JP2004071238A - Colored lamp with plated layer on the surface of glass tube, and manufacturing method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored lamp capable of emitting light of diversified colors, and a manufacturing method of the same. <P>SOLUTION: For the colored lamp, a thin plated layer is formed on a glass tube. The manufacturing process of the colored lamp includes a process of forming fine irregularities on the surface of the glass tube, a process of applying metal catalyst nuclei, and a process of applying electroless plating. <P>COPYRIGHT: (C)2004,JPO

Description

【００１１】
ガラス管表面のめっき層の厚さは、めっき時間にほぼ比例する。めっき層の厚さと透過光の強さは、ほぼ反比例するから、めっき層が薄すぎると望みの発色が得られない。しかし、めっき層が厚すぎると、透過光が少なくなる。
好ましい、めっき時間はめっき液の種類、めっき金属によって異なるが、５〜９０秒程度であり、無電解めっきによる膜厚が０．００１〜０．３μｍであることが望ましく、０．００５〜０．０５μｍがとくに好ましい。
また、めっき層は、異なる金属の層を重ねて用いても良い。
【００１２】
本発明の着色ランプは、めっき層の上に、透明保護被膜を設けることができる。本発明において、とくにめっき金属が酸化されやすい銅、銀、スズ、ニッケル、コバルトのような金属の場合、空気中の酸素により酸化され、変色するので、変色を防止する意味で、透明保護被膜を設ける。
透明保護被膜としては、無機質の透明被膜が望ましく、水ガラスや周知のゾル−ゲルマトリックス（シリカ前駆体、シリカ系複合酸化物前駆体、ジルコニア前駆体等）が用いられる。
例えば、シリカ（ＳｉＯ_２）−ジルコニア（ＺｒＯ_２）、アルコール系溶剤からなるゾルをガラス管表面に塗布し、溶剤を蒸発させ、約３００℃で焼結するとガラス管表面上に透明保護被膜が得られる。
【００１３】
本発明の実施の形態をまとめると、以下のとおりである。
（１）　ランプのガラス管の表面にめっき層による薄膜を設けた着色ランプ。
（２）　めっき層が、ニッケル、コバルト、金、銀、銅、パラジウム、白金、スズ、ロジウム、インジウム、ルテニウムのいづれかひとつ、又は２種以上の組み合わせである上記１に記載した着色ランプ。
（３）　めっき層の上に、透明保護被膜を設けた上記１又は上記２に記載した着色ランプ。
（４）　ランプのガラス管の表面に、微細な凹凸を設ける工程、金属触媒の核を設ける工程、無電解めっきを行う工程からなるめっき層を有する着色ランプの製造方法。
（５）　微細な凹凸を設ける工程が、バフ研磨、サンドブラスト、ホーニングから選ばれる物理的処理、及び／又は、フッ酸、硝酸から選ばれる酸に浸漬する化学的処理である上記４に記載しためっき層を有する着色ランプの製造方法。
（６）　金属触媒の核を設ける工程で用いられる金属が、Ｐｄ及び／又はＳｎである上記４又は上記５に記載しためっき層を有する着色ランプの製造方法。
（７）　無電解めっきの膜厚が０．００１〜０．３μｍである上記４ないし蒸気６のいずれかひとつに記載しためっき層を有する着色ランプの製造方法。
（８）　無電解めっき液が、無電解ニッケル、無電解コバルト、無電解金、無電解銀、無電解銅、無電解パラジウム、無電解白金、無電解スズ、無電解ロジウム、無電解インジウム、無電解ルテニウムのいづれかひとつである上記４ないし上記７のいずれかひとつに記載しためっき層を有する着色ランプの製造方法。
【００１４】
次に本発明の具体例を示す。
（実施例１）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度２５℃の塩化第一錫３０ｇ／ｌ、濃塩酸１５ｍｌ／ｌを含む処理液に、２分間浸漬して、ガラス表面を感受性化した後、ランプのガラス管表面を、温度２５℃の塩化パラジウム０．３ｇ／ｌ、濃塩酸３ｍｌ／ｌを含む処理液に、２分間浸漬して、ガラス表面を活性化した。
