GB1572032A - Gels comprising silica and an aqueous acid - Google Patents
Gels comprising silica and an aqueous acid Download PDFInfo
- Publication number
- GB1572032A GB1572032A GB375876A GB375876A GB1572032A GB 1572032 A GB1572032 A GB 1572032A GB 375876 A GB375876 A GB 375876A GB 375876 A GB375876 A GB 375876A GB 1572032 A GB1572032 A GB 1572032A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition
- acid
- gel
- silicon dioxide
- sodium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
- A61Q11/02—Preparations for deodorising, bleaching or disinfecting dentures
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/06—Solidifying liquids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
Description
(54) GELS COMPRISING SILICA AND AN AQUEOUS ACID
(71) We, HOECHST UK LIMITED, a British body corporate, of Salisbury Road, Ilounslow, Middlesex, TW4 6JH, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to gels comprising silica and an aqueous acid, to a process for their manufacture, to their use, and to their precursor compositions.
Acids are used industrially for many purposes. including cleaning. for example, heavy goods vehicles. railway carriages. metal and stone facades, and swimming pools, and as pickling agents. They are used in the printing industry, in the textile industry. nd domestically. One of the problems of using an acid is the danger of spillage and splashing, with resulting damage to the material inadvertently contacted with the acid, so to overcome this problem attempts have been made to produce acid gels, which are easier and safer to handle and give better surface adhesion. The gelling agents used previously were organic polymers. but the results obtained have not been satisfactory as the gels were difficult to handle at the high polymer concentrations required to give suitable viscosity, and on storage the gels showed a loss of viscosity.
The present invention is based on the observation that the addition of fumed silicon dioxide to a concentrated aqueous acid gives a thixotropic gel that is stable on storage and is easy to handle.
The present invention accordingly provides a composition having a pH of less than 4 and comprising fumed silicon dioxide and an aqueous acid, the composition being a thixotropic gel or being capable of becoming a thixotropic gel on standing.
Fumed silicon dioxide is a well-known form of silica obtainable from silicon tetrachloride or silicon tetrafluoride in a flame hydrolysis process with oxygen-hydrogen gas, cf. for example. German Patent Specification No. 762 723. It is available commercially, for example. under the Trade Marks Aerosil, Cab-O-Sil and Fluosil, in various grades, for example. Aerosil 200, which has a BET surface area of 200 +25 m2/g and an average primary particle size of 12 millimicrons.
The acid may be a mineral acid. for example, hydrochloric, sulphuric or phosphoric acid, or may be an organic acid. for example, acetic acid.
The pH of the composition is. for example, less than 3. Advantageously the pH of the composition is less than 2, because it has been found, surprisingly, that below this pH, increasing the concentration of the acid results in an increase in viscosity. Very satisfactory results are obtained at pH values below l.
The composition mav further comprise an alkali metal halide eg. sodium chloride. and/or a surfactant. both of which increase the rate of gel formation. The surfactant may be cationic. anionic. or non-ionic. Suitable anionic surfactants are, for example, triethanolamine lauryl sulphate or alkane sulphates and a suitable non-ionic surfactant is nonylphenoxv-polvethoxv ethanol. The presence of a surfactant increases the wetting power of the gel.
The composition of the invention may further comprise one or more substances selected from colouring agents. flavouring agents and abrasives.
The invention also provides a process for the preparation of a composition having a pH of less than 4 and comprising fumed silicon dioxide and an aqueous acid, which comprises admixing fumed silicon dioxide, the acid and, if necessary, water, the amount of silicon dioxide being such that gel formation will occur on standing.
As indicated above, gel formation occurs on standing, and the rate of gel formation can be increased by adding an alkali metal halide and/or a surfactant. It can also be increased bv increasing the temperature at which the composition is allowed to stand. Conversely. the rate of gel formation can be decreased by decreasing the temperature of the composition on standing.
The viscosity of the resulting gel can be varied by varying any one or more of the following: the concentration of the fumed silicon dioxide, the concentration of the acid. the content of surfactants, and the concentration of alkali metal halide. especially sodium chloride which is preferably present in an amount of at least 2.5ago w/w calculated on the composition, advantageously at least 5% w/w. Generally at least 1C/c w/w is used.
The proportions of fumed silicon dioxide and the acid can be varied widely depending, for example, on the acid used, the degree of thixotropy required and the gel strength required. In general below pH 1, to increase the gel strength and thixotropy, the amount of fumed silicon dioxide should be increased.
