JP2003073116A - Gelatinizer of acidic cleaning liquid for metallic material - Google Patents

Gelatinizer of acidic cleaning liquid for metallic material

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Publication number
JP2003073116A
JP2003073116A JP2001309209A JP2001309209A JP2003073116A JP 2003073116 A JP2003073116 A JP 2003073116A JP 2001309209 A JP2001309209 A JP 2001309209A JP 2001309209 A JP2001309209 A JP 2001309209A JP 2003073116 A JP2003073116 A JP 2003073116A
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JP
Japan
Prior art keywords
amended
amendment
hydrofluoric acid
document name
aqueous solution
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
Application number
JP2001309209A
Other languages
Japanese (ja)
Inventor
Takeshi Kojima
毅 小嶋
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Individual
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Individual
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Filing date
Publication date
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Priority to JP2001309209A priority Critical patent/JP2003073116A/en
Publication of JP2003073116A publication Critical patent/JP2003073116A/en
Pending legal-status Critical Current

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  • Colloid Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a compound capable of increasing viscosity of an acidic liquid containing hydrofluoric acid or gelatinizing it. SOLUTION: When a compound obtained from the reaction of magnesium sulfate with ammonium hydrogenfluoride at a molar rate of 1:1 is mixed with an aqueous solution containing hydrofluoric acid at an optional rate, the viscosity of the solution is gradually increased and it is gelatinized.

Description

【発明の詳細な説明】 【0001】硫酸マグネシウムと弗化水素アンモニウム
水溶液を1:1モルにて混合攪拌させると、請求項1式
(I)の硫酸マグネシウム・弗化アンモニウムが得ら
れ、各原料となる硫酸マグネシウム、弗化アンモニウム
とはまったく異なった性質をもつ化合物が得られる。混
合前の弗化水素アンモニウムは、約75%水溶液に調整
しておく。 【0002】得られたゲル溶液はそのままで使用可能だ
が、アセトン等により結晶化し粉末状に精製する事が出
来る。 【発明の属する技術分野】本発明は、金属表面処理(化
学研磨)技術に関するものである。 【0003】化学研磨薬品、弗化水素酸混合液体に上記
式(I)を混ぜゲル化し、化学研磨を施す対象部分に塗
布、或いはポンプを利用し特殊ノズルにて吹き付けを行
う。 【従来の技術】従来の弗化水素酸を含むゲル化剤は、安
定性が悪く温度によって分解しやすいか或いは、化学研
磨後の対象物の美観が悪い。 【0004】ポンプを利用し、特殊ノズルで吹き付けた
り塗布する際、粘りがあるため作業性が悪い。 【0005】化学研磨対象物に膜を形成し易く、化学研
磨後の研磨剤除去が困難である。 【発明が解決しようとする課題】しかし従来のゲル化剤
では、弗化水素酸、或いは強酸によって分解したり、粘
りが強いため取り扱いが難しかった。そこで本発明は、
弗化水素酸或いは強酸によって分解せず、粘性はチクロ
トピー性を有する化学物質を見出す事を課題とする。 【0006】弗化水素酸、或いは強酸に安定な事を課題
とする。 【0007】作業性の良い(粘りの少ない)事を課題と
する。 【0008】化学研磨後の対象物の美観の良い事を課題
とする。 【0009】ゲル化剤は、水洗いによって簡単に洗い流
せる事を課題とする。 【問題を解決するための手段】上記課題を解決するため
に、請求項1式(1)の硫酸マグネシウム・弗化アンモ
ニウムは、化学研磨剤に混ぜる事により、ゲル化剤とし
て優れた性質を持つ事が様々な実験から明らかになっ
た。 【0010】弗化水素酸、或いは強酸に安定。 【0011】粘りが少なく、粘性はチクロトピー性を有
し、液ダレしない。 【0012】対象物の化学研磨後の美観が良い。 【0013】ゲル化剤は、水洗いによって簡単に洗い流
せる。 【0014】請求項1式(1)で得られた化合物を、化
学研磨剤に混ぜる量は、筆などで塗る場合と、ポンプを
利用し、特殊ノズル等で吹き付ける場合を考慮し濃度を
調整する。 【実施例】 【0015】7〜8%弗化水素酸、15〜17%硝酸、
請求項1式(1)で得られた化合物10%をよく混合
し、ゲル化化学研磨剤を得る。 【0016】化学研磨を施す金属に、筆で均一に塗る。
この時の塗る厚さは、2〜4mmが望ましい。 【0017】3時間経過後、蒸留水にてゲル化化学研磨
剤を洗い流し、化学研磨を施した金属を乾燥させると、
美しい金属表面を得る事ができる。 【発明の効果】本発明は、以上に説明したような構成
に、次の様な効果を奏する。請求項1に記載されている
発明は、弗化水素酸に安定な化合物なので、弗化水素酸
などを含む水溶液をゲル化することができる。
