JP2005089244A - Laminated glass - Google Patents

Laminated glass Download PDF

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JP2005089244A
JP2005089244A JP2003325046A JP2003325046A JP2005089244A JP 2005089244 A JP2005089244 A JP 2005089244A JP 2003325046 A JP2003325046 A JP 2003325046A JP 2003325046 A JP2003325046 A JP 2003325046A JP 2005089244 A JP2005089244 A JP 2005089244A
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Prior art keywords
film
laminated glass
laminated
glass
infrared
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JP2003325046A
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Isao Nakamura
Masaji Onishi
Chiharu Takimoto
功 中村
正司 大西
千晴 瀧本
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Central Glass Co Ltd
セントラル硝子株式会社
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Priority to JP2003325046A priority Critical patent/JP2005089244A/en
Priority claimed from PCT/JP2004/013406 external-priority patent/WO2005028393A1/en
Publication of JP2005089244A publication Critical patent/JP2005089244A/en
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Abstract

A heat insulating laminated glass in which conductive ultrafine particles having heat ray shielding properties are dispersed in a laminated interlayer film has a low reflectance in the near infrared region of 1000 nm or less, and it is difficult to say that the heat insulating performance is sufficient. .
An infrared reflecting film that selectively reflects near infrared rays and has a sheet resistance value in a range of 1 kΩ / port to 10 GΩ / port is formed on at least one transparent glass plate constituting the laminated glass. . An infrared reflective film is a film in which a low refractive index layer and a high refractive index layer are periodically laminated, or a metal, oxide, or nitride that absorbs and reflects in the infrared region, or is alternately laminated. It is.
[Selection] Figure 1

Description

  The present invention relates to a laminated glass excellent in infrared (heat ray) reflectivity and radio wave transmission used for window glass for vehicles, window glass for buildings, and the like.

  In recent years, heat insulating glass having heat ray (infrared ray) shielding properties for the purpose of shielding solar radiation energy that passes into a room or vehicle in building glass or vehicle glass, and reducing the temperature rise or cooling load in the room or vehicle, Furthermore, in order to be friendly to both human and physical aspects and the environment, glass for vehicles is added with ultraviolet shielding.

  Among them, recently, heat insulating laminated glass in which conductive ultrafine particles are dispersed in an interlayer film for laminated glass is excellent in visible light transmission, radio wave transmission, etc. in addition to the above heat insulating properties, ultraviolet shielding properties, and patents related thereto. An application is being made.

  For example, in Patent Document 1, in a laminated glass having an intermediate layer between two transparent glass plates, fine particles having functionality such as conductivity of 0.2 μm or less are dispersed in the intermediate film layer. A laminated glass comprising a pair of glasses and a soft resin provided between the glasses is disclosed in Patent Document 2, wherein the soft resin layer contains a heat ray-blocking metal oxide. Laminated glass is disclosed.

  Further, in Patent Document 3, in a laminated glass in which a laminated interlayer film composed of three layers is provided between at least two transparent glass plates, the particle size of the interlayer film of the second layer in the three layers is A laminated glass formed by dispersing functional ultrafine particles of 0.2 μm or less is disclosed in Patent Document 4 in which a plasticizer in which a heat ray shielding inorganic compound having a particle size of 0.1 μm or less is dispersed is added to a transparent resin. A method for producing a transparent resin molded product characterized by molding a resin is disclosed.

  Among solar rays, infrared rays having a wavelength of 780 nm or more (especially, near infrared rays having a wavelength of 780 nm to 2100 nm) are released as heat when the thermal action is greatly absorbed by a substance, resulting in a temperature rise. It is known that heat insulation can be improved by suppressing the temperature rise of vehicles and buildings if the infrared rays entering from the window glass are cut off.

JP-A-8-259279 JP-A-8-217500 Japanese Patent Laid-Open No. 10-297945 Japanese Patent No. 3040681

  However, the heat insulating laminated glass described in Patent Documents 1 to 4 in which conductive ultrafine particles having heat ray shielding properties are dispersed in the laminated intermediate film is a general-purpose material that does not contain heat ray shielding ultrafine particles in the laminated intermediate film. Compared to ordinary laminated glass using laminated interlayer film, the heat ray reflection performance is significantly improved, but even in the infrared, the reflectivity in the near infrared region below about 1000 nm where the energy is large is small, and the heat insulation performance is sufficient. Is hard to say.

