JPH08120460A - Chemical solution for artificial verdigris and treatment of artificial verdigris - Google Patents
Chemical solution for artificial verdigris and treatment of artificial verdigrisInfo
- Publication number
- JPH08120460A JPH08120460A JP27977494A JP27977494A JPH08120460A JP H08120460 A JPH08120460 A JP H08120460A JP 27977494 A JP27977494 A JP 27977494A JP 27977494 A JP27977494 A JP 27977494A JP H08120460 A JPH08120460 A JP H08120460A
- Authority
- JP
- Japan
- Prior art keywords
- artificial
- verdigris
- chemical solution
- chemical conversion
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 36
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 title abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 241001311547 Patina Species 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 abstract description 3
- 239000011592 zinc chloride Substances 0.000 abstract description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 2
- 229910003944 H3 PO4 Inorganic materials 0.000 abstract 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 1
- 230000032683 aging Effects 0.000 abstract 1
- 235000011150 stannous chloride Nutrition 0.000 abstract 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- -1 copper inorganic compound Chemical class 0.000 description 5
- 239000011701 zinc Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- BTDKBQVILGOJTJ-UHFFFAOYSA-L [Cu](Cl)Cl.P(O)(O)(O)=O Chemical compound [Cu](Cl)Cl.P(O)(O)(O)=O BTDKBQVILGOJTJ-UHFFFAOYSA-L 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は銅または銅合金材の表面
に人工緑青皮膜を形成するための化成液および人工緑青
処理方法に関し、特に屋根材に好適に適用されるもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical conversion solution for forming an artificial patina film on the surface of a copper or copper alloy material and an artificial patina treatment method, and is particularly preferably applied to a roofing material.
【０００２】[0002]
【従来の技術】人工緑青の形成方法には大別して、薬液
で化学処理する方法、緑青成分物質を含有する塗料を塗
装する方法、薬液で電解処理する方法がある。2. Description of the Related Art Artificial patina can be roughly classified into a method of chemical treatment with a chemical, a method of applying a paint containing a patina component, and a method of electrolytic treatment with a chemical.
【０００３】これらの方法の中で薬液で化学処理する方
法による人工緑青皮膜は刹離し易く、変色する傾向があ
った。また、塗装法による人工緑青皮膜は塗膜が経時劣
化する傾向がある。さらに、電解法による人工緑青皮膜
も刹離し易い傾向がある。Of these methods, the artificial patina film formed by chemical treatment with a chemical solution tends to separate easily and tends to discolor. Further, the artificial patina film formed by the coating method tends to deteriorate with time. Further, the artificial patina film formed by the electrolysis method also tends to separate easily.
【０００４】特に、薬液による人工緑青処理は、塩化ア
ンモニウム等を主体とした薬剤により塩基性塩化銅を生
成させることが多い。しかし、塩基性塩化銅を主体とし
た皮膜は、密着性が悪く刹離する傾向が強い。[0004] In particular, the artificial patina treatment with a chemical solution often produces basic copper chloride with a chemical mainly composed of ammonium chloride or the like. However, a film mainly composed of basic copper chloride has poor adhesion and has a strong tendency to separate.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、これらの課
題を解消し、薬液による方法で密着性があり、黒色や褐
色に変色するということのない緑青皮膜を工業的に形成
する人工緑青用化成液および人工緑青処理方法を提供す
ることを目的とする。DISCLOSURE OF THE INVENTION The present invention solves these problems and provides an artificial patina which industrially forms a patina film which is adherent by a chemical solution and does not discolor to black or brown. It is an object of the present invention to provide a chemical conversion solution and an artificial patina treatment method.
【０００６】[0006]
【課題を解決するための手段】本発明はＨ2Ｏ2による酸
化作用とＣｌ-、Ｚｎ2+の銅との反応を介して、りん酸
銅を主体とした青白色の密着性のよい人工緑青皮膜（銅
無機化合物青色系皮膜）を形成させるという知見に基づ
くものである。According to the present invention, a blue-white artificial body mainly composed of copper phosphate having a good adhesion is obtained through the oxidation of H 2 O 2 and the reaction of Cl − and Zn 2+ with copper. This is based on the finding that a patina film (copper inorganic compound blue film) is formed.