Description: When magnesium sulfate and an aqueous solution of ammonium hydrogen fluoride are mixed and stirred at a molar ratio of 1: 1, magnesium sulfate / ammonium fluoride of the formula (I) is obtained. Thus, a compound having properties completely different from those of magnesium sulfate and ammonium fluoride can be obtained. Ammonium hydrogen fluoride before mixing is adjusted to about 75% aqueous solution. Although the obtained gel solution can be used as it is, it can be crystallized with acetone or the like and purified into a powder. The present invention relates to a metal surface treatment (chemical polishing) technique. [0003] The above formula (I) is mixed with a liquid mixture of a chemical polishing chemical and hydrofluoric acid to form a gel, which is applied to a portion to be subjected to chemical polishing, or sprayed by a special nozzle using a pump. 2. Description of the Related Art A conventional gelling agent containing hydrofluoric acid has poor stability and is easily decomposed by temperature, or the appearance of an object after chemical polishing is poor. When spraying or applying with a special nozzle using a pump, workability is poor due to stickiness. [0005] It is easy to form a film on an object to be chemically polished, and it is difficult to remove an abrasive after chemical polishing. However, conventional gelling agents have been difficult to handle because they are decomposed by hydrofluoric acid or a strong acid, or have a high viscosity. Therefore, the present invention
An object of the present invention is to find a chemical substance which is not decomposed by hydrofluoric acid or a strong acid and has a viscosity of cyclotopy. It is an object to be stable to hydrofluoric acid or strong acid. It is an object of the present invention to have good workability (less stickiness). [0008] It is an object of the present invention to improve the appearance of an object after chemical polishing. It is an object of the present invention to provide a gelling agent that can be easily washed away with water. Means for Solving the Problems In order to solve the above problems, the magnesium sulfate / ammonium fluoride of the formula (1) has excellent properties as a gelling agent when mixed with a chemical polishing agent. The thing became clear from various experiments. Stable to hydrofluoric acid or strong acid. [0011] It has low stickiness, viscosity is cyclotropic and does not drip. The appearance of the object after chemical polishing is good. The gelling agent can be easily washed off by washing with water. Claim 1 The amount of the compound obtained by the formula (1) is mixed with a chemical polishing agent by adjusting the concentration in consideration of the case of painting with a brush or the like and the case of spraying with a special nozzle or the like using a pump. . EXAMPLES 7-8% hydrofluoric acid, 15-17% nitric acid,
Claim 1 A 10% compound obtained by the formula (1) is mixed well to obtain a gelling chemical polishing agent. The metal to be chemically polished is evenly applied with a brush.
The thickness to be applied at this time is desirably 2 to 4 mm. After a lapse of 3 hours, the gelled chemical abrasive is washed away with distilled water, and the chemically polished metal is dried.
A beautiful metal surface can be obtained. The present invention has the following effects in the structure described above. Since the invention described in claim 1 is a compound stable to hydrofluoric acid, an aqueous solution containing hydrofluoric acid or the like can be gelled.

