CA2323022A1 - Thixotropic aqueous cleaner - Google Patents
Thixotropic aqueous cleaner Download PDFInfo
- Publication number
- CA2323022A1 CA2323022A1 CA 2323022 CA2323022A CA2323022A1 CA 2323022 A1 CA2323022 A1 CA 2323022A1 CA 2323022 CA2323022 CA 2323022 CA 2323022 A CA2323022 A CA 2323022A CA 2323022 A1 CA2323022 A1 CA 2323022A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- metal
- weight
- nanoparticulate
- acid
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/1246—Silicates, e.g. diatomaceous earth
Abstract
A thixotropic aqueous cleaning composition comprises one or more nanoparticulate inorganic compounds selected from the group consisting of metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates, metal phosphates, and silicates, and may be used as a hand dishwashing detergent, machine dishwashing detergent, bath or toilet cleaner, all-purpose cleaner, laundry detergent, or spray cleaner.
Description
, CA 02323022 2000-10-06 THIXOTROPIC AQUEOUS CLEANER
Field of the Invention The invention relates to a thixotropic aqueous cleaning composition which can be used to clean hard surfaces.
Background of the Invention Products for cleaning in the household sector, such as hand dishwashing detergents, machine dishwashing deter gents, bath and toilet cleaners, all-purpose cleaners, and laundry detergents, for example, are sold in different forms with which specific user-relevant benefits are associated. Tablets, for example, facilitate the dosing and handling of a product. Products in gel form (gels) may be employed with precision on stains, since they adhere longer to the particular surface to be cleaned, while highly liquid products are used to clean large areas and are notable for ease of handling, being substantially easier to mix with water, for dilution purposes, for example, than viscous products or gels.
In various sectors of household cleaning it is desirable from the standpoint of the consumer to use products which permit both precise, concentrated cleaning and also large-area cleaning with or without dilution, and which combine the advantages of a gel with those of a liquid.
Standard commercial cleaning compositions for flushable toilets, known as toilet cleaners, for example, have a relatively high viscosity in the state of rest (zero-shear viscosity), which ensures good adhesion on inclined surfaces, especially vertical surfaces. On the other hand, they have a relatively low viscosity under shear load, so that they may be applied by the user from the bottle with little effort. These rheological properties are achieved by virtue of specific polymeric thickeners such as xanthan gum.
When using conventional polymeric thickeners, however, there are limits on the attainable pseudoplasticity (dependency of viscosity on shear rate) or thixotropy (dependence of viscosity on time). When a sufficiently high zero-shear viscosity or even a yield point (minimum shear stress which must be imposed to cause a substance to flow) is established, liquefication of the product, by shaking, for example, is not possible with an application of force which it is reasonable to expect from the user, whereas the products which are sufficiently liquefiable by a shaking effort which is acceptable to the user possess a zero-shear viscosity which is too low.
Suamnary of the Invention It is an object of the present invention to provide a cleaning composition which in the state of rest is present as a gel with a yield point, which is reversibly liquefiable by user-compatible effort, by shaking, for example, and which after just a short time, a few minutes, for example, forms a gel again.
The invention provides a thixotropic aqueous cleaning composition which comprises one or more nanoparticulate inorganic compounds from the group consisting of metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates, metal phosphates, and silicates.
A particular advantage of the compositions of the invention is their transparency, which - provided no pearlescent agents or the like are included - is not impaired by the nanoparticulate inorganic compounds.
Field of the Invention The invention relates to a thixotropic aqueous cleaning composition which can be used to clean hard surfaces.
Background of the Invention Products for cleaning in the household sector, such as hand dishwashing detergents, machine dishwashing deter gents, bath and toilet cleaners, all-purpose cleaners, and laundry detergents, for example, are sold in different forms with which specific user-relevant benefits are associated. Tablets, for example, facilitate the dosing and handling of a product. Products in gel form (gels) may be employed with precision on stains, since they adhere longer to the particular surface to be cleaned, while highly liquid products are used to clean large areas and are notable for ease of handling, being substantially easier to mix with water, for dilution purposes, for example, than viscous products or gels.
In various sectors of household cleaning it is desirable from the standpoint of the consumer to use products which permit both precise, concentrated cleaning and also large-area cleaning with or without dilution, and which combine the advantages of a gel with those of a liquid.
Standard commercial cleaning compositions for flushable toilets, known as toilet cleaners, for example, have a relatively high viscosity in the state of rest (zero-shear viscosity), which ensures good adhesion on inclined surfaces, especially vertical surfaces. On the other hand, they have a relatively low viscosity under shear load, so that they may be applied by the user from the bottle with little effort. These rheological properties are achieved by virtue of specific polymeric thickeners such as xanthan gum.
When using conventional polymeric thickeners, however, there are limits on the attainable pseudoplasticity (dependency of viscosity on shear rate) or thixotropy (dependence of viscosity on time). When a sufficiently high zero-shear viscosity or even a yield point (minimum shear stress which must be imposed to cause a substance to flow) is established, liquefication of the product, by shaking, for example, is not possible with an application of force which it is reasonable to expect from the user, whereas the products which are sufficiently liquefiable by a shaking effort which is acceptable to the user possess a zero-shear viscosity which is too low.
Suamnary of the Invention It is an object of the present invention to provide a cleaning composition which in the state of rest is present as a gel with a yield point, which is reversibly liquefiable by user-compatible effort, by shaking, for example, and which after just a short time, a few minutes, for example, forms a gel again.
The invention provides a thixotropic aqueous cleaning composition which comprises one or more nanoparticulate inorganic compounds from the group consisting of metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates, metal phosphates, and silicates.