ガラス管表面を水洗により洗浄したのち、硫酸ニッケル　３０ｇ／ｌホスフィン酸ナトリウム　１０ｇ／ｌ、クエン酸ナトリウム　１０ｇ／ｌを含むｐＨ４の無電解ニッケル液を用いて、めっき温度９０℃で、０．０１５μｍのめっきを行った。
ガラス管表面に薄いニッケル層が形成された。水洗して乾燥後に、電流を流してランプを点灯したところ、真珠色の発色が見られた。
【００１５】
（実施例２）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度４０℃のアクチベーターネオガント（シェーリング社製）４０ｍｌ／ｌ、水酸化ナトリウム４ｇ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面に触媒を吸着させた後、ランプのガラス管表面を、温度３０℃のリデューサーネオガント（シェーリング社製）５０ｍｌ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面についた触媒を還元した。
ガラス管表面を水洗により洗浄したのち、硫酸銅　　１０ｇ／ｌ、ＥＤＴＡ　３０ｇ／ｌ、ＨＣＨＯ　３ｍｌ／ｌ、ピピリジル　微量、ＰＥＧ微量を含むｐＨ　１２．２の無電解銅めっき浴を用いて、めっき温度７０℃で、０．０３μｍのめっきを行った。
ガラス管表面に薄い銅層が形成された。水洗して乾燥後に、電流を流してランプを点灯したところ、赤系統の真珠色の発色が見られた。
【００１６】
（実施例３）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度３０℃のキャタリストＣ（奥野製薬工業社製）４０ｍｌ／ｌ、濃塩酸１００ｍｌ／ｌを含む処理液に、３分間浸漬して、ガラス表面を触媒化した後、ランプのガラス管表面を、温度３５℃の濃塩酸１００ｍｌ／ｌを含む処理液に、２分間浸漬して、ガラス表面上の触媒を促進化した。
ガラス管表面を水洗により洗浄したのち、塩化ニッケル０．０２ｍｏｌ／ｌ、酒石酸ナトリウム０．０２ｍｏｌ／ｌ、ヒドラジン　１．０ｍｏｌ／ｌを含むｐＨ１０の無電解ニッケル液を用いて、めっき温度９５℃で０．０１μｍのめっきを行った。
ガラス管表面に薄いニッケル層が形成された。水洗して乾燥後に、電流を流してランプを点灯したところ、真珠色の発色が見られた。
【００１７】
（実施例４）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度２５℃の塩化第一錫３０ｇ／ｌ、濃塩酸１５ｍｌ／ｌを含む処理液に、２分間浸漬して、ガラス表面を感受性化した後、ランプのガラス管表面を、温度２５℃の塩化パラジウム０．３ｇ／ｌ、濃塩酸３ｍｌ／ｌを含む処理液に、２分間浸漬して、ガラス表面を活性化した。
ガラス管表面を水洗により洗浄したのち、シアン化金カリウム０．０３ｍｏｌ／ｌ、シアン化カリウム０．１ｍｏｌ／ｌ、水酸化カリウム０．２ｍｏｌ／ｌ、水素化ほう素ナトリウム０．２ｍｏｌ／ｌを含むｐＨ１０の無電解金めっき浴を用いて、めっき温度７０℃で０．０２μｍめっきを行った。
ガラス管表面に薄い金層が形成された。水洗して乾燥後に、電流を流してランプを点灯したところ、赤系統の真珠色の発色が見られた。
【００１８】
（実施例５）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度４０℃のアクチベーターネオガント（シェーリング社製）４０ｍｌ／ｌ、水酸化ナトリウム４ｇ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面に触媒を吸着させた後、ランプのガラス管表面を、温度３０℃のリデューサーネオガント（シェーリング社製）５０ｍｌ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面についた触媒を還元した。
水洗により洗浄したのち、硫酸銅　　１０ｇ／ｌ、ＥＤＴＡ　３０ｇ／ｌ、ＨＣＨＯ　３ｍｌ／ｌ、ピピリジル　微量、ＰＥＧ微量を含むｐＨ　１２．２の無電解銅めっき浴を用いて、めっき温度７０℃で、０．００５μｍのめっきを行った。銅の薄いめっき層が確認された。