─────────────────────────────────────────────────────
【手続補正書】 【提出日】平成14年6月28日(2002.6.2
8) 【手続補正1】 【補正対象書類名】明細書 【補正対象項目名】特許請求の範囲 【補正方法】変更 【補正内容】 【特許請求の範囲】 【請求項1】 化1で表わされる酸性ゲル化剤の主成
分。 【化1】 【手続補正2】 【補正対象書類名】明細書 【補正対象項目名】0001 【補正方法】変更 【補正内容】 【0001】 硫酸マグネシウムと弗化水素ア
ンモニウム、2:2モルの水溶液を昇温混合攪拌する
と、請求項1、化1のゲル化水溶液を得る。そのゲル化
水溶液に2モルのアンモニアを加え攪拌すると、弗化マ
グネシウム、硫酸アンモニウムのゲル化した中性水溶液
が得られる。弗化マグネシウムは水に難溶解性だが、反
応により得られた図面図1、図2の弗化マグネシウムは
微粒子で硫酸アンモニウムとの混合水溶液において、弗
素イオンは水素結合性が強い為に時間と共に溶解し、会
合ゲル化する。 【手続補正4】 【補正対象書類名】明細書 【補正対象項目名】図面の簡単な説明 【補正方法】追加 【補正内容】 【図面の簡単な説明】 図1、図2は請求項1、化1で得られたゲル化剤を乾燥
後水洗浄し、水に不溶性の弗化マグネシウムをろ過し乾
燥した後の顕微鏡写真。 【手続補正5】 【補正対象書類名】明細書 【補正対象項目名】0003 【補正方法】変更 【補正内容】 【0003】 化学研磨薬品、弗化水素酸混合液体に請
求項1化1を混ぜゲル化し、化学研磨を施す対象部分に
塗布、或いはポンプを利用し特殊ノズルにて吹き付けを
行う。 【手続補正6】 【補正対象書類名】明細書 【補正対象項目名】0009 【補正方法】変更 【補正内容】 【0009】 【問題を解決するための手段】 上記課題を解決するた
めに、請求項1化1は、化学研磨剤(弗化水素酸と硝酸
などの混合水溶液)に混ぜる事により、ゲル化剤として
優れた性質を持つ事が様々な実験から明らかになった。 【手続補正7】 【補正対象書類名】明細書 【補正対象項目名】0010 【補正方法】変更 【補正内容】 【0010】 弗化水素酸を含む強酸液、或いは中性か
ら弱アルカリ液に安定。 【手続補正8】 【補正対象書類名】明細書 【補正対象項目名】0011 【補正方法】変更 【補正内容】 【0011】 粘りが少なく液ダレしない。 【手続補正9】 【補正対象書類名】明細書 【補正対象項目名】0014 【補正方法】変更 【補正内容】 【0014】 請求項1化1で得られた化合物を、化学
研磨剤に混ぜる量は、筆などで塗る場合と、ポンプを利
用し特殊ノズル等で吹き付ける場合を考慮し濃度を調整
する。 【手続補正10】 【補正対象書類名】明細書 【補正対象項目名】0015 【補正方法】変更 【補正内容】 【0015】 結晶硫酸マグネシウム246.48g、
弗化水素アンモニウム57.04g水250gを混合攪
拌し、62%硝酸288gを加え攪拌を続けると透明な
ゲル化水溶液を得、55%弗化水素酸76gを加え攪拌
を続けると、ゲル化した化学研磨剤を得る。 【手続補正11】 【補正対象書類名】明細書 【補正対象項目名】0017 【補正方法】変更 【補正内容】 【0017】 【発明の効果】 本発明は、以上に説明したような構成
に、次の様な効果を奏する。請求項1に記載されている
発明は、弗化水素酸に安定な物質なので、弗化水素酸な
どを含む水溶液をゲル化する事が出来る。 【手続補正12】 【補正対象書類名】明細書 【補正対象項目名】0005 【補正方法】変更 【補正内容】 【0005】 【発明が解決しようとする課題】 しかし従来のゲル化
剤では、弗化水素酸水溶液、或いは弗化水素酸を含む強
酸水溶液によって分解したり、粘りが強いため取り扱い
が難しかった。そこで本発明は、弗化水素酸水溶液或い
は弗化水素酸を含む強酸水溶液によって分解しない粘度
の少ないゲル化剤を見出す事を課題とする。 【手続補正13】 【補正対象書類名】明細書 【補正対象項目名】0006 【補正方法】変更 【補正内容】 【0006】 弗化水素酸水溶液或いは弗化水素酸を含
む強酸水溶液に安定な事を課題とする。 【手続補正14】 【補正対象書類名】図面 【補正対象項目名】図1 【補正方法】追加 【補正内容】 【図1】 【手続補正15】 【補正対象書類名】図面 【補正対象項目名】図2 【補正方法】追加 【補正内容】 【図2】 ─────────────────────────────────────────────────────
【手続補正書】 【提出日】平成14年10月7日(2002.10.
