JP3073834B2 - Method of forming metal plating layer on surface of inorganic building material product and inorganic building material product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a plating film on the surface of an inorganic building material product such as a cement product, and to an inorganic building material product provided with a plating film.

[0002]

2. Description of the Related Art Conventionally, inorganic building materials represented by cement products have been widely used as exterior materials.
However, inorganic building materials that have been generally used in the past are poorly decorative because the color tone is gray and monotonous,
In addition, there was a drawback that it was weak to acid rain and easily corroded. Therefore, recently, in order to improve the conventional disadvantages, a metal plating is applied to the surface of the inorganic building material product, thereby improving the decoration effect, and at the same time, a method and product for manufacturing the inorganic building material product having high corrosion resistance. Has come to be developed.

[0003] Conventional methods for applying metal plating to inorganic building material products are broadly classified into wet methods and dry methods. In the former wet method, a silver mirror reaction is performed with a silver salt on the surface of the inorganic building material product, and then electroplating is performed.A resin such as an ABS resin or an epoxy resin is coated on the surface of the inorganic building material product. Chemically etch the resin layer with chromate or sandblast,
A method is known in which the surface is roughened by a mechanical method such as liquid honing, and further activated by a sensitizer and an activator treatment, and then chemical plating and metal plating using an electroplating method are sequentially performed. Further, as the latter dry method, a method of directly spraying a metal onto the surface of an inorganic building material product, a method of sprinkling, a method of performing CVD, and the like are known.

[0004]

However, when the former wet method is carried out, the adhesion between the synthetic resin layer and the various metal plating layers is insufficient, so that the metal plating is finally applied. When machining inorganic building material products, there is a problem that metal plating is peeled off. In addition, when the above-mentioned conventional wet method is performed, air bubbles are generated in the laminated synthetic resin layer due to the pores of the inorganic material, and the air bubble mark formed in the synthetic resin layer is a surface of the metal plating. And there is a problem that the aesthetic appearance of the inorganic building material product is significantly impaired. Furthermore, the latter dry method requires spraying, sprinkling, etc. on the surface of the inorganic building material product, so the processing equipment is large and extremely expensive, and it is difficult to mass-produce economically. There were problems such as insufficient adhesion.

[0005] The method for forming a metal plating layer on the surface of an inorganic building material according to the present invention and the inorganic building material product are completely novel techniques developed in view of the above-mentioned conventional problems, and in particular, have a specific technology. By using synthetic resin,
The adhesion between the synthetic resin layer and the metal plating layer of inorganic building material products is significantly improved, preventing the metal plating from peeling off during processing, and preventing the appearance of air bubble marks on the surface of the metal plating, and An object of the present invention is to provide a technique capable of mass-producing inorganic building materials at relatively low cost.

[0006]

The method of forming a metal plating layer on the surface of an inorganic building material product according to the present invention is a technique which fundamentally improves the above-mentioned conventional problems, and its gist is that of a cement product. A nitrile rubber-based resin is applied to the surface of an inorganic building material product made of tile, stone, paper, etc. to form a laminated resin layer, and a sensitizer solution method and an activator treatment method are sequentially applied to the nitrile rubber-based resin layer. Activating the nitrile rubber-based resin layer by applying the same, and further providing a metal plating layer by applying chemical plating and electroplating to the surface of the nitrile rubber-based resin layer, respectively. This is a method of forming plating. Further, the inorganic building material product according to the present invention is characterized in that metal plating is integrally laminated via a nitrile rubber-based resin layer on the surface of an inorganic building material product such as a cement product, a tile, a stone material, and paper. It is an inorganic building material product.

[0007]

The method for forming a metal plating layer on the surface of an inorganic building material product according to the present invention has a low surface tension as described above,
The nitrile rubber-based resin, which is rich in fluidity and small in film thickness, is applied to the surface of the inorganic product to form a laminated resin layer, so that the application of the resin is extremely easy, and between the applied nitrile rubber-based resin layers. The generation of air bubbles can be prevented.

Further, since the nitrile rubber-based resin applied to the surface of the inorganic building material has an extremely strong adhesive force, and has a characteristic originally used as an adhesive, the resin layer made of the nitrile rubber-based resin is used for the inorganic building material. Can be firmly adhered to the surface of Therefore, as described above, when a metal plating layer is provided by activating the nitrile rubber-based resin layer laminated on the surface of the inorganic building material product and further performing chemical plating and electroplating on the surface thereof, It is possible to prevent the formation of air bubble marks on the surface of the layer.