水洗して乾燥後、銅の薄いめっき層が形成されたガラス管表面を、シアン化金カリウム０．０３ｍｏｌ／ｌ、シアン化カリウム０．１ｍｏｌ／ｌ、水酸化カリウム０．２ｍｏｌ／ｌ、水素化ほう素ナトリウム０．２ｍｏｌ／ｌを含むｐＨ１０の無電解金めっき浴を用いて、めっき温度７０℃で０．０１μｍのめっきを行った。
ガラス管表面に薄い金層が形成された。水洗して乾燥後に、電流を流してランプを点灯したところ、赤系統の真珠色の発色が見られた。
【００１９】
（実施例６）
自動車のサイドランプのガラス管表面を、５分間、砥粒を付けたバフにより研磨した。水洗して乾燥後、ランプのガラス管表面を、温度４０℃のアクチベーターネオガント（シェーリング社製）４０ｍｌ／ｌ、水酸化ナトリウム４ｇ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面に触媒を吸着させた後、ランプのガラス管表面を、温度３０℃のリデューサーネオガント（シェーリング社製）５０ｍｌ／ｌ、硼酸５ｇ／ｌを含む処理液に、５分間浸漬して、ガラス表面についた触媒を還元した。
水洗により洗浄したのち、硫酸銅　　１０ｇ／ｌ、ＥＤＴＡ　３０ｇ／ｌ、ＨＣＨＯ　３ｍｌ／ｌ、ピピリジル　微量、ＰＥＧ微量を含むｐＨ　１２．２の無電解銅めっき浴を用いて、めっき温度７０℃で、０．０２μｍのめっきを行った。銅の薄いめっき層が確認された。
シリカ（ＳｉＯ_２）−ジルコニア（ＺｒＯ_２）前駆体となるジルコニア変性オルガノシロキサン縮合物２０ｗｔ％、２−プロパノール５５ｗｔ％、メタノール１５ｗｔ％、プロピレングリコールメチルエーテル１０ｗｔ％からなるゾルを、前記０．０２μｍの銅の薄いめっき層の上に塗布し、溶剤を蒸発させてゲル状とし、３００℃で焼結して厚さ２．０μｍの透明保護被膜を形成した。
電流を流してランプを点灯したところ、赤系統の真珠色の発色が見られた。
【００２０】
【発明の効果】
本発明の着色ランプは、無電解めっきにより、大量に製造できるばかりか、めっきする金属を変えることにより、多種多様な着色光を放ち、しかも長時間使用しても、劣化しやすい有機バインダーを含まないため、変色することがない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to lamps such as headlamps, tail lamps, and directional lamps used for vehicle lighting, particularly for automobile lighting, and to a method of manufacturing the same.
[0002]
[Prior art]
Conventionally, lamps used for automobile certification are xenon lamps, halogen lamps, and incandescent lamps, which are white light with a yellow tint when an electric current is applied.Cobalt oxide films are used to control color temperature and the like. For the purpose of coating and ensuring the safety of automobiles, the stop lamps are coated with pigments such as red and the direction lamps are coated with pigments such as orange, and lamps having various functional colors are mounted.
However, since the lamps of automobile lamps have recently become transparent lenses, when light bulbs of red, blue, orange, etc. are attached to the lamps, especially when looking at the lamps in the daytime, only one point is red, blue, orange, etc. At present, the design has been impaired due to the appearance.
