JPS6134185A - Method for coloring base body surface of metal and inorganic material - Google Patents
Method for coloring base body surface of metal and inorganic materialInfo
- Publication number
- JPS6134185A JPS6134185A JP12477184A JP12477184A JPS6134185A JP S6134185 A JPS6134185 A JP S6134185A JP 12477184 A JP12477184 A JP 12477184A JP 12477184 A JP12477184 A JP 12477184A JP S6134185 A JPS6134185 A JP S6134185A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- cerium
- base body
- compd
- metal
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は金遍、ガラス質物等の無機質物の基体表面に着
色する方法に関する。更に詳しくは、前記基体表面にセ
リウム含有チタン酸化物系の酸化皮膜を形成させ、その
膜厚を制御して濃淡の黄色乃至黄金色に着色する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for coloring the surface of an inorganic substrate such as a gold plate or a glassy substance. More specifically, the present invention relates to a method of forming a cerium-containing titanium oxide-based oxide film on the surface of the substrate, controlling the film thickness, and coloring the substrate in a shade of yellow to golden yellow.
従来技術
従来、金属の表面を着色する方法として種々な方法が知
られている。例えば、
（１）強酸化性の高温溶液中で酸化皮膜を形成する方法
。BACKGROUND OF THE INVENTION Conventionally, various methods are known for coloring the surface of metal. For example, (1) A method of forming an oxide film in a strongly oxidizing high temperature solution.
（２） はうろう法。(2) Harou method.
（３）直接酸化法。(3) Direct oxidation method.
（４） めっき法。(4) Plating method.
（５） 金属蒸着法。(5) Metal vapor deposition method.
等がある。etc.
また、ガラス質物等の無機質物の表面に着色する方法と
しては、（１）塗装法、（２）高温溶着法、所謂うわ薬
洗またはプリント着色法等が知られている。Further, as methods for coloring the surface of an inorganic material such as a glassy material, (1) a painting method, (2) a high temperature welding method, a so-called glazing method, a print coloring method, etc. are known.
発明の目的
本発明は前記従来法とは異なるセリウム含有チタン酸化
物系の酸化皮膜を形成させて着色する方法を提供するに
ある。OBJECTS OF THE INVENTION The present invention provides a method for forming and coloring a cerium-containing titanium oxide-based oxide film, which is different from the conventional method.
発明の構成
本発明者らは、金属、ガラス等の表面への酸化物層コー
ティングについての研究を行っていたと。Structure of the Invention The present inventors have been conducting research on coating oxide layers on the surfaces of metals, glass, etc.
ころ、セリウム化合物を溶解したチタン有機化合物溶液
を前記基体表面に塗布し加熱すると、その表面が黄色乃
至黄金色することを知見し得た。この知見に基いて本発
明を完成した。It was discovered that when a titanium organic compound solution in which a cerium compound is dissolved is applied to the surface of the substrate and heated, the surface becomes yellow to golden yellow. The present invention was completed based on this knowledge.
本発明の要旨は、基体表面にチタンの有機化合物とセリ
ウム化合物の混合液を付着させた後、２００℃以上乃至
基体の変形または変質を起す温度未満に加熱してセリウ
ム含有チタン、酸化物系の酸化皮膜を形成させて着色す
ることを特徴とする金属、無機質物の基体表面に着色す
る方法にある。The gist of the present invention is to deposit a mixed solution of a titanium organic compound and a cerium compound on the surface of a substrate, and then heat it to a temperature of 200°C or higher or lower than a temperature that causes deformation or alteration of the substrate to form a cerium-containing titanium or oxide-based solution. A method for coloring the surface of a metal or inorganic substrate, which is characterized by forming an oxide film and coloring the surface.
本発明における金属基体としては、白金、金。The metal substrate in the present invention is platinum or gold.
銀等の貴金属、アルミニウム、ステンレス、ジュラルミ
ン等の金属、また金属メッキした本のけすべて使用し得
られる。また無機質物としては、ガラス質物、例えばソ
ーダライム系ガラス、鉛含有のクリスタルガラス、アル
ミノけい酸系ガラス、燐酸系ガラス、ハロゲン化物ガラ
ス等、また、セラミック等、少なくとも２００℃以上に
耐えるものであればよい。It can be obtained by using precious metals such as silver, metals such as aluminum, stainless steel, duralumin, and metal-plated books. Inorganic materials include glassy materials such as soda lime glass, lead-containing crystal glass, aluminosilicate glass, phosphoric acid glass, halide glass, etc., and ceramics that can withstand temperatures of at least 200°C or higher. Bye.
