JPH02233534A - Heat ray-reflecting glass plate - Google Patents

Abstract

PURPOSE:To provide a durable glass plate having high chemical resistance, high wear resistance and excellent heat ray-reflecting property by forming a SUS nitride thin coating film as the first layer on the surface of a transparent glass plate and successively forming the thin coating films of a specific nitride, an oxide, etc. CONSTITUTION:A SUS nitride thin coating film (film thickness: 30-250Angstrom , preferably 50-120Angstrom ) is formed on the surface of a transparent glass plate. On the formed first coating film, the nitride or nitrogen oxide thin coating film of Ti, Cr or Ta as the second layer is formed under a coating atmosphere having an N2:O2 ratio of 100:0-50:50 and subsequently the oxide thin coating film of Ti, Sn, Cr or Ta as the third layer is formed. If necessary, the oxide or nitrogen oxide thin coating film of a Si alloy such as Si.Al, Si.Ni or Si.Ti is further formed under an atmosphere of a N2:O2 ratio of 0:100-50:50 to provide a heat ray-reflecting glass especially having a visible light transmittance of <= approximately 30%, a solar radiation transmittance of <= approximately 20% and a visible light reflectance of <= approximately 45%, capable of being used even in a state of a single glass plate and suitable as window glass for buildings.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a heat-reflecting glass plate that reduces the transmittance of solar radiation to improve the cooling and heating effect, and has improved chemical resistance and abrasion resistance, especially visible light. The present invention relates to a heat ray reflective glass plate which can be used as an architectural window glass having a transmittance of about 30% or less, a solar transmittance of about 20% or less, and a visible light reflectance of about 45% or less, and can also be used as a single plate.

[Conventional technology]

Conventionally, high visible light transmittance has been achieved, for example, in architectural window glass with a transparent dielectric or transparent conductive film/silver/transparent dielectric or transparent conductive film composition, and the high reflective performance of silver has been used to reduce solar transmittance. It is used by making low insulating glass and making it into laminated glass. However, silver film has poor abrasion resistance and moisture resistance, and if it is left untreated on laminated glass, abnormalities will appear in the film within a few days, causing discoloration and deterioration of the film, and even if it is touched by hand. It was extremely weak, causing peeling phenomena.

For this reason, various types of glass panels have recently been proposed that are weather resistant and durable and can be used as a single sheet instead of laminated glass. For example, Japanese Unexamined Patent Publication No. 63-242948 describes a heat ray reflective glass, in which a metal film, a nitride film, and an oxide film are laminated on the surface of a glass substrate in order from the substrate side. A heat ray reflective glass with a visible light reflectance of 20% or less is disclosed, and Crs T as a metal film is disclosed.
isZrs Hfs Tas Si and alloys thereof,
and selected from stainless steel, nitrides selected from Tis Zr, Tas CrSKf nitrides and composite nitrides thereof, and oxides selected from TiSCrs Zrs st, AI% Hfs T
as Nb oxide and composite oxides thereof, specifically, glass substrate/chromium film/titanium nitride film/titanium oxide film, or glass substrate/
The structure of stainless steel film/titanium nitride III/titanium oxide film is described. In addition, for example, JP-A-6
1-151045 describes a product for reflecting solar energy and its manufacturing method,
a transparent substrate, a transparent film of a metal compound deposited on the surface of the transparent substrate and exhibiting color due to absorption and interference effects, and a highly reflective transparent metal deposited on the transparent film of the metal compound. The transparent substrate is glass, the highly reflective transparent metal film is selected from the group consisting of silver, gold, copper, aluminum and mixtures thereof, and the metal compound is stainless steel. ,
Films by sputtering, being selected from the group consisting of nickel alloys, oxides and nitrides of copper, iron, cobalt and their mixtures? to form,
It is also described that it exhibits a golden color when reflected from the glass surface side.