A particular advantage of the compositions of the invention is their transparency, which - provided no pearlescent agents or the like are included - is not impaired by the nanoparticulate inorganic compounds.
. CA 02323022 2000-10-06 Detailed Description of the Invention Nano~articulate compounds The amount of one or more nanoparticulate inorganic compounds from the group consisting of the metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates, metal phosphates, and silicates, is usually from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 8% by weight, with particular preference from 2 to 6% by weight, and with very great preference from 3 to 5% by weight, for example, 4% by weight.
The average particle size of the nanoparticulate compounds is usually from 1 to 200 nm, preferably from 5 to 100 nm, in particular from 10 to 50 nm, the figure relating to the particle diameter in the lengthwise direction, i.e., in the direction of greatest extent of the particles.
Examples of suitable nanoparticulate oxides are magnesium oxide, aluminum oxide (A1203), titanium dioxide, zirconium dioxide, zinc oxide, and silicon dioxide. A suitable nanoparticulate oxide hydrate is, for example, aluminum oxide hydrate (boehmite), and examples of suitable nanoparticulate hydroxides are calcium hydroxide and aluminum hydroxide. Examples of suitable nanoparticulate silicates are magnesium silicate and aluminosilicates such as zeolites.
Nanoparticulate oxides, oxides hydrates or hydroxides may be prepared by known methods, e.g., in accordance with EP-A-0 711 217 (Nanophase Technologies Corp.). Very finely divided oxide hydrates and hydroxides are also available through hydrolysis of organometallic compounds.
The average particle size of the nanoparticulate compounds is usually from 1 to 200 nm, preferably from 5 to 100 nm, in particular from 10 to 50 nm, the figure relating to the particle diameter in the lengthwise direction, i.e., in the direction of greatest extent of the particles.
Examples of suitable nanoparticulate oxides are magnesium oxide, aluminum oxide (A1203), titanium dioxide, zirconium dioxide, zinc oxide, and silicon dioxide. A suitable nanoparticulate oxide hydrate is, for example, aluminum oxide hydrate (boehmite), and examples of suitable nanoparticulate hydroxides are calcium hydroxide and aluminum hydroxide. Examples of suitable nanoparticulate silicates are magnesium silicate and aluminosilicates such as zeolites.
Nanoparticulate oxides, oxides hydrates or hydroxides may be prepared by known methods, e.g., in accordance with EP-A-0 711 217 (Nanophase Technologies Corp.). Very finely divided oxide hydrates and hydroxides are also available through hydrolysis of organometallic compounds.
Under the trade-mark NanoTek~, the company Nanophase Technologies Corp. markets the nanoparticulate oxides NanoTek~ Aluminum Oxide (average particle size 37 nm), - NanoTek~ Antimony Tin Oxide, NanoTek~ Barium Titanate, NanoTek~ Bari um S Iron ti um Ti tana te, NanoTek~ Ceri um Oxi de (average particle size 11 mm), NanoTek~ Copper Oxide, NanoTek~ Indium Oxide, NanoTek~ Indium Tin Oxide (average particle size 14 nm), NanoTek~ Iron Oxide (average particle size 26 nm) , NanoTek~ Iron Oxide, Black, NanoTek~
Silicon Dioxide, NanoTek~ Tin Oxide, NanoTekO Ti tanium Dioxide (average particle size 34 nm), NanoTek~ Yttrium Oxide and NanoTek~ Zinc Oxide (average particle size 36 nm), and NanoTek~ Barium Oxide, Nanotek~ Calcium Oxide, NanoTek~ Chromium Oxide, NanoTek~ Magnesium Oxide, NanoTek~ Manganese Oxide, NanoTek~ Molybdenum Oxide, Nanotek~ Neodymium Oxide, NanoTek~ Strontium Oxide and NanoTek~ Strontium Titanate, and also the nanoparticulate silicate NanoTek~ Zirconium Silicate. Suitable silicates are avai lable under the trade-mark Optigel~ from Siid-Chemie AG or Laponite~
from Laporte Ltd.
Preferred silicates are the sheet silicates (phyllosilicates), especially bentonites (containing as main minerals smectites, and especially montmorillonite), montmorillonites (A1z [ (OH) 2/Si401o]
nH20 or A1203 ~ 4Si02 ~ H20 ~ nHzO, clay mineral belonging to the dioctahedral (mica) smectites), kaolinite (Al2[(OH)4/Si205]
or A1203 ~ 2Si02 ~ 2H20, triclinic two-sheet clay mineral (1 : 1 phyllosilicate)), talc (hydrated magnesium silicate of composition Mg3 [ (OH) z/Si401o] or 3Mg0~4Si02~Hz0) and, with particular preference, hec-torite (M+o.a (Mga.~Lio.3) [Si4W o (OH) a] , M+ usually - Na+, monoclinic clay mineral belonging to the smectites and similar to montmorillonite).
Silicon Dioxide, NanoTek~ Tin Oxide, NanoTekO Ti tanium Dioxide (average particle size 34 nm), NanoTek~ Yttrium Oxide and NanoTek~ Zinc Oxide (average particle size 36 nm), and NanoTek~ Barium Oxide, Nanotek~ Calcium Oxide, NanoTek~ Chromium Oxide, NanoTek~ Magnesium Oxide, NanoTek~ Manganese Oxide, NanoTek~ Molybdenum Oxide, Nanotek~ Neodymium Oxide, NanoTek~ Strontium Oxide and NanoTek~ Strontium Titanate, and also the nanoparticulate silicate NanoTek~ Zirconium Silicate. Suitable silicates are avai lable under the trade-mark Optigel~ from Siid-Chemie AG or Laponite~
from Laporte Ltd.