  In addition, a coating of a noble metal such as silver generally called Low-E is effective in reducing the amount of energy absorbed by reflecting heat rays, but it is easily degraded by moisture in the atmosphere, There has been a problem of attenuating radio waves of a vehicle communication system used in ETC or the like.

  The present invention has been made in view of such problems of the prior art, and uses an intermediate film in which conductive ultrafine particles are dispersed in an intermediate film (hereinafter referred to as a functionally combined intermediate film). An extremely high performance heat-insulated laminated glass having radio wave transmission performance is provided by providing an infrared reflection film that selectively reflects wavelengths in a specific region of near infrared rays on at least one of two opposing glass substrates.

  That is, the laminated glass of the present invention is a laminated glass having an intermediate film layer between at least two transparent glass plates, and functional ultrafine particles having a particle size of 0.2 μm or less are contained in the intermediate film layer. An infrared reflecting film having a sheet resistance value in the range of 1 kΩ / port to 10 GΩ / port is formed on at least one transparent glass plate that is dispersed and constitutes a laminated glass, and selectively reflects near infrared rays. The functional ultrafine particles are Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo metals. , Oxides, nitrides, sulfides, Sb and F dopes, or composites selected from at least two of these, or organic resins for each of these singles or composites A mixture, including Is a laminated glass characterized by comprising in the each single compound or coating was coated composite, or antimony-doped tin oxide and / or tin-doped indium oxide.

  The laminated glass of the present invention is a laminated glass characterized in that the infrared reflective film is a film having a structure in which a low refractive index layer and a high refractive index layer are periodically laminated.

  In addition, the laminated glass of the present invention is a laminated glass characterized in that the infrared reflective film is formed by laminating a single layer and alternately a metal, an oxide, and a nitride having absorption and reflection in the infrared region. .

  The laminated glass of the present invention is a laminated glass characterized in that the sheet resistance value of the infrared reflective film is 1 kΩ / □ or more and is used for a window of a building.

  The laminated glass of the present invention is a laminated glass characterized in that the sheet resistance value of the infrared reflecting film is 20 kΩ / □, and it is used for a vehicle window.

  The highly heat-insulated laminated glass of the present invention provides a laminated glass that transmits radio waves and has high heat ray shielding performance.

  The highly heat-insulated laminated glass according to the present invention has the performance of a radio tower, can reduce reception interference in broadcasting of AM radio waves, FM radio waves, TV radio bands, etc., and has radio wave transmission performance equivalent to that of float glass. Therefore, it is possible to reduce the radio wave interference such as a ghost phenomenon without deteriorating the reception performance of the glass antenna for a vehicle TV, radio, mobile phone, etc. A comfortable environment inside and outside can be secured.

  Furthermore, it can be used as laminated glass such as glass and glass, glass and synthetic resin plate, barrier, etc., and the color tone can be selected from various colors from colorless to window glass used for openings in architecture, automobiles, airplanes, etc. In addition, a radio wave transmission type highly insulated laminated glass is provided.

  The present invention is a laminated glass in which at least two transparent glass plates are laminated using a functional laminated interlayer in which functional ultrafine particles are dispersed, and two transparent glass plates An infrared reflecting film having radio wave transmission performance is formed on at least one surface. FIG. 1 shows a simple configuration example of the laminated glass of the present invention, in which one functional laminated intermediate film 3 is used and the infrared reflective film 4 is composed of one layer.

  When the particle size of the functional ultrafine particles dispersed in the interlayer film is 0.2 μm or less, the functional properties of the ultrafine particles such as shielding infrared rays (heat rays) are sufficiently exhibited while suppressing scattering reflection in the visible light region. While maintaining ultra-low haze value, radio wave transmission performance, transparency, and maintaining conventional physical properties such as adhesion, transparency, durability, etc., even if ultrafine particles are included, This is because a laminated vitrification process can be performed in a normal operation of a normal laminated glass production line.