[0003]
[Problems to be solved by the invention]
Conventionally, when a color bulb is attached to a lamp with a transparent lens, only one point appears to be colored, thus impairing the design of the automobile.
The present invention provides a high-quality color light bulb which has a high light transmittance, is a metallic color that melts into the color of the lamp of a transparent lens before lighting, and emits a variety of pearlescent lights when lighting, and a method of manufacturing the same. I do.
[0004]
[Means for Solving the Problems]
The present invention is a colored lamp having a thin-film layer formed by forming a thin plating layer in a thin film on the surface of a glass tube of the lamp, and has a high light transmittance by plating the glass on the surface of the lamp. By changing the type of metal, we succeeded in creating a colored lamp that can be mounted on a lamp that emits a variety of pearl-like lights.
In the present invention, a plating layer is provided in a thin film on the glass surface of the lamp, and the thickness of the plating layer can be adjusted by changing the plating time.
Further, in the present invention, an electroless plating method is used as a method for plating the glass surface of the lamp.
That is, the method includes a step of providing fine irregularities on the surface of the glass tube of the lamp, a step of providing a core of a metal catalyst, and a step of performing electroless plating.
In the present invention, the step of providing fine irregularities includes a physical treatment selected from buffing, sand blasting and honing, and a chemical treatment immersed in an acid selected from hydrofluoric acid and nitric acid. In the present invention, the physical treatment and the chemical treatment can be used in combination. By this treatment, fine irregularities are formed on the surface of the glass tube of the lamp, and the step of providing a nucleus which is a step for forming a scaffold for plating in the next step can be performed well.
In the present invention, the step of providing a nucleus of the metal catalyst, in the electroless plating, when the metal ions are fixed to the surface, is to serve as a scaffold for firmly fixed to the surface, used as a catalyst in a chemical reaction Pd and Sn are used.
[0005]
The step of providing the core of the metal catalyst in the present invention can be broadly classified into the following three types.
{Circle around (1)} One example of the sensitization-activation method is as follows. A glass tube surface of a lamp is treated with a treatment solution containing 20 to 40 g / l of stannous chloride and 10 to 20 ml / l of concentrated hydrochloric acid at a temperature of 20 to 30 ° C. After soaking for 2-3 minutes to sensitize the glass surface, the surface of the glass tube of the lamp contains 0.1-0.5 g / l of palladium chloride at a temperature of 20-30 ° C. and 1-5 ml / l of concentrated hydrochloric acid. The glass surface is activated by immersion in the treatment liquid for 2-3 minutes.
{Circle around (2)} As an example of the catalyzing-promoting method, the surface of a glass tube of a lamp is coated with Catalyst C (manufactured by Okuno Pharmaceutical Co., Ltd.) at a temperature of 15 to 40 ° C., 20 to 60 ml / l, and concentrated hydrochloric acid at 100 to 180 ml / l. Is immersed in a treatment solution containing 1 to 10 minutes to catalyze the glass surface, and then the surface of the glass tube of the lamp is treated with a treatment solution containing concentrated hydrochloric acid 80 to 120 ml / l at a temperature of 30 to 40 ° C. Soak for 3 minutes to promote catalyst on glass surface.
Instead of concentrated hydrochloric acid, it may be accelerated with 40 to 60 ml / l of concentrated sulfuric acid at 40 to 50 ° C.
{Circle around (3)} As an example of the adsorption-reduction method, the surface of a glass tube of a lamp is treated with an activator neogant (manufactured by Schering Company) at a temperature of 30 to 50 ° C., 30 to 50 ml / l, and sodium hydroxide 3 to 5 g / l. After being immersed in a treatment solution containing 4 to 6 g / l of boric acid for 4 to 8 minutes to adsorb the catalyst on the glass surface, the surface of the glass tube of the lamp is reduced to a temperature of 20 to 35 ° C. using a reducer Neogant (Schering Co., Ltd.). Immersion in a treatment solution containing 40 to 60 ml / l and boric acid 4 to 6 g / l for 4 to 5 minutes to reduce the catalyst on the glass surface.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The electroless plating solution used in the present invention is, as typical examples, electroless nickel, electroless copper, electroless cobalt, electroless gold, electroless silver, electroless platinum, electroless palladium, electroless tin, There are electroless rhodium, electroless indium, electroless ruthenium and the like.
