状化
合物薄膜は、結晶配向性が高く、層剥離を伴いながら層
状化合物が電析することが明らかになった。Means for Solving the Problems The present inventors studied immobilization by electrophoresis as an alternative to spin coating or LB. Although the film formation by the electrophoresis method is a conventionally known technique, no example of applying the method to the formation of a layered compound has been reported so far. As a result of investigations and studies by the present inventors, it has been clarified that the layered compound thin film fixed by electrophoresis has a high crystal orientation and the layered compound is electrodeposited with delamination.
【０００４】本発明は、このような知見をベースに完成
されたものであり、結晶配向性のある層状化合物を有機
溶媒中で直流電圧又は交流電圧を印加して電気泳動させ
て基板上に電析させ、電析した層状化合物を薄膜とする
ことを特徴とする。有機溶媒としては、メタノール，エ
タノール，プロパノール，アセトン，ヘキサン等が使用
される。有機溶媒に分散させた層状化合物を分散させて
いる有機溶媒に、たとえば０．１〜１ｋＶの直流又は交
流電圧を印加すると、層状化合物は剥離を繰り返しなが
ら、それぞれの電荷に応じて陽極及び陰極上に電析す
る。その結果、陽極及び陰極上に２種類の層状化合物薄
膜が生成する。The present invention has been completed on the basis of such findings, and a layered compound having a crystalline orientation is electrophoresed by applying a DC voltage or an AC voltage in an organic solvent and electrophoresed on a substrate. Characterized in that the layered compound deposited and deposited is made into a thin film. As the organic solvent, methanol, ethanol, propanol, acetone, hexane and the like are used. When a DC or AC voltage of, for example, 0.1 to 1 kV is applied to the organic solvent in which the layered compound dispersed in the organic solvent is dispersed, the layered compound is repeatedly peeled off, and on the anode and the cathode in accordance with the respective charges. Electrodeposit. As a result, two types of layered compound thin films are formed on the anode and the cathode.
【０００５】層状化合物としては、グラファイト，マイ
カ，ハイロフィライト，タルク等があり、層状構造に由
来して二次元的物性やイオン交換等の特異な性質や機能
を呈する。なかでも、チタン系層状酸化物，ニオブ系層
状酸化物，タンタル系層状酸化物等の無機層状酸化物
は、ｎ型半導体特性を示すため、光触媒や電池の電極材
料等への応用が期待される。[0005] Examples of the layered compound include graphite, mica, phyllolite, talc and the like, and exhibit unique properties and functions such as two-dimensional physical properties and ion exchange derived from the layered structure. In particular, inorganic layered oxides such as titanium-based layered oxides, niobium-based layered oxides, and tantalum-based layered oxides exhibit n-type semiconductor properties, and are therefore expected to be applied to photocatalysts, battery electrode materials, and the like. .
【０００６】[0006]
【作用】本発明者等は、電気泳動法で層状化合物薄膜を
作製する調査・研究過程で、層剥離を伴いながら陽極と
陰極に別れて層状化合物が電析することを見出した。こ
のような電析は、層間に存在するイオン種によって層状
化合物が異なる電荷を帯びることに原因があるものと推
察される。The present inventors have found in the course of investigation and research for producing a layered compound thin film by an electrophoresis method that the layered compound is separated into an anode and a cathode while delamination occurs, and the layered compound is electrodeposited. It is presumed that such electrodeposition is caused by the layered compound having different charges depending on the ion species existing between the layers.
【０００７】すなわち、層状化合物は、層を形成するネ
ットワーク状の層部分と層間に存在するイオンや分子に
分けることができる。層状化合物の層間に存在するイオ
ンや分子は、比較的容易に他のイオンや分子と置換でき
る特性を備えている。また、層の部分の電荷は、層間の
物質や層状化合物を分散させる溶液の状態（ｐＨ等）に
よって電荷状態（プラスかマイナス）が異なる。たとえ
ば、チタン酸セシウム化合物では、層状構造を示す図１
のモデルにみられるように、チタン酸シートとセシウム
イオンが相互に重なった層構造を形成している。チタン
酸シートには、マイナスの電荷を帯びる格子欠陥（□で
表す）がある。そのため、電極に電場をかけて粒子を泳
動電析させる電気泳動法を利用すると、電極に容易に固
定でき、しかも層の電荷に応じて陽極や陰極に層状化合
物が固定される。That is, the layered compound can be divided into a network-like layer portion forming a layer and ions and molecules existing between the layers. The ions and molecules existing between the layers of the layered compound have the property of being relatively easily replaced with other ions and molecules. Further, the charge state (plus or minus) of the charge of the layer portion differs depending on the state (pH or the like) of the solution in which the substance and the layered compound between the layers are dispersed. For example, in a cesium titanate compound, FIG.