7) 【手続補正1】 【補正対象書類名】明細書 【補正対象項目名】発明の名称 【補正方法】変更 【補正内容】 【発明の名称】 金属材料、酸性洗浄液のゲル化剤。 【手続補正書】 【提出日】平成14年10月30日(2002.10.
30) 【手続補正1】 【補正対象書類名】明細書 【補正対象項目名】特許請求の範囲 【補正方法】変更 【補正内容】 【特許請求の範囲】 【請求項1】 硫酸マグネシウム、弗化アンモニウムを
主原料としたゲル化剤。 【手続補正2】 【補正対象書類名】明細書 【補正対象項目名】0001 【補正方法】変更 【補正内容】 【0001】硫酸マグネシウムと弗化水素アンモニウム
を1:1モルにて水溶液中で混合攪拌させると、請求項
1のゲル化剤が得られ、各原料となる硫酸マグネシウ
ム、弗化アンモニウムとはまったく異なった性質をもつ
化合物が得られる。 【手続補正3】 【補正対象書類名】明細書 【補正対象項目名】図面の簡単な説明 【補正方法】削除 【手続補正4】 【補正対象書類名】明細書 【補正対象項目名】0003 【補正方法】変更 【補正内容】 【0003】化学研磨薬品、弗化水素酸混合液体に請求
項1を混ぜゲル化し、化学研磨を施す対象部分に塗布、
或いはポンプを利用し特殊ノズルにて吹き付けを行う。 【手続補正5】 【補正対象書類名】明細書 【補正対象項目名】0009 【補正方法】変更 【補正内容】 【0009】 【問題を解決するための手段】 上記課題を解決するた
めに、請求項1の硫酸マグネシウム、弗化アンモニウム
は、化学研磨剤に混ぜる事により、ゲル化剤として優れ
た性質を持つ事が様々な実験から明らかになった。 【手続補正6】 【補正対象書類名】明細書 【補正対象項目名】0010 【補正方法】変更 【補正内容】 【0010】弗化水素酸、或いは強酸に安定。 【手続補正7】 【補正対象書類名】明細書 【補正対象項目名】0014 【補正方法】変更 【補正内容】 【0014】請求項1で得られた化合物を、化学研磨剤
に混ぜる量は、筆などで塗る場合と、ポンプを利用し、
特殊ノズル等で吹き付ける場合を考慮し濃度を調整す
る。 【手続補正8】 【補正対象書類名】明細書 【補正対象項目名】0015 【補正方法】変更 【補正内容】 【0015】7〜8%弗化水素酸、15〜17%硝酸、
請求項1の硫酸マグネシウムと弗化アンモニウム、1:
1モル10%を水溶液中でよく混合し、ゲル化化学研磨
剤を得る。 【手続補正9】 【補正対象書類名】図面 【補正対象項目名】図1 【補正方法】削除 【手続補正10】 【補正対象書類名】図面 【補正対象項目名】図2 【補正方法】削除
────────────────────────────────────────────────── ───
[Procedure amendment] [Submission date] June 28, 2002 (2002.6.2
8) [Procedure amendment 1] [Document name to be amended] Description [Item name to be amended] Claims [Amendment method] Change [Contents of amendment] [Claims 1] Main component of acidic gelling agent. Embedded image [Procedure amendment 2] [Document name to be amended] Description [Item name to be amended] 0001 [Correction method] Change [Content of amendment] [0001] Magnesium sulfate and ammonium hydrogen fluoride, 2: 2 mol aqueous solution heated and mixed Upon stirring, a gelled aqueous solution according to claim 1 or 1 is obtained. When 2 mol of ammonia is added to the gelled aqueous solution and stirred, a gelled neutral aqueous solution of magnesium fluoride and ammonium sulfate is obtained. Magnesium fluoride is hardly soluble in water, but the magnesium fluoride in Figures 1 and 2 of the drawings obtained by the reaction is fine particles. In a mixed aqueous solution with ammonium sulfate, fluoride ions dissolve with time due to strong hydrogen bonding. , Forming an association gel. [Procedure amendment 4] [Document name to be amended] Description [Item name to be amended] Brief explanation of drawings [Amendment method] Addition [Content of amendment] [Brief explanation of drawings] FIGS. A photomicrograph of the gelling agent obtained in Chemical formula 1 after drying and washing with water, and filtering and drying water-insoluble magnesium fluoride. [Procedure amendment 5] [Document name to be amended] Description [Item name to be amended] 0003 [Correction method] Change [Contents of amendment] [0003] Claim 1 is mixed with a liquid mixture of chemical polishing chemicals and hydrofluoric acid. It is gelled and applied to the target part to be chemically polished, or sprayed with a special nozzle using a pump. [Procedure amendment 6] [Document name to be amended] Description [Item name to be amended] 0009 [Amendment method] Change [Contents of amendment] [Means for Solving the Problems] Various experiments have revealed that item 1 has excellent properties as a gelling agent when mixed with a chemical polishing agent (a mixed aqueous solution of hydrofluoric acid and nitric