JPH08133792A - Heat rays reflecting ultraviolet rays absorbing transparent body - Google Patents

Abstract

PURPOSE: To shield UV rays without damaging an optical characteristic and a heat rays and IR rays shielding performance and especially to sufficiently shield UV rays/ visible rays region at near 400nm, to remarkably increase scuffing resistance, wear resistance and durability while keeping the characteristics and to produce the subject body usable not only as a single plate window material for construction but also for the window material for an automobile for a long time. CONSTITUTION: In the heat rays reflecting and UV rays absorbing transparent body, a polysilazane based mixture soln. is applied to form film on a surface of a hard coat type heat ray reflecting and UV rays absorbing film obtained by applying in order by forming a multilayered film containing at least >=1 layer of a noble metal based thin film or a heat rays reflecting film consisting of at least >=1 layer among metal, oxide, nitride, carbide and oxide-nitride on the surface of a transparent base material as a ground layer, then forming an UV rays absorbable thin film by applying a synthetic resin based primer coating soln. in which a fluorescent brightener and the UV rays absorber are dissolved thereon and heat-curing, then forming a protective thin film by applying a silicone based hard coating soln. obtained by dissolving siloxane pre-polymer in an org. solvent thereon and heat-curing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly used as a window material for vehicles such as automobiles, buildings, etc. to shield and insulate heat rays (IR) generated by sunlight inside the vehicle and indoors, and to glare direct sunlight. Or you can improve the habitability by mitigating the heat, etc., while also blocking ultraviolet rays (UV) to prevent sunburn and deterioration of people and interior materials, and presenting a neutral reflection color that has a dull appearance. The present invention relates to a useful heat ray-reflecting ultraviolet absorbing transparent body.

It can be widely used not only for the above-mentioned vehicles or buildings but also for window glasses of ships and aircrafts, especially window materials for automobiles, various lamps and covers for displays.

[0003]

2. Description of the Related Art In recent years, various infrared or ultraviolet shielding transparent bodies have been proposed aiming at transparent window materials capable of freely controlling sunlight energy.

The most prominent one is a heat ray-reflecting glass for cutting off solar energy and mainly for energy saving such as reduction of cooling load. Various materials such as metal and oxide have been proposed as a transparent thin film coating material. ing.

Further, a low radiation glass for improving heating efficiency
Has high transmittance in the visible range and high reflectance in the infrared range.
Conventionally, as an article having a reflection of dielectric / silver / dielectric
A configuration has been proposed, for example, JP-A-63-239043.
Visible light transmission from the substrate with ZnO / Ag / ZnO / Ag / ZnO
Infrared reflective articles having a rate of 60% or more are also disclosed in, for example, JP-A-2-11.
In the 1644 publication, ITO / Ag / ITO / Ag / ITO is neutral.
Insulated laminated glass with a perfect color tone is further disclosed, for example, in JP-A-6-
In Japanese Patent No. 24806, a tin-doped oxide film is used as a functional film.
Indium film (ITO), aluminum-doped suboxide
Lead film (ZnO: Al), indium-doped zinc oxide film (ZnO: Al)
O: In), tin-doped zinc oxide film (ZnO: Sn), fluorine
Doped zinc oxide film (ZnO: F), fluorine-doped acid
Tin oxide film (SnO ₂: F) as an intermediate film between the substrate and the functional film.
A functional film consisting of a film based on oxygen, silicon, carbon, etc.
The provided window glass etc. are proposed respectively.

Regarding the shielding of ultraviolet rays, among the proposed methods such as a method of mixing and blending an ultraviolet absorber with a transparent material such as glass or resin film, or a method of coating a ZnOx thin film on a substrate, the present applicant In Japanese Patent Laid-Open No. 6-145387, which has already been filed, a specific silicone-based hard coat protective thin film is formed on the surface of an ultraviolet absorbing thin film formed with a synthetic resin-based primer coating solution consisting of a fluorescent whitening agent and an ultraviolet absorber. We have proposed a UV-absorbing transparent material that has been coated with, and can be used without any trouble in other than usage under severe environment and conditions such as long-term sliding contact.
The ultraviolet / visible region near 400 nm can be shielded very sharply.

Further, for example, as a method of imparting heat ray reflectivity and ultraviolet ray absorbability to a transparent body such as a glass substrate at the same time, first, a transparent body mixed with an ultraviolet ray absorbing compound is used, and heat ray reflection is performed on the surface. A method of forming a film, a method of sandwiching a laminated film containing an ultraviolet absorbing compound with a transparent body coated with a heat ray reflective film to form a laminated glass, further coating an ultraviolet ray absorbing film on the surface of the transparent body, and PVD the heat ray reflective film.
There is a method of forming a laminated coating film by a method such as Japanese Patent Laid-Open No.
ー 133004 is available.

[0008] On the other hand, various silazanes have been conventionally used for various purposes. Among them, the followings are related to so-called surface modification of articles. For example,
Japanese Patent No. 1-138107 discloses a modified polysilazane, a method for producing the same, and a use thereof. The raw material polysilazane having perhydropolysilazane as a starting material, orthoxylene as a solvent, and silicon carbide as a filler are disclosed. It describes a solution prepared, coated on a SUS substrate, and formed into a film.

Further, for example, in Japanese Patent Laid-Open No. 5-311120,
Disclosed are a composition for forming an ultraviolet-shielding glass protective film and an ultraviolet-shielding glass, and the surface of the glass coated with an ultraviolet-shielding film such as ZnO or TiO ₂ (SiH ₂ -based Si-H
(Number of bonds) / (Number of all Si-H bonds) = 0.13 to 0.45, containing polysilazane having a number average molecular weight of 200 to 100,000 as an essential component, and diluted with a solvent such as xylene. An ultraviolet-shielding glass coated with a protective film-forming composition is described.

Further, for example, Japanese Patent Laid-Open No. 5-310444 discloses a water repellent article and a method for producing the same,
A base material, a silicon dioxide-containing coating formed by reacting, for example, SiH ₄ gas, N ₂ gas for separation, and O ₂ gas on the surface of the base material, and poly-silicon such as hexamethyldisilazane formed on the surface of this coating. A water repellent layer composed of a nitrogen analog of siloxane or an organic silazane compound which is a fluorine-containing disilazane system is described.