  Furthermore, the particle size is preferably 0.15 μm or less, and more preferably in the range of 0.10 to 0.001 μm. In addition, about the range of particle size distribution, it is good to make it uniform with 0.03-0.01 micrometer, for example.

  The mixing ratio of the functional ultrafine particles to the laminated interlayer film is preferably 10.0% by weight or less. By making it 10.0% by weight or less, it is possible to sufficiently exhibit the functional characteristics of shielding the heat ray while suppressing the scattering reflection in the visible light region, as well as the particle size of the ultrafine particles. Even if it is made to have permeation performance and transparency, and even if it contains ultrafine particles, as a conventional laminated interlayer film, for example, it maintains physical properties such as adhesiveness, transparency, durability, etc. This is because the laminated vitrification process can be performed in a normal operation.

  If the mixing ratio of functional ultrafine particles exceeds 10.0% by weight, it will be difficult to achieve transparency, radio wave transmission, adhesion, etc., especially for automotive windowpanes as well as architectural windowpanes. is there. For example, in the case of highly heat-insulated laminated glass for construction, the mixing ratio is required to be 10 to 0.1% by weight, more preferably 8.0 to 0.05% by weight, which is preferable for automobiles. The mixing ratio is about 2.0 to 0.01% by weight, more preferably 1.5 to 0.05% by weight, and still more preferably 1.0 to 0.1% by weight. In any case, it is desirable to appropriately determine the mixing ratio (content) in view of maintaining the performance as a laminated glass and the functional performance aimed at.

  As the resin for the functionally bonded interlayer film, a polyvinyl butyral resin film (PVB system) or an ethylene-vinyl acetate copolymer resin film (EVA system) can be used. Therefore, it is not particularly limited as long as it is a laminated interlayer film that can match the quality of the laminated glass with the needs. Specific examples include plastic PVB [manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.], EVA [manufactured by DuPont Co., Ltd., Takeda Pharmaceutical Co., Ltd., Duramin], modified EVA [manufactured by Tosoh Corporation, Mersen G], and the like. In addition, ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, fillers, coloring agents, adhesive preparation agents, and the like are appropriately added and blended. In particular, it is more preferable to add an ultraviolet absorber to the resin for the interlayer film because it can cut both ultraviolet rays as well as infrared rays.

  In addition, as a laminated intermediate film, for example, a functional laminated intermediate film containing ultrafine particles and a conventional laminated intermediate film are overlapped, or a functional laminated intermediate film containing ultrafine particles is sandwiched between conventional laminated intermediate films, etc. It may be configured.

  Functional ultrafine particles include Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo metals, oxidation , Nitrides, sulfides, Sb and F dopes, or composites selected from at least two of them, and each single or composite contains an organic resin. It is desirable to use a mixture or a film coated with an organic resin, or to use ultrafine particles having conductivity such as antimony-doped tin oxide and / or tin-doped indium oxide.

  In particular, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO), which are transparent in the visible light region and highly reflective to light in the infrared region, are variously required for construction and automobile use. This is particularly preferable because it exhibits the functionality and performance of a laminated glass.

  In the case of PVB (polyvinyl butyral) or EVA (ethylene-vinyl acetate copolymer) laminated interlayer film, functional ultrafine particles are dispersed in a plasticizer to form an ultrafine particle dispersed plasticizer, and then the ultrafine particle dispersion When a plasticizer is added to a PVB-based or EVA-based resin solution, and other additives are added as appropriate, and mixed and kneaded to obtain from the film raw resin, the functional ultrafine particles are uniformly distributed in the plasticizer solution. Can be dispersed.

  Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate (DOP) diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), tricresyl phosphate (TCP), and trioctyl phosphate. (TOP) phosphate esters, tributyl citrate, methyl acetyl ricinolate (MAR) fatty acid esters, triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol dihexanol And the like, and also a mixture thereof.

  As for the organic ultraviolet absorber or the organic infrared absorber, examples of the organic ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy). -3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2' -Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole and other benzotriazoles Derivatives, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy Ci-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4 Benzophenone derivatives such as methoxy-5-sulfobenzophenone and cyanoacrylate derivatives such as 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate Etc. Specifically, for example, TINUVIN327 (manufactured by Ciba Geigy) or the like.