The amount of fumed silicon dioxide in a composition of the invention may be varied inter alia according to the acid used, for example for HCI gels and acetic gels 15% w/w or less, for phosphoric acid gels 10% w/w or less, for sulphuric acid gels 7% w/w or less.
The invention also provides a process for preparing an acid gel. which comprises mixing fumed silicon dioxide, an acid and water, and allowing the mixture to stand at room temperature or at a temperature above room temperature. As an alternative. or in addition to standing at an elevated temperature. the rate of gel formation may be increased by incorporating in the mixture a surfactant and/or an alkali metal halide. especially sodium chloride.
The invention further provides a process for preparing an acid gel, which comprises mixing fumed silicon dioxide, an acid and water, and allowing the mixture to stand at a temperature below room temperature.
The thixotropic gels of the invention may be thinned before use, for example, by shaking, stirring or sonication. They are stable on storage, and less susceptible to spillage and leakage, have less irritating fumes than the untreated acids and, furthermore, have better adherence to surfaces. Surface wetting is increased in the presence of a surfactant.
The gels of the invention may be used for cleaning a surface or article, for example. heavy goods vehicles and railway carriages. metal and stone facades, floors. and swimming pools.
They may be used domestically for cleaning dentures. Further uses are as pickling agents, and in the textile industry. for example. to produce perforations in the manufacture of broderie Anglaise. All these applications of the gels of the invention are themselves part of the invention.
The invention further provides a container for transport by road. rail. water or air, which contains a gel of the invention.
The following Examples illustrate the invention.
Example I
Conc. HCI 10 % w/w
Aerosil 200 10 % w/w
Water to 100 % Method
Mix lOg Conc. HCI solution with 80 ml water in a non-metallic vessel. Add 10g Aerosil 200 under rigorous stirring and continue stirring for about 2 minutes.
After standing at 50"C for approximately 12 hours or at 220C for approximately 26 hours, a gel forms which can be easily thinned by stirring.
Example 2
Conc. H2SO4 26 % w/w
Aerosil 200 7 % w/w
Water to 100 % Metizod Add 26g Conc. sulphuric acid carefully to 67 ml water under constant stirring.
Incorporate 7 g Aerosil under rigorous mixing and continue mixing for approximately 2 minutes. A firm gel develops rapidly and is easily thinned by stirring.
Example 3
Glacial acetic acid 5 % w/w
Aerosil 200 15 % w/w
Water to 100 % Mediod The same method as for Example 2 is used. A firm gel forms after three days at room temperature.
Example 4
Glacial acetic acid 10 % w/w
Aerosil 200 15 % w/w
Water to 100 %
Method
The same method as for Example 3 is used. A firm gel forms after a few minutes.
Example 5
Denture Cleaving Gel
Conc. HCI 10 % w/w
Aerosil 200 10 % wlw Hostapur SAS 60 5 % w/w
Acid Fuchsin 0.002 % w/w
Spearmint 'flavour' 0.2 % w/w
Propylene glycol 4 % w/w
Water to 100 % * "Hostapur" is a Trade Mark
Method
10 g Aerosil 200 is slurried with 7().8 g of water and homogenised for 2 minutes. 10 g
Conc. HCI is added carefully and mixed well. 5 g Hostapur SAS 6(). 2 mg Acid Fuchsin. 200 mg Spearmint Flavour and 4 g Propylene glycol are added and stirred in gently to avoid foaming.
The gel forms after 24 hours at room temperature.
Alternatively. 10 g Aerosil 200 is slurried with 4 g propvlene glycol for 2 minutes. 2 mg
Acid Fuchsin is dissolved in 46 g water and added to the Aerosil/propylene glycol slurry. 10 g Conc. HCI is then added carefully and mixed well. Finally 5 g Hostapur SAS 60 and 200 mg Spearmint Flavour dissolved in '4.8 g water are added with gentle stirring to avoid foaming.
The gel forms after 24 hours at room temperature.
