WO2002053508A1 - Procede de preparation de verre decoratif au moyen d'une composition de gravure sur verre - Google Patents
Procede de preparation de verre decoratif au moyen d'une composition de gravure sur verre Download PDFInfo
- Publication number
- WO2002053508A1 WO2002053508A1 PCT/JP2001/011408 JP0111408W WO02053508A1 WO 2002053508 A1 WO2002053508 A1 WO 2002053508A1 JP 0111408 W JP0111408 W JP 0111408W WO 02053508 A1 WO02053508 A1 WO 02053508A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- etching composition
- ether
- water
- glass surface
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/72—Decorative coatings
Definitions
- the present invention uses a relatively low-concentration hydrofluoric acid that does not contain a strong acid such as hydrofluoric acid for use in silk screen printing and other printing methods.
- Glass etching consisting of a substance and water and a water-miscible organic solvent
- a glass etching composition which comprises a composition and which can be subjected to frosting on a flat, curved, tubular or any other glass surface by using this glass etching composition, and a glass etching composition comprising the same.
- the present invention relates to a method for frosting a glass surface using a method. Background art
- the most suitable method for frosting the glass surface to reveal ground glass with complicated patterns and patterns, and for producing the same material in large quantities is to combine silk screen printing and glass etching composition.
- a plate is produced using a silk screen and printed with an ink, and then the ink is used as a masking agent, frosted with a glass etching composition, and then the ink is removed, or directly using the produced plate.
- a method of performing frost processing by printing with a glass etching composition is conceivable.
- a glass etching composition containing hydrofluoric acid, sulfuric acid, and the like has been the most representative.
- the present invention solves the above-mentioned disadvantages by a glass etching composition and a method of frosting a glass surface using the same.
- w / v%) 1 to 20 weight / volume (hereinafter referred to as w / v%) (preferably 3 to 8 w / v%) fluoride is added to 20 to 80 volume / volume (hereinafter referred to as v / v%) (preferably 20-50 v / v%) and 20-80 v / v% (preferably 50-80 v / V%) of a water-miscible organic solvent to form a liquid state by adding a hydrophilic ointment to the glass etching composition.
- w / v% 1 to 20 weight / volume (hereinafter referred to as w / v%) (preferably 3 to 8 w / v%) fluoride is added to 20 to 80 volume / volume (hereinafter referred to as v / v%) (preferably 20-50 v / v%) and 20-80 v / v% (preferably 50-80 v / V%) of a water-miscible organic solvent
- the present invention is also characterized by the following configuration.
- a glass-etching composition obtained by adding a dye to the composition according to any of the above and coloring the composition.
- the fluoride is selected from sodium fluoride, potassium fluoride, ammonium fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, ammonium fluoride, ammonium fluoride, or ammonium fluoride.
- the water-miscible organic solvent is glycols such as glycerin-methyl glycol, methyl glycol, methylene glycol, ethylene glycol, propylene glycol, dimethylene glycol, diethylene glycol, dipropylene glycol, polymethylene glycol, polyethylene glycol, etc.
- Tylene glycol monomethyl ether ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, methylene glycol monobutyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, zip Glycol ethers such as glycol monobutyl ether, methyl 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,
- the glass etching composition according to any one of the above which is at least one compound selected from alcohols such as 1,2,3-propanetriol, 1,2,6-hexanthriol and sorbitol.
- Anionic surfactants such as sodium dodecylbenzenesulfonate, sodium alkylbenzenesulfonate, calcium ligninsulfonate, perfluoroalkylsulfonate, perfluoroalkylcarboxylate, perfluoroalkylphosphate, etc.
- Activator polyoxyethylene acetyl ether, polyoxyethylene ethylene ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether, polyoxyethylene octyl phenyl ether, Polyoxyshettirennonylfe, sodium sorbate, sorbitan palmitate, sorbitan lateate, sorbitan stearate, polyoxyethylene sorbitan monolaure
- Non-ionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.
- the glass etching composition
- a frosting method for a glass surface comprising applying a coating with a brush or brush and a squeegee to perform etching, washing the glass surface again, and removing a glass etching composition remaining on the glass surface.
- composition according to any of the above comprising a tube, a ballpoint pen, a sign-in, a marker pen, a felt pen, a brush pen, a container having a brush, brush or sponge tip, or an air gun spray.
