JPH0478575B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a pharmaceutical composition for forming an infrared reflective film on the surface of glass. Conventional configurations and their problems Infrared reflective glass is constructed by uniformly forming a transparent film of tin oxide or indium oxide on the surface of the glass.In order to ensure strong infrared reflective performance, It is customary to dope with small amounts of impurities. It is known that the elements antimony and fluorine are introduced into tin oxide, and the use of tin element into indium oxide provides good infrared reflection characteristics. In the case of an indium oxide film, the visible light transmittance of the formed film is poor because it easily becomes opaque, and the film has low strength and is easily scratched. Currently, infrared reflective glass coated with a tin oxide film is highly prized because it is less prone to such defects. The main agent for forming a tin oxide film is stannous chloride, an organic stannous alkoxide or acyloxy compound (hereinafter referred to as an organic stannous compound), or dimethyltin oxide. The method of forming a tin oxide film with these agents is limited due to their properties.Since stannous chloride has a high sublimation and scattering property, it is necessary to heat the glass substrate to 450°C or higher in advance.
Organic stannous compounds are suitable for catalytic thermal decomposition (hereinafter referred to as the hot substrate spraying method) by spraying fine particles onto the surface of the substrate. Since this method requires time, a method is used in which a chemical is applied to the surface of a substrate at room temperature, dried, and then gradually heated to thermally decompose it (hereinafter referred to as the cold coating and baking method). In the method of forming a tin oxide film by spraying stannous chloride onto a hot substrate, a film thickness of approximately 3000 Å can be easily formed in a single treatment process, so a thin film has sufficient infrared reflective properties. On the other hand, a large amount of hydrochloric acid gas and hydrogen fluoride gas is generated in the heated atmosphere, which is highly corrosive to equipment, and it is difficult to treat exhaust gas pollution. is not easy. The cold coating and firing method using organic stannous compounds can significantly reduce the generation of corrosive gases, but
The decomposition of the drug tends to be uneven, resulting in a partially cloudy, discontinuous film. Therefore, in an attempt to avoid this drawback, the thickness of the infrared reflective film that can be formed in one treatment has been reduced to 600 Å or less, resulting in insufficient infrared reflective properties. Furthermore, when using an organic stannous compound, the thermal decomposition of the organic stannous compound to tin oxide on the surface of the substrate is slow, and the doping agent used for the purpose of improving infrared reflection properties is removed during thermal decomposition. It easily scatters and a sufficient doping effect cannot be obtained. According to the method of spraying an organic stannous compound onto a hot substrate, the formed film contains undecomposed organic matter and is highly colored, making it impractical. Therefore, there is a strong desire for a pharmaceutical composition that uses organic stannous compounds, which are advantageous in terms of pollution treatment, to enable the formation of infrared-reflecting glass with excellent visible light transmittance and good infrared-reflecting properties. was. Purpose of the Invention In view of the above-mentioned circumstances, the present invention provides a composition for forming an infrared reflective coating that causes very little pollution problems, is free from coloring through a single formation process, and has excellent visible light transmittance and infrared reflective performance. The purpose is to provide something. Structure of the Invention The composition for forming an infrared reflective film of the first invention includes:
Selected from the group consisting of alkoxide compounds represented by the general formula Sn(OR) ₂ and acyloxy compounds represented by the general formula Sn(OOCR) ₂ (wherein R represents an alkyl group having 4 to 8 carbon atoms). However, 100 parts by weight of at least one type of aliphatic primary amine represented by the general formula R'- _NH2 (wherein R' represents an alkyl group having 1 to 6 carbon atoms) and boron trifluoride are added. It is characterized in that a mixture of 3 to 15 parts by weight of the compound is uniformly mixed in methyl alcohol. The second invention also provides an alkoxide compound represented by the general formula Sn(OR) ₂ and an acyloxy compound represented by the general formula Sn(OOCR) ₂ (wherein R represents an alkyl group having 4 to 8 carbon atoms). 100 parts by weight of at least one selected from the group consisting of:
3 parts by weight to 15 parts by weight of a complex compound of an aliphatic primary amine represented by the general formula R'- _NH2 (wherein R' represents an alkyl group having 1 to 6 carbon atoms) and boron trifluoride.
