TW201605754A - Method for treating the surface of thin glass substrates - Google Patents

Abstract

The invention relates to a method for treating the surface of a thin or ultra-thin glass substrate, comprising the following steps: - treating the surface of the glass substrate by flame treatment with at least one oxidizing flame, wherein the glass substrate and/or the at least one oxidizing flame are moved past each other at such a speed that the following applies to the temperature (T) in the glass substrate during the flame treatment: T < Tg, wherein Tg is the glass transition temperature of the glass, and - after treatment of the surface, the contact angle is less than 10 DEG , preferably less than 8 DEG , in particular less than 5 DEG , preferably less than 3 DEG ; and - laminating a film onto the surface of the glass substrate. For thin or ultra-thin glass, the method according to the invention is suitable for carrying out the removal of adsorbed water layers reliably and in a reproducible manner without causing deformation or warping of the glass.

Description

Thin glass substrate surface treatment method

The present invention relates to a method of treating the surface of a thin glass substrate, and a thin glass substrate obtained by the method.

Almost all common surfaces are provided with additional layers, such as chemically bonded reaction layers, adsorbed layers, impurities, etc., which determine the chemical and physical properties of the surface. For example, when two glass sheets are broken to produce two newly formed surfaces, a plurality of exposed bonding points in the form of irregular cells are generated, thereby forming a plurality of regions having a relatively high degree of polarization, and the regions are highly reactive. Such highly polarized areas, for example, react with atmospheric water vapor in the environment. Therefore, when a newly formed glass surface is produced, contact with air is caused, and water is accumulated in the form of a surface layer. Therefore, the glass substrate has certain aging characteristics in ambient air. Such aging means that the chemical and physical properties of the glass substrate change due to one or more surface layers. Such a layer prevents the coating from adhering smoothly and well to the glass. The adhesion of the coating applied to such an aged surface is generally small because the moisture bound to the surface is combined in the form of one or more gel layers, thereby adversely affecting the adhesion characteristics of the layer to be plated. .

In addition, the surface quality also determines whether a uniform coating can be produced with high repeatability. For example, the surface usually has local bulges or similar chemical modifications after it has aged, in which case the degree of bonding of the coating in certain areas will be large. In other areas, resulting in a non-uniform coating.

In view of this, surface treatment is usually performed to change the surface characteristics of the surface. One of the goals is to treat the surface of the glass in such a way that a consistent and uniform surface is obtained with the adsorbed water removed. Conventional methods for achieving this project are, for example, acid bath, wax encapsulation, flame treatment, and plasma and corona pretreatment. Another conventional method of removing adsorbed water from a glass substrate is, for example, heating the glass to a temperature of about 250 ° C in a vacuum or alternatively heating to a temperature of 300 to 400 ° C in air.

Numerous related solutions have been disclosed in the prior art: for example, GB 816 479 describes a method and apparatus for treating a glass surface that applies a high frequency, high voltage spark discharge between the two electrodes, thereby transmitting a strong Local heating to rapidly evaporate the adsorbed water vapor to achieve the effect of dehydrogenating the surface.

GB 2 428 427 B describes the activation of the surface of a glass disk wherein the activation is achieved by rubbing with a closed strip of mold particles and the glass plate is pressed against the disk with a robotic arm. Therefore, the surface here is mechanically regenerated by friction.

DD 236 516 A1 also discloses a method of making a transparent, electrically conductive metal oxide layer on a tantalum substrate, wherein the surface of the substrate is treated using flame spray cleaning and flame spray coating. Wherein under normal ambient pressure, the substrate is first treated with a flame spray at a temperature of 800 to 1500 ° C. The flame jet is composed of oxygen-enriched gas to oxidize the metal oxide or metal used for upgrading. The mixture of materials or the metal or metal alloy on which the oxide is based is sputtered and sprayed onto a substrate at a temperature in the range of 300 to 800 ° C and taken in the next flame spray Adjust the transparency and conductivity with a reduced gas composition.

EP 1 148 036 B1 also relates to a method for surface modification of compact substrates, in particular glass, ceramics and/or porcelain, and to substances obtained by this method. The surface is surface modified with at least one oxidizing flame, and the second step is to modify the surface produced by the foregoing method with at least one deuterated flame, and at least one printing ink is plated to the surface.