- a frosting method in which a hand spray or aerosol is filled and applied or sprayed directly on the glass surface.
- composition according to any one of the above is coated and laminated on a soft film or sheet to form a sheet-like composite, and the sheet-like composite is formed into one sheet via a release film.
- a frosting method in which the material is in the form of a roll and is brought into direct contact with the glass surface.
- (1 2) After cleaning the glass surface, completely wipe off the cleaning solution, if necessary, shield portions of the glass surface that do not require etching by a masking method, and directly apply the glass etching composition by any of the methods described above.
- a frosting method for a glass surface characterized by etching by applying, contacting or spraying the glass surface, washing the glass surface again, and removing the glass etching composition remaining on the glass surface.
- the frosted surface is excellent in density and uniformity. As the volume ratio of glycerin to polyethylene glycol 400 increases, the density of the frosted surface decreases.
- the amount of hydroxypropylcellulose is preferably in the range of about 1 to 4 w / v% of the total amount for applying with a brush, and 4 w / v for extruding and applying to glass using a tube. % Or more is preferable.
- the average viscosity of hydroxypropylcellulose is not limited, it is about 150 to 400 mps (2% aqueous solution, 20 ° C) in view of the density of frost processing and the ease of handling. It is the preferred range.
- hydroxypropyl Some require significant amounts compared to Lulose.
- the glass plate, glass cup, and mirror are washed with tap water, the water is wiped off, a necessary portion is masked using a blue oil-based resin, and then immersed in the above-mentioned glass etching composition for 5 to 20 minutes.
- a glass plate having an unmasked surface portion frosted was obtained.
- the concentration of ammonium fluoride the density of the frosted surface becomes deeper and the immersion time is shortened, but the concentration of ammonium fluoride is 3 to 8 wZv% and the concentration of hydrochloric acid or nitric acid is 0.5.
- ⁇ 2 vZv% a good frosted surface could be obtained.
- the volume ratio of glycols, glycerin and polyethylene glycol 400 to the aqueous solution is about 2 to 3, it is considered that the frosted surface is superior in terms of the density and uniformity. As the volume ratio of glycerin and polyethylene glycol 400 increases, the density of the frosted surface decreases.
- Ammonium fluoride 9-24 w / v%, hydrochloric acid or nitric acid 3-6 v / v%, and polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene sorbitan as surfactant Add one or more of monolaurate, calcium ligninsulfonate or sodium dodecylbenzenesulfonate or a mixture of any of them to 1 volume of aqueous solution containing 0 to 3 v / v% or w / v%, and add Edible Green No. 3 to 1 volume. After green coloring, 2 volumes of propylene glycol were added and mixed to prepare a glass etching composition.
- the concentration of the ammonium hydrogen fluoride in the whole is 3 to 8 w / v%.
- a glass plate with the unmasked surface frosted was obtained.
- the above surfactant did not significantly affect the shading of the frosted surface, but helped the glass etching composition to adhere uniformly to the glass surface. Similar results can be obtained with other surfactants, albeit to varying degrees.
- the frosted surface becomes darker and darker, and the immersion time is shortened.However, the glass surface may be partially polished, or the frosted surface may be rough. May become noticeable. Addition of a surfactant may tend to improve these conditions somewhat.
- the amount of hydroxypropylcellulose is preferably in the range of about 1 to 4 w / v% of the total amount for applying with a brush, and 4 w / v for extruding and applying to glass using a tube. % Or more is preferable.
- the average viscosity of hydroxypropylcellulose is not limited, it is about 150 to 40 Omps (2% aqueous solution, 20 ° C) in view of the density of frosting and the ease of handling. In the preferred range is there. With other gelling agents, some require a considerable amount of hydroxypropyl cellulose to obtain a uniform gel. In addition, there are cases where it is difficult to obtain a thin and uniform processed surface due to the frosting density.
- a mixture of ammonium fluoride and ammonium fluoride in an aqueous solution containing 3 to 30 w / v% and hydrochloric acid or nitric acid in a volume of 0 to 10 v / v% was colored green by adding Edible Green No. 3 to 1 volume. Thereafter, 1 to 4 volumes of propylene glycol were added and mixed to prepare a glass etching composition. Therefore, the concentration of fluoride with respect to the whole is 0.6 to 15 w / v%.