  Furthermore, as an organic type infrared absorber, for example, NIR-AM1 [manufactured by Teikoku Chemical Industry Co., Ltd.], and particularly as a near infrared absorber, SIR-114, SIR-128, SIR-130, SIR-132, SIR -169, SIR-103, PA-1001, PA-1005 [manufactured by Mitsui Toatsu Chemicals] and the like. Needless to say, it can be used without limitation as long as it exhibits the quality of laminated glass required for construction and automobiles.

  In addition, fine particles of fluororesin such as PTFE, organic resin such as silicone resin and silicone rubber can be used, and these can be appropriately used to reduce the adhesive strength between the PVB intermediate film and a transparent substrate such as glass. . That is, ultrafine particles of metal oxides such as ATO and ITO may give a bond strength higher than the standard, so the Pummel value, which is an evaluation standard for the adhesive strength of laminated glass, falls outside the standard value. In order to prepare appropriately, it can be used for the same purpose as, for example, application of a primer to the surface of the glass substrate, and a film coated with an organic resin such as the fluororesin, silicone resin, or silicone rubber.

  The infrared reflective film used in the present invention is a single layer film that selectively absorbs / reflects a wavelength in a specific region of near infrared, or a structure in which a low refractive index layer and a high refractive index layer are periodically laminated. A membrane can be used.

  It is desirable to make the wavelength range for absorption and reflection different from the wavelength range of infrared rays shielded by the functional alignment intermediate film, since the heat ray shielding performance is improved.

  Infrared reflective film is coated on a transparent glass plate, laminated so that the coated infrared reflective film is placed on the intermediate film side, and laminated glass is a problem of weather resistance of the infrared reflective film Is preferable.

    Although not limited, the metal includes silicon having a refractive index of 4.00 to 5.00, stainless steel having a refractive index of 3.00 to 4.00, chromium having a refractive index of 13.01 to 14.00, and nitride. As silicon nitride having a refractive index of 1.50 to 2.50, chromium nitride having a refractive index of 1.50 to 2.50, titanium nitride having a refractive index of 0.50 to 1.50, and a refractive index of 2.00 to 3. As an oxide such as 00 nitrided stainless steel, silicon oxide having a refractive index of 1.20 to 2.50, titanium oxide, zinc oxide, tin oxide, tantalum oxide, ITO, oxidation having a refractive index of 0.10 to 1.00 A single layer or alternately laminated layers of chromium, oxidized stainless steel, nichrome oxide, and the like can be suitably used as the infrared reflecting film.

  In addition, metal and nitride films have conductivity and reflect radio waves depending on the film formation conditions and film thickness. Therefore, film thickness and film components can be determined so as not to reflect radio waves. preferable.

  For example, for a metal film such as chromium or stainless steel, it is preferable that the film thickness is 10 nm or less, or oxygen or nitrogen of 10% by weight or less is included in the film. For nitrides such as silicon nitride, chromium nitride, titanium nitride, and stainless steel nitride, it is preferable that the film thickness be 15 nm or less, or 5 wt% or less oxygen be included in the film.

  The method for forming the infrared reflecting film is not particularly limited in accordance with the component and film thickness of the film to be coated, but may be appropriately selected from various coating means such as PVD, CVD or sol-gel method. .

  Transparent glass plate-like materials include inorganic glass, organic glass or composite glass thereof, in particular, inorganic and transparent clear to colored glass produced by the so-called float method, tempered glass or similar glass, primer and various functional films. The glass with an equal coating film, preferably, for example, green glass or bronze glass, and further, for example, gray glass or blue glass can be employed. Moreover, it cannot be overemphasized that it can use as various plate glass products, such as a laminated glass, a barrier glass, etc. besides a laminated glass, and also a flat plate or a bending plate.

  The plate thickness of the transparent glass plate is, for example, from 1.0 mm to 12 mm, preferably from 2.0 mm to 10 mm for construction, and from 1.5 mm to 3 mm for automobiles. 0 mm or less is preferable, More preferably, it is 2.0 mm or more and 2.5 mm or less.