Parts by weight of palladium chloride or chloroplatinic acid are uniformly mixed in methyl alcohol. The composition for forming infrared reflective glass of the present invention can be applied to a method of spraying onto a hot substrate or a cold coating and baking method as a method for forming a reflective film, and can form an infrared reflective glass that satisfies the object of the present invention. It is configured to do so. Description of Examples Hereinafter, the present invention will be described in detail based on Examples. The organic stannous compound can easily be used alone as a solution in a solvent such as alcohol to obtain a film thickness of 1000 to 3000 Å by spraying onto a hot substrate. However, the color becomes dark red to dark brown with a very high degree of coloration and has poor visible light transmittance.
This infrared reflection characteristic is based on R-280 manufactured by Hitachi, Ltd.
The results were measured using a model infrared spectrophotometer with an IRR-3 model infrared reflection shell attached and the reflectance of the chrome mirror surface set at 100%.The vertical axis shows the infrared reflectance (%), and the horizontal axis shows the infrared wavelength. In FIG. 1, the area (μ) is curve 2, which shows almost no reflection effect compared to curve 1, which shows the infrared reflection characteristics of only the glass substrate. In addition, the visible light average transmittance (%) is measured using a spectrophotometer UV-
120 device as the average value of visible light transmittance in the wavelength range 0.4 to 2.5μ, it was found that the film thickness was 1000Å and
When the thickness is changed to 3000 Å, the degree of coloring of the film becomes significantly lower as shown in Nos. 2 and 3 compared to only the soda glass of No. 1 in Table 1. On the other hand, a solution of the organic stannous compound alone in a solvent such as alcohol was applied to the surface of the substrate, dried and then heated at 550°C.
The film thickness of the film formed by the so-called cold coating and baking method obtained by thermal decomposition for 30 minutes was 600 Å and
The average visible light transmittance (%) and coloring state of the film are shown in Table 1 Nos. 4 and 5, and the infrared reflection characteristics are shown in curve 2 in Figure 1.
It is a state where it is included in. General formula Sn(OR)
Alkoxide compound represented by ₂ and general formula Sn
(OOCR) At least one selected from the group consisting of acyloxy compounds represented by ₂ (wherein R represents an alkyl group having 4 to 8 carbon atoms),
A complex compound of an aliphatic primary amine represented by the general formula R'- _NH2 (wherein R' represents an alkyl group having 1 to 6 carbon atoms) and boron trifluoride is mixed, and this is mixed with an alcohol, etc. An infrared reflective glass is formed by spraying the composition of the present invention as a solution in a solvent of
In the figure, curves 3 (film thickness 1000 Å) and 4 (film thickness 3000 Å) are shown. In addition, the visible light average transmittance (%) is the first
It is shown in Table No. 6-7. This composition was used to form infrared reflective glass by a cold coating and firing method, and the infrared reflective characteristics were measured by curves 5 (600 Å film thickness) and 6 in Figure 1.
(film thickness 1500Å), average visible light transmittance (%) is
Shown in Nos. 8 and 9 in Table 1. Based on these conditions, the composition for forming an infrared reflective film according to the present invention exhibits good visible light transmittance up to an infrared reflective film thickness of about 1500 Å when an infrared reflective glass is formed by a cold coating and firing method, and Since it is possible to secure an infrared reflection characteristic of 50% or more, which is considered to be the minimum requirement for practical use, the object of the present invention can be fully satisfied. However, when forming infrared reflective glass by spraying onto a hot substrate, the moment the sprayed fine particles of the drug composition come into contact with the heated substrate surface, the organic stannous compound converts into tin oxide. Thermal decomposition to
The coloring is large and the visible light average transmittance is insufficient. In the present invention, when a spraying method is employed on a hot substrate, a composition to which chloroplatinic acid or palladium chloride is added has a remarkable effect on visible light average transmittance and disappearance of coloring. becomes. The results are shown in Nos. 10 to 11 in Table 1. The composition of the present invention to which chloroplatinic acid or palladium chloride is added has no problem when applied to the cold coating and baking method, and provides more favorable results.

