JPH039187B2 - - Google Patents
Info
- Publication number
- JPH039187B2 JPH039187B2 JP24934686A JP24934686A JPH039187B2 JP H039187 B2 JPH039187 B2 JP H039187B2 JP 24934686 A JP24934686 A JP 24934686A JP 24934686 A JP24934686 A JP 24934686A JP H039187 B2 JPH039187 B2 JP H039187B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- substrate
- solution
- cerium
- yellow
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- -1 titanium organic compound Chemical class 0.000 claims description 13
- 238000004040 coloring Methods 0.000 claims description 12
- 150000001785 cerium compounds Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 239000013212 metal-organic material Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000007654 immersion Methods 0.000 description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は金属、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酸化物−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 Industrial Application The present invention relates to a method for coloring the surface of an inorganic substrate such as a metal or a glassy material. More specifically, the present invention relates to a method of forming a cerium oxide-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。Prior Art Conventionally, various methods are known as methods for coloring the surface of metal. For example, (1) A method of forming an oxide film in a strongly oxidizing high temperature solution.
(2) ほうろう法。(2) Enamel method.
(3) 直接酸化法。(3) Direct oxidation method.
(4) めつき法。(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
うわ薬法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 glaze method, a print coloring method, etc. are known.
本発明者らはさきにこれらの方法とは異なるセ
リウム酸化物−チタン酸化物系の酸化皮膜を形成
させて着色する方法、即ち基体表面にチタンの有
機金属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
起こす温度未満の温度に加熱して金属・無機質物
の基体表面に着色する方法を開発した。（特願昭
59−124771号）
該方法によると、黄色乃至黄金色の着色が容易
に得られるが、チタンの有機化合物とセリウム化
合物の混合液は不安定で、沈殿物が生成し、混合
液調整直後、あるいはゲル化直前でなければ透明
な黄色乃至黄金色のコーテイング膜が得られない
問題点があつた。 The present inventors have previously developed a method of forming and coloring a cerium oxide-titanium oxide-based oxide film, which is different from these methods, in which a mixed solution of a titanium organometallic compound and a cerium compound is attached to the surface of a substrate. After that, we developed a method for coloring the surface of a metal or inorganic material by heating it to a temperature above 200°C or below the temperature that causes deformation or alteration of the substrate. (Tokugansho
59-124771) According to this method, a yellow to golden color can be easily obtained, but the mixed solution of the organic titanium compound and the cerium compound is unstable and a precipitate is formed, and the mixed solution is There was a problem that a transparent yellow to golden yellow coating film could not be obtained unless it was immediately before gelation.
発明の目的
本発明は前記方法における問題点を解決すべく
なされたもので、その目的は該混合液の調整後、
長時間放置しても透明な黄色乃至黄金色のコーテ
イング膜が得られる方法を提供するにある。Purpose of the Invention The present invention was made to solve the problems in the above method, and the purpose is to:
To provide a method by which a transparent yellow to golden yellow coating film can be obtained even if left for a long time.
発明の構成
本発明者らは前記目的を達成すべく鋭意研究の
結果、チタンの有機化合物とセリウム化合物の混
合液をゲル化させるにはPHが影響し、かつ沈殿物
の生成は含水分に影響されることが分かり、該混
合液に酸を加え、PHを3.5〜５とし、かつ含水分
を８％以下とするときは、これらの問題点が解決
し得られることを究明し得た。この知見に基づい
て本発明を完成した。Composition of the Invention As a result of intensive research to achieve the above object, the present inventors found that gelation of a mixed liquid of a titanium organic compound and a cerium compound is influenced by pH, and the formation of a precipitate is influenced by moisture content. It was found that these problems could be solved by adding an acid to the mixed solution to adjust the pH to 3.5 to 5 and the water content to 8% or less. The present invention was completed based on this knowledge.