Preferred silicates are the sheet silicates (phyllosilicates), especially bentonites (containing as main minerals smectites, and especially montmorillonite), montmorillonites (A1z [ (OH) 2/Si401o]
nH20 or A1203 ~ 4Si02 ~ H20 ~ nHzO, clay mineral belonging to the dioctahedral (mica) smectites), kaolinite (Al2[(OH)4/Si205]
or A1203 ~ 2Si02 ~ 2H20, triclinic two-sheet clay mineral (1 : 1 phyllosilicate)), talc (hydrated magnesium silicate of composition Mg3 [ (OH) z/Si401o] or 3Mg0~4Si02~Hz0) and, with particular preference, hec-torite (M+o.a (Mga.~Lio.3) [Si4W o (OH) a] , M+ usually - Na+, monoclinic clay mineral belonging to the smectites and similar to montmorillonite).
A preferred carbonate is hydrotalcite (international nonproprietary name for dialuminum hexamagnesium carbonate hexadecahydroxide tetrahydrate, Al2Mgs (OH) isC03' 4Hz0) .
Particular preference is given to nanoparticulate boehmite (A10(OH), aluminum oxide hydrate), which is available, for example, under the trade-marks Disperal~
Sol P3 and Di speral ~ Sol P2 from the company Condea .
In one particular embodiment of the invention, nanoparticulate inorganic compounds having a specific surface area of more than 200 m2/g are used. One preferred such nanoparticulate compound is magnesium silicate of the sheet silicate type having a specific surface area of from 200 to 500 m2/g, in particular from 300 to 400 mz/g.
This material is available inexpensively in large amounts. The product is available under the trade-marks Optigel~ SH (Siid-Chemie AG) and Laponite~ XLG (Laporte Ltd.).
Surface modification In another particular embodiment of the invention, the nanoparticulate inorganic compounds may have been treated with one or more surface modifiers.
Suitable surface modifiers for the nanoparticles are all monobasic and polybasic carboxylic acids having 2 to 8 carbon atoms, examples thus being acetic acid, propionic acid, oxalic acid, glutaric acid, malefic acid, succinic acid, phthalic acid, adipic acid, and suberic acid.
Preferred candidates are the hydroxy carboxylic acids and fruit acids such as glycolic acid, lactic acid, citric acid, malic acid, tartaric acid, and gluconic acid, for example. Particular preference as carboxylic acid is given to the use of a hydroxy carboxylic acid from the group consisting of lactic acid, citric acid, malic acid, and tartaric acid.
The inorganic nanoparticles are preferably surface-s modified by treatment with an aqueous solution of a carboxylic or hydroxy carboxylic acid, by treating the nanoparticles with a solution of from 0.05 to 0.5 mol of the carboxylic acid per mole of the nanoparticulate inorganic compound. This treatment preferably takes place over a period of from 1 to 24 hours at a temperature of at least 20°C, more preferably at the boiling point of water under atmospheric pressure (100°C). If pressure is applied, the treatment may also take place at temperatures above 100°C in a correspondingly shorter time.
The treatment with the carboxylic acids or hydroxy carboxylic acids modifies the surface of the nanoparticles. It is assumed that the carboxylic or hydroxy carboxylic acids are attached by ester linkages to the surface of the nanoparticles.
The surface-modified nanoparticles are preferably isolated from the reaction mixture by dewatering. For this purpose, the dispersion is preferably subjected to freeze drying. In this procedure the solvent is removed by sublimation at low temperature under a high vacuum.
Inorganic nanoparticles modified by this process contain between 1 and 30~s by weight, preferably between 5 and 20°s by weight, of the organic surface modifier, based on the overall weight of the surface-modified inorganic nanoparticles.
For surface modification of the nanoparticles it is also possible to use functional silanes of the type (OR) 4_nSiRn (R are organic radicals containing functional groups such as hydroxyl, carboxyl, ester, amine, epoxy etc.), quaternary ammonium compounds, or amino acids. Depending on the polarity of the modifiers, the above-described modification is conducted in water or in organic solvents (alcohols, ethers, ketones, hydrocarbons, etc.), the reaction conditions being selected in analogy to those in water. Sheet silicates such as hectorites, for example, may also be subjected to ion exchange, with rations such as quaternary ammonium compounds, for example, being incorporated between the sheets of the material. Examples of further suitable surface modifiers are gelatins, starch, dextrin, dextran, pectin, gum arabic, casein, gums, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidone, polyvinyl butyrals, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, or else emulsifiers such as fatty alcohol polyglycol ethers, fatty alcohol polyglycosides, fatty arid alkanolamides, glycerol esters, sorbitan esters or alkoxylated esters and derivatives thereof, for example.
The composition of the invention may be formulated alternatively to be acidic, neutral, or alkaline.
Particularly suitable acids are formic acid, acetic acid, citric acid, amidosulfonic acid, and the mineral acids hydrochloric, sulfuric, and nitric acid, and mixtures thereof. Suitable bases are alkali metal hydroxide solutions, ammonia, and amines.
In an acidic embodiment the pH is preferably from 1 to 4, in particular from 1.5 to 3.5.
Particular preference is given to nanoparticulate boehmite (A10(OH), aluminum oxide hydrate), which is available, for example, under the trade-marks Disperal~
Sol P3 and Di speral ~ Sol P2 from the company Condea .
In one particular embodiment of the invention, nanoparticulate inorganic compounds having a specific surface area of more than 200 m2/g are used. One preferred such nanoparticulate compound is magnesium silicate of the sheet silicate type having a specific surface area of from 200 to 500 m2/g, in particular from 300 to 400 mz/g.
