JPH01222081A - Formation of oxide film - Google Patents
Formation of oxide filmInfo
- Publication number
- JPH01222081A JPH01222081A JP4602388A JP4602388A JPH01222081A JP H01222081 A JPH01222081 A JP H01222081A JP 4602388 A JP4602388 A JP 4602388A JP 4602388 A JP4602388 A JP 4602388A JP H01222081 A JPH01222081 A JP H01222081A
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- film
- suspension
- deposited
- salts
- 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
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000001962 electrophoresis Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000002576 ketones Chemical class 0.000 claims abstract description 6
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 125000002524 organometallic group Chemical group 0.000 abstract description 3
- 150000004075 acetic anhydrides Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethyl silica Chemical compound 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、形状が複雑なものの表面に均一な厚みの金属
酸化物を形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming a metal oxide of uniform thickness on the surface of an object having a complex shape.
（従来技術）
＾１、Ｓｉ％Ｔｉ、 Ｚｒのアルコキシド、アセチルア
セトネート塩、オクチル酸塩は、加熱すると、熱分解し
て・＾１・Ｓｉ、 Ｔｉ、 Ｚｒの酸化物となる。従っ
て、これらの有機金属塩をアルコールなどの有機溶媒に
溶解して、加工物に塗布し、空気中もしくは酸化雰囲気
中で熱分解すれば、加工物表面に金属酸化物の皮膜を形
成できる。(Prior art) ^1, Si%Ti, Zr alkoxides, acetylacetonate salts, and octylate salts are thermally decomposed when heated to become .^1.Si, Ti, and Zr oxides. Therefore, if these organic metal salts are dissolved in an organic solvent such as alcohol, applied to a workpiece, and thermally decomposed in air or an oxidizing atmosphere, a metal oxide film can be formed on the surface of the workpiece.
従来、この加工物表面への塗布は、ロールコート法、ス
プレー法、浸漬法など公知方法で行っているが、有機溶
媒液は、粘性がほとんどなく、厚膜に塗布できない、こ
のため、有機溶媒液に水を加えて加水分解によりゾル化
し、粘性を高くして塗布している。Conventionally, this application to the surface of the workpiece has been carried out using known methods such as roll coating, spraying, and dipping, but organic solvent solutions have almost no viscosity and cannot be applied to thick films. Water is added to the liquid to form a sol through hydrolysis, increasing the viscosity before application.
（発明が解決しようとする問題点）
しかし、酸化物皮膜を厚くするために、有機金属塩濃度
を高くすると、ゾル粘度が高（なりすぎるため、ロール
コート法やスプレー法での塗布が困難になり、また、浸
漬法で塗布すると、表面が凹凸になってしまう。このた
め、酸化物皮膜を厚膜にするには、適性なる粘度で複数
回塗布する方法によっていた。(Problem to be solved by the invention) However, when increasing the concentration of organic metal salt in order to thicken the oxide film, the sol viscosity becomes too high, making it difficult to apply by roll coating or spraying. Moreover, when applied by dipping, the surface becomes uneven.For this reason, in order to make the oxide film thick, it has been necessary to apply it multiple times at an appropriate viscosity.
ところで、近年、加工物は、表面が平らなものだけでな
く、凹凸を有していたり、形状が複雑なものが多くなり
、これらのものを適性粘度で１回塗りもしくは複数回塗
りすると、凸部のゾル液は流れて、その部位の塗膜が薄
くなり、熱分解後ピンホールが生じてしまうものであっ
た。By the way, in recent years, many workpieces have not only flat surfaces, but also those with uneven surfaces or complex shapes. The sol solution flowed away, making the coating thinner in that area and causing pinholes after thermal decomposition.
そこで、本発明は、かかる問題を解決するために、加工
物表面が凹凸でも、また、複雑な形状のものでも均一な
膜厚の酸化物皮膜を形成できる方法を提供するものであ
る。Therefore, in order to solve this problem, the present invention provides a method that can form an oxide film of uniform thickness even if the surface of the workpiece is uneven or has a complicated shape.
（問題点を解決するための手段）
本発明者らは、有機金属塩溶液を懸濁液にして、帯電し
た有機金属塩を電気泳動法により加工物表面に析着させ
、均一な塗膜を全体に形成できるようにした。(Means for solving the problem) The present inventors made an organic metal salt solution into a suspension and deposited the charged organic metal salt on the surface of the workpiece by electrophoresis, thereby forming a uniform coating film. It was made possible to form the whole.
