JPH0214851A - Production of multi-colored type heat radiation shielding sheet - Google Patents

Abstract

PURPOSE:To enable the production of the title shielding sheet in high productivity without enlarging the apparatus thereof by forming a transparent metal oxide film used as the first layer on a transparent substrate such as glass using a specific method and then forming a visible light absorbing coating film used as the second layer thereon. CONSTITUTION:A transparent metal oxide film used as the first layer, preferably film consisting of oxide of Ti, Sn, Zn, Zr, Hf, Al, Bi, W, Mo, Ta or In or oxide mixture thereof is formed on a transparent substrate such as glass by subjecting a metal to be converted to a metal oxide to arc discharge and then a visible light absorbing coating film of metal, nitride, etc., used as the second layer, preferably coating film consisting of Ti, Cr, Fe, Ni, Co or Zr or alloy thereof or TiN, Cr2N, ZrN or nitride of stainless alloy is formed on the first layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a multicolored heat ray shielding plate for buildings and automobiles that exhibits a beautiful external color and effectively blocks solar radiant energy.

[Conventional technology]

As a conventional method for manufacturing this type of heat ray shielding plate, the method disclosed in, for example, Japanese Patent Application Laid-Open No. 60-36355 is well known. This manufacturing method involves forming a metal oxide film as a first layer on a transparent substrate such as glass, a chromium nitride film as a second layer, and then an oxide layer as a third layer if necessary. The layers are formed sequentially, and the sputtering method is used as the film forming method. And the above first
By changing the thickness of the metal oxide layer, it is possible to make light of various wavelengths in the visible light region strengthen each other through optical interference, and as a result, it is possible to obtain a variety of reflected colors. . In this case, if the thickness of the metal oxide film, which is the first layer, is extremely close to zero, the color reflected from the surface of the transparent substrate on which no coating is formed will be the color of the visible light absorbing coating, which is the second N layer.

Normal metals and nitrides are gray, except for some special cases.
Usually, it is a neutral color that is not very strong, such as light brown or silver. When the thickness of the first metal oxide film is increased, the reflectance in the short wavelength range of visible light first decreases due to optical interference, resulting in a yellowish reflected color. Become. Furthermore, gold J, 7
Increasing the thickness of the X oxide film broadens the wavelength range in which the reflectance decreases, and as a result, the reflected color becomes reddish. Furthermore, when the thickness of the metal oxide film is increased, the reflected color becomes purple.
It changes from blue to blue-green to green. When the thickness of this film is further increased, the reflected color returns to yellow, but the color is much more vivid than the yellow that initially appeared. The color then changes from red to purple to blue to blue-green to green, all of which are also more vivid than the color they first appeared. The above results are based on the above JP-A-60
It is also described in Publication No. 36355, where the first
When the thickness of the tin oxide layer was increased from 1Qnm to 120nm, the reflected color changed from silver to bronze to blue to blue.
It is said that it turned green. Such a change in reflected color is not limited to the film structure described in the above publication; a transparent metal oxide film is formed as a first layer on a transparent substrate, and then a visible light absorbing film is formed. This is a typical structure for a film formed with .

[Problem to be solved by the invention]

As mentioned above, in the above-mentioned conventional method for manufacturing heat ray shielding plates, when trying to obtain a blue, green, bright yellow, bronze color, etc., the first layer of metal oxide film is removed. It must be very thick. In order to obtain such a very thick metal oxide film using the sputtering method, the transport speed of the substrate passing through the target must be extremely slow, which significantly reduces work efficiency. In order to avoid this, it is necessary to increase the number of targets, which naturally leads to a significant decrease in productivity and an increase in the size of the device, resulting in an increase in the cost of the heat ray shield.

[Means to solve the problem]

In order to solve the above conventional problems, the present invention forms a transparent metal oxide film as a first layer on a transparent substrate such as glass, and a visible light absorbing film such as a metal or nitride as a second layer. In the method for manufacturing a colored thermal cotton shielding plate formed by forming a coating, at least the first layer of metal oxide is formed by arc discharging the metal that will become the metal oxide.

[Effect]

According to the present invention, since the transparent metal oxide film as the first layer on the substrate is formed using arc discharge, the film is formed at a much faster rate, and conventional sputtering is not used. Heat ray shielding plates with reflective colors such as blue, green, bright yellow, bronze color, etc., which caused a decrease in productivity and an increase in the size of the equipment when forming can be produced at high throughput.

