WO2006098451A1

WO2006098451A1 - Automatic heat conditioning color tone conditioning light shielding glass and method for producing the same

Info

Publication number: WO2006098451A1
Application number: PCT/JP2006/305457
Authority: WO
Inventors: Ping Jin
Original assignee: National Institute Of Advanced Industrial Science And Technology
Priority date: 2005-03-17
Filing date: 2006-03-17
Publication date: 2006-09-21
Also published as: JP5147034B2; JP2006256902A

Abstract

An automatic heat conditioning color tone conditioning light shielding glass, and its production method. Vanadium dioxide based light control glass having a drawback that transmittance of visible light is low is utilized effectively as light shielding glass by reversal in idea, and color tone can be conditioned by employing a unique color tone conditioning method utilizing a principle of complementary color. Window glass of buildings, vehicles and other mobiles, especially, new glass having a plurality of functions such as energy saving, health and comfortableness, privacy protection, and color tone conditioning can be provided, and its production method can also be provided.

Description

Automatic thermal color-harmonic shading glass and manufacturing method

Technical field

TECHNICAL FIELD [0001] The present invention relates to an automatic heat-control color-harmonic light-shielding glass and a manufacturing method. More specifically, the present invention relates to a visible light transmittance of 70% or less, excellent light-shielding properties, and infrared transmittance according to environmental temperature. Can be adjusted automatically, and the color tone such as transparent color can be adjusted freely according to the preference, the building, and the exterior of the moving body, so it can be used as a window glass for moving bodies such as windows of buildings and automobiles. It is a new environmentally friendly new product that is expected to be applied and spread as an environmentally friendly new product with functions such as energy saving, health and comfort, and privacy protection. The present invention fundamentally solves the problem of diacid-vanadium-based dimming and heat-controlling glass that has been difficult to put into practical use, in particular, the problem that the base glass is colored to a strong inherent yellow color. It is a new product that can harmonize the color tone with an arbitrary color tone, and provides an automatic thermal color tone light-shielding glass having a color tone harmony function.

Background art

[0002] As an energy-saving window glass that can be dimmed, glass that automatically dims, for example, electochromic (EC: reversibly coloring and decoloring by applying voltage) glass gas Chromic (GC: repeated coloring and decoloring by introduction of hydrogen gas) glass has been studied. However, these windowpanes have high dimming capability, but the structure is complex, and additional equipment (voltage application system and gas introduction system) is required for dimming. There was a drawback of becoming higher.

[0003] On the other hand, vanadium dioxide (VO) crystal is a thermocouple due to the semiconductor 'metal phase transition at 68 ° C.

2

It is well known that it exhibits chromic properties (reversible changes in optical properties depending on temperature), and that the transition temperature can be lowered to room temperature by adding metallic elements such as tungsten (w) (non-patented). Reference 1 and Patent References 1 and 2). A window coating material that can adjust solar light autonomously only by the environmental temperature using the temperature change of its optical characteristics has been studied (Non-patent Document 1). For diacid-vanadium dimmable glass, the structure is very simple. In addition, since dimming is performed automatically and automatically according to changes in environmental temperature, no extra equipment is required.

[0004] Regarding the research on thermochromic light control glasses with vanadium diacid, for example, their production method (Patent Documents 3 and 4), the thermoguchimic body and its production method (Patent Document 5), and Others (Patent Documents 1, 2, 6, 7), etc. disclose the production method and element addition method for controlling the transition temperature.

[0005] However, as described above, the conventional diacid-vanadium-based thermochromic dimming material (1) originally has a low visible light transmittance due to strong absorption at short wavelengths including visible light. (2) Low thermal insulation with low reflectivity to room temperature radiant heat, (3) The phase diagram of the vanadium oxide system is very complex, and it is very difficult to form a single-phase thin film of vanadium dioxide. In particular, it is extremely difficult to form a single-phase large-area and optically uniform film. (4) Formation method of vanadium dioxide thin film suitable for industrial production, especially industry using high-efficiency DC sputtering. Due to the fact that production has not been established, and (5) there is a problem of strong yellow coloring due to the solid absorption of vanadium dioxide thin films, there have been high obstacles to practical use. .

[0006] As a result of continual researches on automatic light control glass using a diacid-vanadium thin film for many years, the present inventor has been able to solve some of the above problems. For example, by creating a new multi-layer structure, the visible light transmittance can be greatly improved, and at the same time, high value-added glass can be obtained by adding multiple functions such as full UV cut, enhanced heat ray reflection function, and photocatalytic effect. It has been developed (Patent Documents 8 and 9). In addition, regarding the difficulty of forming vanadium dioxide thin films, the thermal insulation effect is dramatically improved by the structural template design, and the diacid-vanadium dimming films have a large area at a lower substrate temperature than ever before. In addition, an effective manufacturing method for optically uniform formation has been developed (Patent Document 9).

[0007] However, in spite of research and inventions including the invention of the present inventors so far, (1) low visible light transmittance, (2) diacid-vanadium dimming film Issues such as strong yellow, its elimination and color harmony, (3) manufacturing method suitable for industrial production, and (4) most appropriate use, ie product, have not been solved yet, and the practical use of this material Large There was a serious obstacle.

[0008] Although not automatic, low-emission glass (Low-E glass) that always transmits visible light but reflects infrared rays (part of solar radiation and radiant heat), or mainly shields solar heat. There are glasses that selectively control solar heat, such as heat-reflecting glass (Non-patent Document 2). This glass is spreading widely due to its excellent optical properties and relatively low cost. However, all of these glasses only reflect heat rays with fixed optical properties. There is no function to adjust the heat radiation, that is, the function of automatically dimming the heat according to the environmental temperature.

[0009] In recent years, there has been a rapid increase in UV-cutting and infrared-cutting glass that pursues energy saving and comfort, such as reducing the cooling load, preventing deterioration of indoor items and preventing skin burn, shading, and protecting privacy. For example, dark-colored glass for the purpose of privacy protection, such as the rear seats of automobiles, or glass having an ultraviolet ray or infrared ray cut function simultaneously with privacy protection has been developed (Patent Documents 10 to 15). These strongly colored glasses have been developed for the purpose of preventing ultraviolet rays and infrared rays, protecting privacy, etc., but until now, dark colored glasses that have a function of automatically adjusting the temperature depending on the environmental temperature have been very attractive. Not.

