JPH04193959A - Formation of patina - Google Patents
Formation of patinaInfo
- Publication number
- JPH04193959A JPH04193959A JP32498390A JP32498390A JPH04193959A JP H04193959 A JPH04193959 A JP H04193959A JP 32498390 A JP32498390 A JP 32498390A JP 32498390 A JP32498390 A JP 32498390A JP H04193959 A JPH04193959 A JP H04193959A
- Authority
- JP
- Japan
- Prior art keywords
- patina
- copper
- thin film
- chemical conversion
- conversion treatment
- 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
- 241001311547 Patina Species 0.000 title claims abstract description 59
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 239000010949 copper Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- 239000010409 thin film Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 35
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 40
- 238000007747 plating Methods 0.000 claims description 6
- 239000010408 film Substances 0.000 abstract description 12
- 239000002585 base Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- 238000005422 blasting Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007788 roughening Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- -1 u(OH)2 Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、基材との密着性に優れた緑青を生産性良く
安定して形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for stably forming a patina with excellent adhesion to a substrate with good productivity.
〈従来技術とその課題〉
従来から、神社・仏閣の屋根材等に用いられた銅の表面
が長い年月の間に大気中の酸素、水蒸気。<Conventional technology and its challenges> Over the years, the surface of copper, which has been used for the roofing of shrines and temples, has been exposed to oxygen and water vapor in the atmosphere.
炭酸ガス、硫化物乃至は塩化物等の作用によって優雅で
美しい緑色の緑青（Ｃｕ ＣＯ２・Ｃｕ（ＯＨ）ｚ。An elegant and beautiful green patina (CuCO2/Cu(OH)z) due to the action of carbon dioxide gas, sulfides or chlorides.
ＣｕＳ Ｏ，−３Ｃｕ（ＯＨ）ｚ、 Ｃｕ（Ｊｚ・３Ｃ
ｕ（ＯＨ）２等の塩基性銅塩）に覆われることは良く知
られているが、この緑青層は重厚で独特の美観を醸し出
すばかりでなく防食皮膜としての作用をも発揮し、その
ため緑青に覆われた銅屋根等は数百年に及ぶ耐久性を示
すこととなる。CuSO, -3Cu(OH)z, Cu(Jz・3C
It is well known that the patina layer is covered with basic copper salts such as u(OH)2, but this patina layer not only creates a profound and unique aesthetic appearance, but also acts as an anti-corrosion film, and therefore has a patina. Copper roofs and other structures covered with copper have a durability of hundreds of years.
そこで、近年、天然に近い緑青を人工的に短期間で発生
させて基材の腐食防止や装飾乃至美術的な効果を狙った
“緑青被膜形成品”が、屋根材のみならず建築内壁材や
装飾品等にも見られるようになり、これまでにも天然に
近い緑青被膜を人工的に形成させる手段に関する提案が
数多くなされてきた。Therefore, in recent years, "patina film-forming products" that artificially generate a natural-looking patina in a short period of time to prevent corrosion of base materials and have decorative or artistic effects have been developed, which can be used not only for roofing materials but also for interior wall materials in buildings. It has come to be seen in ornaments, etc., and many proposals have been made to date on means of artificially forming a patina that is close to natural.
これら従来の人工緑青形成手段を大別すると次の通りで
ある。These conventional artificial patina formation means can be broadly classified as follows.
（Ａ）薬液と接触させる化成処理法（例えば特公昭５７
−５１４６８号として提案された方法等）。(A) Chemical conversion treatment method in which contact is made with a chemical solution (for example,
-51468, etc.).
（Ｂ）薬液中で電解処理する方法（例えば特公昭５５−
１２１１７号として提案された方法等）。(B) Method of electrolytic treatment in a chemical solution (for example,
12117, etc.).
（Ｃ）基材を化成処理した後、その上に更に塗装を施す
方法（例えば特開昭５５−８４９１号として提案された
方法等）。(C) A method in which a base material is subjected to a chemical conversion treatment and then further coated (for example, a method proposed in JP-A No. 55-8491).
（Ｄ）緑青色形成物質を含む塗料で塗装する方法（例え
ば特開昭５５−１３９４６７号として提案された方法等
）。(D) A method of painting with a paint containing a green-blue-forming substance (for example, the method proposed in JP-A-55-139467).
（Ｅ）サンドブラストにより表面を粗面化した銅板表面
に銅又は銅合金の粉末を接着剤で接着した後、塩化アン
モニウムや硫酸アンモニウム等の人工緑青発生液を塗布
する方法（例えば特公昭５７−５２４２５号として提案
された方法等）。(E) A method in which copper or copper alloy powder is bonded with an adhesive to the surface of a copper plate whose surface has been roughened by sandblasting, and then an artificial patina-generating liquid such as ammonium chloride or ammonium sulfate is applied (for example, Japanese Patent Publication No. 57-52425 methods proposed as such).