Example 6
The effects of increasing the concentration of (I) the acid and (I1) sodium chloride in compositions of the invention were investigated as follows:
Formulation
I - Aerosil 200 10% wlw Concentrated hydrochloric acid 0.5: 1.0: 2.0: A.0: 6.0: 8.0;
10.0:12.0; 1.0: 15.0: 16.0: 18.0: w/w
Sodium chloride 0% Purified water to 100%
II - Aerosil 200 10% w/w
Concentrated hydrochloride acid 10% w/w
Sodium chloride 0; 2.5; 5; 10% w/w
Purified water to 100% w/w
Method
The Acrosil was weighed and to it was added the purified water, and the mixture was mixed until smooth. The hydrochloric acid was added carefully and aglin mixed until smooth. The sodium chloride, if appropriate, was then added and the mixture was stirred until this component had dissolved. .3() ,e aliquots of the mixture were placed in petri dishes which were scaled in plastics bags for storage at room temperature. Samples were analysed at five intervals within one week. an unused sample being taken for each test.
IVesl lts Figure 1 of the accompanying drawings shows thit increasing the concentration of the acid increases both the viscosity and the rate of gel formation, nnd ligure 2 shows that sodium chloride has the same effect.
WHAT WE CLAIM IS:
1. A composition comprising fumed silicon dioxide and an aqueous acid and having a pH of less than A. the composition being a thixotropic gel or being capahle of becoming a thixotropic gel on standing.
2. A composition as claimed in claim 1, having a pH of less than 3.
3. A composition as claimed in claim 2. having a pH of less thin 2.
4. A composition as claimed in any one of claims I to 3, which also comprises an alkali metal halide.
5. A composition as claimed in claim 4. wherein the alkali metal halide is sodium chloride.
6. A composition as claimed in claim 5, which comprises at least 2.5% w/w calculated on the composition of sodium chloride.
7. A composition as claimed in claim (. which comprises at least 5'-, w/w of sodium chloride.
8. A composition as claimed in any one of claims I to 7. which also comprises a surfactant.
9. A composition as claimed in claim X. wherein the surfactant is an anionic or non-ionic surfactant.
10. A composition as claimed in claim 9, wherein the surfactant is triethanolamine laurvl sulphate.
I f. A composition as claimed in any one of claims I to 10. wherein the acid is a mineral acid.
12. A composition as claimed in claim 11. wherein the acid is hvdrochloric acid.
13. A composition as claimed in claim 13. which comprises up to 15 w/w of fumed silicon dioxide.
14. A composition as claimed in claim 11. wherein the acid is phosphoric acid.
15. A composition as claimed in claim 12, which comprises up to 10r/; w/w of silicon dioxide.
16. A composition as claimed in claim 11. wherein the acid is sulphuric acid.
17. A composition as claimed in claim 16. which comprises up to 7% w/w of fumed silicon dioxide.
18. A composition as claimed in any one of claims I to 10, wherein the acid is an organic acid.
19. A composition as claimed in claim 18, wherein the acid is acetic acid.
20. A composition as claimed in claim 19, which comprises up to 15 % w/w of fumed silicon dioxide.
21. A composition as claimed in any one of claims 1 to 3(), which further comprises any one or more of the following: coloring agents, flavouring agents, and abrasives.
22. A composition as claimedin claim 1. substantially as described in any one of the
Examples herein.
23. A process for the preparation of a composition as claimed in claim 1. which comprises mixing. in any order and any combination. fumed silicon dioxide. an acid and. if necessary. water, the amount of silicon dioxide being such that gel formation will occur on standing.
24. A process as claimed in claim '3. carried out substantially as described in any one of the Examples herein.
25. A composition as claimed in claim 1. whenever prepared bv a process as claimed in claim '3 or claim 24.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (34)
1. A composition comprising fumed silicon dioxide and an aqueous acid and having a pH of less than A. the composition being a thixotropic gel or being capahle of becoming a thixotropic gel on standing.
2. A composition as claimed in claim 1, having a pH of less than 3.
3. A composition as claimed in claim 2. having a pH of less thin 2.
4. A composition as claimed in any one of claims I to 3, which also comprises an alkali metal halide.
5. A composition as claimed in claim 4. wherein the alkali metal halide is sodium chloride.
6. A composition as claimed in claim 5, which comprises at least 2.5% w/w calculated on the composition of sodium chloride.
7. A composition as claimed in claim (. which comprises at least 5'-, w/w of sodium chloride.
8. A composition as claimed in any one of claims I to 7. which also comprises a surfactant.
9. A composition as claimed in claim X. wherein the surfactant is an anionic or non-ionic surfactant.
10. A composition as claimed in claim 9, wherein the surfactant is triethanolamine laurvl sulphate.
I f. A composition as claimed in any one of claims I to 10. wherein the acid is a mineral acid.
