KR102192920B1 - A composition for healing glass - Google Patents

Abstract

Glass containing A) 1% to 20% by weight of hydrofluoric acid, B) 0.1% to 5% by weight of ammonium fluoride, C) 1% to 20% by weight of inorganic acid, and D) the balance of water It is about a healing composition.

Description

Composition for healing glass {A composition for healing glass}

The present invention relates to a composition for healing glass comprising the composition A) hydrofluoric acid, B) ammonium fluoride, C) inorganic acid and D) water.

Tempered glass used for a touch screen panel often causes micro cracks on the surface by laser cutting and CNC processing, which causes a decrease in the strength of the glass. Therefore, it is necessary to increase the strength of the glass by improving the elongation of the tempered glass, but research on this is insignificant.

Meanwhile, Korean Patent Application Publication No. 2012-0053191 describes a process of healing the front end of a glass substrate using a solution based on hydrofluoric acid while describing a touch screen panel and its manufacturing method. However, the above disclosed patent relates to a process for slimming the substrate for the entire front/rear surface of the organic substrate, and the problem of realizing healing properties for holes inside the glass and improving the elongation rate of the glass still remains.

Republic of Korea Patent Publication No. 2012-0053191

In order to solve the above-described problem, it is an object to provide a composition for ultimately improving the elongation of glass by reducing the stress concentration phenomenon in the crack portion of the reinforced substrate due to micro cracks.

An object of the present invention is to provide a glass with improved elongation.

In addition, an object of the present invention is to provide a method of healing glass so that the elongation is improved.

In order to achieve the above object, the present invention is based on the total weight of the composition A) hydrofluoric acid 1% to 20% by weight, B) ammonium fluoride 0.1% to 5% by weight, C) inorganic acid 1% to 20% by weight, and D) It provides a glass healing composition containing water so that the total weight of the total composition is 100% by weight.

According to an example of the present invention, the inorganic acid may be at least one selected from nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid.

According to another example of the present invention, the glass healing is to improve the elongation of the glass to be 0.8% or more.

According to another example of the present invention, the glass is a tempered glass.

According to another example of the present invention, the glass healing is to improve the elongation by forming a blunt on the glass surface and lowering the stress concentration coefficient.

In addition, the present invention provides a glass treated with the above composition and having an elongation of 0.8% or more.

The present invention provides a glass treated with the composition, forming a blunt shape on the surface, and having a blunt size of 6 to 12 μm.

According to an example of the present invention, the blunt has a circular or elliptical shape, and a value (y/x) obtained by dividing the major axis diameter y by the minor axis diameter s may be 1 to 3.

The present invention provides a glass healing method comprising the step of treating the glass to be healed for 30 seconds to 5 minutes.

The glass healing composition of the present invention concentrates stress on the crack part of the reinforced substrate due to micro cracks that occur when laser and CNC processing of a reinforced glass substrate used for a plurality of touch screens It has the effect of reducing the phenomenon and ultimately improving the elongation of the tempered glass.

1 is a side portion or hole-processed surface (left picture) after laser cutting and CNC processing of a glass to be healed by the composition of the present invention, and a surface treated with healing of the portion. Shows the shape of the Blunt (right picture).
2 is a graph showing the relationship between elongation and blunt size.
3 is a diagram showing a glass surface treated with a composition of the present invention and a composition of a comparative example, respectively.
4 is a diagram showing a shape of a blunt formed according to a healing time (Examples 1, 7, 8, and 9) and a method of measuring the circularity of the blunt shape.
5 is a graph showing the relationship between elongation and blunt size.

Hereinafter, the present invention will be described in more detail.

The present invention is a crack of a reinforced substrate due to micro cracks that occur when laser and CNC processing of a reinforced glass substrate used for a plurality of touch screens in a method of manufacturing a thin film transistor display device A glass healing composition for reducing the negative stress concentration phenomenon and ultimately improving the elongation of tempered glass, a glass healed by the composition, and a glass healing method using the composition.