本発明の要旨は、
チタンの有機化合物とセリウム化合物の混合液
に酸を加えてPHを3.5〜５となし、全溶液中の含
有水分を８％以下に調整し、この混合液を基体表
面に付着させた後、200℃以上乃至基体の変形ま
たは変質する温度未満の温度に加熱してセリウム
酸化物−チタン酸化物系の酸化被膜を形成させて
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 add acid to a mixed solution of a titanium organic compound and a cerium compound to adjust the pH to 3.5 to 5, adjust the water content in the entire solution to 8% or less, and apply this mixed solution to the surface of a substrate. A metal or inorganic material characterized by being colored by forming a cerium oxide-titanium oxide based oxide film by heating it to a temperature of 200°C or higher or lower than the temperature at which the substrate is deformed or altered after being deposited. A method for coloring the surface of a substrate.
本発明において使用する混合液のPHが3.5より
低いとゲル化までの時間が長くなり過ぎ、PHが５
を超えると、混合液の調整直後か、長時間放置後
のゲル化直前で使用しなければ透明な黄色コーテ
イング膜が得られない。 If the pH of the mixed solution used in the present invention is lower than 3.5, the time until gelation will be too long, and the pH will be lower than 3.5.
If the amount exceeds 0.05, a transparent yellow coating film cannot be obtained unless the mixture is used immediately after preparation or immediately before gelation after being left for a long time.
また、含水分が８％を超えると混合液調整直後
に沈殿が生じ、均一なコーテイング膜が得難い。 Moreover, if the water content exceeds 8%, precipitation will occur immediately after the mixture is prepared, making it difficult to obtain a uniform coating film.
PH調整酸としては、塩酸、硝酸、硫酸等の鉱
酸、また酢酸等の有機酸、いずれも使用し得られ
る。 As the pH adjusting acid, mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as acetic acid can be used.
本発明における金属基体としては、白金、金、
銀等の貴金属、アルミニウム、ステンレス、ジユ
ラルミン等の金属、また金属メツキしたものであ
つてもよい。また、無機物質としては、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等、また
はセラミツクス等の少なくとも200℃に耐えるも
のであればよい。 The metal substrate in the present invention includes platinum, gold,
It may be made of a noble metal such as silver, a metal such as aluminum, stainless steel, or duralumin, or a metal plated material. Further, the inorganic substance may be a glassy substance such as soda lime glass, lead-containing crystal glass, aluminosilicate glass, or ceramics, as long as it can withstand temperatures of at least 200°C.
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 TiO 2 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
媒としては、メチルアルコール、エチルアルコー
ル、ブチルアルコール、プロピルアルコールが使
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CeO2に換算して、重量比
で１：５〜250：１の範囲であることが黄色を発
生させるのに好ましい。 Methyl alcohol, ethyl alcohol, butyl alcohol, and propyl alcohol are used as the solvent for the solution of the titanium organic compound and the cerium compound. The mixing ratio of the organic titanium compound and the cerium compound is preferably in the range of 1:5 to 250:1 by weight in terms of TiO 2 and CeO 2 to generate yellow color.
混合液を基体表面に付着させた後の加熱は大気
中または酸化雰囲気であることが好ましい。還元
雰囲気の場合はチタン有機化合物の炭素の一部が
セリウム酸化物−チタン酸化物系の膜中に残存
し、良好な黄色系単色が得難い。 It is preferable that heating is performed in the air or in an oxidizing atmosphere after the mixed liquid is attached to the substrate surface. In the case of a reducing atmosphere, a part of the carbon of the titanium organic compound remains in the cerium oxide-titanium oxide film, making it difficult to obtain a good yellowish monochromatic color.
加熱温度が200℃より低いと、生成膜が弱く、
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。加熱時間は５分〜60分でよ
い。 If the heating temperature is lower than 200℃, the formed film will be weak.
Since the color development is also not clear, the heating temperature must be 200°C or higher, and the maximum heating temperature is a temperature at which the substrate does not deform or change in quality. Heating time may be 5 minutes to 60 minutes.
加熱後冷却または放冷すると、チタン有機化合
物の濃度が濃い場合には基体表面に白色の薄膜層
が形成されるが、これはスポンジ等で洗い落とす
と黄色が現われる。 When cooled after heating or left to cool, if the concentration of the titanium organic compound is high, a white thin film layer is formed on the surface of the substrate, but when this is washed off with a sponge or the like, a yellow color appears.