Further, JP-A-64-3036 describes a low-reflection coated article, which includes a transparent film of a colored metal alloy oxide deposited on the surface of a transparent substrate (glass) and a transparent film of a metal alloy oxide deposited on the surface of a transparent substrate (glass). A low-reflection transparent metal alloy (group consisting of nickel and chromium) film deposited on an alloy oxide (stainless steel, oxides thereof) film is disclosed, which can be deposited on a spasoter or from a glass surface. It is described that it exhibits a bronze color when reflected. Furthermore, JP-A-63-247352 describes a transparent coating by reactive sputtering, and the coated article includes a base material, a coating film on the base material, and a protective film on the coating. , the target whose protective film is an alloy containing aluminum and silicon is exposed to a reactive gas, especially 02% N2+0.
■Reaction products formed by sputtering in a proportion of 10 to 30% in the gas? It is described that the film includes a regular layer, and specifically, a film that is used as a protective film for AI-SiRx (R: reactive gas such as 0.3 o, +o.7 Nz, etc.) is disclosed.

[Problem that the invention seeks to solve]

With the conventional single-layer or double-layer structure in which a SUS (stainless steel) thin film is first formed on the surface of a glass substrate as described above, for example, a glass substrate/SUS/TiN structure, heat ray reflection performance can be obtained, but it is relatively poor. It has poor chemical resistance, especially acid resistance, and relatively weak alkali resistance, such as concrete melt, which may cause the film to peel off, and wear resistance is not necessarily sufficient. However, even if the membrane is used on architectural window glass with the membrane side facing indoors, there is a concern that the membrane may deteriorate or become scratched if it is rubbed very strongly during cleaning etc. , Japanese Patent Publication No. 63-242948
Even if an oxide film such as TiO■ is overcoated as described in Japanese Patent Application Laid-Open No. 63-247,
Even if a protective film such as AI or SiRx is overcoated as described in Publication No. 352, it cannot necessarily be said that the film as a whole has sufficient durability such as chemical resistance or abrasion resistance. Improvements were also desired for architectural window glass.

Means for Solving Problem C] The present invention has been made in view of the above-mentioned drawbacks of the conventional art.
Particularly high chemical resistance can be achieved by depositing at least one layer as a layer and by skillfully combining, in sequence, a specific nitride or nitrogen oxide thin film, a specific oxide thin film, and a specific oxide or nitrogen oxide thin film. It has a visible light transmittance of about 30% or less, a solar radiation transmittance of about 20% or less, a visible light reflectance of about 45% or less, and has sufficient heat ray reflection performance, and can be used as a single plate. To provide a heat ray reflective glass plate having sufficient durability.

That is, in the present invention, at least SUS nitride III is formed on the surface of a transparent glass plate. After forming a SUS nitride thin film on the surface of the heat-reflecting glass plate and transparent glass plate, Ti , Cr, Ta nitride or nitrogen oxide thin film is formed on the surface of the heat ray reflective glass plate and the transparent glass plate. After forming the SUS nitride thin film on the surface of the transparent glass plate, Nz:02 ratio of 100:0~5
A thin film of TiSCrSTa nitride or nitrogen oxide was deposited under 0:50, and then TiSSnsCrsT
A heat ray reflective glass plate characterized by laminating the oxide thin film of A, and after forming SUS nitride thin pus on the surface of the transparent glass plate, the N2:O2 ratio in the atmosphere at the time of coating Ti, Crs T when is 100:0~50:50
A nitride or nitrogen oxide thin film is formed, and then Ti
s Sns Crx Ta oxide thin film is laminated, and the N2:O2 ratio in the atmosphere at the time of coating is O:1 on the surface.
Si・AI% Si-Ni- under 00-50:50
．． Si-Ti Si alloy oxide or nitrogen oxide m
The present invention provides a heat ray reflective glass plate characterized by laminating s.

Here, we decided to use at least SUS nitride thin 111 (hereinafter referred to as S [JSNx) as the eleventh film to be formed on the surface of the transparent glass plate.
This is because the adhesion to the transparent glass plate and the strength of the film itself are improved, and the acid resistance is particularly improved. The reflected color on the plate side is a silver tone, and the required color tone, visible light transmittance, and visible light reflectance can be varied within the above range.For example, the thicker the plate, the more silver it becomes. It is also possible to make it thinner and adjust the color tone by changing the thickness of the second and third layers, and it can be made to have a paring effect. If it exceeds the size of a person, it becomes too much of a mirror effect and the visibility becomes very low.For example, the visible light transmittance becomes less than about 10%, making it unsuitable for architectural window glass, and the color tone with the second layer, third layer, etc. It becomes impossible to maintain balance.

What about when looking for the mirror effect? Needless to say, this is not the case. N2 in the atmosphere during coating as the second layer
20 ■ Tis C when the ratio is 100:0 to 50:50
The reason for using rSTa nitride or nitrogen oxide thin film is TiNxOy (0<X≦1, 0≦y≦2),
CrNxOy (0<x≦1, 0≦y≦372),
TaNxOy (0<x≦1, O≦y≦572)
As the first layer SUSNx! ! This is because it has great adhesion to the film and also has good adhesion to the third layer of oxide film that is subsequently formed.Furthermore, as an interference film, it is useful for adjusting color tone and visible light transmittance, and it also has excellent wear resistance. It also shows an improvement trend in properties and chemical resistance, and furthermore, nitrides and nitrogen oxides such as TiN
When iNxOy is used, there is a tendency that the wear resistance is improved more when an oxide such as Tidy is contained to some extent, preferably 10% or less, and the film thickness is 150~100%. 600 people, preferred《
is between 200 and 500 people, and if it is less than 150 people,
This is because the visible light reflectance of the membrane becomes too high, making it difficult to maintain color tone variation and reducing the strength of the membrane.If the number of people exceeds 600, the visible light transmittance decreases too much. . TISSns CrS as the third layer
The reason for using the Ta oxide thin film is because of TiOx, SnOx (0 < x≦2), Crux (0
χ≦372), TaOx (0<x≦572) has relatively good adhesion with nitrides such as TiNx, but it is particularly effective when the second layer is made of nitrogen oxides such as TiNxOy, and the adhesion from the first layer to This improves adhesion to the third layer, improves chemical resistance and abrasion resistance, and allows the protective film to be more effective, and also serves as an anti-reflection coating on the film surface. Yes, the film thickness is 50-4
00 people, preferably 100 to 300 people, if it is less than 50 people, the protective film performance and anti-reflection performance will be inferior, and it is not preferable.If it exceeds 400 people, the anti-reflection performance will decrease. This is because forming an oxide film is rather time consuming, so making the film thicker than necessary will directly affect productivity.

Note that ZnSnOx (0 < x≦3
) can be adopted. This is particularly effective when overcoating the fourth layer. As the fourth N, the i'(7)NzFOz ratio in the atmosphere during coating is O:100 to 5o:5o(7)1? Si・AIXSi・Nis The reason why we decided to use Si alloy oxide or nitrogen oxide thin film of Si-Ti is because Si・AINxOy (0≦X≦7/3, Q
<y≦772), Si-TiNxOy (0≦x<7/3
, O<y≦4), SiNiNxOy (0≦x<7/3.
0<y≦3), the film can be formed by the DC coating method, which is very advantageous in terms of manufacturing, and improves productivity.
Since it is a thin film of only oxide containing 120i or a composite of oxide and nitride, it has a composition close to glass and has high wear resistance. It also improves the adhesion between each layer leading to the layering, and prevents peeling etc. of the laminated multilayer film as a whole, leading to increased strength.The film thickness is preferably 300 or more, preferably is 400 to 2,000 people, optimally 500 to 1,000 people, and it is particularly preferable that the total thickness of the third and fourth layers is 500 people or more.For example, CS-10F (wear-resistant) )
In order to keep the change in visible light transmittance to 4% or less after 1,000 rotations in the Taber test using the same method as shown in Fig. This has the effect of making film defects less noticeable for a longer period of time, and it is preferable to use less than 2,000 people because if it is too thick, defects such as cracks will gradually appear. There is a tendency for it to become easier to maintain, as well as a thickness of more than 2000 people.
This is because the effect as a film cannot be expected to increase much and remains almost constant. In any case, as mentioned above, the fourth
This is because glass in which the layers are layered one after another can significantly improve the abrasion resistance and chemical resistance as a whole, making it useful as a single-pane window glass. It goes without saying that any colorless or colored inorganic or organic glass plate can be used as the transparent glass plate.