Further, for example, Japanese Patent Application Laid-Open No. 5-163174 filed by the applicant of the present invention discloses an ultraviolet blocking glass for a vehicle. At least one ultraviolet blocking film is formed on the glass, and the ultraviolet blocking film is formed on the outside, for example. It describes that a layer containing silicon is formed, such as by coating and forming a compound having at least CH ₃ —Si bond and / or a compound having Si—N bond.

[0012]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in the case of only the above-mentioned glass with a heat ray reflective thin film, the durability such as scratch resistance, chemical resistance or abrasion resistance, which is not necessarily used as a single plate. Is not only excellent, it may be necessary to make laminated glass or double glazing, and because the shielding effect against ultraviolet rays is not sufficient,
It was necessary to use laminated glass in order to impart an ultraviolet shielding effect.

Further, for example, a heat ray-shielding article containing a silver-based film,
Since infrared reflective articles reflect solar energy and radiant energy, they are extremely effective in reducing the heating and cooling load, but silver-based films are particularly susceptible to deterioration due to moisture and moisture. , Aggregates silver and does not exhibit sufficient shielding performance, and the adhesion strength decreases, so it cannot be used as a single plate, and it is necessary to process it in multiple layers, and it is difficult to handle. Met. Further, since the shielding effect against ultraviolet rays is not sufficient, it is necessary to use laminated glass to provide the ultraviolet shielding effect.

Further, for example, since an ultraviolet absorbing substrate does not have the effect of reflecting heat rays or infrared rays, it is necessary to laminate various reflecting films on this substrate in order to impart these effects, and ultraviolet rays are cut sharply. This is not always the case, and, for example, the ZnO film that is generally commercialized has a columnar orientation when the UV performance is improved,
In addition, since it is extremely easy to ionize, its durability against chemicals is extremely weak, so that the places where it can be used are extremely limited.For buildings and vehicles, scratch resistance, chemical resistance, or wear resistance. It is not always said that the durability is excellent, and it is difficult to use it with a single plate.

More recently, the influence of ultraviolet rays due to ozone layer depletion is becoming more important as well as the effective use of solar energy. From this point as well, in addition to solar control, which is the conventional effective use of solar energy, ultraviolet shielding is also important. ing.

In the method described in, for example, the above-mentioned Japanese Patent Laid-Open Publication No. Hei 4-133004, an attempt is made to provide ultraviolet ray shielding performance with a ZnOx film, so that a very complicated multilayer film structure is provided for both moisture resistance and protection of the film. However, laminated glass or double glazing is more practical for construction and vehicle use because it is expensive and poor in durability.

Further, for example, in the ultraviolet absorbing transparent body described in JP-A-6-145387, the ultraviolet absorbing property, abrasion resistance, chemical resistance, weather resistance and the like are remarkably improved as compared with conventional ones. Although it can be used in most places or environments, it can be used in harsh environments such as long-term sliding contact, such as windshields, rear windows, and side window glass that moves up and down. There are some parts that are not always reliable enough to be used stably in the environment or in the environment for a long period of time, for example, as little damage or deterioration that would cause trouble after use for about 6 months to 1 year. Met.

On the other hand, for example, in the ultraviolet blocking glass for vehicles described in Japanese Patent Laid-Open No. 5-163174 mentioned above, it is sure that the ultraviolet blocking property is excellent, or that the glass is excellent in resistance to damage or weathering when it is moved up and down, scratched or rubbed. However, when adopting a relatively low temperature curing type ultraviolet absorbing thin film as shown in the ultraviolet absorbing transparent body described in JP-A-6-145387, it is not always immediately adopted. is there.

Similarly, for example, the above-mentioned Japanese Patent Laid-Open No. 1-138107.
In the modified polysilazane described in Japanese Patent Laid-Open No. JP-A No. 6-145387, it is difficult to say that the modified polysilazane, the method for producing the same, and the use thereof are relatively low-temperature curable types. In addition, it cannot be used for a transparent body that requires sufficient transparency.

Further, for example, in the composition for forming an ultraviolet-shielding glass protective film and the ultraviolet-shielding glass described in the above-mentioned JP-A-5-311120, a relatively low temperature curing type described in the above-mentioned JP-A-6-145387 is used. Are likewise unacceptable.

Furthermore, in the water repellent article and the method for producing the same described in, for example, Japanese Patent Application Laid-Open No. 5-310444, a silicon dioxide coating is used as an underlayer on the glass surface, and an organic silazane compound is added onto the silazane water repellent. However, it cannot be used at all in the case where the relatively low temperature curing type ultraviolet absorbing thin film described in JP-A-6-145387 is used as the undercoating layer and the hard coating is carried out.

[0022]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has a sufficient heat ray shielding performance and infrared reflection performance, for example, a laminated film containing a noble metal thin film. In addition, an acrylic resin containing, for example, a silicone component, which has a unique ultraviolet-shielding property in the underlayer that is a single-layer or laminated coating using at least a film made of metal, oxide, nitride, nitrogen oxide, etc. In addition, a solution of a polysilazane-based mixture is applied and formed on a hard coat type heat ray reflective UV absorbing film that is skillfully laminated and combined with a silicone-based hard coating resin, so that the underlayer is cured at a low temperature without being damaged by cure or the like. By coating with mold treatment, the durability, such as chemical resistance, scratch resistance, and abrasion resistance, which are the above-mentioned problems, is significantly improved. There are protective effect is obtained sufficiently be used for veneers or exterior, and can performance simultaneously and sufficiently expression of each of the heat ray alone configuration sufficient performance could not be obtained shielding and UV shielding, in particular 40
Ultraviolet rays can be sharply shielded near 0 nm, and while maintaining the effect of neutralizing the reflection color, it can be used not only for veneers for building and veneer, but also under various severe conditions. However, the present invention provides a useful heat-ray-reflecting UV-absorbing transparent material which is remarkably excellent in abrasion resistance, scratch resistance and durability and can be used for a long period of time.

That is, according to the present invention, a multilayer film formed by laminating a film containing at least one noble metal thin film on the surface of a transparent substrate, and / or metal, oxide, nitride, carbide and oxynitride. A heat ray reflective film of at least one of these is formed as an underlayer, and then, on the underlayer,
A silicone-based hard coat made by dissolving a siloxane prepolymer in an organic solvent after applying a synthetic resin-based primer coating solution prepared by dissolving and adding an optical brightener and an ultraviolet absorber to form an ultraviolet-absorbing thin film. Characterized in that a solution of a polysilazane-based mixture is formed by coating on the surface of a hard coat type heat ray reflective ultraviolet ray absorbing film formed by sequentially coating a coating solution and heating and curing to form a protective thin film. A heat ray reflective, ultraviolet absorbing transparent body.

