JPS6242032B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a surface treatment solution for industrially forming a film having the effect of promoting patina on the surface of copper or copper alloy products, particularly copper plates for building materials used as roofing materials. It is related to. [Prior Art] Many patent applications have been filed so far as means for industrially forming a verdigris film on the surface of copper or copper alloy products, particularly copper plates for building materials used as roofing materials. Broadly speaking, these methods can be divided into methods of treating with chemical solutions, that is, chemical conversion treatment methods, electrolytic treatment methods with chemical solutions, methods of chemical conversion treatment and further painting, methods of painting with paints containing patina-forming substances, and methods of surface treatment using sandblasting etc. After adhering copper powder or copper alloy powder to the roughened copper surface with adhesive,
Examples include a method of forming a verdigris film by applying a treatment liquid having a verdigris effect. As a method that falls under the above method,
-110235, 122637, Japanese Patent Application Publication No. 1973-
122638, JP-A No. 55-8490, JP-A No. 56-9270, JP-A No. 56-30396, and JP-A No. 57-51468, but in all of these methods, the rate of generation of patina is slow and drying after treatment is done naturally. There are problems in terms of quality and production, such as the need for repeated treatment and drying, and poor adhesion of the patina film. As a method that corresponds to the method of
122641, Japanese Patent Publication No. 55-12117, Japanese Patent Publication No. 55-14157, Japanese Patent Publication No. 55-15558, and Japanese Patent Publication No. 177997, etc., but all of these methods produce patina on the copper surface in a short time during the electrolytic treatment process. However, there are problems in that the formed patina film is likely to peel off and a large amount of capital investment is required. As applicable to the method of
8491 and JP-A No. 56-13483, etc., but all of these methods have the problem that it is difficult to stably form a patina film. As a method that falls under the method of
139467, but it has the problem that the adhesion of the patina film is poor. As a method that corresponds to the method of
69375, and Japanese Patent Publication No. 57-52425, but all of these methods require a large number of steps to form a patina film, and have problems in terms of productivity and processing cost. [Object of the Invention] The present invention has been made with the aim of eliminating the above-mentioned problems, that is, drawbacks, and has the purpose of eliminating patina on the surface of copper or copper alloy, particularly copper plates for building materials used as roofing materials. Forms an organic film containing a compound that promotes chemical reaction, and short-term outdoor exposure
It is an object of the present invention to provide a novel patina-promoting coating treatment solution that generates a patina with a uniform and calm color tone and good adhesion, and which is also excellent in terms of industrial production. [Structure of the invention] The present invention has been made to achieve the above object,
An aqueous solution or suspension containing an aqueous resin, a compound that forms an inorganic complex salt with copper ions, and a compound that also chelates with copper ions, wherein the content of the aqueous resin is 10 to 300 g / and
The total content of the compound that forms an inorganic complex salt with the copper ion and the compound that chelates with the copper ion is 20 to 500 g/, of which the content of the compound that chelates with the copper ion is 10 g/
The treatment liquid for a patina-promoting film as described above, which is applied to a clean copper or copper alloy surface and immediately forcedly dried to form a film with an excellent patina-promoting effect. It is. The water-based resin may be either water-soluble or water-dispersible, and commonly used resin compositions such as acrylic, alkyd, urethane, and polyester resins can be used. The resin content in the processing liquid is 10 to 10% as solid content.
300g/(preferably 50-300g/).
When formed with a treatment liquid containing less than 10 g/l, the adhesion between the treated film and the generated patina is poor.
It was not possible to prepare a treatment liquid containing 300 g/or more of solid content because the solid content of the aqueous resin used in the examples of the present invention was lower than 50%. Therefore, it was not possible to confirm the effect through experiments, but if the treatment solution is prepared with an aqueous resin with a solid content of 50% or more, it is possible to increase the amount to 300g/or more, and in this case, copper complex salts may be added to the treatment solution. It is presumed that the object of the present invention can be achieved by blending and using a large amount of a forming compound and a compound that chelates with copper ions. Substances that form inorganic complex salts with copper ions (hereinafter referred to as complex salt-forming compounds) include aqueous ammonia, ammonium salts,