An example of a typical basic composition of electroless nickel will be described.
(I)
Nickel sulfate 30g / l
Sodium phosphinate 10g / l
Sodium citrate 10g / l
pH 4-6 Plating temperature 90 ℃
(Ii)
Nickel sulfate 30g / l
Sodium malonate 34g / l
Boric acid 30g / l
Rochelle salt 30g / l
DMAB 3.4 g / l
pH 5-7 Plating temperature 50-70 ° C
(Iii)
Nickel chloride 0.02mol / l
Sodium tartrate 0.02mol / l
Hydrazine 1.0mol / l
pH 10 Plating temperature 95 ℃
[0007]
An example of a typical basic composition of electroless copper will be described.
Copper sulfate 10g / l
EDTA 30g / l
HCHO 3ml / l
Pipyridyl trace PEG trace pH 12.2 Plating temperature 70 ℃
An example of a typical basic composition of electroless cobalt will be described.
Cobalt sulfate 0.05mol / l
Sodium phosphinate 0.2mol / l
Sodium tartrate 0.5mol / l
Sodium sulfate 0.5mol / l
pH 10 Plating temperature 90 ° C
[0008]
An example of a typical basic composition of electroless gold will be described.
Potassium gold cyanide 0.03mol / l
Potassium cyanide 0.1mol / l
Potassium hydroxide 0.2mol / l
Sodium borohydride 0.2mol / l
pH 10 Plating temperature 70 ° C
An example of a typical basic composition of electroless silver will be described.
1.98 g / l of silver potassium cyanide
Potassium cyanide 1.4g / l
Potassium hydroxide 2.4 g / l
DMAB 30g / l
pH 10 Plating temperature 55-60 ° C
[0009]
An example of a typical basic composition of electroless palladium will be described.
Palladium chloride 0.01mol / l
Ethylenediamine 0.08mol / l
Sodium phosphinate 0.06mol / l
Thiodiglycolic acid 30ppm
pH 6-8 Plating temperature 50 ℃
An example of a typical basic composition of electroless platinum will be described.
Sodium hexahydroxoplatinate 10g / l
Sodium hydroxide 5g / l
Ethylenediamine 10g / l
Hydrazine 1g / l
pH 10 Plating temperature 35 ° C
An example of a typical basic composition of electroless tin will be described.
Stannous chloride dihydrate 0.08mol / l
EDTA2Na dihydrate 0.09mol / l
Citric acid 3Na dihydrate 0.24mol / l
Nitrilo triacetic acid 0.10 mol / l
0.04 mol / l titanium trichloride (25% soln.)
pH 7.0 Plating temperature 60 ° C
[0010]
An example of a typical basic composition of electroless rhodium will be described.
Electroless rhodium [Rh (NH ₃ )] Cl ₃ 0.12 g
0.1 g of NH ₂ OH · HCl
5 ml of NH ₂ NH ₂ .H ₂ O
10 ml of NH ₄ OH (28%)
500ml water
PH 11.5 Bath temperature 70-80 ° C
An example of a typical basic composition of electroless indium will be described.
Electroless indium _{In 2 (SO 4) 3 ·} 9H 2 O 0.08mol / L
Citric acid 0.34mol / L
Ti ₂ (SO ₄ ) ₃ 0.04 mol / L
Nitrilo triacetic acid 0.2 mol / L
PH 9 ~ 10.5 Bath temperature 70 ~ 90 ° C
An example of a typical basic composition of electroless ruthenium will be described.