The glass healing of the present invention refers to a process of improving the elongation of glass by forming a shape of a blunt on the glass surface or by adjusting the blunt size. In particular, the glass healing may be to improve the elongation of the glass to be 0.8% or more, and specifically, the glass healing may be to improve the elongation by forming a blunt on the glass surface and lowering the stress concentration coefficient. .

The glass healing composition of the present invention not only forms a blunt on the glass surface, but also allows control of the blunt size. Using the glass healing composition of the present invention, a specific size and shape on the glass surface It was experimentally confirmed that the elongation of the glass was significantly improved when the blunt was formed. In the present invention, blunt means a circle or elliptical shape generated on the glass surface by treatment with the composition of the present invention, as shown in FIG. 1.

The glass of the present invention may be a tempered glass.

The composition for glass healing of the present invention contains A) hydrofluoric acid, B) ammonium fluoride, C) inorganic acid and D) water. Specifically, the composition for healing glass of the present invention, based on the total weight of the composition A) hydrofluoric acid 1% to 20% by weight, B) ammonium fluoride 0.1% to 5% by weight, C) inorganic acid 1% to 20% by weight , And D) may include water so that the total weight of the total composition is 100% by weight.

First, A) The hydrofluoric acid is a major tempered glass etching agent, and has a strong glass dissociation ability as a material in which H cations and F anions coexist when dissociated in distilled water (DI). The hydrofluoric acid is contained in an amount of 1% to 20% by weight based on the total weight of the glass healing composition. If the content of the hydrofluoric acid is less than 1% by weight, it is difficult to form a blunt, and thus the elongation cannot be increased. If the content of hydrofluoric acid is higher than 20% by weight, it is difficult to control the degree of blunt generation because the etching rate is too fast, and accordingly, the incidence of damage to glass other than the blunt formation site increases.

B) ammonium fluoride contained in the glass healing composition of the present invention allows the shape of the blunt to be further improved while controlling the etching rate of the glass through adhesion and pH control on the glass surface. It is preferable to include from about 0.1% to about 5% by weight based on the total weight of the ammonium fluoride composition. If the amount of ammonium fluoride is less than 0.1% by weight, it is difficult to control the etching rate of the tempered glass, and thus it is difficult to perform the buffer role. When the content of the ammonium fluoride is higher than 5% by weight, the etching rate is significantly lowered, making it difficult to form a blunt within a desired healing time.

C) Inorganic acid contained in the composition for glass healing of the present invention serves to create an environment in which the rate of formation of the glass blunt can be appropriately increased or decreased by controlling the pH to be lowered. The content of the C) inorganic acid is preferably included in an amount of 1% to 20% by weight based on the total weight of the composition. If the inorganic acid is less than 1% by weight, the influence of the pH is insufficient, so that the rate of formation of the blunt of the tempered glass may be rapidly decreased. When the content of the inorganic acid exceeds 20% by weight, the etching rate of the glass increases and the rate of damage to the layer other than the healing layer increases. C) The inorganic acid may be at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid.

D) Water contained in the glass healing composition of the present invention is not particularly limited, but deionized water is preferred. More preferably, it is preferable to use deionized water having an unsteady value of water (ie, the degree of ion removal in water) of 18 MΩ/cm or more.

The etchant composition of the present invention may further include conventional additives in addition to the above-described components, and representative examples of the additives include surfactants (anionic, nonionic surfactants) and thickeners.

It is preferable that A) hydrofluoric acid B) ammonium fluoride C) inorganic acid and D) water used in the glass healing composition of the present invention have a purity for semiconductor processing, but affects the etch rate change by anionic impurities Because you can give.

The present invention includes a glass healed by the above composition, and the glass of the present invention preferably has an elongation of 0.8% or more, and even more preferably 1.0% or more. If the elongation is less than 0.8%, there is a problem that the glass strength is lowered.

In addition, the present invention includes glass healed by the composition, and the glass forms a blunt form on the surface, and may have a blunt size of 6 to 12 μm, more preferably 8 to 12 μm. have. When the blunt size is less than 6 μm, there is a problem that the glass strength is lowered, and when the blunt size is larger than 12 μm, there is a problem that the glass cross section is overetched. Even more preferably, it is a glass that satisfies both the elongation and the blunt size.