[0010] In addition, a coating glass with a multilayer thin film having remarkable sunlight shielding properties has been proposed! (Patent Document 16). However, in terms of selectivity, it is defined that the luminous transmittance is greater than the solar radiation acquisition rate (or Sorough Actor), and it mainly seeks remarkable solar radiation shielding characteristics. Functions and various color harmony functions cannot be expected. In addition, laminated glass for the purpose of safety, strengthening and crime prevention is commercially available. However, there is no such product that has an automatic temperature control function based on the ambient temperature or its idea.

Patent Document 1: Japanese Patent Application Laid-Open No. 50-50294

Patent Document 2: Japanese Translation of Special Publication 2002-516813

Patent Document 3: Patent No. 2735147 Specification

Patent Document 4: Patent No. 2600117 Specification

Patent Document 5: Japanese Unexamined Patent Publication No. 2000-137251

Patent Document 6: Japanese Unexamined Patent Publication No. 2000-273619 Patent Document 7: JP-A-8-40749

Patent Document 8: Japanese Patent Application Laid-Open No. 2004-004795

Patent Document 9: Japanese Unexamined Patent Application Publication No. 2003-094551

Patent Document 10: Japanese Unexamined Patent Application Publication No. 2004-115359

Patent Document 11: Japanese Patent Laid-Open No. 2003-342038

Patent Document 12: Japanese Unexamined Patent Application Publication No. 2002-173340

Patent Document 13: Japanese Unexamined Patent Application Publication No. 2002-12451

Patent Document 14: JP 2001-64035 A

Patent Document 15: Japanese Patent Laid-Open No. 2001-322835

Patent Document 16: Japanese Unexamined Patent Publication No. 2000-119045

Special Reference 1: S.M.Babulanam, T.S.Eriksson, G.A.Niklasson and C.G.Granqvist: Solar Energy Matrials, 16 (1987) 347

Non-Patent Document 2: Niyu Glass Handbook, New Glass Handbook Editorial Committee, pp. 449-452, 1991, Maruzen

Disclosure of the invention

Problems to be solved by the invention

Under such circumstances, the present inventor has developed a new technology that solves the problems of the conventional technology and enables practical application of the vanadium dioxide thin film in view of the conventional technology. For many years, the results of diligent research and experiments and knowledge about window glass on the diacid-vanadium dimming thin film and the knowledge about window glass have been used to concentrate on the protection and privacy of commercial buildings and automobiles. In view of the color shading glass, the weakness of the conventional thermo-chromic dimming glass, that is, the feature of low visible light transmittance, is used by reversing the idea as an excellent shading property, and it has not been solved until now. On the other hand, it was found that the intended purpose of the strong intrinsic yellow color, which is the biggest problem of vanadium dioxide thin films, can be achieved by utilizing coloring substances and coloring base materials based on the complementary color principle. It has been completed.

That is, according to the present invention, the color tone of glass can be freely harmonized, excessive solar heat can be shielded in summer, solar heat can be introduced in winter, and its function is automatically controlled by the environmental temperature. Can be selected freely according to preferences and the exterior of the environment. Furthermore, it is an object of the present invention to provide an automatic heat-adjusting color-tone harmonized light-shielding glass and a method for manufacturing the same. In addition, the present invention is a new functional glass, that is, a glass having various functions such as automatic heat control, color harmony, UV protection, heat insulation, comfortable illuminance, and privacy protection. The purpose is to provide a completely new glass product that can provide functions such as energy saving, health and comfort, privacy protection, and color harmony to the window glass of buildings, vehicles, and other moving objects that are less than% and its manufacturing method. It is what.

Means for solving the problem

In order to achieve the above object, the present invention comprises the following technical means.

(1) An automatic heat-adjusting color tone characterized in that, in a diacid-vanadium-based automatic heat-adjusting glass, a base material is coated with a diacid-vanadium-based automatic heat-adjusting film and a toning film. Harmonic glass.

(2) The diacid-vanadium-based automatic heat control glass is characterized in that the base material is coated with a diacid-vanadium-based automatic heat-control film, a toning film, and a functional film. Automatic heat tone harmonized glass.

(3) The inherent color of the automatic heat-adjusting film is controlled to a predetermined color tone by arbitrarily adjusting the toned film or a combination of the toning film and the functional film based on the complementary color principle (1) ) Or (2).

(4) The automatic heat-adjusting color tone described in (1) or (2) above is controlled to a predetermined color tone by coloring the base glass based on the complementary color principle. Harmonic glass.

(5) The intrinsic color of the self-adjusting film is determined by sticking a colored film to the base glass based on the complementary color principle, sandwiching it between two or more plate glasses, or bonding two or more glasses with a colored resin. The automatic thermal color tone harmony glass according to the above (1) or (2), which is controlled to a predetermined color tone.

(6) The automatic heat control film according to (1) or (2), wherein the intrinsic color of the automatic heat control film is controlled to a predetermined color tone by applying a coloring material to the base glass based on the complementary color principle. Color harmony glass.

(7) A vanadium dioxide-based automatic heat control glass is coated with a vanadium dioxide-based automatic heat control material, a color-adjusting material, and optionally a functional material applied to a plastic or synthetic resin film. Are distributed, and the inherent color of the automatic heat-adjusting material is controlled to a predetermined color tone by the above-mentioned color-adjusting material based on the complementary color principle, or an automatic heat-adjusting color-harmonic film or film thereof Automatic heat-adjusting color harmony glass.

(8) The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), which is a glass for a window glass of a building or a moving body.

(9) The self-regulating light according to any one of (1) to (8) above, wherein the visible light transmittance is 70% or less, excellent in light-shielding properties, and at the same time, is an automatic thermal color harmony light-shielding privacy glass in which the color tone is adjusted. Dynamic tone color tone harmony glass.

(10) The toning film is a film that also has a complexing power of a transition metal having a coloring function and Z or a compound thereof, a rare earth metal and Z or a compound thereof, or any combination of the above substances. The automatic heat-tone color harmony glass according to any one of the above (1) force and (7).

(11) The toning film is a transition metal having a coloring function and Z or a compound thereof, a rare earth metal and

The above (1) force formed by applying or dispersing Z or a compound thereof, or a combination of the above substances alone or in any combination of two or more kinds on a transparent substance matrix is also described in V of (7). Automatic heat tone color harmony glass.

(12) The coloring material of the toning film is an inorganic substance having a coloring function, an organic substance, a mixture of an inorganic substance and an organic substance, or a dispersion thereof. Automatic thermal color-harmonic glass described in 1.