In addition, the multilayer film including at least one layer of the noble metal thin film is a 3- to 7-layer film formed by sequentially laminating a dielectric, a noble metal or its alloy, a metal, a dielectric, or a repetitive lamination thereof. The heat ray-reflecting ultraviolet absorbing transparent body as described above, characterized in that.

Further, the precious metal-based thin film is made of Ag, Au, Cu,
The heat ray-reflecting ultraviolet absorbing transparent body as described above, which is Pt or an alloy thereof. Further, the dielectric of the multilayer film, Si, Ti, Sn, Al, Cr, SUS, Ta, Zn, In, SiC and oxides of these alloys, nitrides, oxynitride thin film, characterized in that The heat ray-reflecting ultraviolet absorbing transparent body described above.

Further, the heat ray reflective film is made of Si, Ti, Sn,
A single-layer film or a multi-layer film composed of at least one of oxides, nitrides, carbides and oxynitride thin films of Al, Cr, SUS, Ta, Zn, In, SiC and their alloys. The heat ray-reflecting ultraviolet absorbing transparent body described above.

Further, the heat ray reflective film is made of Sn, Al, In,
The heat ray-reflecting ultraviolet absorbing transparent body as described above, which is a metal oxide or a complex oxide doped with at least one of Sb and F 2.

Furthermore, the above-mentioned heat ray-reflecting ultraviolet absorbing transparent body, wherein the synthetic resin-based primer coating solution is an acrylic-based primer coating solution containing a silicone component.

Further, the above-mentioned heat ray-reflecting ultraviolet absorbing transparent body, wherein the ultraviolet absorbing agent contains at least an indole compound. Furthermore, the polysilazane-based mixture is a low-temperature-curable polysilazane-based mixture, and the above-mentioned heat ray-reflecting ultraviolet-absorbing transparent body.

The low-temperature curable polysilazane-based mixture is mainly composed of a poly (perhydrosilazane) -based mixture, and each of the above-mentioned heat-ray-reflecting ultraviolet absorbing transparent bodies is provided.

Here, as described above, a multilayer film formed by laminating films containing at least one or more noble metal-based thin films as the underlying layer is formed by first forming a dielectric material, a noble metal-based material or its alloy-based material, or a metal-based material. , A 3 to 7-layer film formed by sequentially laminating dielectrics, or repeating lamination thereof, for example, heat ray shielding, infrared reflection is a dielectric / silver alloy film / dielectric multilayer laminate,
Specifically, in the case of a 5-layer system of ITO / silver / ITO / silver / ITO on a transparent substrate, the visible light transmittance is high, and the reflectance in the near infrared to long wavelength infrared region is extremely high. This is because a reflective film can be obtained.

Further, as the noble metal-based thin film, Ag, Au,
Cu, Pt or an alloy thereof, and as the dielectric of the multilayer film, Si, Ti, Sn, Al, Cr, SUS, Ta, Zn, In,
Thin films of oxides, nitrides, and nitrogen oxides of SiC and these alloys, such as those with low visible light transmittance, include titanium nitride, which is a normal solar control film. The tin oxide film produced by the method also has high transparency and is excellent in durability.

Specifically, for example, the refractive index from the transparent substrate side
About 2.0 nm transparent dielectric about 40 nm, silver film about 10-15 nm,
About 40 nm of transparent dielectric with a refractive index of about 2.0, or about 40 nm of transparent dielectric with a refractive index of about 2.0 from the transparent substrate side, silver-based film
Transparent dielectric with about 10 to 15 nm and refractive index of about 2.0 About 70 to 80 nm, silver-based film about 10 to 15 nm, transparent dielectric with about 2.0 of refractive index
A layered coating with a thickness of about 400 nm is preferable because the visible ray transmittance can be increased due to the balance with the entire constituent film of the heat ray reflective UV absorbing transparent body, that is, thin film interference, and sufficient heat ray shielding, infrared ray reflection, and ultraviolet ray shielding. Is.

The various thin films described above are formed by, for example, a sputtering method, a spray method, a CVD method, or the like, and have a high visible light transmittance, for example, and satisfy the heat ray shielding, infrared ray reflecting, and ultraviolet ray shielding properties. Visible light transmittance of 65% or more, solar radiation transmittance of 60% or less, emissivity of 0.15 or less, 370 nm transmittance of 10% or less, preferably visible light transmittance of 70% or more, solar radiation transmittance of 55% or less. The emissivity is 0.10 or less and the transmittance at 370 nm is 5% or less.

The heat ray reflective film made of at least one of the above metals, oxides, nitrides, carbides and oxynitrides is formed as the underlayer because of various heat ray shielding functions and color tones, and the film. This is because the adhesiveness or film strength of itself and other various functions such as a function for radio waves may be provided together.

Further, as the heat ray reflective film, for example,
Single layer film or multi-layer film composed of at least one of oxides, nitrides, carbides and oxynitride thin films of Si, Ti, Sn, Al, Cr, SUS, Ta, Zn, In, SiC and alloys thereof. And is a metal oxide or complex oxide doped with at least one of Sn, Al, In, Sb, and F, so long as it does not adversely affect the UV absorbing film to be coated Can be selected appropriately and used individually or in a plurality, and the film is formed by a sputtering method, a spray method, a CVD method or the like.

Further, a synthetic resin-based primer coating solution prepared by dissolving and adding a fluorescent whitening agent and an ultraviolet absorber was applied and cured by heating to form an ultraviolet absorbing thin film, in particular in the ultraviolet / visible region boundary. While applying a brightening agent to the coating agent composition to cut very sharply without coloring, a synthetic resin primer, especially a silicone component, with good adhesion to the surface of the glass substrate, especially the transparent substrate, is applied. This is because it is dissolved and added to the acrylic primer coating solution containing it, and coexists with an ultraviolet absorber to absorb fluorescence, so that a coating film with less visible fluorescence can be formed at a relatively low temperature.