【table】

[Table] Evaluation criteria ○ Good, △ Fair, × Bad When palladium chloride or chloroplatinic acid is thermally decomposed together with an organic stannous compound, an oxidation-promoting catalytic effect is added, and the decomposition and scattering of organic components is extremely low. The transition to the tin oxide component is completed smoothly and completely. In FIG. 2, which shows the state of the infrared reflection characteristics due to changes in the film thickness of the reflective film formed by the composition for forming an infrared reflective film of the present invention, curve 1 (thickness: 600 Å), curve 2 (thickness: 1000 Å), curve 3 ( film thickness 2000Å), curve 4
(film thickness 3000 Å), curve 5 (film thickness 4000 Å), curve 6
(Film thickness: 5000 Å) The dependence of the infrared reflection characteristics on the film thickness is large up to 3000 Å, but becomes extremely small at film thicknesses exceeding this. The composition for forming an infrared reflective film according to the present invention has no coloration even at a film thickness of 1500 Å when applied by a cold coating and baking method, or 3000 Å when applied to a hot substrate by a spraying method, and has a good average visible light transmittance, which is useful for practical use. 50 considered to be the minimum required
% or more of infrared reflection characteristics can be ensured. Even with the optimal combination of doping materials that gives the best infrared reflection characteristics, the dependence on film thickness is 3000.
In the alkoxide or acyloxy compound represented by the general formula Sn(OR) ₂ or Sn(OOCR) ₂ used in the present invention,
When the alkyl group represented by R has 3 or less carbon atoms, it is difficult to dissolve in various solvents and is not suitable for the purpose of the present invention. In addition, as the number of carbon atoms increases, the amount of thermal decomposition and scattering during film formation increases, and the thickness of the formed infrared reflective film has a large influence when the cold coating and baking method is applied. The vertical axis is the film thickness (Å) of the infrared reflective glass, and the horizontal axis is the carbon number of the alkyl group of the organic stannous compound. Figure 3 shows the infrared reflective film thickness of the infrared reflective glass obtained by the cold coating and firing method. In the curve, the number of carbon atoms in the alkyl group of the organic stannous compound that can ensure infrared reflection characteristics of 50% or more (can form a film thickness of 1000 Å or more) is 8 or less to satisfy the purpose. In the complex compound of aliphatic primary amines represented by the general formula R′-NH ₂ and boron trifluoride used in the present invention to ensure infrared reflective properties,
The number of carbon atoms in the alkyl group represented by R′ is 3 mm in plate thickness.
On only one side of the soda glass, the carbon number of the aliphatic primary amine is 1, per 100 parts by weight of diethoxytin.