The glass healed by the composition of the present invention forms a blunt shape on the surface, and the blunt shape may be a circle or an oval shape. When the blunt shape is an asymmetrical elongated shape, the uniformity of the stress distribution is disadvantageous. When the blunt shape is a symmetrical circular shape, the stress distribution is uniform and the elongation is greatly improved. In particular, by adjusting the composition of the composition of the present invention, the shape of the blunt can be a symmetrical circle. The circularity of the blunt can be expressed as a value (y/x) obtained by dividing the major axis diameter (y) of the blunt by the minor axis diameter (s), and the glass of the present invention has the circularity (y/x) of 1 to 3 It can be. As the circularity (y/x) is closer to 1, the blunt on the glass surface shows the shape of a symmetrical circle.

The present invention includes a glass healing method comprising the step of treating the glass to be healed with the above composition. In particular, in the present invention, the relationship between the blunt size and the glass elongation was revealed by the graphs of FIGS. 2 and 5, and based on this, more effective glass healing is possible.

For example, the glass healing method of the present invention can be performed as follows: First, 1) laser cutting of glass and after CNC process (a) side or (b) hole processing Measure the size of the (c) blunt shape and diameter of the surface treated with healing of the surface (FIG. 1). 2) At this time, since the size of the diameter of the blunt, that is, the blunt size, is an important measure that influences the elongation rate, which is a measure of the degree of reinforcement of the glass, the blunt size and the elongation rate must be properly adjusted. 3) The blunt size can be adjusted based on the composition design of the glass healing composition, and optimized composition design is possible based on the correlation between the blunt and the elongation (Fig. 2) based on the elongation measurement of a substrate of 4 inches or more. . 4) In order to prevent damage to the laminated material on the glass substrate exposed by the cutting (Damage Free), a film must be attached, and the laminated material except for the exposed side and the glass end surface to be hole-healed. A composition design that can minimize erosion is required (Fig. 5). In addition, 5) If the blunt formation model does not form a circle that approximates symmetry, it may cause a decrease in the rate of loss due to an external shock (STRESS).Therefore, it is fluorinated with a sufficient healing time and a buffer solution. The addition of ammonium can secure a better blunt shape and elongation than that without the addition.

In the glass healing method of the present invention, it is preferable to treat the above composition on the healing target glass for 30 seconds to 5 minutes.

In addition, the present invention provides a touch screen panel substrate including at least one of a tempered glass slide (Glass Side) portion and a tempered glass hole (Hole) portion healed using the glass healing composition (FIG. 1). The touch screen panel substrate may be used for an array substrate for a liquid crystal display device.

In addition, it includes a method of manufacturing the touch screen panel substrate. The method of manufacturing a touch screen panel of the present invention includes an ion substitution process for forming a reinforcing layer on the upper/lower surface of the glass, a process of forming a touch screen panel for each cell unit on the upper surface of the reinforced glass substrate, and each touch screen panel is formed. Laser and CNC processes for cutting and processing a substrate for separation by cell, a process of forming a film layer on the top/bottom of the tempered glass substrate cut by each cell unit, and after the top/bottom film process of the substrate It may be to sequentially perform the steps of a healing process for enhancing the elongation of the glass by removing micro cracks from the cut surface of the glass substrate using the composition of the present invention.

Specifically, the method of manufacturing a touch screen panel of the present invention comprises the steps of forming a strengthened glass through an ion exchange process on the surface of Na ions contained in the glass into k ions; Performing a hole processing such as a speaker or a home button inside the glass and the separation plate of a desired cell unit through a laser; Processing the rough surface cut and processed with a laser into a finer surface through a CNC process; And removing micro-cracks on the surface processed by laser and CNC through the glass healing process using the composition of the present invention, forming a blunt, and increasing the blunt size.