【０００７】すなわち、本発明の人工緑青用化成液は、
ＺｎＣｌ2１０〜２００ｇ／ｌ、Ｈ3ＰＯ4５０〜５００
ｇ／ｌ、Ｈ2Ｏ2２０〜２００ｇ／ｌと残部水からなり、
ｐＨが−１〜２であることを特徴とする。That is, the chemical liquid for artificial patina of the present invention comprises:
ZnCl 2 10~200g / l, H 3 PO 4 50~500
g / l, H 2 O 2 20-200 g / l and the balance water,
It is characterized in that the pH is -1 to 2.
【０００８】また、本発明の人工緑青用化成液は、上記
成分に加えて、下記（１）〜（３） （１）ＮａＯＨ５０ｇ／ｌ以下、（２）Ｚｎ５０ｇ／ｌ
以下、（３）ＳｎＣｌ2、ＣｏＣｌ2、ＮｉＣｌ2、エチ
レンジアミン四酢酸（ＥＤＴＡ）から選ばれる１種以上
１０ｇ／ｌ以下、のいずれかを少なくとも含有すること
ができる。In addition to the above-mentioned components, the chemical conversion solution for artificial patina of the present invention has the following (1) to (3) (1) NaOH 50 g / l or less and (2) Zn 50 g / l.
In the following, at least one selected from (3) SnCl 2 , CoCl 2 , NiCl 2 , and ethylenediaminetetraacetic acid (EDTA) can be contained in an amount of at least 10 g / l.
【０００９】本発明の人工緑青化成液において、塩化亜
鉛（ＺｎＣｌ2）は銅のりん酸化合物を形成することを
助長する作用があり、その含有量は１０〜２００ｇ／ｌ
である。その含有量が１０ｇ／ｌ未満ではその作用が不
足し、２００ｇ／ｌ超では塩化物が過剰となり密着性が
低下する。In the artificial patina conversion liquid of the present invention, zinc chloride (ZnCl 2 ) has an action of promoting formation of a copper phosphate compound, and its content is 10 to 200 g / l.
Is. If the content is less than 10 g / l, the effect is insufficient, and if it exceeds 200 g / l, the chloride is excessive and the adhesion is reduced.
【００１０】りん酸（Ｈ3ＰＯ4）は銅のりん酸化合物を
主成分とする皮膜の主成分であり、その含有量は５０〜
５００ｇ／ｌである。その含有量が５０ｇ／ｌ未満では
りん酸化合物が形成されにくく、５００ｇ／ｌ超では増
量効果がない。Phosphoric acid (H 3 PO 4 ) is a main component of a film containing a copper phosphoric acid compound as a main component, and its content is 50 to 50%.
It is 500 g / l. When the content is less than 50 g / l, a phosphate compound is not easily formed, and when the content is more than 500 g / l, there is no effect of increasing the amount.
【００１１】過酸化水素水（Ｈ2Ｏ2）は酸化剤であり、
反応の促進に効果があり、その含有量は２０〜２００ｇ
／ｌである。その含有量が２０ｇ／ｌ未満では効果が薄
く、２００ｇ／ｌ超では増量効果がない。Hydrogen peroxide solution (H 2 O 2 ) is an oxidant,
It has the effect of promoting the reaction, and its content is 20-200g.
/ L. If the content is less than 20 g / l, the effect is weak, and if it exceeds 200 g / l, there is no effect of increasing the amount.
【００１２】水酸化ナトリウム（ＮａＯＨ）は化成液の
ｐＨを調整するために任意に添加するものである。この
ＮａＯＨは他の強アルカリ性物質に代替することも可能
である。Sodium hydroxide (NaOH) is optionally added to adjust the pH of the chemical conversion solution. This NaOH can be replaced with another strong alkaline substance.