- the amount of hydroxypropylcellulose is preferably in the range of about l to 4 w Zv% based on the total amount for application with a brush, and about 4 w / v% or more for extrusion by using a tube on glass. Is preferred.
- the average viscosity of hydroxypropylcellulose is not limited, but is preferably about 150 to 40 Omps (2% aqueous solution, 20 ° C) in view of the density of frost processing and its ease of handling. Range. With other gelling agents, some require a significant amount of hydroxypropyl cellulose to obtain a uniform gel. Further, there are cases where the density of the frost processing is difficult to obtain a thin and uniform processed surface.
- At least one compound selected from ammonium fluoride, ammonium fluoride, or sodium hydrogen fluoride contains 0 to 10 v / v% of hydrochloric acid or nitric acid 0 to 2 volumes of water, propylene glycol 1 Add 2 to 8 volumes of at least one ointment base selected from hydrophilic ointment, hydrogel ointment or lyogel ointment, and mix to prepare a uniform creamy glass etching composition. At this time, the concentration of fluoride with respect to the whole is adjusted to be 5 to 20 w / v%.
- the glass etching composition of the present invention is applied with a brush and left for 15 minutes. After the glass etching composition was washed away with tap water, the toner was wiped off with a lacquer thinner to obtain a glass plate on which desired patterns, figures, characters and the like were frosted.
- lithographic films such as under-print phyzolem or high contrast or half tone are created by digital processing using a computer or photoengraving.
- a screen of a silk screen is prepared based on the underlay film composed of the light-transmitting portion and the non-light-transmitting portion, and the plate is brought into close contact with a glass plate.
- the glass etching of the present invention is performed using a squeegee. Apply the composition evenly to a thickness of 1-2 mm and let stand for 10 minutes. When the glass etching composition was washed away with tap water, a glass plate on which desired photographs, pictures, patterns, figures, characters, and the like were frosted was obtained.
- the present invention is constituted by the glass etching composition and the frost processing method as described above, the following effects can be obtained.
- the frost processing of the present invention does not contain hydrofluoric acid, which is extremely harmful to the human body, and contains only a very small amount of fluoride. That is, in the present invention, a hydrogen fluoride ammonium or a fluoride ammonium capable of obtaining the best frosted surface out of a combination of a fluoride or a fluoride and an acid. In, the concentrations of 4 w / v% or less are both sufficient, which is extremely safe.
- LD 5 0 values oral for mice off Uz hydrogen Anmoniumu solution of this concentration is exceeded 3000 mg / kg, LD 5 oral to mouse is a criterion of Japanese deleterious substances. The value is at least 10 times safer than the value of 30-300 mg / kg. Also, when frosting is performed using a more secure ammonium fluoride, the concentration of the combined hydrochloric acid or nitric acid of 1 V / V% or less is sufficient. Therefore, in order to perform the work safely, it is essential to wear protective equipment such as goggles and rubber gloves, and the glass provided by the present invention is compared with the conventional fluorine-based glass etching composition which requires exhaust equipment. The etching composition can be handled with bare hands without the need for an exhaust system, and even if it adheres to the skin, no problem occurs in the frost processing time of the present invention.
- the ratio of water and a water-miscible organic solvent such as glycols and glycerin in the glass etching composition of the present invention completely different from that of the conventional method, a fluoride such as ammonium hydrogen fluoride can be obtained.
- the concentration of ammonium fluoride could be significantly reduced. Therefore, the etching action of the glass etching composition of the present invention was very mild, and the size of the formed bits was made uniform, and the pits themselves were also very fine.
- the machined surface is very handy and comparable to ordinary clear glass. Therefore, when printing characters and designs using gold, silver or other ink on the frosted surface, it is possible to obtain a very elegant and elegant glass product without losing the gloss of the ink. is there.
- the frosting process using the glass etching composition of the present invention is unavoidable at room temperature because the etching rate is still moderate. For example, in minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes By changing the etching time, the frost processing can be provided with shading.
- the frosting process can be shaded.
- a water-miscible organic solvent such as glycols and glycerin.