チタンの有機化合物としては、チタンアルコキシド、例
えばチタンプロポキシド、チタンブトキシド等が好まし
い。しかし、これに限定されるものではなく、加熱によ
り分解してＴｉＯ２を生成するチタン有機化合物であれ
ばよい。As the organic compound of titanium, titanium alkoxides such as titanium propoxide and titanium butoxide are preferred. However, the material is not limited thereto, and any titanium organic compound that can be decomposed by heating to produce TiO2 may be used.
セリウム化合物としては、例えばセリウム塩化物、硫酸
塩、硝酸塩等の無機塩類、セリウムのアルコキシド等の
セリウム有機化合物が挙げられる。Examples of the cerium compound include inorganic salts such as cerium chloride, sulfate, and nitrate, and cerium organic compounds such as cerium alkoxide.
チタン有機化合物、セリウム化合物の溶液の溶媒として
ｌｄ、メチルアルコール、エチルアルコール、フチルア
ルコール、フロビルアルコールカ使用される。チタンの
有機化合物とセリウム化合物の混合割合は、ＴｉＯ２と
ＯｅＯ□に換算して、重量比で１：１〜２５０ ： １
の範囲であることが黄色を発生させるのに好ましい。ld, methyl alcohol, ethyl alcohol, phthyl alcohol, and flobyl alcohol are used as solvents for solutions of titanium organic compounds and cerium compounds. The mixing ratio of the organic titanium compound and the cerium compound is 1:1 to 250:1 by weight in terms of TiO2 and OeO□.
It is preferable for the yellow color to be within the range of .
チタン有機化合物、例えばチタンアルコキシドとセリウ
ム化合物の溶液を清浄化された基体表面に、塗布法、ス
プレー法、浸漬法等により付着させ、大気中で２〜３分
以上放置する。その後２００℃〜基体の変形または変質
を起す温度未満の温度に加熱すると、脱水縮合して、基
体表面上にセリウム含有チタン酸化物膜が形成される。A solution of a titanium organic compound, such as a titanium alkoxide and a cerium compound, is applied to the surface of a cleaned substrate by a coating method, a spray method, a dipping method, etc., and is left in the atmosphere for 2 to 3 minutes or more. Thereafter, when heated to a temperature of 200° C. to a temperature lower than the temperature at which deformation or alteration of the substrate occurs, dehydration condensation occurs and a cerium-containing titanium oxide film is formed on the surface of the substrate.
加熱の雰囲気は大気中またはｔｌｖ−化雰囲体であるこ
とが好せしい。還元雰１ｔｉｌ気の場合はチタンアルコ
キシドの炭素の一部がセリウム含有チタン酸化物の膜中
に残存し、良好な黄色系単色が得難い。加熱温度が２０
０℃より低いと、生成膜は弱く、発色も鮮明でないので
、２００℃以上であることが必要であり、最高加熱温度
は基体が変形または変質しない温度であることが必要で
ある。加熱時間は５分〜６０分でよい。加熱後、冷却ま
たは放冷すると、チタンアルコキシド溶液の濃度が濃い
場合には基体表面に白色の薄膜層が形成され木が、これ
はスボン、・３ 竺−ｒｍ 孔１４３（→ト Ｌ 帖
！ ａｔ 苓＃ Ｊ−、ｉ＠ Ｊ−Ｉｔ
＾ｒ ｊト コオチタン酸化物膜の厚さの制御によ
り黄色から黄金色の濃淡のものに変化させることができ
る。この厚さの調整は、チタンの有機化合物とセリウム
化合物の溶液の付着−加熱工程を繰返し行うか、あるい
は溶液の濃度を変えることによって行うことができる。The heating atmosphere is preferably the air or a TLV-enhanced atmosphere. In the case of a reducing atmosphere, a part of the carbon of the titanium alkoxide remains in the cerium-containing titanium oxide film, making it difficult to obtain a good yellowish monochromatic color. Heating temperature is 20
If it is lower than 0°C, the produced film will be weak and the color development will not be clear, so the heating temperature needs to be 200°C or higher, and the maximum heating temperature needs to be a temperature at which the substrate does not deform or change in quality. The heating time may be 5 minutes to 60 minutes. After heating, if the titanium alkoxide solution is cooled or left to cool, a white thin film layer will be formed on the surface of the substrate if the concentration of the titanium alkoxide solution is high.蓓# J-、i＠ J-It
By controlling the thickness of the titanium oxide film, it is possible to change the color from yellow to golden yellow. The thickness can be adjusted by repeating the process of depositing and heating a solution of an organic titanium compound and a cerium compound, or by changing the concentration of the solution.