[0011]
The thickness of the plating layer on the surface of the glass tube is almost proportional to the plating time. Since the thickness of the plating layer and the intensity of the transmitted light are almost inversely proportional, if the plating layer is too thin, the desired coloring cannot be obtained. However, when the plating layer is too thick, transmitted light is reduced.
The preferred plating time varies depending on the type of plating solution and plating metal, but is about 5 to 90 seconds, and the film thickness by electroless plating is preferably 0.001 to 0.3 μm, and 0.005 to 0.3 μm. 05 μm is particularly preferred.
Further, the plating layer may be formed by stacking different metal layers.
[0012]
In the colored lamp of the present invention, a transparent protective film can be provided on the plating layer. In the present invention, particularly in the case of a metal such as copper, silver, tin, nickel, and cobalt, in which the plating metal is easily oxidized, the metal is oxidized and discolored by oxygen in the air. Provide.
As the transparent protective film, an inorganic transparent film is desirable, and water glass or a well-known sol-gel matrix (silica precursor, silica-based composite oxide precursor, zirconia precursor, etc.) is used.
For example, a sol composed of silica (SiO ₂ ) -zirconia (ZrO ₂ ) and an alcohol-based solvent is applied to the surface of a glass tube, the solvent is evaporated, and sintering is performed at about 300 ° C. to obtain a transparent protective film on the surface of the glass tube. Can be
[0013]
The embodiments of the present invention are summarized as follows.
(1) A colored lamp in which a thin film made of a plating layer is provided on the surface of a glass tube of the lamp.
(2) The colored lamp according to the above 1, wherein the plating layer is any one of nickel, cobalt, gold, silver, copper, palladium, platinum, tin, rhodium, indium, and ruthenium, or a combination of two or more thereof.
(3) The colored lamp as described in (1) or (2) above, wherein a transparent protective film is provided on the plating layer.
(4) A method for producing a colored lamp having a plating layer comprising a step of providing fine irregularities on a surface of a glass tube of a lamp, a step of providing a core of a metal catalyst, and a step of performing electroless plating.
(5) The plating as described in 4 above, wherein the step of providing fine irregularities is a physical treatment selected from buffing, sand blasting, and honing, and / or a chemical treatment immersed in an acid selected from hydrofluoric acid and nitric acid. A method for producing a colored lamp having a layer.
(6) The method for producing a colored lamp having a plating layer according to the above (4) or (5), wherein the metal used in the step of providing the core of the metal catalyst is Pd and / or Sn.
(7) A method for producing a colored lamp having a plating layer according to any one of the above (4) to (6), wherein the film thickness of the electroless plating is 0.001 to 0.3 μm.
(8) The electroless plating solution is electroless nickel, electroless cobalt, electroless gold, electroless silver, electroless copper, electroless palladium, electroless platinum, electroless tin, electroless rhodium, electroless indium, 8. A method for producing a colored lamp having a plating layer according to any one of the above items 4 to 7, which is any one of electrolytic ruthenium.
[0014]
Next, specific examples of the present invention will be described.
(Example 1)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing and drying, the surface of the glass tube of the lamp was immersed in a treatment solution containing 30 g / l of stannous chloride and 15 ml / l of concentrated hydrochloric acid at a temperature of 25 ° C. for 2 minutes to sensitize the glass surface. The surface of the glass tube of the lamp was immersed in a treatment solution containing 0.3 g / l of palladium chloride and 3 ml / l of concentrated hydrochloric acid at a temperature of 25 ° C. for 2 minutes to activate the glass surface.
After washing the surface of the glass tube by washing with water, using an electroless nickel solution having a pH of 4 containing 30 g / l of nickel sulfate 10 g / l of sodium phosphinate and 10 g / l of sodium citrate at a plating temperature of 90 ° C. and 0.015 μm Plating was performed.
A thin nickel layer was formed on the surface of the glass tube. After washing with water and drying, the lamp was turned on by passing an electric current, and a pearl color was observed.