The laminated glass of the present invention can be used as various architectural windowpanes, etc. Of course, particularly as windowpanes for automobiles, for example, windshields, rear glasses, particularly rear glasses with shade bands, side glasses, sunroof glasses, or other It can be used for various glasses.
The optical characteristics of the laminated glass of the present invention are as follows when the clear glass (FL2) is used as two opposing glass substrates, the visible light transmittance (wavelength 380 to 780 nm) is 65% or more, and the sunlight is transmitted. The rate (wavelength 300 to 2100 nm) is preferably 65% or less. In particular, in the case of an automobile window glass, it is more preferable that the visible light transmittance is 70% or more and the solar radiation transmittance is 60% or less. The solar reflectance is preferably 7.0% or more. Further, when converted to the case where green glass (MFL2) is used as the two glass substrates, the visible light transmittance is preferably 70% or more and the solar radiation transmittance is preferably 60% or less, and the solar reflectance is 7.0. % Or more is more preferable.

  In particular, for automotive window glass, radio wave transmission performance is comparable to that of transparent glass plates, and infrared (heat ray) shielding performance is dramatically improved to a solar radiation transmittance of 50% or less. As a result of further improvements, the visibility of the visible light transmittance required by drivers and passengers for safety, etc. is 65% or higher, for example, the visible light transmittance is 70% or higher, etc. In addition, the visible light reflectivity necessary for preventing loss of transparency, misperception or eye fatigue in drivers and passengers can be further reduced from the conventional value. A radio wave transmission type high heat insulation laminated glass is obtained. For automobiles, the visible light transmittance is preferably 68 to 70% or more, the visible light reflectance is 14% or less, and the solar radiation transmittance is 60% or less. For construction, preferably visible light is used. The transmittance is 30% or more, the visible light reflectance is 20% or less, and the solar radiation transmittance is 65% or less.

  The sheet resistance value of the infrared reflecting film is preferably in the range of 500Ω / port to 10 GΩ / port in order to transmit radio waves, and in the range of 1 kΩ / port to 10 GΩ / port in order to transmit radio waves sufficiently. It is preferable.

  In addition, when used as automotive glass, such as an automobile windshield, rear glass, or side glass, it is preferably 20 kΩ / □ or more, and when a communication antenna is provided on the glass, 10 MΩ / □ or more. It is preferable that

  When used for window glass of buildings, the sheet resistance value of the infrared reflecting film is set to prevent reception interference in broadcasting of AM radio waves, FM radio waves, etc. or radio interference such as ghost phenomenon in TV images. 1 kΩ / □ or more is desirable.

  The laminated glass of the present invention is heated in the same manner as the laminated glass usually used in automobiles and buildings, that is, from room temperature to 120 ° C. under reduced pressure, and then heated in the temperature range of 80 to 120 ° C. for 20 to 30 minutes. , And can be produced by a combination process by an autoclave method.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the examples.

Example 1
(1) Production of functionally matched interlayer film 10 g of BBP (butylbenzyl phthalate) in which 20 wt% ITO ultrafine particles (particle size of 0.02 μm or less) are dispersed and 90 g of ordinary BBP are added to 322 g of PVB (polyvinyl butyral) resin. The mixture was kneaded and mixed at about 70 ° C. for about 15 minutes with a mixer of three rolls together with other ultraviolet absorbers and the like. The obtained raw material resin for film formation was formed into a film having a thickness of about 0.8 mm at around 190 ° C. by a mold extruder, and a roll-up functionally matched intermediate film was produced on a roll. The film surface was provided with uneven irregularities.

(2) Formation of Infrared Reflective Film A transparent plate glass produced by a float method having a plate thickness of 2 mm was used for a transparent glass plate. After the plate glass was washed with a neutral detergent and pure water, an infrared reflection film was formed by the following procedure using a sputtering apparatus. First, after attaching a metal target necessary for film formation to the sputtering apparatus, the inside of the sputtering apparatus was evacuated until the degree of vacuum was about 10 −3 Pa before film formation. In this method, a transport roll is installed under the target in the vacuum chamber, and when a glass substrate reciprocates on the transport roll, a predetermined metal film nitride film and oxide are glass from the target to which power is applied. A film is formed on a plate. In the first pass, the atmosphere of the film formation chamber was maintained in an oxidizing atmosphere (O 2 : Ar = 95: 5), and ZnO as a first layer of the first dielectric layer was formed to 14 nm with a Zn target. As the second pass, the atmosphere of the film formation chamber was maintained in an argon atmosphere (Ar = 100), and an SST target as a second layer was formed with a thickness of 8 nm. As the third pass, the atmosphere of the film formation chamber was kept in an oxidizing atmosphere (O 2 : Ar = 95: 5), and a ZnO film of 14 nm was formed as a third layer with a Zn target. The glass after film formation was discharged from the vacuum chamber.