[Effect]

As mentioned above, the heat ray reflective glass plate of the present invention has a SilSNx thin film formed as the first layer on the surface of the transparent glass plate, and a specific T on the surface of the SUSNX thin film.
is a stack of Cr, Ta nitride or nitrogen oxide thin films, and also the SUSNx thin film and a specific T
i, Crs Ta nitride or nitrogen oxide thin film followed by Ti, . Sns CrSTa oxide thin films are sequentially laminated, and a specific Si layer is added to the surface of the three layers.
By skillfully combining and disposing the alloy oxide or nitrogen oxide II film overcoated with a single layer to 411, the visible light transmittance is about 30% or less, the solar transmittance is about 20% or less, and the visible light transmittance is about 20% or less. It has a light reflectance of about 45% or less, has a sufficient heat insulation effect, has a silver tone, and can improve the adhesion of each thin film layer. The special arrangement of nitrogen oxides and nitrogen oxides improves the abrasion resistance and corrosion resistance of the laminated multilayer film as a whole, making it suitable for use as a durable single-panel heat-reflecting glass sheet for architectural window glass. Of course, it can also be used in special locations as vehicle window glass. In particular, if the thin film layer of the present invention is arranged on a transparent glass plate in a unique pattern such as a lattice, blind, polka dot, honeycomb, etc., the visibility can be further improved and the insulation performance can be adjusted. It is something that can be made unique.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these embodiments.

Clear plate glass (FL3) with visible light transmittance of approximately 89.5%, size 600 x 600 2, thickness 3, On
After sequentially washing with a neutral detergent, rinsing with water, and isobrobyl alcohol, and drying, the sample was set so that it could reciprocate above the SuS316 target set in the vacuum chamber of the DC magnetron reaction sputtering device. Then, the inside of the tank was heated to about 5 X IO-”Tor using a vacuum pump.
After degassing to r, N2 gas is introduced into the vacuum chamber to maintain the degree of vacuum at approximately 2.5 x 10-' Torr,
A power of about 2.5KH was applied to the SuS316 target, and the speed was about 40O above the SuS316 target in the DC magnetron reaction sputtering.
By conveying the plate glass at n/win, approximately 1
A SUSNxll film with a thickness of 50 mm was formed as a single layer.

Regarding the heat ray reflective glass plate having the obtained single-layer film, visible light transmittance and visible light reflectance (380 to 780r+
m) and solar transmittance (340 to 1800 nm) using a 340-type self-recording spectrophotometer (manufactured by Hitachi) and JI
The optical properties were determined according to SZ8722 and JISR3106, respectively. In addition, regarding the difference in transmittance due to the Taber test, a Taber tester (MODEL503, TY
A 10CII 1 square test piece with the membrane side facing up was set in a wear ring (C
After rotating the sample 300 times and 1000 times, the visible light transmittance is measured and compared with the measured value before the test to determine the amount of change, that is, the difference. It is a numerical value expressed by . Furthermore, regarding the acid resistance test of chemical resistance, approximately I
After immersing the specimen for 6 hours in an ICl solution of N. The test piece was immersed in a 15N HCI solution for about 48 hours, and then the deterioration state of the membrane was observed.In the alkali resistance test, the test piece was immersed in a 15N HCI solution for about 48 hours, and the alkali resistance test was conducted with a Nail of about IN at room temperature as alkali 8.
{After immersing the test piece in the solution for about 6 hours, also as alkali B at a temperature of about 60°C, about 0. 125N NaOH
After immersing the test piece in the solution for about 48 hours, and after crushing the test piece in a NaOH solution of about 0.58 as alkali C at a temperature of about 60°C for about 48 hours, the state of deterioration of the membrane was visually determined. The O marks indicate almost no deterioration, the X marks indicate clearly noticeable deterioration, and the Δ marks are in between. The above measured values are as shown in Table 1, and the product has optical properties such as excellent heat insulation, which indicates better livability, sufficient abrasion resistance and corrosion resistance, and improved weather resistance and durability. Therefore, it can be useful as a single-pane window glass, and it is clear that it is superior to the SUSIM of Comparative Examples 1 and 2 described later. Note that the color tone of this example when viewed from the glass surface was a pale silver color.