[0015]
(Example 2)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing with water and drying, the surface of the glass tube of the lamp is immersed for 5 minutes in a treatment liquid containing 40 ml / l of activator neogant (manufactured by Schering), 4 g / l of sodium hydroxide, and 5 g / l of boric acid at a temperature of 40 ° C. Then, after adsorbing the catalyst on the glass surface, the surface of the glass tube of the lamp was immersed for 5 minutes in a treatment liquid containing 50 ml / l of reducer neogant (manufactured by Schering) and 5 g / l of boric acid at a temperature of 30 ° C. Thus, the catalyst on the glass surface was reduced.
After the surface of the glass tube was washed with water, a plating temperature of 70 g was used using an electroless copper plating bath having a pH of 12.2 containing 10 g / l of copper sulfate, 30 g / l of EDTA, 3 ml / l of HCHO, a trace amount of piperidyl and a trace amount of PEG. 0.03 μm plating was performed at ℃.
A thin copper layer was formed on the surface of the glass tube. After washing with water and drying, a current was applied to turn on the lamp, and a reddish pearl color was observed.
[0016]
(Example 3)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing with water and drying, the surface of the glass tube of the lamp was immersed for 3 minutes in a treatment solution containing 40 ml / l of Catalyst C (manufactured by Okuno Pharmaceutical Co., Ltd.) and 100 ml / l of concentrated hydrochloric acid at a temperature of 30 ° C. After catalysis, the surface of the glass tube of the lamp was immersed in a treatment solution containing 100 ml / l of concentrated hydrochloric acid at a temperature of 35 ° C. for 2 minutes to promote the catalyst on the glass surface.
After the surface of the glass tube is washed by washing with water, a plating temperature of 95 ° C. is applied using an electroless nickel solution of pH 10 containing 0.02 mol / l of nickel chloride, 0.02 mol / l of sodium tartrate and 1.0 mol / l of hydrazine. Plating of 0.01 μm was performed.
A thin nickel layer was formed on the surface of the glass tube. After washing with water and drying, the lamp was turned on by passing an electric current, and a pearl color was observed.
[0017]
(Example 4)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing and drying, the surface of the glass tube of the lamp was immersed in a treatment solution containing 30 g / l of stannous chloride and 15 ml / l of concentrated hydrochloric acid at a temperature of 25 ° C. for 2 minutes to sensitize the glass surface. The surface of the glass tube of the lamp was immersed in a treatment solution containing 0.3 g / l of palladium chloride and 3 ml / l of concentrated hydrochloric acid at a temperature of 25 ° C. for 2 minutes to activate the glass surface.
After washing the surface of the glass tube with water, a pH of 10 containing 0.03 mol / l of potassium gold cyanide, 0.1 mol / l of potassium cyanide, 0.2 mol / l of potassium hydroxide, and 0.2 mol / l of sodium borohydride was used. 0.02 μm plating was performed at a plating temperature of 70 ° C. using an electroless gold plating bath.
A thin gold layer was formed on the surface of the glass tube. After washing with water and drying, a current was applied to turn on the lamp, and a reddish pearl color was observed.
[0018]
(Example 5)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing with water and drying, the surface of the glass tube of the lamp is immersed for 5 minutes in a treatment liquid containing 40 ml / l of activator neogant (manufactured by Schering), 4 g / l of sodium hydroxide, and 5 g / l of boric acid at a temperature of 40 ° C. Then, after adsorbing the catalyst on the glass surface, the surface of the glass tube of the lamp was immersed for 5 minutes in a treatment liquid containing 50 ml / l of reducer neogant (manufactured by Schering) and 5 g / l of boric acid at a temperature of 30 ° C. Thus, the catalyst on the glass surface was reduced.
After washing by washing with water, 10 g / l of copper sulfate, 30 g / l of EDTA, 3 ml / l of HCHO, a trace amount of piperidyl, and a trace amount of PEG were used. 0.005 μm plating was performed. A thin copper plating layer was observed.
