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
Links
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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)
| 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) |
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 |
|---|---|
| JPH08120460A (en) | 1996-05-14 |
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