しかしながら、上記の人工緑青形成手段は、実際上 ａ）緑青の発生速度が遅い。However, the above-mentioned artificial patina formation means are practically a) The rate of development of patina is slow.
ｂ）緑青被膜が剥離し易く、製造設備に多額の費用かか
かる。b) The patina coating is likely to peel off, requiring a large amount of cost for manufacturing equipment.
Ｃ）緑青色を安定して形成させることができず、不均一
で色調が劣る。C) Unable to stably form green-blue color, resulting in non-uniformity and poor color tone.
ｄ）緑青の密着性が良くない。d) Poor adhesion of patina.
ｅ）緑青色被膜を形成するための工数が多く、生産性が
悪い。e) Many man-hours are required to form the green-blue coating, resulting in poor productivity.
等の問題が指摘されるものであり、更には、何れも一般
的に基材が銅又は銅合金にほぼ限定される上、発生させ
た緑青の表面を塗装等によって保護しなければ基材との
十分な密着性を保てないとの問題を有するものでもあっ
た。しかも、塗料膜に □よる緑青の保護策では、紫外
線によって塗膜組成物の劣化が起きることから上記問題
の根本的な解決策となり得るものではなかった。Problems such as these have been pointed out, and furthermore, the base material is generally limited to copper or copper alloy, and if the patina surface is not protected by painting etc. There was also the problem that sufficient adhesion could not be maintained. Moreover, the protection of patina by using a paint film cannot be a fundamental solution to the above problem because the paint film composition deteriorates due to ultraviolet rays.
このようなことから、本発明の目的は、 ［密着性に優
れた均一色調の緑青被膜を、基材の種類を問わず、また
特殊な設備を要することなく、短時間に安定して形成し
得る比較的安価な手段］を確立することに置かれた。Therefore, the purpose of the present invention is to stably form a patina film with excellent adhesion and uniform color tone in a short time regardless of the type of substrate and without requiring special equipment. The aim was to establish relatively inexpensive means of obtaining
〈課題を解決するための手段〉
本発明者等は、上記目的を達成すべく様々な観点に立っ
て鋭意研究を重ねた結果、
ａ）緑青を形成しようとする基材表面に銅又は銅合金か
ら成る薄膜を形成し、次いでこの薄膜を特に“酸化剤を
添加した化成処理液”で処理した場合には、前記“銅又
は銅合金から成る薄膜”と“酸化剤を添加した化成処理
液”との間で化成反応（腐食生成物形成反応）と腐食生
成物の酸化反応とが同時に進行することとなって、基材
表面に強固に密着し、かつ天然緑青に酷似した重厚で均
一な色調の緑青被膜を短時間で形成させることができる
。<Means for Solving the Problems> As a result of intensive research from various viewpoints in order to achieve the above object, the present inventors have found that: a) copper or copper alloy is applied to the surface of the base material on which patina is to be formed; When a thin film is formed and then this thin film is treated with a "chemical conversion treatment liquid to which an oxidizing agent has been added", the above-mentioned "thin film consisting of copper or copper alloy" and "a chemical conversion treatment liquid to which an oxidizing agent has been added" A chemical reaction (corrosion product formation reaction) and an oxidation reaction of the corrosion products proceed simultaneously, resulting in a solid and uniform color tone that strongly adheres to the surface of the base material and closely resembles natural patina. A patina film can be formed in a short time.
ｂ） Ｌかも、基材表面に銅又は銅合金から成る薄膜を
形成させる手段として電着法を採用すれば、薄膜形成の
ため格別に特殊な設備を要することがなく、また基板の
取り扱いが容易であってコスト的にも有利であるばかり
か、電着条件の調整によって生成する緑青の密着性をよ
り一段と向上させることができる。b) If electrodeposition is used as a means of forming a thin film made of copper or copper alloy on the surface of a substrate, no special equipment is required to form the thin film, and the substrate can be easily handled. Not only is this advantageous in terms of cost, but also the adhesion of the patina produced can be further improved by adjusting the electrodeposition conditions.
との知見を得ることができた。We were able to obtain this knowledge.
本発明は、上記知見事項等を基にして完成されたもので
あり、
「緑青を形成しようとする基材表面に銅又は銅合金から
成る薄膜を電着形成させた後、該薄膜を“酸化剤を添加
した化成処理液”で処理することにより、密着性に優れ
た良好な外観の緑青を短時間に安定形成し得るようにし
た点」
に特徴を有している。The present invention was completed based on the above-mentioned findings, etc., and consists of: ``After forming a thin film made of copper or copper alloy by electrodeposition on the surface of a base material on which patina is to be formed, the thin film is oxidized. It is characterized by the ability to stably form a patina with excellent adhesion and a good appearance in a short period of time by treating it with a chemical conversion treatment solution containing additives.