The fluorescent whitening agent absorbs in the ultraviolet region,
Any substance that emits fluorescence in the visible range and can be dissolved and added to a synthetic resin-based primer, especially an acrylic-based primer coating agent, and does not denature during heat curing of a coating film at a relatively low temperature, Moreover, it has appropriate heat resistance, and the absorption wavelength is in the ultraviolet / visible region boundary (for example, 400n
m vicinity), for example, UVITEX-OB (manufactured by Ciba-Geigy, 2,5 bis (5'-tert-butylbenzoxazolyl) thiophene, 2- (3,5di-t-butyl-2-hydroxyphenyl)) -5-chlorobenzotriazole], or EB
-501 (manufactured by Mitsui Toatsu Dye Co., Ltd.) and the like.

[0039] For example, the amount of UVITEX-OB added is about 0.02 to 0.5 wt%, and if it is less than 0.02 wt%, there is no effect, and if it exceeds 0.5 wt%, the solubility becomes close to the limit, and As crystals start to precipitate, coating film defects tend to occur, and adding more than necessary becomes uneconomical.

Examples of the UV absorbers that can coexist include benzophenone-based, benzotriazole-based, cyanoacrylate-based or salicylate-based UV absorbers. TINUVIN327 (manufactured by Ciba-Geigy), NIOSOR
B100 (manufactured by Kyodo Pharmaceutical Co., Ltd., 2,4 dihitroxybenzophenone), SEESOR B706 [manufactured by Cypro Kasei Co., 2- (2'-hydroxy
-5'-methyl-3 '-(3'',4'',5'',6''-tetrahydrophthalimidylmethylphenyl) benzotriazole], SEES
ORB712 [Cypro Kasei Co., 2,4-di-t-butylphenyl 3 '
5'-di-t-butyl 4'-hydroxybenzoate], and examples of indole compounds include BONASORB
-UA3901 (manufactured by Orient Chemical Co., Ltd.) should be included, and the absorption wavelength should be in the ultraviolet / visible region boundary (for example, 40
It is effective in the vicinity of 0 nm).

Further, for example, the above-mentioned TINUVIN327, NIOSORB100,
The amount of SEESORB706 or 712 added is about 0.1 to 1.5 wt%, and if it is less than 0.1 wt%, it has no effect, and if it exceeds 1.5 wt%, it approaches the solubility limit and precipitates recrystallization. Coating defects are likely to occur, and addition of more than necessary becomes uneconomical, and the addition amount of BONASORB-UA3901 is about 0.02 to 0.3 wt%. When it exceeds%, it becomes noticeable as soon as it starts to become yellowish.

The fluorescent whitening agent and the ultraviolet absorber are used in a molar ratio of about 1: 0.5 to 1: 3.0 (weight ratio of about 1: 0.5 to 1:10), preferably about 1: 1. It is (preferably about 1: 3 to 6), and when the amount of the fluorescent whitening agent is large, the transparency deteriorates due to the fluorescence, and when it is too small, the desired ultraviolet absorbing power cannot be obtained.

Further, regarding the synthetic resin primer, particularly the acrylic primer, since it is necessary to sufficiently dissolve the above-mentioned fluorescent brightening agent and the ultraviolet absorber, diacetone alcohol is used in an ether alcohol solvent such as ethyl cellosolve. It is advisable to use a mixed solvent prepared by combining a ketone alcohol solvent such as the above, a ketone, an ether, or an aromatic solvent so as not to attack the heat ray reflective transparent substrate. Especially when the transparent substrate is a glass plate or the like, it is preferable to use a ketone solvent such as cyclohexanone which has a dissolving power.

Further, the synthetic resin for the primer is, for example, an acrylic resin, a urethane resin, a fluorine resin or a polyester resin, and among them, the acrylic resin is commercially available, for example, an acrylic resin diamond. Nal BR88, 85 or 80 (manufactured by Mitsubishi Rayon Co., Ltd.) may be used depending on the concentration, viscosity or film thickness, and the resin content may be 1 to 15 wt%. 0.5 as total concentration
~ 2 wt%, viscosity is about 10-800 cP, and film thickness is preferably about 1-10 µ, more preferably about 2-8 µ, and optimally about 3 µ, for a total film thickness. Is about 5 to 11 μ.

Especially when the transparent substrate is made of glass,
In order to further improve the adhesion, it is often possible to use an adhesion improver such as a silicone compound such as a silane coupling agent,
For example, it is preferable to add OS808A (acrylic modified silicone manufactured by Daihachi Chemical Co., Ltd., solid content about 30 wt%, main solvent cellosolve acetate) or the like at about 1/4 to 4 times the resin content concentration. If it is too small, it will be ineffective, and if it is too large, it will be uneconomical.

Furthermore, the ultraviolet absorbing synthetic resin primer prepared as described above, especially the ultraviolet absorbing acrylic primer, has a uniform film thickness.
For example, dipping method, spray method, flow coating method,
It is applied by spin coating or printing to form a film,
For example, it is dried by heating at about 80 ° C. or higher for about 1 hour. If the heating is insufficient, the primer component is likely to elute into the protective film which is a silicone-based hard coat to easily cause clouding or cracks. If the heating is excessive, the adhesion of the protective film, which is a silicone-based hard coat, deteriorates.

The silicone hard coating solution is preferably based on an alcohol solution of a siloxane prepolymer obtained by hydrolyzing an organoalkoxysilane, which has been already proposed by the applicant. Those containing colloidal silica such as the coating composition described in JP-A No. 62-220531 are more preferable because of excellent abrasion resistance. In the case of commercial products, for example, Tosgard 510 (made by Toshiba Silicone) or Si coat 2
(Manufactured by Daihachi Chemical Co., Ltd.) can be used. The resin content in the solution is about 10 to 50%, the viscosity is about 15 to 5000 cP,
Further, the film thickness is preferably about 1 to 6 μm.

Further, the coating environment is, for example, a temperature of about
About 15 to 25 ° C, a humidity of about 40 to 50 RH%, and a cleanliness of about 10,000 or less are preferable from the viewpoint of preventing coating film defects. As the coating method, as in the case of the ultraviolet absorbing synthetic resin primer, especially the ultraviolet absorbing acrylic primer,
For example, a dipping method, a spray method, a flow coating method, a spin coating method, a printing method, or the like can be used so as to obtain a uniform film thickness. The film thickness is more preferably about 2 to 5 μm, and if it is thin, the effect of the surface protective film is lost, and if it is thick, cracks are likely to occur during heat-drying and curing.
Furthermore, a temperature of about 80 ° C or higher is good for heat drying and curing.
Especially when the transparent substrate is a glass plate or the like, a treatment at about 150 ° C. for about 2 hours is preferable for increasing the surface hardness.