acid). [Procedure amendment 7] [Document name to be amended] Description [Item name to be amended] 0010 [Amendment method] Change [Content of amendment] [0010] Stable in strong acid solution containing hydrofluoric acid or neutral to weak alkaline solution . [Procedure amendment 8] [Document name to be amended] Description [Item name to be amended] 0011 [Correction method] Change [Content of amendment] [0011] There is little stickiness and no liquid dripping occurs. [Procedure amendment 9] [Document name to be amended] Description [Item name to be amended] 0014 [Amendment method] Change [Content of amendment] [0014] The amount of the compound obtained in claim 1 mixed with a chemical polishing agent Is adjusted in consideration of the case of painting with a brush or the like and the case of spraying with a special nozzle or the like using a pump. [Procedure amendment 10] [Document name to be amended] Description [Item name to be amended] 0015 [Amendment method] Change [Content of amendment] Crystalline magnesium sulfate 246.48 g,
57.04 g of ammonium hydrofluoride and 250 g of water are mixed and stirred, 288 g of 62% nitric acid is added and stirring is continued to obtain a transparent gelled aqueous solution, and 76 g of 55% hydrofluoric acid is added and stirring is continued to obtain a gelled chemical. Obtain an abrasive. [Procedure amendment 11] [Document name to be amended] Description [Item name to be amended] 0017 [Amendment method] Change [Contents of amendment] [0017] The present invention has the following structure. The following effects are obtained. Since the invention described in claim 1 is a substance that is stable to hydrofluoric acid, it is possible to gel an aqueous solution containing hydrofluoric acid or the like. [Procedure amendment 12] [Document name to be amended] Description [Item name to be amended] 0005 [Correction method] Change [Content of amendment] [0005] However, in the conventional gelling agent, fluorine It was difficult to handle because it was decomposed by an aqueous hydrofluoric acid solution or an aqueous solution of a strong acid containing hydrofluoric acid, or had a strong viscosity. Accordingly, an object of the present invention is to find a gelling agent having a low viscosity which is not decomposed by a hydrofluoric acid aqueous solution or a strong acid aqueous solution containing hydrofluoric acid. [Procedural amendment 13] [Document name to be amended] Description [Item name to be amended] 0006 [Amendment method] Change [Content of amendment] Stable in hydrofluoric acid aqueous solution or strong acid aqueous solution containing hydrofluoric acid As an issue. [Procedure amendment 14] [Document name to be amended] Drawing [Item name to be amended] Fig. 1 [Correction method] Added [Content of amendment] [Fig. 1] [Procedure amendment 15] [Document name to be amended] Drawing [Item name to be amended] Fig. 2 [Correction method] Added [Content of amendment] [Fig. 2] ────────────────────────────────────────────────── ───
[Procedure amendment] [Submission date] October 7, 2002 (2002.10.
7) [Procedure amendment 1] [Document name to be amended] Description [Item name to be amended] Title of invention [Amendment method] Change [Content of amendment] [Title of invention] Metal material, gelling agent for acidic cleaning solution. [Procedure amendment] [Date of submission] October 30, 2002 (2002.10.