ここで、“緑青を形成しようとする基材”とは銅及び銅
合金に代表される金属材料のみならず、セラミック７瓦
、木材１合成樹脂等の何れであっても差し支えがなく、
格別にその材質が制限されるものではない。ただ、基材
が金属材料以外の場合には、電着法により“銅又は銅合
金から成る薄膜”を形成するための前処理、例えば無電
解めっき又はスパッタリング法等の公知の方法により予
め導電化する処理を施す必要のあることは言うまでもな
い。Here, the "base material on which patina is to be formed" is not limited to metal materials such as copper and copper alloys, but may also be ceramic tiles, wood, synthetic resin, etc.
The material is not particularly limited. However, if the base material is not a metal material, it must be pretreated to form a "thin film made of copper or copper alloy" by electrodeposition, such as by making it conductive by a known method such as electroless plating or sputtering. Needless to say, it is necessary to perform some processing.
以下、本発明をその作用・効果と共により詳細かつ具体
的に説明する。Hereinafter, the present invention will be explained in more detail and concretely along with its functions and effects.
本発明に係る緑青形成法においては、まず緑青を形成さ
せようとする基材の表面に電着法によって“銅又は銅合
金から成る薄膜”が形成される。In the patina formation method according to the present invention, a "thin film made of copper or copper alloy" is first formed by electrodeposition on the surface of the base material on which patina is to be formed.
薄膜の厚さは特に限定されるものではないが、通常は１
〜１００悶程度、好ましくは５〜４０同程度とするのが
良い。勿論、膜厚が１卿未満であっても緑青の形成は可
能であるが、この場合には薄膜に亀裂等が生じ易いため
好ましくない。一方、膜厚が１００Ｉｘｍを超えると満
足できる色調を得ることが難しくなり、また生産コスト
の面でも好ましくない。The thickness of the thin film is not particularly limited, but is usually 1
It is good to set it to about 100 to 100, preferably about 5 to 40. Of course, it is possible to form a patina even if the film thickness is less than 1 thick, but in this case it is not preferable because cracks are likely to occur in the thin film. On the other hand, if the film thickness exceeds 100 Ixm, it becomes difficult to obtain a satisfactory color tone and is also unfavorable in terms of production cost.
基材表面への金属系薄膜形成手段としては、電着法のほ
かに真空蒸着法、スパッタリング法、イオンブレーティ
ング法、溶射法等が知られているが、電着法の場合には
、前述した如く、［“銅又は銅合金から成る薄膜”を形
成させる際に特殊な設備を必要としない（、［基材の取
り扱いが容易である１、［コスト的に有利であるｊ等の
利点を有するほか、電着条件の調整によりその後に生成
させる緑青の密着性をより一段と向上させることができ
るので極めて有利となる。In addition to electrodeposition, vacuum evaporation, sputtering, ion blasting, thermal spraying, and other methods are known as means for forming a metallic thin film on the surface of a substrate. As mentioned above, special equipment is not required when forming a "thin film made of copper or copper alloy", [it has advantages such as easy handling of the base material1, and cost advantage]. In addition to this, the adhesion of the patina produced subsequently can be further improved by adjusting the electrodeposition conditions, which is extremely advantageous.
なお、本発明に従い電着法によって“銅又は銅合金薄膜
”を形成させるには、例えば公知の“酸性の硫酸銅浴”
或いは“アルカリ性のファン化銅浴”等の電解液組成、
電解条件等をそのまま適用するだけでも良いが、出来れ
ば本出願人が先に提案した電気銅めっき法（特願平１−
２３２８６６号）における条件、即ち電流密度ニア５Ａ
／ｄｍ以上で、めっき液の流速： ｌ ｍ／ｓｅｃ以上
なる条件（電流密度は１００Ａ／ｄｉ程度、めっき液流
速は１．５ｍ／ｓｅｃ程度がより好適）の下で“銅又は
銅合金薄膜”を電着させるのが望ましい。なぜなら、上
記条件下で“銅又は銅合金薄膜“を電着形成させた場合
は、その後の処理によって生成する緑青の密着性が更に
一段と良好になり、基材とより強固に密着した緑青層を
より安定に形成できるからである。In addition, in order to form a "copper or copper alloy thin film" by electrodeposition according to the present invention, for example, a known "acidic copper sulfate bath" is used.
