JPH08217500A - Safety glass - Google Patents

Abstract

PURPOSE: To obtain safety glass effectively shielding heat ray without dropping a visible light transmittance, producible without changing the conventional production process of safety glass, by laying a non-rigid resin layer containing a heat ray shielding metal oxide between a pair of glass plates. CONSTITUTION: In safety glass comprising a pair of glass plates and a non-rigid resin layer laid between a pair of glass plates, a heat ray shielding metal oxide is added to the non-rigid resin layer. SnO2 or In2 O3 having >=0.lμm particle diameter is especially suitable as the heat ray shielding metal. The reason why the particle diameter is 0.1μm is that the scattering and absorption of visible light are enlarged and transparency can not be obtained when the particle diameter exceed 0.1μm. It is known that the light scattering by particles is maximized when the particle diameter is a size of 1/2 wavelength and is proportional to the sixth power of particle diameter in the region smaller than it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass having a heat ray shielding function, and more particularly to a laminated glass having a soft resin layer containing a heat ray shielding metal oxide.

[0002]

2. Description of the Related Art A pair of glass plates are bonded with a soft resin layer,
Laminated glass that prevents scattering of broken pieces when damaged is used for vehicle window glass for automobiles, railways, aircrafts, etc., window glass for construction, crime prevention glass, and the like. As a method of imparting heat ray shielding performance to laminated glass, a method of using heat ray reflective glass, a method of mixing an organic dye in a soft resin layer to form a colored film, a method of using a heat ray reflective film in a soft resin layer, etc. have been conventionally performed. It is being appreciated.

Among the above-mentioned conventional techniques, as a method using a heat ray reflective glass, for example, in Japanese Patent Laid-Open No. 6-144891, a glass in which tungsten oxide and a silver thin film are laminated by a vacuum vapor deposition method, a sputtering method or the like is used. . In addition, the method of coloring the organic dye is to knead the organic dye into a resin such as polyvinyl butyral and color it into green, blue, brown or the like to absorb a part of visible light and reduce the heat energy of sunlight. ing.

Furthermore, a method using a heat ray reflective film is disclosed in, for example, JP-A-56-3252 and JP-A-63.
In JP-A-134332, silver and oxide thin films are laminated on a plastic film such as polyester by a vacuum deposition method, a sputtering method or the like, sandwiched with polyvinyl butyral, and laminated with glass. And, JP-A-60-127152 and JP-A-6-191906.
In the publication, a heat ray reflecting layer or film and a near infrared absorbing agent coating layer or film are laminated to improve the shielding performance.

[0005]

In the conventional method for imparting heat ray shielding performance to laminated glass, for example, in the method using heat ray reflective glass, the vacuum evaporation method or the sputtering method is used, resulting in poor productivity and high cost. However, in the method of forming a colored film by mixing an organic dye into the soft resin layer, the visible light transmittance is lowered, which is very inconvenient in applications not intended for coloring. However, the method of using the heat ray reflective film for the soft resin layer uses a vacuum evaporation method or a sputtering method to produce the heat ray reflective film, resulting in poor productivity and cost. However, the conventional method for producing laminated glass using only polyvinyl butyral resin has to be changed. Also it occurs a problem that.

The present invention has been made in view of the above problems, and can be produced without changing the conventional manufacturing process of laminated glass, and the effect of heat rays can be obtained without lowering the visible light transmittance. The present invention intends to provide a laminated glass that can be shielded selectively.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above-mentioned problems, and found that in the soft resin layer used for laminated glass, fine particles that do not absorb visible light but absorb heat rays are uniform. The present invention has been found to be possible to obtain a laminated glass that effectively absorbs heat rays without reducing the visible light transmittance without changing the conventional manufacturing process of laminated glass at all, and thus reached the present invention.

That is, the laminated glass according to claim 1 of the present invention is a laminated glass comprising a pair of glasses and a soft resin layer provided between the glasses, wherein the soft resin layer contains a heat ray shielding metal oxide. It is characterized by containing.

The laminated glass according to claim 2 is
It is desirable that the heat ray-shielding metal oxide is either tin oxide or indium oxide having a particle diameter of 0.1 μm or less.

