JP2001316134A - Heat-reflective colored film-coated glass and sputtering target - Google Patents

Abstract

(57) [Summary] [Problem] To provide a heat-ray reflective colored film-coated glass which is excellent in silver print coloring without causing whitening defect in ceramic color print. Heat ray reflection coloring obtained by heat-treating a glass provided with a film containing cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide laminated on one side of a glass substrate. Film-coated glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-reflective colored film-coated glass and a sputtering target.

[0002]

2. Description of the Related Art In recent years, as one means for improving the cooling efficiency of vehicles such as automobiles, solar energy transmittance (the ratio of directly transmitted energy to incident solar energy) is known.
The heat ray reflection glass having a low temperature is being used. There are two ways to lower the solar energy transmittance: a method using colored glass, and a method of coating a transparent soda lime glass or a colored glass with high transmittance with a colored film with excellent heat ray reflectivity. The latter is more desirable in terms of properties and heat ray reflectivity.

[0003] Such a heat-reflective colored film-coated glass is required to have a low solar energy transmittance, a high visible light transmittance as compared with the solar energy transmittance, and to have a sufficient transmittance for vehicles and the like. It is durable, has a color tone that does not impair the design of the vehicle, and has high sheet resistance. The heat ray reflective colored film-coated glass satisfying these requirements is an oxide containing cobalt oxide as a main component, iron in an amount of 10% by mass or more (ratio to the total metal amount, the same applies to the following description), and chromium in an amount of 5% by mass or more. Glass in which a film is formed to a thickness of 10 to 50 nm by a spray method is known. However, such a glass has a problem that there are many irregularities in film thickness, composition, and the like, and the yield is poor.

[0004]

Further, it has been conventionally possible to screen-print a ceramic paste in which a ceramic color composition is pasted on a peripheral portion or a central portion of a window glass of an automobile, dry it, and bake it in a bending process. Is being done. The ceramic color paste is used to prevent the adhesive from being deteriorated by ultraviolet rays and to prevent the adhesive portion from being seen from outside the vehicle by forming a colored opaque layer by baking the peripheral portion of the glass or the like. As such a ceramic color composition, a mixture of a glass frit and a heat-resistant coloring pigment is known, and is usually used in a form exhibiting a black or dark gray color tone. Such is called a black ceramic paint. However, when a conventional oxide film containing cobalt oxide as a main component and containing 10% by mass or more of iron and 5% by mass or more of chromium was formed by a spray method, such a ceramic color paste is printed. There is a problem that the color becomes whitish and the color is poor.

Further, when used as a rear glass of an automobile, a so-called silver print, in which a silver paste as a heat generating material is linearly printed and fired to prevent fogging, is performed. Glass formed by spraying an oxide film containing 10% by mass or more of iron and 5% by mass or more of chromium also has a problem that the silver print has poor coloration.

On the other hand, it is also known in the literature to obtain a glass on which a film containing cobalt oxide as a main component and containing iron oxide and chromium oxide is formed by a sputtering method. For example, JP-A-9-30837 discloses that
A heat ray reflective glass in which a coating of these oxides is formed with a metal composition of 65 to 96% by mass of cobalt, 2 to 25% by mass of chromium, and 2 to 33% by mass of iron is described. As a method, a sputtering method is mentioned. However, the deposition rate is much faster than the conventional method, and it is suitable for mass production of a film having a uniform thickness and composition. In the sputtering method, since the alloy target made of cobalt and iron is a ferromagnetic material, magnetic flux of the magnetron is not formed on the target surface, so that it cannot be practically used. Also in the above publication, there is no description about the sputtering method, and only the spray method is described in the examples. Therefore, the heat ray reflective colored film-coated glass is, in fact, cannot be manufactured by using the magnetron sputtering method, and also causes unevenness in the case of manufacturing by the above-described spray method, a whitish color defect in ceramic color print, The problem of poor silver print coloring has not been solved.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-reflective colored film-coated glass which is excellent in color development of silver print without causing whitening defect in ceramic color print. Another object of the present invention is to provide a heat-ray reflective colored film-coated glass which can be produced by a sputtering method, has excellent film thickness and composition uniformity, and has excellent heat-ray reflectivity.

