JP2640432B2 - Chemical conversion solution for artificial patina and artificial patina treatment method - Google Patents
Chemical conversion solution for artificial patina and artificial patina treatment methodInfo
- Publication number
- JP2640432B2 JP2640432B2 JP6279774A JP27977494A JP2640432B2 JP 2640432 B2 JP2640432 B2 JP 2640432B2 JP 6279774 A JP6279774 A JP 6279774A JP 27977494 A JP27977494 A JP 27977494A JP 2640432 B2 JP2640432 B2 JP 2640432B2
- Authority
- JP
- Japan
- Prior art keywords
- artificial patina
- chemical conversion
- patina
- artificial
- 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.)
- Expired - Lifetime
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- Chemical Treatment Of Metals (AREA)
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 on a copper or copper alloy material and a method for treating the patina, and more particularly 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剥離し易く、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
も剥離し易い傾向がある。[0003] Among these methods, the artificial patina film obtained by a chemical treatment with a chemical solution tends to peel off and tends to be discolored. Further, the artificial patina film formed by the coating method tends to deteriorate with time. Furthermore, the artificial patina film by the electrolytic method also tends to peel off.
【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、密着性が悪く剥離する傾向が強い。[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 tends to peel off.
【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。SUMMARY OF THE INVENTION The present invention provides a blue-white artificial patina mainly composed of copper phosphate with good adhesion through an oxidizing action by H 2 O 2 and a reaction between Cl − and Zn 2+ with copper. This is based on the finding that a film (copper inorganic compound blue-based film) is formed.
【0007】すなわち、本発明の人工緑青用化成液は、
ZnCl210〜200g/l、H3PO450〜50
0g/l)H2O220〜200g/lと残部水からな
り、pHが−0.5〜0.4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 50~50
Consists 0g / l) H 2 O 2 20~200g / l and balance water, pH is characterized in that it is a -0.5~0.4.
【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10
g/l以下、のいずれかを少なくとも含有することがで
きる。[0008] The chemical conversion solution for artificial patina of the present invention further comprises the following components (1) to (3): (1) NaOH 50 g / l or less, (2) Zn 50 g / l or less, (3) SnCl 2 , CoCl 2 , NiCl 2 , ethylenediaminetetraacetic acid (EDTA)
g / l or less.
【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 chemical solution of the present invention, zinc chloride (ZnCl 2 ) has an effect of promoting the formation of a copper phosphate compound, and its content is 10 to 200 g / l.
It 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 mainly composed of a copper phosphate compound.
500500 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20〜20
0g/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。Aqueous hydrogen peroxide (H 2 O 2 ) is an oxidizing agent and is effective in accelerating the reaction.
0 g / 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。[0012] 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のかた
ちで添加するばかりでなく、液中のCl−イオンの量比
をZn++イオンの2倍量より抑え、Zn++イオンを
過剰にすると、密着性が向上するので任意に粉末の形等
でさらに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。[0013] Zinc (Zn) is not only added in the form of ZnCl 2 as described above, Cl in the liquid - suppressed than 2 times the amount of Zn ++ ions the amount ratio of the ions, when an excess of Zn ++ ions, adhesion It is arbitrarily added in the form of a powder or the like because the property is improved.
【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) can be used arbitrarily because they form fine phosphate compounds and improve the adhesion. Alternatively, they are contained in combination, but there is no effect of increasing the amount even if the content exceeds 10 g / l.
【0015】りん酸皮膜を生成するために、化成液のp
Hは−0.5〜0.4に調整する必要があり、またこの
範囲で皮膜の密着性を確保することができる。In order to form a phosphoric acid film, p
H needs to be adjusted to -0.5 to 0.4, and in this range, the adhesion of the film can be secured.
