CN110885197A - Glass plate with functional film and preparation method thereof - Google Patents

Abstract

The present invention relates to a glass plate comprising a glass substrate having first and second main surfaces opposed to each other, a functional film formed on the first main surface of the glass substrate, and conductive threads formed on the functional film. The glass sheet is produced by the steps of: applying a coating liquid onto a first main surface of a glass substrate to form a first precursor film thereon; subjecting the coated glass substrate to a first bake at a first temperature of 550 ℃ -; thereby converting the first precursor film into a second precursor film; printing a metal-containing paste on a portion of the second precursor film, thereby forming a lead wire thereon; and respectively converting the second precursor film and the leading wire into a functional film and a conductive wire. The second main surface of the glass substrate has a recess at a position corresponding to the wire. The depth of the depression does not exceed 1 μm. Therefore, the glass sheet can be used as an automobile rear window glass.

Description

Glass plate with functional film and preparation method thereof

Technical Field

The invention relates to the field of glass manufacturing, in particular to a glass plate with a functional film and a preparation method thereof.

Background

In recent years, there have been proposed automobile glass panes having various functional films, such as colored films for providing heat shielding, ultraviolet shielding, privacy, and the like. The color film contains (1) an oxide of at least one metal selected from the group consisting of Ti, Si, Zr, Ta, Sn and Zn as its main component, and (2) fine particles of a metal and/or a metal oxide dispersed therein. JP- ｃA-930836 discloses ｃA glass pane having ｃA light-shielding film prepared by coating ｃA coating liquid containing inorganic pigments (CuO, Fe2O3 and Mn2O3) and ｃA silicｃA sol (i.e., ｃA silicｃA precursor containing ｃA sol). JP-A-9156962 discloses ｃA composition for forming ｃA metal oxide film. The composition contains a metal salt and an alkanolamine. JP- ｃA-640252 discloses an automotive glass pane having ｃA portion through which light emitted from ｃA stop lamp mounted in ｃA high position passes. This portion is designed to have a higher visible light transmittance. Pat in the United states. No.6075490, corresponding to JP-A10-212137, discloses an automotive glass pane having a heat insulating film formed on the inside thereof. The film is partially removed or modified to increase visible light transmission therethrough. Conductive lines are formed on the heat shielding film to provide antenna and/or anti-fog functions.

Disclosure of Invention

It is an object of the present invention to overcome the above-mentioned deficiencies of the prior art and to provide a glass sheet with a functional film and a method for making the same that provides an undistorted image or view taken through the glass pane.

The technical scheme of the invention is as follows: a glass substrate including first and second major surfaces opposite to each other; a functional film formed on the first main surface of the glass substrate by a wet method, the functional film including at least one oxide; and a conductive filament prepared by printing META; a paste containing L on the functional film, wherein the second main surface of the glass substrate has a depression at a position corresponding to the conductive filament, the depression having a depth of greater than 0 and less than or equal to 1 μm; the conductive filament has at least one function selected from the group consisting of anti-fog and antenna; the at least one oxide of the functional film is selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, and tantalum oxide.

The light transmittance is 40% or less and the haze value is 0.5% or less to provide privacy.

A method for manufacturing a glass sheet comprising a glass substrate having first and second major surfaces opposite one another; a functional film formed on the first main surface of the glass substrate by a wet process, the functional film including at least one oxide; a lead prepared by printing a metal-containing paste on the functional film, wherein the second main surface of the glass substrate has a depression at a position corresponding to the conductive filament, the depression having a depth of greater than 0 and less than or equal to 1 μm; applying a coating liquid on the first main surface of the glass substrate to form a first precursor film thereon; the coated glass substrate is subjected to a first bake at a first temperature of 550-620 ℃ to convert the first precursor film into a second film. A precursor film; printing a metal-containing paste on a portion of the second precursor film, thereby forming leading conductive filaments thereon; and subjecting the coated glass substrate to a second baking at a second temperature of 600-670 ℃ higher than the first temperature to pull the second precursor film and the lead wire into the functional film and the conductive wire, respectively.