[0008]

As a result of intensive studies, the present inventor has found that a glass substrate and cobalt oxide, iron oxide, titanium oxide and / or tantalum laminated on one side of the glass substrate. A heat-reflective colored film-coated glass comprising an oxide and a specific film containing the same, and a heat-ray reflective colored film-coated glass obtained by heat-treating the heat-reflective colored film-coated glass, have low solar energy transmittance. The basics are that the visible light transmittance is higher than the solar energy transmittance, that it has sufficient durability for vehicles, etc., that it has a color tone that does not impair the design of vehicles, etc., and that sheet resistance is high. Completed the present invention, not only satisfying the required characteristics, but also excellent color development in silver print without causing whitening defect in ceramic color print It was. As a result of earnest research, the present inventors have found that a specific metal sputtering target containing cobalt, iron, titanium and / or tantalum, and a cobalt oxide, an iron oxide, a titanium oxide and / or Alternatively, the present inventors have found that a specific metal oxide sputtering target containing tantalum oxide can be used in a magnetron sputtering method and is suitably used for laminating a film of the heat ray reflective colored film-coated glass, and completed the present invention. did.

[0009] The present invention provides a heat ray reflection comprising a glass substrate, and a film containing cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide laminated on one side of the glass substrate. A glass coated with a colored film, wherein the coating is such that the amount of cobalt, iron, and titanium and tantalum relative to the total amount of metal is: cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, total of titanium and tantalum. : 2 to 10% by mass.

The present invention also provides a glass coated with a heat-reflective colored film obtained by heat-treating the glass coated with a heat-reflective colored film.

The heat-reflective colored film-coated glass after the heat treatment is
The surface sheet resistance of the film-coated surface is 10 ^FiveΩ / □ or more
Is preferred.

The heat-reflective colored film-coated glass after the heat treatment is
The visible light transmittance is 20 to 40%, and the visible light reflectances of the film-coated surface and the other surface are 20 to 40% and 1 respectively.
It is preferably from 0 to 25%.

Further, the present invention relates to a metal sputtering target containing cobalt, iron, titanium and / or tantalum, wherein cobalt, iron, and cobalt with respect to the total amount of metal in the metal sputtering target.
A metal sputtering target (hereinafter, also referred to as “sputtering target A”) in which the amount of titanium and tantalum is cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, and the total of titanium and tantalum: 2 to 10% by mass. .)I will provide a.

Further, the present invention relates to a metal oxide sputtering target containing a cobalt oxide, an iron oxide, a titanium oxide and / or a tantalum oxide, wherein A metal oxide having a composition of cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, and total of titanium and tantalum: 2 to 10% by mass with respect to the amount of metal, based on the amount of metal. A sputtering target (hereinafter, also referred to as “sputtering target B”) is provided.

Further, the present invention is characterized in that a film is laminated on one surface of a glass substrate by sputtering using a sputtering target A in a sputtering gas atmosphere containing an oxidizing gas. Provided is a method for producing a glass coated with a reflective colored film.

Further, according to the present invention, a film is formed on one surface of a glass substrate by sputtering using a sputtering target B in a sputtering gas atmosphere containing no oxidizing gas or in a sputtering gas atmosphere containing an oxidizing gas. And a method for producing the glass coated with a heat-reflection colored film.

Furthermore, the present invention includes a step of applying a ceramic color paste and / or a silver paste to the glass coated with the heat ray reflective colored film obtained by any one of the above-mentioned production methods, and a step of subsequently performing a heat treatment. A method for producing the heat ray reflective colored film-coated glass is provided.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The heat-reflective colored film-coated glass of the present invention is a heat-reflective colored film-coated glass comprising a glass substrate and a predetermined film laminated on one side of the glass substrate.

The glass substrate used for the heat ray reflective colored film-coated glass of the present invention is not particularly limited, and is a colorless transparent soda lime glass, green, or the like which is generally widely used.
A heat ray absorbing glass colored in bronze, gray, or the like, or a glass having heat ray absorbing / ultraviolet absorbing properties can be used.