As shown in the model, a titanate sheet and cesium ions form a layered structure overlapping each other. The titanate sheet has negatively charged lattice defects (indicated by □). Therefore, by using an electrophoresis method in which particles are electrophoretically deposited by applying an electric field to the electrodes, the particles can be easily fixed to the electrodes, and the layered compound is fixed to the anode or the cathode according to the charge of the layer.
【０００８】このようにして電気泳動によるとき、結晶
配向性のある層状化合物が基板に膜状に固定化される。
層状化合物は、剥離を伴いながら基板に固定化されるた
め、陽極，陰極それぞれに２種類の層状化合物薄膜が作
成される。また、電気泳動法による成膜のため、所定方
向の表面が優先的に基板に指向し、基板との密着性が良
好な薄膜が形成される。しかも、他の成膜法に比較して
器具や操作が簡便で、しかも早い析出速度が得られ、膜
厚制御も可能となる。更に、高い電場で層状粒子が異な
った電荷状態の層になっている場合、それぞれの粒子
は、剥離しながら電荷状態に応じた電極に電析する。こ
の点、電気泳動法は、層剥離及び層状化合物の高純化に
も有効である。[0008] In this way, when electrophoresis is performed, the layered compound having crystal orientation is immobilized on the substrate in the form of a film.
Since the layered compound is fixed to the substrate while peeling off, two types of layered compound thin films are formed for each of the anode and the cathode. Further, since the film is formed by electrophoresis, the surface in a predetermined direction is preferentially directed to the substrate, and a thin film having good adhesion to the substrate is formed. In addition, compared to other film forming methods, the apparatus and operation are simple, a high deposition rate can be obtained, and the film thickness can be controlled. Furthermore, when the layered particles are in different charge state layers under a high electric field, each particle is deposited on an electrode corresponding to the charge state while peeling off. In this regard, the electrophoresis method is also effective for delamination and purification of a layered compound.
【０００９】[0009]
【実施例】本実施例では，チタン酸セシウム化合物を用
いた例を説明しているが、ニオブ酸カリウム，タンタル
酸ルビジウム，チタン酸カリウム，チタン酸ニオブ酸カ
リウム等、他の層状化合物も同様に電気泳動法で結晶性
配向性のある化合物薄膜にすることができる。EXAMPLE In this example, an example using a cesium titanate compound is described. However, other layered compounds such as potassium niobate, rubidium tantalate, potassium titanate, potassium titanate, and the like are similarly used. A compound thin film having crystalline orientation can be formed by electrophoresis.
【００１０】メタノール１００重量部に対し，エチレン
グリコール５０重量部，炭酸セシウム３重量部，チタニ
ウムテトラプロポオキシド１３重量部及び無水クエン酸
５０重量部を混合した溶液を調製した。溶液を３００℃
に加熱して有機物を分解することによりチタン酸セシウ
ム前躯体を得、チタン酸セシウム前躯体を８００℃で２
時間焼結してチタン酸セシウム粉末を作製した。チタン
酸セシウムは、原子レベルで層状構造をもち、一般にｂ
軸（０ｎ０）方向に劈開がある。図２は、チタン酸セシ
ウム粉末のＳＥＭ写真である。A solution was prepared by mixing 50 parts by weight of ethylene glycol, 3 parts by weight of cesium carbonate, 13 parts by weight of titanium tetrapropoxide and 50 parts by weight of citric anhydride with 100 parts by weight of methanol. Solution at 300 ° C
Cesium titanate precursor was obtained by heating the mixture to decompose organic matter,
After sintering for a time, a cesium titanate powder was produced. Cesium titanate has a layered structure at the atomic level, and is generally b
There is a cleavage in the axis (0n0) direction. FIG. 2 is an SEM photograph of the cesium titanate powder.