【００１３】亜鉛（Ｚｎ）は上記したＺｎＣｌ2のみで
含有させるより、Ｃｌを抑えＺｎを過剰にすると、密着
性が向上するので任意に粉末の形等で添加するものであ
るが、添加量が５０ｇ／ｌ超では密着性がかえって低下
する。Zinc (Zn) is arbitrarily added in the form of powder, etc., since the adhesion is improved when Cl is suppressed and Zn is excessive, compared with the case of containing only ZnCl 2 described above. If it exceeds 50 g / l, the adhesion will rather deteriorate.
【００１４】塩化スズ（ＳｎＣｌ2）、塩化コバルト
（ＣｏＣｌ2）、塩化ニッケル（ＮｉＣｌ2）、エチレン
ジアミン四酢酸（ＥＤＴＡ）は、りん酸化合物を微細に
生成させ、密着性を向上させるので任意に単独または組
み合わせて含有するものであるが、１０ｇ／ｌ超含有さ
せても増量効果がない。Tin chloride (SnCl 2 ), cobalt chloride (CoCl 2 ), nickel chloride (NiCl 2 ), and ethylenediaminetetraacetic acid (EDTA) form a phosphoric acid compound finely and improve the adhesion, so any of them can be used alone. Alternatively, they are contained in combination, but even if the content exceeds 10 g / l, there is no effect of increasing the amount.
【００１５】りん酸皮膜を生成するために、化成液のｐ
Ｈは−１〜２に調整する必要があるが、望ましくはｐＨ
−０．５〜０．４とすることが皮膜の密着性を確保する
上で望ましい。In order to form a phosphoric acid film, p of the chemical conversion solution is
H must be adjusted to -1 to 2, but preferably pH
A value of −0.5 to 0.4 is desirable for ensuring the adhesion of the film.
【００１６】本発明の人工緑青処理方法に当っては、銅
または銅合金材に通常の酸洗やブラスト処理等の前処理
を行った後、表面にスプレー、ロールコート等の方法で
上記した化成液を塗布する。発色を十分行うためには化
成液の量を乾燥後の重量（乾燥皮膜量）で２０ｇ／ｍ2
以上となるように銅または銅合金材の表面に塗布する必
要がある。この段階で生成する皮膜は淡褐色と淡青色と
が混ざったものであるが、これを養生処理すれば淡青色
の密着性の良い皮膜が得られる。養生処理の条件は２０
〜８０℃で湿度６０％以上の環境が必要である。湿度が
６０％未満では皮膜の青色への転換が不十分となる。時
間は発色の程度を見ながら決定すればよいが、１時間以
上、通常は７時間以上、望ましくは２４時間以上であ
る。In the artificial patina treatment method of the present invention, the copper or copper alloy material is subjected to pretreatments such as ordinary pickling and blasting, and then the surface is sprayed or roll-coated. Apply liquid. In order to achieve sufficient color development, the amount of the chemical conversion liquid is 20 g / m 2 in terms of the weight after drying (dry film amount).
It is necessary to apply to the surface of the copper or copper alloy material so as to be as described above. The film formed at this stage is a mixture of light brown and light blue. If this film is cured, a light blue film having good adhesion can be obtained. Curing treatment conditions are 20
An environment at ~ 80 ° C and a humidity of 60% or more is required. If the humidity is less than 60%, the conversion of the film to blue becomes insufficient. The time may be determined while observing the degree of color development, but is 1 hour or more, usually 7 hours or more, and preferably 24 hours or more.
【００１７】[0017]
【実施例】次に本発明の実施例について説明する。EXAMPLES Next, examples of the present invention will be described.
【００１８】実施例１ ＺｎＣｌ2８７．９ｇ／ｌ、Ｈ3ＰＯ4３３１．２ｇ／
ｌ、Ｈ2Ｏ2１２５．０ｇ／ｌ、ＳｎＣｌ2１．２２ｇ／
ｌ、残部水、ｐＨ−０．２０の化成液を調合し、この化
成液をりん脱酸銅板の上に刷毛にて５０ｇ／ｍ2の乾燥
皮膜量となるように塗布し、乾燥した。その後、このり
ん脱酸銅板を５０℃、湿度９０％の恒温恒湿器の中で２
４時間保持した。 Example 1 ZnCl 2 87.9 g / l, H 3 PO 4 331.2 g / l
1, H 2 O 2 125.0 g / l, SnCl 2 1.22 g /
1, the balance water, and a chemical conversion solution having a pH of 0.20 were prepared, and the chemical conversion solution was applied onto a phosphorus-deoxidized copper plate with a brush so that the dry film amount was 50 g / m 2 , and dried. Then, this phosphorous deoxidized copper plate is placed in a thermo-hygrostat at 50 ° C and a humidity of 90% for 2 hours.