[0020] The coating of the glass coated with the heat ray reflective colored film of the present invention contains cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide. In the present invention, within the following composition range, in addition to these oxides, niobium oxide, molybdenum oxide, manganese oxide, silicon oxide, copper oxide, vanadium oxide, zinc oxide, It can contain zirconium oxide, carbon and the like. The coating is cobalt based on the total amount of metal,
The amounts of iron and titanium and tantalum are 70 to 93% by mass of cobalt, 5 to 20% by mass of iron, and 2 to 10% by mass of titanium and tantalum in total. With the above composition, a film can be formed by a magnetron sputtering method. Preferably, cobalt: 82 to 90% by mass, iron: 5 to 8% by mass, the total of titanium and tantalum:
5 to 10% by mass. The thickness of the coating can be selected according to the desired optical properties of the glass coated with a heat-reflective colored film described later. For example, the visible light transmittance of the heat ray reflective colored film-coated glass is set to 20 to 40%, and the visible light reflectance of the film-coated surface and the other surface is set to 20 to 40% and 1 respectively.
In the case of 0 to 25%, the thickness of the coating is 10 to 80 n
m is preferable.

In the present invention, for the purpose of improving the durability and changing the reflectance, silicon, titanium, zinc,
A layer made of an oxide or nitride of at least one element selected from the group consisting of tin, copper, zirconium, manganese, niobium, and aluminum can be provided.

One preferred embodiment of the glass coated with a heat-reflective colored film of the present invention is a glass coated with a heat-reflective colored film obtained by heat-treating the above-mentioned glass coated with a heat-reflective colored film. Details of the heat treatment will be described later.

The glass coated with a heat ray reflective colored film of the present invention has excellent heat ray reflection ability. Specifically, the solar energy transmittance is preferably smaller than the visible light transmittance, and particularly preferably 40% or less.

The glass coated with a heat-reflective colored film of the present invention preferably has a surface sheet resistance of 10 ⁵ Ω / □ or more on the film-coated surface. When the thickness is within the above range, the transparency of radio waves from radios, televisions, mobile phones, car phones, and the like can be sufficiently ensured in vehicles such as automobiles. Further, in the case where the glass coated with a heat ray reflective colored film of the present invention is used as a rear glass of an automobile to form an antenna, the surface sheet resistance of the film-coated surface is preferably 10 ⁶ Ω / □ or more.

The heat-reflective colored film-coated glass of the present invention has a visible light transmittance of 20 to 40%, and the visible light reflectance of the film-coated surface and the other surface is 20 to 40% and 10%, respectively.
２５25% is an example of a preferable value. This is because when the content is in the above range, it is suitable for applications such as automobiles.

Although the reason for the glass coated with a heat ray reflective colored film of the present invention is not known, an oxide film containing a conventional cobalt oxide as a main component and containing 10% by mass or more of iron and 5% by mass or more of chromium is used. Unlike glass formed by a spray method, when printed with a ceramic color paste such as a black ceramic paint, the color becomes whitish and the coloring does not become defective.

Although the reason for the glass coated with a heat ray reflective colored film of the present invention is not known, an oxide containing a conventional cobalt oxide as a main component and containing 10% by mass or more of iron and 5% by mass or more of chromium. Unlike the glass in which the film is formed by the spray method, the silver print is excellent in coloring.

The method for producing the heat-reflective colored film-coated glass of the present invention is not particularly limited. Examples include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method and a sputtering method; and a thermal decomposition method such as a spray method and a CVD method. Examples of the sputtering method include a DC sputtering method, a high-frequency sputtering method, and a magnetron sputtering method. Alternatively, reactive sputtering can be performed using a reactive gas. The spray method is, for example,
A solution spray method and a powder method are mentioned. Either the online spray method or the offline spray method can be used. The CVD method includes, for example, a thermal CVD method, a plasma CVD method, and a photo CVD method, and these are classified into a normal pressure CVD method and a reduced pressure CVD method according to the pressure at the time of coating. Usually, a normal pressure thermal CVD method is used. Either the online CVD method or the offline CVD method can be used.

Among them, the sputtering method is preferred in terms of excellent film thickness uniformity, composition uniformity and film thickness controllability, and high yield, and particularly, the magnetron sputtering method is preferable in terms of excellent film formation rate and the like. .

Hereinafter, the method for producing the glass coated with the heat ray reflective colored film of the present invention by the sputtering method will be described. The following manufacturing method is one of preferred examples, and the method for manufacturing the heat-reflective colored film-coated glass of the present invention is not limited to this.