30) [Procedure amendment 1] [Document name to be amended] Description [Item name to be amended] Claims [Amendment method] Change [Contents of amendment] [Claims] [Claim 1] Magnesium sulfate, fluoride Gelling agent mainly composed of ammonium. [Procedure amendment 2] [Document name to be amended] Description [Item name to be amended] 0001 [Correction method] Change [Content of amendment] Magnesium sulfate and ammonium hydrogen fluoride are mixed in an aqueous solution at 1: 1 mol. When the mixture is stirred, the gelling agent of claim 1 is obtained, and a compound having properties completely different from magnesium sulfate and ammonium fluoride as the respective raw materials is obtained. [Procedure amendment 3] [Document name to be amended] Description [Amendment item name] Brief explanation of drawings [Amendment method] Deleted [Procedure amendment 4] [Document name to be amended] Specification [Amendment item name] 0003 Correction method: Change [Contents of correction] [0003] A claim 1 is mixed with a liquid mixture of chemical polishing chemicals and hydrofluoric acid to form a gel, which is applied to a portion to be subjected to chemical polishing.
Alternatively, spraying is performed by a special nozzle using a pump. [Procedure amendment 5] [Document name to be amended] Description [Item name to be amended] 0009 [Amendment method] Change [Content of amendment] [Means for solving the problem] Various experiments have revealed that magnesium sulfate and ammonium fluoride of item 1 have excellent properties as a gelling agent when mixed with a chemical polishing agent. [Procedure amendment 6] [Document name to be amended] Description [Item name to be amended] 0010 [Correction method] Change [Content of amendment] [0010] Stable in hydrofluoric acid or strong acid. [Procedure amendment 7] [Document name to be amended] Description [Item name to be amended] 0014 [Amendment method] Change [Contents of amendment] When painting with a brush etc., use a pump,
Adjust the density in consideration of the case of spraying with a special nozzle or the like. [Procedure amendment 8] [Document name to be amended] Description [Item name to be amended] 0015 [Amendment method] Change [Content of amendment] 7-8% hydrofluoric acid, 15-17% nitric acid,
The magnesium sulfate and ammonium fluoride according to claim 1,
One mole 10% is mixed well in an aqueous solution to obtain a gelling chemical polishing agent. [Procedure amendment 9] [Document name to be amended] Drawing [Item name to be amended] Figure 1 [Correction method] Deleted [Procedure amendment 10] [Document name to be amended] Drawing [Item name to be amended] Figure 2 [Correction method] Deleted

Claims (1)

【特許請求の範囲】 【請求項1】下記式(I)で表される硫酸マグネシウム
・弗化アンモニウムの製造方法。 MgSO・NHF・HF・6HO 式(I)
Claims: 1. A method for producing magnesium sulfate / ammonium fluoride represented by the following formula (I). MgSO 4 .NH 4 F.HF.6H 2 O Formula (I)
JP2001309209A 2001-08-31 2001-08-31 Gelatinizer of acidic cleaning liquid for metallic material Pending JP2003073116A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005047182A1 (en) * 2003-11-17 2005-05-26 National Institute Of Advanced Industrial Science And Technology High silica cds-1 zeolite
KR100719661B1 (en) * 2006-02-28 2007-05-17 삼성에스디아이 주식회사 Pixel and organic light emitting display and driving method using the pixel
KR100719662B1 (en) * 2006-02-28 2007-05-17 삼성에스디아이 주식회사 Pixel and organic light emitting display and driving method using the pixel
JP2009275276A (en) * 2008-05-16 2009-11-26 Tokyo Ohka Kogyo Co Ltd Three-dimensional structure having conductive layer and manufacturing method of three-dimensional metal structure

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005047182A1 (en) * 2003-11-17 2005-05-26 National Institute Of Advanced Industrial Science And Technology High silica cds-1 zeolite
KR100719661B1 (en) * 2006-02-28 2007-05-17 삼성에스디아이 주식회사 Pixel and organic light emitting display and driving method using the pixel
KR100719662B1 (en) * 2006-02-28 2007-05-17 삼성에스디아이 주식회사 Pixel and organic light emitting display and driving method using the pixel
JP2009275276A (en) * 2008-05-16 2009-11-26 Tokyo Ohka Kogyo Co Ltd Three-dimensional structure having conductive layer and manufacturing method of three-dimensional metal structure

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