WO 2006/66507 A1 discloses the coating of a polymer layer having a thickness of from 1 μm to 200 μm to a glass film having a thickness of from 10 μm to 500 μm. In WO 2000/66507 A1, the polymer layer is always plated in the liquid phase. The method of plating a glass film to a thin glass by lamination described in the prior art is considered to be a disadvantage in WO 2000/66507 A1, in particular in terms of optical properties. The surface treatment described in WO 2000/66507 A1 is limited to UV-irradiation in an ozone environment. The glass temperature required for coating is provided in a tempering module. This case does not describe the use of the tempering unit to change the surface characteristics.

EP 1 148 036 A1 describes a method for surface modification of a compact substrate, which may also be glass. In this case, the surface was modified with an oxidizing flame and a deuterated flame. By this treatment, a uniform, micro-conformal surface can be plated to the glass layer. This case does not describe the implementation of plating by lamination.

DE 10 2009 051 397 A1 describes a method of pretreating the glass surface of a photovoltaic module. The surface of the glass disk described in DE 10 2009 051 397 A1 is cleaned by flame treatment and the wettability of the glass disk is increased. The ignited glass mixture has a flame temperature of from 700 ° C to 1000 ° C. DE 10 2009 051 397 A1 does not mention the use of thin glass substrates or ultra-thin glass substrates.

DE 42 37 921 A1 describes the use of a surface for a bismuth glass substrate Method and device for qualitative modification. For this purpose, DE 42 37 921 A1 proposes flame cracking. The bismuth glass substrate includes a float glass substrate having a thickness of 3 mm. A coating is plated onto the surface of the float glass substrate by flame cracking.

A disadvantage of the above prior art is that the above method is difficult to apply to thin glass or ultra-thin glass. Such a glass is originally extremely thin, and the mechanical friction method causes a large load on the surface, which is liable to cause glass breakage, and thus is not applicable. In addition, thin glass can deform, such as wrinkle, when the temperature is too high, causing the thin glass to bend or bulge. When the temperature is too high, it may cause the glass to melt and the glass surface to shrink; this is similar to the shrinkage of the plastic film. In view of this, thin glass or ultra-thin glass is much more sensitive than thick glass, making it difficult to remove harmful surface layers. Thin glass and ultra-thin glass are used in a wide range of applications, especially where chemical and physical properties such as transparency, chemical and heat resistance, and light weight are important. For example, thin glass and ultra-thin glass are widely used in electronics, such as in sensors.

Therefore, the conventional methods of the prior art are unable to uniformly and reproducibly reduce the gel layer composed of adsorbed water and completely remove it from the thin glass or ultra-thin glass.

It is also difficult to remove organic impurities.

In view of this, there is a need in the prior art to provide a method of treating the surface of a thin glass.

It is an object of the present invention to obviate the disadvantages of the prior art and to provide a method of treating the surface of a glass, which is particularly applicable to thin glass and ultra-thin glass. The method can be implemented simply and inexpensively, which maximizes the removal of the adsorbent layer composed of water molecules in a uniform and repeatable manner.

The solution to achieve the above object of the present invention is a method for treating the surface of a thin glass substrate or an ultra-thin glass substrate, comprising the steps of: - surface treatment of the glass substrate by flame treatment with at least one oxidizing flame Processing, wherein the glass substrate and/or the at least one oxidizing flame are moved through each other at a speed such that the temperature T in the glass substrate during the flame treatment is: T < Tg, wherein Tg The glass transition temperature of the glass, and - a film is laminated to the surface of the glass substrate.

Therefore, after the method of the present invention is employed, the gel layer composed of the adsorbed water can be reliably removed by flame treatment even on a thin glass or an ultra-thin glass, and a uniform glass surface can be obtained. Subsequent lamination operations have excellent adhesion characteristics.

The method of the present invention is carried out under normal pressure in an exposure system, and it is not necessary to use expensive chemicals and solvents, wherein the pretreatment of the glass surface also cleans and activates the substrate and improves the adhesion on the glass substrate.

The process of the invention can be combined directly with glass production. However, this method is usually not required because the gel layer composed of adsorbed water molecules is not substantially formed on the surface of the newly produced glass immediately after the glass is formed. Therefore, it is advantageous to apply the method of the present invention to a thin glass surface that is not just finished. For example, a thin glass substrate that has been stored for a certain period of time can be treated so that the aged surface of the thin glass is reactivated and cleaned as if it were just made, and has the desired chemical and physical properties, ie, similar to the new system. Into the glass surface. In particular, organic impurities can also be removed.

The thin or ultra-thin glass or glass substrate in the present invention refers to the thickness 2mm, preferably 1.2mm, especially good 1.0mm, better than less 500μm, especially 400μm, best 300 μm glass or glass substrate. Ultra-thin glass, for example, thickness 300 μm, especially 200μm, better 100μm, best 50 μm glass.