12. A composition as claimed in claim 11. wherein the acid is hvdrochloric acid.
13. A composition as claimed in claim 13. which comprises up to 15 w/w of fumed silicon dioxide.
14. A composition as claimed in claim 11. wherein the acid is phosphoric acid.
15. A composition as claimed in claim 12, which comprises up to 10r/; w/w of silicon dioxide.
16. A composition as claimed in claim 11. wherein the acid is sulphuric acid.
17. A composition as claimed in claim 16. which comprises up to 7% w/w of fumed silicon dioxide.
18. A composition as claimed in any one of claims I to 10, wherein the acid is an organic acid.
19. A composition as claimed in claim 18, wherein the acid is acetic acid.
20. A composition as claimed in claim 19, which comprises up to 15 % w/w of fumed silicon dioxide.
21. A composition as claimed in any one of claims 1 to 3(), which further comprises any one or more of the following: coloring agents, flavouring agents, and abrasives.
22. A composition as claimedin claim 1. substantially as described in any one of the
Examples herein.
23. A process for the preparation of a composition as claimed in claim 1. which comprises mixing. in any order and any combination. fumed silicon dioxide. an acid and. if necessary. water, the amount of silicon dioxide being such that gel formation will occur on standing.
24. A process as claimed in claim '3. carried out substantially as described in any one of the Examples herein.
25. A composition as claimed in claim 1. whenever prepared bv a process as claimed in claim '3 or claim 24.
26. A composition as claimed in any one of claims 1 to 22 or claim 25 in the form of a
thixotropic gel.
27. A process for the preparation of a gel as claimed in claim 26, which comprises allowing a composition as claimed in any one of claims 1 to 22 or claim 25 to stand at room temperature, or at a temperature above or below room temperature.
28. A process as claimed in claim 27, carried out substantially as described in any one of the Examples herein.
29. A thixotropic gel as claimed in claim 26 whenever prepared by I process as claimed in claim 27 or claim 28.
3(). A method of cleaning a surface or article, which comprises applying to the surface or article a gel as claimed in claim 26 or claim 29.
31. A method as claimed in claim 3(), wherein the article is a denture.
32. A method as claimed in claim 3(), wherein the surface or article is I heavy goods vehicle, a railway carriage, a metal or stone facade, a swimming pool or a floor.
33. A process for the production of broderie Anglaise, wherein a gel as claimed in claim 26 or claim 29 is applied to those areas of the material at which it is desired to produce a perforation.
34. A container for transport by road, rail, water or air, which contains a gel as claimed in claim 26 or claim 3'j).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB375876A GB1572032A (en) | 1977-01-31 | 1977-01-31 | Gels comprising silica and an aqueous acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB375876A GB1572032A (en) | 1977-01-31 | 1977-01-31 | Gels comprising silica and an aqueous acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1572032A true GB1572032A (en) | 1980-07-23 |
Family
ID=9764406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB375876A Expired GB1572032A (en) | 1977-01-31 | 1977-01-31 | Gels comprising silica and an aqueous acid |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1572032A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614607A (en) * | 1984-09-26 | 1986-09-30 | The Boeing Company | Non-chromated deoxidizer |
| US4960534A (en) * | 1988-02-01 | 1990-10-02 | Ecc International Limited | Method of thickening an aqueous solution of sulphamic acid |
| EP0407003A1 (en) * | 1989-04-19 | 1991-01-09 | H.A. Milton Holdings Pty. Ltd. | Gelling composition |
| EP0533279A1 (en) * | 1991-09-16 | 1993-03-24 | Dentip International B.V. | Use of a combination of a gel and a solution, both containing an organic acid for cleaning dentures |
| EP0733357A1 (en) * | 1995-03-22 | 1996-09-25 | Dompé S.P.A. | Pharmaceutical formulations in form of thixotropic gel |
| WO1997004061A1 (en) * | 1995-07-16 | 1997-02-06 | Yankee Polish Lüth Gmbh + Co. | Liquid cleaning agent and its use |
