JPH02111644A - Laminated glass for vehicle - Google Patents

Abstract

PURPOSE:To obtain a laminated glass having improved visibility and air-conditioning performance by alternately laminating an ITO thin film having a specific thickness and an Ag thin film and combining the obtained multilayer film with a colorless or colored glass plate. CONSTITUTION:A laminated glass for vehicle having a visible light transmittance of >=70%, a solar radiation transmittance of <=55%, a visible light reflectance of <=10%, an electrical resistance of 1.0-6.5OMEGA/square, an excitation purity of <=5% and a dominant wavelength of reflection of 460-530nm 550-590nm is produced by alternately laminating ITO(In-Sn oxide) thin film layers and Ag thin film layers on the surface of a colorless or colored transparent glass plate having a visible light transmittance of >=78% from an In2O3+SnO2 target in an atmosphere having an O2 content of <=3% by DC sputtering process to form a sputtered electrically conductive film composed of multilayer film and laminating a colorless or colored transparent glass plate integrated with a bonding interlayer on the sputtered multilayer film. The thickness of the 1st and the outermost ITO thin film layer is 200-600Angstrom each and that of the other ITO thin film layers constituting odd intermediate layers are 500-1,000Angstrom . The Ag thin film layers constitute the even layers each having a thickness of 40-90Angstrom . The total number of the laminated thin films is 5, 7 or 9.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is a colorless (ordinary clear glass) to thin colored glass with high visible light transmittance, which has a heat ray reflecting function and is visible inside and outside a car. It prevents light reflection and eliminates the mirror effect, making it similar to ordinary glass, providing insulation and heat retention performance in cold seasons, and preventing damp condensation on the window glass surface. It exhibits appropriate blocking performance for air conditioning effects, and has sufficient conductive performance due to its low area resistance, allowing it to have water melting and anti-fogging functions. It has the ability to make the outlines of objects clearer, and in particular, the reflected color tone seen from outside the car is not reddish but has a natural neutral tone (that is, the same color tone as the base plate), which is as close as possible to laminated glass. The purpose of the present invention is to provide a laminated glass with high functionality, which is a flat or curved laminated glass for a vehicle, and which is particularly suitable for a windshield window glass.

[Prior Art] Various types of conductive transparent plate-like bodies have been proposed in the past. For example, Japanese Patent Application Laid-Open No. 110507/1983 discloses a transparent body and a metal oxide attached to the surface of the transparent body. A transparent conductor having a high refractive index consisting of a thin film made of a metal sulfide, a metal layer made of a metal or an alloy deposited on the thin film, and a metal oxide deposited on the metal layer. The high refractive index is I mouth z03, S n
A transparent conductor is described which is a metal oxide mainly composed of at least one of In10B doped with Oz, Cd01SbY03 or 5n02, and the metal oxides include TiO2, Ta205-ZnO1In203, Bi2
It is disclosed that a material having a high refractive index such as O2 or ZnS, and a metal layer containing at least one of Au, Ag, Cu, AI, Pd, and Rh as a main component are used.

In addition, as an infrared reflecting object, for example, JP-A-63-1
No. 34232 discloses that on a transparent substrate, a first layer of transparent oxide, a second layer of silver, a third layer of transparent oxide,
In an infrared reflective material provided with a five-layer coating consisting of a fourth layer of silver and a fifth layer of transparent oxide, the thickness of the silver layer is 110 Å or less and the visible light transmittance is 70% or more. An infrared reflector with a characteristic high transmittance is described, and transparent oxides include TiO2, ZrOz
, In, 03.5n02. Materials with high refractive index (n・1.7~
2.5) is disclosed. Furthermore, JP-A No. 62-41740 discloses that a first layer made of a metal oxide is formed on the surface of a glass plate by direct current sputtering, and a precious metal is formed on the surface of this first layer by direct current sputtering in a non-oxidizing atmosphere. A second layer consisting of a metal oxide is formed on the surface of the second M, and a third layer consisting of a metal oxide is formed by performing DC sputtering on the surface of the second M using a metal oxide as a target in an oxidation-free atmosphere or an atmosphere with a low oxygen partial pressure. A method for producing a heat-reflecting glass is described, and Japanese Patent Application Laid-Open No. 165001/1987 describes a method for producing a heat-reflecting glass using a first compound selected from the group of arsenic acids, tin oxides, and mixed acids. a metallic silver thin film having an oxide thin film, a second thin film having a thickness of 5 to 15 nm consisting of silver and another oxide thin film selected from the group of indium oxide, oxides and mixed oxides thereof; and said another oxide thin film selected from the group of indium oxide, tin oxide, and mixed oxides thereof, with a sufficient thickness of an acid selected from the group of aluminum, tantalum, chromium, manganese, and zirconium. A plate glass having a high transmission property in the visible spectrum region and a high reflection property against heat rays is described, in which a thin film with a diameter of 1 to 5 nm is arranged, and furthermore, in 1983-4
Publication No. 6441 describes a heat ray reflective laminated glass in which a heat ray reflective film is provided between the inner surface of the outer glass plate and the outer surface of the inner glass plate, in which at least one of the inner glass plate and the intermediate film is blue. The first layer of the heat ray reflective film is formed by reactive sputtering of tin oxide, indium oxide containing tin oxide, zinc oxide, antimony oxide, or indium oxide, and on this first layer, no A metal layer of silver, gold, copper, palladium, or rhodium is formed as the second layer by sputtering in an oxidizing atmosphere, and as No. 3711, the same oxide metal layer as the first layer is formed. It is known that this has been disclosed.