According to the method of the present invention, at least one oxidizing flame is first applied to the surface of the thin glass substrate or the ultra-thin glass substrate. Oxidized flame in the present invention means any ignited gas, gas/air mixture, gas gel or spray containing excess oxygen and/or oxidizing. The strong oxidizing environment obtained by the oxygen excess of the gas in the flame spray range reduces the moisture in the form of a combination of water molecules and preferably removes it substantially completely, thereby obtaining the desired advantageous properties. In addition, organic impurities are removed.

The present invention can employ a common gas to generate a flame, and particularly preferably uses, for example, propane gas, butane gas, illuminating gas, and/or natural gas. In order to provide a strong oxidizing environment, it is advantageous to have a corresponding gas excess or excess oxygen, and the ratio of gas:air or gas:oxygen is, for example, 1:10 to 1:30, preferably 1:15 to 1:30. More preferably from 1:20 to 1:30.

The reason for choosing such an excessive proportion of air content or oxygen content is that the energy input per unit time is small in this case, and the energy input is not too large for the thin glass, but is still sufficient to remove the adsorbed water molecules. The constituent layers and/or in particular the organic impurities comprising OH groups.

In addition to the gas/air or oxygen mixture, a cerium-containing material may be introduced into the oxidizing flame and plated to the surface in such a manner that the cerium-containing material undergoes flame cracking decomposition. It is especially preferable to use decane as a cerium-containing substance. A preferred ruthenium containing compound is, for example, tetramethoxy decane. An SiO _x coating is formed on the surface of the glass substrate by flame cracking of the cerium-containing compound. Adding bismuth-containing substances does not have a negative impact on energy input.

In the method of the invention, the energy input needs to be taken into account in relation to the speed of movement. In the case of thin glass and ultra-thin glass, in order to clean and activate the thin glass surface during the flame treatment with at least one oxidizing flame, the best effect is achieved in removing the adsorbed water molecules, especially the glass. The substrate passes through the flame The speed, or the speed at which the flame passes through the glass substrate, or the speed of the glass substrate and flame, is adjusted or adjusted. According to a preferred embodiment, the moving speed is selected in such a manner that the temperature T generated by the flame treatment in the glass substrate is: T < Tg, particularly preferably T < Tg, where Tg is the glass transition temperature of the glass.

The speed at which the oxidizing flame and/or the glass substrate are moved through each other, that is, the moving speed for performing the flame treatment, is controlled in such a manner that the temperature T in the glass and the glass transition temperature of the glass substrate Tg maintains a sufficient gap.

After the surface treatment is finished, the surface is strongly hydrophilic and the surface is easily wetted by water. After the surface treatment of the present invention, the contact angle after the flame treatment is less than 10, preferably less than 8, especially less than 5, and most preferably less than 3. Thus, a film can be plated to the thin glass by lamination. This flame treatment achieves better film adhesion on thin glass. Preferably, the lamination is carried out within a certain period of time after the flame treatment is completed, during which the contact angle does not exceed 10°, preferably does not exceed 8°, particularly does not exceed 5°, and preferably does not exceed 3°. As indicated by the tests in Table 5, the period of time is less than 2 hours, preferably less than 1 hour, especially less than 20 minutes, preferably less than 5 minutes. Of course, this time period is related to environmental factors, especially related to air composition and temperature.

The invention measures the contact angle on a stationary droplet by means of a goniometer. The contact angle is taken from a still droplet by a camera.

The impurities on the surface, in particular organic impurities, are also removed by the flame treatment. The size of the contact angle determines how much organic impurities are removed from the surface by flame treatment.

According to another preferred embodiment of the invention, the upper cooling temperature is used in place of the Tg. Therefore, the moving speed for _{performing the} flame treatment is controlled in such a manner that the temperature T in the glass is sufficiently different from the upper cooling temperature T _{kühl of} the glass substrate. The cooling temperature T _kühl (annealing temperature) above the glass substrate refers to the temperature at which the glass has a viscosity of 10 ¹³ dPas.

Since the thickness of the thin glass substrate is small, the surface temperature of the glass substrate can be regarded as substantially equal to the internal temperature of the glass. Thus, the temperature T can be measured on the surface of the glass substrate. The temperature T on the surface of the glass during the flame treatment is usually 300 to 650 °C.

The temperature T in the glass substrate is sufficiently different from the glass transition temperature Tg, which is preferably the case where the two temperatures differ by about 10 to 50 ° C, preferably about 50 to 100 ° C, and more preferably about 100 to 200 ° C. , preferably about 200 to 350 ° C. If the difference from the glass transition temperature Tg is not followed, the energy input to the glass may be too large, and the thin glass may be deformed or bent.

