TW201544577A - Composition and method for healing glass, and glass treated with the composition - Google Patents

Abstract

Disclosed is a composition for healing glass, including: based on the total weight of the composition, (A) 1 ~ 20 wt% of hydrofluoric acid, (B) 0.1 ~ 5 wt% of ammonium fluoride, (C) 1 ~ 20 wt% of an inorganic acid, and (D) a remainder of water.

Description

Composition and method for repairing glass and glass treated by the composition

The present invention relates to a composition for repairing glass comprising: A) hydrofluoric acid, B) ammonium fluoride, C) mineral acid, and D) water.

The tempered glass for a touch panel frequently causes microcracks on its surface due to laser cutting and CNC processing, undesirably deteriorating the strength of the glass. Therefore, it is necessary to increase the elongation of the tempered glass to enhance the strength of the glass, but the research on this is still insignificant.

Korean Patent Application Publication No. 2012-0053191 discloses a touch panel and a method of manufacturing the same, including a repairing step of cutting a section of a glass substrate using a hydrofluoric acid-based solution. However, since this patent has a step of making the front and back sides of the glass substrate elongated, there is still a problem in that the glass inner hole is repaired or the glass elongation is low.

(previous technical literature) (Patent Literature)

Patent Document 1: Korean Patent Publication No. 10-2010-0109437

Therefore, in view of the above problems encountered in the related art, the present invention has been made. It is an object of the present invention to provide a composition which can reduce the stress concentration phenomenon existing on the crack portion of the reinforcing substrate due to microcracks, and ultimately increase the elongation of the glass.

Another object of the present invention is to provide a glass having improved elongation.

It is yet another object of the present invention to provide a method for repairing glass to increase its elongation.

In order to achieve the above object, the present invention provides a composition for repairing glass comprising: A) 1 to 20% by weight of hydrofluoric acid, B) 0.1 to 5% by weight of ammonium fluoride, relative to the total weight of the composition, C) 1 to 20% by weight of the mineral acid, and D) the balance of water such that the total weight of the composition is 100% by weight.

In an embodiment of the invention, the aforementioned inorganic acid may include at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid.

In another embodiment of the invention, the aforementioned glass can be repaired such that its elongation is increased to 0.8% or more.

In still another embodiment of the present invention, the glass may be tempered glass.

In still another embodiment of the present invention, the aforementioned glass may be repaired in such a manner that a blunt portion is formed on the surface of the glass and the stress concentration factor is decreased to increase the elongation.

Further, the present invention provides a glass which has been treated with the above composition and has an elongation of 0.8% or more.

Further, the present invention provides a glass which has been treated with the above composition and has a passivation portion having a blunt size of 6 to 12 μm on its surface.

In the embodiment of the present invention, the passivation portion may be a circular or elliptical shape having a value (y/x) of 1 to 3 obtained by dividing the major axis diameter (y) by the minor axis diameter (x).

Further, the present invention provides a method for repairing glass comprising treating the aforementioned glass with the above composition for 30 seconds to 5 minutes.

According to the present invention, the composition for repairing glass can reduce the stress concentration phenomenon on the crack portion of the tempered glass substrate for a touch panel due to microcracks during laser processing and CNC processing, thereby increasing the elongation of the tempered glass. rate.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

Figure 1 shows the side portion or processed hole portion of the glass after laser cutting and CNC machining (left image), and the surface passivation portion formed by repairing the corresponding portion using the composition according to the present invention (right image); The point is: point 1, 2, 3 or 4 is the hole straight line and the R repair portion; and point 5, 6 or 7 is the small unit straight line and the R repair portion.

Figure 2 is a graph showing the relationship between elongation and passivation size.

Figure 3 shows the surface of a glass treated with the composition of the present invention and the comparative composition.

Figure 4 shows the passivation shape (Examples 1, 7, 8, and 9) depending on the repair time and the roundness measurement of the passivated shape.

Figure 5 is a graph showing the relationship between time, elongation and passivation size.

The invention will be described in detail below.

The present invention provides a composition for repairing glass which can reduce stress concentration existing on a cracked portion of a tempered glass substrate, and finally increase elongation of the tempered glass, wherein the cracked portion of the tempered glass substrate is manufactured A thin film transistor display is produced by laser and CNC machining microcracks generated by a tempered glass substrate for a touch panel; a glass repaired by the composition; and a method of repairing the glass using the composition.

In the present invention, glass repair refers to the step of forming a passivation on the surface of the glass or adjusting the passivation size to increase the elongation of the glass. Specifically, glass repair is performed to increase the glass elongation to 0.8% or more. Specifically, the glass repair is performed in such a manner that a passivation portion is formed on the surface of the glass and the stress concentration factor is lowered to increase the elongation.