Needless to say, a flow improver, a rheology control agent or the like may be appropriately added in order to improve the coating performance of the above-mentioned ultraviolet absorbing acrylic primer or silicone hard coating solution.

Furthermore, as the polysilazane-based mixture, a low temperature-curable polysilazane-based mixture is preferable, and for example, a poly (perhydrosilazane) -based mixture [for example, manufactured by Tonensha Co., Ltd.] is particularly preferable. The solid content concentration in the solution of the mixture is about 5 to 40 wt% (the rest is, for example, xylene and a curing catalyst).

The coating film of the mixture can be formed by a dipping method, a spray method, a flow coating method, a spin coating method, a printing method, or the like so as to obtain a uniform film thickness. About 3μ,
It is preferably about 1.0 to 2.0 μ, and when it is thin, the effect of strengthening the surface protection is reduced, and when it is thick, cracks are likely to appear during heat-drying and curing, and it is not economical. Further, since the heat-drying and curing contains an organic ultraviolet absorber, a fluorescent brightening agent and a resin, it is necessary to treat at a temperature of about 100 ° C. or higher and about 250 ° C. or lower. In the case of etc., it is about 150-220 ℃, about 10
A treatment for about 60 minutes, preferably about 30 minutes, is preferable for increasing the surface hardness. The application environment is, for example, a temperature of about 25 ° C and a relative humidity of about 25 ° C.
It is carried out in an air-conditioned environment of about 20 to 50% RH, preferably about 40% RH.

As the diluting solvent in the solution of the polysilazane-based mixture, aromatic compounds such as benzene, toluene and xylene, and ether compounds such as ethyl ether and tetrahydrofuran (THF) can be used.
The chlorine compound is, for example, methylene chloride, carbon tetrachloride, and the ketone compound is, for example, butyl carbitol acetate.

Furthermore, as the transparent substrate, not only an inorganic material but also an organic material may be used as long as it is transparent, and for example, inorganic glass such as float glass is preferable. Further, the shape and the like are not particularly limited, and various shapes,
In addition to the size or structure, such as bent plate glass, various tempered glass and strength-up glass,
It goes without saying that it can be used as a flat plate or a single plate, and can be applied as a multi-layer glass or a laminated glass.

[0054]

As described above, according to the present invention, a multilayer film formed by laminating films containing at least one noble metal thin film,
Further, an ultraviolet ray having a peculiar structure in which a heat ray-reflecting thin film made of at least one of metal, oxide, nitride or nitrogen oxide is used as a base layer and a primer solution in which a fluorescent whitening agent and an ultraviolet absorber are coexist Since it is a transparent body with a coating film with excellent shielding properties and a hard coat type heat ray reflection ultraviolet ray absorption film coated with a sufficient protective film, which is further coated with a solution of a polysilazane-based mixture, it has a heat ray reflection function and an infrared ray reflection function. It develops, works in a neutral color tone without impairing the heat ray shielding property, absorbs the fluorescence of the fluorescent whitening agent with an ultraviolet absorber and can be formed at a relatively low temperature as a non-obtrusive film, and its surface is a hard coat specified A unique silica-based film obtained from a solution of a polysilazane-based mixture (for example, in a surface analysis such as SIMS, a partial portion of the film, for example, It becomes a double protective film with N remaining in the coating adhesion part, etc., and in particular, it can cut the boundary of the ultraviolet / visible region extremely sharply around 400 nm, and has good adhesion, chemical resistance, scratch resistance or durability. In addition to those having excellent properties, in particular the above-mentioned peculiar silica-based film with a relatively thick film thickness can also have high adhesion to the hard coat film by low temperature treatment without the occurrence of cracks, etc. Moreover, for example, the pencil hardness is as hard as 9H or more, and the film strength and smoothness are also improved. Especially, abrasion resistance, scratch resistance or durability is significantly improved, sufficient visual field can be secured, and habitability is remarkably improved. It can be used as a single plate or exterior for buildings, houses, vehicles or various window materials, especially for windshields, rear windows and elevators of automobile window glass. For example, a transparent heat ray-reflecting UV-absorbing transparent material that can be used as a useful heat ray-shielding and UV-shielding window can be used for long-term use even under severer operating conditions and environments such as side door glass. The present invention can be easily and inexpensively obtained by a simple coating process such as a film forming method or a low temperature curing process.

[0055]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to the embodiment. Liquid A (Preparation of UV absorbing acrylic primer) [For glass coating] 350 g of cyclohexanone and 493 g of propylene glycol monomethyl ether as a solvent are put into a 1000 ml round bottom flask equipped with a stirrer and a reflux condenser, and acrylic BR is stirred at room temperature. -Introduce 52g of 88 resin (manufactured by Mitsubishi Rayon). UVITEX-OB optical brightener while continuing to stir
(Ciba-Geigy) 2g and UV absorber TINUVIN327 (Ciba-Geigy) 8g are added, and the temperature is raised to about 95 ° C in an oil bath for about 30 minutes, and then held for about 30 minutes to completely dissolve. Then, the heating was stopped, and after the temperature was lowered to room temperature, 95 g of acrylic modified silicone resin OS-808A was added and dissolved by stirring to obtain an ultraviolet absorbing acrylic primer for glass coating.

The ultraviolet absorbing acrylic primer solution was transparent and had a solid content of about 8.5% and a viscosity of about 550 cP. Liquid B (preparation of silicone-based hard coating solution) 100 g of methyltriethoxysilane and 10 g of 3-glycidoxypropyltrimethoxysilane were placed in a 500 ml round bottom flask equipped with a stirrer and a circulator, and 0.04 g of phthalic anhydride was added.
Is added and heated in a hot water bath to about 40 ° C to dissolve it, and then
Weakly basic colloidal silica aqueous solution Snowtex C (manufactured by Nissan Chemical Co., average particle size of about 15 μm, SiO ₂ content of about 20%) 100 g was added and reacted at about 40 ° C. for about 5 days, and GPC ( ULC802A manufactured by Tosoh Co., Ltd. was used to obtain a composition having a number average molecular weight of about 1100 and a solid content of about 29%. to this
145 g of isopropyl alcohol was added, and the molecular weight cut-off was 10
The mixture was concentrated with an 00 ultrafilter (manufactured by Nippon Millipore) to obtain a composition having a number average molecular weight of about 1200 by GPC and a solid content of about 20%. About 0.1% of dicyandiamide was added to the composition as a curing catalyst.
About 1 part was added to obtain a silicone-based hard coating solution. Solution C (Preparation of polysilazane-based mixture solution) A curing catalyst and the like were mainly composed of poly (perhydrosilazane), and xylene was used as a diluent solvent to obtain a solution having a solid content concentration of about 20 wt%. [Polysilazane manufactured by Tonensha Co., Ltd.] (Performance evaluation method) Heat ray reflection UV absorption: Absorption spectrum pattern is measured with an ultraviolet / visible / infrared spectrophotometer. (Hitachi-U4000 type) Wear resistance: JIS R 3221 compliant, wear wheel CS-10
F, load 500g, ΔH (haze) value (%) after 1000 rotations.