(13) The self-adjusting color-tone glass according to (11), wherein the transparent material matrix is a crystalline material having a rutile crystal structure, or a combination of two or more kinds.

(14) The transparent material matrix is composed of a transparent dielectric material such as oxides, nitrides, fluorides, and sulfides other than the rutile crystal structure, or a transparent conductive material alone or in any combination of two or more thereof ( The self-adjusting color tone-shading glass described in 11).

(15) The self-adjusting color-tone glass according to (11), wherein the transparent material matrix is a transparent or translucent plastic film, a synthetic resin, or a film thereof.

(16) By sandwiching a colored film or colored resin between two or more sheet glasses or bonding two or more sheets of glass, the visible light transmittance can be kept low to 70% or less, and appropriate illuminance and The automatic heat-adjusting color-harmonic glass as described in (9) above, which is a passy protective glass.

(17) In order to harmonize the color tone, a self-adjusting film and a transition metal and Z or a compound thereof, a rare earth metal and Z or a compound thereof, or a composite of any of the above substances, or any combination thereof The automatic heat-adjusting color-harmonic glass according to any one of the above (1) to (7), to which is added.

(18) In order to harmonize the color tone, a transition glass having a coloring function and Z or a compound thereof, a rare earth metal and Z or a compound thereof, or a combination of any of the above substances alone or in combination of two or more thereof is used for the color harmony. The self-adjusting and color-adjusting glass according to any one of (1) to (7), wherein the body is mixed so that the strong intrinsic color of the diacid-vanadium-based film can be adjusted in color.

(19) In order to harmonize the color tone, the following colored substances having a coloring function are added to the base glass: l) Nd and its compounds, and the NdO reference content in mass percentage display is 0.1% or more, 2

twenty three

) Co and its compounds, CoO standard content of mass percentage display is lppm or more, 3) Nd and Co are contained under the conditions of 1) and 2) at the same time, and by coloring blue, diacid The self-adjusting color-tone glass according to any one of (1) to (7), wherein the strong intrinsic yellow color of the vanadium film is harmonized near a neutral color.

(20) An automatic heat-adjusting film, a toning film, and optionally a functional film are installed in any combination on the same side of the glass, or are installed separately on both sides of the glass, or on multiple sheets of glass. The automatic heat-adjusting color-harmonic glass according to any one of (7) and (1)

(21) An automatic heat control membrane is one of the following methods: 1) The main component is vanadate oxide V O, or

2 5 is a conductive target obtained by mixing, molding or sintering a vanadium metal into a vanadium oxide having VO (2 <x <2.5) or a mixture thereof, and containing inert gas or oxygen. Sputtering in an inert gas, 2) Compound terse consisting mainly of diacid vanadium VO

2

The get is heated to a temperature above the phase transition temperature, and the conductive target resulting from the phase transition to the metal phase is sputtered in an inert gas or an inert gas containing oxygen. A compound target with vanadium force is RF sputtered and the target temperature is raised above the phase transition temperature. The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7) above, which is formed by a DC (including pulsed DC) magnetron sputtering method by sputtering in an inert gas.

(22) The self-adjusting color-tone glass according to (21), wherein the target includes addition of a trace element for lowering the transition temperature.

(23) At least one of the automatic heat-adjusting film, the color-adjusting film, and the optional functional film uses the thermal environment inside the float bath or annealing furnace on the float glass production line, and the glass surface has a high temperature. The automatic heat-adjusting color-harmonic glass according to any one of (1) to (7), wherein the glass is formed alone or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure.

(24) At least one of the automatic heat-adjusting film, the color-adjusting film, and the optional functional film uses the thermal environment of glass strengthening and bending processes, and is at a normal temperature or reduced pressure within a predetermined temperature range. The self-adjusting color-harmonic glass according to any one of (1) to (7), which is formed alone or continuously by a general-purpose thin film forming method.

(25) After at least one of the automatic heat-adjusting film, toning film, and optional functional film is formed at a low temperature including room temperature by a general-purpose thin film formation method, use the thermal environment of glass strengthening and bending processes And (1) to (7) formed by heat treatment in a predetermined temperature range! The self-adjusting color tone harmony glass described in any of the above.

Next, the present invention will be described in more detail.

The present invention utilizes a semiconductor's metal phase transition that occurs near 68 ° C in a vanadium diacid-based material, and the property that the phase transition temperature can be set to a suitable temperature near room temperature by adding elements, etc. The ability to transmit solar heat at low temperatures The point of constituting an automatic heat control film for glass that shields excessive solar radiation and radiant heat at high temperatures such as summer, and that can automatically perform these only by changing the environmental temperature. It is a feature. In addition, the present invention has a low transmittance, which is a weak point of the conventional vanadium diacid-based thin film. In addition, it is possible to freely adjust the color tone according to the neutrality or purpose by using the coloring material positively and using the complementary color principle. It has the feature of solving the big problem of vanadium exhibiting a strong inherent yellow color. It is.

[0016] In the present invention, the vanadium dioxide-based automatic heat-adjusting film A, the color-adjusting film B, and the functional film C are coated with a combination of at least two layers of A and B. The inherent color of film A can be arbitrarily adjusted by the combination of toning film B or toning film B and functional film C based on the toning principle, so that the color tone of a given transmitted color can be freely controlled. it can. The vanadium dioxide-based thin film A can be applied to a vanadium dioxide single compound or a known knowledge based on, for example, a metallic element, non-metallic element, or any combination thereof for controlling the transition temperature. ) SM Babulanam, Tb Eriksson, GA Niklasson and T. uranqvist: Solar Energy Matrials, 16 (1987) 347, 2) JP 50-50294, 3) Special Table 2002 516813, etc. The types of additive elements are known. ].

One of the most important points in the present invention is to introduce a color-adjusting material or color-adjusting film for color-tone adjustment into a diacid-vanadium-based thin film system. That is, the toning film B has transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W , Re, Os, Ir, Pr, Au) and Z or their compounds, preferably Co, Mn, Cr, Cu, Ni, Fe, Mo, W, Ag, Au, Ti, which are often used for glass coloring And / or its compound, or rare earth metal (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and Z or its Compound, preferably Nd, Er, Ce, Pr and Z effective for coloring glass or a compound thereof, and further, the above-mentioned additive alone or a composite coloring material arbitrarily combining two or more kinds. Can do.