【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, copper or copper alloy material is subjected to ordinary pretreatment such as pickling or blasting, and then the surface is subjected to the above-described chemical conversion by a method such as spraying or roll coating. Apply liquid. In order to perform color development sufficiently, the amount of the chemical conversion solution is determined to be 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。Next, an embodiment 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
24時間保持した。 Example 1 ZnCl 2 87.9 g / l, H 3 PO 4 331.2 g /
l, H 2 O 2 125.0g / l, SnCl 2 1.22g
/ L, the remaining water, and a chemical conversion solution having a pH of 0.20 were prepared, and the chemical conversion solution was applied on a phosphor-deoxidized copper plate with a brush so as to have a dry film amount of 50 g / m 2 and dried. Thereafter, the phosphor-deoxidized copper plate was kept in a thermo-hygrostat at 50 ° C. and 90% humidity for 24 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倍の内側曲げ半径で180゜曲げしたとこ
ろ、曲げ部にはクラックは生じたが剥離はなかった。As a result, a pale blue chemical conversion film was obtained. When this film was bent at an inner bending radius of 4 times the plate thickness by 180 °, cracks occurred in the bent portions but no peeling occurred.
【0020】実施例2 ZnCl256.8g/l、H 3 PO4189.0g/
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
l, the remaining water and a chemical conversion solution having a pH of 0.20 were prepared, and this chemical conversion solution was applied on a phosphor-deoxidized copper with a brush so as to have a dry film amount of 40 g / m 2. % 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倍の内側曲げ半径で180゜曲げしたとこ
ろ、曲げ部にはクラックは生じたが剥離はなかった。As a result, a pale blue chemical conversion film was obtained, which was bent 180 ° at an inner bending radius of four times the plate thickness. As a result, cracks occurred in the bent portions but no peeling occurred.
【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
トを実施したが、1mmの大きさの碁盤目100箇所の
うち、セロハンテープで剥離する部分は5%以下という
基準を満たし合格した。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 added 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. Cracks hardly occurred in the bent portion of the obtained pale blue conversion coating, and a cross-cut test in which a cross-cut of 1 mm was inserted was performed. Among 100 cross-cuts of 1 mm in size, cellophane tape was used. The portion that peeled off was satisfied with the standard of 5% or less and passed. 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.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−48572(JP,A) 特開 昭61−26783(JP,A) 特開 平8−120463(JP,A) 特開 平5−25654(JP,A) 特開 昭63−60288(JP,A) 特開 昭62−192586(JP,A) 特開 昭60−96769(JP,A) 表面技術、43〜11!(1992.11)、社 団法人 表面技術協会、P.1035−1039 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-48572 (JP, A) JP-A-61-26783 (JP, A) JP-A-8-120463 (JP, A) JP-A-5-120463 25654 (JP, A) JP-A-63-60288 (JP, A) JP-A-62-192586 (JP, A) JP-A-60-96769 (JP, A) Surface technology, 43-11! (1992.11), Surface Technology Association, P.S. 1035-1039
Claims (3)
H3PO450〜500g/1、H2O220〜200
g/lと残部水からなり、pHが−0.5〜0.4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 50~500g / 1, H 2 O 2 20~200
A chemical conversion liquid for artificial patina, comprising g / l and the balance water, and having a pH of -0.5 to 0.4.
ジアミン四酢酸 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 , ethylenediaminetetraacetic acid The chemical liquid for artificial patina according to claim 1, which contains at least any one of 10 g / l or more.
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℃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。3. The chemical conversion solution according to claim 1 or 2,
An artificial patina treatment method characterized by adhering 20 g / m 2 or more in a dry film amount to copper or a copper alloy material and then curing in an environment at 20 to 80 ° C. and a humidity of 60% or more.
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 JPH08120460A (en) | 1996-05-14 |
JP2640432B2 true JP2640432B2 (en) | 1997-08-13 |
Family
ID=17615735
Family Applications (1)
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JP6279774A Expired - Lifetime JP2640432B2 (en) | 1994-10-20 | 1994-10-20 | Chemical conversion solution for artificial patina and artificial patina treatment method |
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Country | Link |
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JP (1) | JP2640432B2 (en) |
Families Citing this family (3)
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 |
DE10354527B4 (en) * | 2003-11-17 | 2008-08-28 | Kme Germany Ag | Process for patination of copper |
Family Cites Families (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
Non-Patent Citations (1)
Title |
---|
表面技術、43〜11!(1992.11)、社団法人 表面技術協会、P.1035−1039 |
Also Published As
Publication number | Publication date |
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JPH08120460A (en) | 1996-05-14 |
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