The laminated glass according to claim 3 is
It is preferable that the heat ray-shielding metal oxide is blended so as to be 0.4 g / m ² or more.

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. The present invention is achieved by uniformly dispersing a heat ray-shielding metal oxide in a soft resin forming an interlayer film of laminated glass.

Any of the heat ray-shielding metal oxides used in the present invention can be used as long as it absorbs as little visible light as possible and has a large absorption at 780 to 2500 nm, which is generally regarded as heat rays. Is. Examples of such materials include SnO ₂ , In ₂ O ₃ , CdO, Cd ₂ SnO ₄ , and F.
Examples thereof include transparent conductive oxides such as eO, Fe ₃ O ₄ , ZnO, VO ₂ , and V ₂ O ₅ .

Particularly in the present invention, the particle size is 0.1 μm.
The following SnO ₂ or In ₂ O ₃ are suitable. The reason why the particle size is set to 0.1 μm is that when the particle size exceeds 0.1 μm, the scattering and absorption of visible light becomes large and transparency cannot be obtained. It is known that the scattering of light by particles is maximum when the particle size is half the wavelength, and is proportional to the sixth power of the particle size in the smaller range.

The inventors of the present invention have dispersed metal oxides having different particle diameters, and examined the dispersed particle diameter and the transparency of visible light. We found that it became transparent, and came to this conclusion. Further, the smaller the particle diameter, the more preferable, and the more preferable diameter is 0.05 μm or less. For the above reason, the SnO ₂ used in the present invention is
Alternatively, In ₂ O ₃ is not particularly limited as long as it has a particle size of 0.1 μm or less, more preferably 0.05 μm or less.

As a method for producing SnO ₂ , the method described in JP-A-2-105875 can be mentioned. There is no problem in doping with a different element for the purpose of improving the heat ray shielding performance. Sb, P, Te, W, Cl, F are suitable as the dopant.

As a method for producing In ₂ O ₃ , a precipitate formed by neutralizing an aqueous solution of an indium salt such as indium chloride, indium nitrate and indium sulfate with an alkali such as NaOH and NH ₄ OH is filtered and washed. However, a method of firing in a reducing atmosphere can be exemplified. There is no problem in doping with a different element for the purpose of improving the heat ray shielding performance. As the dopant, Sn, Mo, Z
r, Ti, Sb, W and F are suitable.

As the soft resin used for the laminated glass of the present invention, polyvinyl butyral resin is mainly used, but other resins may be used. For example, in the case of so-called injection type laminated glass in which a liquid resin is injected and cured between two glass plates, the liquid resin
A heat ray-shielding metal oxide can be dispersed.

That is, according to the present invention, a laminated glass obtained by laminating two glass plates with a polyvinyl butyral resin film, a solution of a polyvinyl butyral resin is applied to one glass to form a film, and then the other glass is adhered. It can be used as a laminated glass or the like which is produced by injecting a liquid resin such as acrylic resin between the laminated glass and two sheets of glass and curing the resin.

As a method for dispersing the heat ray-shielding metal oxide in the soft resin, a conventional dispersing method can be adopted. That is, it is possible to use a dispersion device such as a ball mill, a sand mill, or an attritor. At this time, it is desirable to use a dispersant such as a surfactant or a polymer compound that does not adversely affect the performance of the soft resin. When an additive such as a solvent, a plasticizer, a stabilizer or a colorant is used for the soft resin, it is possible to disperse the additive in advance and then mix it with the resin. This method is particularly effective when the resin is solid at room temperature, or when it is liquid but has high viscosity and requires a large amount of energy for dispersion.

For example, as a method for dispersing a heat ray-shielding metal oxide in a polyvinyl butyral resin, first, it is dispersed in a plasticizer such as dioctyl phthalate, tributyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate and dibutyl sebacate, A method of forming a film into a film according to a conventional molding method for polyvinyl butyral resin can be adopted.