[Problems to be Solved by the Invention] As mentioned above, in the conventional structure in which a multi-N film is formed by sandwiching a metal layer such as silver with a transparent oxide on the surface of a transparent substrate such as a glass substrate, a transparent layer is formed after the metal layer. When layering oxides, it is necessary to use metal oxides as targets and accurately control the amount of oxygen to create a low-oxygen atmosphere using sputtering, or to provide a metal protective film to ensure uniform thickness. If the metal layer is not properly maintained, there is a problem in that the metal layer tends to migrate and the conductivity and infrared reflection characteristics deteriorate, and it has always been difficult to achieve sufficient stability.

Furthermore, conventional products tend to be colored green or bronze, and in addition, if the migration occurs too much, the visible light transmittance may drop to 70% or less.

Furthermore, 3 or 5 in which AgM is sandwiched between metal oxide films
Even if layers are simply laminated to form a multilayer film, even if it has heat ray reflection performance and visible light transmittance of 70% or more, it is difficult to truly provide the desired performance as a vehicle window glass. Furthermore, even if the heat ray reflection and at least one of the inner plate glass and the interlayer film are made blue, as mentioned above, it is difficult to truly achieve the desired result as a vehicle window glass.
It has sufficiently high performance and multiple functions, can sufficiently ensure the safety of the driver, and does not give off a sense of discomfort to those outside the vehicle, such as reflecting a reddish (for example, pinkish, reddish-purple) color, compared to a base plate of the same color. Therefore, it has been difficult to obtain laminated glass for vehicles that is also durable.

[Means for Solving the Problems] The present invention has been made in view of the drawbacks of the conventional art, and is based on an ITO (indium-#'A oxide) thin film layer and an Agl
A multilayer film formed by combining film layers with a specific thickness, and a desired high visible light transmittance, low visible light reflectance, low thermal emissivity, and reduced solar transmittance, as well as high electrical conductivity. Therefore, it is more versatile, and with a specific dominant wavelength and low irritation purity, the reflected color is as close as possible to that of the same-colored base plate, making it safer. To provide an optimal vehicle window glass that is high in height and comfortable for the driver and passengers, but also does not give a sense of discomfort to those outside the vehicle.

That is, the present invention provides a vehicle laminated glass consisting of transparent glass/sputter conductive film/adhesive interlayer/transparent glass plate, wherein the transparent glass plate is a colorless or colored glass with a visible light transmittance of 78% or more. 5 The sputter conductive film is formed by DC sputtering on the surface of a transparent glass plate using a [n203 +5n02 target and an atmosphere of 3% or less 0□. Fi! The vehicle laminated glass has a visible light transmittance of 70% or more, a solar transmittance of 55% or less, a visible light reflectance of 10% or less, and a thermal emissivity. is 0.15 or less, electrical resistance is 1
．． 0 to 6.5 Ω/□, and the stimulus purity is 5% or less, and the main wavelength of reflection is 460 to 530n + 1.550
The present invention provides a laminated glass for a vehicle, characterized in that the laminated glass is in the range of nu to 590 nu.