The coated glass substrate is subjected to at least one of bending or tempering when the coated glass substrate is subjected to the second bake.

The first baking is performed at a first temperature of 51-620 ℃ for about 5-30 minutes.

The invention has the beneficial effects that: an undistorted image or view taken through the glass pane can be provided.

Drawings

Fig. 1 is a schematic structural view of the present invention.

Detailed Description

In fig. 1, the present invention provides a glass plate having a functional film, comprising a glass substrate 2, a functional film 1 formed on a first main surface 3 of the glass substrate 2, and conductive threads 5 formed on the functional film 1. The second main surface 4 of the glass substrate has recesses 6 at positions corresponding to the conductive filaments 5. The recess 6 may be adjusted to have a depth a of not more than 1 μm. The second main surface 4 of the glass substrate is free from such depressions. Images taken with conventional glass panes not according to the invention, which have a similar structure to the glazing according to the invention, may be distorted by the depressions formed on the uncoated side. A stereoscopic glass pane. We have also surprisingly found that such depressions at the positions corresponding to the conductive wires of conventional glass panes are caused by deformation or distortion of the glass substrate, because there is a difference in the degree of thermal shrinkage between the first portions on which the leads have been formed and the second portions that have not been formed. According to the present invention, the above-mentioned first baking is performed before the metal-containing paste is printed so as to relax or release the deformation of the glass substrate. This distortion is caused by the thermal shrinkage of the functional film. By performing the first baking, the degree of deformation of the glass substrate of the produced glass pane can be surprisingly small. In fact, the above-described depressions may be adjusted to have a depth of 1 μm or less. Thereby, a glass pane may be produced which is capable of providing an undistorted image or view taken through it. In fact, the depth of the depression can be measured by using a commercial surface texture measuring device. The depth a is the distance between the second main surface 4 of the glass substrate 2 and the bottom of the groove 6. The conductive wire of the present invention has the function of antifogging and/or antenna. The glass pane according to the invention can suitably be used as a rear window pane of a motor vehicle, the fixing angle of which is 45 degrees or less than horizontal. The coated side of the glass sheet is usually arranged on the inside of the vehicle. The use of the glass pane is not particularly limited. Can be used for architectural decorative windows, industrial glass and the like. In the above process, when the second baking is performed, the bending and/or tempering operations may be performed simultaneously. As described above, the first baking is performed at the first temperature of 550-620 ℃. For example, in the case of producing tempered glass, the first baking is preferably performed at a first temperature of about 51 to 620 ℃ for about 5 to 30 minutes. In the case of producing laminated glass, the first baking is preferably performed at a first temperature of about 550-600 ℃ for about 5 to 30 minutes. The time of the first baking depends on the thickness of the glass substrate. Therefore, when the thickness of the glass substrate becomes large, the first baking is preferably performed for a long time. The first precursor film is shrunk into the second precursor film by the first baking. Therefore, after the second baking, a slight difference between the first portion of the functional film where the conductive wire has been formed and the second portion of the functional film where the conductive wire has not been formed can be obtained. Thereby, the recess can be adjusted to a depth of 1 μm or less. The coating liquid for forming the functional film is not particularly limited as long as it is in a liquid form. Particularly preferred are the sols used in sol-gel processes. The coating liquid contains at least one raw material of an oxide formed by baking. The raw material can be arbitrarily selected depending on the use and use of the functional film. For example, the functional film may be a heat-shielding film, an ultraviolet-shielding film, a hydrophilic antifogging film, an electromagnetic shielding film, a non-reflective film, a radio-transmissive film, a conductive film, or a decorative film by appropriately selecting raw materials. Optionally, additives (e.g., colorants) are added. Preferably, the coating liquid (sol) contains an alkoxide of at least one element selected from Si, Ti, Zr, Sn, Zn, and Ta. Such an alkoxy group may be an alkoxy group in which the alkoxy moiety is substituted with other alkoxy groups or alkyl groups or ligands such as a diketo group. If a silicon alkoxide is contained in the coating liquid, a functional film made of SiO2 is formed. The film is improved in strength and chemical durability. In addition, the refractive index of SiO2 was also as small as 1.45. Therefore, the total refractive index of the functional film is made lower. Therefore, light reflection from the functional film can be suppressed. Therefore, the functional film preferably contains SiO2 as its main component. Examples of silicon alkoxides are Tetraethoxysilane (TEOS), methyltriethoxysilane, tetra-n-butoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane. Similar examples of other alkoxides of metals (e.g., Ti, Zr, Sn, Zn, and Ta) may also be used. In the case where an alkoxide is contained in the coating liquid, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid is preferably added as a hydrolysis catalyst for the alkoxide. The coating liquid preferably further contains a solvent capable of dissolving the alkoxide or the metal salt. Examples of solvents are alcohols, such as methanol, isopropanol and ethanol, glycols, such as ethylene glycol oligomers, polyethylene glycol, propylene glycol oligomers and hexylene glycol, water, cellulose, carbon alcohols. In the case of producing a functional film having a certain color, the first, second, and/or third liquid may be added to the coating liquid. The first liquid is a liquid in which an oxide of at least one metal selected from Cu, Cr, Mn, Fe, Co, Ni, Zn, V, Ti, Al, and the like is dispersed. The second liquid is a liquid containing a metal salt of at least one metal. The third liquid is a liquid in which fine particles of a metal selected from gold, platinum, palladium, rhodium, and silver are dispersed. Examples of metal salts for the second liquid are nitrates, acetates, carbonates, chelates, hydrochlorides and the like. Among them, nitrates are preferably used because they are inexpensive and easy to handle. The coating liquid may further contain other additives such as a thickener. The coating method of the coating liquid is not particularly limited. Wet processes such as dip coating, flow coating, spin coating, spray coating, reverse roll coating, flexographic printing, screen printing, and the like may be used.