すなわち、本発明は、＾１、Ｓｉ％Ｔｉ、 Ｚｒのアル
コキシド、アセチルアセトネート塩、オクチル酸塩の１
種または２種以上をアルコール系もしくはケトン系溶媒
に懸濁させた懸濁液中に酸化物皮膜を表面に形成する対
象物を入れて、その対象物を一方の極として電気泳動法
により前記有機金属塩を表面に析着させ、しかる後にそ
の析着物を酸化雰囲気中で２００〜４００℃に加熱して
酸化するようにした。That is, the present invention provides ^1, Si%Ti, Zr alkoxide, acetylacetonate salt, octylate salt.
An object on which an oxide film is to be formed is placed in a suspension of a species or two or more species suspended in an alcoholic or ketone solvent, and the organic A metal salt was deposited on the surface, and the deposit was then heated to 200-400° C. in an oxidizing atmosphere to oxidize it.
本発明でアルコキシド、アセチルアセトネート金属塩、
オクチル酸金属塩を分散させる溶媒をアルコールＰ、ま
たはケトン系にしたのは、それらの有機金属塩がアルコ
ール系やケトン系溶媒に比較的溶解しやすく、安定であ
るからである。In the present invention, alkoxide, acetylacetonate metal salt,
The reason why alcohol P or a ketone type solvent is used for dispersing the octylic acid metal salt is that these organic metal salts are relatively easily soluble in alcohol type or ketone type solvents and are stable.
アルコールとしては、メチルアルコール、エチルアルコ
ール、プロピルアルコール、ブチルアルコールなどの低
級アルコールでよく、ケトンとしては、カルボニル基に
結合するアルキル基が低級アルキルのものでよい。The alcohol may be a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol, and the ketone may be one in which the alkyl group bonded to the carbonyl group is lower alkyl.
懸濁させる界面活性剤としては、公知のものでよく、有
機金属塩濃度としては、０．０１〜０．３ｍｏｌ／Ｃに
するのが好ましい。As the surfactant for suspending, any known surfactant may be used, and the concentration of the organic metal salt is preferably 0.01 to 0.3 mol/C.
電気泳動は、形成する酸化物皮膜の厚さにより変エルカ
、例ｔｉ？、１００−５００Ｖで０．５−２０分行えば
、熱分解後５〜２００μ論程度の酸化物皮膜にすること
ができる。酸化物皮膜を部分的に形成したい場合には、
この電気泳動の際、その部分以外をマスキングして析着
させればよい。Electrophoresis varies depending on the thickness of the oxide film formed. , 100-500V for 0.5-20 minutes, it is possible to form an oxide film with a thickness of about 5-200 μm after thermal decomposition. If you want to partially form an oxide film,
At the time of this electrophoresis, it is sufficient to mask the area other than that part for deposition.
電気泳動により析着させたＩ！膜は、塗膜中に溶媒をほ
とんど含有していないので、直ちに熱分解することがで
きる。熱分解は、２００〜４００℃で行う、２００℃未
満であると、有機金属塩を完全に熱分解できず、４００
℃より高くしても、４００℃で熱分解する場合と熱分解
時間は変わらない。I! deposited by electrophoresis The film can be immediately thermally decomposed since it contains almost no solvent in the coating. Thermal decomposition is carried out at a temperature of 200 to 400°C. If the temperature is less than 200°C, the organometallic salt cannot be completely thermally decomposed,
Even if the temperature is higher than 400°C, the thermal decomposition time is the same as when thermally decomposed at 400°C.
本発明による酸化物皮膜の形成は、酸化物皮膜が剥離し
やすい支持体を用いて、熱分解後剥離して、種々の形状
の酸化物皮膜を製造する方法にも適用できる。The formation of an oxide film according to the present invention can also be applied to a method of producing oxide films of various shapes by using a support from which the oxide film is easily peeled off and peeling it off after thermal decomposition.
（実施例）
実施例１
エタノールのエチルシリケート０．１鎗ｏ１／ｇ ｓ濁
液にエンボス加工を施した陽極酸化処理Ａｌ板を入れて
、１００■で１分間電気泳動を行い、表面にエチルシリ
ケートを析着させた。その後このＡｌ板を３００℃の電
気炉で１０分間加熱して熱分解したところ、シリカ皮膜
が表面に均一に形成されていた。(Example) Example 1 An embossed anodized Al plate was placed in a suspension of 0.1 o1/g s of ethyl silicate, and electrophoresis was performed at 100 μm for 1 minute to remove ethyl silicate on the surface. was deposited. Thereafter, when this Al plate was heated in an electric furnace at 300° C. for 10 minutes to thermally decompose it, a silica film was uniformly formed on the surface.