At this time, the blending ratio of the heat ray-shielding metal oxide to the plasticizer is preferably 10 to 400%, and the concentration in the polyvinyl butyral resin is 0.4 g / m ² depending on the shielding performance. It is desirable to mix them as described above. The reason is 0.4 g /
If it is less than m ² , the difference between the solar radiation transmittance and the visible light transmittance is 5
%, And the shielding effect is small. Further, when the polyvinyl butyral resin is dissolved in a solvent to form a liquid, and in the case of a liquid injection resin such as an acrylic resin, a direct dispersion method can be used.

As a method for producing a laminated glass from a film or solution of a soft resin in which a heat ray-shielding metal oxide is dispersed, a conventional method for producing a laminated glass can be adopted as it is. For example, in the case of using a polyvinyl butyral film, the polyvinyl butyral film is sandwiched between two glass plates, and a glass temperature of 80 to
Pre-bonding at 100 ° C and a degree of vacuum of 650 mmHg or more, then temperature 120-150 ° C, pressure 10-15 kg / c
A laminated glass can be obtained by performing main bonding for 20 to 40 minutes in an m ² autoclave.

As the glass material used for the laminated glass of the present invention, any of those generally used for construction or vehicles can be used, and ordinary plate glass, float glass, heat ray absorbing glass, etc. can be used. it can. In the laminated glass of the present invention, a heat ray absorbing glass is particularly suitable, and high shielding performance can be obtained over the entire near infrared wavelength range.

[0024]

EXAMPLES The present invention will now be described in more detail with reference to Examples. (Example 1) [Preparation of SnO ₂ ] 46.2 parts by weight of SbCl ₃ and 67
0 parts by weight of SnCl ₄ .5H ₂ O was dissolved in 3000 parts by weight of 6N-HCl solution, and 2000 parts by weight of 25% ammonia solution was added and reacted to obtain a sol dispersion liquid. It was filtered and washed until ammonium chloride could not be detected.

Then, this was heated to 350 ° C. in a closed container and kept for 5 hours, then, in the cooling process, water vapor was released, and the solid content was concentrated to 25% by weight to obtain an antimony-containing tin oxide having an average particle size of 50 Å (hereinafter , Abbreviated as ATO). 1 part of octadecylamine was added to 400 parts by weight of this dispersion.
0 parts by weight was added to obtain a coagulated precipitate. The aggregate was taken out by filtration and dried at 100 ° C. for 2 hours to obtain ATO powder.

[Preparation of Dispersion] ATO powder 36.3
By weight, 73.7 parts by weight of toluene were mixed and dispersed for 5 minutes with an ultrasonic disperser. To this dispersion, 3 parts by weight of a 10% toluene solution of an anionic surfactant was added and mixed well, and 114 parts by weight of dioctyl phthalate was further mixed. This mixed solution was distilled under reduced pressure at 95 ° C. for 15 minutes to remove toluene. This liquid is dioctyl phthalate A
It is a liquid in which TO is uniformly dispersed in 20%.

[Production of Intermediate Film and Laminated Glass] With respect to 100 parts by weight of polyvinyl butyral resin, 5 parts by weight of the above dispersion, 35 parts by weight of dioctyl phthalate, and an ultraviolet absorber (manufactured by Ciba Geigy, trade name: 0.15 parts by weight of TINUVIN P) were mixed and sufficiently kneaded, and the mixture was extruded to form a polyvinyl butyral film having an ATO content of about 8.4 g / m ² and a thickness of 0.76 mm. Then, the obtained film was sandwiched between 3 mm plate glass and adhered at a glass temperature of 70 ° C. and a pressure of 5 kg / cm ² , and further a temperature of 135 ° C. and a pressure of 1
A laminated glass was produced by pressing with an autoclave of ² kg / cm ² . The visible light transmittance of this laminated glass is 7
The solar radiation transmittance is 3.9% and the solar radiation transmittance is 57.0%. The optical properties of the produced laminated glass are the same as those of conventional laminated glass (3 mm
Float glass + 0.76mm polyvinyl butyral +
The optical characteristics of 3 mm float glass) are shown in FIG. As shown in the figure, the transmittance of the conventional laminated glass was 100%, but it was significantly reduced to about 900 nm.
By the above, it became 1/2 or less of the conventional value, and it became 1/3 or less of the conventional value at about 1100 nm or more.