Or electrolyte composition such as "alkaline fanned copper bath",
It is possible to simply apply the electrolytic conditions as they are, but if possible, it would be better to use the electrolytic copper plating method proposed earlier by the present applicant (Patent Application No.
232866), i.e. current density near 5A
/dm or more, and the flow rate of the plating solution is 1 m/sec or more (the current density is preferably about 100 A/di, and the plating solution flow rate is more preferably about 1.5 m/sec). It is desirable to electrodeposit. This is because when a "copper or copper alloy thin film" is electrodeposited under the above conditions, the adhesion of the patina produced by subsequent processing becomes even better, creating a patina layer that adheres more firmly to the base material. This is because it can be formed more stably.
そして、基材上に形成される“銅又は銅合金から成る薄
膜”自体の表面粗さについては特に限定されるものでは
ないが、薄膜表面の粗さが３卿未満では緑青の発色度合
いが低く、一方、５０犀を超えると母材と薄膜の密着強
度が低下する傾向が見られることから、通常は３〜５０
即、好ましくは５〜４０Ｍとするのが良い。The surface roughness of the "thin film made of copper or copper alloy" itself formed on the base material is not particularly limited, but if the roughness of the thin film surface is less than 3 degrees, the degree of patina will be low. On the other hand, if it exceeds 50, the adhesion strength between the base material and the thin film tends to decrease, so it is usually 3 to 50.
That is, it is preferably 5 to 40M.
ところで、基材表面への“銅又は銅合金から成る薄膜”
の形成に先立って該基材表面を粗面化することは、基材
と“銅又は銅合金から成る薄膜”との密着性の向上、ひ
いては形成される緑青被膜の密着性を向上させる上で極
めて好ましいことである。従って、銅又は銅合金から成
る薄膜形成処理の前には、必要に応じて基材表面の粗面
化処理が施され、基材表面の−様な粗化と一時的な表面
の活性化が図られる。By the way, "thin film made of copper or copper alloy" on the surface of the base material
Roughening the surface of the base material prior to the formation of the coating improves the adhesion between the base material and the "thin film made of copper or copper alloy", and thus the adhesion of the patina coating to be formed. This is extremely desirable. Therefore, before forming a thin film made of copper or copper alloy, the surface of the base material is roughened as necessary to prevent roughening of the base material surface and temporary surface activation. It will be planned.
基材表面の粗面化法としては、一般に化学的方法（電気
化学的方法も含む）と物理的方法（機械的方法）の２種
類が知られている。前者の例としては“酸又はアルカリ
に浸漬する方法（即ち、エツチング処理法）”や“電解
法”等が、そして後者の例としては“ブラスト法”、′
ウォータージェット法”、“動カニ具法”、“手工具法
”等を挙げることができる。従って、本発明に係る“銅
又は銅合金から成る薄膜”の形成に先立つ基材の粗面化
に際しては、該基材の種類や目的とする緑青形成高表面
の粗さ等によって粗面化法を適宜選択する必要がある。Generally, two types of methods for roughening the surface of a substrate are known: a chemical method (including an electrochemical method) and a physical method (mechanical method). Examples of the former include "method of immersion in acid or alkali (i.e., etching method)" and "electrolytic method," and examples of the latter include "blasting method,"
Examples include "water jet method", "moving crab method", "hand tool method", etc. Therefore, when roughening the surface of the base material prior to forming the "thin film made of copper or copper alloy" according to the present invention, It is necessary to appropriately select a surface roughening method depending on the type of the substrate and the desired roughness of the patina-forming high surface.
例えば、基材が金属材料の場合には、基材表面の粗面化
を高能率で実施できる上、同時に基材表面に発生してい
た錆その他の腐食生成物等の除去も成される“ブラスト
法”が好適と言える。For example, when the base material is a metal material, the surface of the base material can be roughened with high efficiency, and at the same time, rust and other corrosion products generated on the base material surface can be removed. It can be said that "blasting method" is suitable.
しかも、ブラスト法では、研削材として砕砂、スティー
ルグリ装置 スティールショソト、溶融アルミナ（人造
コランダム）、アランダム、カーボランダム、グラスビ
ーズ、合成樹脂粒子等の如き各種の硬度７粒度を持った
ものが使用されるので、基材の種類その他に合わせて好
適なものを適宜選択することが可能であることに加え、
ブラスト条件により表面粗さの調整も可能であると言う
長所もある。Moreover, in the blasting method, various materials with a hardness of 7 grains, such as crushed sand, steel grinding equipment, fused alumina (artificial corundum), alundum, carborundum, glass beads, and synthetic resin particles, are used as abrasive materials. In addition to being able to select a suitable one according to the type of base material etc.
Another advantage is that the surface roughness can be adjusted by changing the blasting conditions.
