JP3696139B2 - Cyan blue coloring composition and patina formation method - Google Patents
Cyan blue coloring composition and patina formation method Download PDFInfo
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- JP3696139B2 JP3696139B2 JP2001279781A JP2001279781A JP3696139B2 JP 3696139 B2 JP3696139 B2 JP 3696139B2 JP 2001279781 A JP2001279781 A JP 2001279781A JP 2001279781 A JP2001279781 A JP 2001279781A JP 3696139 B2 JP3696139 B2 JP 3696139B2
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- patina
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Description
【０００１】
【発明の属する技術分野】
本発明は、銅又は銅を分散固化した基材上、或いは銅酸化膜が生成した基材上に促進的に緑青を形成する緑青発色組成液及び緑青形成方法に関する。
【０００２】
【従来の技術】
人工緑青を銅の基材上に形成させる方法及び、人工緑青発色液としては塩基性塩化銅を生成する組成液（特開平４−１９３９６１号公報）が提案されている。この特開平４−１９３９６１号公報にて提案の塩基性塩化第二銅を生成する緑青発色液の組成は、塩化アルミニウム等の処理液を強制的に酸化をするため、二酸化マンガン、二酸化鉛等の酸化剤を添加することにより、緑青成分として塩基性塩化第二銅が形成されることが示されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、前記特開平４−１９３９６１号公報の提案は、発色処理液に添加した酸化剤の二酸化マンガンの酸化作用を利用する緑青発色工程において、厳密な湿気分と温度の管理が必要であった。従って、屋外の構築物や大型の重量物等の基材表面上に人工緑青を形成する場合、湿度管理と温度管理が十分でなくなり、緑青を形成するには多くの問題があった。例えば高所且つ大型の構築物の屋根を対象とする場合、湿度調整、温度調整のための設備を運搬する必要があるため、作業は極めて面倒且つ危険が伴うものであった。
そこで本発明者らは、既存の銅屋根の基材表面上に緑青を形成するため、従来法の酸化剤による酸化と厳密な湿度管理と温度管理を必要とせず、開放状態で自然の湿気分と大気中の酸素により、屋外の構築物や大型の重量物等の基材表面上に早期に人工緑青が生成することができる緑青発色組成液及び緑青形成方法を提案することを目的とする。
【０００４】
【課題を解決するための手段】
本発明は、上記に鑑み提案されたもので、塩化ナトリウム、塩化アルミニウム、塩化亜鉛、塩化錫から選ばれる１種または２種以上の水溶液に、塩化第二銅と炭酸ナトリウムを調合してなる緑青発色組成液に関するものである。
また、本発明は、前記緑青発色組成液を用いた緑青形成方法をも提案するものであり、銅又は銅を分散固化した基材上、或いは銅酸化膜が形成された基材上に前記緑青発色組成液を塗布し、ブラッシングすることにより、開放状態において、緑青発色組成液中の炭酸ナトリウムの炭酸イオンの媒晶作用（結晶析出作用）により、促進的に塩基性塩化第二銅と塩基性炭酸銅の複合型人工緑青が容易に形成される知見を得るに至った。
【０００５】
【発明の実施の形態】
本発明が適用される基材のうち、銅基材は、銅の板状材、条材、線材、粉末を指し、銅を分散固化した基材とは、銅粉末を樹脂その他の無機物と共に混合し、樹脂等のバインダーにて樹脂板等の表面に固着された銅粉入り塗膜を有するものや銅を溶射した全ての銅溶射素材を指し、銅酸化膜が形成された基材は表面全面に銅酸化膜が形成されたものでも一部にのみ形成されたものでも良い。
【０００６】
また、これらの基材は、建築資材としての原料材料であっても良いし、既に施工された屋外構築（建築）物の屋根材などであっても良い。さらに、屋外構築物とは、特に限定しないが、陸上又は海洋構築物並びに船舶・船底等の海面下に使用する基材等の全てを指す。
即ち人工緑青は建築屋根材としての利用が一般的であり、一方装飾、美術的役割を果たしているが、緑青成分の抗菌力は古くから知られ、海洋における船舶の船底や港の構築物に使用する基材に人工緑青を形成することにより、コンブ類や藻類、貝類の付着を防止することが可能である。
【０００７】