For example, the method of manufacturing a touch screen panel substrate of the present invention can be carried out in the following steps:

a) forming a tempered glass layer above and below the glass;

b) forming a touch screen panel for each cell unit on the upper surface of the tempered glass;

c) forming a hole such as a speaker and a home button inside the glass and separation plate of a desired cell unit through a laser through the tempered glass;

d) processing the cut surface of the tempered glass cut and processed with the laser through a CNC process; And

e) removing micro-cracks on the CNC-machined surface through a healing process and forming a blunt.

In particular, step d) includes bonding an organic film to protect the top/bottom of the cell other than CNC processing on the substrate, and step e) is a step of washing with distilled water (DI) for removing inorganic substances remaining after healing. It may include.

According to the present invention, it is possible to solve the problem that the large-sized glass is separated by cells and then broken even with a small force when manufacturing the touch screen panel without healing treatment by increasing the elongation through the healing process. Through this healing effect, in particular, it is possible to strengthen the glass breaking strength of the panel for a touch screen, and ultimately improve mass production. In addition, the glass breaking strength of the touch screen panel can be strengthened without affecting the touch screen panel already formed for each cell unit on the upper surface of the strengthened glass substrate during the healing process.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example And Comparative example

According to the composition shown in Table 1 below, a glass healing composition of Examples and Comparative Examples was prepared.

HF (% by weight) AF (% by weight) Nitric acid (% by weight) water Example 1 7 0.5 7 Balance Example 2 7 0.5 6 Balance Example 3 7 0.7 7 Balance Example 4 7 0.7 6 Balance Example 5 7 One 7 Balance Example 6 7 One 20 Balance Example 7 7 0.3 7 Balance Example 8 7 0.1 7 Balance Comparative Example 1 One - - Balance Comparative Example 2 5 - - Balance Comparative Example 3 7 - - Balance Comparative Example 4 7 One - Balance Comparative Example 5 7 3 - Balance Comparative Example 6 4 - 4 Balance Comparative Example 7 7 One Less than content Balance Comparative Example 8 7 0.5 22 Balance

Experimental example 1: Blunt size of the glass by the composition of the present invention and Elongation Evaluation of improvement effect

Using the compositions of Examples 1 to 6 and Comparative Examples 1 to 7 prepared according to Table 1, the glass healing process was performed in the following manner, and the blunt size and elongation were measured.

The composition prepared above was prepared on a 10 kg basis, and was stored in a container made of PE material without fear of damage to hydrofluoric acid while maintaining a constant temperature (25°C) in the experimental equipment, and prepared reinforced substrates (Confidential) were stored in a cartridge of an appropriate size. ) In a number of times and immersed in the composition solution in a dipping method for 3 minutes, and then the healing process was completed through a predetermined cleaning process. After the healing process was completed, the tempered glass was observed with a scanning electron microscope (SEM) to measure the size of the blunt, and the elongation was measured, and is shown in Table 2. Further, the relationship between the elongation and the blunt size is shown in FIG. 2.

Blunt size (㎛) Elongation (%) Example 1 9.5 1.12 Example 2 9.3 1.01 Example 3 9.3 1.02 Example 4 9.1 1.00 Example 5 9.1 1.02 Example 6 10.5 1.10 Comparative Example 1 1.20 0.41 Comparative Example 2 1.85 0.52 Comparative Example 3 3.5 0.61 Comparative Example 4 3.4 0.58 Comparative Example 5 3.3 0.56 Comparative Example 6 2.0 0.50 Comparative Example 7 3.8 0.72 Comparative Example 8 9.6 1.11

The compositions of the present invention of Examples 1 to 6 exhibit a blunt size of 6 to 12 μm and an elongation of 0.8% or more to be implemented by the present invention. However, under the conditions of Comparative Examples 1, 2, and 3, as a result of increasing only the content of hydrofluoric acid with the composition of hydrofluoric acid and DI (distilled water), the blunt size was not formed large within the desired healing time (3 min), and the elongation accordingly was also the minimum target value. The result was less than 0.8% phosphorus (Fig. 3).