This material is available inexpensively in large amounts. The product is available under the trade-marks Optigel~ SH (Siid-Chemie AG) and Laponite~ XLG (Laporte Ltd.).
Surface modification In another particular embodiment of the invention, the nanoparticulate inorganic compounds may have been treated with one or more surface modifiers.
Suitable surface modifiers for the nanoparticles are all monobasic and polybasic carboxylic acids having 2 to 8 carbon atoms, examples thus being acetic acid, propionic acid, oxalic acid, glutaric acid, malefic acid, succinic acid, phthalic acid, adipic acid, and suberic acid.
Preferred candidates are the hydroxy carboxylic acids and fruit acids such as glycolic acid, lactic acid, citric acid, malic acid, tartaric acid, and gluconic acid, for example. Particular preference as carboxylic acid is given to the use of a hydroxy carboxylic acid from the group consisting of lactic acid, citric acid, malic acid, and tartaric acid.
The inorganic nanoparticles are preferably surface-s modified by treatment with an aqueous solution of a carboxylic or hydroxy carboxylic acid, by treating the nanoparticles with a solution of from 0.05 to 0.5 mol of the carboxylic acid per mole of the nanoparticulate inorganic compound. This treatment preferably takes place over a period of from 1 to 24 hours at a temperature of at least 20°C, more preferably at the boiling point of water under atmospheric pressure (100°C). If pressure is applied, the treatment may also take place at temperatures above 100°C in a correspondingly shorter time.
The treatment with the carboxylic acids or hydroxy carboxylic acids modifies the surface of the nanoparticles. It is assumed that the carboxylic or hydroxy carboxylic acids are attached by ester linkages to the surface of the nanoparticles.
The surface-modified nanoparticles are preferably isolated from the reaction mixture by dewatering. For this purpose, the dispersion is preferably subjected to freeze drying. In this procedure the solvent is removed by sublimation at low temperature under a high vacuum.
Inorganic nanoparticles modified by this process contain between 1 and 30~s by weight, preferably between 5 and 20°s by weight, of the organic surface modifier, based on the overall weight of the surface-modified inorganic nanoparticles.
For surface modification of the nanoparticles it is also possible to use functional silanes of the type (OR) 4_nSiRn (R are organic radicals containing functional groups such as hydroxyl, carboxyl, ester, amine, epoxy etc.), quaternary ammonium compounds, or amino acids. Depending on the polarity of the modifiers, the above-described modification is conducted in water or in organic solvents (alcohols, ethers, ketones, hydrocarbons, etc.), the reaction conditions being selected in analogy to those in water. Sheet silicates such as hectorites, for example, may also be subjected to ion exchange, with rations such as quaternary ammonium compounds, for example, being incorporated between the sheets of the material. Examples of further suitable surface modifiers are gelatins, starch, dextrin, dextran, pectin, gum arabic, casein, gums, polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidone, polyvinyl butyrals, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, or else emulsifiers such as fatty alcohol polyglycol ethers, fatty alcohol polyglycosides, fatty arid alkanolamides, glycerol esters, sorbitan esters or alkoxylated esters and derivatives thereof, for example.
The composition of the invention may be formulated alternatively to be acidic, neutral, or alkaline.
Particularly suitable acids are formic acid, acetic acid, citric acid, amidosulfonic acid, and the mineral acids hydrochloric, sulfuric, and nitric acid, and mixtures thereof. Suitable bases are alkali metal hydroxide solutions, ammonia, and amines.
In an acidic embodiment the pH is preferably from 1 to 4, in particular from 1.5 to 3.5.
Surfactants The composition of the invention may comprise one or more nonionic, anionic, amphoteric, and/or cationic surfactants.
Preferably, the composition of the invention comprises one or more nonionic surfactants, examples being alkyl polyglycosides and/or alkyl polyglycol ethers, or anionic surfactants, examples being alkyl sulfates, alkyl ether sulfates, alkylsulfonates and/or alkyl-benzenesulfonates, especially one or more nonionic and anionic surfactants.
Other incrredients Depending on the configuration of the composition of the invention, it may comprise one or more other ingredients customary for the particular intended use of the composition, these ingredients being in particular from the group consisting of solvents (e. g., lower alcohols such as ethanol), electrolyte salts (e. g., NaCl, aluminum chlorohydrate), dyes, and fragrances.
The compositions of the invention are sprayable, both using a spray pump and as an aerosol. The invention therefore also provides for the use of the composition of the invention as a spray cleaner.
The compositions of the invention are suitable for use as hand dishwashing detergents, machine dishwashing detergents, bath and toilet cleaners, all-purpose cleaners, and laundry detergents. The invention therefore also provides for the use of the composition of the invention as a hand dishwashing detergent, machine dishwashing detergent, bath or toilet cleaner, all-purpose cleaner, or laundry detergent.
Preferably, the composition of the invention comprises one or more nonionic surfactants, examples being alkyl polyglycosides and/or alkyl polyglycol ethers, or anionic surfactants, examples being alkyl sulfates, alkyl ether sulfates, alkylsulfonates and/or alkyl-benzenesulfonates, especially one or more nonionic and anionic surfactants.
Other incrredients Depending on the configuration of the composition of the invention, it may comprise one or more other ingredients customary for the particular intended use of the composition, these ingredients being in particular from the group consisting of solvents (e. g., lower alcohols such as ethanol), electrolyte salts (e. g., NaCl, aluminum chlorohydrate), dyes, and fragrances.
The compositions of the invention are sprayable, both using a spray pump and as an aerosol. The invention therefore also provides for the use of the composition of the invention as a spray cleaner.
