JP4520075B2 - Surface processing of glass products with sandblasting - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glass etching composition capable of making a surface of a glass product having a plane, curved surface, tubular shape or other arbitrary shape subjected to sandblasting translucent, and a surface processing method of a glass product using the same.
[0002]
[Prior art]
Conventionally, since many sharp flaws exist on the surface of a glass product that has been matte by sandblasting, it has a feeling of roughness and has not been able to bring out a very elegant image without gloss. Also, dust, oil, grease, fingerprints, hand dirt, etc. are easily attached, and even after washing, these stains cannot be easily removed, so they become very ugly, and cracks grow easily due to sharp flaws, reducing strength. I often did.
Therefore, in order to give a glass product that has been sandblasted with a semi-transparent and elegant appearance with appropriate luster and gloss, the glass surface is treated with a glass etchant containing hydrofluoric acid or sulfuric acid, or a resin. In addition, it is necessary to perform a process for producing gloss and gloss by spraying an inorganic substance or the like.
[0003]
[Problems to be solved by the invention]
However, conventionally used glass etchants contain very high concentrations of hydrofluoric acid and sulfuric acid. Therefore, since it is extremely dangerous and cannot be used easily, there is a disadvantage that it can only be used in a place with no special equipment and having daily life. On the other hand, the method of glazing by spraying resin, inorganic substances, etc. on the glass surface is complicated and has problems with uniformity of spraying, and the sprayed film is prone to peeling and damage. was there. The present invention constitutes a glass etching composition that reduces the risk of human injury and environmental pollution, and by using this glass etching composition, a plane, curved surface, tubular and other arbitrary shapes that have been sandblasted are used. The object of the present invention is to provide a surface processing method for giving a glass product a semi-transparent and elegant appearance with appropriate gloss and gloss.
[0004]
[Means for Solving the Problems]
In order to achieve the above object, the present invention significantly increases the amount of hydrofluoric acid and sulfuric acid added by adding a fluoride and a water-miscible organic solvent, which are much safer than hydrofluoric acid. The invention relates to a reduced glass etching composition and a surface processing method using the glass etching composition.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a glass etching composition in which a water miscible organic solvent such as polyethylene glycol 200 (polyethylene glycol having an average molecular weight of about 200) is mixed with an aqueous solution obtained by adding water and an acid such as sulfuric acid or hydrofluoric acid to fluoride such as ammonium fluoride. It is about things. This glass etching composition can be gelled by adding a gelling agent such as tragacanthum, a dye can be added to serve as a guide during waste liquid treatment, and sucrose can be added as a stabilizer. In addition, surfactants such as polyoxyethylene octylphenyl ether can be added to help adhere the glass etching composition to the glass surface.
[0006]
Embodiments of the present invention for surface processing include ammonium fluoride (10-30 w / v%), ammonium hydrogen fluoride (0-20 w / v%), hydrofluoric acid (0-15 v / v%), sulfuric acid (5-25 v / v%), hydrochloric acid (5-20 v / v%), (sucrose (0-5 w / v%), surfactant (0-5 w / v% or v / v%) and dye A glass etching composition obtained by mixing propylene glycol, polyethylene glycol 200 (polyethylene glycol having an average molecular weight of about 200) or glycerin as a water miscible organic solvent with a volume ratio of 4: 6 to 8: 2, and the glass etching composition thereof Although it demonstrates based on the glass etching composition which added the gelatinizer (0-15 w / v%) to this, this invention is not limited to this.
[0007]
[Example 1]
Glass mixed with an aqueous solution containing 20 w / v% ammonium fluoride or ammonium hydrogen fluoride and 15 v / v% sulfuric acid and propylene glycol, glycerin or polyethylene glycol 200 as a water-miscible organic solvent in a volume ratio of 7: 3 The etching composition was adjusted.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. This glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 60 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. The combination of ammonium fluoride and propylene glycol or polyethylene glycol 200 caused precipitation, but ammonium hydrogen fluoride did not. However, the transparency of the glass plate surface-treated with a mixed solution of ammonium fluoride and polyethylene glycol 200 was the highest.
[0008]
[Example 2]
A glass etching composition obtained by mixing an aqueous solution containing 10 to 20 w / v% ammonium fluoride and 5 to 20 v / v% sulfuric acid, hydrochloric acid or a mixture of both with polyethylene glycol 200 in a volume ratio of 4: 6 to 8: 2. It was adjusted.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. This glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 60 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. The transparency increased depending on the concentration of ammonium fluoride and the concentration of sulfuric acid and hydrochloric acid, but the combination of ammonium fluoride and sulfuric acid produced a gloss on the glass surface. The solubility of ammonium fluoride increased depending on the concentration of sulfuric acid, but precipitation of ammonium fluoride occurred when the concentration of hydrochloric acid was 15 v / v% or more. Further, when the capacity of the polyethylene glycol 200 was 30 to 50, there was no unevenness and the transparency was excellent.
