JPH04132635A - Ceramic coating glass - Google Patents

Abstract

PURPOSE:To increase adhesion of coating to glass, to improve denseness and smoothness of coating and to thicken a film by forming a ceramic coating film comprising silicon and nitrogen as essential components on the surface of glass. CONSTITUTION:An amorphous film comprising silicon and nitrogen as essential components and at least one selected from a group consisting of oxygen, hydrogen and a metal (one or more metals selected from a group of metal elements of group I to group VIII of the periodic table) as an arbitrary component in atomic ratio of the elements of <=3 N/Si, <=15 O/Si and <=5 M/Si (M is one or more metals selected from a group consisting of group I to group VIII of periodic table) is used as a ceramic coating film formed on the surface of glass. The ceramic coating glass is obtained by applying a polysilazane having a repeating unit shown by formula I and about 100-500,000 number-average molecular weight to glass and baking.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to ceramic coated glass.

More specifically, it is a glass that is coated with a ceramic coating to prevent alkali-containing glass, especially soda glass, from burning and elution of soda, or to improve the strength, hardness, and smoothness of the glass surface. Regarding.

[Conventional technology]

Alkali-containing glass, especially soda glass, can cause glass burn.
In other words, the moisture in the atmosphere and the sodium on the glass surface may react, producing dew-like foreign matter rich in sodium at the contact area, and furthermore, the sodium inside the glass may diffuse in equilibrium to the surface layer in the form of ions. Due to the interdiffusion of hydrogen ions and alkali ions in the water, soda content is eluted to the surface. Further, when handling the glass, there is a problem that contact scratches occur on the surface due to contact with other members, resulting in a decrease in strength or loss of smoothness. In order to solve these problems, a method of forming a silica film on the surface of soda glass is being considered.

- Methods for forming silica films by boat include vapor deposition and sputtering, but these methods have the disadvantage of being poor in mass production.

On the other hand, the silicon compound RnSi (OH) 4-1
A method with excellent mass productivity has been developed in which a coating solution containing No. 1 and a glass-forming agent dissolved in an organic solvent is applied to a glass surface, and the coating is fired to form a film containing silicon oxide (SiO□) as the main component.

Additionally, coating with various preceramic polymers is being considered for the purpose of improving the strength of glass. This is intended to improve strength by filling in scratches that can be the starting point for fracture.

[Problem to be solved by the invention]

The above coating liquid contains a silicon compound RnS i (OH) a
- It is a glass-forming agent with an organic binder added, and it is applied to the glass surface by spin coating, dipping, etc. and baked at a temperature of about 500'C to form a SiO□ film. Since the thermal decomposition yield is not high, the density is not sufficient, and the thickness of the formed film is about 0.05 to 0.2 microns, making it difficult to increase the thickness. Therefore, it is desired to develop a dense film that can be made thicker and has fewer pinholes.

In addition, there is still room for improvement in the above-mentioned preceramic polymer coating in terms of adhesion between the coating and glass, denseness, smoothness, thickening, and the like.

[Means to solve the problem]

In order to solve the above problems, the present invention provides a ceramic coating film containing silicon and nitrogen as essential components, oxygen, hydrogen, and metals (selected from the group of metal elements of Groups 1 to 2 of the Periodic Table of Elements). The optional component is at least one selected from the group consisting of one or more metals, and the ratio of each element expressed in atomic ratio is N/Si3 or less, 0/Si15 or less, M/S 15 or less ( M is one or more metals selected from the group of metal elements of Groups T to Group (III) of the Periodic Table of the Elements), and is amorphous. provide.

The ceramic coating film of the present invention is a coating film containing silicon and nitrogen as essential components, and oxygen and metals as optional components, and has crystallinity regardless of whether it is crystalline or amorphous, but substantially Preferably, the material is amorphous.

That is, those that are amorphous as determined by X-ray diffraction analysis or those that contain microcrystalline phases whose crystallite size (measured using the X-ray diffraction half-maximum method (JONES method)) are 2000 Å or less in all directions. preferable. A particularly preferable crystallite size is 1
000 Å or less, and the more preferable crystallite size is 5
00 Å or less.

The ratio of each element constituting the ceramic coating used in the present invention, expressed as an atomic ratio, is N/Si3 or less 0/Si15 or less N/Si5 or less, and the preferable atomic ratio is N/Si1.4 or less 0/SilO or less. M/Si is 2.5 or less. A more preferable atomic ratio is N/Si 1.3 or less and 0/Si 4 or less M/Sil or less.

If the element ratio is not within the above range, the strength of the ceramic coating film cannot be exhibited.

Further, as the metal M, at least one selected from the group of metal elements of Groups 1 to 2 of the Periodic Table of the Elements is used, and more preferred metals are Groups 1a and 1 to V of the Periodic Table of the Elements. Examples include one or more metals selected from the group of metal elements, and particularly preferred metals are aluminum, titanium, zirconium, and the like.