Hardness: Pencil hardness. Adhesion: JIS K5400 compliant, cross-cut (1 mm
Mouth) The remaining number of tape peeling is displayed as / 100.

Chemical resistance: Acid resistance --------- 3 wt% Dilute H ₂ SO ₄ immersion test for 24 hours. Alkali resistance --- 3wt% NaOH aqueous solution 24 hours in immersion test. Solvent --- 100% ethanol 4 hours by drip test.

Weather resistance: In accordance with JIS D0205,
Time until visual anomalies (film cracks, peeling, noticeable yellowing) are seen on the sunshine carbon weather meter.
(However, glass surface irradiation) Example 1 A clear float glass substrate having a size of about 300 mm x 300 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, water rinse, isopropyl alcohol, and dried, and then a DC magnetron spatula was used. The Ti target set in the vacuum tank of the ring device is set so as to be able to reciprocate upward, facing the Ti target, and then the inside of the tank is deaerated by a vacuum pump to about 5 × 10 ⁻⁶ Torr or less, and then the vacuum is applied. Ar gas and N ₂ gas (however, Ar gas and N ₂
The gas flow rate ratio may be in the range of 0: 100 to 50:50) and the degree of vacuum is maintained at about 2 × 10 ^-3 Torr.
A power of about 1.0 kw was applied to the Ti target, and the glass substrate was transported at a speed of about 85 mm / min above the Ti target in the DC magnetron reaction spatula with N ₂ gas to cause a TiNx thickness of about 35 nm. A thin film was formed. After the film formation is completed, the application to the Ti target and the gas supply are stopped.

The non-coated surface of the obtained glass substrate with a heat ray reflective film was film-masked and dipped in the above-prepared solution A which is a UV-absorbing acrylic primer solution for glass coating, and was about 0.1 cm 2 / sec. It is pulled up at about the same speed, dried at about 120 ° C for about 0.5 hours, and the film thickness is about 7μ.
An ultraviolet absorbing film having a certain degree was formed.

Next, the heat ray reflective glass substrate with the ultraviolet absorbing film was immersed in the above-prepared silicone hard coating solution B, and pulled up at a speed of about 1 cm / sec and about 0.5 at about 120 ° C. About 150 hours
The film was dried and hardened at about 0 ° C. for about 0.5 hours to form a protective film with a thickness of about 4 μm.

Then, the glass substrate with a laminated film coated with the hard coat protective film was treated with the above prepared polysilazane mixture solution C in an air-conditioned clean room at about 25 ° C. and about 40% RH. Approximately 10 after dipping in liquid
The film was air-dried for 1 minute, and then placed in a hot-air circulation dryer at about 200 ° C. for about 30 minutes to cure, and a silica-based film was obtained. The film was colorless and transparent and had no cracks, and the film thickness was about 1.5 μm. In the case of a far-infrared furnace, it could be cured at about 200 ° C for about 15 minutes.

The obtained glass substrate, which is a heat ray-reflecting ultraviolet absorbing transparent body, was evaluated according to the above-described performance evaluation method. As a result, in addition to the conventional heat ray reflection performance, a new
Near m, the boundary between the UV and visible regions can be cut very sharply with sufficient transparency without coloring, and the light transmittance in the visible and infrared regions is improved by about 5%. In particular, the light transmittance up in the visible region makes the appearance of the TiNx thin film look neutral.

Also, the surface hardness is 9H or more, which is hard, and the haze value (ΔH) after the Taber test is about 2.7% (a value less than about half of that without silica film) and abrasion resistance. The scratch resistance was also extremely excellent. Also weather resistant
It was a heat-ray-reflecting UV-absorbing transparent body having no visible abnormality after 1000 hours or more, chemical resistance, especially acid resistance after 24 hours, and excellent durability and a visible light transmittance of about 35%.

Example 2 Using the same clear float glass substrate as in Example 1,
Set up so that it can reciprocate upwards, facing the target of Zn and SUS (stainless steel) set in the vacuum chamber of the DC magnetron sputtering device, and then the chamber is vacuum-pumped to about 5x10 ^-6 Torr or less. After degassing up to 10 minutes, Ar gas and O ₂ gas (provided that the flow rate ratio of Ar gas and O ₂ gas is in the range of 0: 100 to 50:50) are introduced into the vacuum chamber and vacuumed. At a temperature of about 2 × 10 ^-3 Torr, an electric power of about 1.0 kw is applied to the Zn target, and the glass magnet at a speed of about 1300 mm / min is passed through the DC magnetron reaction spatter of O ₂ gas above the Zn target. By transporting the substrate, a ZnOx thin film having a thickness of about 10 nm was formed as the first layer. After the film formation is completed, the application to the Zn target and the gas supply are stopped.

Next, with the glass substrate being placed in the vacuum chamber, Ar gas was introduced into the vacuum chamber so that the degree of vacuum was about 2 ×.
Hold at 10 ^-3 Torr, apply about 0.15kw electric power to the SUS target, and move the DC magnetron reaction sputter by Ar gas to the speed above the SUS target.
By transporting the glass substrate at 2000 mm / min, a SUS thin film having a thickness of about 3.5 nm was formed as a second layer on the ZnOx film forming surface of the glass substrate. After film formation is completed, SUS
The application to the target and the supply of gas are stopped.

Then, with the glass substrate being placed in the vacuum chamber, Ar gas and O ₂ gas (however, the flow rate ratio of O ₂ gas to Ar gas was in the range of 100: 0 to 50:50) were placed in the vacuum chamber. Is maintained at about 2 × 10 ^-3 Torr, and a power of about 1.0 kw is applied to the Zn target, and the inside of the DC magnetron reaction sputter by O ₂ gas is introduced into the Zn target. By transporting the glass substrate above at a speed of about 1300 mm / min, a ZnOx thin film having a thickness of about 10 nm was formed as a third layer on the SUS film forming surface of the glass substrate. After the film formation is completed, the application to the Zn target and the gas supply are stopped.