セリウム酸化物−チタン酸化物系の厚さの制御
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。この厚さの調整は混合液の付着−
加熱工程を繰返し行うか、あるいは溶液の濃度を
変えることによつて行うことができる。 By controlling the thickness of the cerium oxide-titanium oxide system, it is possible to change the color from yellow to golden yellow. Adjustment of this thickness is based on the adhesion of the mixed liquid.
This can be done by repeating the heating step or by changing the concentration of the solution.
基本が耐化学性、特に耐酸性に弱い場合は、必
要に応じセリウム酸化物−チタン酸化物系皮膜の
上にSiO2の皮膜を形成させると耐酸性を強める
ことができる。 If the basic material is weak in chemical resistance, especially acid resistance, the acid resistance can be strengthened by forming a SiO 2 film on the cerium oxide-titanium oxide film, if necessary.
実施例
実施例 １
アルミニウム箔の表面に、塩化セリウム2.52
ｇ、チタンテトライソプロポキシド２c.c.、エタノ
ール30c.c.、30％酢酸２c.c.を撹拌混合しPHを４とし
た溶液を、浸漬法により付着させた。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分間熱処理した。薄黄色に着色したも
のが得られた。次にこれを前記溶液中に浸漬し、
同様な熱処理する操作を繰返すと、黄色が濃くな
り、黄金色のものとなつた。色度計で黄金色度合
を測定したところ、C.I.E色度図において、（ｘ、
ｙ）の値は１回浸漬で（0.308、0.314）、２回浸
漬で（0.334、0.356）、５回浸漬で（0.392、
0.443）となり、次第に着色濃度が増し黄金色と
なつた。Examples Example 1 Cerium chloride 2.52 on the surface of aluminum foil
A solution containing 2 c.c. of titanium tetraisopropoxide, 30 c.c. of ethanol, and 2 c.c. of 30% acetic acid and adjusting the pH to 4 was deposited by dipping. This was left to dry in the air for 5 minutes, then placed in an electric furnace at 500°C and heat treated for 10 minutes. A pale yellow colored product was obtained. Next, this is immersed in the solution,
When the same heat treatment procedure was repeated, the yellow color deepened to a golden color. When we measured the degree of golden color using a chromaticity meter, we found that (x,
The values of y) are (0.308, 0.314) for 1-time immersion, (0.334, 0.356) for 2-time immersion, and (0.392, 0.392, 5-time immersion).
0.443), 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１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。
これにより黄色透明な所望形状が画かれたスライ
ドガラス板が得られた。Example 2 The same solution as in Example 1 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 transparent glass slide plate with a desired shape drawn thereon was obtained.
色度計で黄色の度合を測定したところ、C.I.E.
色度図において、（ｘ、ｙ）の値は、１回塗布で
（0.321、0.357）、２回塗布で（0.372、0.401）、４
回塗布で（0.393、0.427）の値であつた。 When measuring the degree of yellow with a color meter, CIE
In the chromaticity diagram, the values of (x, y) are (0.321, 0.357) for one application, (0.372, 0.401) for two applications, and 4.
The values were (0.393, 0.427) after one application.
実施例 ３
ステンレス板の表面に、硝酸セリウム18ｇ、チ
タンテトライソプロポキシド22c.c.、エタノール55
c.c.、1NHCI0.5c.c.、水１c.c.を混合撹拌し、PH4.2の
混合溶液をスプレー法により付着させた。その後
350℃の電気炉中に入れ、50分間熱処理を行つた。
薄黄色に着色したステンレス板が得られた。Example 3 18 g of cerium nitrate, 22 c.c. of titanium tetraisopropoxide, and 55 g of ethanol were placed on the surface of a stainless steel plate.
cc, 0.5 c.c. of 1NHCI, and 1 c.c. of water were mixed and stirred, and a mixed solution of PH4.2 was applied by spraying. after that
It was placed in an electric furnace at 350°C and heat treated for 50 minutes.
A stainless steel plate colored pale yellow was obtained.