Urasenshi 1 A SilSNdl film with a thickness of about 200 mm was formed using the same method as in Example 1, except that the transparent glass plate was conveyed at a speed of about 300/min.

The obtained heat ray reflective glass plate was tested in the same manner as in Example 1, and as shown in Table 1, it was found to be equivalent to or better than Example 1, and was superior to Comparative Examples 1 and 2. It is clear that this has been achieved. Note that the color tone of this example was also approximately the same as that of Example 1.

1st process In the same manner as in Example 1 above, the first layer was prepared in N2 gas at a vacuum level of about 2.5 x 10-3 Torr by applying a power of about 2.5K to a conveying speed of about 100 On/wi.
A SUSNx@ film with a thickness of about 60 mm was formed using n, and then a Ti target was used as the second layer at a vacuum degree of about 2.
．． 5X10-3Torr, Nz:Ot:O. 95:0
．． 05 gas, electricity approximately 2.5KW, conveyance speed approximately 86m
A TiNxOy thin film approximately 350 mm thick was deposited using m/win.

The obtained heat ray reflective glass plate was tested in the same manner as in Example 1, and as shown in Table 1, it had excellent heat insulation properties as in Examples 1 and 2, and its corrosion resistance and abrasion resistance were as good as in Examples 1 and 2.
The glass plates of Comparative Examples 3 and 4 below/
It can be seen that a film structure superior to that of SUS/TiN or TaN was obtained. Note that the color tone of this example and the like when viewed from the glass surface was a pale blue-ish silver color.

Using the same method as in Example 3, the first layer was a transparent glass plate with a conveyance speed of about 667 u/win and a thickness of about 90 layers, a thickness of about 120 layers at a speed of about 500 m/win, and then A TiNxOy thin film was used as the second layer in the same manner as in Example 3, and a Ta target was used for the TaNxOy 11 film at a vacuum degree of approximately 2.5X10'''TorrSNz:
Q! -0.95: 0.05 gas, electric power approximately 2.5k Approximately 78n/sin, approximately 450 people thick, and T
For the iN thin film, a Ti target is used at a vacuum level of 2.
Each test was carried out to a thickness of about 350 people at a power of 2.5 KW at 5 x 10-' Torrs and a conveyance speed of about 10 On+/min, and the three-layer film structure shown in Table 1 was laminated. The obtained heat ray reflective glass plate was tested in the same manner as in Example 1, and as shown in Table 1, it showed almost the same optical properties and corrosion resistance as Example 3, and in particular, in terms of abrasion resistance, it was better than Example 3. It showed improved durability. The color tone was almost the same as that of Example 3.

Layer up to the second layer in the same manner as in Examples 3 to 6 above,
A TiO2 thin film was formed on the surface as a third layer using a Ti target, and the vacuum level was 2.5 x 10-3 Torr. Gas, electricity 2.5KW, conveyance speed approximately 500mm/min
The layers were stacked to a thickness of about 200 people. TazOsf again! The films were laminated to a thickness of about 250 layers using a Ta target under the above-mentioned conditions at a transport speed of about 400 m/win to obtain a three-layer film structure as shown in Table 1.

The obtained heat ray reflective glass plate was tested in the same manner as in Example 1, and as shown in Table 1, it exhibited almost the same optical properties as Examples 1 to 6, and among chemical resistance, alkali resistance was further improved. In addition, especially regarding abrasion resistance, the transmittance difference in the Taber test was less than 5% after 1000 tests, making it a durable and desirable product that can be used as a single-pane window glass. It can be seen that, compared to the three-layer film configurations of Comparative Examples 5 and 6 described later, better abrasion resistance, chemical resistance, and alkali resistance were obtained. Note that the color tone of this example and the like when viewed from the glass surface was a pale greenish silver color.