【００１１】チタン酸セシウム層状粉末０．５ｇをメタ
ノール５０ｍ１に入れ、大きさ１ｃｍ×１ｃｍの白金電
極（電極間距離３ｃｍ）を用いて数１０ｍＡの電流を流
すと数１０Ｖの電圧がかかり、層状酸化物の状態に応じ
て陽極と陰極に層状酸化物が電析した。このとき、プロ
トン置換したチタン系層状酸化物は、ホストのＴｉ−Ｏ
層がマイナスに電荷を帯びているので陽極側に電析し
た。他方、Ｃｓを層間に含んだチタン系層状酸化物は、
一般にＴｉ−Ｏ層がプラスの電荷を帯びているので陰極
に電析するが、一部にプロトン置換が生じているため層
が剥離して、陰極と陽極の両電極に電析した。この場
合、陰極にはＣｓ置換体が、陽極にはプロトン置換体が
電析する。When 0.5 g of the cesium titanate layered powder is placed in 50 ml of methanol and a current of several tens mA is passed through a platinum electrode of 1 cm × 1 cm (distance between the electrodes is 3 cm), a voltage of several tens of volts is applied, resulting in a layered oxidation. Depending on the state of the material, a layered oxide was deposited on the anode and the cathode. At this time, the proton-substituted titanium-based layered oxide is converted into a host Ti—O
Since the layer was negatively charged, it was electrodeposited on the anode side. On the other hand, a titanium-based layered oxide containing Cs between layers is:
In general, the Ti—O layer has a positive charge and thus is deposited on the cathode. However, the proton is partially substituted, so that the layer was separated and deposited on both the cathode and the anode. In this case, a Cs-substituted product is deposited on the cathode, and a proton-substituted product is deposited on the anode.
【００１２】作製された薄膜は、基板に対する密着性が
良く、Ｘ線回折分析によって結晶配向性も高いことが判
った。具体的には、チタン酸セシウム層状酸化物の粉末
では、図３のＸ線回折パターンにみられるように、ｂ軸
方向（０ｎ０）以外に（１３０）方向の回折ピークがあ
り、種々の方向を向いた粉末が混合されていることが判
る。なお、泳動電着には、エタノール溶媒中で１００Ｖ
の直流電圧を印加する条件を採用した。The thin film thus formed has good adhesion to the substrate and has high crystal orientation by X-ray diffraction analysis. Specifically, in the powder of the cesium titanate layered oxide, as shown in the X-ray diffraction pattern of FIG. 3, there are diffraction peaks in the (130) direction other than the b-axis direction (0n0), It can be seen that the suitable powder is mixed. For electrophoresis, 100 V in ethanol solvent was used.
The conditions for applying the DC voltage were adopted.
【００１３】他方、チタン酸セシウム層状酸化物０．５
ｇをメタノール５０ｍｌに分散させ、電極間距離を３ｃ
ｍに設定して電流を供給すると電気泳動が生じ、プラス
及びマイナスの白金電極（１ｃｍ×１ｃｍ）に電着し
た。電極上に堆積した粉末で形成された薄膜は、印加電
圧に応じてそれぞれ図４に示すＸ線回折パターンをもっ
ていた。図４から明らかなように、プラス極では印加電
圧に拘らず（０２０）のピークが強くなっており、ばら
ばらであった粉体がｂ軸方向を配向しながら電着したこ
とが窺われる。他方、マイナス極では低電圧を印加した
ときに（１３０）配向の膜が得られているが、（１３
０）配向は印加電圧の増加に従って弱くなっている。こ
のような薄膜の配向性は、層状酸化物のｂ軸（０ｎ０）
方向の面がよりマイナスの帯電しているためプラス側の
薄膜がｂ軸配向となり、（１３０）方向の面がよりプラ
スに帯電しているためマイナス側の薄膜が（１３０）配
向になる結果である。On the other hand, cesium titanate layered oxide 0.5
g in 50 ml of methanol, and the distance between the electrodes is 3c.
When an electric current was supplied at a setting of m, electrophoresis occurred, and electrodeposition was performed on positive and negative platinum electrodes (1 cm × 1 cm). The thin film formed of the powder deposited on the electrode had an X-ray diffraction pattern shown in FIG. 4 according to the applied voltage. As is apparent from FIG. 4, the peak of (020) is strong at the positive electrode regardless of the applied voltage, which indicates that the powder that was separated was electrodeposited while being oriented in the b-axis direction. On the other hand, when a low voltage is applied to the negative electrode, a (130) oriented film is obtained.
0) The orientation becomes weaker as the applied voltage increases. The orientation of such a thin film depends on the b-axis (0n0) of the layered oxide.
Since the surface in the direction is more negatively charged, the plus side thin film has the b-axis orientation, and the surface in the (130) direction is more positively charged, and the minus side thin film has the (130) orientation. is there.