なお、プラスト法については種々の観点から種類分けが
なされており、例えば研削材の吹付は手法の観点からは
“圧縮空気によってプラストする方法”と“遠心力によ
ってプラストする方法”とに分類でき、また吹付ける研
削材の乾湿状態からは“乾式法”と“湿式法”に分類で
きるが、本発明においてはその種類や組み合わせに格別
な制限はない。In addition, the blasting method is classified into types from various viewpoints.For example, from the viewpoint of the method, spraying of abrasive material can be classified into "method of blasting using compressed air" and "method of blasting using centrifugal force." Further, depending on the dry and wet state of the abrasive to be sprayed, it can be classified into "dry method" and "wet method", but in the present invention, there are no particular restrictions on the types or combinations thereof.
粗面化処理後の基材の表面粗さは、３卿以上、好ましく
は１０〜３０卿とするのが良い。これは、該表面粗さが
３悶未満では“銅又は銅合金から成る薄膜”との密着性
改善効果が顕著ではないからである。一方、上記表面粗
さが５０１Ｋｍを超えた場合には、前記密着性は良好と
なるものの母材（基材）に生しる歪が問題となるなど現
実的ではない。The surface roughness of the base material after the surface roughening treatment is preferably 3 degrees or more, preferably 10 to 30 degrees. This is because when the surface roughness is less than 3 mm, the effect of improving the adhesion with the "thin film made of copper or copper alloy" is not significant. On the other hand, if the surface roughness exceeds 501 Km, the adhesion will be good, but it is not realistic because distortion in the base material may become a problem.
さて、本発明において、基材の表面に“銅又は銅合金か
ら成る薄膜”が電着形成された後、該薄膜に本発明の大
きな特徴の１つである「酸化剤を添加した化成処理液に
よる処理」が施され、化成処理と共に生成する化成処理
被膜の酸化処理が同時進行的に行われる。Now, in the present invention, after a "thin film made of copper or copper alloy" is electrodeposited on the surface of a base material, the thin film is coated with a "chemical conversion treatment solution containing an oxidizing agent", which is one of the major features of the present invention. The oxidation treatment of the chemical conversion film produced along with the chemical conversion treatment is performed simultaneously.
一般に、“化成処理”とは成る金属を特定条件に調整さ
れた腐食液（化成処理液）と化学反応させ、その金属の
表面に固着性のある水に不溶性の腐食生成物層を形成さ
せる処理を言い、その腐食生成物の物理的又は化学的性
質を利用して防錆、塗装下地、塑性加工用潤滑下地等へ
の適用がなされている。In general, "chemical conversion treatment" is a process in which a metal is chemically reacted with a corrosive solution (chemical treatment solution) adjusted to specific conditions to form a layer of water-insoluble corrosion products that adhere to the surface of the metal. The physical or chemical properties of the corrosion products are used to prevent rust, paint bases, lubrication bases for plastic working, etc.
本発明で言う「化成処理２もほぼ同し概念であるが、本
発明においては、特に、基材上に形成された“銅又は銅
合金から成る薄膜”を“酸化剤を添加した化成処理液”
で処理して特性の際立った緑青を形成させる点で特異な
ものと言うこともできる。"Chemical conversion treatment 2" referred to in the present invention has almost the same concept, but in the present invention, in particular, the "thin film made of copper or copper alloy" formed on the base material is treated with a "chemical conversion treatment solution containing an oxidizing agent." ”
It can also be said to be unique in that it is processed to form a distinctive patina.
本発明で使用される“酸化剤添加前の化成処理液”は、
銅又は銅合金表面に水に不溶性の腐食生成物層を形成す
るものであればその種類を問うものではない。そして、
このようなものとして、従来よりアンモニウム塩、塩酸
、カセイソーダ、硫化物、硫酸塩、硝酸塩、酢酸塩、炭
酸塩２重炭酸塩、ミョウバン等を含んだ溶液及びこれら
を組合わせたもの（人工緑青発生液と称されるものを含
むことは勿論であり、溶媒も水に限るものではない）が
知られているが、より具体的なものの例として次の化成
処理液が挙げられる。The “chemical conversion treatment liquid before oxidizing agent addition” used in the present invention is
The type is not critical as long as it forms a water-insoluble corrosion product layer on the surface of copper or copper alloy. and,
As such, conventional solutions containing ammonium salts, hydrochloric acid, caustic soda, sulfides, sulfates, nitrates, acetates, carbonates, bicarbonates, alum, etc., and solutions containing these (artificial patina) Of course, it includes what is called a liquid, and the solvent is not limited to water), but more specific examples include the following chemical conversion treatment liquid.