Hold for 4 hours.
【００１９】その結果、淡青色の化成皮膜が得られ、こ
れを板厚の４倍の内側曲げＲで１８０°曲げしたとこ
ろ、曲げ部にはクラックは生じたが刹離はなかった。As a result, a light blue chemical conversion coating was obtained. When this was bent 180 ° with an inner bending R of 4 times the plate thickness, cracks were generated in the bent portion, but there was no separation.
【００２０】実施例２ ＺｎＣｌ2５６．８ｇ／ｌ、Ｈ3ＰＯ4１８９．０ｇ／
ｌ、Ｈ2Ｏ2４３．７ｇ／ｌ、ＳｎＣｌ2０．４０ｇ／
ｌ、残部水、ｐＨ０．２０の化成液を調合し、この化成
液をりん脱酸銅の上に刷毛にて４０ｇ／ｍ2の乾燥皮膜
量となるように塗布し、そのまま６０℃、湿度８０％の
恒温恒湿器の中に４８時間保持した。 Example 2 ZnCl 2 56.8 g / l, H 3 PO 4 189.0 g /
1, H 2 O 2 43.7 g / l, SnCl 2 0.40 g /
l, the balance water, and a chemical conversion solution having a pH of 0.20 were prepared, and the chemical conversion solution was applied onto a phosphor-deoxidized copper with a brush so that a dry film amount of 40 g / m 2 was obtained. % In a thermo-hygrostat for 48 hours.
【００２１】その結果、淡青色の化成皮膜が得られ、こ
れを板厚の４倍の内側曲げＲで１８０°曲げしたとこ
ろ、曲げ部にはクラックは生じたが刹離はなかった。As a result, a light blue chemical conversion film was obtained. When this was bent 180 ° with an inner bending R of 4 times the plate thickness, cracks were generated in the bent portion but there was no separation.
【００２２】実施例３ 実施例１の化成液に、さらにＥＤＴＡ２ｇ／ｌ、ＮａＯ
Ｈ１５ｇ／ｌ、Ｚｎ１０ｇ／ｌを添加したｐＨ０．１の
化成液を調合し、実施例１と同様に試験した。得られた
淡青色の化成皮膜の曲げ部にはクラックがほとんど生じ
ず、１ｍｍの大きさのクロスカットを入れる碁盤目テス
トにも合格した。また、約６ケ月経過した天曝試験片に
は何等問題はなかった。 Example 3 The chemical conversion solution of Example 1 was further supplemented with 2 g / l of EDTA and NaO.
A chemical conversion solution having a pH of 0.1 to which 15 g / l of H and 10 g / l of Zn were added was prepared and tested in the same manner as in Example 1. Almost no cracks were formed in the bent portion of the obtained light blue chemical conversion film, and it passed the cross-cut test in which a cross cut having a size of 1 mm was inserted. There was no problem with the exposed test specimens after about 6 months.
【００２３】このようにして得られた化成皮膜のＸ線回
析試験を行ない、結果を図１に示す。この結果、人工緑
青皮膜の主成分は、塩化第一銅（ＣｕＣｌ）とりん酸銅
（Ｃｕ3（ＰＯ4）2・３Ｈ2Ｏ）となっていた。An X-ray diffraction test was performed on the chemical conversion film thus obtained, and the results are shown in FIG. As a result, the main component of the artificial patina coating has been a cuprous (CuCl) and phosphoric acid copper chloride (Cu 3 (PO 4) 2 · 3H 2 O).
【００２４】[0024]
【発明の効果】以上説明したように、本発明により化成
処理された人工緑青皮膜は、優れた加工性を備え、耐候
性にも優れている。従って、本発明によって、特に屋根
材として極めて有益な人工緑青皮膜を形成することがで
きるAs described above, the artificial patina coated with the chemical conversion treatment according to the present invention has excellent workability and excellent weather resistance. Therefore, according to the present invention, it is possible to form an artificial patina film which is extremely useful especially as a roofing material.