The compositions of the invention are suitable for use as hand dishwashing detergents, machine dishwashing detergents, bath and toilet cleaners, all-purpose cleaners, and laundry detergents. The invention therefore also provides for the use of the composition of the invention as a hand dishwashing detergent, machine dishwashing detergent, bath or toilet cleaner, all-purpose cleaner, or laundry detergent.
The compositions of the invention may be prepared by combining the ingredients, with the use of ultrasound if desired.
Examples The compositions El to E17 of the invention were prepared. Tables 1 to 3 show their compositions in % by weight and usually also their pH directly after prepara-tion and one day after preparation.
Prior to final pH adjustment, the compositions El to Ell were adjusted initially to a pH of from about 11 to 11.5 using an aqueous NaOH solution with a concentration of 0.5 mol/1.
The resulting compositions were transparent gels which were both sprayable and liquefiable by shaking, and which in the state of rest reverted to a gel.
Examples The compositions El to E17 of the invention were prepared. Tables 1 to 3 show their compositions in % by weight and usually also their pH directly after prepara-tion and one day after preparation.
Prior to final pH adjustment, the compositions El to Ell were adjusted initially to a pH of from about 11 to 11.5 using an aqueous NaOH solution with a concentration of 0.5 mol/1.
The resulting compositions were transparent gels which were both sprayable and liquefiable by shaking, and which in the state of rest reverted to a gel.
Table 1 Composition E1 E2 E3 E4 E5 E6 Disperal~ Sol P3~a~5 5 3 4 4 4 Disperal~ Sol P2~b~- _ _ _ _ _ HCI - - 1.8 - - -Formic acid 1.8 1.8 1.8 1.8 - 0.8 Citric acid - 3.9 - - - -Amidosulfonic acid - - - - 1.8 1.8 NaCI - - - - - 0.0175~9~
ACH solution (50% - - - - - _ AS)~~~
APG~ 220 UP~d~ - _ _ _ _ _ Texapon~ LS 35~8~ - - - - - -Ethanol (96%) - - - - - -Perfume - - - - - _ Water, fully deionizedad ad ad ad 100 ad ad 100 pH after preparation1.4 2.1 2.6 2.8 1.6 1.4 pH one day later - - - 3.2 2.4 1.9 ~a~ nanoparticulate boehmite powder (Condea) ~b~ nanoparticulate boehmite powder (Condea) ~°~ 50% strength by weight aqueous solution of aluminum chlorohydrate (ACH) ~d~ Cs-~o alkyl 1.5-glucoside, 63% by weight, aqueous (Cognis Deutschland GmbH) ~e~ C12-14 fatty alcohol sulfate sodium salt, 35% by weight, aqueous (Cognis Deutsch.Iand GmbH) ~f~ surface-modified with lactic acid ~g~ used in the form of an aqueous NaCl solution with a concentration of 0.02 mol/1 Table 2 Composition E7 E8 E9 E10 E11 E12 Dispera~ So! P3~a~4 3 3 4 4 4 Disperal~ Sol P2tbt- - - _ _ _ HCI - - - _ _ _ Formic acid - 1.0 1.0 1.2 1.4 -Citric acid - - - - _ _ Amidosulfonic acid1.8 1.0 1.0 1.0 1.1 1.2 NaCI 1 - - - - _ ACH solution (50% - 5 10 - - -AS)~~
APG~ 220 UP~d~ - - - 1 1 1 Texapon~ LS 35~Q~ - - - - - _ Ethanol (96%) - - - 2 2 2 Perfume - - - 0.42 0.42 0.42 Water, fully deionizedad 100 ad ad ad ad 100 ad pH after preparation 1.3 2.2 2.0 1.9 1.8 pH one day later 2.2 3.0 3.4 2.7 2.7 See Table 1 Table 3 Composition E13 E14 E15 E16 E17 Disperalh' So! P3ta~4 - - - -Disperal~ So! P2~b~- 3 4 4 4 HCI - - - - -Formic acid - 1.76 3.85 1.2 1.0 Citric acid - 3.85 - - -Amidosulfonic acid 1.4 - 1.76 1 0.25 NaCI - - - - -ACH solution (50% - - - - -AS)t~~
APG~ 220 UP~d~ 1 1 - 1 1 Texapon~ LS 35~8~ - 2.2 - - -Ethanol (96%) 2 2 2 2 2 Perfume 0.42 0.42 0.42 0.42 0.42 Water, fully deionizedad 100 ad 100 ad 100 ad 100 ad 100 pH after preparation- 2.2 1.3 1.5 2.0 pH one day later - - 1.8 2.0 2.5 see Table 1 The compositions El to E11 and E14 to E17 were tested as WC cleaners. Applied either via a squirter valve from a container, or sprayed, they adhered to the surfaces for considerably longer than conventional WC cleaners.
Because of the long time of action, the cleaning performance was considerably higher than that of conventional WC cleaners.
Rheological properties The rheological properties of the compositions E12 and E13 were investigated using the Paar Physica UDS 2000 shear-rate-controlled rotational rheometer (geometry:
cone/plate with 5 cm diameter and an angle of 1°) at 25°C.
ACH solution (50% - - - - - _ AS)~~~
APG~ 220 UP~d~ - _ _ _ _ _ Texapon~ LS 35~8~ - - - - - -Ethanol (96%) - - - - - -Perfume - - - - - _ Water, fully deionizedad ad ad ad 100 ad ad 100 pH after preparation1.4 2.1 2.6 2.8 1.6 1.4 pH one day later - - - 3.2 2.4 1.9 ~a~ nanoparticulate boehmite powder (Condea) ~b~ nanoparticulate boehmite powder (Condea) ~°~ 50% strength by weight aqueous solution of aluminum chlorohydrate (ACH) ~d~ Cs-~o alkyl 1.5-glucoside, 63% by weight, aqueous (Cognis Deutschland GmbH) ~e~ C12-14 fatty alcohol sulfate sodium salt, 35% by weight, aqueous (Cognis Deutsch.Iand GmbH) ~f~ surface-modified with lactic acid ~g~ used in the form of an aqueous NaCl solution with a concentration of 0.02 mol/1 Table 2 Composition E7 E8 E9 E10 E11 E12 Dispera~ So! P3~a~4 3 3 4 4 4 Disperal~ Sol P2tbt- - - _ _ _ HCI - - - _ _ _ Formic acid - 1.0 1.0 1.2 1.4 -Citric acid - - - - _ _ Amidosulfonic acid1.8 1.0 1.0 1.0 1.1 1.2 NaCI 1 - - - - _ ACH solution (50% - 5 10 - - -AS)~~
APG~ 220 UP~d~ - - - 1 1 1 Texapon~ LS 35~Q~ - - - - - _ Ethanol (96%) - - - 2 2 2 Perfume - - - 0.42 0.42 0.42 Water, fully deionizedad 100 ad ad ad ad 100 ad pH after preparation 1.3 2.2 2.0 1.9 1.8 pH one day later 2.2 3.0 3.4 2.7 2.7 See Table 1 Table 3 Composition E13 E14 E15 E16 E17 Disperalh' So! P3ta~4 - - - -Disperal~ So! P2~b~- 3 4 4 4 HCI - - - - -Formic acid - 1.76 3.85 1.2 1.0 Citric acid - 3.85 - - -Amidosulfonic acid 1.4 - 1.76 1 0.25 NaCI - - - - -ACH solution (50% - - - - -AS)t~~
APG~ 220 UP~d~ 1 1 - 1 1 Texapon~ LS 35~8~ - 2.2 - - -Ethanol (96%) 2 2 2 2 2 Perfume 0.42 0.42 0.42 0.42 0.42 Water, fully deionizedad 100 ad 100 ad 100 ad 100 ad 100 pH after preparation- 2.2 1.3 1.5 2.0 pH one day later - - 1.8 2.0 2.5 see Table 1 The compositions El to E11 and E14 to E17 were tested as WC cleaners. Applied either via a squirter valve from a container, or sprayed, they adhered to the surfaces for considerably longer than conventional WC cleaners.
Because of the long time of action, the cleaning performance was considerably higher than that of conventional WC cleaners.
Rheological properties The rheological properties of the compositions E12 and E13 were investigated using the Paar Physica UDS 2000 shear-rate-controlled rotational rheometer (geometry:
cone/plate with 5 cm diameter and an angle of 1°) at 25°C.
The parameters measured were the modulus of elasticity or storage modulus G', the modulus of viscosity or loss modulus G", the yield point ifl and the zero-shear viscosity r~o (Table 4) and also the viscosity r~ as a function of the shear rate (Table 5), the viscosity being determined at shear rate 1; 10, 30, 50 and 100 s-1 in the order of both increasing shear rate (figures in the columns headed "up") and decreasing shear rate (figures in the columns headed "down").
Table 4 ..
G G yxr ifi X10 (Pa) (Pa) E12 18 7 0.16 2.88 1140 E13 115 13 0.1 11.5 1160 Table 5 Viscosity r) (Pa s) at shear rate in s-1 s-1 s-1 s-1 s-1 s-1 up down up down up down up down up down E12 4.5 2 0.7 0.4 0.29 0.2 0.19 0.15 0.11 0.1 E13 7 3 0.9 0.4 0.3 0.18 0.19 0.135 0.11 0.098 Furthermore, the viscosity was monitored both with continuous increase and decrease of the shear rate (i.e., rate gradient) and, after 2.5 minutes of initial shearing at a shear rate of 10, 20, 30, 50, and 100 s-1, respectively, during subsequent relaxation at a shear rate of only 10-4 s-1.
Brief Description of the Drawings Figure 1 shows the log-log viscosity/shear rate diagram for E12 (symbol for points measured: triangle) and E13 (symbol for points measured: solid rhombus) with two curves in each case - one measured for increasing shear rate (right-facing arrows top and bottom) and once for decreasing shear rate (left-facing arrows, top).
F~crure 2 gives the viscosity/time diagram for E12, with five curves for the five different initial shear rates, viscosity being plotted logarithmically.
Figure 3 gives the viscosity/time diagram for E13, with likewise five curves for the five different initial shear rates, viscosity again being plotted logarithmically.
The rheological investigations forcefully demonstrate the pronounced pseudoplasticity (Table 5; gradient of the curves in Figure 1) and thixotropy of E12 and E13 (difference in the "up" and "down" figures in Table 5;
hysteresis of the curves in Figure 1; Figures 2 and 3).
The higher amidosulfonic acid content in E13 in comparison to E12 results in higher viscosities and also in an even greater pseudoplasticity and, in particular, thixotropy, whereas the zero-shear viscosity is virtually identical.
Figures 2 and 3 illustrate the fact that E12 and E13 may be liquefied by a shear load, such as by vigorous shaking, remain liquid for about 2.5 minutes after the shear load has ceased, and subsequently gel again (form a gel) with a very sharp increase in viscosity.
Table 4 ..
G G yxr ifi X10 (Pa) (Pa) E12 18 7 0.16 2.88 1140 E13 115 13 0.1 11.5 1160 Table 5 Viscosity r) (Pa s) at shear rate in s-1 s-1 s-1 s-1 s-1 s-1 up down up down up down up down up down E12 4.5 2 0.7 0.4 0.29 0.2 0.19 0.15 0.11 0.1 E13 7 3 0.9 0.4 0.3 0.18 0.19 0.135 0.11 0.098 Furthermore, the viscosity was monitored both with continuous increase and decrease of the shear rate (i.e., rate gradient) and, after 2.5 minutes of initial shearing at a shear rate of 10, 20, 30, 50, and 100 s-1, respectively, during subsequent relaxation at a shear rate of only 10-4 s-1.