Ａ）塩酸、硝酸及び硫酸アンモニウムにアルカリ金属塩
化物及び／又はアルカリ土類金属塩化物を加えた水溶液
。A) An aqueous solution prepared by adding an alkali metal chloride and/or an alkaline earth metal chloride to hydrochloric acid, nitric acid, and ammonium sulfate.
Ｂ）塩化第二銅を添加した水溶液。B) Aqueous solution with addition of cupric chloride.
Ｃ）アルカリ金属塩化物及び／又はアルカリ土類金属塩
化物（例えばＮａ（Ｊ 、 Ｋ Ｃ１、Ｎ Ｈ４（Ｊ
等）に硫酸銅を加えた水溶液。C) Alkali metal chlorides and/or alkaline earth metal chlorides (e.g. Na(J, K C1, N H4(J
etc.) with copper sulfate added.
一方、本発明において上記化成処理液に添加される酸化
剤にも格別な制限はなく、例えばａ） 二酸化マンガン
（Ｍｎ Ｏｚ） 。On the other hand, in the present invention, there are no particular restrictions on the oxidizing agent added to the chemical conversion treatment solution, such as a) manganese dioxide (MnOz).
ｂ） 二酸化鉛（ＰｂＯ□）。b) Lead dioxide (PbO□).
Ｃ）過マンガン酸塩（ＫＭｎＯ４，ＮａＭｎ０ａ他）ｄ
） クロム酸塩及び／又は重クロム酸塩（クロム酸及び
重クロム酸塩をも含む）。C) Permanganate (KMnO4, NaMn0a, etc.) d
) Chromates and/or dichromates (including chromic acid and dichromates).
ｅ） フリーの沃素を含有する沃素化合物（例えば、フ
リーの沃素を含有するヨードカリ溶液等）
などを例示することができ、これらを単独又は組み合わ
せて使用することもできる。e) Iodine compounds containing free iodine (for example, iodopotassium solution containing free iodine, etc.) can be exemplified, and these can be used alone or in combination.
上述したように、本発明においては化成処理液やそれに
添加する酸化剤の種類には格別な制限はなく、それら化
成処理液（有効成分濃度も格別に限定されないが、通常
は５〜５０重量％、好ましくは２０〜３０重量％である
）と酸化剤（酸化剤の添加量にも特に制限はないが、通
常は３重量％以上、好ましくは５〜２０重量％である）
を適宜組み合わせて混合した処理液を基材上に形成した
“銅又は銅合金から成る薄膜”に塗布、スプレー等の方
法、又は該薄膜を前記化成処理液に浸漬する等の方法で
接触させ、化成処理反応と同時に酸化反応を生しさせる
。As mentioned above, in the present invention, there is no particular restriction on the type of chemical conversion treatment liquid or oxidizing agent added thereto, and the concentration of these chemical conversion treatment liquids (the concentration of active ingredients is also not particularly limited, but usually 5 to 50% by weight). , preferably 20 to 30% by weight) and an oxidizing agent (the amount of the oxidizing agent added is also not particularly limited, but is usually 3% by weight or more, preferably 5 to 20% by weight).
A treatment solution prepared by mixing an appropriate combination of is brought into contact with a "thin film made of copper or copper alloy" formed on a base material by a method such as coating or spraying, or by a method such as immersing the thin film in the chemical conversion treatment solution, An oxidation reaction is caused simultaneously with a chemical conversion reaction.
この処理を行うと、−瞬ではあるが“銅又は銅合金から
成る薄膜”が白色化する。そして、その後は時間の経過
と共に緑青の生成してくることが薄膜の色の変化により
認められる。When this treatment is carried out, the "thin film made of copper or copper alloy" turns white, albeit momentarily. Thereafter, as time passes, the formation of a patina can be observed by changes in the color of the thin film.
この場合、電着によって形成された“銅又は銅合金から
成る薄膜”は化学反応が生じ易く、好結果が得られる。In this case, a "thin film made of copper or a copper alloy" formed by electrodeposition easily undergoes a chemical reaction, and good results can be obtained.
これは、電着皮膜は金属組織の結合が弱くて非晶質に近
いため、該皮膜の電極電位が比較的型な状態となってい
ることに起因していると考えられる。This is thought to be due to the fact that the electrodeposited film has weak metallographic bonds and is nearly amorphous, so that the electrode potential of the film is relatively regular.