The sputtering target is, for example, a metal sputtering target containing cobalt, iron, titanium and / or tantalum, or a cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide. A contained metal oxide sputtering target can be used, and among them, it is preferable to use the sputtering target A of the present invention or the sputtering target B of the present invention. The structure and structure of these sputtering targets are not particularly limited, and two or more metals or metal oxides may form one crystal phase, may be a solid solution, or may be two or more metals. Alternatively, a crystal phase or an amorphous phase of a metal oxide may be mixed. In addition, the sputtering targets A and B of the present invention are suitably used for producing the heat-reflective colored film-coated glass of the present invention. However, cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide are preferably used. Can be widely used for the production of a coating containing, for example.

(1) When using a sputtering target A The sputtering target A according to the present invention comprises cobalt,
A metal sputtering target containing iron and titanium and / or tantalum, wherein the amount of cobalt, iron, and titanium and tantalum relative to the total amount of metal in the metal sputtering target is: cobalt: 70 to 93% by mass; It is a metal sputtering target having a composition of iron: 5 to 20% by mass and total of titanium and tantalum: 2 to 10% by mass.

On one surface of the glass substrate, the above sputtering target A is used for sputtering in a sputtering gas atmosphere containing an oxidizing gas.
The coatings can be laminated to produce a heat-reflective colored film-coated glass.

A sputtering gas containing an oxidizing gas is used. The oxidizing gas includes, for example, oxygen and ozone, and may be a mixed gas of oxygen and ozone. The sputtering gas is not particularly limited as long as it contains the above oxidizing gas. For example, a mixed gas of an oxidizing gas and an inert gas can be used. Examples of the inert gas include helium, neon, argon, krypton, and xenon. Among them, argon is preferable in terms of economy and ease of discharge. These are used alone or in combination of two or more.

When the sputtering target A is used, a magnetron sputtering apparatus excellent in film-forming speed or the like is usually used, but a sputtering apparatus that does not use a magnetic field can also be used. As the power supply, either a DC power supply or a high-frequency power supply can be used.

(2) When Using Sputtering Target B The sputtering target B of the present invention is a metal oxide sputtering target containing a cobalt oxide, an iron oxide, a titanium oxide and / or a tantalum oxide. The amount of cobalt, iron, titanium, and tantalum relative to the total amount of metals in the metal oxide sputtering target is as follows: cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, and the total of titanium and tantalum: 2 A metal oxide sputtering target having a composition of 10 to 10% by mass.

On one surface of the glass substrate, a film is laminated by sputtering using the above sputtering target B in a sputtering gas atmosphere containing no oxidizing gas or in a sputtering gas atmosphere containing an oxidizing gas. And a glass coated with a heat reflective colored film.

As the sputtering gas, a gas containing no oxidizing gas may be used, or a gas containing an oxidizing gas may be used. Examples of the sputtering gas containing no oxidizing gas include an inert gas such as helium, neon, argon, krypton, and xenon. Among them, argon is preferable in terms of economy and ease of discharge. These are used alone or in combination of two or more. As in the case (1), a mixed gas of an oxidizing gas and an inert gas can be used.

The apparatus used for sputtering is as follows:
This is the same as the case (1).

As described above, when the sputtering target A or B of the present invention is used, the heat ray reflective colored film-coated glass of the present invention can be manufactured by performing a sputtering method such as a magnetron sputtering method. Therefore, the industrial production of the glass coated with a heat-reflection colored film of the present invention is easy and economically advantageous. As described above, it is preferable to use the sputtering target A or B of the present invention for the heat-ray reflective colored film-coated glass of the present invention, but instead of a so-called composite made of a different kind of metal material or metal oxide material. Targets can also be used. For example, instead of the sputtering target A, a cobalt sputtering target on which an iron chip and a titanium chip are mounted, or a cobalt sputtering target on which an iron chip and a tantalum chip are mounted can be used.

