JP2005139039A - Processing method of glass sheet, cap for sealing organic el display unit and glass chip - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method of glass sheet whereby a precise image can be formed at a low cost without any labor and without lowering the strength of the glass sheet. <P>SOLUTION: The processing method comprises a step wherein a hydrofluoric acid-resistant film 12 is formed on one side of the glass sheet 11, a step wherein a blast-resistant film 13 is formed to form the image on the hydrofluoric acid-resistant film 12, a step wherein the hydrofluoric acid-resistant film 12 and the glass sheet on the part which is not covered with the blast-resistant film 13 is removed by blasting, the glass sheet 11 exposed through blasting is etched with hydrofluoric acid and a step wherein the hydrofluoric acid-resistant film 12 and the blast-resistant film 13 are removed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for processing a glass plate when an image is formed on the glass plate. Furthermore, the present invention relates to a glass sealing cap used in an organic EL display device and a glass chip that performs a chemical reaction.

Glass is excellent in transparency, chemical resistance, durability, and low expansion with respect to temperature and humidity compared to other materials, so it is used as a base material for cathode ray tubes and thin displays. Furthermore, in recent years, as a new application of glass, a sealing cap for an organic EL display device that protects the back side of the organic EL display device in order to prevent moisture from entering, and a reaction that performs a chemical reaction of a small amount of sample on the glass. Glass chips that are devices are being studied.
By the way, in order to obtain a sealing cap for an organic EL display device, a glass chip, or the like, it is necessary to dig a groove or make a hole in the glass plate. Processing of such a glass plate includes a sand blast method in which a particulate abrasive impinges on the glass plate, an etching method in which a hydrofluoric acid-containing liquid is brought into contact with the glass plate and melted, and a leather that is melt processed by irradiation with a laser beam. The beam processing method etc. are mentioned. Conventionally, a glass plate has been processed by any one of these methods.

  However, the sandblasting method enables grooving and drilling in a large amount and at a relatively low cost, but on the other hand, microcracks (chipping) occur due to particle collisions, so that the strength of the glass is lowered. In addition, the processed surface has large irregularities and low transparency, and the irregular surface is liable to become dirty.

In addition, the etching method uses a highly corrosive acid containing hydrofluoric acid, so although it is possible to easily groove or drill a glass plate, there is a problem that there is no material for a corrosion resistant film that can sufficiently withstand the strong acid. Met. Therefore, for example, when an image of a rubber photosensitizer is used as a corrosion-resistant film and a glass plate is etched with hydrofluoric acid, the corrosion-resistant film is also dissolved, so that long-time etching is difficult, and the depth is 5 to 10 μm. Shallow etching was the limit.
In addition to the above method, a method is known in which a wax is melted and thinly coated on a glass plate, and the wax is shaved with a sharp blade so that a desired image is obtained, and then etching is performed. According to this method, etching can be performed relatively deeply, but when etching becomes deeper, a part of the lateral wall of the groove is eroded (the erosion of the lateral wall is sometimes referred to as undercut), and finally the glass on the surface side is broken. Therefore, a groove having a width wider than that at the time of design may be formed. Therefore, accurate image formation could not be reproduced. In addition, the work of shaving the wax to form an image is a time-consuming work.
Furthermore, a method is known in which a film in which a pressure-sensitive adhesive or a hot melt adhesive is applied on one side is attached to a glass plate, and the film to be etched is peeled off before etching. According to this method, etching can be performed relatively deeply, but there is a problem in that it is difficult to form a delicate image and the productivity is low because it takes time for the peeling operation.

In the etching method, glass is sometimes etched using a chromium film on which an image is formed as a corrosion-resistant film. The method of forming the chromium film on which the image is formed is as follows. First, a chromium film is formed on the glass surface by sputtering or vapor deposition of metallic chromium, and an image of a photosensitive agent (mainly positive type) is formed thereon, Further, an image is formed by etching the chromium film with a second cesium nitrate solution using the photosensitizer image as a corrosion-resistant film. Since this method uses a photosensitizer, it is easy to form an image and can be etched relatively deeply. However, as described above, undercutting tends to prevent accurate image formation from being reproduced. Therefore, in order to prevent collapse due to undercut, a method of further forming a gold film on the chromium film has been tried, but it cannot be completely solved, and it is not possible to form a chromium film or a gold film. Expensive and practical.
The present invention has been made in view of the above circumstances, and provides a method for processing a glass plate that does not reduce the strength of the glass plate and that can form an accurate image at low cost without requiring labor. For the purpose. It is another object of the present invention to provide a sealing cap and a glass chip for an organic EL display device having high strength and an accurate image.