前記本発明の緑青発色組成液を上述の基材上に塗布するには、公知のどのような塗布方法をも用いることができ、スプレー、液滴下、刷毛塗り、ローラー塗り等特に限定するものではない。さらに、美術成形品等の場合には浸漬する等の方法でも良い。
また、本発明は、従来の方法のように厳密な湿度管理及び温度管理を必要としないので、屋外構築物の処理に好適であるが、有害成分を発生することもないので、勿論室内における処理も同様に容易に行うことができる。
さらに、基材表面の形状も限定することがなく、例えば凹凸状の基材面上にも容易に人工緑青を形成することができる。
【０００８】
このように、本発明は屋外の構築物の一つである既存の銅屋根のような、高所且つ大型の処理対象物（基材）に対しても、自然環境の開放状態で安全に特殊な酸化剤の必要なく、調湿・調温することなく、自然の湿気分と大気中の酸素により、比較的短時間に塩基性塩化第二銅と塩基性炭酸銅の複合型人工緑青が形成することができるものである。
【０００９】
【作用】
本発明の緑青発色液の人工緑青生成作用について説明する。
本発明は、塩化ナトリウム（NaCl）、塩化アルミニウム（AlCl3）、塩化亜鉛（ZnCl2）、塩化錫（SnCl2）から選ばれる、１種または２種以上の水溶液に塩化第二銅（CuCl2）と炭酸ナトリウム（Na2CO3）を調合してなる緑青発色組成液を、銅又は銅を分散固化した基材上、或いは銅酸化被膜が生成された基材上に塗布してブラッシングすることにより、基材の銅（Cu）が溶出すると共に、次第に基材上に塗布された緑青発色組成液中の銅（Cu）濃度が高くなり、組成液中の炭酸ナトリウム（Na2CO3）の中和作用と結晶析出の媒晶作用により、塩基性炭酸銅（CuCO3・３Cu(OH)3）と塩基性塩化第二銅(CuCl2・３Cu(OH)2)の複合型緑青が基材上に生成される。
【００１０】
【実施例】
〔実施例１〕
塩化アルミニウム（AlCl3６H2O）200ｇ、塩化第二銅（CuCl2２H2O）90ｇを水600ｇに溶解した。
この水溶液に炭酸ナトリウム結晶（Na2CO310H2O）160ｇ溶解した水溶液を加えて調合し、緑青発色組成液を得た。
得られた緑青発色組成液を大気中（湿度50〜70％、温度20〜30℃）で建築後３年を経過した銅屋根上に塗布し、刷毛でブラッシングを重ねることにより、粘度の高い粘膜が生成された。
これを自然放置することにより、密着性のよい人工緑青が形成された。
この人工緑青の一部を採取してＸ線回析による分析をした結果、塩基性塩化第二銅(CuCl2・３Cu(OH)2)と塩基性炭酸銅（CuCO3・３Cu(OH)3）の複合緑青であることを確認した。
【００１１】
〔実施例２〕
塩化ナトリウム（NaCl）25ｇ、塩化亜鉛（ZnCl2）60ｇ、塩化第二銅（CuCl2・２H2O）90ｇを水200ｇに溶解した。
この水溶液に炭酸ナトリウム結晶（NaCO310H2O）160ｇを溶解した液を加えて調合し、緑青発色組成液を得た。
セメント板上に、合成樹脂と共に銅粉末を混合し固化したものを基材とした。
得られた緑青発色組成液を、上記の基材上に塗布し、前記実施例１に従い、人工緑青を形成させた。
【００１２】
〔実施例３〕
金属鉄板上に、合成樹脂塗料と共に銅粉末を混合した乾燥塗膜を粗面化したものを基材とした。
前記実施例１に従い、同じ緑青発色組成液を、上記の基材上に塗布し、人工緑青を形成させた。
【００１３】
〔実施例４〕
銅板上に銅を溶射して粗面化したものを基材とした。
前記実施例１に従い、同じ緑青発色組成液を、上記の基材上に塗布し、人工緑青を形成させた。
【００１４】
〔実施例５〕
前記実施例４において得た人工緑青を港の構築物に吊るして海水中に浸漬し、海藻類、貝類の付着試験を行った。
その結果、６ヶ月海水中に浸漬しても人工緑青の剥離はなく、海藻類、貝類の付着はなかった。
【００１５】
【発明の効果】
以上説明したように本発明の緑青発色組成液及び緑青形成方法は、従来のように厳密な湿度管理や温度管理を必要としないので、室内の調湿、調温された場所のみならず、屋外の構築物や大型の重量を伴う基材表面上に、大気中で処理することができ、容易に人工緑青を形成することができるものである。そのため、例えば高所且つ大型の構築物を対象とする場合にも、容易に且つ安全に作業を実施することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a patina-coloring composition liquid and a patina formation method for forming patina on a base material on which copper or copper is dispersed and solidified or on a base material on which a copper oxide film is formed.