In the production of the glass coated with a heat-reflective colored film of the present invention, it is preferable to heat-treat the film after laminating the film. By the heat treatment, the surface sheet resistance of the film-coated surface is improved, and the surface sheet resistance of the film-coated surface is preferably 10 ⁵ Ω /
□ or more, radio wave permeability is improved. Therefore, it is suitably used for vehicles and buildings. The heat-reflective colored film-coated glass before the heat treatment has a lower radio wave permeability than that after the heat treatment, but is suitably used for construction. Further, the visible light reflectance of the film-coated surface is reduced by the heat treatment, preferably to 20 to 40%, which is one of the values suitable for vehicles.

The heat treatment is not particularly limited, and conditions can be changed according to desired optical characteristics. Among them, as one of the preferred specific examples, a heat treatment is performed at 500 to 700 ° C. for 3 to 5 minutes in an atmosphere containing oxygen (for example, an air atmosphere).

The heat-ray reflective colored film-coated glass of the present invention is suitably used for vehicles such as automobiles. Glass used for automobiles and the like is 630-69 when bent.
Heat treatment is performed at 0 ° C. or more for about 3 to 7 minutes. Therefore, the heat-ray reflective colored film-coated glass before the heat treatment can be subjected to bending, and the heat treatment at that time can be used.

When the heat ray reflective colored film-coated glass of the present invention is printed with a ceramic color paste such as black ceramic paint or silver print, 630-69.
Heat treatment (firing) is performed at 0 ° C. or more for about 3 to 7 minutes. Therefore, the heat-reflective colored film-coated glass after the heat treatment of the present invention can be obtained by performing printing with a ceramic color paste or silver print on the heat-reflective colored film-coated glass before the heat treatment, and utilizing the heat treatment at that time. it can. Further, the bending and the printing using the ceramic color paste or the silver printing may be performed simultaneously, and the heat treatment at that time may be used.

That is, as a method for producing the glass coated with a heat-reflective colored film obtained by the heat treatment of the present invention, the glass coated with the heat-ray-reflective colored film obtained by the above-mentioned method (1) or (2) is added to a ceramic color paste And / or a step of applying a silver paste, and then performing a heat treatment. The application of the ceramic color paste and / or the silver paste can be performed by a general method. For example, there is a method of screen printing using a screen printing machine. When applying both ceramic color paste and silver paste, they may be applied separately,
You may apply simultaneously. The conditions of the heat treatment are the same as in the case where these are not applied. Examples of the ceramic color paste include those containing a crystalline glass frit (and / or an amorphous glass frit), a heat-resistant coloring pigment, and a refractory filler. The ceramic color paste is, for example, uniformly mixing a crystalline glass frit (and / or an amorphous glass frit), a heat-resistant coloring pigment and a refractory filler in an organic vehicle,
It is used after adjusting to a viscosity suitable for coating.

The application of the glass coated with a heat ray reflective colored film of the present invention is not particularly limited. For example, it is used for vehicles such as automobiles and for construction. The heat-ray reflective colored film-coated glass of the present invention may be a laminated glass or a multi-layer glass.

As described above, the glass coated with a heat-reflective colored film of the present invention not only satisfies the basic required characteristics, but also does not cause whitening defects in ceramic color printing and is excellent in silver print coloring. So
It is suitably used for various applications.

[0048]

The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. 1. Production of heat-reflection colored film-coated glass (Example 1) 3.5 mm thick cut into 100 mm square
Green colored soda lime glass with cerium oxide powder
And neutral detergent, rinse with pure water and ethanol,
The substrate glass was used. The green colored soda lime gala
Has a visible light transmittance of 81.6% and a visible light reflectance of 7.4.
%, The solar transmittance is 59.5%, and the solar reflectance is 6.2%.
there were. A 5 mm square iron chip 40 is attached to the substrate glass.
1 with 20 pieces and 20 5mm square titanium chips
52.4mm cobalt sputtering target
(Surface area ratio on sputtering target surface:
Baltic 91.8%, iron 5.5%, titanium 2.7%)
And a DC magnetron sputtering device _TwoMoth
Pressure 2.6 × 10^-1Pa, input power 0.5 kW, film formation
The film is formed under the condition of 140 seconds, and a film having a thickness of 30 nm is formed.
Then, a glass coated with a heat ray reflective colored film of the present invention was obtained.