- the liquid glass etching composition of the present invention comprises an extremely small amount of a fluoride, such as ammonium fluoride or ammonium fluoride, and a glycoform used in cosmetics and pharmaceuticals. It is made of le
- the creamy glass etching composition is prepared by adding an ointment base such as a hydrophilic ointment. Therefore, the glass etching composition of the present invention has an effect of solving one of the most important problems in the fluorine-based glass etching agent, that is, environmental pollution and danger to the human body.
- the glass etching composition of the present invention can be applied to a silk screen printing method and other printing methods suitable for etching complicated patterns, pictures, characters, and the like on a glass surface. Therefore, decorative glass with frosted fine patterns, designs, and patterns can be produced in the same number of times without the need for skilled technology, and this has the effect of greatly reducing the manufacturing cost. Therefore, its industrial value is large.
- the glass etching composition of the present invention can be masked using an oil-based pen, oil-based paint, resin paint, acrylic paint, or a seal or adhesive sheet. Therefore, since an individual can easily and safely apply a frosting process to a glass surface of a picture, a pattern, a character, or the like, it has an effect of being able to enjoy it as a hobby.
- the glass etching composition of the present invention does not cause environmental pollution, is extremely safe and easy, and can completely or mask an extremely thin glass, a flat or curved surface, a tubular surface or any other shape of glass surface, which has been difficult by the conventional method. By doing so, one or more parts of the glass surface can be frosted with pictures, patterns, letters, etc. Has an effect.
- the glass etching composition of the present invention has an effect applicable to cleaning and etching of the surface of a cathode ray tube panel or a semiconductor substrate.
- the glass etching composition of the present invention has high weather resistance to temperature, humidity and ultraviolet rays, and can be used repeatedly. Furthermore, since the glass etching composition of the present invention can be separated into a fluoride-containing aqueous phase and a water-miscible organic solvent phase by filtering with a special filter paper, only the deteriorated fluoride-containing aqueous phase is used. It has the effect that it can be discarded and the water-miscible organic solvent phase can be recovered.
- sucrose has an effect of contributing to the stability of the glass etching composition.
- the glass etching is promoted by lowering the interfacial tension to promote the glass etching. This has the effect of promoting uniform adhesion of the composition to the glass surface.
- the glass etching composition is colored by adding a pigment, it is possible to visually enhance the safety and to use it as a guide when disposing of the glass etching composition by diluting with water.
- Dyes are not limited to water-soluble ones, and can be used widely.
- the glass etching composition of the present invention is shielded by a masking method and immersed in the glass etching composition of the present invention, or the glass etching composition of the present invention is applied with a brush, a brush, and a squeegee. Since etching and subsequent cleaning are performed, desired patterns, patterns, and the like can be freely displayed with a simple operation, and this has the effect of making it a high-tech product.
- the glass etching composition is supplied to a tube, a ball-point pen, a felt-tip pen, a marker pen, and a feather.
- glass etching mainly composed of fluoride attached to the glass surface The composition has an effect that the composition can be easily and reliably washed with water.
- a portion of the glass surface that does not require etching is shielded by a masking method, and when etching with the glass etching composition of the present invention, the material of the masking is used.