[0002]
[Prior art]
As a method for forming artificial patina on a copper base material and an artificial patina coloring liquid, a composition liquid for producing basic copper chloride (Japanese Patent Laid-Open No. 4-193961) has been proposed. The composition of the green-blue color developing solution for producing basic cupric chloride proposed in Japanese Patent Laid-Open No. Hei 4-193961 is forcibly oxidizing a processing solution such as aluminum chloride, so that manganese dioxide, lead dioxide, etc. It has been shown that basic cupric chloride is formed as a patina component by adding an oxidizing agent.
[0003]
[Problems to be solved by the invention]
However, the proposal of the above-mentioned Japanese Patent Laid-Open No. Hei 4-193961 necessitates strict moisture and temperature control in a patina-coloring process utilizing the oxidizing action of manganese dioxide as an oxidizing agent added to the color processing solution. Therefore, when artificial patina is formed on the surface of a base material such as an outdoor structure or a large heavy object, humidity management and temperature management are not sufficient, and there are many problems in forming patina. For example, when a high-rise and large structure roof is targeted, it is necessary to transport equipment for humidity control and temperature control, so that the work is extremely troublesome and dangerous.
Therefore, the present inventors form patina on the surface of the existing copper roof base material, so that oxidation by a conventional oxidant and strict humidity management and temperature management are not required, and natural moisture content in an open state. It is an object of the present invention to propose a patina-coloring composition liquid and patina formation method capable of generating artificial patina at an early stage on the surface of a substrate such as an outdoor structure or a large heavy object due to oxygen in the atmosphere.
[0004]
[Means for Solving the Problems]
The present invention has been proposed in view of the above, and is a patina obtained by preparing cupric chloride and sodium carbonate in one or more aqueous solutions selected from sodium chloride, aluminum chloride, zinc chloride and tin chloride. The present invention relates to a coloring composition liquid.
The present invention also proposes a patina formation method using the patina coloring composition liquid, and the patina is formed on a base material on which copper or copper is dispersed and solidified or on a base material on which a copper oxide film is formed. By applying and brushing the coloring composition liquid, the basic cupric chloride and the basicity are promoted in an open state by the crystallization action of the carbonate of sodium carbonate in the patina coloring composition liquid. It came to the knowledge that the composite artificial patina of copper carbonate was easily formed.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Among the base materials to which the present invention is applied, the copper base material refers to a copper plate-like material, strip material, wire material, and powder. The base material in which copper is dispersed and solidified is a mixture of copper powder together with resin and other inorganic substances. It refers to all copper sprayed materials that have a copper powder-coated film fixed on the surface of a resin plate or the like with a binder such as a resin, or copper sprayed, and the substrate on which the copper oxide film is formed is the entire surface In addition, a copper oxide film may be formed or may be formed only partially.
[0006]
Further, these base materials may be raw material materials as building materials, or roof materials of outdoor construction (building) structures that have already been constructed. Further, the outdoor structure is not particularly limited, and refers to all of a land or marine structure and a base material used under the sea surface such as a ship and a ship bottom.
In other words, artificial patina is commonly used as a building roof material, while it plays a decorative and artistic role, but the antibacterial activity of patina is known for a long time and is used for ship bottoms and harbor structures in the ocean. By forming artificial patina on the base material, it is possible to prevent adhesion of kombu, algae and shellfish.
[0007]
In order to apply the green-blue color forming composition liquid of the present invention on the above-mentioned substrate, any known application method can be used, and it is not particularly limited to spraying, under a droplet, brush coating, roller coating, etc. Absent. Further, in the case of an art molded article or the like, a method such as dipping may be used.
In addition, the present invention does not require strict humidity control and temperature control unlike the conventional method, so it is suitable for the treatment of outdoor structures, but it does not generate harmful components, so of course it can be treated indoors. It can be done easily as well.
Further, the shape of the substrate surface is not limited, and for example, artificial patina can be easily formed on an uneven substrate surface.
[0008]
As described above, the present invention is safe and special in an open state of the natural environment even for a high-place and large-sized processing object (base material) such as an existing copper roof which is one of outdoor structures. Without the need for oxidizers, natural artificial moisture and atmospheric oxygen form a complex artificial patina of basic cupric chloride and basic copper carbonate in a relatively short time due to natural moisture and atmospheric oxygen. It is something that can be done.