According to another specific example, a sufficient difference between the temperature T in the glass substrate and the upper cooling temperature T _kühl of the glass substrate is set in such a manner that T<T _{kühl is achieved} , wherein preferably, the two temperatures differ by about 10 to 50 ° C, preferably about 50 to 100 ° C, more preferably about 100 to 200 ° C, most preferably about 200 to 350 ° C. If T _{kühl is selected} instead of Tg, it is advantageous to use T<T _kühl to prevent excessive energy of the input glass and deformation, bending or even breakage of the thin glass.

According to a preferred embodiment of the invention, the glass substrates are passed through a stationary burner system having at least one oxidizing flame at a certain moving speed. The preferred moving speed is from 8 m/min to 15 m/min, wherein A moving speed of 10 m/min, in particular from 10 m/min to 15 m/min, is particularly advantageous for thin glass and ultra-thin glass. Below this preferred speed of 10 m/min, the energy input to the thin glass substrate is typically too large and therefore detrimental.

Those skilled in the art will be able to set the distance of the surface of the glass substrate of thin glass or ultra-thin glass from the at least one oxidizing flame according to the prior art. This depends primarily on the type of gas selected, the ratio of oxygen to the flame length, the glass composition, and other parameters obtained. As a rule of thumb, a distance of about 80 to 200 mm, particularly preferably about 80 to 150 mm, is preferably used. The common flame length for this flame treatment is typically from 100 to 200 mm.

According to another preferred embodiment, the glass may additionally be cooled during the flame treatment to maintain the temperature inside the glass at the lowest possible level. Surprisingly, this did not cause significant stress in the glass.

The thin glass or ultra-thin glass in the present invention is not particularly limited. It is especially preferred to use calcium soda glass, borosilicate glass, aluminum bismuth glass, lithium aluminum silicate glass and glass ceramics.

Lithium aluminum niobate glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive for the oxide, such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , A rare earth oxide having a content of 0-1% by weight, and a refined preparation having a content of 0 to ₂ % by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl, F, CeO ₂ .

Calcium sodium bismuth glass (in wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ .

Preferably, borosilicate glass (in wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ .

Preferably, an alkali alumina glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ .

Preferably, an alkali-free aluminum-bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ .

Preferably, a low alkali aluminum bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ .

The surface treatment of the thin glass by the flame treatment of the present invention, in addition to removing the adsorbed water molecules, also causes activation of the glass surface, thereby making the surface highly hydrophilic. This hydrophilicity makes the surface extremely wettable by water evenly distributed thereon.

The so-called "contact angle" determines the wettability of the surface. The contact angle refers to the angle of the droplet on the surface of the solid with the surface. The size of the contact angle is related to the interaction between the contact surface of the droplet and the surface of the glass. The smaller the interaction, the larger the contact angle. Therefore, the contact angle indicates certain characteristics of the glass surface. Taking water as an example, when the contact angle is small, the surface is called hydrophilic, when the angle is about 90°, it is called hydrophobic, and when the angle is larger, it is called superhydrophobic. The method of treating a glass surface of the present invention can change the contact angle, and the method significantly reduces the contact angle in the case of using water, i.e., achieves strong hydrophilicity of the surface.

The present inventors have found that the contact angle of the glass surface remains substantially unchanged for only a few hours after the flame treatment is completed, and then increases almost sharply, but continuously. In view of this, the present invention is preferably 80±5 after the end of the processing step of performing the flame treatment. The subsequent lamination process step is carried out within minutes, preferably within 60 ± 5 minutes, and optimally within 30 ± 5 minutes.

The contact angle of the thin glass is usually about 45 to 50 before the surface treatment of the present invention. After the flame treatment was completed, a contact angle of about 5 was obtained. After about 80 minutes, the contact angle increased to about 25°. Therefore, the cerium-containing compound can be used to maintain a contact angle in the range of about 5° in about 80 minutes after the completion of the flame treatment. The present inventors have unexpectedly discovered that the same contact angle can be obtained with or without surface treatment with a cerium-containing compound.

If the time after the surface flame treatment is too long, the glass surface will be reactivated due to, for example, the accumulation of water molecules derived from ambient air, in which case the glass surface and the coating to be plated are not There is excellent adhesion.

According to another aspect of the invention, a plurality of successive processes are performed by flame treatment, that is, the first processing step is performed in multiple steps. In the case where a ruthenium-containing compound is added, a plurality of ruthenium-containing layers may be plated to the glass surface in a plurality of processes.