Here, when forming a multilayer film by alternately laminating layers on the surface of a transparent glass plate, an ITOi'I film was formed by DC sputtering using the In203+Sn○2 target in an atmosphere with a concentration of 3% or less. This is because if the amount of 0□ in the atmosphere is 3% or less, it is difficult to color, and even if it is colored, the visible light transmittance can be maintained at 70% or more, and migration is difficult to occur, so it is preferable. The ITO thin film has an almost colorless neutral color tone (same color tone as the base plate) when 0% in the atmosphere is 1 to 2%.Using this ITO thin film eliminates the need for a barrier of a conductive Ag thin film, and furthermore, By dividing and combining the Ag thin film layer of a specific thickness with the ITON film layer of a specific thickness, multilayer interference is caused, resulting in high visible light transmittance, which was difficult to achieve with a three-layer configuration.
It satisfies specifications such as low solar transmittance, low visible light reflectance, and low resistance, and also prevents the reflected color from becoming reddish due to the specific dominant wavelength and low irritation purity, and maintains the original color tone of the base glass. The aim is to provide something that does not make people feel uncomfortable.

In other words, the reason why the thickness of the Ag thin film layer was set to 40 to 90 people was to ensure the stimulus purity of 5% or less and to
g In addition to the degree of interference due to the thickness of the thin film, if there are fewer than 40 people, it will be difficult to obtain a uniform film thickness, and even if the visible light transmittance can be increased to 70% or more, the solar transmittance will be 55%.
% or less, thermal emissivity is 0.15% or less, and electrical resistance is 1
．． 0-6.5Ω/Hard to talk about, if it exceeds 90 people, the visible light transmittance is 70% or more and the visible light reflectance is 10%.
This is because it is difficult to reduce the amount to less than 50%.
There were about 80 people. In addition, the reason why the thickness of the TTO film layer in the first (11th) and outermost layer was set to 200 to 600 layers is because if the thickness is less than 200 layers, it is not possible to sufficiently control the reflection of the thin metal film. Light transmittance is 7
This is because it is difficult to obtain a visible light reflectance of 0% or more and a visible light reflectance of 10% or less, and it is not sufficient to protect the metal film, and the ITOri film body strength becomes weak.
This is because if the number of people exceeds 00, it is difficult to achieve a visible light transmittance of 70% or more and a visible light reflectance of 10% or less, and in particular, if the number of people is not 200 to 600, the stimulus purity will not be less than 5%. 300-500 people. Furthermore, the thickness of each of the ITO thin film layers, which are the intermediate odd-numbered layers, is set to 500 to 1000 layers.The reason why the thickness of each of the ITO thin film layers, which are the intermediate odd-numbered layers, is set to 500 to 1000 is that outside this range, the reflection mitigation effect of the metal RI film will not be sufficient, so the visible light transmittance, solar radiation transmittance, This is because it is difficult to achieve the desired light reflectance, stimulation purity, etc., and in particular, it is difficult to exhibit the protection of the metal RIM with less than 500 people, and preferably 600 to 900 people.

Furthermore, the visible light transmittance is set to 70% or more because the standard for vehicle window glass is to ensure 70% or more from the driver's safety perspective, and preferably 75% or more as per the European standard. It is to ensure that The reason why the solar transmittance is set to 55% or less is to reduce the amount of solar energy entering and exiting the vehicle and to improve the efficiency of cooling and heating the interior of the vehicle. It is preferable that the value decreases and becomes a low value. Preferably it is 50% or less. The reason why the visible light reflectance is set to 10% or less is to prevent scenery or lights from reflecting on the vehicle window glass, causing glare or driving errors. This is in order to further improve safety by approaching the 8%
Preferably it is 9% or less. In addition, as mentioned above, the thermal emissivity is set to 0.15 or less to suppress heat radiation to the outside of the vehicle, increase the heat insulation effect especially during heating, eliminate cold radiation, and prevent condensation from occurring. This is to appropriately enhance the cooling effect, and is preferably 0.10 or less. The stimulus purity is 5% or less, and the dominant wavelength is 460 to 530 nm (clear, blue, gray) or 550 to 5900 nm.
Bronze refers to the purity of the stimulation of reflections, for example, when viewed from outside the car, it looks reddish, or when viewed from inside the car, it looks pale, which tends to cause discomfort. For safety reasons, the stimulus purity is set to 5% or less and a specific dominant wavelength, and preferably the stimulus purity is 4% or less. The electrical resistance is set to 1.0 to 6.5 Ω/hole because when used as anti-fog glass or ice-melting glass, if it exceeds 6.5 Ω/hole, it will be difficult due to the electrode arrangement, its size, voltage, etc. It cannot exhibit sufficient performance, and is preferably 5 Ω/mouth or less, more preferably 5 to 2 Ω/mouth or less for ice-melting glass.