The composition for repairing glass according to the present invention enables the formation of a passivation on the surface of the glass and is also capable of adjusting the passivation size. As experimentally confirmed, when a composition for repairing glass according to the present invention is used to form a passivation portion of a specific size and shape on a glass surface, the elongation of the glass is remarkably increased. In the present invention, as shown in Fig. 1, a passivation portion in the form of a circle or an ellipse is provided on the surface of the glass with the composition of the present invention.

In the present invention, the glass may be tempered glass.

Compositions for repairing glass include: A) hydrofluoric acid, B) ammonium fluoride, C) mineral acid, and D) water. Specifically, the composition for repairing the glass may include: A) 1 to 20 wt% of hydrofluorol relative to the total weight of the composition. The acid, B) 0.1 to 5 wt% of ammonium fluoride, C) 1 to 20 wt% of the mineral acid, and D) the balance of water such that the total weight of the composition is 100 wt%.

In the composition of the present invention, A) hydrofluoric acid is used as a main etchant for tempered glass and has a strong ability to decompose glass because it is a coexistence of H cation and F anion when dissociated in deionized water (DI). material. The hydrofluoric acid is contained in an amount of 1 to 20% by weight based on the total weight of the composition. If the amount of hydrofluoric acid is less than 1% by weight, it is difficult to form a passivation portion, and elongation cannot be increased. On the contrary, if the amount of hydrofluoric acid is more than 20% by weight, the etching rate is excessively increased, thereby making it difficult to control the degree of generation of the passivation portion, and finally increasing the damage to the glass region outside the region where the passivation portion is formed.

In the compositions of the present invention, B) the function of ammonium fluoride is to control the etch rate of the glass and to improve the passivation shape by adhering to the glass surface and pH adjustment. The ammonium fluoride is preferably contained in an amount of about 0.1 to 5% by weight based on the total weight of the 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 it is difficult to exhibit a buffering function. On the contrary, if the amount of ammonium fluoride is more than 5% by weight, the etching rate is remarkably lowered, and it is difficult to form a passivation portion in a desired repair time.

In the compositions of the present invention, the function of the C) mineral acid is to lower the pH to enable the environment to appropriately increase or decrease the rate at which the passivation is formed on the glass. Thus, it is preferred to include C) a mineral acid in an amount of from 1 to 20% by weight based on the total weight of the composition. If the amount of the inorganic acid is less than 1% by weight, the rate at which the passivation portion is formed on the tempered glass is drastically lowered due to the weak pH effect. On the contrary, if the amount of the inorganic acid exceeds 20% by weight, the etching rate of the glass and the rate of damage to the layer other than the repair layer increase. In addition, C) inorganic acid can At least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid is included.

In the composition of the present invention, D) water is not particularly limited, but is preferably DI water. More preferably, DI water having a resistivity (i.e., a degree of ion removal from water) of 18 M?/cm or more is used.

According to the present invention, in addition to the above composition, the etching liquid composition may further include a typical additive, and examples of the additive may include a surfactant (anionic surfactant or nonionic surfactant) and a thickener.

A) hydrofluoric acid, B) ammonium fluoride, C) mineral acid and D) water used in the composition for repairing glass according to the present invention are preferably of a purity suitable for semiconductor processing because the etching rate may be It changes due to anionic impurities.

The present invention provides a glass which is repaired by the above composition, which glass preferably has an elongation of 0.8% or more, and more preferably has an elongation of 1.0% or more. If the elongation is less than 0.8%, the strength of the glass may be lowered.

Further, the present invention provides a glass repaired by the above composition, which is configured to form a passivation portion having a passivation size of 6 to 12 μm, and preferably 8 to 12 μm, on the surface of the glass. If the passivation size is less than 6 μm, the glass strength may be lowered. On the contrary, if the passivation size exceeds 12 μm, the cross section of the glass may be excessively etched. More preferred is a glass that simultaneously meets the requirements for elongation and passivation size.

The glass repaired by the composition of the present invention is configured to form a passivation on the surface of the glass, and the passivation portion may be circular or elliptical. When the passivation is In the case of an asymmetric ellipse, the uniformity of stress distribution may be reduced. On the other hand, when the passivation portion is a symmetrical circle, the stress distribution can become uniform, thereby significantly increasing the elongation. In particular, a symmetrical circular passivation can be provided by adjusting the composition of the composition. The circularity of the passivation portion is defined as the value (y/x) obtained by dividing the major axis diameter (y) of the passivation shape by its minor axis diameter (x). In the present invention, the roundness (y/x) of the glass may be 1 to 3. When the roundness (y/x) is close to 1, the passivation of the glass surface is provided in a symmetrical circular shape.