After washing with water and drying, the surface of the glass tube on which the thin copper plating layer was formed was treated with 0.03 mol / l of potassium gold cyanide, 0.1 mol / l of potassium cyanide, 0.2 mol / l of potassium hydroxide, and boron hydride. Using an electroless gold plating bath having a pH of 10 and containing 0.2 mol / l of sodium, plating was performed at a plating temperature of 70 ° C and 0.01 µm.
A thin gold layer was formed on the surface of the glass tube. After washing with water and drying, a current was applied to turn on the lamp, and a reddish pearl color was observed.
[0019]
(Example 6)
The surface of the glass tube of the side lamp of the automobile was polished for 5 minutes with a buff provided with abrasive grains. After washing with water and drying, the surface of the glass tube of the lamp is immersed for 5 minutes in a treatment liquid containing 40 ml / l of activator neogant (manufactured by Schering), 4 g / l of sodium hydroxide, and 5 g / l of boric acid at a temperature of 40 ° C. Then, after adsorbing the catalyst on the glass surface, the surface of the glass tube of the lamp was immersed for 5 minutes in a treatment liquid containing 50 ml / l of reducer neogant (manufactured by Schering) and 5 g / l of boric acid at a temperature of 30 ° C. Thus, the catalyst on the glass surface was reduced.
After washing by washing with water, 10 g / l of copper sulfate, 30 g / l of EDTA, 3 ml / l of HCHO, a trace amount of piperidyl, and a trace amount of PEG were used. .02 μm was plated. A thin copper plating layer was observed.
A sol comprising 20% by weight of a zirconia-modified organosiloxane condensate serving as a silica (SiO ₂ ) -zirconia (ZrO ₂ ) precursor, 55% by weight of 2-propanol, 15% by weight of methanol, and 10% by weight of propylene glycol methyl ether was mixed with the 0.02 μm sol. It was applied on a thin copper plating layer, the solvent was evaporated to a gel state, and sintered at 300 ° C. to form a 2.0 μm thick transparent protective film.
When the lamp was turned on by passing an electric current, a reddish pearl color was observed.
[0020]
【The invention's effect】
The colored lamp of the present invention can be manufactured in large quantities by electroless plating, and also emits a variety of colored lights by changing the metal to be plated, and contains an organic binder that is easily deteriorated even when used for a long time. There is no discoloration.

Claims (8)

A colored lamp in which a thin film made of a plating layer is provided on the surface of the glass tube of the lamp. 2. The colored lamp according to claim 1, wherein the plating layer is any one of nickel, cobalt, gold, silver, copper, palladium, platinum, tin, rhodium, indium, and ruthenium, or a combination of two or more thereof. The colored lamp according to claim 1 or 2, wherein a transparent protective film is provided on the plating layer. A method for producing a colored lamp having a plating layer comprising a step of providing fine irregularities on a surface of a glass tube of a lamp, a step of providing a core of a metal catalyst, and a step of performing electroless plating. The step of providing fine irregularities is a physical treatment selected from buffing, sand blasting and honing, and / or a chemical treatment immersed in an acid selected from hydrofluoric acid and nitric acid. Production method of a colored lamp having the same. The method for producing a colored lamp having a plating layer according to claim 4 or 5, wherein the metal used in the step of providing the core of the metal catalyst is Pd and / or Sn. The method for producing a colored lamp having a plating layer according to any one of claims 4 to 6, wherein the film thickness of the electroless plating is 0.001 to 0.3 µm. The electroless plating solution is made of electroless nickel, electroless cobalt, electroless gold, electroless silver, electroless copper, electroless palladium, electroless platinum, electroless tin, electroless rhodium, electroless indium, electroless ruthenium. A method for producing a colored lamp having a plating layer according to any one of claims 4 to 7, which is any one of the methods.