Moreover, a multilayer film of 7.9 layers is preferable than that of 5 layers because of its lower resistance.The transparent glass plate is made of colorless or colored glass with a visible light transmittance of 78% or more because the glass is either inorganic or organic. Colorless transparent glass refers to ordinary transparent glass, which naturally has a visible light transmittance of 78% or more, but in order to ensure the stimulus purity of 5% or less, colored glass is preferable, especially the five layers mentioned above. In this case, the visible light transmittance of laminated glass for vehicles will not be 70% or more unless it has a visible light transmittance of 78% or more. The visible light transmittance of the glass plate is 80% or more.

The colored glass may be body-colored, or may be coated with a thin film such as TiN or CrN. The transparent glass plate may be flat, bent, or film-shaped, especially when laminated glass has a coating surface. It is preferable to place the layer on the interlayer film side, and it is also suitable for windshield glass.

Particularly when using a single plate, it goes without saying that it is more preferable to further provide a protective layer such as a 5iAIN thin film on the surface of the exclusion side layer.

[Function] As mentioned above, the laminated glass for vehicles of the present invention has the above-mentioned I
A multilayer film of 5 to 9 layers, in which TO thin film and Ag thin film are alternately laminated with specified film thicknesses, is skillfully combined with a colorless or colored glass plate having a specific visible light transmittance. By specifying the solar transmittance, visible light reflectance, thermal emissivity, electrical resistance, stimulation purity, and dominant wavelength, we have created a thin film with high reflectivity for heat rays, low electrical resistance, and anti-reflection performance. It is possible to effectively interfere with the thin film of laminated glass for vehicles, allowing control of the visible light transmittance, reflectance, and stimulus purity of laminated glass for vehicles, as well as providing sufficient protection, weather resistance, and durability, and efficient conduction. This makes it possible to use a low power supply voltage, and the generated thermal energy can be effectively used due to its high thermal conductivity.
% or more, low solar transmittance of 55% or less, low visible light reflectance of glass and coating surfaces of 10% or less, low thermal emissivity of 0.15 or less, low electrical resistance of 1.0 to 6.5 Ω/
□, particularly low irritation purity of 5% or less and dominant wavelength of 460~5
30 nm, 550 to 590 rv, heat insulation functions such as heat ray reflection performance and LOW-E performance, ice melting and anti-fog functions, and additionally electromagnetic shielding performance. It is possible to provide laminated glass for vehicles that is multi-functional, versatile, has high visibility, high cooling/heating properties, and is safe and comfortable to live in. In particular, it is possible to provide a windshield glass that is suitable for vehicles by lamination.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Clear plate glass (Fl2.3
After washing with a neutral detergent, rinsing with water, and isopropyl alcohol in sequence, and drying, place the In203 in a vacuum chamber of a DC magnetron reaction sputtering device.
+ 5wtZSnOz and Ag targets were set so that they could reciprocate above the target, and then the inside of the tank was degassed to about 5X 10 Torr using a vacuum pump (not shown), and then an amount of 02 1 was placed in the vacuum tank. %-containing Ar gas was introduced to maintain the vacuum degree at 3X10-3 Torr.
Approximately 2Kw for 203 + 5wtZSnO2 target
is applied, and the above-mentioned I
Speed approximately 640mm/- above TO target
An ITO thin film having a thickness of about 250 mm was formed by transporting the plate glass in an in-line container.

After the ITO film formation was completed, while leaving the plate glass in the vacuum chamber, the supply of Ar gas containing 1% of 0zi was stopped, the vacuum level was again increased to approximately 5 X to torr, and Ar gas was introduced to increase the vacuum level to approximately 3 X IQ torr, applying about 700 - to the Ag target, and applying DC magnetron sputtering above the Ag target at a speed of about 3000 s + i/win to a thickness of about 50 mm on the ITO film-formed surface of the plate glass. A thin Ag film is formed and laminated.

Next, stop the static gas and reduce the vacuum level to about 5 x 1 again.
At a speed of about 265 tan/sin, an ITO thin film of about 600 tan/sin was formed and laminated in the same manner as described above, and then about 50 thin Ag thin films and ITO thin films were sequentially deposited in the same manner as described above. Films were formed and laminated alternately.

