KR900002707B1 - Method of manufacturing hot-reflective glass - Google Patents

Abstract

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Description

Method of manufacturing hot-reflective glass

1 is a schematic cross-sectional view of a sputtering apparatus for implementing the method of the present invention.

2 is an enlarged cross-sectional view of a heat ray reflecting glass produced by the method of the present invention.

* Explanation of symbols for main parts of the drawings

1: vacuum chamber 5, 6: magnetron cathode

10, 11: gas supply pipe 12: conveying belt

13, 14: target 15: holder

16: glass plate 17, 19: metal oxide layer

18: precious metal layer

The present invention relates to a method for manufacturing hot-reflective glass used as a window pane or automobile window pane of a building.

Heat-reflecting glass for blocking heat from the outside and preventing the heat of the room from falling out to the outside to maintain a constant indoor temperature has been known in the art.

The heat ray reflecting glass forms a metal oxide as a first layer by reactive sputtering on the glass surface, that is, by sputtering in an atmosphere containing oxygen, and forms precious metals by sputtering in an anoxic atmosphere on the surface of the first layer. It forms as a 2nd layer, and forms the metal oxide layer as a 3rd layer similarly to a 1st layer on the surface of a 2nd layer, and is manufactured.

Therefore, in order to form the metal oxide layer of the third layer, a metal is used as a target to oxidize the second layer of the noble metal already formed at the time of the sputtering for reactive sputtering in the oxidizing atmosphere, or the second layer is oxygenated. There is a disadvantage in that the heat reflection function is degraded due to the migration that blows.

Here, as proposed in Japanese Patent Laid-Open No. 59-165001, a metal layer made of any one of Zn, Al, Sn, Ar, Ti, etc. is formed between the second layer made of noble metal and the third layer made of metal oxide. And protecting the second layer of noble metal when forming the third layer in reactive sputtering.

As described above, interposing the metal layer between the second layer (noble metal) and the third layer (metal oxide) prevents the second layer from oxidizing when the third layer is formed in reactive sputtering. By this means, the number of targets used for sputtering becomes large, and as a result, not only the equipment becomes large, but also the number of manufacturing processes increases. Conversely, reducing the number of targets has the disadvantage of requiring time to exchange targets and increasing the number of processes.

In addition, in order for the metal layer to intervene, the adhesive force of the noble metal layer is weak, so that the third layer is formed by direct current sputtering in a reactive atmosphere. In the case of the conventional method, since the moisture resistance and heat resistance of the second layer (noble metal) are poor, for example, when manufacturing the heat reflection glass as the windshield for automobiles, the heat reflection film is formed before the glass plate is bent and then bent. When formed, the heat ray reflection film (noble metal film) deteriorates, and the heat ray reflection property and visible light transmittance are greatly reduced. For this reason, conventionally, the heat ray reflection treatment (sputtering) is performed after the bending is formed, but according to this method, there is a problem that it is difficult to form a uniform reflective film because the glass plate is curved.

The present invention, which solves the above problems, forms a second layer of a noble metal in an oxidizing atmosphere and then targets a metal oxide on the surface of the second layer, and direct current sputtering is performed in an oxidizing atmosphere or an atmosphere having low oxygen partial pressure. And a third layer of metal oxide was formed.

In order to perform sputtering as a metal oxide target, a metal oxide can be formed as a third layer without making a reactive atmosphere, and the third layer can be made into a dense structure, and the second layer (noble metal layer) and the first layer can be formed. And adhesive force with the third layer (metal oxide layer).

EXAMPLE

Embodiments of the present invention will be described below with reference to the accompanying drawings.

1 is a schematic diagram of a sputtering apparatus for carrying out the method of the present invention, wherein the sputtering apparatus is an exhaust port 3 provided with a variable valve 2 in a part of an earthed vacuum chamber 1. ) Is connected to a vacuum pump (not shown) via this exhaust port 3, and the pressure inside the vacuum chamber 1 is reduced. In the bottom of the vacuum chamber 1, a pair of magnetron cathodes 5 and 6 are provided apart from each other via electrical insulators 4a and 4b, and the magnetron cathodes 5 and 6 and the direct current are installed. The power sources 7a and 7b are connected via the switches 8a and 8b. In addition, the gas supply pipe (10) and the gas supply pipe (10, 11) provided with valves (9a) and (9b) penetrate the bottom of the vacuum chamber (1) in the vicinity of the magnetron cathodes (5) and (6). 11, an inert gas such as argon gas is supplied into the vacuum chamber 1, and a mixed gas of oxygen gas and inert gas such as argon gas and the like is supplied from the gas supply pipe 11 into the gas supply pipe 11.

Moreover, the transfer valve 12 which can be reciprocated is arrange | positioned above each cathode 5 and 6 in the vacuum chamber 1. As shown in FIG.

The method of forming a hot wire thin film using the sputtering apparatus of the above structure is explained in full detail below.