〔Example〕

FIG. 1 is a schematic diagram of a vacuum film forming apparatus for implementing the present invention. In the figure, an integral grounded vacuum chamber 1 consisting of a first and second chamber 2.3 is evacuated by a vacuum pump (not shown). At the bottom of this vacuum chamber l, an arc discharge cathode '5 and a sputtering cathode 6 are arranged via electric insulators 4a and 4b, and a DC power source 7.
8 via a switch 9.10. Further, in the vicinity of each cathode 5.6, a gas supply pipe 13.14 that penetrates the bottom of the vacuum chamber 1 and is provided with valves 11 and 12 is provided. A reactive gas such as oxygen or argon or an inert gas can be supplied through the gas supply pipes 13 and 14. Further, a trigger 15 for causing arc discharge is provided near the arc discharge cathode 5, and this trigger 15 is connected to the DC power supply 7 via a switch 16. Furthermore, inside the vacuum chamber l,
A conveyor belt 17 is installed, and a glass substrate 18 is
A film is formed while passing each cathode 5.6 on this conveyor belt 17. In that case, the thickness of the coating to be formed is adjusted by adjusting the moving speed of the conveyor belt 17. A mechanism is provided that allows movement between the chambers 2.3 by opening and closing the gate valve 19.

A method of forming a heat ray shielding plate using the vacuum film forming apparatus configured as described above will be described with reference to the following experimental example. First, titanium 20 is attached as a vapor deposition source to the upper surface of the cathode 5 for arc discharge, and stainless steel alloy 21 is attached as a vapor deposition source 1- to the upper surface of the cathode 6 for sputtering. Further, a glass substrate 18 is held in a holder (not shown), and this holder is set in the first chamber 2 of the vacuum chamber 1. The following experiment was conducted in this state. First, the inside of the vacuum chamber l is
After the pressure was reduced to 1, the valve 11 was opened and argon gas and oxygen gas were supplied from the gas supply pipe 13.

The mixing ratio was 50% by volume of argon gas and 50% by volume of oxygen gas. Subsequently, the gate pulp 19 was opened. The pressure in the vacuum chamber 1 after introducing the gas was adjusted to 0.5 Pa. Then, the switch 9 was turned on, and then the switch 16 of the trigger 15 was turned on to cause a current of 100 A to flow through the cathode 5.

The discharge voltage at this time was 20V. Thereafter, the transport belt 17 was run at a speed of 200 mm/min, and the glass substrate 18 was passed over the cathode 5 and sent to the second chamber. Then, the conveyor belt 17 was stopped running, the switch 9 of the cathode 5 was turned off to stop the discharge, and the gas introduction valve 11 was closed. As a result, as shown in FIG. 2, 30 TiO□ layers of approximately 1,000 layers were formed on the surface of the glass substrate 18.

Subsequently, the valve 12 was opened and argon gas was supplied from the gas supply pipe 14. The pressure in the vacuum chamber l after gas introduction is 0.5
It was adjusted to Pa. Next, the switch 10 of the cathode 6 was turned on, a negative voltage of 350 .mu. Then, the conveyor belt 17 was run at a speed of 1000 mm/min to pass the glass substrate 18 above the cathode 6. Then, the conveyor belt 17 was stopped, the switch 10 of the cathode 6 was turned off to stop the discharge, and the gas introduction valve 14 was closed. In this way, about 200 stainless steel alloy layers 31 were formed on the T'rO□ layer 30, as shown in FIG.

Subsequently, under the same conditions as for forming the TiO□ layer 30 (however, the conveyor belt 17 was run from left to right at a speed of 500 mrn/min), the stainless steel shown in FIG. A TiO□ layer 32 was formed on the alloy layer 31.

Through the above procedure, TiO□, stainless steel alloy, and TiO are sequentially deposited on the glass substrate 18, as shown in FIG.
A glass 22 having three layers of □ and colored heat rays ξ was obtained.

FIG. 3 shows a light transmittance curve 41 and a light reflectance curve 42 representing the heat ray shielding function and reflected color of the heat ray shielding glass 22.

<Comparative Experimental Example> Using the same apparatus, stainless steel alloy 21 was attached as a vapor deposition source to the upper surface of cathode 5 for 7-layer vapor deposition, and titanium 20 was attached as a target to the upper surface of cathode 6 for sputtering. Glass substrate 1 in a holder (not shown)
8, and this holder was set in the second chamber 3 of the vacuum layer 1. After reducing the pressure in the vacuum layer l to 10-'Pa,
Open the valve 12 and supply argon gas 5 from the gas supply pipe 14.
A mixed gas consisting of 0% by volume and 50% by volume of oxygen gas was supplied, and then the gate valve 19 was opened. The pressure of the vacuum layer after gas introduction was adjusted to 0.5 Pa.

Next, switch 10 was turned on and a negative voltage of 400 V was applied from power source 8 to flow current to 5 to cause sputter discharge. The conveyor belt 17 was run at a speed of 20 mm/min to pass the glass substrate 18 above the cathode 6.