(3) Production of laminated glass Using the functional laminated interlayer produced in (1) above, a transparent glass plate formed on the surface of the infrared reflective film produced in (2) and a float method having a thickness of 2 mm The produced plate glass was laminated and processed to produce a laminated glass.

  As shown in FIG. 1, the infrared reflection film 4 was positioned on the functional alignment intermediate film side 3.

  The laminated glass was produced as follows.

The transparent glass plate 1 on which the infrared reflecting film was formed and the functional matching intermediate film 3 were stacked, and then the transparent glass plate 2 was stacked on the functional matching intermediate film. Furthermore, the functional alignment intermediate film 3 that protruded from the edges of the transparent glass plates 1 and 2 was cut along the edges. Next, the laminated transparent glass plate-like body 5 is put in a rubber vacuum bag, the inside of the bag is degassed and depressurized, held at 80 to 110 ° C. for 20 to 30 minutes, once brought to room temperature, and taken out from the bag. It put into the autoclave apparatus, pressure was heated at the pressure of about 10-14 kg / cm < 2 >, the temperature of 110-140 degreeC for 20 minutes, the laminated glass was processed, and the laminated glass of this invention was produced.

  The produced laminated glass was subjected to the following measurements and evaluations.

  [Optical characteristics]: Transmittance between wavelengths of 300 to 2100 nm is measured with a spectrophotometer (manufactured by Hitachi, 340), and visible light transmittance, visible light according to JIS Z 8722, JIS R 3106 or JIS Z 8701 The reflectance (380 to 780 nm, D65 light source), solar transmittance, and solar reflectance (300 to 2100 nm) were determined.

  [Radio wave transmissivity]: By KEC method measurement (electric field shielding effect measuring instrument), the reflection loss value (dB) in the radio wave range of 10 to 1000 MHz is compared with a normal clear glass (FL3) single plate product with a thickness of 3 mm. The absolute value (ΔdB) of the difference was determined to be within 2 dB.

  [Adhesiveness]: After adjusting for 16 ± 4 hours at a temperature of −18 ± 0.6 ° C., the degree of exposure of the laminated interlayer film by hammering was evaluated. .

  [Heat resistance]: After boiling in boiling water at 100 ° C. for 2 hours, except for the periphery of 10 mm, a product having no abnormality such as generation of bubbles in the remaining portion, cloudiness, and cracking of the glass was regarded as acceptable.

  [Humidity resistance]: After leaving for 2 weeks in the preparation of 50 ± 2 ° C. and relative humidity 95 ± 4 ° C., a product having no abnormalities such as generation of bubbles, cloudiness, and glass cracking was regarded as acceptable.

  [Electrical Characteristics]: Measured by a surface height resistance meter (HIRESTA HT-210) manufactured by Mitsubishi Oil Chemical Co., Ltd., and a sheet resistance value (MΩ / port) of 0.02 MΩ / port or more was determined to be acceptable.

  In addition, evaluation of adhesiveness, heat resistance, and moisture resistance was applied to JIS R 3212 safety glass.

  As shown in Table 2, the evaluation results have a visible light transmittance of 74.8%, a visible light reflectance of 11.0%, a solar transmittance of 59.1%, and a solar reflectance of 8.8%. An infrared shielding heat insulating laminated glass having high visible light transmittance and low solar transmittance was obtained. Compared to Comparative Example 1 described later which has the same glass configuration, the glass of Example 1 has a visible light transmittance of 65% or more, and the solar radiation transmittance is improved by about 9.0%. It can be seen that the effect of the reflective film is great.

  In addition, regarding the radio wave transmissivity, the resistance value of the infrared reflecting film was as extremely high as 0.2 MΩ / □, and the radio wave transmissivity equivalent to that of a normal single plate glass was exhibited.

  Moreover, adhesiveness, heat resistance and moisture resistance were equivalent to those of ordinary laminated glass.

Example 2 to Example 11
Examples 2 to 11 are laminated glass produced in the same manner as in Example 1 except that only the infrared reflecting film formed on the transparent plate is different from that in Example 1.

  Each layer constituting the infrared reflective film of each example was formed by the same method as in Example 1 under the conditions of the target metal, gas composition, power and pressure shown in Table 1.

  As a result of evaluating the obtained highly heat-insulated laminated glass, as shown in Table 2, any laminated glass of Example 2 to Example 11 has lower solar radiation transmittance than that of Comparative Example 1, and has good infrared shielding heat insulating performance. A laminated glass was obtained. Moreover, the sheet resistance value of the infrared reflective film of each Example was high resistance, and the radio wave permeability was good.

  Moreover, the performance as laminated glass, such as adhesiveness, heat resistance, and moisture resistance, all passed as in Example 1.

Comparative Example 1
A laminated glass was produced in the same manner as in Example 1 except that no infrared reflecting film was provided. As shown in Table 1, the visible light transmittance was 87.9%, the visible light reflectance was 8.5%, the solar transmittance was 68.1%, and the solar reflectance was 5.7%. .

Comparative Example 2
A laminated glass was produced in the same manner as in Example 1 using a film called LOW-E using an Ag film as an infrared reflecting film. As a result of the evaluation, as shown in Table 1, the visible light transmittance is 74.9%, the visible light reflectance is 14.1%, the solar transmittance is 52.0%, and the solar reflectance is 27.5%. The solar radiation transmittance was lower than in Examples 1 to 11 and excellent in heat insulation performance, but the infrared reflective film had a sheet resistance value of 7Ω / □ and almost no radio wave transmission performance.

  Table 3 shows the transmittance in the near-infrared region (wavelength range of 800 to 1000 nm) that is relatively high energy in the solar radiation of the infrared reflective film used in Examples 1 to 5 and Comparative Example 1. Comparative Example 1 is a transmittance in the infrared region only by the intermediate film in which the functional ultrafine particles made of ITO are dispersed without forming the infrared reflective film, and the infrared reflective film used in Examples 1 to 5 is The transmittance in the near-infrared region is lowered, which cannot be achieved only by an intermediate film formed by dispersing functional ultrafine particles. Therefore, according to the present invention, a laminated glass having heat ray shielding performance and radio wave transmission performance, which cannot be achieved only by an intermediate film formed by dispersing functional ultrafine particles, was obtained.

It is sectional drawing of the laminated glass of this invention.

Explanation of symbols

1, 2: Transparent glass plate 3: Functional laminated interlayer film 4: Infrared reflective film 5: Laminated glass

Claims (5)

  1. In a laminated glass having an intermediate film layer between at least two transparent glass plates, functional ultrafine particles having a particle size of 0.2 μm or less are dispersed in the intermediate film layer to form at least a laminated glass. An infrared reflective film having a sheet resistance value in the range of 1 kΩ / mouth to 10 GΩ / mouth, which selectively reflects near infrared rays, is formed on one transparent glass plate, and the functional ultrafine particles are: Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, oxide, nitride, sulfide Alternatively, each Sb or F dope, or a composite comprising at least two or more selected from these, or each single or a mixture containing an organic resin in the composite, or each single Or cover the composite The coating material, or antimony-doped tin oxide and / or laminated glass characterized by comprising tin-doped indium oxide.
  2. The laminated glass according to claim 1, wherein the infrared reflective film is a film having a structure in which a low refractive index layer and a high refractive index layer are periodically laminated.
  3. 2. The laminated glass according to claim 1, wherein the infrared reflecting film is formed by laminating a single layer and alternately a metal, an oxide, and a nitride having absorption and reflection in the infrared region.
  4. The laminated glass according to any one of claims 1 to 3, wherein the infrared reflective film has a sheet resistance value of 1 kΩ / □ or more and is used for a window of a building.
  5. 4. The laminated glass according to claim 1, wherein the infrared reflective film has a sheet resistance value of 20 kΩ / □ and is used for a window of a vehicle.
JP2003325046A 2003-09-17 2003-09-17 Laminated glass Pending JP2005089244A (en)