この“銅又は銅合金から成る薄膜を酸化剤添加化成処理
液で処理した際の緑青形成機構”については現在のとこ
ろ明確に解明されていないが、Ｘ線回折により該処理に
よって生成した緑青が化学的；こ安定な塩基性塩化第二
銅（ＣｕｌＪｚ、３Ｃｕ（ＯＨ）ｚｌであると確認され
ている。また、化成処理液に添加する二酸化マンガン等
の酸化剤は、その種類にもよるが単なる酸化反応に係わ
るだけでな（Ｃｕ。This "mechanism of patina formation when a thin film made of copper or copper alloy is treated with an oxidizing agent-added chemical conversion treatment solution" has not been clearly elucidated at present, but X-ray diffraction has revealed that the patina formed by the treatment is chemically It has been confirmed that this is a stable basic cupric chloride (CulJz, 3Cu(OH)zl).In addition, the oxidizing agent such as manganese dioxide added to the chemical conversion treatment solution may be Not only is it involved in oxidation reactions (Cu.
Ｃｕｚ○、 Ｃｕ１ｌＪ等の酸化に対する触媒的な働き
をしていることも推測される。It is also speculated that it acts as a catalyst for the oxidation of Cuz○, Cu1lJ, etc.
酸化剤を添加した化成処理液での処理によって緑青が形
成した基材は、好適には乾燥を兼ねた養生にまわされる
。この養生では特に加熱する必要はなく、通常、室温で
２〜２４時間行えば十分である。The base material on which a patina has been formed by treatment with a chemical conversion treatment solution containing an oxidizing agent is preferably subjected to curing that also serves as drying. There is no particular need for heating in this curing, and it is usually sufficient to carry out the curing at room temperature for 2 to 24 hours.
このようにして、密着性の極めて優れた均一色調の緑青
を短時間で形成することができる。In this way, it is possible to form a uniformly colored patina with extremely good adhesion in a short time.
続いて、本発明を実施例乙こよって更に具体的に説明す
る。Next, the present invention will be explained in more detail with reference to Example B.
〈実施例〉
実施例 １
まず、予め脱脂された銅板（２２Ｏｔｍ幅Ｘ２５０ｗｍ
長×０．３ｆｌ厚）を準備し、粒径＃５０〜＃２５０の
アランダム粉を用いた空気圧１．５〜５ ｋｇ／ｃｕｔ
（ケージ圧）での吹付はブラスト処理によって銅板表
面の粗面化処理を行った。<Example> Example 1 First, a pre-degreased copper plate (22 Otm width x 250 wm
(length x 0.3 fl thickness) and air pressure 1.5 to 5 kg/cut using alundum powder with particle size #50 to #250.
The spraying at (cage pressure) roughened the surface of the copper plate by blasting.
次に、前記銅板（粗化面）を陰極、そして鉛板を陽極と
し、硫酸銅溶液（ＣｕＳ Ｏ４・５ ＨｚＯ： １５０
ｇ／Ｌ Ｈ２Ｓ○ａ ： ８０ｇ／ ｌ ）を電解液
に用いて、電流密度： ８０Ａ／ｄｍ。Next, using the copper plate (roughened surface) as a cathode and the lead plate as an anode, a copper sulfate solution (CuSO4.5 HzO: 150
g/L H2S○a: 80 g/l) was used as the electrolyte, and the current density was 80 A/dm.
めっき液の流速： １．５ｍ／ｓｅｃ。Flow rate of plating solution: 1.5 m/sec.
液温：５５℃
の条件で５分間電解を行い、上記銅板の表面に新たな銅
の薄膜を電着形成させた。Electrolysis was performed for 5 minutes at a liquid temperature of 55° C. to form a new copper thin film by electrodeposition on the surface of the copper plate.
次いで、前記銅薄膜に“化成処理液である塩化第二銅３
０重量％の水溶液の中に二酸化マンガン粉末を５重量％
添加した溶液”を刷毛で均一に塗布して反応層を生成さ
せた後、室温で８時間の乾燥を兼ねた養生を行った。Next, the copper thin film is coated with cupric chloride 3 which is a chemical conversion treatment solution.
5% by weight of manganese dioxide powder in a 0% by weight aqueous solution
The added solution was applied uniformly with a brush to form a reaction layer, and then cured at room temperature for 8 hours, which also served as drying.
そして、上記処理によって形成された緑青の観察を行っ
たところ、該緑青は重厚な青味を帯びた緑色の色調を呈
しており、緑青被膜を指先でこすっても全く剥離物を生
ずることがなく、天然緑青と同等以上に優れた密着性を
有していることが確認された。When the patina formed by the above treatment was observed, it was found that the patina had a deep bluish green tone, and even when the patina film was rubbed with a fingertip, no peeling occurred. It was confirmed that the adhesion was superior to that of natural patina.
更に、Ｘ！回折による分析よって、本発明法により形成
された緑青は天然緑青の主成分である塩基性塩化第二銅
（ＣｕＣｆｚ・３Ｃｕ（ＯＨ）ｚ）であることも確認さ
れた。Furthermore, X! Diffraction analysis also confirmed that the patina formed by the method of the present invention is basic cupric chloride (CuCfz.3Cu(OH)z), which is the main component of natural patina.