The cathode 6 causing sputter discharge in this way
After passing through the glass substrate 18 repeatedly five times, the sample was sent to the first chamber 2. Then, the transport bell (17) was stopped, the switch 10 of the cathode 6 was turned off to stop the discharge, and the gas introduction valve 12 was closed.

As a result, as shown in FIG. 2, a Tioz layer 30 of about t, ooo thickness was formed on the surface of the glass substrate 18.

Subsequently, the valve 11 was opened, and realbon gas was supplied through the gas supply pipe 13. The pressure in the vacuum chamber l after gas introduction is 0.
It was adjusted to 5Pa. Next, the switch 9 of the capacitor 5 was turned on, and then the switch 16 of the trigger 15 was turned on to cause a current of 100 A to flow through the cathode 5.

At this time, the discharge voltage was 20V. Thereafter, the conveyor belt 17 was run at a speed of 1.200 rn nt 7 minutes, and the glass substrate 18 was passed above the cathode 5 .

Next, the conveyor belt 17 was stopped running, the switch 9 of the cathode 5 was turned off to stop the discharge, and the gas introduction valve 11 was closed. As a result, as shown in Figure 2, approximately 2
A stainless steel alloy layer 31 was formed on the Ti02 layer 30.

Subsequently, under the same conditions as those used for forming the TiO□ layer 30, the glass substrate 18 is repeatedly passed over the cathode 6 which is undergoing sputtering twice to form a stainless steel alloy as shown in FIG. TiO2 on layer 31-
Layer 32 was formed.

Through the above procedure, a heat ray shielding glass 22 exactly the same as that shown in the previous experimental example was obtained.

From the above experimental results, when obtaining heat ray shielding glass with the same film structure and green reflective color, sputtering is used as a method for forming an oxide layer (titanium oxide in the experimental examples and comparative experimental examples). The formation rate can be compared between the case of using the arc discharge described in the present invention and the case of using the arc discharge described in the present invention. 1st (7)'rioz layer 30 and 30th (7)T
iOzJ! The results of comparing the time required to form 32 are shown in the table below. The time was calculated taking into account that the length of the two chambers 2.3 in the vacuum chamber 1 was 800 mm.

Comparison of Formation Speed □□d'' Comparing the two methods shows that the formation time is 50 times different.

Metal oxide films that can be used in the present invention include titanium, tin, zinc, zirconium, hafnium, aluminum,
These include oxides of bismuth, tungsten, molybdenum, tantalum, and indium, or mixed oxides thereof. If the second layer of metal or nitride and the third layer of metal oxide are formed using arc discharge in the same way as the first layer, the overall throughput will be reduced due to the advantage of faster film formation speed. increases, leading to improved productivity, but the first
Since the film thickness is not so thick compared to the thickness of the layer, there is no serious problem even if the film is formed using the conventional squirrel battering method.

〔Effect of the invention〕

As described above, according to the present invention, the conventional problems of low productivity and increased cost of increasing the size of equipment can be solved, and a heat ray shielding temporary that exhibits reflective colors such as n-color, green, bright yellow, and bronze color can be manufactured. , it is possible to produce at high throughput without increasing the size of the equipment.

[Brief explanation of the drawing]

FIG. 1 is a vertical cross-sectional view of a device for producing a multicolor shield, FIG. 2 is a cross-sectional view of a heat ray shield, and FIG. 3 is a light transmittance and light reflectance curve. In addition, in the symbols used in the drawings, 1B----Glass substrate 30-----4iO□ layer 31-----Ag layer 32----T i O□ layer be.

Claims (5)

[Claims] (1) A transparent metal oxide film is formed as a first layer on a transparent substrate such as glass, and a visible light absorbing film of metal, nitride, etc. is formed on this first layer as a second layer. In the method for manufacturing a polychromatic heat ray shielding plate, at least the first layer of the metal oxide film is formed by arc discharging a metal that will become the metal oxide film. A method for manufacturing a colored heat ray shielding board. (2) The method for manufacturing a multicolor heat ray shielding plate according to claim 1, further comprising forming a third layer made of a transparent dielectric material on the second layer. (3), the metal oxide forming the first layer is titanium,
The method for producing a multicolor heat shielding plate according to claim 1, which is an oxide of tin, zinc, zirconium, hafnium, aluminum, bismuth, tungsten, molybdenum, tantalum, indium, or a mixed oxide thereof. (4) The visible light absorbing coating forming the second layer is
Titanium, chromium, iron, nickel, cobalt, zirconium and alloys thereof, titanium nitride, chromium nitride,
The method for manufacturing a polychromatic heat ray shielding plate according to claims 1 and 2, wherein the material is zirconium nitride or a nitride of a stainless steel alloy. (5) The method for manufacturing a polychromatic heat ray shielding plate according to claim 2, wherein the dielectric material forming the third layer is titanium oxide.