[0018] In the toning film B, the coloring material is a coloring material of glass centered on blue, which is the complementary yellow-brown color of vanadium oxide, for example, cobalt oxide, copper oxide, chromium oxide, oxidation oxide. Kel, manganese oxide, neodymium oxide, erbium oxide, praseodymium oxide, cerium oxide, iron oxide, etc. are suitable for obtaining neutral colors, but as long as various color tones can be obtained by color tone adjustment, It is not limited. In particular, the cobalt ion Co ²⁺ exhibits a blue color by absorption of visible light near 65 Onm, thereby becoming a yellow complementary color of ihivanadium diacid, and is effective in obtaining a neutral color by neutralizing it.

[0019] In the present invention, the colorant of the toning film B may be an organic or inorganic substance having functions such as a pigment, a phosphor, a dye, and coloring. In addition, the colored film B is a single film made of a colored substance. In addition, the coloring substance may be applied or dispersed in the transparent substance matrix. For example, in order to adjust the color tone, a normal transparent or translucent plastic film or a colored film made of resin is affixed to the glass, or two or more plate glasses are bonded with the substance, and the predetermined transparent color. Etc. can be freely controlled. In that case, in order to match the laminated glass manufacturing process, the laminated glass for safety, crime prevention and strengthening purposes can have functions such as automatic heat control, light shielding, and color harmony.

[0020] The use of a base material such as colored glass by directly adding a coloring substance to a transparent base material such as glass or applying it to a glass base material can also harmonize the color tone of the system. It is one of the simplest and most effective methods, but in order to harmonize the strong inherent yellow color of the diacid-vanadium film, it has a relatively strong tinting strength and sharpness compared to conventional colored glass. A special glass substrate for coloring is required. In order to harmonize the strong intrinsic yellow color of divanadium vanadium-based films near neutral colors by the complementary color principle, a glass substrate that is slightly intensely colored in blue is desired. For example, Nd and its compounds, Co and its compounds, which are used as blue colorants in glass, are suitable.

[0021] Conventionally, light blue plate glass made of Nd and its compound, Co and its compound

No. 115359 (Nd) and JP 2000-143283 (Co)), but in order to obtain a light blue color, the amount added is small (mass percentage: NdO, 0.1% or less, CoO, lppm or less

twenty three

). Therefore, in order to harmonize the strong intrinsic yellow color of the diacid-vanadium-based film close to the neutral color by the complementary color principle, a slightly strong blue-colored glass substrate is desirable, and its additive elements and amounts are expressed in mass percentages. Nd O, 0.1% or more, CoO, lppm or more,

twenty three

It is preferable to limit.

[0022] Although the above-mentioned methods of color tone harmony have been exemplified, some of the unique colors of the vanadium dioxide automatic heat-adjusting film have a color tone such as a predetermined transmission color by using a toning material based on the toning principle. It is not limited to these examples as long as it can be controlled. Further, the functional film C can be introduced in a single layer or a plurality of layers into the glass system of the present invention. The functional film C refers to a thin film layer capable of adding functions other than automatic heat adjustment and color harmony to the glass of the present invention. For example, an antireflection film for controlling the transmittance of visible light, a structural template film for making the crystal growth of vanadium dioxide thin film advantageous, and a protective film for enhancing the mechanical properties of the system. Examples include a protective film, a photocatalytic thin film for providing a self-cleaning effect, a barrier film for preventing the diffusion of impurities of glass power, and a transparent conductive film for enhancing heat reflection characteristics and heat insulation.

[0023] Substances used to achieve the purpose include oxides, nitrides, oxynitrides, carbides, oxycarbides, carbon (DLC), fluorides, sulfides, and other transparent insulators, dielectrics Body, semiconductor, or any combination thereof. For example, the substrate glass force is also in order, the structural template layer (rutile phase thin film such as TiO, SnO), on the diacid-vanadium layer

twenty two

Furthermore, there is an example in which the glass of the present invention is constituted by vapor-depositing a titanium oxide layer serving as a photocatalyst thereon. In the present invention, colored glass may be used for color tone harmonization, and there is no limitation as long as color tone harmony is possible by mixing a colorant in an arbitrary layer.

[0024] The vanadium dioxide automatic heat control film is preferably produced by, for example, a sputtering method. DC magnetron sputtering is desirable when manufacturing by sputtering, especially for highly efficient industrial production. Conventionally known to perform DC magnetron reactive sputtering in an atmosphere containing vanadium metal in oxygen. To obtain a VO crystalline film stoichiometrically.

2

The process control is very difficult. To obtain a stoichiometric composition close to VO,

2

Sputtering of VO compound target is necessary, but conventionally, sputtering of oxide is inefficient.

2

Furthermore, since VO compounds are weakly conductive at room temperature and cannot be used by RF sputtering,

2

The speed is further reduced. Therefore, in the present invention, a DC magnetron sputtering method in which the composition is more easily controlled and high in efficiency is preferably used.

That is, instead of the conventional diacid-vanadium compound target with poor conductivity, the main components are vanadium oxide (V O) and vanadium metal V (addition source for controlling the transition temperature).

twenty five

A mixture of conductive powders that are stoichiometrically close to VO

2

By conducting DC magnetron sputtering of a conductive target having a shape or sintered strength in an inert gas or in a mixed gas atmosphere containing a small amount of oxygen, a vanadium dioxide self-regulating film can be produced with high efficiency. In addition, when using a compound target whose main component including the additive is vanadium dioxide, the conductivity is weak at room temperature because vanadium dioxide is a semiconductor, but the target is above the phase transition temperature, preferably above 70 ° C. In By conducting DC magnetron sputtering of a conductive target formed by phase transition to a metal phase by heating in an inert gas or a mixed gas atmosphere containing a small amount of oxygen, vanadium dioxide is obtained. An automatic heat control film is produced with high efficiency.

[0026] In addition, a compound target whose main component including an additive also has vanadium diacid power is first RF-sputtered, and the surface temperature is increased by ion bombardment caused by plasma generation, so that the target temperature undergoes phase transition. After raising the temperature above the temperature, DC magnetron sputtering is performed on the conductive target based on the metal phase in an inert gas or a mixed gas atmosphere containing a small amount of oxygen. Produced.