実施例 ２
銅板表面の粗面化を“公知の化学研磨液を用いたエツチ
ング処理”により行い、また二酸化マンガンを添加する
前の化成処理液として食塩（ＮａＣ１）１０重量％と硫
酸銅２０重量％を含む水溶液を用いた以外は、実施例１
と同様の方法で緑青の形成を行った。Example 2 The surface of the copper plate was roughened by "etching using a known chemical polishing solution", and 10% by weight of common salt (NaCl) and 20% by weight of copper sulfate were used as the chemical conversion solution before adding manganese dioxide. Example 1 except that an aqueous solution containing
A patina was formed in the same manner as described above.
このようにして得られた緑青被膜は、均一で剥離物の全
くない密着性の極めて優れたものであった。The patina coating thus obtained was uniform and had extremely excellent adhesion with no peeling material.
これらの実施例以外にも、銅又は銅合金薄膜の形成に種
々条件の電着法、また公知の種々の化成処理液（人工緑
青発生液と呼ばれるものをも含む）、に公知の種々の酸
化剤を添加した処理液による処理とを様々に組み合わせ
た試験を行ったが、何れも本発明法に従えば前記実施例
の場合とほぼ同様に良好な結果を得られることが確認さ
れた。In addition to these examples, various electrodeposition methods under various conditions for forming copper or copper alloy thin films, various known chemical conversion treatment solutions (including those called artificial patina generation solutions), and various known oxidation methods can be used to form copper or copper alloy thin films. Tests were conducted using various combinations of treatment with a treatment solution containing a treatment agent, and it was confirmed that in all cases, if the method of the present invention was followed, good results similar to those of the above-mentioned Examples could be obtained.
く効果の総括〉
以上に説明した如く、この発明によれば、天然緑青とほ
ぼ同し重厚な色調を呈すると共に極めて密着性の優れた
緑青をあらゆる種類の基材上に短時間に安定して形成す
ることができ、また格別に特殊な設備等を要することが
ないため現場施工も可能で、例えば緑青製品の補修等へ
の適用も容易である。従って、屋根材のみならず建築内
壁材や装飾品等の幅広い分野での適用が期待されるなど
、産業上極めて有用な効果がもたらされる。Summary of Effects> As explained above, according to the present invention, it is possible to stably form a patina on all kinds of substrates in a short period of time, which exhibits a deep color tone similar to that of natural patina and has extremely excellent adhesion. In addition, since no special equipment is required, on-site construction is possible, and it is easy to apply, for example, to the repair of patina products. Therefore, it is expected to be applied not only to roofing materials but also to a wide range of fields such as building interior wall materials and decorative items, resulting in extremely useful effects industrially.
Claims (3)
から成る薄膜を電着形成させた後、該薄膜を“酸化剤を
添加した化成処理液”で処理することを特徴とする緑青
の形成方法。(1) A patina characterized by electrodepositing a thin film made of copper or a copper alloy on the surface of a base material on which patina is to be formed, and then treating the thin film with a "chemical conversion treatment solution containing an oxidizing agent." How to form.
７５Ａ／ｄｍ＾２以上， めっき液の流速：１ｍ／ｓｅｃ以上 にそれぞれ制御しつつ実施する、請求項１に記載の緑青
の形成方法。(2) Electrodeposition of thin films made of copper or copper alloys at current density:
The method for forming a patina according to claim 1, which is carried out while controlling the flow rate of the plating solution to be 75 A/dm^2 or more and a flow rate of the plating solution to be 1 m/sec or more.
の後で銅又は銅合金から成る薄膜を電着形成させる、請
求項１又は２に記載の緑青の形成方法。(3) The method for forming a patina according to claim 1 or 2, wherein the surface of the substrate on which the patina is to be formed is roughened, and then a thin film made of copper or a copper alloy is formed by electrodeposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32498390A JPH04193959A (en) | 1990-11-27 | 1990-11-27 | Formation of patina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32498390A JPH04193959A (en) | 1990-11-27 | 1990-11-27 | Formation of patina |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04193959A true JPH04193959A (en) | 1992-07-14 |
Family
ID=18171819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32498390A Pending JPH04193959A (en) | 1990-11-27 | 1990-11-27 | Formation of patina |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04193959A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07150365A (en) * | 1993-11-30 | 1995-06-13 | Nikko Kinzoku Kk | Formation of verdigris |
-
1990
- 1990-11-27 JP JP32498390A patent/JPH04193959A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07150365A (en) * | 1993-11-30 | 1995-06-13 | Nikko Kinzoku Kk | Formation of verdigris |
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