Example 2 [Preparation of In ₂ O ₃ ] 154.5 parts by weight of indium chloride,
Dissolve 5.2 parts by weight of stannic chloride in 2000 parts by weight of pure water to form a uniform solution, and add ammonia water to adjust the pH to 12
Until a white precipitate was formed, and ammonium chloride could not be detected, the mixture was filtered and washed.

Pure water was added to the precipitate of the cleaning agent so that the solid content was 5% by weight to form a slurry, which was dried with a spray dryer to obtain a white powder. The obtained white powder was calcined in the air at 450 ° C. for 5 minutes, and further in a mixed gas of N ₂ and H ₂ at 275 ° C. for 40 minutes. The obtained powder is indium oxide (hereinafter referred to as ITO) having a particle size of 0.03 μm and 3% by weight of tin oxide dissolved therein.

[Decomposition into plasticizer]
By weight, 70 parts by weight of dioctyl phthalate and 3 parts by weight of an anionic surfactant were mixed and dispersed for 3 hours with a sand grinder.

[Kneading into Resin] 2 parts by weight of the above dispersion liquid, 38 parts by weight of dioctyl phthalate, and an ultraviolet absorber (trade name: Tinuvin P, manufactured by Ciba-Geigy Co.) are used with respect to 100 parts by weight of polyvinyl butyral resin. 0.
A polyvinyl butyral film having an ITO content of about 5.0 g / m ² and a thickness of 0.76 mm was produced by mixing 15 parts by weight, thoroughly kneading the mixture, and extruding the mixture. The film thus obtained was sandwiched between 3 mm plate glasses, adhered at a glass temperature of 70 ° C. and a pressure of 5 kg / cm ² , and further pressed in an autoclave at a temperature of 135 ° C. and a pressure of 12 kg / cm ² to produce laminated glass. The laminated glass has a visible light transmittance of 84.6% and a solar radiation transmittance of 65.2%. The optical characteristics of the produced laminated glass are shown in FIG. As shown in the figure, the transmittance is about 1050.
When it is more than 1 nm, it becomes 1/2 or less of the conventional value, and when it is more than 1500 nm, it becomes substantially 0%.

(Embodiment 3) In this embodiment 2, the case where one of the pair of glasses is a heat ray absorbing glass is manufactured by the same manufacturing process as that of the embodiment 2. The visible light transmittance of this laminated glass was 77.5%, and the solar radiation transmittance was 65.2.
%. The optical characteristics of the laminated glass in this case are shown in FIG. As shown in the figure, the transmittance is about 850 nm.
With the above, it becomes 1/2 or less of the conventional value, and 900 nm to 1400
In nm, it was reduced to 1/3 or less of the conventional value, and in 1400 nm or more, it was substantially 0%.

[0033]

Therefore, in the laminated glass according to the first aspect of the present invention, since the pair of glasses and the soft resin layer provided between the glasses contain the heat ray-shielding metal oxide, the conventional laminated glass is used. It is possible to realize a laminated glass having a heat ray-shielding property at low cost without changing or adding a glass manufacturing method.

Further, in the laminated glass according to claim 2, since the heat ray-shielding metal oxide is either tin oxide or indium oxide having a particle diameter of 0.1 μm or less, absorption of visible light is minimized, Moreover, it is possible to realize a laminated glass having a good heat ray shielding property.

Further, in the laminated glass according to claim 3, the heat ray-shielding metal oxide has a compounding ratio of 0.4.
Since the composition is blended so as to be g / m ² or more, the difference between the visible light transmittance and the solar radiation transmittance can be 5% or more.

[Brief description of drawings]

FIG. 1 is a graph showing optical characteristics of a laminated glass of the present invention.

Claims (3)

[Claims] 1. A laminated glass comprising a pair of glasses and a soft resin layer provided between the glasses, wherein the soft resin layer contains a heat ray shielding metal oxide. 2. The heat ray-shielding metal oxide has a particle size of 0.1.
The laminated glass according to claim 1, which is either tin oxide or indium oxide having a size of not more than μm. 3. The laminated glass according to claim 1, wherein the heat ray-shielding metal oxide is blended in a proportion of 0.4 g / m ² or more.