[0027] In addition to the force sputtering method described above, for example, physical vapor deposition methods classified into PVD such as vacuum vapor deposition (for example, published by Asakura Shoten, "Glass Engineering Nord Book" pages 423-428), One of the general-purpose coating methods such as the thermal decomposition method (Id., Pp. 428-432) and the sol-gel method (Id., Pp. 432-438) classified as spray method and CVD method (including Paiguchi Zoro method) Needless to say, the glass can be coated by a plurality of methods. In order to form a thin film on the glass of the present invention, in particular, to form a vanadium dioxide heat-regulating film, it is usually essential to heat the substrate to 100 to 700 ° C. For industrial production, it is usually not desirable to coat the substrate by heating it because of equipment and cost issues.

[0028] However, the so-called on-line spray method and on-line CVD method (published by Asakura Shoten, “Glass Engineering Nord Book”, pages 428-432), which use the thermal environment of the heat treatment process on the float glass production line as is, have been developed. Has been. Conventionally, these methods have been used to produce transparent conductor films such as tin oxide doped with elements, TiO films, and SiO films.

twenty two

Power used as a method of line coating In recent years, it has also been reported as a method for forming VO thin films.

2

(E.g. l) Troy D. Manning, Ivan P. Parkin: Polyhedron, 23 (2004) 3 087—3095, 2) D. Vernardou, MEPemble, DWSheel: Surface & Coatings Technology, 188- 189 (2004) 250-254].

Accordingly, in the present invention, the problem of difficult substrate heating can be solved by incorporating the film forming process into a heat treatment step indispensable for the formation and processing of conventional plate glass. That is, at least one of the thin film groups of the glass structure of the present invention, such as the automatic heat-adjusting film A, the toning film B, and the functional film C, is a float bath or a slow cooling kiln on the float glass production line. Of Using the thermal environment of the part, the glass surface temperature is kept at a high temperature of 100 to 700 ° C, and it is formed alone or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure.

[0030] In the above method, it is possible to independently form a vanadium dioxide thin film by online coating, but an appropriate thin film of the structural thin film group of the present invention, such as a structural template or a functional film. It is most preferable to perform on-line coating continuously. For example, after structural oxides and tin oxide thin films with heat ray reflection function, VO heat control

2 It is most desirable to continuously form a thin film online.

[0031] At least one of the automatic heat-adjusting film A, the color-adjusting film B, and the functional film C, which is the same as described above, uses the thermal environment in the heat treatment of the glass strengthening or bending cache process, and the glass surface temperature is 10 In the range of 0 to 750 ° C., it is formed singly or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure. In addition, after at least one of the automatic heat-adjusting film A, toning film B, and functional film C is formed at a low temperature including room temperature by a general-purpose thin film forming method, the thermal environment of glass strengthening and bending processes is used. It is formed by heat treatment in the range of 100 to 750 ° C for 5 seconds to 1 hour.

[0032] The automatic heat-adjusting film A, the color-adjusting film B, and the functional film C are arbitrarily combined and installed on the same side of the glass, or separately on both sides of the glass as necessary, or a plurality of sheets The automatic heat-adjusting color-harmonic light-shielding glass is formed by installing the glass separately, sandwiching it between a plurality of glasses, or adhering a plurality of glasses. The formed glass can be used for the window glass of buildings and moving objects (cars, ships, trains, airplanes, etc.). In particular, they are used as self-adjusting color tone-shading privacy glass, which has a visible light transmittance of 70% or less and excellent light-shielding properties, and at the same time the color tone can be freely adjusted.

[0033] Further, the formed glass is a window glass of a building or a moving body (car, ship, train, airplane, etc.), in particular, a toning film, a colored film or colored resin, etc. In addition to the conventional safety, strengthening, and crime prevention functions, the visible light transmittance is 70% or less and the light shielding property is excellent. It is used as an automatic heat-adjusting color tone-shading laminated glass that can be suitably used for the purpose.

The invention's effect

[0034] According to the present invention, (1) comfort is achieved by automatic temperature adjustment, simultaneous reduction of heating and cooling load, color Glass with various functions such as harmony, UV protection, shading, privacy protection, etc., can provide new window glass for buildings, vehicles and other moving objects, and its manufacturing method. (2 ) A vanadium dioxide type automatic heat control film that allows visible light to always pass through a transparent or translucent substrate such as glass, but mainly allows infrared light to adjust its transmittance automatically in response to changes in ambient temperature. (3) Disadvantage of low visible light transmittance of conventional type divanadium divanadium-based dimmable glass by appropriate combination with toning film, coloring substrate and other functional film Can be turned into effective use as light-shielding glass by the idea of reversal. (4) Furthermore, it is possible to provide a unique color harmony method using the complementary color principle. Automatic thermal color tone harmony that can freely harmonize color tone There is an effect that a light shielding glass and a manufacturing method can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example

[0036] (1) Formation of automatic heat control multilayer structure

1. Formation of structural template film

In this example, a general-purpose magnetron sputtering apparatus was used for the production of the thin film. The equipment can be arranged 1) up to 3 force swords, 2) each can be arbitrarily controlled with high frequency power supply or DC power supply, 3) In this equipment, the substrate can be rotated, The plate temperature can be precisely set in the range from room temperature to 800 ° C.

[0037] TiO and SnO having the same rutile structure as vanadium diacid are structural template thin

twenty two

A membrane was obtained. This structural template film consists of a TiO compound target (diameter 50mm, thickness 5m

2

m, purity 99.9%), or SnO (Sb Dob) composite compound target (diameter 50mm, thickness 5mm)

2

, Purity 99.9%). That is, knock ground vacuum 2 X 10 ^{_ 6} Pa, argon flow rate 30 sccm, total pressure 0.6 Pa, substrate temperature 200-600. A structural template film with a thickness of 5 to 200 nm was formed on quartz glass, heat-resistant glass, silicon single crystal and sapphire single crystal substrate under the conditions of C and RF power of 120W. [0038] 2. Formation of diacid-vanadium thin films

After the above structural template was formed, a vanadium dioxide thin film was continuously formed thereon by the following method.

1) Sputtering with a commercially available vanadium target

A commercially available vanadium target (V, diameter 50 mm, thickness 5 mm, purity 99.9%) or a commercially available vanadium-tungsten alloy target (V: W = 1.6 at%) is mixed in a mixed gas of oxygen and argon. A vanadium dioxide thin film was formed by RF, DC or DC sputtering. The main sputtering conditions are as follows. That is, Bruno Kkugurando vacuum 2 X 10 ^_6 Pa, argon flow rate 30 sccm, the oxygen flow rate 0 to 3. OOsccm, total pressure 0. of 6 Pa, the substrate temperature 400 to 600. Quartz glass, heat-resistant glass, silicon single crystal, and sapphire single crystal were used as the substrate under the conditions of C, RF power 200 W, or DC voltage 200 to 400 V, current 0.10 to 0.30 A.