Examples of substances that chelate with copper ions include polyaminocarboxylic acid salts such as ethylenediaminetetraacetate, oxycarboxylic acids such as citric acid, and condensed phosphates, and these substances can be arbitrarily selected. It can be used as The content of these compounds in the processing solution is 20~
500g/(preferably 50-400g/),
A film formed with a treatment solution having a content of 20 g/min or less will have insufficient patina or will not progress much. Although a film formed with a treatment solution containing 500 g/g or more is sufficiently patinaed, the adhesion of the film to the copper or copper alloy surface tends to decrease. In this case, although adhesion can be improved by increasing the water-based resin content, the cost of the treatment liquid itself increases, which is not desirable from an economical point of view. In addition, one of the effects of containing a compound that forms a chelate bond with copper ions (hereinafter referred to as a chelate compound) is that the synergistic effect of the effect of forming an inorganic complex salt with copper ions and the effect of forming a chelate bond with copper ions promotes patina. The other is to stabilize the treatment solution for the patina-promoting film (hereinafter referred to as treatment solution).In other words, the aqueous resin contained in the treatment solution generally tends to precipitate or gel, but the chelate compound Since it has the effect of suppressing such precipitation, gelation, etc., it can contribute to the stability of the processing solution. In order to exhibit the above effects satisfactorily, the content of the chelate compound in the treatment liquid must be about 10 g/min or more. Although the content range of the chelate compound is not specified, it is usually within about 10 to 100 g. Next, as a method for applying the treatment liquid according to the present invention,
For example, roll coater coating, air knife method, etc. can be mentioned, but these methods are not particularly specified, and the dry amount of the treatment liquid is uniformly applied to the surface of copper or copper alloy so that the amount is 0.5 to 5 g/ ^m2 . Any coating method may be used as long as it is capable of coating. When the dry adhesion amount is less than 0.5 g/m ^{2 ,} it is difficult to form a patina, and when it is more than 5 g/m ² , it becomes difficult to form a patina due to insufficient penetration of rainwater into the coating film. Examples of forced drying means include methods using hot air or infrared rays. The drying method is not specified, but usually 100
Tack-free drying is performed at ~150°C. [Function] The very thin film formed on the surface of copper or copper alloy material by the method of the present invention has air permeability and water permeability, so after the film is formed, it can be left outdoors for a short period of time, for example, one month. Upon exposure, air, dew, rainwater, etc. can penetrate the coating and reach the metal surface, ionizing the copper on that surface. This copper ion combines with the complex-forming compound and the chelate compound in the film, each consisting of a copper complex salt and a copper chelate compound, but these compounds turn green due to the action of moisture that has passed through the film and carbon dioxide gas in the air. As the coating progresses and is exposed to the outdoors for a short period of time, due to the mutual effect with the binding effect of the resin, it forms a uniform and calm patina with good adhesion. Furthermore, since the treatment liquid of the present invention contains a chelate compound, it is stable and has excellent storage stability for a relatively long period of time. Examples of the present invention are shown below along with comparative examples. [Examples] (1) Compounds used in the preparation of treatment liquids The compounds used in the preparation of the treatment liquids used in the examples and comparative examples of the present invention are as follows. Compounds that form complex salts with copper ions Ammonium chloride (first class reagent) Ammonium carbonate (first class reagent) Compounds that form chelate bonds with copper ions Tetrasodium ethylenediaminetetraacetate (EDTA-4Na, first class reagent) Water-based resin Phthalkyd W-760A Resin solid content 47 %
(Alkyd emulsion, Hitachi Chemical Co., Ltd.)
(manufactured by) Primal HA-8 Resin solid content 45.5%
(acrylic emulsion, manufactured by Rohm & Haas Japan Co., Ltd.)
1010C Resin solid content 40% (urethane emulsion, manufactured by Dainippon Ink and Chemicals Co., Ltd.) (2) Preparation of treatment liquid Add the calculated amount of complex salt-forming compound and copper chelate compound to an appropriate amount of water and stir well. Add a calculated amount of water-based resin to this aqueous solution or suspension,
Further water was added to bring the total volume to 1, and the mixture was further stirred to prepare a treatment liquid. Table 1 shows the composition of the treatment liquid used in the Examples and Comparative Examples of the present invention.