【００１４】図４の結果は、層状酸化物を電気泳動で電
着させるとき、極性及び印加電圧を変えることによって
配向状態が異なる薄膜を作製できることを示している。
層状酸化物のｂ軸（０ｎ０）方向の面は、よりマイナス
に帯電しているためプラス側でｂ軸配向の膜となり、一
方（１３０）方向はよりプラスに帯電しており、マイナ
ス極に電着しやすいものと考えられる。また、スピンコ
ート法で作製した層状化合物の密着性がテープ重量負荷
試験によると２０〜５０ｇ／ｃｍ2であったのに対し、
電気泳動法で作成した膜は５００〜１０００ｇ／ｃｍ2
と優れた密着性を示した。The results in FIG. 4 show that when the layered oxide is electrodeposited by electrophoresis, thin films having different orientations can be produced by changing the polarity and applied voltage.
The surface of the layered oxide in the direction of the b-axis (0n0) is more negatively charged, so that it becomes a film of b-axis orientation on the plus side, while the surface in the (130) direction is more positively charged and the negative electrode is charged. It is considered easy to wear. In addition, according to the tape weight load test, the adhesion of the layered compound produced by the spin coating method was 20 to 50 g / cm 2 ,
500-1000 g / cm 2 membrane prepared by electrophoresis
And excellent adhesion.
【００１５】[0015]
【発明の効果】以上に説明したように、本発明において
は、電気泳動法で層状化合物を電極上に堆積させること
により、結晶配向性の高い層状化合物薄膜を作製してい
る。得られた薄膜は、結晶配向性が高く、基板に対する
密着性にも優れている。しかも、他の成膜法に比較して
器具や操作が簡便で、しかも早い析出速度が得られ、膜
厚制御も可能となる。このようにして得られた薄膜は、
高い結晶配向性を活用した超格子等の電子デバイス，優
れた密着性を活用した光触媒，光反応を利用する電池，
サイズ認識センサー等として、広範な分野における高機
能材料として使用される。As described above, in the present invention, a layered compound thin film having a high crystal orientation is produced by depositing a layered compound on an electrode by electrophoresis. The obtained thin film has high crystal orientation and excellent adhesion to the substrate. In addition, compared to other film forming methods, the apparatus and operation are simple, a high deposition rate can be obtained, and the film thickness can be controlled. The thin film thus obtained is
Electronic devices such as superlattices utilizing high crystal orientation, photocatalyst utilizing excellent adhesion, batteries utilizing photoreaction,
It is used as a high-performance material in a wide range of fields, such as a size recognition sensor.
【図１】 チタン酸セシウムの層状構造を示すモデルFig. 1 Model showing the layered structure of cesium titanate
【図２】 チタン酸セシウム粉末のＳＥＭ写真FIG. 2 SEM photograph of cesium titanate powder
【図３】 チタン酸セシウム粉末のＸ線回折パターンFIG. 3 X-ray diffraction pattern of cesium titanate powder
【図４】 電気泳動で成膜したチタン酸セシウム薄膜の
Ｘ線回折パターンFig. 4 X-ray diffraction pattern of cesium titanate thin film formed by electrophoresis
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年１０月１９日（２０００．１０．
１９）[Submission date] October 19, 2000 (2000.10.
19)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】[0009]
【実施例】本実施例では，チタン酸セシウム化合物を用
いた例を説明しているが、ニオブ酸カリウム，タンタル
酸ルビジウム，チタン酸カリウム，チタン酸ニオブ酸カ
リウム等、他の層状化合物も同様に電気泳動法で結晶配
向性のある化合物薄膜にすることができる。EXAMPLE In this example, an example using a cesium titanate compound is described. However, other layered compounds such as potassium niobate, rubidium tantalate, potassium titanate, potassium titanate, and the like are similarly used. A compound thin film having crystal orientation can be formed by electrophoresis.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１２】作製された薄膜は、基板に対する密着性が
良く、Ｘ線回折分析によって結晶配向性も高いことが判
った。具体的には、チタン酸セシウム層状酸化物の粉末
では、図３のＸ線回折パターンにみられるように、ｂ軸
方向（０ｎ０）以外に（１３０）方向の回折ピークがあ
り、種々の方向を向いた粉末が混合されていることが判
る。The thin film thus formed has good adhesion to the substrate and has high crystal orientation by X-ray diffraction analysis. Specifically, in the powder of the cesium titanate layered oxide, as shown in the X-ray diffraction pattern of FIG. 3, there are diffraction peaks in the (130) direction other than the b-axis direction (0n0), It can be seen that the suitable powder is mixed.
Claims (2)
中で直流電圧又は交流電圧を印加して電気泳動させて基
板上に電析させ、電析した層状化合物を薄膜とすること
を特徴とする結晶配向層状化合物膜の作製方法。The present invention is characterized in that a layered compound having a crystalline orientation is electrophoresed by applying a DC voltage or an AC voltage in an organic solvent and electrodeposited on a substrate, and the deposited layered compound is formed into a thin film. For producing a crystallographically oriented layered compound film.