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JP2003325046A JP2005089244A (en) 2003-09-17 2003-09-17 Laminated glass
PCT/JP2004/013406 WO2005028393A1 (en) 2003-09-17 2004-09-15 Laminated glass
US10/572,321 US7517583B2 (en) 2003-09-17 2004-09-15 Laminated glass
EP20040773079 EP1674433A4 (en) 2003-09-17 2004-09-15 Laminated glass

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007020791A1 (en) * 2005-08-16 2007-02-22 Asahi Glass Company, Limited Laminated glass for vehicle window
WO2007049478A1 (en) * 2005-10-26 2007-05-03 Central Glass Company, Limited Near infrared ray reflective substrate and near infrared ray reflective laminated glass employing that substrate, near infrared ray reflective double layer glass
JP2007148330A (en) * 2005-11-04 2007-06-14 Central Glass Co Ltd Near infrared ray reflective substrate and near infrared ray reflective laminated glass using the same
JP2007145689A (en) * 2005-10-26 2007-06-14 Central Glass Co Ltd Near infrared ray-reflective substrate and near infrared ray-reflective laminated glass using the substrate, and near infrared ray-reflective double-glazed unit
US7629040B2 (en) 2005-08-16 2009-12-08 Asahi Glass Company, Limited Infrared reflection glass plate and laminated glass for vehicle window
JP2009285864A (en) * 2008-05-27 2009-12-10 Bridgestone Corp Heat ray shielding film, and heat ray shielding glass laminate using the same
US7760424B2 (en) 2006-06-22 2010-07-20 Toyoda Gosei Co., Ltd. Infrared reflecting device
US8009351B2 (en) 2007-07-13 2011-08-30 Toyoda Gosei, Co., Ltd. Infrared reflective member, and infrared reflective device and method of making same
WO2013099564A1 (en) * 2011-12-28 2013-07-04 コニカミノルタ株式会社 Infrared shielding film, heat reflective laminated glass using same, and method for producing heat reflective laminated glass

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007020791A1 (en) * 2005-08-16 2007-02-22 Asahi Glass Company, Limited Laminated glass for vehicle window
JP5076896B2 (en) * 2005-08-16 2012-11-21 旭硝子株式会社 Laminated glass for vehicle windows
US7629040B2 (en) 2005-08-16 2009-12-08 Asahi Glass Company, Limited Infrared reflection glass plate and laminated glass for vehicle window
US7638184B2 (en) 2005-08-16 2009-12-29 Asahi Glass Company, Limited Laminated glass for vehicle window
WO2007049478A1 (en) * 2005-10-26 2007-05-03 Central Glass Company, Limited Near infrared ray reflective substrate and near infrared ray reflective laminated glass employing that substrate, near infrared ray reflective double layer glass
JP2007145689A (en) * 2005-10-26 2007-06-14 Central Glass Co Ltd Near infrared ray-reflective substrate and near infrared ray-reflective laminated glass using the substrate, and near infrared ray-reflective double-glazed unit
JP2007148330A (en) * 2005-11-04 2007-06-14 Central Glass Co Ltd Near infrared ray reflective substrate and near infrared ray reflective laminated glass using the same
US7760424B2 (en) 2006-06-22 2010-07-20 Toyoda Gosei Co., Ltd. Infrared reflecting device
US8009351B2 (en) 2007-07-13 2011-08-30 Toyoda Gosei, Co., Ltd. Infrared reflective member, and infrared reflective device and method of making same
JP2009285864A (en) * 2008-05-27 2009-12-10 Bridgestone Corp Heat ray shielding film, and heat ray shielding glass laminate using the same
WO2013099564A1 (en) * 2011-12-28 2013-07-04 コニカミノルタ株式会社 Infrared shielding film, heat reflective laminated glass using same, and method for producing heat reflective laminated glass
JPWO2013099564A1 (en) * 2011-12-28 2015-04-30 コニカミノルタ株式会社 Infrared shielding film, heat ray reflective laminated glass using the same, and method for producing heat ray reflective laminated glass

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