【table】

[Table] (3) Test plate Copper plate for roofing material (99% copper content, plate thickness = 0.5mm)
Dimensions: 70mm x 150mm. (4) Treatment method The test plate was treated with Perco Cleaner N364S (alkali cleaner manufactured by Nippon Parkerizing Co., Ltd.) 20g/
Spray clean at 60℃ for 1 minute, then rinse with water and drain and dry. Next, while stirring the treatment solution for each test plate, use a bar coater to reduce the dry coating weight to 2 g/
m ² (However, in the case of Comparative Examples 1 to 3, the dry adhesion amount is
1.4g/m ² ) and then immediately apply 120
A film was formed by forced drying at ℃ for 30 seconds. (5) Test method a: Patina generation After the treated test plates were exposed outdoors for two weeks and one month, the development of patina on the test plates was visually observed. 〇…A uniform patina appears on the entire surface. △……Pale or uneven patina occurs. x: Almost no patina is observed. b Adhesion test After leaving the treated test plate for a day and night, fold the test plate by stacking four plates of the same thickness (0.5 mm) as the test plate and sandwiching them. Next, cellophane tape was pressed onto the outer surface of the bent portion of the test plate, and then it was peeled off at once, and the state of peeling of the film at the bent portion was observed. 〇……Does not peel off at all. △...There are some parts that peel off. ×...All peeled off. C. Adhesion test after outdoor exposure The treated test board was exposed outdoors for one month, then washed with water and dried to clean the surface. Next, cellophane tape was applied and peeled off, and the state of peeling of the film was visually observed. The judgment criteria are shown in three levels: ○, △, and ×, as in the case of the b adhesion test. d Processing liquid stability After the processing liquid was prepared and left at room temperature for one week, the appearance of the processing liquid was visually observed. 〇...No abnormality △...Slight gelation or precipitation of resin components ×...Significant gelation and/or precipitation is observed The above test results are shown in Table 2. Comprehensive comparison of Examples and Comparative Examples in terms of patina generation, adhesion, and adhesion after outdoor exposure showed that Examples were clearly superior, confirming the effects of the present invention. . That is, due to the mutual effect of the complex salt-forming compound and copper-chelate compound that have the function of promoting patina formation and the aqueous resin that has the adhesive function, a patina film with a subdued color tone can be formed evenly by short-term outdoor exposure. Moreover, it can be formed with good adhesion. Further, since the processing liquid has stability, it is preferable from the viewpoint of processing liquid management and economical efficiency. On the other hand, in Comparative Examples 1 and 2, none of the applied treatment solutions contained a water-based resin that had a film adhesion function, so the adhesion of the film was poor, and the film was not easily eroded by rainwater or dew when exposed outdoors. Because of this, almost no patina-forming effect was exhibited. Furthermore, since Comparative Example 3 does not contain a chelate compound, the rate of patina formation upon outdoor exposure is somewhat slow, and the stability of the treatment solution is also insufficient. In Comparative Example 4, the total amount of complex salt-forming compound and copper chelate compound was insufficient in the treatment solution applied to them, so although the adhesion of the film was excellent, a slight patina-forming effect was evident. was inferior to Comparative Example 5 contained a relatively large amount of a complex salt-forming compound and had good patina formation and film adhesion, but the treatment solution stability was extremely poor. . As explained above, the present invention is a unique accelerated treatment method for stably forming a uniform patina film with adhesive properties and a subdued color tone on the surface of copper or copper alloy. When applying the coating to a copper plate for material use, if you first form the coating of the present invention on the copper plate and then cover the roof with the treated copper plate, the above-mentioned patina coating will be formed within one month. This is a very preferable method in terms of quality and industrial production.

【table】

Claims (1)

[Claims] 1 An aqueous solution or suspension containing a water-based resin, a compound that forms an inorganic complex salt with copper ions, and a compound that also chelates with copper ions, wherein the content of the water-based resin is 10 to 300 g in terms of solid content. /l, and the total content of the compound forming an inorganic complex salt with the copper ion and the compound chelating with the copper ion is 20 to 500 g/l, and the content of the copper ion and the chelate binding compound is 20 to 500 g/l. Content is 10g/
A treatment liquid for a blue-recording accelerating film having a water content of 1 or more.