[0039] Under the above conditions, when forming a single-phase vanadium dioxide thin film by reactive sputtering, it is most important to precisely control the oxygen flow rate to a predetermined level. The result shows that a single-phase thin film of hibihidium dioxide is formed only in the flow rate range. On the other hand, after a structural template such as TiO or SnO is formed on the substrate in advance,

twenty two

It was found that if a vanadium dioxide thin film was formed subsequently, the formation of a single-phase thin film of vanadium dioxide was almost certain. However, in order to form a vanadium dioxide single-phase thin film by reactive sputtering as described above, precise control of the process, such as the oxygen flow rate, is strictly required. It was difficult for mass production because it easily fluctuated due to wear. Therefore, the following methods were considered and developed.

[0040] 2) Sputtering with a diacid-vanadium compound target

Vanadium dioxide powder (VO purity 99.5%) and acid-tungsten powder (WO, 99.

twenty three

99%) is mixed at a 1.0% molar ratio, mixed for 1-3 hours in an automatic mortar and crushed and pressed into a disk with a diameter of 50 mm and a thickness of about 5 mm by press forming and heat treatment. A vanadium diacid-based thin film was formed, that is, a knock ground vacuum degree of 2 X 10_6 Pa, an argon flow rate of 30 sccm, an oxygen flow rate of 0 to 0.5 sccm, a total pressure of 0.6 Pa, a substrate temperature of 400 to 600 ° C, Sputtered under the condition of RF power 100W, quartz glass, heat-resistant glass, single silicon A vanadium dioxide thin film was formed on single crystal and sapphire single crystal substrates.

[0041] A stable vanadium dioxide thin film was formed by the reactive sputtering method using a vanadium metal target. However, in the case of RF sputtering, there was a drawback that the film formation rate was slow. The diacid vanadium-based compound target does not show much conductivity in the semiconductor phase at room temperature. Therefore, inefficient RF sputtering is necessary. However, the present inventor succeeded in making the target conductive by the following method so that it can be sputtered even by DC. In other words, RF sputtering is performed only at the beginning, and the temperature force on the target surface rises to above the phase transition temperature of vanadium dioxide, and when it becomes a metal phase, it switches to efficient DC sputtering.

[0042] 3) Sputtering with conductive target

As a more advanced method, a conductive target was formed by the following method, and a vanadium dioxide thin film was formed by DC sputtering. That is, vanadium pentoxide (V O, 99.

twenty five

9%) Vanadium metal (V, 99.9%) is mixed with the powder in a 0.25 molar ratio, and WO is further added.

Three

The total composition was (V + W): 0 = 1: 2 with a 1% molar ratio. This was mixed and pulverized and pressed into a disk with a diameter of 50 mm and a thickness of about 5 mm by press molding or heat treatment, and the target was used. Since the target that also has a mixture force has conductivity due to the metal vanadium, a thin film of vanadium diacidate was formed by a DC-sutter.

[0043] By the above methods 1) to 3), after forming an amorphous thin film having a vanadium dioxide composition without heating the substrate, annealing is performed in air at 400 ° CZ for 30 minutes. A good diacid-vanadium thin film was obtained. In the present invention, an arbitrary functional film can be further formed on the surface of the structural template and the vanadium oxide thin film formed on the substrate.

[0044] 3. Formation of functional film

The surface of the structural template and the oxide vanadium thin film formed on the substrate was further coated with a TiO functional film serving as an anti-reflection and photocatalyst with an appropriate thickness. Formed structural template

2

The typical transmission characteristics and color characteristics of a self-adjusting multilayer structure including a thin film, vanadium oxide thin film, and titanium oxide thin film were examined using a spectrophotometer or the like. An example is as follows: (Sample 1)

VO heat control film with a thickness of 50 nm on a quartz glass substrate, visible light transmittance of 58%, chromaticity coordinates

2

: x = 0.376, y = 0.398, dominant wavelength power 71nm, 朿 lj high purity power 5.3%, and strong yellow transmission.

(Sampnore 2)

On a quartz glass substrate, 70nm thick VO heat control film, visible light transmittance 40%, chromaticity coordinates

2

: x = 0.400, y = 0.410, dominant wavelength is 575nm, excitation purity is 50%, mainly yellow strong transmission.

[0045] (2) Color harmony of diacid-vanadium thin films with colored films

1.Outline of vanadium dioxide color harmony

Based on the complementary color principle, changes in the color tone of diacid-vanadium thin films due to complementary colors were investigated. In other words, based on the three RGB primary colors, a color sheet with 12 hues was created by additive color mixing. The transmittance was adjusted appropriately and superimposed with Sample 1 or Sample 2, the white light source was transmitted through the knocklight, the change in transmitted color was photographed, and the effect of color harmony was confirmed. The results are summarized in Fig. 1. As can be seen from Fig. 1, by using the complementary color principle, the unique strong yellow color of the diacid-vanadium thin film can be arbitrarily changed to a color that matches the exterior of the building or the moving body. I was divided. In particular, it was confirmed that if a near V or complementary color is used for No. 9 (No. 9) blue, a near-neutral color and a transmitted color can be obtained.

[0046] That is, for the diacid-vanadium heat control thin film, the strong yellow coloring inherent to the vanadium diacid-based thin film, which is the most obstacle to its application, can be changed to any color tone including neutral colors by the complementary color principle. I was able to set it. Although the visible light transmittance is further reduced by the complementary color design, there is no contradiction with the purpose of the present invention, i.e., light-shielding glass or privacy protection glass, etc. It became possible to

[0047] 2. Harmonic diacid-vanadium color harmony with toning film

(Example of color harmony 1)

42% visible light transmittance, chromaticity coordinates in the XYZ color system: x = 0.258, y = 0.253, dominant wavelength 479nm, stimulus purity 24%, slightly strong blue transmission colored film (S1 ) Made. SI is applied to a VO-based thermal conditioning film (sample 1) with a thickness of 50 nm on a quartz glass substrate.

2

It was sandwiched between one quartz glass plate and fixed by heating and pressing. Figure 2 shows an outline of the structure.