- the use of a method similar to these, such as the silk screen printing method and other printing methods, enables simple and sophisticated patterns, designs and patterns to be revealed, further improving the industrial value of the product. There is an effect that can be.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002554630A JPWO2002053508A1 (ja) | 2000-12-27 | 2001-12-25 | ガラスエッチング組成物を用いた装飾ガラスの製造法 |
EP01995006A EP1357092A1 (en) | 2000-12-27 | 2001-12-25 | Method for preparing decorative glass using glass etching composition |
US10/465,966 US7276181B2 (en) | 2000-12-27 | 2001-12-25 | Method for preparing decorative glass using glass etching composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000396498 | 2000-12-27 | ||
JP2000-396498 | 2000-12-27 | ||
JP2001-299482 | 2001-09-28 | ||
JP2001299482 | 2001-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002053508A1 true WO2002053508A1 (fr) | 2002-07-11 |
Family
ID=26606759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/011408 WO2002053508A1 (fr) | 2000-12-27 | 2001-12-25 | Procede de preparation de verre decoratif au moyen d'une composition de gravure sur verre |
Country Status (4)
Country | Link |
---|---|
US (1) | US7276181B2 (ja) |
EP (1) | EP1357092A1 (ja) |
JP (1) | JPWO2002053508A1 (ja) |
WO (1) | WO2002053508A1 (ja) |
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KR100491015B1 (ko) * | 2002-10-01 | 2005-05-24 | 박진국 | 유리의 저반사 표면처리를 위한 부식 수용액조성물 |
WO2011137141A1 (en) | 2010-04-30 | 2011-11-03 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
WO2011137144A1 (en) | 2010-04-30 | 2011-11-03 | Corning Incorporated | Anti-glare surface and method of making |
WO2012074811A1 (en) | 2010-11-29 | 2012-06-07 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
WO2012074943A1 (en) | 2010-11-30 | 2012-06-07 | Corning Incorporated | Anti-glare glass sheet having compressive stress equipoise and methods thereof |
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WO2013181007A1 (en) | 2012-05-29 | 2013-12-05 | Corning Incorporated | Method for texturing a glass surface |
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US20060157901A1 (en) * | 2001-08-27 | 2006-07-20 | Sting Free Company | Vibration dampening material and method of making same |
US20060115651A1 (en) * | 2004-11-30 | 2006-06-01 | Guardian Industries Corp. | Painted glass tiles, panels and the like and method for producing painted glass tiles and panels |
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2001
- 2001-12-25 JP JP2002554630A patent/JPWO2002053508A1/ja active Pending
- 2001-12-25 EP EP01995006A patent/EP1357092A1/en not_active Withdrawn
- 2001-12-25 US US10/465,966 patent/US7276181B2/en not_active Expired - Fee Related
- 2001-12-25 WO PCT/JP2001/011408 patent/WO2002053508A1/ja not_active Application Discontinuation
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JPS54127425A (en) * | 1978-03-28 | 1979-10-03 | Toshio Izumi | Glass surface treatment |
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US5281350A (en) * | 1992-08-14 | 1994-01-25 | Tae Hwan Kim | Glass etching composition |
JPH06227842A (ja) * | 1993-02-01 | 1994-08-16 | Nippon Sheet Glass Co Ltd | フロート板ガラス物品の表面スズ除去方法 |
US5804317A (en) * | 1993-05-06 | 1998-09-08 | Saint-Gobain Vitrage International | Process for reinforcing glass objects |
EP0887323A1 (en) * | 1997-06-25 | 1998-12-30 | International Business Machines Corporation | Selective etching of silicate |
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KR100491015B1 (ko) * | 2002-10-01 | 2005-05-24 | 박진국 | 유리의 저반사 표면처리를 위한 부식 수용액조성물 |
US9017566B2 (en) | 2010-04-30 | 2015-04-28 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
WO2011137141A1 (en) | 2010-04-30 | 2011-11-03 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
WO2011137144A1 (en) | 2010-04-30 | 2011-11-03 | Corning Incorporated | Anti-glare surface and method of making |
EP3178796A1 (en) | 2010-04-30 | 2017-06-14 | Corning Incorporated | Glass article comprising anti-glare surface |
US9651720B2 (en) | 2010-04-30 | 2017-05-16 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
US9279912B2 (en) | 2010-04-30 | 2016-03-08 | Corning Incorporated | Anti-glare glass article and display system |
US9085484B2 (en) | 2010-04-30 | 2015-07-21 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
US8992786B2 (en) | 2010-04-30 | 2015-03-31 | Corning Incorporated | Anti-glare surface and method of making |
WO2012074811A1 (en) | 2010-11-29 | 2012-06-07 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
US8778496B2 (en) | 2010-11-30 | 2014-07-15 | Corning Incorporated | Anti-glare glass sheet having compressive stress equipoise and methods thereof |
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US9302933B2 (en) | 2011-04-20 | 2016-04-05 | Corning Incorporated | Method for texturing a glass surface |
WO2013066850A2 (en) | 2011-11-02 | 2013-05-10 | Corning Incorporated | Method for sparkle control and articles thereof |
WO2013181007A1 (en) | 2012-05-29 | 2013-12-05 | Corning Incorporated | Method for texturing a glass surface |
Also Published As
Publication number | Publication date |
---|---|
EP1357092A1 (en) | 2003-10-29 |
US20040055994A1 (en) | 2004-03-25 |
JPWO2002053508A1 (ja) | 2004-04-30 |
US7276181B2 (en) | 2007-10-02 |
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