Visible light average for infrared reflective glass with an infrared reflective film of 2000 Å using a homogeneous mixed composition of alcohol to which 8 parts by weight of boron trifluoride complex compounds modified as 2, 4, 5, 6, and 8 were added. The transmittance (%) was determined and the curve shown in FIG. 4 was obtained. From this result, the effective carbon number of R' in the complex compound of aliphatic primary amines and boron trifluoride (BF ₃ :NH ₂ -R') is 6 or less. Complex compounds of aliphatic primary amines and boron trifluoride that satisfy this condition include boron trifluoride methylamine complex, boron trifluoride ethylamine complex, boron trifluoride propylamine complex, and boron trifluoride propylamine complex. They are boron butylamine complex compound, boron trifluoride pentylamine complex compound, and boron trifluoride hexylamine complex compound. The amount of the complex compound of aliphatic primary amines and boron trifluoride to be combined with the organic stannous compound is not particularly limited in the present invention, but the amount of the complex compound with respect to the organic stannous compound can be adjusted as appropriate. When the thickness of the infrared reflective film is set to 2000 Å using the changed alcohol uniformly dissolved composition, the infrared reflective properties of the infrared reflective glass are as follows: infrared wavelength 3.75μ (500℃)
As shown in Figure 5, the vertical axis is the reflectance and the horizontal axis is the amount of the complex compound of aliphatic primary amines and boron trifluoride. On the other hand, it is preferably 3 parts by weight or more. However, from the perspective of ensuring good transparency
It is preferably within 15 parts by weight. In the composition for forming an infrared reflective film in the present invention, palladium chloride, which has a good average transmittance of visible light and is particularly effective in removing coloration from a film when sprayed onto a hot substrate, is divalent palladium (PdCl ₂ ).
It is. In addition, chloroplatinic acid is chloroplatinic acid (H ₂
[PtCl ₄ ]) or platinic chloride (H ₂
[PtCl ₆ ]), it meets the purpose of the present invention, and there is no particular problem even if it contains water of crystallization. Although the range of the amount of palladium chloride or chloroplatinic acid to be used for the organic stannous compound used in the present invention is not particularly limited,
The minimum amount necessary to contribute to the thermal decomposition of the organic stannous compound may be determined in consideration of the price of the infrared reflective glass to be obtained. It is important to mix the various agents in the composition for forming an infrared reflective film and maintain a uniform solution system in order to form an infrared reflective glass that satisfies the object of the present invention. Alcohol-based solvents are particularly effective for achieving this, and mixtures of small amounts of monohydric alcohols, dihydric alcohols (glycols), and polyhydric alcohols are used, and if they are selected and used appropriately, there will be no particular problem. . The conditions for the base material necessary to form infrared reflective glass are not particularly limited, as long as it is an inorganic material such as ceramic, porcelain, or hollow and has heat resistance that allows the formation of a film. However, if it is intended to be used as a peephole, transparent materials such as soda glass or heat-resistant glass are preferred. Example 1 Dibutoxytin 92.0 parts by weight Boron trifluoride ethylamine complex 8.0 parts by weight Hexyl alcohol 16.5 parts by weight Butyl alcohol 16.5 parts by weight The above materials were uniformly mixed to prepare a composition for forming an infrared reflective film. Plate thickness 3mm, size 100×
A 100 mm piece of soda glass was immersed in this composition, pulled up, dried at 150°C for 30 minutes, repeated the same process, wiped off one side with a cloth soaked in acetone, and dried at 550°C for 30 minutes. It was fired to form an infrared reflective glass. This film thickness is
Manufactured by PANKPRECISION INDUSTRIES LTD
Using TALYSTEP-1, a part of the infrared reflective film was removed by reduction using zinc powder and hydrochloric acid, and the height difference between the exposed glass surface and the exposed glass surface was measured to be 1400 Å. This infrared reflective glass is uncolored and has a wavelength range of 0.4 to 2.5μ when measured using a spectrophotometer UV-120 device manufactured by Shimadzu Corporation.
The average visible light transmittance was found to be 74.0%. The infrared reflection characteristics were measured by the same method as shown above, and the results are shown in Table 2, No. 1. Example 2 Dibutoxytin 92.0 parts by weight Boron trifluoride ethylamine complex 8.0 parts by weight Chloroplatinic acid [H ₂ (PtCl ₆ )・6H ₂ O] 0.5 parts by weight Hexyl alcohol 25.0 parts by weight Butyl alcohol 25.0 parts by weight The above materials They were mixed uniformly to prepare a composition for forming an infrared reflective film. Plate thickness 3mm, size 100×
A 100 mm piece of soda glass was heated to 600°C and sprayed onto one side of the glass using an air pressure of 2.0 kg/cm ² to form an infrared reflective glass having an infrared reflective film of 3000 Å. This glass had no coloration, had an average visible light transmittance of 71%, and had the results of infrared reflection characteristics shown in Table 2, No. 2. Example 3 In the same manner as in Example 1, an infrared reflective glass was formed using the composition for forming an infrared reflective film shown in Example 2 by a cold coating and firing method.