実施例 ４
実施例１と同様な混合溶液を調整後、48時間後
において、ソーダライム系のスライド板に付着さ
せ、その後実施例１と同様な操作で処理した。こ
れにより黄色透明なコーテイング皮膜を有するス
ライド板が得られた。Example 4 After preparing the same mixed solution as in Example 1, it was applied to a soda lime slide plate 48 hours later, and then treated in the same manner as in Example 1. As a result, a slide plate having a yellow transparent coating film was obtained.
これから明らかなように、この混合溶液は溶液
調整後48時間経ても使用可能である。 As is clear from this, this mixed solution can be used even 48 hours after solution preparation.
比較例
実施例１において、30％酢酸を加えない溶液を
調整した。PHは5.5であつた。Comparative Example In Example 1, a solution was prepared without adding 30% acetic acid. The pH was 5.5.
この溶液を調整直後に実施例１と同じ操作でガ
ラス板に付着させ、大気中に５分間放置乾燥させ
た後、500℃の電気炉中で５分間加熱処理した。
これにより薄黄色のコーテイング膜が得られた。 Immediately after preparation, this solution was applied to a glass plate in the same manner as in Example 1, left to dry in the air for 5 minutes, and then heat-treated in an electric furnace at 500°C for 5 minutes.
This resulted in a pale yellow coating film.
しかし、この溶液を24時間放置した後に同様な
操作で乾燥、加熱処理した。得られたコーテイン
グ膜は透明性がなくなり、白色気味の薄黄色であ
つた。 However, after allowing this solution to stand for 24 hours, it was dried and heated in the same manner. The resulting coating film lost its transparency and had a whitish, pale yellow color.
この溶液を５日間放置し、同様に処理して得た
コーテイング膜は透明性がなく、白色気味の薄黄
色であつた。 This solution was allowed to stand for 5 days, and the coating film obtained by the same treatment was not transparent and had a whitish pale yellow color.
しかし、この溶液を更に長時間放置し、ゲル化
直前の26日間放置後、同様にコーテイング、乾
燥、熱処理したところ、透明性の薄黄色のコーテ
イング膜が得られた。 However, when this solution was allowed to stand for an even longer period of time for 26 days just before gelation, it was coated, dried, and heat treated in the same manner, resulting in a transparent pale yellow coating film.
このように酸を添加しない（PH5.5以上）溶液
で透明性の黄色コーテイング膜を得るには、溶液
調整直後と長時間放置してゲル化直前の溶液にお
いてのみ得られるに過ぎない。 In this way, a transparent yellow coating film can only be obtained with a solution to which no acid is added (pH 5.5 or higher) immediately after the solution is prepared and immediately before it gels after being left for a long time.
実施例 ５
アルミニウム箔の表面に、塩化セリウム5.87
ｇ、チタンテトライソプロポキシド２c.c.、エタノ
ール30c.c.、30％酢酸２c.c.を撹拌混合し（TiO2、
CeO2換算でTiO2：CeO2＝１：５）、PHを3.5とし
た溶液を、浸漬法により付着させた。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分間熱処理した。薄黄色に着色したも
のが得られた。次にこれを前記溶液中に浸漬し、
同様な熱処理する操作を繰返すと、黄色が濃くな
り、黄金色のものとなつた。色度計で黄金色度合
を測定したところ、C.I.E色度図において、（ｘ、
ｙ）の値は１回浸漬で（0.308、0.310）、２回浸
漬で（0.326、0.339）、４回浸漬で（0.338、
0.347）となり、次第に着色濃度が増し黄色とな
つた。Example 5 Cerium chloride 5.87% on the surface of aluminum foil
g, titanium tetraisopropoxide 2c.c., ethanol 30c.c., and 30% acetic acid 2c.c. were stirred and mixed (TiO 2 ,
A solution of TiO 2 : CeO 2 =1:5 (in terms of CeO 2 ) with a pH of 3.5 was applied by dipping. This was left to dry in the air for 5 minutes, then placed in an electric furnace at 500°C and heat treated for 10 minutes. A pale yellow colored product was obtained. Next, this is immersed in the solution,
When the same heat treatment procedure was repeated, the yellow color deepened to a golden color. When we measured the degree of golden color using a chromaticity meter, we found that (x,
The values of y) are (0.308, 0.310) for 1-time immersion, (0.326, 0.339) for 2-time immersion, and (0.338, 0.338, 4-time immersion).