Brief Description of the Drawings Figure 1 shows the log-log viscosity/shear rate diagram for E12 (symbol for points measured: triangle) and E13 (symbol for points measured: solid rhombus) with two curves in each case - one measured for increasing shear rate (right-facing arrows top and bottom) and once for decreasing shear rate (left-facing arrows, top).
F~crure 2 gives the viscosity/time diagram for E12, with five curves for the five different initial shear rates, viscosity being plotted logarithmically.
Figure 3 gives the viscosity/time diagram for E13, with likewise five curves for the five different initial shear rates, viscosity again being plotted logarithmically.
The rheological investigations forcefully demonstrate the pronounced pseudoplasticity (Table 5; gradient of the curves in Figure 1) and thixotropy of E12 and E13 (difference in the "up" and "down" figures in Table 5;
hysteresis of the curves in Figure 1; Figures 2 and 3).
The higher amidosulfonic acid content in E13 in comparison to E12 results in higher viscosities and also in an even greater pseudoplasticity and, in particular, thixotropy, whereas the zero-shear viscosity is virtually identical.
Figures 2 and 3 illustrate the fact that E12 and E13 may be liquefied by a shear load, such as by vigorous shaking, remain liquid for about 2.5 minutes after the shear load has ceased, and subsequently gel again (form a gel) with a very sharp increase in viscosity.
Claims (16)
1. A thixotropic aqueous cleaning composition, which comprises one or more nanoparticulate inorganic compounds selected from the group consisting of metal oxides, metal oxide hydrates, metal hydroxides, metal carbonates, metal phosphates, and silicates.
2. The composition as claimed in claim 1, wherein the average particle size of the nanoparticulate compounds is from 1 to 200 nm.
3. The composition as claimed in claim 2, wherein the particle size is from 5 to 100 nm.
4. The composition as claimed in claim 2, wherein the particle size is from 10 to 50 nm.
5. The composition as claimed in any of claims 1 and 4, comprising one or more nanoparticulate compounds in an amount of from 0.1 to 20% by weight.
6. The composition as claimed in claim 5, wherein the amount is from 0.5 to 10% by weight.
7. The composition as claimed in claim 5, wherein the amount is from 1 to 8% by weight.
8. The composition as claimed in claim 5, wherein the amount is from 2 to 6% by weight.
9. The composition as claimed in claim 5, wherein the amount is from 3 to 5% by weight.
10. The composition as claimed in any of claims 1 to 9, comprising boehmite.
11. The composition as claimed in any of claims 1 to 10, comprising one or more acids or bases.
12. The composition as claimed in any of claims 1 to 11, comprising one or more surfactants.
13. The composition as claimed in any of claims 1 to 12, comprising one or more nonionic or anionic surfactants.
14. The use of a composition as claimed in any of composition claims 1 to 13 as a hand dishwashing detergent, machine dishwashing detergent, bath or toilet cleaner, all-purpose cleaner, or laundry detergent.
15. The use of a composition as claimed in any one of composition claims 1 to 13 as a spray cleaner.
16
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999148859 DE19948859A1 (en) | 1999-10-08 | 1999-10-08 | Thixotropic aqueous detergent |
| DE19948859.2 | 1999-10-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2323022A1 true CA2323022A1 (en) | 2001-04-08 |
Family
ID=7925184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2323022 Abandoned CA2323022A1 (en) | 1999-10-08 | 2000-10-06 | Thixotropic aqueous cleaner |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU7909900A (en) |
| CA (1) | CA2323022A1 (en) |
| DE (1) | DE19948859A1 (en) |
| WO (1) | WO2001027236A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846512B2 (en) | 2001-01-30 | 2005-01-25 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US7977296B2 (en) | 2006-12-15 | 2011-07-12 | Colgate-Palmolive Company | Liquid detergent composition comprising an acrylic polymer/viscosity control agent mixture |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10021726A1 (en) * | 2000-05-04 | 2001-11-15 | Henkel Kgaa | Nanoparticles are used for loosening dirt and/or reducing resoiling of hard surface or textile, especially in a textile finish, washing, pretreatment or after-treatment agent |
| US7267728B2 (en) | 2001-01-30 | 2007-09-11 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US20020028288A1 (en) * | 2000-06-14 | 2002-03-07 | The Procter & Gamble Company | Long lasting coatings for modifying hard surfaces and processes for applying the same |
| US6562142B2 (en) | 2001-01-30 | 2003-05-13 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| DE10028974A1 (en) * | 2000-06-16 | 2002-01-03 | Henkel Kgaa | Thixotropic oral and dental care products |
| US6635613B1 (en) | 2000-09-19 | 2003-10-21 | Trojan Technologies, Inc. | Urea phosphate cleaning formulation and method of cleaning a surface |
| FR2814064B1 (en) * | 2000-09-20 | 2005-06-17 | Oreal | WASHING COMPOSITION COMPRISING ALUMINUM OXIDE PARTICLES, AT LEAST ONE CONDITIONING AGENT AND AT LEAST ONE DETERGENT SURFACTANT |
| FR2814065B1 (en) * | 2000-09-20 | 2005-06-17 | Oreal | WASHING COMPOSITION COMPRISING ALUMINUM OXIDE PARTICLES, AT LEAST ONE ANIONIC SURFACTANT AND AT LEAST ONE AMPHOTERIC OR NON-IONIC SURFACTANT |