実施例２
実施例１におけるエチルシリケート懸濁液の代わりにイ
ンプロパツールへの＾１アセチルアセトネー ） ０．
０８ｍｏｌ／ｅＦ！濁液を用いて、同要領で電気泳動、
加熱（２１０℃）を行い、＾ｌ鋼板表面に皮膜を形成し
た。この皮膜は、アルミナから構成され、皮膜は均一で
あった。Example 2 ^1 acetylacetonate to Impropatol instead of the ethylsilicate suspension in Example 1) 0.
08mol/eF! Electrophoresis is carried out in the same manner using a suspension liquid.
Heating was performed (210°C) to form a film on the surface of the steel plate. This film was composed of alumina and was uniform.
実施例３
実施例１におけるエチルシリケー）１１濁液の代わりに
７セトンへのＴｉオクチル酸０．１２ｍｏｌ／ｅＦＪ濁
液を用いで、同要領で電気泳動、加熱（３５０℃）を行
い、＾１板表面に皮膜を形成した。形成された皮膜は、
酸化チタンから構成され、皮膜は均一であった。Example 3 Electrophoresis and heating (350°C) were performed in the same manner as in Example 1, using a Ti octylic acid 0.12 mol/eFJ suspension in 7 setone instead of the ethyl silica) 11 suspension. A film was formed on the surface. The film formed is
It was composed of titanium oxide, and the film was uniform.
実施例４
実施例１におけるエチルシリケート懸濁液の代わりにエ
チルエチルケトンへのＺｒブトキシド０．０６ｍｏｌ／
ｅ懇濁液を用いて、同要領で電気泳動、加熱（３８０℃
）を行い、ＡＩ鋼板表面に皮膜を形成した。Example 4 0.06 mol/Zr butoxide in ethyl ethyl ketone instead of the ethyl silicate suspension in Example 1
Electrophoresis and heating (380°C) were carried out in the same manner using e-suspension
) to form a film on the surface of the AI steel plate.
形成された皮膜は、酸化ジルコニウムから構成され、皮
膜は均一であった。The formed film was composed of zirconium oxide and was uniform.
（発明の効果）
以上のように、本発明は、有機金属塩懸濁液を用いて、
電気泳動法により有機金属塩を析着させるのであるから
、加工物が表面凹凸のものまたは複雑な形状のものであ
っても、均一な厚みの塗膜を形成できる。従って、その
塗膜を熱分解により酸化物皮膜にしても、凸部にピンホ
ールは生じなＩ／１６
また、電気泳動により析着させた塗膜は、塗膜中に溶媒
をほとんど含有していないので、熱分解の際、徐々に加
熱する必要がなく、熱分解時間を短くすることができる
。(Effect of the invention) As described above, the present invention uses an organic metal salt suspension to
Since the organic metal salt is deposited by electrophoresis, a coating film of uniform thickness can be formed even if the workpiece has an uneven surface or a complex shape. Therefore, even if the coating film is made into an oxide film by thermal decomposition, no pinholes will occur on the convex parts.I/16 Furthermore, the coating film deposited by electrophoresis contains almost no solvent in the coating film. Therefore, there is no need for gradual heating during thermal decomposition, and the thermal decomposition time can be shortened.
Claims (1)
トネート塩、オクチル酸塩の１種または２種以上をアル
コール系もしくはケトン系溶媒に懸濁させた懸濁液中に
酸化物皮膜を表面に形成する対象物を入れて、その対象
物を一方の極として電気泳動法により前記有機金属塩を
表面に析着させ、しかる後にその析着物を酸化雰囲気中
で２００〜４００℃に加熱して酸化することを特徴とす
る酸化物皮膜の形成方法。Forming an oxide film on the surface of a suspension of one or more of Al, Si, Ti, and Zr alkoxides, acetylacetonate salts, and octylate salts in an alcoholic or ketone solvent. Putting a target object and depositing the organic metal salt on the surface by electrophoresis using the target object as one pole, and then heating the deposit to 200 to 400°C in an oxidizing atmosphere to oxidize it. A method for forming an oxide film characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4602388A JPH01222081A (en) | 1988-02-29 | 1988-02-29 | Formation of oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4602388A JPH01222081A (en) | 1988-02-29 | 1988-02-29 | Formation of oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01222081A true JPH01222081A (en) | 1989-09-05 |
Family
ID=12735453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4602388A Pending JPH01222081A (en) | 1988-02-29 | 1988-02-29 | Formation of oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01222081A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014175389A (en) * | 2013-03-07 | 2014-09-22 | Mitsubishi Materials Corp | Method of forming alumina insulation film |
-
1988
- 1988-02-29 JP JP4602388A patent/JPH01222081A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014175389A (en) * | 2013-03-07 | 2014-09-22 | Mitsubishi Materials Corp | Method of forming alumina insulation film |
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