After laminating three layers in almost the same manner as in Examples 7 to 10, except for changing some of the film thicknesses, a fourth layer of A was added to the surface.
Using I・Si (Al:Si・50:50) target soto, vacuum degree 2.5X10 Torrs Nz:Oz
= 1:1 gas, power 3.0k, conveyance speed approx. 201
A1/SiNxOyll with a thickness of about 500 at 1/min
The membranes were laminated to obtain a four-layer membrane structure as shown in Table 1.

The obtained heat ray reflective glass plate was tested in the same manner as in Example 1, and as shown in Table 1, the optical properties were almost the same as those of Examples 1 to 10, and the chemical resistance and abrasion resistance were In particular, the abrasion resistance showed a transmittance difference of 4% or less after 1000 tests, making it sufficiently durable as a single-pane window glass. It should be noted that, compared to the four-layered film structure of Comparative Example 7 described later, a film with better abrasion resistance, chemical resistance, and alkali resistance was obtained. Further, the color tone of the present example and the like when viewed from the glass surface was a silver color ranging from pale green to yellow.

The membrane structure shown in Table 1 could be laminated by the same method as in each of the above Examples. Regarding SUSIII, SUS
Using a 316 target, vacuum degree 3.0X 10-
3 Torr, Ar gas, power 1.0XW, rapid delivery speed of about 60 On/Illin, thickness of about 100 people, about 30
The film was formed to a thickness of about 200 at a rate of 0 m/win, to a thickness of about 30 at a rate of about 2000 n/win, and so on.

The obtained heat ray reflective glass was evaluated according to the same measuring method as in Example 1, and the results are shown in Table 1. Comparing each film layer from a single layer to four layers with the examples, it is clear that the abrasion resistance and chemical resistance are inferior, and it is a heat ray reflective glass plate that is difficult to use as a single-pane window glass. there were. It should be noted that the color tone was almost the same from single layer to four layers corresponding to the above embodiment.

〔Effect of the invention〕

As mentioned above, the present invention uses normal sputtering,
By uniquely combining thin films of specific substances such as SUSNx, nitrides, oxides, and nitrogen oxides, the optical properties can be made to have specific properties. The present invention is a high-grade insulating glass that is particularly excellent in abrasion resistance, corrosion resistance, and weather resistance, and can provide a heat-reflecting glass plate that is also useful as a single-pane window glass.

Claims (4)

[Claims] (1) A heat ray reflective glass plate characterized in that at least a SUS nitride thin film is formed on the surface of the transparent glass plate. (2) After forming a SUS nitride thin film on the surface of a transparent glass plate, the N_2:O_2 ratio in the atmosphere during coating is 1.
A heat ray reflective glass plate characterized in that a thin film of Ti, Cr, Ta nitride or nitrogen oxide is formed under the conditions of 00:0 to 50:50. (3) After forming a SUS nitride thin film on the surface of a transparent glass plate, the N_2:O_2 ratio in the atmosphere during coating is 1.
A thin film of Ti, Cr, Ta nitride or nitrogen oxide is formed under the conditions of 00:0 to 50:50, and then Ti, Sn,
A heat ray reflective glass plate characterized by laminating Cr and Ta oxide thin films. (4) After forming a SUS nitride thin film on the surface of a transparent glass plate, the N_2:O_2 ratio in the atmosphere during coating is 1.
A thin film of Ti, Cr, Ta nitride or nitrogen oxide is formed under the conditions of 00:0 to 50:50, and then Ti, Sn,
A thin oxide film of Cr and Ta is laminated, and the N_2:O_2 ratio in the atmosphere at the time of coating is 0:100 to 50.
A heat ray reflective glass plate characterized in that a thin film of an oxide or nitrogen oxide of an Si alloy of Si.Al, Si.Ni, or Si.Ti is laminated under the following conditions: :50.