The ceramic coating film used in the present invention has a repeating unit represented by the general formula II H +5i-N+ and has a number average molecular weight of 10.
It can be obtained by coating and firing a polysilazane consisting of a cyclic or chain inorganic polysilazane having a molecular weight of 0 to 500,000, a mixture thereof, or a composite thereof.

Such polysilazane can be obtained, for example, by reacting a halosilane such as dichlorosilane with a base such as pyridine, and then reacting an adduct of dichlorosilane and a base with ammonia (JP-A-60-145903). reference).

In addition, the above polysilazane is heated to form a high polymer (number average molecular weight 200 to 500,000) (Japanese patent application No. 6
2-202765 and 63-74918),
Alternatively, a polysilazane modified by a dehydrogenation condensation reaction of the above-mentioned inorganic polysilazane with ammonia or hydrazine can be used (see Japanese Patent Application No. 62-202767 and No. 63-74919).

Furthermore, polymetallosilazane disclosed by the present applicant in Japanese Patent Application No. 61-223970, etc., or
Polysiloxazane disclosed in Japanese Patent Publication No.-195024 can also be used.

Next, the polysilazane obtained above is made into a coating solution, which is then coated and fired to produce ceramic coated glass.

Polysilazane is applied to various types of glass by various methods such as dipping, spin cording, brushing, and spraying. Since polysilazane itself is a liquid having an appropriate viscosity depending on its molecular weight, it can be applied as is, but if necessary, it can be dissolved in various organic solvents to form a coating liquid.

Since polysilazane is infusible to heat, there is no need for infusibility treatment, and the coating film does not sag due to melting.

The type of glass that can be used in the present invention is not particularly limited, but the ceramic coating of the present invention is particularly effective for alkali-containing glass, especially soda glass, because it has an excellent protective effect against elution of alkali content (soda content). .

Firing is performed under vacuum or with an inert gas such as nitrogen argon,
It is carried out under a gas atmosphere consisting of ammonia, hydrogen or a mixture thereof.

The firing temperature is usually 200°C to 1000°C,
Firing time is 1 minute to 10 hours. The maximum heat treatment temperature depends on the type of glass.

The ceramic coating of the present invention has the following features.

(1) Since the thermal decomposition yield is high, the shrinkage rate during the firing process is small, and pinholes and cracks are less likely to occur.

Therefore, it is dense and can be made thick (for example, 2 thick or more). In other words, it greatly contributes to improvements in alkali resistance, strength, hardness, and smoothness.

(2) Si, N, and O, which basically do not contain organic groups.

Since it is a polymer consisting only of H, it is chemically active and has high adhesion to glass whose main composition is Si and O. Therefore, even after firing, the adhesive strength with glass is high.

(3) Since it is a thermosetting polymer with no melting point, there is no need for infusibility treatment, and the coating film does not sag due to melting.

The present invention can be widely applied to glass substrates for thin film transistor type liquid crystal panels, other optical glasses, various window glasses, etc. by taking advantage of the features of ceramic coatings.

[For production]

The ceramic coating of the present invention is dense, can be formed into a thick film, and has good adhesion to glass, so it is effective for improving the strength, hardness, and smoothness of glass or as a protective film for alkali glass.

〔Example〕

1. Flame 1 A four-bottle flask with an internal volume of 10 L was equipped with a gas blowing tube, a mechanical stirrer, and a dewar condenser.

After the inside of the reactor was replaced with deoxygenated dry nitrogen, 5 L of degassed dry pyridine was placed in a four-necked flask and cooled on ice. Next, 516 g of dichlorosilane was added to produce a white solid adduct (SiHzCE z.2C5H6N). The reaction mixture was ice-cooled, and while stirring, 510 g of purified ammonia was blown into the reaction mixture through a sodium hydroxide tube and an activated carbon tube. After the reaction was completed, the reaction mixture was centrifuged, washed with dry pyridine, and further filtered under a nitrogen atmosphere to obtain 8.5 L of filtrate. The number average molecular weight of the obtained inorganic polysilazane was 980 as measured by GPC.

In addition, a pyridine solution of the inorganic polysilazane obtained in Reference Example 1 (
(inorganic polysilazane concentration, 6.2%) was placed in a pressure-resistant reaction vessel with an internal volume of 300 mL, and the reaction was carried out at 120° C. for 3 hours with stirring in a nitrogen atmosphere in a closed system. During this time, a large amount of gas was generated, which was determined to be hydrogen by gas chromatography. The pressure increase before and after the reaction was 2 kg/cfl. After cooling to room temperature, add 400 mL of dry 0-xylene and reduce the pressure to 3-5.
When the solvent was removed at mmHg and a temperature of 50 to 70°C,
10.9 g of white powder was obtained, which was soluble in organic solvents. The number average molecular weight of the polymer powder is 1388
The weight average molecular weight was 3968, and the Si/N ratio was 1.33.

