JPS5869743A - Electrically conductive glass and its production - Google Patents

Abstract

PURPOSE:After an electrically conductive coating film is formed on glass plate surfaces, hard coating films of oxide, nitride or carbide of a specific metal are formed thereon to produce conductive glass with high wearing and chemical resistance. CONSTITUTION:A glass plate 2 coated with an electrically conductive coating film on its surfaces is put on the support 9 in the vacuum dome 1. The glass plate is used as the anode and the air in the dome 1 is evacuated with a vacuum pump 5, then, an inert gas such as nitrogen or carbon dioxide gas is introduced through the pipe 7 into the dome 1. An acceleration voltage from the high- frequency electric source 8 is applied to the cathode 3 of an oxide of Si, Ti or Al to effect sputtering to form a hard coating film of oxide, nitride or carbide of Si, Ti or Al on the conductive film of the glass 2 in a thickness of 1,000- 1,500Angstrom .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a conductive glass having excellent abrasion resistance and a method for producing the same.

Conductive glass is used to prevent fogging and freezing of window glass, and is widely used as anti-fog glass for automobiles, aircraft, and other types of transportation, and as glass for preventing radio noise.

There is also a method of using this kind of conductive glass as a base material and forming a film of metal such as copper, nickel, stainless steel, Hastelloy, etc. on the surface of this base material by sputtering or vacuum evaporation method, but there is also a transparent method. Therefore, when transparency and especially antifogging properties are required, an aqueous solution of tin chloride is sprayed onto inorganic glass and fired to form a thin film of several hundred millimeters in size that is mainly composed of tin oxide. method is being done.

However, tin oxide and tin oxide-based conductive films, in which antimony or indium oxides are added to tin oxide, do not have sufficient hardness, are easily worn out by friction, and do not last long under harsh usage conditions such as on automobile window glasses. There was a drawback that it could not withstand use for a long period of time.

As a result of repeated research in search of a conductive film with excellent wear resistance, the inventors of the present invention created a conductive film of tin oxide by spraying an aqueous solution of, for example, tin chloride onto the glass surface, drying, and baking it. After the formation, a cured film made of an oxide, nitride, or carbide such as 81 + Ti sAl, for example, SiOx * TiCh * is formed on the conductive film by sputtering.
The above objective was successfully achieved by forming a hard film such as Altos*Tic, TiN, etc.

The feature of the present invention is that SiO! is formed on the conductive film. t T
20x *A hard film of various inorganic oxides, including Altos, is formed to provide wear resistance.If transparency is not particularly required, the conductive film can be a widely used metal film, i.e., Copper, nickel, stainless steel, Hastelloy, or the like may be formed on glass by sputtering or vacuum vaporization. In addition to oxides of silicon, titanium, aluminum, etc., carbides or nitrides of these may be used as the wear-resistant film. Father above \2f] 12i1
It may be a single product.

Examples of the conductive glass of the present invention and its manufacturing method will be described below with reference to the drawings.

Example 10% aqueous solution of stannic chloride containing 1% antimony chloride
5qb hydrochloric acid toocc was added to 00CC to prepare an aqueous solution for spraying. This aqueous solution was sprayed onto automobile glass. Next, the above glass plate was dried at 100℃, and then dried at 650℃ for 1 hour.
A toughened tin-based conductive film was formed by firing for a period of time. In the above, antimonochloride is used as an auxiliary agent since antimony changes the specific resistance of the conductive film. Indium may be used in addition to antimony. The area resistivity of the obtained conductive film was 70 ohms/c
Ii, the film thickness was 2,500 angstroms (250 millimicrons).

Next, a wear-resistant film was further formed on the above conductive film using a spackling device as shown in the drawings. In the figure, 1
The dome is made of vacuum pressure glass and may be made of steel.

2 is the above-mentioned conductive glass serving as a sample and serves as an anode, and 3 is a SiOx plate serving as a cathode. In the sputtering apparatus, the inside of the dome 1 is evacuated to 10@-6 Hf using the vacuum bonder 5, and then argon gas is introduced from the argon gas introduction pipe 7 to obtain a vacuum degree of 101 mHt. Next, when an accelerating voltage of 10 Kv and 1i56 MHr is applied to the cathode by the high-frequency power source 8, the argon gas is ionized, and the generated cations collide with the cathode, giving kinetic energy to the S i Ox molecules on the surface and moving toward the anode. It spreads. After forming a film to a predetermined thickness, the shutter 4 was closed to block the flow of SiOx molecules, and sputtering was completed. The thickness of the 5i02 film thus obtained was 1000 to 1500 angstroms (100 to 150 millimicrons).

Furthermore, the abrasion resistance was compared between the conductive glass of the present invention and a conventional conductive glass without an abrasion-resistant film using a test method assuming the usage conditions of an automobile windshield. That is, as a result of repeatedly applying back-and-forth friction with a wiper blade while applying a suspension of 2 parts of clay to water on the above two types of conductive glass for 10 hours, the conductive glass according to the present invention suffered almost no damage. However, most of the conductive film formed by the conventional method was worn away, leaving the glass substrate exposed.

The wear-resistant film formed in this example was on Sl, but on TiO! t Various inorganic oxides such as AhOs may be used, or carbides and nitrides such as silicon and titanium may be formed. In the case of carbides and nitrides such as TlC- and TiN, the metal may be heated with nitrogen gas or carbide. The film may be formed by a reactive sputtering method in which sputtering is performed in a hydrogen gas atmosphere.

The present invention has many excellent effects such as being able to impart physical strength such as abrasion resistance to a conductive film using a simple method, and also being able to impart chemical properties such as chemical resistance depending on the sputtering film. is obtained.

[Brief explanation of drawings]

The figure shows a schematic diagram of a sputtering apparatus. In the figure, 1... Vacuum glass dome 2... Conductive glass 5.
...5iOf board'...Shutter 5...k27 bomb 6...Valve 7...Argon gas introduction pipe
8... High frequency power supply 9... Sample support stand 1o...
・Shutter support shelf (#1 or 1 person)

Claims (2)

[Claims] (1) Conductivity characterized by forming a conductive film on the glass surface, and forming a hard film of one or more oxides of silicon, titanium, aluminum, etc., or nitrides or carbides thereof. glass. (2) After forming a conductive film on the glass surface, sputtering an oxide such as silicon, titanium or aluminum in an inert gas, or sputtering these metal elements in a nitrogen gas or hydrocarbon gas atmosphere. A method for producing conductive glass, characterized by forming a hard film by doing so.