As described above, the inorganic building material product according to the present invention has a metal plating layer integrally laminated on the surface of the inorganic building material product via a nitrile rubber-based resin layer, and the nitrile rubber-based resin is as described above. In addition to having strong adhesion,
Further, since it has the following characteristics, the metal plating layer can be firmly fixed to the inorganic building material product via the nitrile rubber-based resin layer.

That is, the nitrile rubber is obtained by randomly polymerizing butadiene and acrylonitrile, and has the following structure.

[0011]

Embedded image

As in the above-mentioned conventional examples, synthetic resins such as ABS resin and epoxy resin which are conventionally used generally have few surface-sensitive groups and are difficult to impart sensitivity, but are used in the present invention. Diene-based nitrile rubber is particularly-(C
(N) a very large amount of a polar group and a C = C double bond in the main chain, a large amount of sensitive groups, and a physical adhesive force as described above. Since the binding of Sn ²⁺ ions as a sensitizer for chemical plating is excellent in both quantity and strength, the metal plating layer is firmly attached to inorganic products via the nitrile rubber-based resin layer. Can be fixed to the surface.

Therefore, it is not necessary to apply special chemical etching or mechanical roughening to the nitrile rubber-based resin layer, and it is possible to process a large amount of inorganic building material having a large surface area quickly. Further, the diene nitrile rubber can be modified by phenol or carboxy to improve adhesiveness, fluidity, solubility in a solvent, and its performance. Also, in the denaturation, there is no change in the binding of Sn ^{2+ in} the sensitizer.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of a method for forming a metal plating layer on the surface of an inorganic building material product according to the present invention and an inorganic building material product manufactured by using this method will be described below.

First, in developing the present invention, the present inventors have found that, among synthetic resins or synthetic adhesives having various properties, (1) excellent compatibility and adhesion with inorganic materials. And (2) excellent adhesion to the metal plating layer, and (3) results of a long-term test on the finished product having a beautiful metal plating appearance as shown in Table 1. Test results were obtained.

[0016]

[Table 1]

The following is a description of ○, Δ, and × displayed in Table 1.

1) In Table 1 above, in terms of the conformability of the synthetic resin, the synthetic adhesive and the inorganic material, the appearance of a smooth and uniform resin layer in the visual appearance test was evaluated as good. △ indicates that air bubbles were formed in the resin layer due to the effect of the material and some traces of the air bubbles were left, and X indicates that there were many traces of the air bubbles. 2) In addition, in the adhesion between the material and the resin layer, or between the resin layer and the plating layer, a hole is drilled by an electric drill, and a cutting, nailing, peeling test, and a hot / cold repetition test are performed on the resin layer or the plating layer.が な い indicates no peeling, Δ indicates slight peeling, and X indicates noticeable peeling. 3) Further, in the plating appearance test by visual observation, those in which a smooth and uniform plating layer was formed were indicated by ○, those in which a trace of bubbles in the resin layer slightly remained in the plating appearance were indicated by Δ, and those which were conspicuous were indicated by x.

As a result of a test as shown in Table 1 above,
Among various kinds of synthetic resins or adhesives, nitrile rubber-based, especially acrylonitrile-butadiene copolymer modified product, is compatible with inorganic materials, adhesion, adhesion between resin layer and plating layer, plating Both appearances were the best. Further, as a solvent, a ketone type (for example, AC, MEK, MIB)
K), an ester-based (eg, EA, BA), or nitrile rubber-based resin solutionized with a chlorinated solvent exhibited good adhesion to inorganic materials, appearance, adhesion to plated metal, and appearance. However, there was no significant difference in other organic solvents.

According to the present invention, a nitrile rubber-based resin is selected and used based on the test results in Table 1, and the nitrile rubber-based resin is applied to the surface of an inorganic building material product, and the nitrile rubber-based resin layer is formed. A metal plating layer is laminated on the substrate.