Performance side 0 - Thermal polymerization inorganic polysilazane obtained in Reference Example 2 (number average molecular weight Mn: 1388, weight average molecular weight Mw: 396
8. A 20 wt % 0-xylene solution with a Si/N ratio of 1.33) was applied to a soda glass substrate and a soda glass rod with a diameter of 4φ and a length of 4 (1 (mm)) by a dip coating method. After drying, the former was heated to 500°C x Ih,
The latter was heat-treated in N2 to form a 5i-ON coating, and the latter was heat-treated at 500°C for 1 h in air to form a 5i-0-
N-based coating. The film thickness is approximately 0.5 in each case.
ttm, and no pinholes, cracks, etc. were observed.

As a result of measuring the hardness of the coated soda glass substrate using a micro Vickers hardness meter, the hardness increased to 823 Kgf/mm 2 from 450 Kgf/2 cylinders of the soda glass substrate. Furthermore, as a result of measuring the three-point bending strength of the coated soda glass rod, it increased to 37 Kgf/mm2 compared to 14 Kgf/mm2 for the soda glass rod that underwent the same thermal history.

1 ± 1 Thermal polymerization inorganic polysilazane prepared in Reference Example 2 (number average molecular weight Mn: 1388, weight average molecular weight Mn: 39
68, Si/N ratio: '1.33)'s 41h%O
- Using a xylene solution, it was applied to a soda glass substrate by a dip coating method. After drying, 500°C
When heat treated in the air for 1 hour, a dense 540□ coating with a film thickness of 2 feet without pinholes or cracks was obtained.

Dissolution of the inorganic polysilazane obtained in Reference Example 1 in pyridine!
1. (Inorganic polysilazane concentration, 6.2%) 100 mL was placed in a pressure-resistant reaction vessel with an internal volume of 300 mL, 4.5 g of purified anhydrous ammonia was added, and the reaction was carried out with stirring at 50° C. for 3 hours in a closed system. During this time, a large amount of gas was generated, which was determined to be hydrogen by gas chromatography. The pressure increase before and after the reaction is 1 kg.
/ cllI. After cooling to room temperature, add 300 mL of dry 0-xylene, pressure 3-5 mm 1 g, temperature 50
When the solvent was removed at ~70°C, 8.0g of white powder was obtained.
The powder obtained was soluble in organic solvents. The number average molecular weight of the polymer powder is 2352, and the weight average molecular weight is 10.
735, and the Si/N ratio was 1.05.

Modified inorganic polysilazane obtained in Reference Example 3 (number average molecular weight Mn: 2352, weight average molecular weight M: 107)
A 10 wt % 0-xylene solution of No. 35, Si/N ratio: 1.05) was applied to a soda glass substrate using a spin coater. After drying, it was heat-treated at 500° C. x 30 ml in the air to form a 5in2 film. The film thickness was 1100 people.

Seal the edges and back of the glass and heat at 100°C for 25 hours.

When immersed in ultrapure water and analyzed the amount of Na elution, it was found to be 0.
161 Ig/cl, and 1.68 for the plain soda glass.
It decreased to about 1/10 compared to n/cfl. In addition, the same film thickness (110
0 people) SiO. For coating, 0.90μg
/ afl and SiO with polysilazane according to the method of the invention.

The coating was clearly superior.

A SiO□ coating was applied to the surface of soda glass (thickness: 1 mm) according to Example 1 (dipping method) and Example 3 (spin cord method).

The results of measuring the surface roughness of the obtained SiO□ coating are shown in the table below.

[Effects of the Invention] The ceramic coated glass of the present invention has excellent density and thick film properties, and is effective in protecting alkali glass and improving glass strength, hardness, and smoothness.

Claims (1)

[Claims] 1. The ceramic coating film contains silicon and nitrogen as essential components, oxygen, hydrogen and metals (one selected from the group of metal elements of Groups I to VIII of the Periodic Table of Elements) or At least one selected from the group of two or more metals is an optional component, and the ratio of each element is expressed as an atomic ratio of N/Si3.
Hereinafter, O/Si is 15 or less, M/Si is 5 or less (M is one or more metals selected from the group of metal elements of Groups I to VIII of the Periodic Table of the Elements), and is amorphous. Ceramic coated glass characterized by its high quality. 2. It has a repeating unit represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the number average molecular weight is approximately 1.
1. A method for producing ceramic coated glass, which comprises applying polysilazane having a molecular weight of 0.00 to 500,000 on glass and firing it.