The obtained Fl, 2.3 glass plate with a 5M multilayer film and a colorless transparent glass plate (Fl2) with a thickness of 21111 were
．． Laminated glass with 76m+* PVB interlayer,
Visible light transmittance and visible light reflectance (380-780
) and solar transmittance (340 to 1800n+a
) for 340 type self-recording spectrophotometer (newly manufactured by Hitachi)
and JISZ8722, JISR3106, and electric resistance (surface resistance) using four-probe resistance measuring device R.
For thermal emissivity, we measured the spectral reflectance in the infrared region (2.5 to 25 μm) using a 270-30 infrared spectrophotometer (newly manufactured by Hitachi) using JI T-8 (manufactured by NAPSON).
Each was determined by SR3106, and the stimulus purity and dominant wavelength were determined by JISR3106, and the results are shown in Table I-1.However, regarding the symbols in the table, FL is clear, NG is gray, N is
indicates bronze, H indicates blue, and the number indicates its thickness.

The color tone is very close to that of the base plate when viewed from the outside of the car, and it also exhibits unique spectral characteristics in terms of anti-fogging, ice melting, etc., and also in heat insulation.
We were able to obtain a laminated glass for vehicles that is more effective in terms of livability and safety.

Examples 2 to 67 In the same manner as in Example 1, for example, the thickness of about 400 people (about 8
50 people), the sheet glass conveyance speed is approximately 400 mm/sin (approximately 190 mm/win).
), and if the Ag thin film is about 60 (about 80) thick, the conveyance speed of the plate glass is about 2,500 meters (approximately 18
Five layers, seven layers, and nine layers were formed and laminated, respectively, by carrying out the transfer at a conveying speed that was approximately inversely proportional to the thickness (75 cm/in).

The resulting veneer and laminated glass plates with multilayer films of 5, 7, and 9 layers were tested for winter clothes, the structure of the glass plates, the thickness of the winter clothes, and the same measurement method as in Example 1 and in accordance with JIS 3106, etc. Table I shows the obtained characteristic values.
-1-I-3.

Like Example 1, each example is a multifunctional window glass that exhibits various performances, including heat insulation, anti-fog, ice melting performance, etc., and can provide laminated glass for vehicles with superior livability and safety. Met.

Comparative Examples 1 to 60 By the same method as in Example 1, ITO thin film layer and Agl
Tables 11-1 to 1-3 show multilayer films in which film layers are alternately formed and laminated, which are outside the scope of the present invention.

The obtained glass plates and laminated glasses having 5 layers, 7 layers, and 9 layers were subjected to the same measurement method as in Example 1 and Jr.
Characteristic values were obtained in accordance with SR3106 and the like.

Each of them had some parts that were insufficient as a laminated glass for a vehicle compared to the examples, and could not necessarily be said to be suitable.

[Effects of the Invention] As described above, the present invention can achieve I by ordinary sputtering.
TO thin film layers and Ag thin film layers are alternately stacked to a specific thickness to form a flat or curved laminated glass, and its optical, electrical, and safety characteristics can be specified, and it can be used for insulating glass, anti-fog glass, fused glass, etc. It is possible to provide a more economical laminated glass for vehicles that has the performance of ice glass, etc., and has high safety and livability.

Claims (1)

[Claims] In the laminated glass for vehicles comprising a transparent glass plate/sputter conductive film/adhesive interlayer/transparent glass plate, the transparent glass plate is colorless or colored glass with a visible light transmittance of 78% or more, and the sputter The conductive film was formed on the surface of a transparent glass plate by DC sputtering using an In_2O_3+SnO_2 target and the amount of O_2 in the atmosphere was 3% or less, with the initial and outermost film thicknesses being 200 to 600 Å, and an odd number of layers. It consists of a 5-, 7-, and 9-layer multilayer film in which an intermediate layer of ITO thin film layers each having a thickness of 500 to 1000 Å and an even number of Ag thin film layers each having a thickness of 40 to 90 Å are laminated in sequence. ,
The visible light transmittance of the laminated glass for vehicles is 70% or more,
Solar transmittance is 55% or less, visible light reflectance is 10% or less, thermal emissivity is 0.15 or less, and electrical resistance is 1.0 to 6.5.
Ω/□, and the stimulus purity is 5% or less, and the main wavelength of reflection is 460 to 530 nm or 550 to 590 nm.
A laminated glass for vehicles characterized by having glass in each range of m.