Example 1 A calcium silicate plate having a volume of 30 cm × 30 cm × 1 cm was immersed in the following nitrile rubber-based resin solution for 5 minutes, and then left at room temperature for 24 hours to completely cure the resin film. Then, a resin layer was applied to the surface of the calcium silicate plate. Resin Nitrile rubber (Nitrile content 31-41
%) Non-volatile content 30 ± 2% Viscosity 2000-3000 (cps / 25 ° C) Solvent Toluene The above nitrile rubber resin is diluted 1: 3 with diluent toluene.
(Volume ratio). The calcium silicate plate provided with the resin layer was immersed in a solution treatment bath having the following composition and subjected to a sensitizer treatment with tin. Stannous chloride 10 g / l 35% hydrochloric acid 5 ml / l This was sufficiently washed with water, further immersed in the following solution for 1 minute, and subjected to an activator treatment with palladium. Palladium chloride 0.2g / l 35% hydrochloric acid 1ml / l

This was sufficiently washed with water and then immersed in a chemical nickel plating bath having the following composition at a temperature of 40 ° C. for 5 minutes. Nickel chloride 45g / l Sodium hypophosphite 11g / l Sodium citrate 100g / l Ammonium chloride 50g / l pH 8.5 to 9.0 As a result, a nickel plating layer of about 1.5μ was formed.
This was sufficiently washed with water, the nickel plating layer was activated with 5% sulfuric acid, and further thoroughly washed with water, and electroplating was performed in a nickel electroplating bath having the following composition at an electric density of 3 A / dm ² for 20 minutes. did. Nickel sulfate 270g / l Nickel chloride 45g / l Boric acid 40g / l Brightener Suitable amount (manufactured by Nippon Kagaku Sangyo Co., Ltd.) Bath temperature 50-55 ° C pH 4.0 As a result, about 9μ (approx.
0.5 μ) of the nickel plating layer was obtained. As a comparative example, a calcium silicate plate provided with a bisphenol A-type epoxy resin layer was provided with a nickel plating layer in the same manner as described above. The results of Table 2 were obtained when the adhesion test was performed for each of them.

[0023]

[Table 2]

From these results, it was confirmed that when Example 1 was carried out, there was sufficient adhesion between the resin layer and the metal plating layer.

(Example 2) A solution prepared by mixing a calcium silicate plate having a volume of 30 cm x 30 cm x 1 cm with the nitrile rubber-based resin of Example 1 in a diluting solvent EA at a ratio of 1: 2 (volume ratio). For 3 minutes, the resin film was cured in the same manner as in Example 1, and a resin layer was applied to the surface of the calcium silicate plate. Furthermore, chemical nickel plating was performed in the same manner as in Example 1, and a current density of 3 was applied in a copper electroplating bath having the following composition.
Electroplating was performed at A / dm ² for 20 minutes. Copper sulfate 180g / l Sulfuric acid 50g / l Chloride ion 30mg / l Brightener Suitable amount (manufactured by Nippon Kagaku Sangyo Co., Ltd.) Bath temperature 20-30 ° C As a result, a copper plating layer of about 7μ was obtained. Further, in the same manner as in Example 1, electro-nickel plating was performed, and then the current density was 20 A / dm ² , 1 in a chromium electroplating bath having the following composition.
Chromium plating was performed under the conditions of minutes. Chromic anhydride 200g / l concentrated sulfuric acid 2mg / l Bath temperature 40 ~ 55 ℃

As a result, a copper-nickel-chromium plating layer of about 7 μm of copper plating, about 9 μm of nickel plating and about 0.1 μm of chromium plating was obtained. When an acid resistance test was performed on the copper-nickel-chromium surface calcium silicate plate thus obtained, the results shown in Tables 3 to 6 were obtained.

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

As a result, in any of Tables 3 to 6,
It was found to be effective as a countermeasure against corrosion of inorganic materials due to acid rain.

Example 3 The nitrile rubber-based resin of Example 1 was applied to an asbestos cement board having a volume of 30 cm × 30 cm × 1 cm by a spray method, and heated at 80 ° C. for 15 minutes by a hot air dryer. After drying, the resin film was completely cured, and a resin layer was applied to the surface of the asbestos cement board. Further, a sensitizer process and an activator process were performed in the same manner as in Example 1.
The resin layer was activated. Next, chemical nickel plating and electric nickel plating were performed in the same manner as in Example 1, and chromium plating was further performed in the same manner as in Example 2. As a result, about 9μ of nickel plating (approx.
10.5 μ) and a nickel-chromium plating layer of about 0.1 μm chromium plating was obtained. The nickel thus obtained
When a corrosion resistance test was performed on the chromium surface asbestos cement board, the results in Table 7 were obtained in a salt spray test (1000 hours).

[0033]

[Table 7]

From the results, as shown in Table 7, it was confirmed that when Example 3 was carried out, the corrosion resistance was good.