実施例
実施例１゜
アルミニウム箔の表面に、塩化セリウム１５２、チタン
テトライソプロポキシド２０Ｃｅ、エタノール３００
ＣＣを混合攪拌した溶液を浸漬法によシ付着させた。こ
れを５分間大気中に放置乾燥させた後、５００℃の電気
炉中に入れ、１０分間熱処理を行った。電気炉より取出
し、表面に付着している白色物質を除去することにより
、薄黄色に着色したものが得られた。Examples Example 1゜ Cerium chloride 152, titanium tetraisopropoxide 20Ce, ethanol 300
A mixed and stirred solution of CC was deposited by a dipping method. After leaving it to dry in the air for 5 minutes, it was placed in an electric furnace at 500° C. and heat-treated for 10 minutes. By taking it out of the electric furnace and removing the white substance adhering to the surface, a pale yellow colored product was obtained.
次に、これを前記溶液中に浸漬し、同様に熱処理操作を
繰返すと、黄色が濃くなり、黄金色のものとなった。色
度計で黄色度合を測定したところ、Ｃ，１，Ｅ、色度図
において、（ｘ ＋ ’！ ）の値は３回浸漬で（０，
３３３、０，３４７＋、６回浸漬でｆｏ、３７２゜０．
４０７）、７回浸漬で（０，４１１、０，４３０）とな
り、次第に着色濃度が増し、黄金色となった。Next, when this was immersed in the solution and the heat treatment operation was repeated in the same manner, the yellow color became deeper and became golden yellow. When the degree of yellowness was measured with a chromaticity meter, it was found that in the C, 1, E, chromaticity diagram, the value of (x + '!) became (0,
333, 0,347+, 6 times immersion fo, 372°0.
407), and (0,411, 0,430) after 7 immersions, and the coloring density gradually increased and became golden yellow.
実施例２゜
ソーダライム系ガラスのスライドガラス板の表面に、実
施例と同じ溶液を筆で、所望の形状の部分に塗布し、以
後、実施例１と同様な処理を行つ′た。これにより黄色
の所望形状が画かれたスライドガラス板が得られた。色
度計で黄色の度合を測定したところ、Ｏ，１，Ｅ色度図
において、（ｘ＋ｙ）の値は、１回塗布で（０，３２７
、０，３６０）、２回塗布で（０，３４６、０，３７７
）、３回塗布で（０，３６６゜０．３９８ ）の値であ
った。Example 2 The same solution as in Example was applied to the surface of a slide glass plate made of soda lime glass in a desired shape using a brush, and the same treatment as in Example 1 was then carried out. As a result, a yellow glass slide plate with a desired shape drawn thereon was obtained. When the degree of yellow was measured with a chromaticity meter, the value of (x+y) in the O, 1, E chromaticity diagram was (0,327
, 0,360), with two applications (0,346, 0,377
), and the value was (0,366°0.398) after 3 applications.
実施例３゜
鉛ガラス系のクリスタルガラスの容器の表面に、実施例
２と同じ方法で処理を行った。その結果、黄色の所望形
状が画かれたクリスタルガラス容器゛ が得られた
。Example 3 The surface of a lead glass-based crystal glass container was treated in the same manner as in Example 2. As a result, a yellow crystal glass container with a desired shape was obtained.
実施例４゜
ステンレス板の表面に、硝酸セリウム２４２、チタンテ
トライソグロボキシド６５銭、エタノール４００Ｃｅを
ｆＨ合攪拌して得られた溶液をスプレー法によって付着
させた。１０分分間側中に放置乾燥させた後、３００℃
の電気炉中に入れ、１時間熱処理を行った。ステンレス
板を電気炉中より取出し、表面に付着し２ている白色物
質を取除くと薄黄色・に着色したものが得られた。Example 4 A solution obtained by stirring 242 cerium nitrate, 65 yen titanium tetraisogloboxoxide, and 400 Ce ethanol in fH was deposited on the surface of a stainless steel plate by a spray method. Leave to dry for 10 minutes at 300°C.
The sample was placed in an electric furnace and heat treated for 1 hour. When the stainless steel plate was taken out from the electric furnace and the white substance adhering to the surface was removed, a pale yellow colored plate was obtained.
実施例５゜
実施例４におけると同様な混合溶液中にシリカガラス棒
を浸漬して付着させ、以下実施例４と同様な処理を行っ
て黄色に着色したシリカガラス棒を得た。このガラス棒
を８００℃で２０分間加熱しても、着色した黄色は不変
であった。この着色膜は極めて良く密着されておシ、擦
っても脱色せず、曲げても剥離し々かった。まだ、耐ア
ルカリ性、耐薬品性も優れていた。Example 5 A silica glass rod was immersed in the same mixed solution as in Example 4 to adhere thereto, and the same treatment as in Example 4 was carried out to obtain a yellow colored silica glass rod. Even when this glass rod was heated at 800° C. for 20 minutes, the yellow color remained unchanged. This colored film adhered extremely well, did not discolor even when rubbed, and often peeled off even when bent. However, the alkali resistance and chemical resistance were also excellent.