[0009]
[Example 3]
A glass etching composition in which an aqueous solution containing 10 to 20 w / v% ammonium fluoride, 10 to 20 w / v% ammonium hydrogen fluoride and 15 to 25 v / v% sulfuric acid and polyethylene glycol 200 are mixed at a volume ratio of 7: 3. Adjusted.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. This glass plate is washed with tap water, water is wiped off, and the above glass etching composition is applied with a brush and left for 30 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. In the combination of ammonium fluoride and ammonium hydrogen fluoride, the transparency increased as the concentration of ammonium fluoride increased. Even when the concentration of sulfuric acid was increased, the transparency did not increase much.
[0010]
[Example 4]
Glass etching in which an aqueous solution containing 30 w / v% ammonium fluoride, 10-25 v / v% sulfuric acid and 0-15 v / v% hydrofluoric acid and polyethylene glycol 200 are mixed at a volume ratio of 5: 5-7: 3 The composition was adjusted.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. This glass plate is washed with tap water, water is wiped off, and the above glass etching composition is applied with a brush and left for 30 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. Glass plates with various transparency levels were obtained by combining the sulfuric acid and hydrofluoric acid concentrations. However, when the sulfuric acid concentration exceeded 15 v / v% and the hydrofluoric acid concentration exceeded 10 v / v%, the transparency was too high. No longer increases. As the capacity of polyethylene glycol 200 increased, ammonium fluoride precipitation was likely to occur.
[0011]
[Example 5]
A glass etching composition prepared by mixing an aqueous solution containing 30 w / v% ammonium fluoride, 15 v / v% sulfuric acid and 10 v / v% hydrofluoric acid with polyethylene glycol 200 in a volume ratio of 5: 5 to 7: 3. did.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. This glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 to 60 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. Although the transparency increases depending on the length of the standing time after applying the glass etching composition, a glass plate having the desired transparency was obtained after standing for 15 minutes.
[0012]
[Example 6]
30 w / v% ammonium fluoride, 15 v / v% sulfuric acid and 10 v / v% hydrofluoric acid, and polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaur as surfactants An aqueous solution containing 0 to 5 v / v% or w / v% of any one of rate, calcium lignin sulfonate, sodium dodecylbenzene sulfonate or a mixture thereof and polyethylene glycol 200 are mixed at a volume ratio of 7: 3. The prepared glass etching composition was prepared.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. The glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. The surfactant described above did not significantly affect the transparency of the glass plate, but helped the glass etching composition to adhere uniformly to the glass surface. Even if other surfactants are used, the same result can be obtained with different degrees.
[0013]
[Example 7]
Aqueous solution containing 25 w / v% ammonium fluoride, 15 v / v% sulfuric acid, 5 v / v% hydrofluoric acid, and 0 to 5 w / v% sucrose and polyethylene glycol 200 are mixed at a volume ratio of 7: 3. The prepared glass etching composition was prepared.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a flat glass having a size subjected to sandblasting of 50 mm long × 50 mm wide × 5 mm thick was used. The glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. The addition of sucrose did not significantly affect the transparency of the glass plate.
[0014]
[Example 8]
A glass etching composition prepared by mixing an aqueous solution containing 10 to 20 w / v% ammonium fluoride, 5 to 20 v / v% sulfuric acid, hydrochloric acid or a mixture of both with polyethylene glycol 200 at a volume ratio of 4: 6 to 8: 2. did. A uniform gel-like glass etching composition was prepared by adding 5 to 15 w / v% gum arabic or tragacanth gum to the total amount of this solution and stirring.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a sandblasted size flat glass having a length of 50 mm × width 50 mm × thickness 5 mm and a glass cup having a size of an outer diameter 50 mm × height 90 mm × thickness 1 mm were used. The glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. As the amount of gum arabic or tragacanth was increased, the flowability of the glass etching composition decreased, and it was uniform gel and could be applied to curved glass like glass cups. Further, the glass treated with the glass etching composition added with tragacanth gum than the gum arabic had no unevenness in transparency.
[0015]
[Example 9]
A glass etching composition in which an aqueous solution containing 10 to 20 w / v% ammonium fluoride, 5 to 20 v / v% sulfuric acid, hydrochloric acid or a mixture of both is mixed with polyethylene glycol 200 or propylene glycol at a volume ratio of 4: 6 to 8: 2. I adjusted things. 1-10 w / v% hydroxypropylcellulose (average viscosity 150-400 mps, 2% solution, 20 ° C.) is added to the total amount of this solution and stirred to prepare a uniform gel-like glass etching composition. did.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a sandblasted size flat glass having a length of 50 mm × width 50 mm × thickness 5 mm and a glass cup having a size of an outer diameter 50 mm × height 90 mm × thickness 1 mm were used. The glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. The combination of ammonium fluoride and sulfuric acid did not gel so much. Even a combination of ammonium fluoride and hydrochloric acid did not gel so much when the concentration of hydrochloric acid increased.