[0009]
[Action]
The artificial patina producing action of the patina coloring liquid of the present invention will be described.
In the present invention, cupric chloride (CuCl 2 ) is added to one or more aqueous solutions selected from sodium chloride (NaCl), aluminum chloride (AlCl 3 ), zinc chloride (ZnCl 2 ), and tin chloride (SnCl 2 ). ) And sodium carbonate (Na 2 CO 3 ) on a base material on which copper or copper is dispersed and solidified or on a base material on which a copper oxide film is formed and brushed. As a result, the copper (Cu) of the base material is eluted, and the copper (Cu) concentration in the green and blue coloring composition liquid applied on the base material gradually increases, and the sodium carbonate (Na 2 CO 3 ) in the composition liquid Due to neutralization and crystal precipitation, the base material is a composite patina of basic copper carbonate (CuCO 3 • 3Cu (OH) 3 ) and basic cupric chloride (CuCl 2 • 3Cu (OH) 2 ) Generated on top.
[0010]
【Example】
[Example 1]
Aluminum chloride (AlCl 3 6H 2 O) 200g , cupric chloride (CuCl 2 2H 2 O) 90g was dissolved in water 600 g.
An aqueous solution prepared by dissolving 160 g of sodium carbonate crystals (Na 2 CO 3 10H 2 O) was added to the aqueous solution to prepare a greenish blue coloring composition solution.
Applying the obtained patina color composition liquid in the atmosphere (humidity 50-70%, temperature 20-30 ° C) on a copper roof that has passed 3 years after construction, and brushing with a brush, the mucosa with high viscosity Was generated.
By leaving this naturally, artificial patina with good adhesion was formed.
A portion of this artificial patina was collected and analyzed by X-ray diffraction. As a result, basic cupric chloride (CuCl 2 · 3Cu (OH) 2 ) and basic copper carbonate (CuCO 3 · 3Cu (OH) 3 ) Was confirmed to be a complex patina.
[0011]
[Example 2]
Sodium chloride (NaCl) 25 g, zinc chloride (ZnCl 2 ) 60 g, and cupric chloride (CuCl 2 · 2H 2 O) 90 g were dissolved in water 200 g.
A solution prepared by dissolving 160 g of sodium carbonate crystals (NaCO 3 10H 2 O) was added to the aqueous solution to prepare a greenish blue coloring composition solution.
A material obtained by mixing and solidifying copper powder together with a synthetic resin on a cement plate was used as a base material.
The obtained patina-coloring composition liquid was applied on the above-mentioned base material, and artificial patina was formed according to Example 1.
[0012]
Example 3
A roughened dry coating film obtained by mixing copper powder together with a synthetic resin paint on a metal iron plate was used as a base material.
In accordance with Example 1, the same green-blue coloring composition liquid was applied onto the substrate to form artificial patina.
[0013]
Example 4
A material obtained by spraying copper on a copper plate and roughening it was used as a base material.
In accordance with Example 1, the same green-blue coloring composition liquid was applied onto the substrate to form artificial patina.
[0014]
Example 5
The artificial patina obtained in Example 4 was suspended in a port structure and immersed in seawater, and a seaweed and shellfish adhesion test was performed.
As a result, even when immersed in seawater for 6 months, there was no peeling of artificial patina and no adhesion of seaweeds and shellfish.
[0015]
【The invention's effect】
As described above, the patina-coloring composition liquid and the patina formation method of the present invention do not require strict humidity control and temperature control as in the prior art. It can be processed in the air on the surface of the substrate and the base material with a large weight, and an artificial patina can be easily formed. Therefore, for example, even when a high-rise and large structure is targeted, the work can be easily and safely performed.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001279781A JP3696139B2 (en) | 2001-09-14 | 2001-09-14 | Cyan blue coloring composition and patina formation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001279781A JP3696139B2 (en) | 2001-09-14 | 2001-09-14 | Cyan blue coloring composition and patina formation method |
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| Publication Number | Publication Date |
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| JP2003089880A JP2003089880A (en) | 2003-03-28 |
| JP3696139B2 true JP3696139B2 (en) | 2005-09-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10354527B4 (en) * | 2003-11-17 | 2008-08-28 | Kme Germany Ag | Process for patination of copper |
| GB2468704A (en) * | 2009-03-19 | 2010-09-22 | James Craggs | Anti-microbial copper or brass surfaces |
| CN114622194B (en) * | 2022-03-15 | 2023-06-16 | 东莞振顺五金制品有限公司 | Zinc alloy environment-friendly coloring liquid and coloring process thereof |
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