[0048] The spectral transmittance of the structure of FIG. 2 was measured with a spectrophotometer. Luminous transmittance and chromaticity coordinate values in the CIE color system were calculated from the measured spectral transmittance. The result is as follows. That is, the luminous transmittance was 22%, the chromaticity coordinate values: x = 0.300, y = 0.356, the main wavelength was 530 nm, the stimulation purity was 11%, and a slight green color was exhibited. The technique of adjusting the color tone with the colored film sandwiched as part of the present invention can be added with safety, crime prevention and the like by combination with laminated glass technology.

[0049] (Color tone harmonization example 2)

Color film with visible light transmittance of 16%, chromaticity coordinates in XYZ color system: x = 0.198, y = 0.167, dominant wavelength 468nm, stimulus purity 57% S2) was produced. In other words, quartz glass coated with a VO toning film with a thickness of 70 nm (Sample 2)

2

The above-mentioned very strong! The film was covered with a blue-transmitted colored film (S2), and the spectral transmittance of the system was measured with a spectrophotometer. In order to investigate the heat control characteristics, the system was set to 20 ° C (VO

The optical properties were measured while changing the temperature to 80 ° C (same metal phase) and 2 ° C heat-treating film is a low-temperature semiconductor phase. The system exhibited the following optical color characteristics. Low-temperature phase: transmittance 6%, chromaticity coordinate values: x = 0.226, y = 0.286, dominant wavelength 486 nm, stimulation purity 20%, dark blue. High-temperature phase: Permeability 5%, chromaticity coordinate values: x = 0.298, y = 0.335, dominant wavelength 520nm, stimulation purity 8%, and dark blue color.

[0050] 3. Effect of automatic temperature control

Quartz glass (sample 2) coated with a VO-based toning film with a thickness of 70 nm is very strong as described above.

2

Covered with a colored film (S2) that transmits blue to blue, and changes the spectral transmission characteristic ratio, that is, automatically adjusts the temperature by changing the temperature at 20 ° C (semiconductor phase) and 80 ° C (metal phase). The effect of heat was measured. The results are shown in Fig. 3. At low and high temperatures, a large difference was observed in the transmittance, particularly the wavelength longer than 780 nm and the infrared transmittance, indicating a very good heat treatment effect.

[0051] As described above, according to the present invention, visible light is appropriately transmitted, and infrared light is increased in response to a temperature change. Examples of automatic heat-adjusting color-tone harmonized light-shielding glass showing various changes were shown, but according to the present invention, a diacid-vanadium-based automatic heat-adjusting film, and a colored film or other functional film or substrate having a coloring function For example, the visible light transmittance can be suppressed to 70% or less, and the coloring can be freely adjusted to match the exterior of the building or moving body.Automatic heat adjustment, automatic light adjustment, color harmony, UV protection, heat insulation In addition, it is possible to provide an automatic thermal color tone harmony light shielding glass having a variety of functions such as comfortable illumination and privacy protection, and a manufacturing method.

[0052] Comparative Example

A self-adjusting multilayer structure including a structural template thin film, an oxide vanadium thin film (70 nm), and a titanium oxide thin film is fabricated on a quartz glass substrate, and transmission characteristics at 20 ° C and 80 ° C are measured with a spectrophotometer. The color characteristics were examined. The results are as follows. In other words, a large difference was observed in the transmittance, particularly the transmittance of infrared rays having a wavelength longer than 780 nm, at low and high temperatures, showing a very good heat-control effect. Transmittance 40%, chromaticity coordinate values: x = 0.400, y = 0.410, dominant wavelength 575nm, stimulation purity 50%, strong yellow transmission inherent in vanadium dioxide unless color tone is adjusted. Presented only.

Industrial applicability

[0053] As described above in detail, the present invention relates to an automatic heat-adjusting color-harmonic light-shielding glass and a method for producing the same. According to the present invention, for example, the visible light transmittance is 70% or less, and the light-shielding property is improved. A new ゝ automatic heat-adjusting color tone-shading glass and manufacturing method that can automatically adjust the infrared transmittance according to the environmental temperature and can freely adjust the color tone of the transmitted color. Can be provided. The present invention uses a vanadium dioxide-based automatic heat control film in which infrared light shows a large change in response to a temperature change on a transparent substrate such as glass. In addition, a dark-colored film was added to the structure, and the design based on the inherent yellow color and complementary color principle of the diacid vanadium thin film was neutralized or harmonized with the taste, preference, building, and exterior of moving objects. It develops and provides automatic heat-adjusting color-harmonic shading glass. The present invention effectively uses the weakness of the conventional low visible light transmittance of vanadium dioxide by reversing the idea, keeping the visible light transmittance as low as 70% or less, automatic heat control, shading light control, color control Harmony, UV protection, heat insulation, comfortable illumination, privacy protection, etc. It is possible to provide an automatic thermal color-harmonic shading glass having a colorful function and a manufacturing method. The present invention can be expected to be applied to the building industry and other industries as a new energy-saving, healthy, comfortable, and environmentally friendly glass suitable as a glass for moving objects such as buildings and automobiles. .

Brief Description of Drawings

[Fig. 1] Shows the results of confirming the effect of color harmonization of diacid-vanadium thin film by complementary color using the complementary color principle. The top row shows the results of color harmony between the RCB12 color seal (S) and the vanadium dioxide membrane with a transmittance of 60%. The lower panel shows the change in the color density of the diacid-vanadium film (No. 9) due to the change in the transmittance of the sheet.

FIG. 2 shows an example of the structure of the automatic heat-adjusting color-harmonic shading glass of the present invention.

[Figure 3] Shows the results of measuring the effect of automatic heat control.

Claims

The scope of the claims

[1] Automatic heat-adjusting color tone harmony, characterized in that the substrate is coated with a diacid-vanadium-based automatic heat-adjusting film and a color-adjusting film on the substrate. Glass.

[2] In an automatic heat-control glass based on diacid-vanadium-based heat control, the substrate is coated with a diacid-vanadium-based automatic heat-control film, a toning film, and a functional film. Heat-control color tone Japanese glass.

[3] The specific color of the automatic heat-adjusting film is controlled to a predetermined color tone by arbitrarily adjusting the toned film or a combination of the toning film and the functional film based on the complementary color principle. 2. The self-adjusting color-harmonic glass described in 2.

[4] The automatic heat-adjusting color-harmonic glass according to claim 1 or 2, wherein the intrinsic color of the automatic heat-adjusting film is controlled to a predetermined color by coloring the base glass based on the complementary color principle.

[5] The intrinsic color of the self-adjusting film is applied to the base glass based on the complementary color principle, or

3. The automatic heat-adjusting color-harmonic glass according to claim 1 or 2, wherein the glass is controlled to a predetermined color tone by being sandwiched between two or more plate glasses or by adhering two or more glasses with a colored resin.