The film thickness of this reflective glass was 1200 Å, no clouding or coloring was observed, the average transmittance of visible light was 73%, and the results of infrared reflection characteristics shown in Table 2, No. 3 were obtained.

[Table] Effects of the Invention As is clear from the above description, the composition for forming an infrared reflective film of the present invention can be applied to a hot substrate spraying method and a cold coating and firing method, and can be applied to a single firing. It is free from coloration, has excellent average visible light transmittance, and can easily form a good infrared reflective film. In addition, unlike in the case of compositions containing stannous chloride as a chemical, which were conventionally used in the process of forming infrared reflective glass, there is no generation of large amounts of hydrochloric acid gas, there is almost no corrosiveness to equipment, and there is no exhaust gas. Pollution treatment is also extremely light. The composition for forming infrared reflective glass of the present invention can secure a film thickness of 1000 Å or more by any film forming method, and therefore has excellent scratch resistance when used in various applications as infrared reflective glass. Secured. In addition, since the infrared reflective glass formed from the composition of the present invention has good conductivity, it can also be used as a transparent conductive film, such as electrodes for liquid crystal displays, resistors, etc.

[Brief explanation of drawings]

Figure 1 is a comparison diagram of the infrared reflection characteristics of a conventional product and an example of the present invention in the infrared wavelength range of 3.4 to 7.0μ, and Figure 2 is a comparison diagram of the infrared reflection characteristics of the example of the present invention in the same infrared wavelength range as Figure 1. Figure 3 shows the infrared reflection characteristics of the change in film thickness of the infrared reflective glass using the composition for forming a reflective coating. Figure 4 shows the change in the thickness of the infrared reflective film depending on the size of the infrared reflection film, and Figure 4 shows the infrared reflection caused by changes in the alkyl groups forming the amine of the boron trifluoride primary amines combined in the composition of the example of the present invention. FIG. 5 is a graph showing the average visible light transmittance of the film, and is a graph showing the relationship between the infrared reflection characteristics and the amount of boron trifluoride primary amines combined with the organic stannous compound.

Claims (1)

[Scope of Claims] 1. Alkoxide compounds represented by the general formula Sn(OR) ₂ and acyloxy compounds represented by the general formula Sn(OOCR) ₂ (wherein R is a carbon atom having 4 to 8 carbon atoms)
represents an alkyl group. ) and 100 parts by weight of at least one selected from the group consisting _of
A mixture of 3 to 15 parts by weight of a complex compound of an aliphatic primary amine represented by (where R' represents an alkyl group having 1 to 6 carbon atoms) and boron trifluoride was mixed with methyl A composition for forming an infrared reflective film, characterized in that it is uniformly mixed with alcohol. 2 Alkoxide compounds represented by the general formula Sn(OR) ₂ and acyloxy compounds represented by the general formula Sn(OOCR) ₂ (wherein R is a carbon number of 4 to 8
represents an alkyl group. ) and 100 parts by weight of at least one selected from the group consisting _of
Palladium chloride or platinum chloride is added to 3 to 15 parts by weight of a complex compound of an aliphatic primary amine represented by (where R' represents an alkyl group having 1 to 6 carbon atoms) and boron trifluoride. 1. A composition for forming an infrared reflective film, characterized in that a composition obtained by mixing a mixture with an acid and methyl alcohol is uniformly mixed with methyl alcohol.