【図１】 実施例３により得られた人工緑青皮膜のＸ線
回析図。FIG. 1 is an X-ray diffraction diagram of an artificial patina film obtained in Example 3.
Claims (4)
4５０〜５００ｇ／ｌ、Ｈ2Ｏ2２０〜２００ｇ／ｌと残
部水からなり、ｐＨが−１〜２であることを特徴とする
人工緑青用化成液。1. ZnCl 2 10-200 g / l, H 3 PO
4. A chemical conversion solution for artificial patina, which comprises 50 to 500 g / l, H2O2 20 to 200 g / l and the balance water, and has a pH of -1 to 2 .
アミン四酢酸から選ばれる１種以上１０ｇ／ｌ以下、の
いずれかを少なくとも含有する請求項１に記載の人工緑
青用化成液。2. One of the following (1) to (3) (1) NaOH 50 g / l or less, (2) Zn 50 g / l or less, (3) SnCl 2 , CoCl 2 , NiCl 2 , and ethylenediaminetetraacetic acid. The chemical conversion solution for artificial patina according to claim 1, which contains at least 10 g / l or more.
項１または２に記載の人工緑青用化成液。3. The artificial green-blue chemical conversion liquid according to claim 1, wherein the pH is −0.5 to 0.4.
を、銅または銅合金材に乾燥皮膜量で２０ｇ／ｍ2以上
付着させ、その後２０〜８０℃で湿度６０％以上の環境
で養生することを特徴とする人工緑青処理方法。4. The chemical conversion solution according to claim 1, 2 or 3 is applied to copper or a copper alloy material in a dry film amount of 20 g / m 2 or more, and then in an environment of 20 to 80 ° C. and a humidity of 60% or more. An artificial patina treatment method characterized by curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279774A JP2640432B2 (en) | 1994-10-20 | 1994-10-20 | Chemical conversion solution for artificial patina and artificial patina treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279774A JP2640432B2 (en) | 1994-10-20 | 1994-10-20 | Chemical conversion solution for artificial patina and artificial patina treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08120460A true JPH08120460A (en) | 1996-05-14 |
| JP2640432B2 JP2640432B2 (en) | 1997-08-13 |
Family
ID=17615735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6279774A Expired - Lifetime JP2640432B2 (en) | 1994-10-20 | 1994-10-20 | Chemical conversion solution for artificial patina and artificial patina treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2640432B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020089223A (en) * | 2002-08-29 | 2002-11-29 | 서상환 | The process of a copper patina |
| WO2005049889A1 (en) * | 2003-11-17 | 2005-06-02 | Km Europa Metal Aktiengesellschaft | Method for covering copper with patina |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6126783A (en) * | 1984-07-14 | 1986-02-06 | Nippon Denso Co Ltd | Method for forming chemical conversion film to copper material surface |
| JPS6148572A (en) * | 1984-08-11 | 1986-03-10 | Nippon Denso Co Ltd | Copper-base metallic member having film formed by chemical conversion |
-
1994
- 1994-10-20 JP JP6279774A patent/JP2640432B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6126783A (en) * | 1984-07-14 | 1986-02-06 | Nippon Denso Co Ltd | Method for forming chemical conversion film to copper material surface |
| JPS6148572A (en) * | 1984-08-11 | 1986-03-10 | Nippon Denso Co Ltd | Copper-base metallic member having film formed by chemical conversion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| KR20020089223A (en) * | 2002-08-29 | 2002-11-29 | 서상환 | The process of a copper patina |
| WO2005049889A1 (en) * | 2003-11-17 | 2005-06-02 | Km Europa Metal Aktiengesellschaft | Method for covering copper with patina |
| JP2007511668A (en) * | 2003-11-17 | 2007-05-10 | カーエム・オイローパ・メタル・アクチエンゲゼルシヤフト | How to cover copper with patina |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2640432B2 (en) | 1997-08-13 |
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