Pretreatment is performed using an oxidizing flame to break down water molecules on the surface of the glass substrate by a heating effect and to bond the oxygen components contained in the flame to the breaking points. The heat of the flame accelerates the process, wherein an oxygen-excess air-gas mixture or an oxygen-gas mixture is supplied during the combustion process to oxidize the surface. Thereby a number of polar units are produced in the otherwise non-polar glass material which can be used to carry out the preferred combination, such as the subsequent lamination process.

There is no particular limitation on the lamination in the present invention. In the present invention, a film composed of a polymer material or a metal is preferably plated to the surface of the glass by an adhesive.

The polymeric material is preferably selected from the group consisting of oxime polymers, sol-gel polymers, polycarbonate (PC), polyether oximes, polyacrylates, polyimine (PI), organic oxidation.矽/Polymer-mixed, cycloolefin copolymer, oxime resin, polyethylene, polypropylene polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, polymethyl methacrylate (PMMA), ethylene-acetic acid Vinyl ester copolymer, polyethylene terephthalate (PET), polybutylene terephthalate, polydecylamine, polyacetal, polyphenylene ether, polyphenylene sulfide or polyurethane or a mixture of the above.

The metal of the metal film may be selected from one or more metals, of which an alloy may also be used; for example, iron, aluminum, copper, steel, brass, and the like.

Preferably, the thickness of the laminate film is preferably 500μm, more preferably 100μm, especially good for 50μm, the best is 25 μm. The thickness of the laminate film is preferably 200% or less, more preferably 100% or less, and particularly preferably 50% or less, and even more preferably 20% in some cases. Or smaller, 10% or less on special occasions.

The polymeric material or the metal of the film may employ a construction scheme that provides a very high water vapor transmission rate (WVTR) relative to conventional polymeric materials. The laminated film can additionally provide some of the functions that the glass does not have, such as adhesive properties, color filter functions, or polarization functions.

According to a specific example, the film may be removed again after the lamination is completed, and therefore, the film is only temporarily applied as a protective film on the glass surface of the thin glass substrate. After the film is removed, the thin glass can be further processed, such as by coating.

According to a specific example, another layer having a small bonding force may be provided between the glass and the film. The other layer having a smaller bonding force is in the film or the glass There is a small bonding force between the glass substrates, which is advantageous for separating the film or the glass substrate.

According to another specific example, both sides of the thin glass substrate are pretreated by flame treatment and laminated by a film to form a film-glass-film triple structure, which has particularly good thermal properties.

The lamination process involves the direct lamination of a polymeric film or metal film to the glass substrate with or without an adhesive. Another method of laminating a polymer coated film includes plating a liquid onto the glass substrate to first form a polymer precursor and curing the polymer precursor by an ultraviolet or thermal process. The polymer precursor can be plated, for example, by dip coating, inkjet coating, casting, screen printing, painting or sputtering onto the thin glass.

The adhesive method includes direct lamination, pressing and heating, static electric bonding, laser sealing or sealing, or bonding with an adhesive such as polyfluorene, resin, super glue, epoxy glue. , UV curable adhesives, thermoplastic materials, melt adhesives, OCR, OCA, PSA, latex, and the like.

According to the invention, the laminate of the resulting laminate has an adjustable transmission of from 0 to 90%.

The laminates produced by the present invention are versatile and can be plated, for example, to the surface of other objects. For example, it can be applied to electronic devices (such as touch sensors, tablets, laptops, televisions, thin film batteries, displays, solar cells, mobile phones, cameras, game consoles, mirrors, windows, aircraft windows, furniture). ) and the field of household appliances.

The method of the invention is equally suitable for a continuous process scheme.

The advantages of the invention are that it is extremely diverse: The method of the present invention is suitable for reliably and reproducibly removing the adsorbed aqueous layer on thin glass or ultra-thin glass without causing deformation or bending of the glass.

Therefore, the pretreatment method of the present invention can be easily carried out under normal pressure in an exposure system without requiring a large amount of materials and costs, and a large-area treatment can also be carried out by a continuous process scheme. No need to use expensive special chemicals and solvents, no organic solvent vapors and harmful decomposition products.

The method of the present invention also cleans and activates the substrate while removing the water molecule layer. The invention also activates the aged surface of the thin glass such that it is as fresh as the finished glass surface.