The present invention provides a method for repairing glass comprising treating the glass with the above composition. The relationship between passivation size and glass elongation is confirmed by the graphs of Figures 2 and 5, based on which effective glass repair can be performed.

For example, the method of repairing glass according to the present invention can be carried out in the following procedure. Specifically, 1) repairing the side (a) or the machined hole (b) of the laser-cut and CNC-processed glass and measuring the shape and diameter of the passivation portion (c) generated on the glass surface (Fig. 1). 2) Thus, in terms of the elongation as the glass strength standard, the diameter of the passivation portion, that is, the passivation size is important, and therefore, the passivation size and elongation must be appropriately adjusted. 3) The passivation size can be adjusted according to the composition for repairing the glass, and can be designed based on the relationship between the passivation size and the elongation obtained by measuring the elongation of the substrate of 4 inches or larger (Fig. 2). Optimal composition. 4) In order to prevent damage to the stack on the glass substrate exposed by the cut, a film must be applied, and a corrosion that minimizes the stacking of the stack except for the glass profile including the exposed sides and holes to be repaired is required. Composition (Figure 5). In addition, 5) because, unless the passivation shape is a symmetrical circle, Otherwise, the elongation is lowered due to external stress, so by adding ammonium fluoride as a buffer and continuing a sufficiently long repair time, a more desirable passivation shape and higher elongation can be ensured.

The method for repairing glass according to the present invention is preferably carried out by treating the glass with the composition for 30 seconds to 5 minutes.

Additionally, the present invention provides a touch panel substrate (Fig. 1) comprising one or more of the sides and apertures of the tempered glass repaired using the compositions of the present invention. The touch panel substrate can be applied to an array substrate for a liquid crystal display.

In addition, the present invention provides a method for manufacturing a touch panel substrate. The method for manufacturing a touch panel substrate includes: forming a strengthening layer on an upper surface and a lower surface of the glass using an ion exchange step; forming a touch panel on the upper surface of the strengthened glass substrate with respect to a cell unit; Cutting and processing a substrate including a touch panel into small units using laser and CNC processing; forming a film layer on upper and lower surfaces of the strengthened glass substrate cut into small units; and cutting using the composition of the present invention The glass is repaired to remove microcracks from the cut profile of the glass substrate, thereby increasing the glass elongation.

Specifically, a method for manufacturing a touch panel substrate includes: forming a tempered glass by ion exchange from Na ions in a glass surface to K ions; performing laser processing to cut the glass into small units and performing in the glass Hole processing for a microphone or home button; CNC machining of a rough surface by laser cutting and machining to obtain a smooth surface; and repair of the glass using the composition of the present invention from the surface of the glass processed by laser and CNC The microcracks are removed and to form a passivation and increase the passivation size.

For example, the touch panel substrate can be manufactured by: a) forming a tempered glass layer on the upper and lower surfaces of the glass; b) forming a touch panel on the upper surface of the tempered glass with respect to the small unit; c) performing a lightning Shot processing to cut the tempered glass into small units and to form holes in the glass suitable for the microphone and home button; d) performing CNC on the surface of the tempered glass cut and processed by laser; and e) machining the CNC The surface is subjected to a repair step, thereby removing microcracks and forming a passivation portion.

Specifically, d) may further include bonding an organic film to protect the upper and lower surfaces of each small unit of the substrate other than the surface processed by the CNC, and e) may further include washing with DI water to remove residual after repair Inorganic materials.

According to the present invention, the problem that the touch panel obtained without unrepairing after the bulk glass is cut into small units is broken even under a small force can be solved by increasing the elongation by the repairing step. By such a repairing effect, the bursting strength of the glass for a touch panel can be enhanced, thereby increasing mass productivity. In addition, the repairing step can enhance the bursting strength of the glass for the touch panel without affecting the touch panel that has been formed on the upper surface of the strengthened glass substrate relative to the small unit.

(Example)

The invention is further understood by the following examples, which are not to be construed as limiting. Those skilled in the art can appropriately modify and change these embodiments within the scope of the invention.

Examples and comparative examples

The compositions for repairing the glass in the examples and comparative examples were prepared as shown in Table 1 below.

Test Example 1: Evaluation of the passivation size and elongation of the composition of the present invention on glass

The compositions of Examples 1 to 6 and Comparative Examples 1 to 8 prepared as shown in Table 1 were subjected to the glass repairing step as described above, and the passivation rule was measured. Inch and elongation.

10,000 g of each of the above compositions were prepared and stored in a PE container which was kept at a constant temperature (25 ° C) in the test apparatus without damaging the hydrofluoric acid. The prepared reinforcing substrate (secure) was inserted into a box of a suitable size, immersed in each composition solution for 3 minutes, and then washed, thereby completing the repairing step. After the repair step was completed, the passivation shape of the tempered glass was observed using a scanning electron microscope (SEM) and the passivation size and elongation were measured. The results are shown in Table 2 below. In addition, the relationship between the elongation and the passivation size is shown in Fig. 2.

The compositions according to Examples 1 to 6 of the present invention exhibited a passivation size of 6 to 12 μm and an elongation of 0.8% or more. However, in the compositions of Comparative Examples 1, 2 and 3 including hydrofluoric acid and DI water (in which only the amount of hydrofluoric acid was increased), a large passivation size was not obtained within the desired repair time, and elongation was obtained. Did not reach the minimum target of 0.8% (Figure 3).

Excessive use of hydrofluoric acid (HF) can cause environmental problems. Therefore, in Comparative Examples 4 and 5 in which ammonium fluoride was added, the pH value increased due to the effect of the ammonium ion as a weak base, so the activity of the F anion was lowered, and it was difficult to form passivation. unit.

In the composition containing the composition of the present invention but having a small amount of inorganic acid (Comparative Example 7), a large amount of Al ₂ O ₃ slurry produced by glass etching could not be controlled. In Comparative Example 8, although the amount of nitric acid was increased to 22% by weight to maximize the passivation size to significantly increase the elongation, the passivation size was not large, and there was an improvement in elongation with an insignificant saturation region with an increase in passivation size ( figure 2). As described above, when the amount of the inorganic acid is increased to 20% by weight or more, heat generation and environmental problems occur, and the waste liquid treatment cost is remarkably increased.

Test Example 2: Measurement of passivation size of glass depending on repair time repaired with the composition of the present invention

10,000 g of each of the above compositions were prepared and stored in a PE container which was kept at a constant temperature (25 ° C) in the test apparatus without damaging the hydrofluoric acid. The prepared reinforcing substrate was inserted into a cartridge, immersed in each composition solution for a predetermined period of time (40 seconds, 60 seconds, 180 seconds), and then washed, thereby completing the repairing step. After the repair step is completed, the passivation shape of the tempered glass is observed using SEM, and as shown in FIG. 4, the y-axis value (long-axis diameter) of the passivated shape depending on the repair time is divided by the x-axis value (short-axis diameter), The circularity of the passivation shape is thus calculated. The results are shown in Table 3 below.

The y/x value is close to 1 depending on the increase in repair time and the amount of ammonium fluoride added. As is apparent from Examples 1, 7, and 8, the passivation shape changes from an asymmetrical circle to a symmetrical circle.

Test Example 3: Evaluation of elongation of glass depending on the repair time repaired with the composition of the present invention

10,000 g of each of the above compositions were prepared and stored in a PE container which was kept at a constant temperature (25 ° C) in the test apparatus without damaging the hydrofluoric acid. The prepared reinforcing substrate (secure) is inserted into a box of a suitable size, immersed in the composition solution for a predetermined period of time (40 seconds, 60 seconds, 180 seconds), and then washed, thereby completing the repairing step. After the repair step was completed, the passivation shape of the strengthened glass was observed using SEM, and the elongation (180 seconds) was measured. The results are shown in Table 4 below. In addition, variations in passivation size and elongation depending on the repair time are shown in FIG.

Claims (9)

A composition for repairing glass comprising: A) 1 to 20 wt% of hydrofluoric acid, B) 0.1 to 5 wt% of ammonium fluoride, and C) 1 to 20 wt% of inorganic matter, relative to the total weight of the composition. Acid and D) balance of water. The composition for repairing glass according to claim 1, wherein the inorganic acid includes at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid. The composition for repairing glass according to claim 1, wherein the aforementioned glass is repaired so that the elongation of the aforementioned glass is increased to 0.8% or more. The composition for repairing glass according to claim 1, wherein the glass is tempered glass. The composition for repairing glass according to claim 1, wherein the glass is repaired in such a manner that a passivation portion is formed on the surface of the glass and the stress concentration factor is decreased to increase the elongation. A glass treated by the composition for repairing glass described in claim 1, wherein the glass has an elongation of 0.8% or more. A glass treated by the composition for repairing glass according to claim 1, wherein the glass has a passivation portion having a passivation size of 6 to 12 m on the surface. The glass according to claim 7, wherein the passivation portion has a circular or elliptical shape in which a value (y/x) obtained by dividing a major axis diameter (y) by a minor axis diameter (x) is 1 to 3. A method of repairing a glass comprising treating the aforementioned glass with the composition for repairing glass described in claim 1 for 30 seconds to 5 minutes.