On the obtained glass substrate with a heat ray reflective film, a similar ultraviolet absorbing film of about 6 μm was formed by using the same primer solution A as in Example 1 and by the same film forming method.

Next, the heat ray reflective glass substrate with the ultraviolet absorbing film was immersed in the above-prepared silicone hard coating solution B solution, pulled up at a speed of about 1 cm / sec and about 0.5 at about 120 ° C. About 150 hours
The film was dried and hardened at about 0 ° C. for about 0.5 hours to form a protective film with a thickness of about 3 μ.

Then, a silica film was obtained in the same manner as in Example 1. The film was colorless and transparent and had no cracks, and the film thickness was about 1.5 μm. The obtained glass substrate which is a heat ray reflective ultraviolet absorbing transparent body was evaluated according to the above-described performance evaluation method.

As a result, the visible light transmittance was about 75% and the heat ray reflection characteristics were not better than those of Example 1, but similar effects to those of Example 1 were obtained for the new optical characteristics.
Also, the surface hardness is 9H or more, which is hard, and the haze value (△ H) after Taber test is about 2.9% (value less than about half compared to the one without silica film) and the scratch resistance and abrasion resistance. It was a heat-ray-reflecting UV-absorbing transparent body having excellent properties, weather resistance of 1000 hours or longer, no visual abnormality, no abnormal chemical resistance, and markedly superior durability.

Example 3 Next, the following preparation was carried out. Solution D (Preparation of UV absorbing acrylic primer) [For glass coating] 350g of cyclohexanone and 495g of propylene glycol monomethyl ether as a solvent are put into a 1000ml round bottom flask equipped with a stirrer and a reflux condenser, and acrylic BR is stirred at room temperature. -Introduce 55g of 85 resin (manufactured by Mitsubishi Rayon). While continuing to stir, add 2g of fluorescent whitening agent UVITEX-OB (made by Ciba-Geigy) and 9g of ultraviolet absorber TINUVIN327 (made by Ciba-Geigy) and take about 30 minutes in an oil bath.
After heating to about 95 ° C, hold for about 30 minutes to completely dissolve it. Next, the heating was stopped, and after the temperature was lowered to room temperature, 100 g of the acrylic modified silicone resin OS-808A was added and dissolved by stirring to obtain an ultraviolet absorbing acrylic primer for glass coating. The ultraviolet absorbing acrylic primer solution was transparent and had a solid content of about 9% and a viscosity of about 600 cP.

A clear float glass substrate similar to that used in Example 1 was used, and the Zn and silver targets set in the vacuum chamber of the DC magnetron sputtering device were set facing each other so that they could be reciprocated upward. After degassing the inside of the chamber with a vacuum pump to about 5 × 10 ⁻⁶ Torr or less, Ar gas and O ₂ gas (however, the flow rate ratio of O ₂ gas and Ar gas is
It may be in the range of 100: 0 to 50:50) and the degree of vacuum is maintained at about 2 × 10 ^-3 Torr, about 1.0 kw of electric power is applied to the Zn target, and DC magnetron is generated by O ₂ gas. A ZnOx thin film having a thickness of about 40 nm was formed as a first layer by transporting the glass substrate in the reaction spatter above the Zn target at a speed of about 250 mm / min.
After the film formation is completed, the application to the Zn target and the gas supply are stopped.

Next, with the glass substrate kept in the vacuum chamber, 45 cc of Ar gas was introduced into the vacuum chamber to maintain the degree of vacuum at about 3 × 10 ^-3 Torr, and about 0.1 kw was added to the silver target.
Of the Ar magnet, the speed of about 800m above the silver target in the DC magnetron spatter by Ar gas.
By transporting the glass substrate at m / min, an Ag thin film having a thickness of about 10 nm was formed as a second layer on the ZnOx film forming surface of the glass substrate. After the film formation is completed, the application to the silver target and the gas supply are stopped.

Next, with the glass substrate being placed in the vacuum chamber, Ar gas was introduced into the vacuum chamber so that the degree of vacuum was about 3.
While maintaining at x10 ^-3 Torr and applying a power of about 0.1 kw to the Zn target, the Zn magnet was put in the DC magnetron spatter.
By transporting the glass substrate above the target at a speed of about 1600 mm / min, a Zn thin film having a thickness of about 6 nm was deposited and laminated as a third layer on the Ag deposition surface of the glass substrate. After the film formation is completed, the application to the Zn target and the gas supply are stopped.

Next, with the glass substrate being placed in the vacuum chamber, the same process as the first layer was performed, and a ZnOx thin film having a thickness of about 40 nm was formed and laminated as the fourth layer on the Zn film formation surface of the glass substrate. .
After the film formation is completed, the application and the gas supply are similarly stopped.

In the obtained glass substrate with a heat-insulating film, the above-prepared UV-absorbing acrylic primer solution D was immersed in the solution, pulled up at a rate of about 0.15 cm / sec, and then about 120 ° C. Dry for about 30 minutes,
An ultraviolet absorbing film (UV) having a film thickness of about 8μ was formed.

Next, the heat-insulating glass substrate with the ultraviolet absorbing film was immersed in the above-prepared silicone hard coating solution B, pulled up at a speed of about 1 cm / sec, and at about 120 ° C. for about 0.5 hours. The film was dried and cured at about 140 ° C. for about 0.5 hours to form a hard coat protective film (HC) with a thickness of about 5 μm.

Then, a silica-based film was obtained in the same manner as in Example 1 except that the curing temperature was about 170 ° C. The film was colorless and transparent and had no crack, and the film thickness was about 1.2 μm.

In addition to the above-mentioned performance evaluation method, the obtained heat-reflecting UV-absorbing transparent glass substrate was subjected to visible light transmittance (380 to 780 nm), visible light reflectance (380 to 780 nm) and solar radiation transmittance (340 〜1800nm), 340 type self-recording spectrophotometer (Hitachi) and JIS Z 8722, JIS R 31
The optical characteristics of each of them were determined by 06. Also, regarding the ultraviolet absorption performance, 370 nm with a 340 type self-recording spectrophotometer
It was evaluated by the transmittance. The chemical resistance was judged according to JIS R 3221 by observing the deterioration state of the film. Regarding weather resistance among humidity resistance, the surface condition after storage in an environmental tester at 50 ° C and 90% for about 30 days was visually evaluated.