Next, after adjusting the viscosity of the ceramic color paste and the conductive silver paste to a viscosity suitable for screen printing, the ceramic color paste is printed by a screen printing machine on the film-coated surface of the obtained heat ray reflective colored film-coated glass. And dried, and then a conductive silver paste was printed by a screen printer. After drying at 120 ° C. for 10 to 15 minutes, heat treatment was performed in a belt furnace for about 15 minutes.
The time maintained at 500 ° C or more is about 6 minutes, and the maximum temperature is 6
The time held at 50 ° C. was about 3 minutes. After the heat treatment, it was allowed to cool.

(Example 2) A diameter 15 on which 40 5 mm square iron chips and 20 5 mm square titanium chips were mounted.
Instead of the 2.4 mm cobalt sputtering target, a 152.4 mm diameter cobalt sputtering target (40 surface area ratio on the surface of the sputtering target, on which 40 5 mm square iron chips and 20 5 mm square tantalum chips are mounted) 91.8% cobalt,
Except for using iron 5.5% and tantalum 2.7%), a heat-ray reflective colored film-coated glass of the present invention was obtained in the same manner as in Example 1. Next, after printing and heat-treating the obtained heat-ray reflective colored film-coated glass in the same manner as in Example 1, the glass was allowed to cool.

2. Composition of Coating of Heat-Reflective Colored Film-Coated Glass The coating composition of the coated glass of the heat-reflective colored film before and after heat treatment in Examples 1 and 2 was analyzed. The composition was analyzed by elemental analysis using a high frequency inductively coupled plasma mass spectrometer. As a result, in Example 1, the amounts of cobalt, iron, and titanium were 87% by mass of cobalt, 10% by mass of iron, and 3% by mass of titanium with respect to the total amount of metals in the coating before and after the heat treatment. Was. In Example 2, the amounts of cobalt, iron, and tantalum relative to the total amount of metals in the coating before and after the heat treatment were all cobalt:
87% by mass, iron: 10% by mass, tantalum: 3% by mass.

3. Measurement of Solar Energy Transmittance The heat ray reflective colored film-coated glass obtained in Examples 1 and 2 after the heat treatment was measured for the solar energy transmittance using a spectrometer. As a result, the solar energy transmittance was 29% in each case.

4. Measurement of Surface Sheet Resistance The heat-reflective colored film-coated glass obtained in Examples 1 and 2 after the heat treatment was used to measure the surface sheet resistance of the film-coated surface using a sheet resistance measuring device. As a result, the surface sheet resistance of each of the film-coated surfaces was 2.8 × 10 ⁹ Ω / □.

5. Measurement of Visible Light Transmittance and Visible Light Reflectance Regarding the glass coated with a heat-reflective colored film after heat treatment obtained in Examples 1 and 2, the visible light transmittance and the visible light reflectance of the film-coated surface and the other surface By using a spectrometer
The measurement was performed using a light source. As a result, the visible light transmittance was 33% for all, and the visible light reflectance of the film-coated surface was 34% for all.
%, And the visible light reflectance of the other surface was 20%.

6. Measurement of Scratch Resistance The heat-reflective colored film-coated glass obtained in Examples 1 and 2 after the heat treatment was subjected to 4.9 N using a Taber tester.
A Taber test was performed on the film-coated surface side under the condition of 1,000 rotations under a load of and the visible light transmittance before and after the Taber test was compared. As a result, the change in the visible light transmittance was + 16% in all cases.
Since it was + 20% or less, it had practically sufficient scratch resistance.

7. Measurement of Chemical Resistance The heat-reflective colored film-coated glass obtained in Examples 1 and 2 after the heat treatment was coated with 0.05 mol / L sulfuric acid aqueous solution or 0.1 mol / L sulfuric acid aqueous solution.
It was immersed in a 1 mol / L caustic soda aqueous solution at room temperature for 20 hours for 24 hours, and the visible light transmittance before and after immersion and the visible light reflectance of the film-coated surface and the other surface were compared. As a result, in any of the heat-ray reflective colored film-coated glasses, when a sulfuric acid aqueous solution or a caustic soda aqueous solution is used, the change in visible light transmittance and the visible light reflectance of the film-coated surface and the other surface are smaller than 1%. Value.