[6] The automatic heat-adjusting color tone according to claim 1 or 2, wherein the intrinsic color of the automatic heat-adjusting film is controlled to a predetermined color tone by applying a coloring material to the base glass based on the complementary color principle. Harmonious glass.

[7] Vanadium dioxide-based self-adjusting glass, vanadium dioxide-based self-adjusting material, and color-adjusting material, and optionally functional materials, are applied or dispersed in plastics and synthetic resin films for automatic heat-regulating. An automatic heat-adjusting color-harmonic film or an automatic heat-adjusting color-adjusting glass using the film, wherein the intrinsic color of the material is controlled to a predetermined color by the color-adjusting material based on the complementary color principle.

[8] The automatic heat-adjusting color-harmonic glass according to any one of claims 1 to 7, which is a glass for a window glass of a building or a moving body.

[9] The automatic heat-adjusting color tone according to any one of claims 1 to 8, which is a self-adjusting color-shading light-shielding privacy glass having a visible light transmittance of 70% or less, excellent light-shielding properties, and simultaneously adjusted color tone Harmonic glass.

[10] The toning film is a transition metal having a coloring function and Z or a compound thereof, a rare earth metal and Z or The self-adjusting color-tone glass according to any one of claims 1 to 7, wherein is a compound, or a single film of the above-mentioned substance, or a composite film in which two or more kinds are arbitrarily combined.

[11] The toning film comprises a transition metal having a coloring function and Z or a compound thereof, a rare earth metal and Z or a compound thereof, or a single substance of the above substances, or a complex in which two or more kinds are arbitrarily combined. The self-adjusting color-tone glass according to any one of claims 1 to 7, which is formed by coating or dispersing in a transparent substance matrix.

[12] The automatic according to any one of claims 1 to 7, wherein the colorant of the toning film is an inorganic substance having a coloring function, an organic substance, a mixture of an inorganic substance and an organic substance, or a dispersion thereof. Heat-control color tone harmony glass.

[13] The transparent material matrix power [12] The automatic heat-adjusting color-harmonic glass according to [11], wherein the crystalline material having a rutile crystal structure is used alone or in combination of two or more kinds.

[14] The transparent material matrix is a single or a combination of two or more of transparent dielectric materials such as oxides, nitrides, fluorides, and sulfides other than the rutile crystal structure or a transparent conductive material. Item 12. The self-adjusting color tone-shading glass according to Item 11.

[15] The self-adjusting color-tone harmonized glass according to [11], which is a transparent material-matrix power, a transparent, translucent plastic film, a synthetic resin, or a film thereof.

[16] Appropriate illuminance and privacy can be achieved by holding the colored film or colored resin between two or more glass sheets or by bonding two or more glass sheets to keep the visible light transmittance below 70%. The automatic heat-adjusting color-harmonic glass according to claim 9, wherein the glass is protective glass.

[17] To adjust the color tone, transition metal and Z or a compound thereof, rare earth metal and Z or a compound thereof, or a composite of any one or more of the above substances is added to an automatic heat control film. The automatic heat-adjusting color-harmonic glass according to any one of claims 1 to 7

[18] In order to harmonize the color tone, the transition glass and Z or a compound thereof having a coloring function, a rare earth metal and Z or a compound thereof, or one or more of the above substances are arbitrarily combined with the base glass. The automatic heat-adjusting color tone glass according to any one of claims 1 to 7, wherein the glass is colored so that a strong intrinsic color of the vanadium diacid-based film can be color-adjusted by mixing the complex.

[19] In order to harmonize the color tone, the following coloring substances having a coloring function are added to the base glass: (l) Nd and its compounds, and the Nd O reference content in mass percentage display is 0.1% or more. (2)

twenty three

Co and its compounds, CoO standard content of mass percentage display is lppm or more, and (3) By containing Nd and Co simultaneously under the conditions of (1) and (2), by coloring blue, The self-adjusting color-tone glass according to any one of claims 1 to 7, wherein the strong intrinsic yellow color of the vanadium diacid-based film is harmonized near a neutral color.

[20] Automatic heat-conditioning film, toning film, and optionally functional film, installed in any combination on the same side of the glass, installed separately on both sides of the glass, or separated into multiple sheets of glass The self-adjusting color-tone glass according to any one of claims 1 to 7, which is installed as described above.

[21] The automatic heat control film is any one of the following methods: (1) The main component is vanadate oxide V 2 O, or

25 5 Vanadium oxide having a composition of VO (2 <x <2.5), or a mixture thereof, mixed with a vanadium metal, formed or sintered into a conductive target as an inert gas or an oxygen-containing inert gas (2) Compound target whose main component is diacid vanadium VO

2

The thermal control film is heated to a temperature higher than the phase transition temperature, and the conductive target resulting from the phase transition to the metal phase is sputtered in an inert gas or an oxygen-containing inert gas. DC (pulsed) is obtained by RF sputtering of a compound target with vanadium phosphide force, and the target temperature is raised above the phase transition temperature, and then the metal phase conductive target is sputtered in an inert gas or an oxygen-containing inert gas. The automatic thermal color tone harmony glass according to any one of claims 1 to 7, which is formed by a magnetron sputtering method (including DC).

[22] The self-adjusting color-tone glass according to claim 21, wherein the target includes addition of a trace element for lowering the transition temperature.

[23] At least one of the automatic heat-adjusting film, the color-adjusting film, and the optional functional film uses the thermal environment inside the float bath or annealing furnace on the float glass production line, and the glass surface has a high temperature. The self-adjusting color-tone glass according to any one of claims 1 to 7, wherein the glass is formed independently or continuously by a general-purpose thin film forming method at normal pressure or reduced pressure.

[24] At least one of the automatic heat-adjusting film, the toning film, and the optional functional film uses normal strength or reduced pressure within a predetermined temperature range using the strength of glass and the thermal environment of the bending process. General purpose The self-adjusting and heat-adjusting glass according to any one of claims 1 to 7, which is formed alone or continuously by a thin film forming method.

At least one or more of the automatic heat-adjusting film, color-adjusting film, and optional functional film is formed at a low temperature including room temperature by a general-purpose thin film forming method, and then the predetermined temperature is selected using the thermal environment of glass strengthening and bending processes The self-adjusting color-tone glass according to any one of claims 1 to 7, which is formed by heat treatment in a temperature range of.