As a result, visible light reflectance (hereinafter referred to as D ₆₅ light source)
Is about 10 to 8%, visible light transmittance is high at about 70.6%, solar radiation transmittance is about 50%, solar reflectance is about 22%, UV transmittance at 370 nm is 0% (about 0.1% at 380 nm), etc. It exhibits excellent UV shielding, heat shielding, and infrared shielding, and in particular, it can cut the UV / visible region boundary very sharply at around 400 nm, and has excellent habitability.

Further, the surface hardness is 9H or more, which is hard, and the haze value (ΔH) after the Taber test is about 4.3% (a value less than about half of that without silica film) and scratch resistance. It was a heat ray-reflecting ultraviolet absorbing transparent body having excellent abrasion resistance, excellent weather resistance, and no abnormalities in chemical resistance and chemical resistance, and remarkably excellent durability.

It can be used for a relatively long period of time even on the windshield and rear glass of automobile window glass and the side door glass that moves up and down, and has much more scratch resistance, abrasion resistance and durability than ever before. there were.

Example 4 In the same manner as in Example 3, the film constitution was changed to a glass substrate (F
l3) / ITO (45nm) / AgCu (12nm) / Zn (3nm) / ZnOx
(45nm) / UV (8μ) / HC (5μ) / silica film (1.5
μ) and the same measurement and evaluation as in Example 3 were performed.
The AgCu thin film was formed by DC magnetron sputtering with Ar gas, and the ITO target was formed by DC reactive magnetron sputtering with Ar gas and a small amount of oxygen so as to have a predetermined film thickness.

As a result, visible light reflectance (hereinafter referred to as D ₆₅ light source)
Is about 17 to 22%, visible light transmittance is about 66%, solar radiation transmittance is about 46%, solar radiation reflectance is about 35%, UV transmittance at 370 nm is 0% (0% at 380 nm). It exhibits ultraviolet light shielding, heat ray shielding, and infrared ray shielding, and in particular, it can cut the boundary between the ultraviolet and visible regions extremely sharply around 400 nm, and has excellent habitability.

The surface hardness is 9H or more, which is hard, and the haze value (ΔH) after the Taber test is about 3.8% (a value less than about half of that without silica film) and scratch resistance. It was a heat ray-reflecting ultraviolet absorbing transparent body having excellent abrasion resistance, excellent weather resistance, and no abnormalities in chemical resistance and chemical resistance, and remarkably excellent durability.

It can be used for a relatively long period of time even on windshields and rear windows of window glass for automobiles and side door glass that moves up and down, and has much more scratch resistance, abrasion resistance, and durability than ever before. there were.

[0088]

As described above, according to the present invention,
Reflects heat rays and absorbs and blocks ultraviolet rays without impairing the optical characteristics and heat rays and infrared ray shielding performance, especially 40
It can block UV rays at the boundary between the UV / visible region at around 0 nm very sharply, greatly improving the habitability and further improving the adhesiveness, chemical resistance, scratch resistance or durability. Not only can it be used as a veneer for buildings, houses, vehicles, etc. as a veneer or exterior, but also especially under severe operating conditions and environments such as windshields of automobile window glass, rear glass or side door glass that moves up and down. It is possible to easily and inexpensively provide a useful heat ray-reflecting ultraviolet absorbing transparent body that can be widely used in various fields such as long-term use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C08J 7/04 M C09D 133/00 PGC 183/04 PMS (72) Inventor Haruki Kuramasu Matsusaka City, Mie Prefecture 1510 Oguchimachi Central Glass Co., Ltd. Glass Research Institute

Claims (10)

[Claims] 1. A multilayer film formed by laminating a film containing at least one noble metal thin film on the surface of a transparent substrate, or
And forming a heat ray reflective film made of at least one of metals, oxides, nitrides, carbides and oxynitrides as an underlayer, and then dissolving and adding a fluorescent whitening agent and an ultraviolet absorber onto the underlayer. A synthetic resin-based primer coating solution is applied and cured by heating to form an ultraviolet-absorbing thin film, and then a silicone-based hard coating solution in which a siloxane prepolymer is dissolved in an organic solvent is applied and cured by heating to form a protective thin film. A heat ray-reflecting ultraviolet ray absorbing transparent body, characterized in that a solution of a polysilazane-based mixture is formed on the surface of a hard coat type heat ray-reflecting ultraviolet ray absorbing film formed by sequentially forming the above. 2. A multi-layered film including at least one noble metal-based thin film is a 3- to 7-layer film formed by sequentially laminating a dielectric, a noble metal or an alloy thereof, a metal, a dielectric, or a repetitive lamination thereof. The heat ray reflective ultraviolet absorbing transparent body according to claim 1, wherein 3. The heat ray reflecting ultraviolet absorbing transparent body according to claim 1, wherein the noble metal thin film is made of Ag, Au, Cu, Pt or an alloy thereof. 4. The dielectric material of the multi-layer film is Si, Ti, Sn, A
3. The heat ray reflective ultraviolet absorbing transparent body according to claim 1, which is an oxide, nitride or oxynitride thin film of l, Cr, SUS, Ta, Zn, In, SiC and alloys thereof. 5. The heat ray reflective film is made of Si, Ti, Sn, Al, C.
A single-layer film or a multi-layer film comprising at least one of oxides, nitrides, carbides and oxynitride thin films of r, SUS, Ta, Zn, In, SiC and their alloys. Item 1. A heat ray-reflecting ultraviolet ray absorbing transparent body according to items 1 and 4. 6. The heat ray reflective film comprises Sn, Al, In, Sb, F
6. The heat ray reflective ultraviolet absorbing transparent body according to claim 1, which is a metal oxide or a complex oxide doped with at least one of the above. 7. The synthetic resin-based primer coating solution is an acrylic-based primer coating solution containing a silicone component.
The heat ray-reflecting ultraviolet absorbing transparent body described. 8. The ultraviolet absorber comprises at least an indole compound.
7. A heat ray-reflecting ultraviolet absorbing transparent body as described in 7 above. 9. The heat ray reflective ultraviolet absorbing transparent body according to claim 1, wherein the polysilazane-based mixture is a low temperature-curable polysilazane-based mixture. 10. The heat ray reflective ultraviolet absorbing transparent body according to claim 9, wherein the low temperature-curable polysilazane-based mixture is mainly composed of poly (perhydrosilazane).