| US5663474A (en) * | 1996-03-07 | 1997-09-02 | Alliedsignal Inc. | Alkylation process using hydrogen fluoride-containing alkylation catalysts |
| US5705717A (en) * | 1996-03-07 | 1998-01-06 | Alliedsignal Inc. | Fluorination process using hydrogen fluoride-containing fluorinating agents |
| US6177058B1 (en) | 1996-03-07 | 2001-01-23 | Alliedsignal Inc. | Hydrogen fluoride compositions |
| WO2006013282A1 (en) * | 2004-07-06 | 2006-02-09 | Rhodia Chimie | Method for thickening a liquid medium with surfactant concentration |
| WO2006073896A2 (en) * | 2005-01-07 | 2006-07-13 | The Boc Group, Inc. | Selective surface texturing through the use of random application of thixotropic etching agents |
| AT501567A1 (en) * | 2005-03-10 | 2006-09-15 | Winfried Weiss | Cleaning and impregnating acid stable natural- and artificial stone comprises producing chemical preparation by mixture of acid stable/acid stabilized protective material with acid solution and applying preparation on surface of stone |
| EP2186505A1 (en) * | 2008-11-12 | 2010-05-19 | Hammaslaboratorio Hyvä Hammas Oy | Liquid cleaning agent for removable dental prostheses and equivalent devices |
| US7837890B2 (en) * | 2005-01-11 | 2010-11-23 | Merck Patent Gmbh | Printable medium for the etching of silicon dioxide and silicon nitride layers |
| US7923118B2 (en) * | 2005-08-24 | 2011-04-12 | Lg Display Co., Ltd. | Etching tape and method of fabricating array substrate for liquid crystal display using the same |
-
1977
- 1977-01-31 GB GB375876A patent/GB1572032A/en not_active Expired
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614607A (en) * | 1984-09-26 | 1986-09-30 | The Boeing Company | Non-chromated deoxidizer |
| US4960534A (en) * | 1988-02-01 | 1990-10-02 | Ecc International Limited | Method of thickening an aqueous solution of sulphamic acid |
| EP0407003A1 (en) * | 1989-04-19 | 1991-01-09 | H.A. Milton Holdings Pty. Ltd. | Gelling composition |
| AU622999B2 (en) * | 1989-04-19 | 1992-04-30 | Hamilton Healthscience Pty Ltd | Novel gelling compositions |
| EP0533279A1 (en) * | 1991-09-16 | 1993-03-24 | Dentip International B.V. | Use of a combination of a gel and a solution, both containing an organic acid for cleaning dentures |
| EP0733357A1 (en) * | 1995-03-22 | 1996-09-25 | Dompé S.P.A. | Pharmaceutical formulations in form of thixotropic gel |
| WO1997004061A1 (en) * | 1995-07-16 | 1997-02-06 | Yankee Polish Lüth Gmbh + Co. | Liquid cleaning agent and its use |
| US5877135A (en) * | 1995-07-16 | 1999-03-02 | Yankee Polish Luth Gmbh & Co. | Thixotropic liquid sanitary cleanser and its uses |
| US5705717A (en) * | 1996-03-07 | 1998-01-06 | Alliedsignal Inc. | Fluorination process using hydrogen fluoride-containing fluorinating agents |
| US5663474A (en) * | 1996-03-07 | 1997-09-02 | Alliedsignal Inc. | Alkylation process using hydrogen fluoride-containing alkylation catalysts |
| US6177058B1 (en) | 1996-03-07 | 2001-01-23 | Alliedsignal Inc. | Hydrogen fluoride compositions |
| WO2006013282A1 (en) * | 2004-07-06 | 2006-02-09 | Rhodia Chimie | Method for thickening a liquid medium with surfactant concentration |
| WO2006073896A2 (en) * | 2005-01-07 | 2006-07-13 | The Boc Group, Inc. | Selective surface texturing through the use of random application of thixotropic etching agents |
| WO2006073896A3 (en) * | 2005-01-07 | 2008-01-31 | Boc Group Inc | Selective surface texturing through the use of random application of thixotropic etching agents |
| US7837890B2 (en) * | 2005-01-11 | 2010-11-23 | Merck Patent Gmbh | Printable medium for the etching of silicon dioxide and silicon nitride layers |
| AT501567A1 (en) * | 2005-03-10 | 2006-09-15 | Winfried Weiss | Cleaning and impregnating acid stable natural- and artificial stone comprises producing chemical preparation by mixture of acid stable/acid stabilized protective material with acid solution and applying preparation on surface of stone |
| US7923118B2 (en) * | 2005-08-24 | 2011-04-12 | Lg Display Co., Ltd. | Etching tape and method of fabricating array substrate for liquid crystal display using the same |
| EP2186505A1 (en) * | 2008-11-12 | 2010-05-19 | Hammaslaboratorio Hyvä Hammas Oy | Liquid cleaning agent for removable dental prostheses and equivalent devices |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |