JPS6212183B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a high-performance heat-ray reflective glass that has high heat-ray reflective performance and excellent durability, and a method for manufacturing the heat-ray reflective glass with low pollution. A glass plate that has a thin transparent or semi-transparent coating of metal such as silver, nickel, gold, or aluminum on its surface to reflect and block the heat rays of sunlight or radiant rays is called a heat-reflective glass plate. It is used as single glazing, multiple glazing, or laminated glass in buildings, transportation vehicles, and various devices and appliances. In such metal coated heat reflective glass
Those with a Cu coating have the best heat ray reflection performance, but have insufficient corrosion resistance and have durability problems. On the other hand, those with a nickel coating have sufficient corrosion resistance and have fewer problems with durability, but have the disadvantage that their heat ray reflection performance is inferior to that of Cu. The present invention was developed as a result of research aimed at providing a heat ray reflective glass that does not have the above-mentioned drawbacks.
By combining Ni and Cu, and further combining them with B, the respective advantages of Ni and Cu are exhibited, and the heat ray reflection performance, that is, the heat transmission coefficient (Kvalue) is 2.0 or less and the shielding coefficient (SC) is 0.20.
We have discovered that a heat ray reflective glass having the following properties and also high durability can be obtained, and have proposed the present invention. That is, the present invention provides transparent Ni--Cu-- on the glass surface.
This invention relates to a heat ray reflective glass formed by forming a B alloy film. That is, in the present invention, Ni salts and Cu salts, and borohydride alkalis or amineboranes as reducing agents for reducing the Ni salts and Cu salts are applied to the glass plate surface to chemically reduce the Ni salts and Cu salts. The present invention relates to a method for producing heat ray reflective glass, which is characterized by forming a Ni--Cu--B alloy film by reducing the Ni--Cu--B alloy film. The present invention will be explained in more detail below. The transparent Ni-Cu-B alloy film in the present invention is
Ni to increase sufficient heat ray reflection performance and corrosion resistance
It is an alloy of Cu and B, and transparent Ni
-The composition of each component of the Cu-B alloy film is 1wt% Ni ~
20wt%, Cu 75wt% to 99wt%, B 5wt% or less, more preferably Ni 1wt% to 10wt%, Cu
It is optimal that B is 89wt% to 99wt% and B is 0.001wt% to 1wt%. If the proportion of Ni is greater than 20%, the heat ray reflection performance will deteriorate, which is undesirable;
If it is smaller, the corrosion resistance will be insufficient, which is not preferable. Moreover, if the proportion of Cu is greater than 99%, the corrosion resistance will be insufficient, which is undesirable, and if the proportion of Cu is less than 75%, the heat ray reflection performance will be degraded, which is not preferable. Moreover, if the proportion of B is greater than 5%, the heat ray reflection performance will deteriorate, which is not preferable. The thickness of this transparent Ni-Cu-B alloy film is suitably in the range of 10 Å to 1000 Å so as to obtain transparency or semi-transparency and desired optical properties such as heat reflectance and transmittance. is particularly preferably in the range of 100 Å to 700 Å. The color tone of the Ni-Cu-B alloy film of the present invention is as follows:
By changing the Ni content, it is possible to control the color between neutral and copper. For example, Ni
If the Ni content is increased, a neutral color can be obtained, while if the Ni content is decreased, a copper color can be obtained. As a method for forming such a transparent Ni-Cu-B alloy film on the glass plate surface, Ni salt, Cu salt, Ni,
Ni-
A method of forming a Cu--B alloy film is adopted. More specifically, for example, Ni-Cu-
A B alloy film is formed. (1) Clean the coating surface of the glass plate by washing with water, cleaning with a cleaning agent, or polishing with an abrasive such as cerium oxide. (2) The glass plate surface is briefly contacted with a dilute tin salt solution, such as stannous chloride, at a temperature near room temperature, and then washed with water, preferably distilled or deionized water. (3) If necessary, further treat with dilute tin salt solution and then wash with water. (4) Next, Ni salt, Cu salt, and Ni, Cu salt were applied to the glass plate surface.
A borohydride alkali or an amine borane is used as a reducing agent to reduce the salt, and the Ni salt and Cu salt are chemically reduced almost simultaneously and deposited as a Ni--Cu--B alloy film. (5) Clean the glass plate on which the Ni-Cu-B alloy film is formed. The method of applying Ni salt, Cu salt, and reducing agent to the glass plate surface described above is to simultaneously apply a Ni salt solution and a Cu salt solution, or a mixed solution of Ni salt and Cu salt and a solution containing a reducing agent. A method of spraying, or a method of mixing two or three of the above solutions before spraying, or a method of spraying by mixing two or three of the above solutions before spraying.
A method of coating a glass plate with a mixed solution of seeds by roll coating, or a method of mixing a Ni salt solution and a Cu salt solution, or a mixed solution of these in a spray gun and spraying them as a single solution. The most typical example is the similar method. The Ni salt and Cu salt solution used to form the Ni-Cu-B film include various Ni salts conventionally used in electroless plating methods,
Cu salts and various liquid compositions can be used. For example, the Ni salt solution includes nickel salts of inorganic or organic acids, such as nickel chloride, nickel sulfate,
Contains a mixture of two or more types of nickel acetate or nickel salts, a complexing agent such as Rothsiel's salt, EDTA, sodium citrate, sodium gluconate, a PH buffer, a PH regulator, and appropriate additives as necessary. The most typical example is a solution, especially an aqueous solution. In addition, as the Cu salt solution, for example, the same complexing agent, PH buffer, PH
The most typical example is a solution, especially an aqueous solution, containing a regulator and, if necessary, appropriate additives. Furthermore, Pd can be added to increase the Ni content ratio of the Ni--Cu--B alloy film. in this case,
The appropriate content ratio of Pd is in the range of 1 ppm to 100 ppm. Note that if the Pd content exceeds 100 ppm, the Ni content will become excessive, which is not desirable.
Further, if it is less than 1 ppm, the Ni content will decrease, which is not preferable. As a method of incorporating Pd, Ni-
When forming Cu-B alloy film by chemical plating method, Pd salt type is used to form Ni by reduction reaction.
- A method is adopted in which Cu-B is contained in the form of an alloy film. Moreover, when it is desired to make the color tone of the Ni--Cu--B alloy film neutral, it is effective to add ammonia water to the Ni salt solution and/or the Cu salt solution. The concentration of Ni salt in the above Ni salt solution is 0.01% to 1%
is appropriate, and the concentration of Cu salt in the Cu salt solution is 0.02
% to 2% is appropriate. In addition, as a reducing solution, borohydride is used, which is effective in reducing Ni salt and Cu salt to form a Ni-Cu-B alloy film, and is effective in incorporating B into the Ni-Cu film. Alkali hydrides or amineboranes are most suitable. Examples of alkali borohydrides include borohydride, sodium, potassium borohydride, lithium borohydride, and examples of amineboranes include amineborane, dimethylamineborane, diethylamineborane, and trimethylamineborane. It will be done. In this way, borohydride alkalis or amineboranes are used instead of the harmful formalin normally used as a reducing agent in chemical plating methods, so a Ni-Cu-B alloy film can be formed with low pollution. be able to. Further, when the Ni--Cu--B alloy film is deposited by electroless plating according to the present invention, the plating time is optimally about 30 seconds to 20 minutes, preferably about 1 minute to 10 minutes. In addition, the temperature of Ni or Cu and the reducing solution during electroless plating, or the solution containing these salts and reducing solution, is as follows:
A temperature range of 10°C to 60°C, for example around 30°C, is optimal. Please note that due to temperature changes during electroless plating,
Since the precipitation rates of Ni and Cu are different, it is important to keep the temperature constant during electroless plating, for example at ±3°C, in order to prevent color unevenness. Further, the temperature of the substrate during electroless plating is preferably 10°C to 60°C, more preferably around room temperature. Also, the amount of spray,
The plating time and the like are appropriately selected so as to obtain the desired film thickness. In addition, in the present invention, applying a protective coat or other various functional thin films to the upper layer of the Ni-Cu-B alloy film formed on the glass plate surface, or applying a chemical conversion treatment to the lower layer It is also possible to apply an adhesion-enhancing coat or other various functional thin films to the surface. The types of glass plates that can be used include ordinary plate glass, heat-absorbing glass, and various other types of glass plates.
Furthermore, so-called organic glasses such as polycarbonate and methacrylate resin can also be used. Next, examples of the present invention will be described. Example 1 A glass plate (300
mm x 300 mm x 5 mm) was sensitized by spraying an aqueous solution of stannous chloride (concentration: SnCl ₂ 0.8 g/1 water) at a flow rate of 5 parts ^per square meter of glass plate, and immediately after washing with water, palladium chloride was applied. Aqueous solution (concentration:
Activation treatment was performed by spraying 5 ml of PdCl ₂ /water 1) at the same flow rate as above, and after washing with water, the treated glass plate surface was still wet.
₁ liquid A and ₁ liquid B having the following composition ratios were sprayed simultaneously from separate spray guns so that they overlapped with each other at a volume ratio of approximately 1:1 at a flow rate of 5 parts per ¹ m2 of glass plate, and 6 After holding for a minute, Ni-Cu-B was applied to the glass plate surface by electroless plating method.
An alloy film was deposited. A _1- part nickel sulfate 8.3g / Copper sulfate 1.7g / Rotussel salt 20g / Caustic soda 10g / Palladium chloride (1% solution) 2ml / Aqueous ammonia (29% solution) 0.5ml / Water 1 B _1- part caustic soda 0.25g / Hydrogenation Sodium boron 0.125g/Water 1 The Ni-Cu-B alloy film formed in this way has a thickness of 500 Å and contains 3.4wt% Ni and 96.5wt% Cu.
The alloy film had a composition containing 0.1 wt% of B.
The durability test results for this film are shown in Table 1, and the optical characteristic curve was as shown in c in FIG. Example ₂ A Ni--Cu--B alloy film was formed in the same manner as in Example 1 using the following _two solutions A and B. A _2- part nickel sulfate 8.3g / Copper sulfate 1.7g / Rotussel salt 20g / Caustic soda 10g / Palladium chloride (1% solution) 1ml / Water 1 B _2- part caustic soda 0.25g / Sodium borohydride 0.125g / Water 1 In this way The Ni-Cu-B alloy film formed by
With a film thickness of 500 Å, Ni is 2.0wt%, Cu is 97.9wt%,
The alloy film contained 0.1 wt% of B. The durability test results for this film are shown in Table 1. Example 3 A Ni--Cu--B alloy film was formed in the same manner as in Example 1 using the following ₃ liquids A and ₃ liquids B. A _3- part nickel sulfate 8.3g / copper sulfate 1.7g / Rotussel salt 20g / caustic soda 10g / palladium chloride (1% solution) 2ml / ammonia water 0.5ml / water 1 B _3- part caustic soda 0.25g / amineborane 5g / water 1 Like this The Ni-Cu-B alloy film formed by
500Å film thickness, 3.2wt% Ni, 96.6wt% Cu,
The alloy film had a composition containing 0.2 wt% of B. The durability test results for this film are shown in Table 1. Comparative Example 1 Glass plate polished with ceria and washed with water (300
mm x 300 mm x 5 mm) was sensitized by spraying an aqueous solution of stannous chloride (concentration: SnCl ₂ 0.8 g/1 water) at a flow rate of 5 parts ^per square meter of glass plate, and immediately after washing with water, palladium chloride was applied. Aqueous solution (concentration:
Activation treatment was carried out by spraying PdCl ₂ 5 ml/water 1) at the same flow rate as above, followed by washing with water. after that,
While the surface of the treated glass plate is still wet, apply ₄ liquids A and ₄ liquids B with the following composition ratios to each glass plate 1m ² using separate spray guns so that they overlap each other at a volume ratio of approximately 1:1. Hit 5
The Ni--B alloy film was sprayed at a flow rate of 100 ml and held for 6 minutes to deposit a Ni--B alloy film on the glass plate surface by electroless plating. A ₄ -liquid nickel acetate 5.0g / sodium gluconate 9.0g / aqueous ammonia (39%) 2.0ml / boric acid 2.5g / water 1 B ₄ -liquid sodium borohydride 0.5g / caustic soda 0.2g / water 1 In this way The formed Ni-B alloy film is 500
The film thickness was 1.5 Å. The performance measurement results of this Ni--B alloy film are shown in Table 1. Comparative Example 2 On the surface of a glass plate treated _in the same manner as Comparative Example 1 _{, 5} liquids A and ₅ liquids B with the following composition ratio were applied from separate spray guns so that they overlapped each other in a volume ratio of approximately 1:1 ratio and 1 m ² of glass plate
Spray at a flow rate of 5% per 100ml and hold for 2 minutes to coat the glass plate with Cu-B by electroless plating.
An alloy film was deposited. A ₅ -liquid copper sulfate 5.0g / sodium gluconate 9.0g / aqueous ammonia (39%) 2.0ml / boric acid 2.5g / water 1 B ₅ -liquid sodium borohydride 0.5g / caustic soda 0.2g / water 1 In this way The formed Cu-B alloy film is 500
The film thickness was 1.5 Å. Furthermore, the performance measurement results of this Cu--B alloy film were as shown in Table 1. Comparative Example 3 6 liquids A and ₆ liquids B having the following composition ratio were applied to the surface of a glass plate treated in the same manner as in Comparative Example ₁ using separate spray guns so that they overlapped each other at a volume ratio of approximately 1:1. 5 per ^1m2 glass plate each
The Ni--Cu alloy film was deposited on the glass plate surface by an electroless plating method by spraying at a flow rate of 100 ml and holding it for 6 minutes. A ₆ -liquid copper sulfate 1 g / nickel sulfate 2 g / formalin (38%) 43 ml / palladium chloride solution (1%) 2 ml / water 1 B ₆ -liquid Rothsell's salt 20 g / caustic soda 10 g / water 1 The film formed in this way is The film was a Ni-Cu alloy film with a film thickness of 500 Å and a Ni content of 7 wt% and a Cu content of 93 wt%. The performance measurement results and color tone of this film were as shown in Table 1.

[Table] As is clear from Table 1, the heat ray reflective glass of the present invention has a higher thermal transmittance (2.00 or less) and shielding coefficient ( It is recognized that the thermal properties of the film are excellent (less than 0.20), and the durability is superior to that of the Cu-B film, which has the same heat ray reflection performance as the Ni-Cu-B alloy film. Moreover, it has a neutral color tone and is preferred as a heat-reflecting glass. ● Durability was determined by visual observation of the degree of erosion after being kept at 30°C and 70% RH for one month. (〇 means no damage, × means damage is possible) ● Visible light transmittance (Tv) is measured using a sample with a film formed on a 6m/m thick ordinary glass plate, with light incident on the film side. ● Thermal transmission coefficient (K) and shielding coefficient (Sc) were measured on a glass plate with the above membrane structure and a regular glass plate with a thickness of 6 m/m, which were made into double-glazed glass with an air gap of 12 m/m. It is something.

[Brief explanation of the drawing]

FIG. 1 shows an optical characteristic diagram of the heat ray reflective glass of the present invention obtained in Example 1.

Claims (1)

[Claims] 1. A Cu salt aqueous solution containing a chelating agent with a Cu salt concentration of 0.02% to 2% and a Ni salt concentration of 0.01% to 1%.
Ni salt aqueous solution containing chelating agent, Cu salt and Ni
an aqueous reducing agent solution containing an alkali borohydride or an amine borane as a reducing agent for reducing salt;
An effective amount of Pd salt aqueous solution is applied to the glass plate surface at a temperature of 10℃ to 60℃, and Ni is added to 1wt% or more.
20wt%, Cu 75wt%~99wt%, B 0.01wt%~
A method for producing heat ray reflective glass, characterized in that a transparent Ni--Cu--B alloy layer containing 5 wt% is formed on the surface of the glass plate by electroless plating reaction. 2. The method for producing heat ray reflective glass according to claim 1, characterized in that sodium borohydride is used as the borated alkali.