物又はタンタル系層状酸化物を結晶配向性のある層状化
合物として使用する請求項１記載の作製方法。2. The method according to claim 1, wherein a titanium-based layered oxide, a niobium-based layered oxide, or a tantalum-based layered oxide is used as a layered compound having crystal orientation.
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|---|---|---|---|
| JP2000282064A JP4231196B2 (en) | 2000-09-18 | 2000-09-18 | Method for producing crystalline alignment layered compound film by electrophoresis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000282064A JP4231196B2 (en) | 2000-09-18 | 2000-09-18 | Method for producing crystalline alignment layered compound film by electrophoresis |
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| Publication Number | Publication Date |
|---|---|
| JP2002088500A true JP2002088500A (en) | 2002-03-27 |
| JP4231196B2 JP4231196B2 (en) | 2009-02-25 |
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| JP2000282064A Expired - Fee Related JP4231196B2 (en) | 2000-09-18 | 2000-09-18 | Method for producing crystalline alignment layered compound film by electrophoresis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006297230A (en) * | 2005-04-18 | 2006-11-02 | Tokyo Institute Of Technology | Titanium oxide thin film, titanium oxide thin film-containing photocatalytic material, its manufacturing method, apparatus for cleaning water by using photocatalyst, and method for cleaning water by using photocatalytic reaction |
| WO2007023679A1 (en) * | 2005-08-25 | 2007-03-01 | Otsuka Chemical Co., Ltd. | Light-resistant titanic acid coating film and resin bases with the coating film |
| JP2007284753A (en) * | 2006-04-18 | 2007-11-01 | Kyodo Printing Co Ltd | Hard coating member and its producing method |
| JP2007284752A (en) * | 2006-04-18 | 2007-11-01 | Kyodo Printing Co Ltd | Barrier film and its producing method |
| CN102768231A (en) * | 2011-05-04 | 2012-11-07 | 北京化工大学 | Layered cesium titanium oxide modified foam nickel electrode, and its preparation and application methods |
| KR101425517B1 (en) | 2013-01-29 | 2014-08-05 | 한국세라믹기술원 | Platy ceramic stacking organic-inorganic composite coating method using electrophoretic deposition |
-
2000
- 2000-09-18 JP JP2000282064A patent/JP4231196B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006297230A (en) * | 2005-04-18 | 2006-11-02 | Tokyo Institute Of Technology | Titanium oxide thin film, titanium oxide thin film-containing photocatalytic material, its manufacturing method, apparatus for cleaning water by using photocatalyst, and method for cleaning water by using photocatalytic reaction |
| WO2007023679A1 (en) * | 2005-08-25 | 2007-03-01 | Otsuka Chemical Co., Ltd. | Light-resistant titanic acid coating film and resin bases with the coating film |
| JP2007055858A (en) * | 2005-08-25 | 2007-03-08 | Otsuka Chemical Co Ltd | Light-resistant titanate coating film and light-resistant titanate film-coated resin substrate |
| EP1925590A1 (en) * | 2005-08-25 | 2008-05-28 | Otsuka Chemical Co., Ltd. | Light-resistant titanic acid coating film and resin bases with the coating film |
| EP1925590A4 (en) * | 2005-08-25 | 2010-03-17 | Otsuka Chemical Co Ltd | Light-resistant titanic acid coating film and resin bases with the coating film |
| KR101296489B1 (en) * | 2005-08-25 | 2013-08-13 | 오츠카 가가쿠 가부시키가이샤 | Light-resistant titanic acid coating film and resin bases with the coating film |
| JP2007284753A (en) * | 2006-04-18 | 2007-11-01 | Kyodo Printing Co Ltd | Hard coating member and its producing method |
| JP2007284752A (en) * | 2006-04-18 | 2007-11-01 | Kyodo Printing Co Ltd | Barrier film and its producing method |
| CN102768231A (en) * | 2011-05-04 | 2012-11-07 | 北京化工大学 | Layered cesium titanium oxide modified foam nickel electrode, and its preparation and application methods |
| CN102768231B (en) * | 2011-05-04 | 2014-07-30 | 北京化工大学 | Layered cesium titanium oxide modified foam nickel electrode, and its preparation and application methods |
| KR101425517B1 (en) | 2013-01-29 | 2014-08-05 | 한국세라믹기술원 | Platy ceramic stacking organic-inorganic composite coating method using electrophoretic deposition |
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