In the flame treatment process, the present invention follows T < Tg for the temperature T in the glass substrate, wherein Tg is the glass transition temperature of the glass, thereby reducing the energy input during the flame treatment. Preferably, the temperature T in the glass substrate is selected in some manner and adjusted to be different from the glass transition temperature Tg by about 10 to 50 ° C, preferably about 50 to 100 ° C, more preferably about 100. Up to 200 ° C, preferably about 200 to 350 ° C. According to a preferred embodiment, the upper cooling temperature _Tkühl can also be used instead of the glass transition temperature Tg.

In order to keep the energy input at as low a level as possible, for example an excessive oxygen content ratio can be achieved in the gas/air or oxygen mixture. Another solution for reducing the energy input is to adjust the moving speed of the surface of the glass substrate through the flame treatment device and/or the moving speed of the flame treatment device through the surface of the glass substrate. This moving speed is especially good for 10m/min.

In addition to the gas/air or oxygen mixture, a cerium-containing material that does not adversely affect the energy input can be introduced into the oxidizing flame and plated to the surface.

After using the method of the invention, even on thin glass substrates and ultra-thin glass The contact angle can also be reduced from about 45 to 50 degrees on the substrate to about 5 degrees. If the lamination of the present invention is carried out in about 80 minutes, the laminate film can be plated to the glass surface with excellent adhesion.

The present invention may also perform the first processing step of the flame treatment in multiple steps. In the case where a ruthenium-containing compound has been added, a plurality of ruthenium-containing layers which do not adversely affect the energy input and the obtained contact angle can be plated to the glass surface.

The laminate film composed of a polymer material or a metal may be laminated in any manner. This gives the glass substrate more beneficial properties and functions.

The film can also be removed again in the future, so it is only temporarily plated.

The method of the present invention provides a repeatable uniform surface with excellent adhesion characteristics, in which case film plating by subsequent lamination can produce an excellent bonding effect on the glass surface. This can improve the durability of the plated film and improve the overall quality.

The invention also relates to glass products obtained by the process of the invention.

The invention also relates to a thin glass substrate obtained as an intermediate product of the present invention using at least one oxidized flame after flame treatment, wherein the contact angle is within about 80 ± 5 minutes within the range of the measurement tolerance It remains stable inside. Wherein the contact angle is substantially maintained at this value and varies only within a range of measurement accuracy of about ±5°.

10‧‧‧Flame treatment unit

15‧‧‧ nozzle

18‧‧‧Combustion mixture

20‧‧‧Thin glass substrate, glass substrate

1 is a schematic view of a flame treatment apparatus and a thin glass substrate of the present invention; and FIG. 2 is a diagram showing the relationship between a contact angle (unit: °) and a storage time (in hours) for a plurality of samples.

The invention is described in detail below with reference to the drawings, which are not to be construed as limiting.

1 is a first step of the method of the present invention for flame treating a surface of a thin glass substrate or an ultra-thin glass substrate, wherein at least one oxidizing flame is shown in the flame treatment device 10, and a thin glass substrate 20 is passed through the flame treatment device. . The flame treatment device 10 is supplied with gas/air or gas/oxygen via an unillustrated conduit and optionally a ruthenium containing compound. The gas includes, for example, propane gas, butane gas, illuminating gas, and/or natural gas. Gas, air and oxygen, and optionally ruthenium containing compounds, in the form of a combustion mixture 18 are applied to the surface of the thin glass substrate 20 through the nozzles 15. The gas/air or oxygen mixture has a ratio of excess oxygen so that the mixture acts as an oxidation. In the present example, the thin glass substrate 20 is passed under the flame treatment device in the direction indicated by the arrow. Of course, the flame treatment device 10 can also be moved above and/or below the glass substrate 20 using a movable solution. The surface of the thin glass substrate 20 can pass under the flame treatment device 10, for example, at a speed of from 10 m/min to about 15 m/min.

A preferred ruthenium containing compound is, for example, tetramethoxy decane. An SiO _x coating is formed on the surface of the glass substrate 20 by flame cracking of the cerium-containing compound. Wherein, the moving speed of the glass substrate is selected in such a manner that the temperature T of the glass substrate is lower than the glass transition temperature Tg or alternatively lower than the upper cooling temperature _Tkühl , preferably about 50 to 100 ° C, preferably about 100 to 200 ° C, particularly preferably about 200 to 350 ° C, lower than the glass transition temperature of the glass substrate or T _kühl .

After the flame treatment step, the glass substrate 20 is laminated (not shown) with a film preferably selected from a polymer material or a metal. The next processing step is performed within 80 ± 5 minutes after the end of the first processing step of performing the flame treatment, so that The surface is subjected to good characteristics obtained by the surface treatment method.

Figure 2 is illustrated based on these examples.

The invention is described in detail below with reference to a number of embodiments that do not limit the invention.