Claims (5)

1. A glass sheet characterized by: a glass substrate including first and second major surfaces opposite to each other; a functional film formed on the first main surface of the glass substrate by a wet method, the functional film including at least one oxide; and a conductive filament prepared by printing META; a paste containing L on the functional film, wherein the second main surface of the glass substrate has a depression at a position corresponding to the conductive filament, the depression having a depth of greater than 0 and less than or equal to 1 μm; the conductive filament has at least one function selected from the group consisting of anti-fog and antenna; the at least one oxide of the functional film is selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, and tantalum oxide.

2. A glass sheet according to claim 1, wherein: the light transmittance is 40% or less and the haze value is 0.5% or less to provide privacy.

3. A method for making a glass sheet, characterized by: the glass sheet includes a glass substrate having first and second major surfaces opposite each other; a functional film formed on the first main surface of the glass substrate by a wet process, the functional film including at least one oxide; a lead prepared by printing a metal-containing paste on the functional film, wherein the second main surface of the glass substrate has a depression at a position corresponding to the conductive filament, the depression having a depth of greater than 0 and less than or equal to 1 μm; applying a coating liquid on the first main surface of the glass substrate to form a first precursor film thereon; the coated glass substrate is subjected to a first bake at a first temperature of 550-620 ℃ to convert the first precursor film into a second film. A precursor film; printing a metal-containing paste on a portion of the second precursor film, thereby forming leading conductive filaments thereon; and subjecting the coated glass substrate to a second baking at a second temperature of 600-670 ℃ higher than the first temperature to pull the second precursor film and the lead wire into the functional film and the conductive wire, respectively.

4. A method for making glass sheets as in claim 1 wherein: the coated glass substrate is subjected to at least one of bending or tempering when the coated glass substrate is subjected to the second bake.

5. A method for making glass sheets as in claim 1 wherein: the first baking is performed at a first temperature of 51-620 ℃ for about 5-30 minutes.

Images