[0016]
[Example 10]
Aqueous solution containing 10-30 w / v% ammonium fluoride, 5-20 v / v% sulfuric acid and 0-10 v / v% hydrofluoric acid and polyethylene glycol 200 were mixed at a volume ratio of 5: 5-7: 3. A glass etching composition was prepared. A uniform gel-like glass etching composition was prepared by adding 5 to 15 w / v% tragacanth gum to the total amount of this solution and stirring.
Surface processing is performed as follows using such a glass etching composition. That is, as the substrate to be processed, a sandblasted size flat glass having a length of 50 mm × width 50 mm × thickness 5 mm and a glass cup having a size of an outer diameter 50 mm × height 90 mm × thickness 1 mm were used. The glass plate is washed with tap water, water is wiped off, and the glass etching composition is applied with a brush and left for 15 minutes. When the glass plate was washed again with tap water, a glass plate with a translucent glass surface was obtained. Glass plates with various transparency levels were obtained by combining the concentrations of ammonium fluoride, sulfuric acid and hydrofluoric acid. As the amount of added tragacanth gum increased, the flowability of the glass etching composition decreased, and the gel etching composition exhibited a uniform gel shape and could be applied to curved glass such as a glass cup.
[0017]
Example 11
An aqueous solution colored in yellow by adding 30 w / v% ammonium fluoride, 15 v / v% sulfuric acid, 10 v / v% hydrofluoric acid and 0.5 w / v% bromthymol blue as a dye, and polyethylene glycol 200 A glass etching composition mixed at a volume ratio of ˜7: 3 was prepared.
A 10 w / v% sodium carbonate solution is added to the glass etching composition until the color of the solution changes to blue. The pH of the solution at this time was 6.5-8, and neutralization of this glass etching composition was confirmed.
[0018]
Example 12
A glass etching composition was prepared by mixing an aqueous solution containing 30 w / v% ammonium fluoride, 15 v / v% sulfuric acid and 10 v / v% hydrofluoric acid and polyethylene glycol 200 in a volume ratio of ˜7: 3.
This glass etching composition is added to the scale in a pre-scaled container containing 1 L of 5 w / v% sodium hydroxide solution. The pH of the solution at this time was 6.5-8, and neutralization of this glass etching composition was confirmed.
[0019]
【The invention's effect】
Since the present invention is constituted by the surface processing method of the glass product subjected to the sandblasting as described above, the effect will be described below.
[0020]
By adding a water-miscible organic solvent to the glass etching composition used for the surface processing of the present invention, wetting with respect to the glass surface is promoted and contact efficiency is increased, so that the glass etching composition uniformly adheres to the glass surface and is etched. Therefore, the size of the pits to be formed is made uniform, and the pits themselves become fine, so that very fine irregularities are formed. In addition, water-miscible organic solvents are poorly soluble or insoluble in the water produced by the reaction between glass and hydrofluoric acid, and calcium fluoride and sodium silicofluoride partially cover the glass surface and inhibit etching. There is an effect to prevent. Therefore, it was possible to obtain a glass product having an elegant and elegant processed surface that is easy to touch with the use of a very small amount of hydrofluoric acid or sulfuric acid, is translucent, has an appropriate gloss and luster, and is elegant.
[0021]
Ammonium fluoride in the glass etching composition used for the surface processing of the present invention decomposes the reaction product of glass and hydrofluoric acid and regenerates hydrofluoric acid, so that hydrofluoric acid or sulfuric acid is used. The amount could be greatly reduced. Accordingly, even in the glass etching composition having the highest transparency and the high concentration of hydrofluoric acid and sulfuric acid in the glass etching composition of the present invention, the concentrations of hydrofluoric acid and sulfuric acid are 5 to 7 v / v%, respectively. And 10-14 v / v%, which is 1/3 to 1/4 of the amount of hydrofluoric acid and sulfuric acid used in the conventional method, greatly reducing the danger to the human body and environmental pollution.
[0022]
Since the surface processing with the glass etching composition of the present invention has a moderate etching rate at room temperature, the transparency can be changed by changing the etching time to 10 minutes, 30 minutes, 60 minutes, for example, in minutes. It has an effect that can be.
[0023]
Transparency can be achieved by changing the concentration of fluorides such as ammonium fluoride, hydrofluoric acid, and sulfuric acid in the glass etching composition of the present invention, or by changing the ratio of an aqueous solution and a water-miscible organic solvent such as polyethylene glycol 200. Can be changed. Transparency can also be changed by changing the type of water-miscible organic solvent. Further, by adding a gelling agent, the glass etching composition of the present invention can be imparted with an appropriate viscosity to facilitate surface processing of flat, curved, tubular and other glass products of any shape. The surfactant has an effect of promoting the wetting through the action of decreasing the interfacial tension and promoting the uniform adhesion of the glass etching composition to the glass surface.