Example 4 A having a volume of 30 cm × 20 cm × 10 cm
The following nitrile rubber-phenolic resin is applied to an LC plate by a roll coating method, and then is applied to a hot air drier at 80 ° C.
Heat drying was performed for 15 minutes to completely cure the resin film, and a resin layer was formed on the surface of the ALC plate. Nitrile rubber 55 parts Phenol resin 45 parts Solvent 255 parts The above nitrile rubber-phenolic resin was diluted with diluent M
It was diluted with EK at a ratio of 1: 2 (volume ratio) and used. The ALC plate provided with the resin layer was subjected to a sensitizer treatment and an activator treatment in the same manner as in Example 1 to activate the resin layer. Next, in a chemical copper plating bath of the following composition, 20
Dipped at ~ 26 ° C for 10 minutes. Copper sulfate 10g / l Caustic soda 8g / l Formalin 10ml / l Rossier salt (37% by volume) 20g / l

As a result, a copper plating layer of about 3 μm was obtained. Further, after sufficiently washing with water, electro-nickel plating was performed in the same manner as in Example 1, and 3 μm of copper was applied to the surface layer of the ALC plate.
-A 9 µm nickel plated layer was obtained. This was tested for adhesion in the same manner as in Example 1, and as a result, it was confirmed that the adhesion was sufficient. Further, this was immersed in tap water for 30 days and subjected to a water resistance test. The results shown in Tables 8 and 9 were obtained.

[0037]

[Table 8]

[0038]

[Table 9] As shown in Tables 8 and 9 above, when Example 4 was carried out, an inorganic building material product having good durability with no change in the color tone and glossiness of the plating surface could be obtained.

(Example 5) A wood wool cement board having a volume of 30 cm x 30 cm x 1 cm was immersed in the nitrile rubber-phenolic resin solution of Example 4 for 3 minutes, and then left at room temperature for 4 hours to form a resin film. It was completely cured and a resin layer was applied to the surface of the wood wool cement board. Further, a sensitizer treatment and an activator treatment were performed in the same manner as in Example 1 to activate the resin layer. Next, in the same manner as in Example 1, chemical nickel plating and electric nickel plating were performed, and further, copper and zinc alloy (brass) electroplating was performed in a bath having the following composition. Brass salt 150g / l (manufactured by Nippon Chemical Industry Co., Ltd.) Bath temperature 30 ℃ Current density 1A / dm ² pH 12.6 hours 1 minute

As a comparative example, a wood wool cement board provided with an ABS resin layer was plated with nickel-brass in the same manner as described above. The results shown in Table 10 were obtained for each of them by a visual plating appearance test.

[0041]

[Table 10]

From the results shown in Table 10, it was confirmed that in Example 5, a plating layer having good appearance was obtained.

As is clear from the above Examples 1 to 5, when the present invention is carried out, the adhesion of the metal plating film to the inorganic material is lower than that of the conventional example. It is clear that the performance and appearance have been significantly improved.

[0044]

The method for forming a metal plating layer on the surface of an inorganic building material product according to the present invention has the above-described configuration and action, so that the resin can be applied to the surface of the inorganic building material product with extremely high conformability and adhesion. It can be applied well.

Further, it is possible to prevent bubbles from being generated in the applied resin layer, and thus it is possible to prevent the occurrence of air bubbles on the surface of the metal plating layer.

The method according to the present invention makes it possible to mass-produce products having a large area at low cost without requiring large-scale and expensive equipment.

Since the inorganic building material product according to the present invention has the above-described structure and function, the metal plating layer can be firmly fixed to the inorganic building material product via the nitrile rubber-based resin layer.

Accordingly, the inorganic building material product according to the present invention comprises:
Important post-processing at the construction site, such as screw drilling with an electric drill, cutting with a high-speed cutter, nailing, etc.
The synthetic resin layer and the plating metal layer applied to the surface of the inorganic building material product are not peeled off, and a highly decorative plating film having a smooth and glossy surface can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C23C 18/00-18/54 C23C 28/00 C25D 5/56

Claims (2)

(57) [Claims] 1. A nitrile rubber-based resin is applied to the surface of an inorganic building material product such as a cement product, a tile, a stone, a paper, etc. to form a resin layer on the surface, and a sensitizer solution method is applied to the nitrile rubber-based resin layer. Activating the nitrile rubber-based resin layer by sequentially applying the activator treatment method,
A method of forming a metal plating layer on the surface of an inorganic building material product, further comprising providing a metal plating layer by subjecting the surface of the nitrile rubber-based resin layer to chemical plating and electroplating, respectively. 2. An inorganic building material product characterized in that metal plating is integrally laminated on the surface of an inorganic building material product such as a cement product, a tile, a stone material, and paper via a nitrile rubber-based resin layer.