Since excessive use of hydrofluoric acid (HF) may cause environmental problems, ammonium fluoride was added to Comparative Examples 4 and 5, but the pH was raised due to the influence of the weakly basic ammonium ion, which lowered the activity of the F anion. The formation was disadvantageous.

However, although the composition of the present invention is composed of a small amount of inorganic acid (Comparative Example 7), there is a disadvantage in that it is not possible to control the Al2O3 slurry that is generated in a large amount as a result of glass etching. About this In Comparative Example 8, an attempt was made to increase the elongation significantly by maximizing the blunt size by raising the content of nitric acid to a maximum of 22% by weight, but the saturation section was not larger than expected and the elongation improvement effect due to the increase in the blunt size was insufficient (FIG. 2 ). As mentioned above, when the content of the inorganic acid is increased by 20% by weight or more, heat generation and environmental regulation problems during manufacturing and treatment costs for waste liquid may increase rapidly.

Experimental example 2: by the composition of the present invention healing Measuring the ratio of the blunt size of a glass over time

The composition prepared above was prepared on a 10 kg basis, and was stored in a container made of PE material without fear of damage to hydrofluoric acid while maintaining a constant temperature (25° C.) in the experimental equipment, and a plurality of prepared reinforced substrates were inserted into a cartridge. The composition was immersed in a dipping method for a predetermined period of time (40, 60, 180 sec), and then the healing process was completed through a predetermined cleaning process. After the healing process is completed, the tempered glass is observed with a scanning electron microscope (SEM), and the value of the y-axis (major axis diameter) of the blunt shape formed according to the healing time as shown in FIG. 4 is the value of the X axis (shortened). The circularity of the blunt was calculated by dividing by diameter), and the results are shown in Table 3 below.

Blunt Size (y/x) 40 sec 60 sec 180 sec Example 1 3 2.1 1.3 Example 7 3.2 2.2 1.4 Example 8 3.5 2.4 1.6

It was confirmed that the value of y/x became close to 1 according to the healing time, the addition of ammonium fluoride, and the increase in the content. That is, it was confirmed through the evaluation of Examples 1, 7, and 8 that the blunt shape changes from asymmetric to a symmetric circle shape.

Experimental example 3: by the composition of the present invention healing Of glass over time Elongation evaluation

The composition prepared above was prepared on a 10 kg basis and was stored in a container made of PE material without fear of damage to hydrofluoric acid while maintaining a constant temperature (25°C) in the experimental equipment, and prepared reinforced substrates (Confidential) were stored in a cartridge of an appropriate size (Cassette). ) In a number of times and immersed in the composition solution in a dipping method for a certain period of time (40, 60, 180 sec), and then the healing process was completed through a predetermined cleaning process. After the healing process was completed, the tempered glass was observed with a scanning electron microscope (SEM), and the elongation was measured (180 sec) and shown in Table 4, and the blunt size and elongation change according to the healing time were also shown. It is shown in 5.

Elongation (%) Example 1 1.12 Example 7 1.04 Example 8 1.01

Claims (9)

A) 1% to 20% by weight of hydrofluoric acid, B) 0.1% to 5% by weight of ammonium fluoride, C) 1% to 20% by weight of nitric acid and D) the balance of water,
Glass healing composition, characterized in that to improve the elongation of the glass to be 0.8% or more when healing the glass surface.
delete delete The composition for healing glass according to claim 1, wherein the glass is a tempered glass.
The composition for healing glass according to claim 1, wherein the glass healing improves elongation by forming a blunt on the glass surface and lowering the stress concentration coefficient.
Glass treated by the composition of claim 1, wherein the glass has an elongation of 0.8% or more.
A glass treated with the composition of claim 1, which has a blunt shape on its surface and has a blunt size of 6 to 12 μm.
The glass according to claim 7, wherein the blunt has a circular or elliptical shape in which a major axis diameter (y) divided by a minor axis diameter (s) (y/x) is 1 to 3.
A glass healing method comprising the step of treating the glass to be healed for 30 seconds to 5 minutes with the composition of claim 1.

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