Example:

The glass substrate is stored in a carriage and passed under a stationary burner system having a plurality of oxidizing flames. The glass substrates have the following dimensions: glass sample: 100 x 100 mm

Thickness: 70μm

The flame treatment step is carried out with the following parameters:

Gas type: propane

Gas volume: propane 20L/min + air: 400L/min (1:20 ratio)

Movement speed: 10m/min

Glass-flame tube distance: 100mm

Flame length: 150mm

Cycle: 1 to 4, depending on the example

The contact angles of the glass substrates were then determined. The contact angle measurement is performed by measuring the contact angle with different liquids. Deionized water, toluene and ethanol were used in this example. The size of the contact angle determines how much organic impurities are removed from the surface.

Generally, samples of any size can be used, but the sample must at least have a size sufficient to accommodate the droplets without causing them to collide with the edges of the sample.

Clean the surface of the sample with ethanol before measuring. Then position the sample, Drip the measurement solution and measure the contact angle.

When performing contact angle measurement, optical measurement is performed by a video system combined with image evaluation by drawing an angle on the target photo and performing calculation. Contact angle measurements were performed on static droplets by a goniometer. The measurement results when measuring the contact angle can be ±5°, depending on the surface quality (cleanness and consistency of the surface).

The contact angles of these samples measured before surface treatment are as follows:

According to the method of the present invention, the contact angle of the sample measured after the surface treatment of the flame treatment is as follows:

As mentioned before, only the movement speed is changed. After surface treatment in the form of flame treatment, which is not the method of the present invention, the following sample contact angles are obtained:

The results in Table 3 indicate that the thermal energy in the flame treatment step is too large for the thin glass substrate to bend or even break. The condition of T < Tg or T < T _kühl is not followed. The moving speed is too low, ie <10 m/min, so that the temperature T in the glass is too high and the glass is damaged or destroyed.

Samples 2.2 and 2.7 in Table 2 were covered with paper and their contact angles were measured after a storage time of 80 minutes and 90 minutes of air. The results are as follows:

The results show that the critical period between the flame treatment and subsequent lamination is about 80 minutes in order to plate a laminate film over this time range, which facilitates the good properties of the cleaned and activated glass surface. use. The contact angle unexpectedly remained substantially unchanged during the period of 80 ± 5 minutes. After 90 minutes, the above characteristics were significantly deteriorated, and the contact angle sharply increased. Even if paper is used to cover the thin glass surface, its excellent properties quickly disappear.

More samples were tested after the flame treatment step was completed to determine the change in contact angle after using different temporary storage measures. Samples 1 and 2 were stored under air, and Sample 3 was covered with paper. Three glass substrates were selected for each sample. The measurements were taken twice on about 5 droplets and averaged. The sample size was 125 x 125 mm and the thickness was 70 μm. The droplet size was 5 μl. The measurement tolerance is approximately ±5°.

The measured results obtained for the contact angle are as follows:

Figure 2 shows the results in Table 5 in graphical form. Figure 2 shows the relationship between the contact angle (in °) and the storage time (in hours). The contact angle continuously increases with time without considering temporary storage. Linear compensation curves were plotted for all three samples tested, indicating a continuous increase in contact angle.

The contact angle determines the suitability of the thin glass surface for the coating, particularly for plating by lamination. Test accidents have shown that excellent adhesion can be achieved when the contact angle of the surface is less than 10°, in particular less than 8°, preferably less than 5°, and even more preferably less than 3°. In this case, the surface is sufficiently cleaned by flame treatment and the adsorbed water molecules and/or organic impurities are removed.

10‧‧‧Flame treatment unit

15‧‧‧ nozzle

18‧‧‧Combustion mixture

20‧‧‧Thin glass substrate, glass substrate

Claims (17)