0.347), and the coloring density gradually increased and became yellow.
実施例 ６
アルミニウム箔の表面に、塩化セリウム0.023
ｇ、チタンテトライソプロポキシド10c.c.、エタノ
ール30c.c.、30％酢酸２c.c.を撹拌混合し（TiO2、
CeO2換算でTiO2：CeO2＝250：１）、PHを４とし
た溶液を、浸漬法により付着させた。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分間熱処理した。薄黄色に着色したも
のが得られた。次にこれを前記溶液中に浸漬し、
同様な熱処理する操作を繰返すと、黄色が濃くな
り、黄金色のものとなつた。色度計で黄金色度合
を測定したところ、C.I.E色度図において、（ｘ、
ｙ）の値は１回浸漬で（0.307、0.313）、２回浸
漬で（0.321、0.331）、４回浸漬で（0.329、
0.340）となり、次第に着色濃度が増し黄色とな
つた。Example 6 Cerium chloride 0.023 on the surface of aluminum foil
g, titanium tetraisopropoxide 10c.c., ethanol 30c.c., and 30% acetic acid 2c.c. were stirred and mixed (TiO 2 ,
A solution of TiO 2 :CeO 2 =250:1) with a pH of 4 in terms of CeO 2 was deposited by dipping. This was left to dry in the air for 5 minutes, then placed in an electric furnace at 500°C and heat treated for 10 minutes. A pale yellow colored product was obtained. Next, this is immersed in the solution,
When the same heat treatment procedure was repeated, the yellow color deepened to a golden color. When we measured the degree of golden color using a chromaticity meter, we found that (x,
The values of y) are (0.307, 0.313) for 1-time immersion, (0.321, 0.331) for 2-time immersion, and (0.329, 0.329, 4-time immersion).
0.340), and the coloring density gradually increased and became yellow.
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、また従
来の電界メツキ法における電解設備等を必要とせ
ず、簡単、容易に基体に着色し得られる。更に基
体に付着させる混合液は調整後長期に亘つて安定
であり、これを使用することにより優れた透明な
黄色乃至黄金色のコーテイング膜が得られる優れ
た効果を奏し得られる。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, which requires expensive equipment and can only form a film on a small area at a time. The substrate can be easily and easily colored without requiring any equipment. Furthermore, the mixed solution applied to the substrate is stable for a long period of time after being prepared, and by using this, an excellent effect of obtaining a transparent yellow to golden yellow coating film can be obtained.
Claims (1)
液に酸を加えてPHを3.5〜５となし、全溶液中の
含有水分を８％以下に調整し、この混合液を基体
表面に付着させた後、200℃以上乃至基体の変形
または変質する温度未満の温度に加熱してセリウ
ム酸化物−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TiO2、CeO2に換算して重量比で１：
５〜250：１である特許請求の範囲第１項記載の
方法。[Claims] 1. Add acid to a mixed solution of a titanium organic compound and a cerium compound to adjust the pH to 3.5 to 5, adjust the water content in the entire solution to 8% or less, and apply this mixed solution to the substrate surface. A metal or inorganic material that is colored by forming a cerium oxide-titanium oxide-based oxide film by attaching the material to a substrate and then heating it to a temperature of 200°C or higher or lower than the temperature at which the substrate is deformed or altered. A method of coloring the surface of a substrate. 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: by weight in terms of TiO 2 and CeO 2 .
5 to 250:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24934686A JPS63103083A (en) | 1986-10-20 | 1986-10-20 | Method for coloring solid surface of metal or inorganic substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24934686A JPS63103083A (en) | 1986-10-20 | 1986-10-20 | Method for coloring solid surface of metal or inorganic substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63103083A JPS63103083A (en) | 1988-05-07 |
| JPH039187B2 true JPH039187B2 (en) | 1991-02-07 |
Family
ID=17191659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24934686A Granted JPS63103083A (en) | 1986-10-20 | 1986-10-20 | Method for coloring solid surface of metal or inorganic substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63103083A (en) |
-
1986
- 1986-10-20 JP JP24934686A patent/JPS63103083A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63103083A (en) | 1988-05-07 |
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