8. Measurement of Color Tone of Ceramic Color Print and Silver Print The color tone of the heat-reflective colored film-coated glass obtained in Examples 1 and 2 after heat treatment was measured using a color meter from the glass surface of the ceramic color paste portion. As a result, the color tone was L = 39, a = 7.
5, b = -0.5. Compared with conventional glass in which an oxide film containing 63% by mass of cobalt, 26% by mass of iron, and 11% by mass of chromium is formed by a spray method, the brightness is low and the color tone is close to neutral. Color. Further, the silver paste portion, in the glass on which the film is formed by the conventional spray method, gradually develops a color, and good color cannot be obtained, whereas in the sample of the present invention, the sample develops a reddish brown, Good color development could be obtained.

[0058]

The heat-ray reflective colored film-coated glass of the present invention comprises:
It is suitable as a window glass for automobiles because it not only satisfies the basic required characteristics, but also does not cause whitening defects in ceramic color prints and has excellent silver print coloration. In particular, the heat-reflection colored film-coated glass after heat treatment has high radio wave transmittance and the visible light reflectance of the film-coated surface is one of suitable values for vehicles. This is one of preferred embodiments of glass. Further, the sputtering targets A and B of the present invention are suitably used for the production of the heat-reflective colored film-coated glass of the present invention, and further, cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide. It can be widely used in the production of coatings containing substances and is useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C23C 14/34 C23C 14/34 A F term (Reference) 4F100 AA17B AA21B AA23B AB24B AD00B AG00A BA02 BA10A BA10B CC00 EH662 EJ422 GB31 GB32 HB00B JG04B JL10B JM02B JN01 JN06B YY00 YY00B 4G059 AA01 AB09 AC06 AC08 EA04 EB04 GA01 GA04 GA12 4K029 AA09 BA43 BC07 BD09 CA06 DC04 DC05 GA01

Claims (9)

[Claims] 1. A heat ray reflective colored film comprising a glass substrate and a film laminated on one side of the glass substrate, the film containing cobalt oxide, iron oxide, titanium oxide and / or tantalum oxide. A coated glass, the coating comprising cobalt, iron, and total metal.
A glass coated with a heat-reflective colored film, wherein the amount of titanium and tantalum is 70 to 93% by mass of cobalt, 5 to 20% by mass of iron, and 2 to 10% by mass of titanium and tantalum. 2. Heat-reflective colored film-coated glass obtained by heat-treating the heat-reflective colored film-coated glass according to claim 1. 3. The surface sheet resistance of the film-coated surface is 10 ⁵ Ω /
The glass coated with a heat-reflective colored film according to claim 1 or 2, which is not less than □. 4. The visible light transmittance is 20 to 40%, and the visible light reflectance of the film-coated surface and the other surface is 20 to 4%, respectively.
The heat-ray reflective colored film-coated glass according to any one of claims 1 to 3, which is 0% and 10 to 25%. 5. A metal sputtering target containing cobalt, iron, titanium and / or tantalum, wherein the amount of cobalt, iron and titanium and tantalum relative to the total amount of metal in the metal sputtering target is: A metal sputtering target having a composition of cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, and total of titanium and tantalum: 2 to 10% by mass. 6. A metal oxide sputtering target containing a cobalt oxide, an iron oxide, a titanium oxide and / or a tantalum oxide, wherein the amount of cobalt relative to the total amount of metal in the metal oxide sputtering target is A metal oxide sputtering target having the following composition: iron, iron, and titanium and tantalum in the following composition: cobalt: 70 to 93% by mass, iron: 5 to 20% by mass, and total of titanium and tantalum: 2 to 10% by mass. 7. A film is laminated on one surface of a glass substrate by sputtering using a sputtering target according to claim 5 in a sputtering gas atmosphere containing an oxidizing gas. Terms 1, 3
Or the method for producing a heat-ray reflective colored film-coated glass according to item 4. 8. Sputtering on one surface of a glass substrate in a sputtering gas atmosphere containing no oxidizing gas or a sputtering gas atmosphere containing an oxidizing gas using the sputtering target according to claim 6; 5. The method for producing a heat-reflective colored film-coated glass according to claim 1, wherein a film is laminated. 9. A process for applying a ceramic color paste and / or a silver paste to the glass coated with a heat-reflective colored film obtained by the production method according to claim 7 or 8, and thereafter performing a heat treatment. Item 5. The method for producing a heat-ray reflective colored film-coated glass according to any one of Items 2 to 4.