A method of treating a surface of a thin glass substrate or an ultra-thin glass substrate, comprising the steps of: treating a surface of the glass substrate by flame treatment with at least one oxidizing flame, wherein the glass substrate is made at a certain speed And/or the at least one oxidizing flame is moved through each other such that during the flame treatment, the temperature T in the glass substrate is: T < Tg, wherein Tg is the glass transition temperature of the glass, and the surface After the treatment, the contact angle is less than 10, preferably less than 8, especially less than 5, and most preferably less than 3, and a film is laminated to the surface of the glass substrate treated by flame treatment. The method of claim 1, wherein the thickness is 2mm, preferably 1.2mm, especially good 1.0mm, better than less 500μm, especially 400μm, best 300 μm glass substrate. The method of claim 1 or 2, wherein the temperature T in the glass substrate differs from the glass transition temperature Tg by about 10 to 50 ° C, preferably about 50 to 100 ° C, more preferably about 100 to 200 ° C, The optimum is about 200 to 350 °C. A method according to any one of the preceding claims, wherein the glass transition temperature Tg is replaced by an upper cooling temperature _Tkühl , wherein: T < T _kühl and the two temperatures differ by about 10 to 50 ° C, preferably about 50 to 100 ° C, more preferably about 100 to 200 ° C, most preferably about 200 to 350 ° C. a method as claimed in any one of the preceding claims, Wherein, the gas for the at least one oxidizing flame is selected from the group consisting of propane gas, butane gas, lighting gas and/or natural gas, wherein preferably, the gas: oxygen or gas: air ratio is 1:10 to 1 : 30, preferably from 1:15 to 1:30, more preferably from 1:20 to 1:30. A method according to any one of the preceding claims, wherein a ruthenium-containing compound, preferably decane, is added to the oxidizing flame. The method of any one of the preceding claims, wherein the moving speed of the oxidizing flame and/or the glass substrate moving in a manner to each other is 10 m/min, particularly preferably from 10 m/min to 15 m/min. The method of any one of the preceding claims, wherein the laminating treatment is carried out within 80 ± 5 minutes, preferably within 60 ± 5 minutes, and preferably within 30 ± 5 minutes after the end of the processing step of the flame treatment. step. A method according to any one of the preceding claims, wherein calcium soda glass, borosilicate glass, aluminum bismuth glass, lithium aluminum silicate glass or glass ceramic is used as the thin glass substrate or the ultra-thin glass substrate, preferably, A lithium aluminum niobate glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0-1% by weight, and a refined preparation having a content of 0 to ₂ % by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl, F, CeO ₂ ; Glass composition or composition of calcium sodium bismuth glass (in wt%): And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ ; or a boron bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ ; or an alkaline aluminum-bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ ; or an alkali-free aluminum bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ ; or a low alkali aluminum bismuth glass (unit: wt%) having the following glass composition or consisting of: And optionally adding an additive of an oxide such as Nd ₂ O ₃ , Fe ₂ O ₃ , CoO, NiO, V ₂ O ₅ , Nd ₂ O ₃ , MnO ₂ , TiO ₂ , CuO, CeO ₂ , Cr ₂ O ₃ , a rare earth oxide having a content of 0 to 5% by weight or a "black glass" of 0 to 15% by weight, and a refining agent having a content of 0 to 2% by weight, such as As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , SO ₃ , Cl , F, CeO ₂ . A method according to any one of the preceding claims, wherein the processing step of the flame treatment is carried out in multiple steps before lamination. The method of any one of the preceding claims, wherein the film is selected from the group consisting of a polymeric material or a metal, wherein the polymeric material is preferably selected from the group consisting of: a siloxane polymer, a sol-gel polymer, Polycarbonate (PC), polyether oxime, polyacrylate, polyimine (PI), organic cerium oxide/polymer-mixed, cycloolefin copolymer, oxime resin, polyethylene, polypropylene polyvinyl chloride, Polystyrene, styrene - Acrylonitrile copolymer, polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer, polyethylene terephthalate (PET), polybutylene terephthalate, polyamine, polycondensation An aldehyde, a polyphenylene ether, a polyphenylene sulfide or a polyurethane or a mixture thereof; and the metal of the metal film is preferably selected from one or more metals or alloys, particularly preferably selected from the group consisting of iron, aluminum, copper, steel, brass, and the like. . The method of any one of the preceding claims, wherein the thickness of the film is preferably 500μm, more preferably 100μm, especially good for 50μm, the best is 25 μm, the thickness of the film is preferably 200% or less, more preferably 100% or less, further preferably 50% or less, and particularly preferably 20% or less, most preferably the thickness of the glass. Good is 10% or less. The method of any of the preceding claims, wherein the film is temporarily plated to the thin glass substrate. The method of any one of the preceding claims, wherein the contact angle of the surface of the thin glass substrate or the ultra-thin glass substrate is within about 5° after the completion of the flame treatment step, and the measurement tolerance is Within the range, the contact angle remained stable for approximately 80 ± 5 minutes. A glass product obtained by the method of any one of claims 1 to 14. A thin glass intermediate product obtained after completion of the flame treatment step, wherein preferably the contact angle is less than 10°, especially less than 8°, particularly preferably less than 5°, and most preferably less than 3°. A thin glass intermediate product according to claim 16 wherein the contact angle is stable within about 80 ± 5 minutes within the range of measurement tolerances.