First, Ag is attached to the upper surface of the cathode 5 with the target 13, and ZnO containing 3 mol% of Al ₂ O ₃ is attached to the upper surface of the cathode 6 as the target 14 and the holder 15 is attached. It mounts on the conveyance belt 12. Thereafter, the variable valve 2 is opened to depressurize the inside of the vacuum chamber 1 to 10 ⁻³ Pa, and argon gas and oxygen gas are supplied from the gas supply pipes 10 and 11. In addition, the mixing ratio of the gas supplied in the vacuum chamber 1 lowers the partial pressure of oxygen by argon gas at 95% by volume and oxygen gas at 5% by volume, and makes the vacuum chamber 1 after gas introduction at 0.4 Pa. Thus, the glass plate held on the holder 15 by driving the conveyance belt 12 after the switch 8b was turned on to apply a negative voltage of 350V to the cathode 6 and subjected to sputtering for 10 minutes. 16) is moved on the cathode 6 at a speed of 300 m / m, and as shown in FIG. 2, the metal oxide layer 17 having a predetermined thickness (100 Pa-600 Pa) on the surface of the glass plate 16, specifically, As the first layer, ZnO-Al ₂ O ₃ is formed.

Thus, the switch 8b is turned off, the valves 9a and 9b are closed, and the variable valve 2 is opened again to depressurize the inside of the vacuum chamber 1 to 10 ^-3 Pa.

Thereafter, the valve 9a of the gas supply pipe 10 is opened, argon gas is introduced into the vacuum chamber 1 at 100 sccm, and the variable valve 2 is adjusted to maintain the vacuum chamber 1 at 0.4 Pa and the cathode ( The switch 8a of 5) is turned on to apply a negative voltage of 300V to the cathode 5 and to perform direct current sputtering for about 10 minutes. Thereafter, the conveyance belt 12 is moved and the glass plate 16 held in the holder 15 is moved on the cathode 5 at a speed of 1100 m / m. As shown in FIG. 2, the metal oxide layer 17 The second layer of the noble metal layer 18, specifically Ag, of predetermined thickness (50 micrometers-300 micrometers) is formed on the surface.

Thereafter, DC sputtering is carried out in the same conditions as those in which the electrometal oxide layer 17 is formed, that is, ZnO containing 3 mol% of Al ₂ O ₃ and subjected to direct current sputtering in an atmosphere having a low oxygen partial pressure. As described above, the metal oxide layer 19 made of Al ₂ O ₃ -ZnO having a thickness of about 100 kPa to 600 kPa is formed on the surface of the noble metal layer 18 as the third layer.

In the examples, ZnO (zinc oxide) containing Al ₂ O ₃ is represented as the metal oxide, but in addition, a conductive metal oxide such as tin oxide, tin oxide containing indium oxide, antimony oxide or indium oxide may be used. As the noble metal, gold, copper, palladium, rhodium and the like may be used in addition to silver.

Further, in the embodiment, the oxygen partial pressure is lowered as an atmosphere for forming the metal oxide layer 19, but may be an oxygen-free atmosphere containing no oxygen. In addition, the limit of the mixing ratio of oxygen and argon is 20% by volume of oxygen and 80% by volume of argon, and when oxygen exceeds this value, it was found that the heat and moisture resistance were significantly reduced. Thus, it was clear from the experiment that the proportion of oxygen is preferably less than 10% by volume.

Table 1 shows the results of the heat resistance test and the moisture resistance test of the conventional four-layer structure and the three-layer structure manufactured according to the present invention by interposing the metal layer (Zn) between the metal layer (Ag) and the metal oxide layer (ZnO). It is shown.

TABLE 1

As is apparent from Table 1 above, it can be seen from the present invention that there is almost no change in the transmittance and the heat ray reflectance of visible light before and after the test compared to the conventional products. Therefore, in the case of performing the heat ray reflection treatment on the bent glass, the heat ray reflection film may be formed before the formation of the bend, and may be a uniform heat ray reflection film. As described above, the present invention is excellent in visible transmittance, heat ray reflectance, and the like when the third layer (metal oxide layer) is formed in an oxygen-free atmosphere or in an atmosphere having a low oxygen partial pressure containing oxygen of up to 20% by volume. For this reason, since the noble metal layer does not oxidize or blow oxygen (migrate) during the sputtering of the third layer, and the metal layer is not interposed between the noble metal layer and the metal oxide layer, the adhesive force is considered to be high.

In addition, according to the present invention, since the three-layer structure is sufficient, the number of targets may be reduced and the number of steps may also be reduced.

Claims (6)

The first layer of metal oxides is formed on the surface of the glass plate by direct current sputtering, and the surface of the first layer is subjected to direct current sputtering in an oxidizing atmosphere to form a second layer made of noble metals. A method for producing a hot-reflective glass, characterized by forming a third layer of metal oxide by direct current sputtering in an atmosphere containing 0-20% by volume of oxygen by targeting metal oxide to the surface. The method for producing a hot-reflective glass according to claim 1, wherein the direct current sputtering forming the first layer is performed in an atmosphere containing metal oxide as a target and containing 0-20% by volume of oxygen. The metal oxide constituting the first layer and the third layer is any one of tin oxide, indium oxide containing tin oxide, zinc oxide, antimony oxide, and indium oxide, and the second layer. Precious metal constituting the is a method for producing a heat reflection glass, characterized in that any one of silver, gold, copper, palladium, rhodium. The method of claim 1 wherein the precious metal is silver. The method of claim 4, wherein the metal oxide first layer and the third layer are Al ₂ O ₃ -ZnO. The method of claim 1, wherein the metal oxide first layer and the third layer are Al ₂ O ₃ -ZnO.

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