[0024]
In the surface processing of the glass product subjected to the sand blast processing by the glass etching composition of the present invention, there is no need for special pre-treatment and post-treatment.
[0025]
Since the glass etching composition of the present invention has high weather resistance against temperature, humidity and ultraviolet rays, it can be used repeatedly.
[0026]
According to the present invention, sucrose has the effect of contributing to the stability of the glass etching composition.
[0027]
According to the present invention, since a pigment is added to the glass etching composition for coloring, the safety can be improved visually and at the same time, it can be used as a guide when neutralizing and discarding with an alkaline solution containing slaked lime or the like. There is.
[0028]
According to the present invention, it is easy to shield by a masking method and immerse in the glass etching composition of the present invention or apply the glass etching composition of the present invention with a brush, a brush, a spatula, etc. There is an effect that it is possible to make it an advanced product from work and craft.
[0029]
ADVANTAGE OF THE INVENTION According to this invention, after etching the glass surface with a glass etching composition, it has the effect that the washing | cleaning of the glass etching composition mainly having the fluoride adhering to the glass surface can be performed simply and reliably with water.
[0030]
The glass etching composition of the present invention can be applied not only to surface processing after sandblasting to the glass surface, but also to cleaning and etching processing of the surface of a cathode ray tube panel or semiconductor substrate and metal.

Claims (9)

  Containing 5-40 wt / vol% (hereinafter referred to as w / v%) of any one fluoride selected from ammonium fluoride, ammonium hydrogen fluoride, or a mixture of both, and hydrochloric acid, nitric acid, sulfuric acid, An aqueous solution containing 5 to 50 vol / vol% (hereinafter referred to as v / v%) of any one acid selected from hydrofluoric acid or a mixture thereof and a water-miscible organic solvent have a volume ratio of 4 : Etching the glass surface that has been sandblasted using a glass etching composition mixed at 6 to 8: 2, and finishing the roughened surface to a surface having fine and smooth irregularities. Characteristic surface processing method. These water-miscible organic solvents, glycerin, methyl glycol, ethyl glycol, methylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polyethylene glycol, et Ji glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether , Chill alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, isobutyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2,3-propanetriol, 1,2,6-hexanetriol, the surface processing method according to claim 1, characterized in that the sorbitol Le whether et least one of the compound selected.   The surface processing method according to claim 1, wherein a gelling agent is added to the glass etching composition. The gelling agent is gum arabic, locust bean gum, bean gum, tragacanth gum, xanthan gum, guar gum, karaya gum, Verangamu, rhamsan, gellan gum, the fermentation gas beam, base bentonite, natural hectorite, synthetic hectorite, natural smectite, silica gel, glass fines, aluminum oxide Na, synthesis Sumekutai DOO, glue, starch, pectin acid, gelatin, galactomannan, agar, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, nitrocellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium U arm, Po Riakuriru salts, polyacrylamides, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl Acetate least, acrylic acid ester polymer, isobutyl maleate copolymers, acrylic acid / methacrylic acid copolymers, acrylic acid / maleic acid copolymer, synthetic water-soluble cellulose scan, selected A alginic acid sodium or al It is any one compound, The surface processing method of Claim 3 characterized by the above-mentioned.   The surface processing method according to claim 1, wherein a surfactant is added to the glass etching composition. The surfactant, sodium dodecylbenzene sulfonate, sodium alkylbenzene sulfonate, calcium lignin sulfonate, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphoric acid salts, polyoxyethylene acetyl ether, Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, sorbitan laurate, sorbitan palmitate, sorbitan oleate, Sorbitan stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmite DOO, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate rate, di-methyl betaine, alkyl glycine, betaines, imidazoline, perfluoroalkyl amino acid salts, perfluoroalkyl Baie tie down, Oh octadecyl Dimethylbenzylammonium chloride, alkyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, dioleyldimethylammonium chloride, octadecyltrimethylammonium chloride, alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecylamine acetate, Tetradecylamine acetate, par Surface processing method according to claim 5, characterized in that the Le Oro alkyltrimethylammonium salts, at least one of compounds selected or perfluoroalkyl quaternary ammonium salts, et al.   The surface processing method according to claim 1, wherein sucrose is added to the glass etching composition.   The surface processing method according to claim 1, wherein the glass etching composition is colored by adding a pigment. Or immersion in the etching glass composition, or a brush or a brush and claims 1-8 any one, characterized in that for etching a glass surface sandblasted is performed by applying with f La Surface processing method described in 1.