発明の効果
本発明の方法によると、従来の真空蒸着法における高価
な装置を必要とし、かつ一度に小面積しか膜を形成し得
ない欠点を解消し得られ、まだ従来の電解メッキ法にお
ける電気設備、装置、煩雑さもなく、極めて簡単に基体
に着色し得られる。Effects of the Invention According to the method of the present invention, it is possible to overcome the drawbacks of the conventional vacuum evaporation method, in which expensive equipment is required and a film can only be formed on a small area at a time. The substrate can be colored very easily without any equipment, equipment or complexity.
しかも着色がセリウム含有チタン重化物膜による着色で
あるために、耐腐食性、耐摩耗性の優れた着色が得られ
、かつ表面に強固に結着された着色である優れた効果を
奏し得られる。Moreover, since the coloring is done by a cerium-containing titanium heavy compound film, it is possible to obtain a coloring with excellent corrosion resistance and abrasion resistance, and it also has the excellent effect of being a coloring that is firmly bound to the surface. .
特許出願人 科学技術庁無機材質研究所長後 藤
優Patent applicant Goto, director of the Institute for Inorganic Materials, Science and Technology Agency
Excellent
Claims (1)
物の混合液を付着させた後、２００℃以上乃至基体の変
形または変質を起す温度未満の温度に加熱してセリウム
含有チタン酸化物系の酸化皮膜を形成させて着色するこ
とを特徴とする金属、無機質物の基体表面に着色する方
法。 ２、チタンの有機金属化合物がチタンアルコキシドであ
る特許請求の範囲第１項記載の方法。 ３、チタンの有機金属化合物とセリウム化合物の混合割
合がＴｉＯ＿２、ＣｅＯ＿２に換算して重量比で１：１
〜２５０：１である特許請求の範囲第１項記載の方法。 ４、セリウム含有チタン酸化系の皮膜厚を制御して濃淡
の黄色乃至黄金色に着色する特許請求の範囲第１項記載
の方法。[Claims] 1. After depositing a mixed solution of a titanium organometallic compound and a cerium compound on the surface of a substrate, the cerium-containing titanium is heated to a temperature of 200° C. or higher and lower than the temperature that causes deformation or alteration of the substrate. A method for coloring the surface of a metal or inorganic material substrate, which is characterized by forming an oxide-based oxide film and coloring the surface. 2. The method according to claim 1, wherein the organometallic compound of titanium is a titanium alkoxide. 3. The mixing ratio of the titanium organometallic compound and the cerium compound is 1:1 by weight in terms of TiO_2 and CeO_2.
250:1. 4. The method according to claim 1, wherein the film thickness of the cerium-containing titanium oxide system is controlled to color the film in shades of yellow to golden yellow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12477184A JPS6134185A (en) | 1984-06-18 | 1984-06-18 | Method for coloring base body surface of metal and inorganic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12477184A JPS6134185A (en) | 1984-06-18 | 1984-06-18 | Method for coloring base body surface of metal and inorganic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6134185A true JPS6134185A (en) | 1986-02-18 |
| JPH0222148B2 JPH0222148B2 (en) | 1990-05-17 |
Family
ID=14893705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12477184A Granted JPS6134185A (en) | 1984-06-18 | 1984-06-18 | Method for coloring base body surface of metal and inorganic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134185A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298008A (en) * | 1988-05-26 | 1989-12-01 | Mitsubishi Metal Corp | Production of metal sulfide |
| JPH01298010A (en) * | 1988-05-26 | 1989-12-01 | Mitsubishi Metal Corp | Production of metal selenide |
| CN105177564A (en) * | 2015-09-18 | 2015-12-23 | 东莞市榴花艺术有限公司 | Oxidizing agent for metal foil machining |
-
1984
- 1984-06-18 JP JP12477184A patent/JPS6134185A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298008A (en) * | 1988-05-26 | 1989-12-01 | Mitsubishi Metal Corp | Production of metal sulfide |
| JPH01298010A (en) * | 1988-05-26 | 1989-12-01 | Mitsubishi Metal Corp | Production of metal selenide |
| CN105177564A (en) * | 2015-09-18 | 2015-12-23 | 东莞市榴花艺术有限公司 | Oxidizing agent for metal foil machining |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0222148B2 (en) | 1990-05-17 |
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