The processing method of the glass plate of claim 1 of the present application includes a step of forming a hydrofluoric acid resistant film on one surface of the glass plate,
Providing a blast resistant film on the hydrofluoric acid resistant film so as to form an image;
A step of scraping off the hydrofluoric acid resistant film and the glass plate of the portion not covered with the blast resistant film by blasting;
Etching the glass plate exposed by blasting with hydrofluoric acid;
And a step of removing the hydrofluoric acid resistant film and the blast resistant film.
The processing method of the glass plate of claim 2 of the present application includes a step of forming a hydrofluoric acid resistant film on one surface of the glass plate,
Forming a blast resistant film on the hydrofluoric acid resistant film so as to form an image;
A step of scraping off the hydrofluoric acid resistant film and the glass plate of the portion not covered with the blast resistant film by blasting;
Removing the blast resistant film;
It has a step of etching the exposed glass plate with hydrofluoric acid and a step of removing the hydrofluoric acid resistant film.
In the processing method of the glass plate of this invention, it is preferable that the said hydrofluoric acid resistant film consists of at least 1 type chosen from the group of chromium, gold | metal | money, platinum, molybdenum, and tungsten.
Alternatively, in the method for processing a glass plate of the present invention, the hydrofluoric acid resistant film is composed of at least one selected from the group consisting of petroleum pitch, asphalt, petroleum wax, animal wax, vegetable wax, rubber, and polystyrene resin. It is preferable.
The glass sealing cap for an organic EL display device of the present invention is characterized by being manufactured by the glass plate processing method described above.
The glass chip of the present invention is manufactured by the glass plate processing method described above.

In the processing method of the glass plate of the present invention, since the glass plate is blasted and then etched with hydrofluoric acid, the chipping of the glass plate can be suppressed and the strength reduction of the glass plate can be prevented. Moreover, since it is not processed only by the etching method, even if the dent or groove is deepened, undercut can be prevented and an accurate image can be formed on the glass plate. In addition, since a pattern is not manually formed on the blast-resistant film or hydrofluoric acid-resistant film, labor is not required, mass productivity is high, and it is not necessary to form a special film, which is inexpensive.
Since the sealing cap for an organic EL display device and the glass chip of the present invention are manufactured by the glass plate processing method described above, the strength is high and an accurate image is formed.

The glass plate processing method of the first embodiment according to the present invention will be described with reference to FIGS.
In the processing method of the glass plate of this embodiment, first, a material having hydrofluoric acid resistance is applied, sputtered, vapor-deposited, etc. on one surface of the glass plate 11 as shown in FIG. ), The hydrofluoric acid resistant film 12 is formed.
Next, a dry film of a photosensitive resin is laminated on the hydrofluoric acid resistant film 12, and a mask having a window portion with a pattern formed thereon is placed on the dry film, exposed and developed, and the result shown in FIG. As shown, an anti-blast film 13 on which an image is formed is provided.
Next, as shown in FIG. 1D, the portions of the hydrofluoric acid resistant film 12 and the glass plate 11 that are not covered with the blast resistant film 13 are scraped off by blasting. Here, examples of the abrasive that can be used for blasting include alundum, carborundum, garnet, and iron powder.
Next, as shown in FIG. 2A, the glass plate 11 exposed by blasting is etched with hydrofluoric acid. Here, a preferable etching solution is a mixture of hydrofluoric acid with acetic acid, sulfuric acid, nitric acid or the like for the purpose of removing and dissolving, for example, lead, boron, sodium, potassium and the like other than pure glass components in the glass plate. .
Next, the etched glass plate is immersed in an aqueous caustic soda solution of about 5% by mass to remove the blast resistant film made of a dry film. Next, when the fluorine-resistant film is soluble in an organic solvent, it is immersed in the corresponding organic solvent organic solvent, and when the fluorine-resistant film is heat-meltable such as wax, it is heated. In the case of a metal, it is immersed in a cesium nitrate solution or the like to dissolve or remove the hydrofluoric acid resistant film and the blast resistant film as shown in FIG.
In this way, a glass plate 11 on which an image is formed is obtained.

In the above glass plate processing method, examples of the component of the hydrofluoric acid resistant film 12 include natural organic substances and synthetic organic substances that are chemical industrial products. Here, useful natural organic substances include animal waxes such as beeswax (BEE'S WAX), plant natures such as shellac (SHELLAC), rosin (ROSIN), carnauba (CARNAUBA WAX), and wood wax (JAPAN WAX). Examples of the rubber include rubbers such as wax, natural rubber, cyclized natural chloride, and chloride.
Synthetic organic substances include petroleum pitch (PITCH, tar pitch), asphalt (petroleum asphalt), paraffin (PARAFFINWAX), chlorinated paraffin, petroleum waxes such as low molecular weight polyethylene and low molecular weight polypropylene, chlorinated polyethylene, chlorine Examples thereof include fluorinated polypropylene, synthetic isoprene rubber, synthetic isoprene rubber cyclized rubber, chloride rubber, and polystyrene resin.
These can be used alone, but can also be used as a mixture of two or more, supplementing their properties. For example, chlorinated paraffin is mixed for the purpose of compensating the brittleness of chlorinated rubber, carnauba wax is mixed for the purpose of improving the machinability by blasting of low molecular weight polyethylene, and low molecular weight is used for the purpose of compensating the brittleness of asphalt. Polypropylene or cyclized rubber can also be added and used.

  The hydrofluoric acid resistant film 12 is preferably made of at least one selected from the group consisting of chromium, gold, platinum, molybdenum and tungsten. When such a metal is used for the hydrofluoric acid resistant film, an image can be easily formed.

  Furthermore, an inorganic filler or an organic filler is added to the hydrofluoric acid resistant film 12 of a natural organic material or a synthetic organic material for the purpose of improving the coating property at the time of film formation, or coloring such as pigments or dyes for the purpose of improving visibility. An agent can also be added.

Next, the processing method of the glass plate of 2nd Embodiment based on this invention is demonstrated with reference to FIG. 1 and FIG.
In the processing method of the glass plate of this embodiment example, the hydrofluoric acid resistant film 12 is formed on one surface of the glass plate 11 in the same manner as in the first exemplary embodiment, and an image is formed on this hydrofluoric acid resistant film 12. The blast resistant film 13 is provided, and the hydrofluoric acid resistant film 12 and the glass plate 11 which are not covered with the blast resistant film 13 are scraped off by blasting (see FIG. 1).
Next, the glass plate 11 obtained by blasting the hydrofluoric acid resistant film 12 and the glass plate 11 is immersed in a blast resistant film solution, and the blast resistant film is dissolved and removed as shown in FIG. Next, as shown in FIG. 3B, the glass plate 11 exposed by blasting is etched with hydrofluoric acid, and further immersed in an organic solvent or the like. As shown in FIG. Dissolve and remove.
In this way, a glass plate 11 on which an image is formed is obtained.

In the processing method of the second embodiment, examples of the blast-resistant film solution for dissolving the blast-resistant film 13 include alkaline solutions such as caustic soda, caustic potash aqueous solution, monoenolamine, diethanolamine, triethanolamine, and tetramethylammonium. And an organic aqueous solution. Examples of the organic solvent that dissolves the hydrofluoric acid resistant film 12 include xylene, toluene, and methylene chloride.
Etching conditions for etching the glass plate 11 with hydrofluoric acid are the same as those in the first embodiment.

In the embodiment described above, first, the glass plate on which the hydrofluoric acid resistant film is formed is blasted, and then the glass plate is etched, so that chipping due to blasting can be reduced. As a result, the strength reduction of the glass plate can be prevented.
Moreover, since the glass plate is scraped to some extent by blasting, it is not necessary to etch deeply. Therefore, undercut is unlikely to occur, and blasting can be processed linearly, so that an image can be accurately formed on the glass plate.
Furthermore, this method does not require the use of a special method for forming a hydrofluoric acid resistant film that requires labor, so that it is inexpensive and has high productivity.

The present invention is not limited to the above-described embodiment example. For example, a method of providing the blast resistant film 13 so as to form an image on the hydrofluoric acid resistant film 12 includes a method of applying a blast resistant material so as to form an image, and a blast resistant film on which an image has been previously formed. Examples include a method of laminating on an acid film, a method of laminating a thin film having blast resistance on a hydrofluoric acid resistant film, and then excising a predetermined portion of the thin film to form an image.
Furthermore, examples of a method for producing a blast-resistant film on which an image has been formed in advance include a method of die-cutting a plastic film (plate) such as a polyester film or a metal thin plate, and a method of leather processing. If an adhesive or hot melt adhesive is applied to one side of the blast resistant film on which an image has been formed in advance, it can be easily laminated on the hydrofluoric acid resistant film.

The sealing cap for organic EL display devices of the present invention or the glass chip of the present invention is produced by the glass plate processing method described above. Since the sealing cap or glass chip for an organic EL display device is manufactured by the glass plate processing method described above, the strength is high and an accurate image is formed. Therefore, the quality of the organic EL display device or the glass chip can be improved.
Examples of the glass chip include a glass biochip used for a biochemical reaction and a glass chemical chip used for a normal chemical reaction.

(Test Example 1)
100 g of asphalt powder was dissolved in 200 g of turpentine oil and 50 g of diethylene glycol monobutyl ether acetate, 50 g of fine powder of acrylic resin (MR-2G manufactured by Soken Chemical Co., Ltd.) was further added, and then kneaded with 3 rolls to obtain a viscous solution.
This viscous solution was applied on a glass plate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) with a screen printing plate (400 mesh stainless steel bowl) and dried at 80 ° C. for 20 minutes to form a hydrofluoric acid resistant film having a thickness of 8 μm. Formed. Next, a blast-resistant dry film (BF-405 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was laminated on the hydrofluoric acid resistant film, and a blast resistant film on which an image was formed was provided on the hydrofluoric acid resistant film by exposure and development.
Then, a glass plate provided with a blast-resistant film on a hydrofluoric acid-resistant film is a depression of (1) length 40 mm × width 40 mm under the blast conditions shown in Table 1 using a suction type blasting device (OP-12 manufactured by Nitsch). And (2) blasting was performed so as to form a groove having a width of 300 μm and a length of 10 mm.

  In the blasting process, the number of times of blasting of the workpiece to be blasted by the blasting apparatus and the depth of the recess or groove formed by the blasting process are as shown in Table 2.

Next, the blasted glass plate was dipped in a 5% aqueous caustic soda solution at 40 ° C. to peel off the blast resistant film made of a dry film laminated on the glass plate. Next, the glass plate from which the blast resistant film was peeled was placed in an etching solution at 25 ° C. (30 mass parts of 48 mass% hydrogen fluoride, 40 mass parts of 60 mass% nitric acid, 30 mass parts of 96 mass% acetic acid) for 20 minutes, Etching was performed while being immersed for 80 minutes. Then, the hydrofluoric acid resistant film was removed with a xylene solvent to obtain a glass plate in which depressions and grooves were formed. Table 3 shows the etching depth of the processed glass plate.
In addition, since the processed material-4 formed the groove | channel only by blast processing, it is a thing outside the scope of the present invention.

(Test Example 2)
40 parts by weight of insect white wax and 60 parts by weight of polyethylene having a melting point of 65 to 75 ° C. were put in a beaker, heated and melted, mixed and then cooled to obtain a solid wax.
The solid wax was placed on a glass plate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) placed on a heating iron plate (heat plate), and the solid wax was melted at a plate temperature of 80 ° C. Then, the melted solid wax was spread to form a hydrofluoric acid resistant film having a thickness of 6 μm on the glass plate. Next, a blast-resistant dry film (BF-405 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was laminated on the hydrofluoric acid resistant film, and a blast resistant film on which an image was formed was provided on the hydrofluoric acid resistant film by exposure and development.
And the glass plate by which the blast-proof film | membrane was provided on the hydrofluoric-acid-resistant film | membrane was blasted on the same conditions as Example 1 using the suction type blasting apparatus (Nitchu OP-12).
In the blasting process, the number of times of blasting of the workpiece to be blasted by the blasting apparatus and the depth of the recess or groove formed by the blasting process are as shown in Table 4.

  Next, the blasted glass plate was dipped in a 5% aqueous caustic soda solution at 40 ° C. to peel off the blast resistant film made of a dry film laminated on the glass plate. Next, the glass plate from which the blast resistant film was peeled was placed in an etching solution at 25 ° C. (55 mass parts of 55 mass% hydrogen fluoride, 25 mass parts of 60 mass% nitric acid, 25 mass parts of 98 mass% acetic acid) for 25 minutes, 45 minutes. Etching was carried out while dipping for a minute. Then, the hydrofluoric acid resistant film was removed with a 90 ° C. xylene solvent to obtain a glass plate in which depressions and grooves were formed. Table 5 shows the etching depth of the processed glass plate.

(Test Example 3)
A metal chromium film having a thickness of 0.2 μm was formed by vapor deposition on a glass plate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.), and this was used as a hydrofluoric acid resistant film. Next, an adhesive image film (Nippon Kaken Co., Ltd., trade name NCBR adhesive image) made of an acrylic ester resin for blast resistance is pasted on the hydrofluoric acid resistant film, and on the hydrofluoric acid resistant film, A blast resistant film on which an image was formed was provided.
And the glass plate by which the blast-proof film | membrane was provided on the hydrofluoric-acid-resistant film | membrane was blasted on the same conditions as Example 1 using the suction type blasting apparatus (Nitchu OP-12).
In the blasting process, the number of times of blasting of the workpiece to be blasted in the blasting apparatus and the depth of the recess or groove formed by the blasting process are as shown in Table 6.

  Subsequently, the processed product except processed product-7 was immersed in a methyl ethyl ketone solvent to peel off the blast resistant film. A glass plate of a processed product from which the blast-resistant film has been peeled off or a workpiece that has not been peeled off is subjected to an etching solution at 25 ° C. The composition was etched while being immersed for 20 minutes, 40 minutes, and 100 minutes in a composition composed of 100 parts by weight of pure water). Then, the etched glass plate is immersed at room temperature for 0.5 to 2 minutes in an etching solution for removing a metal chromium vapor deposition film made of ceric ammonium nitrate / perchloric acid (HY solution manufactured by Wako Pure Chemical Industries, Ltd.). The glass plate was oscillated while removing the hydrofluoric acid resistant film made of a metal chromium film to obtain a glass plate having depressions and grooves. Table 7 shows the etching depth of the processed glass plate.

  A glass plate with a 40 mm long x 40 mm wide depression is placed on a smooth metal surface of a strength tester with the depression facing downward, and the glass is broken by a flat metal terminal with a diameter of 5 mm from the center of the depression. A pressure test was applied until the strength of each workpiece was tested. The results are shown in Table 8.

  The width of the groove formed to be 300 mm wide × 10 mm long was measured. The results are shown in Table 9.

In Test Example 1 to Test Example 3, the processed products -1 to 3 and 5 to 10 (particularly processed products -1, 2, 3, 5, 6, 9, and 10) are fluorinated after blasting the glass plate. Since it was obtained by etching, chipping could be suppressed and strength reduction could be prevented. Moreover, since it is not processed only by the etching method, undercutting can be prevented and an accurate image can be formed on the glass plate. In addition, since a pattern is not manually formed on the blast resistant film or hydrofluoric acid resistant film, it does not require labor and is inexpensive.
On the other hand, since the workpiece 4 formed grooves and depressions only by blasting, the strength was low.

  The processing method of the glass plate of this invention is applicable when forming a groove | channel and a hollow precisely in a glass plate besides manufacture of the sealing cap for organic EL display apparatuses, or manufacture of a glass chip.

It is sectional drawing which shows each process in the 1st embodiment example and 2nd embodiment example which concern on this invention. It is sectional drawing which shows each process in the 1st example of an embodiment concerning the present invention. It is sectional drawing which shows each process in the example of 2nd Embodiment based on this invention.

Explanation of symbols

11 Glass plate 12 Hydrofluoric acid resistant film 13 Blast resistant film

Claims (6)

Forming a hydrofluoric acid resistant film on one side of the glass plate;
Providing a blast resistant film on the hydrofluoric acid resistant film so as to form an image;
A step of scraping off the hydrofluoric acid resistant film and the glass plate of the portion not covered with the blast resistant film by blasting;
Etching the glass plate exposed by blasting with hydrofluoric acid;
And a step of removing the hydrofluoric acid resistant film and the blast resistant film. Forming a hydrofluoric acid resistant film on one side of the glass plate;
Providing a blast resistant film on the hydrofluoric acid resistant film so as to form an image;
A step of scraping off the hydrofluoric acid resistant film and the glass plate of the portion not covered with the blast resistant film by blasting;
Removing the blast resistant film;
A method for processing a glass plate, comprising: a step of etching a glass plate exposed by blasting with hydrofluoric acid; and a step of removing a hydrofluoric acid resistant film.   The method for processing a glass plate according to claim 1 or 2, wherein the hydrofluoric acid resistant film is made of at least one selected from the group consisting of chromium, gold, platinum, molybdenum, and tungsten.   3. The hydrofluoric acid resistant film is made of at least one selected from the group consisting of petroleum pitch, asphalt, petroleum wax, animal wax, vegetable wax, rubber, and polystyrene resin. Glass plate processing method.   A glass sealing cap for an organic EL display device, which is manufactured by the method for processing a glass plate according to claim 1. A glass chip manufactured by the method for processing a glass plate according to claim 1.

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