| DE10061897A1 (en) | 2000-12-12 | 2002-06-13 | Clariant Gmbh | Washing or cleaning composition, useful for fabrics or hard surfaces, contains microdisperse, hydrophilic silicate particles that improve soil removal and prevent resoiling |
| AU2001297751A1 (en) | 2001-01-30 | 2002-10-03 | The Procter And Gamble Company | Coatings for modifying hard surfaces and processes for applying the same |
| EP1460125A1 (en) * | 2003-03-18 | 2004-09-22 | Unilever Plc | Abrasive hard surface cleaning compositions |
| EP2004788A2 (en) * | 2006-03-21 | 2008-12-24 | The Procter and Gamble Company | Nano-fluids as cleaning compositions for cleaning soiled surfaces, a method for formulation and use |
| EP2045315A1 (en) * | 2007-09-24 | 2009-04-08 | The Procter and Gamble Company | Dishwashing method |
| CN103502417B (en) * | 2011-04-25 | 2015-10-21 | 荷兰联合利华有限公司 | Hard surface treatment composition |
| DE102014206068A1 (en) | 2014-03-31 | 2015-10-01 | Henkel Ag & Co. Kgaa | toilet cleaner |
| GB2567349B (en) | 2016-08-01 | 2022-03-02 | Procter & Gamble | Sprayable freshening product comprising suspended particles and methods of freshening the air or a surface with the same |
| US11097031B2 (en) | 2016-08-01 | 2021-08-24 | The Procter & Gamble Company | Phase-stable, sprayable freshening compositions comprising suspended particles |
| WO2018026626A1 (en) | 2016-08-01 | 2018-02-08 | The Procter & Gamble Company | Phase-stable, sprayable freshening compositions comprising suspended particles and methods of freshening the air or a surface with the same |
| WO2018026627A1 (en) | 2016-08-01 | 2018-02-08 | The Procter & Gamble Company | Phase-stable, sprayable freshening compositions comprising suspended particles |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956162A (en) * | 1973-06-15 | 1976-05-11 | E. I. Du Pont De Nemours And Company | Thixotropic cleaning composition containing particulate resins and fumed silica |
| US4968445A (en) * | 1987-09-29 | 1990-11-06 | Colgate-Palmolive Co. | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| ZA887068B (en) * | 1987-09-29 | 1990-05-30 | Colgate Palmolive Co | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| US4836948A (en) * | 1987-12-30 | 1989-06-06 | Lever Brothers Company | Viscoelastic gel detergent compositions |
| EP0407187A3 (en) * | 1989-07-07 | 1991-07-17 | Unilever Plc | Aqueous thixotropic cleaning composition |
| US5120465A (en) * | 1990-02-22 | 1992-06-09 | Dry Branch Kaolin Company | Detergent or cleansing composition and additive for imparting thixotropic properties thereto |
-
1999
- 1999-10-08 DE DE1999148859 patent/DE19948859A1/en not_active Ceased
-
2000
- 2000-09-29 WO PCT/EP2000/009543 patent/WO2001027236A1/en active Application Filing
- 2000-09-29 AU AU79099/00A patent/AU7909900A/en not_active Abandoned
- 2000-10-06 CA CA 2323022 patent/CA2323022A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846512B2 (en) | 2001-01-30 | 2005-01-25 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US7977296B2 (en) | 2006-12-15 | 2011-07-12 | Colgate-Palmolive Company | Liquid detergent composition comprising an acrylic polymer/viscosity control agent mixture |
| US8080507B2 (en) | 2006-12-15 | 2011-12-20 | Colgate-Palmolive Company | Liquid detergent composition comprising an alkylbenzene sulfonate surfactant and polypropylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19948859A1 (en) | 2001-11-08 |
| WO2001027236A1 (en) | 2001-04-19 |
| AU7909900A (en) | 2001-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2323022A1 (en) | Thixotropic aqueous cleaner | |
| EP2821469B1 (en) | Liquid cleaning and/or cleansing composition | |
| JP5595844B2 (en) | Composition for protecting glassware from surface corrosion in automatic dishwashers | |
| US4248728A (en) | Liquid scouring cleanser | |
| JP2004503479A (en) | Thixotropic oral and dental care agents | |
| EP2720676A1 (en) | Liquid cleaning and/or cleansing composition | |
| AU2010302493A1 (en) | Viscous acidic abrasive cleaning compositions | |
| CN1636048A (en) | Hard surface cleaning compositions | |
| JPS63170494A (en) | Detergent and softener having imidazoline component | |
| JP2002503269A (en) | Paint anti-sticking agent and precipitant | |
| KR100777887B1 (en) | Zeolite Compositions and Thier Use | |
| JP2011068894A (en) | Corrosion protection agent for treating glassware surface | |
| WO2021041894A1 (en) | A galactarate based metal sequestration composition | |
| WO2004084851A2 (en) | A treatment composition | |
| US20070227403A1 (en) | Mineral Layered Silicate in the Form of a Nanopower | |
| JPH11228127A (en) | Aluminosilicate grain | |
| JP2007204284A (en) | Composite clay composition and its manufacturing method | |
| CA2014220C (en) | Cleaning composition | |
| JPH05320694A (en) | Contaminant removing composition and its preparation | |
| JPH08151597A (en) | Liquid detergent composition | |
| JP4410255B2 (en) | Method for treating the surface of glassware with a corrosion inhibitor | |
| JPH01501157A (en) | Scrubbing and cleaning products that are not harmful to the environment | |
| JP5587938B2 (en) | Composite clay composition | |
| JP4373601B2 (en) | Self-heating builder | |
| JP2000319690A (en) | Inorganic detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |