EP0518401A1 - Reinigungsmittelzusammensetzungen mit eigener Selbstverdickungsfähigkeit - Google Patents
Reinigungsmittelzusammensetzungen mit eigener Selbstverdickungsfähigkeit Download PDFInfo
- Publication number
- EP0518401A1 EP0518401A1 EP92201412A EP92201412A EP0518401A1 EP 0518401 A1 EP0518401 A1 EP 0518401A1 EP 92201412 A EP92201412 A EP 92201412A EP 92201412 A EP92201412 A EP 92201412A EP 0518401 A1 EP0518401 A1 EP 0518401A1
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- European Patent Office
- Prior art keywords
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- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 238000004140 cleaning Methods 0.000 title claims abstract description 13
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- -1 alkyl sulphate Chemical compound 0.000 claims description 8
- 150000003863 ammonium salts Chemical group 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 239000003240 coconut oil Substances 0.000 claims description 6
- 235000019864 coconut oil Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 150000008051 alkyl sulfates Chemical class 0.000 abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002535 acidifier Substances 0.000 description 2
- 229940095602 acidifiers Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Images
Classifications
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- 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
- C11D3/046—Salts
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
- C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the present invention relates to cleaning compositions.
- the compositions according to the present invention are self-thickened, in that they do not require the presence of a thickener compound; furthermore, the compositions according to the present invention are physically stable, even at low temperatures.
- the compositions according to the present invention are useful for instance as hard surface cleaning compositions or as laundry cleaning compositions.
- Thickened cleaning compositions are well known in the art, and have found various applications for instance in the context of hard surface or laundry cleaning compositions.
- compositions which comprise such an anionic surfactant derived from natural coconut oil and an electrolyte.
- the viscosity of such a composition is of course sensitive to temperature, and a new technical problem has been identified in that such compositions are not physically stable at low temperature, where the product undergoes phase separation; As a result, the product has an aesthetically unacceptable aspect.
- Canadian patent CA 1 194 381 discloses scouring compositions containing anionic surfactants, an electrolyte and an ethoxylated alcohol surfactant.
- European patent EP 116 905 teaches the use of an ethoxylated and/or propoxylated alcohol surfactant to reduce the viscosity of industrial-grade synthetic anionic surfactant concentrates.
- European patent application EP 329 209 discloses scouring compositions comprising a surfactant, an electrolyte and a solvent to build viscosity.
- compositions according to the present invention are self-thickened aqueous cleaning compositions having a viscosity of from 50 to 700 cps at 60rpm shear rate at 20°C, which comprise from 1% to 25% by weight of the total composition of an alkyl sulphate anionic surfactant derived from natural coconut oil, from 0.1% to 8% by weight of the total composition of ammonium salts and from 0.5% to 25% by weight of the total composition of a compound of the structure: R1-O ⁇ [(R2O) n (R3O) m ] ⁇ R4, wherein :
- compositions according to the present invention comprise from 1% to 25% by weight of the total composition, preferably from 2% to 8% by weight of the total composition, most preferably 3% to 5% of an alkyl sulphate anionic surfactant derived from natural coconut oil, or mixtures thereof.
- alkyl sulphate anionic surfactants for use herein can be made by the processes well known to the man skilled in the art. Typically, such surfactants are made from coconut alcohol which is sulfated and possibly ethoxylated. Indeed, ethoxylated alkyl sulfate surfactants are also suitable for use herein, but the average degree of ethoxylation of the anionic surfactants to be used herein should not be more than 2.
- the neutralizing cation for the alkyl sulfates derived from natural coconut oil to be used herein can be any of the conventional cations used in detergent technology, such as ammonium, potassium or unsubstituted or N-substituted ammonium salts, or mixtures thereof; preferred are the sodium salts.
- the viscosity of the compositions according to the invention is obtained by using ammonium salts as an electrolyte; suitable ammonium salts for use in the compositions according to the invention include alkanolammonium salts, ammonium chloride, ammonium acetate, ammonium citrate, ammonium carbonate and the like; it is the electrolyte together with the above described surfactants which builds the viscosity.
- the viscosity of the composition depends on the proportion of both ingredients, the general rule being that the more electrolyte is added, the more viscosity is obtained.
- the compositions according to the present invention comprise from 0.1% to 8% by weight of the total composition of ammonium salts, preferably from 0.2% to 6%, most preferably 0.3% to 5%.
- the ratio of ammonium salts to anionic surfactant is adjusted so as to obtain a composition having a viscosity of from 50 to 700 cps at 60rpm shear rate at 20°C, more preferably 80 cps to 350 cps.
- the viscosity of the compositions according to the invention allows to use said compositions on vertical surfaces.
- compositions according to the present invention comprise from 0.5% to 25% by weight of the total composition, preferably from 0.6% to 10% , most preferably from 0.7% to 2% of a compound of the formula: R1-O ⁇ [(R2O) n (R3O) m ] ⁇ R4, wherein :
- R2O and R3O groups may appear in any sequence in the molecule; also, when n and m are greater than 1, different R2O and R3O groups may appear in a same molecule.
- These surfactant are commercially available from ICI under the trade name UKANIL FM® or from BASF under the trade name PLURAFAC LF®.
- Preferred surfactant where m is 0 are available from SHELL under the trade name DOBANOL® from BASF under the trade name LUTENSOL®.
- compositions according to the invention are acidic and have a pH of from 1 to 6, preferably 2.5 to 5.
- the pH of the compositions according to the invention is partially determined by the amount of electrolyte, but the pH of the final composition can be adjusted by the addition of appropriate acidifiers such as organic or inorganic acids, or acidic salts which buffer pH to an acid value.
- suitable acidifiers are sulfuric acid, phosphoric acids, although somewhat undesirable from an environmental viewpoint, hydrochloric acid, phosphonic acid, citric acid, acetic acid, tartaric acid, maleic acid, succinic acid, malonic acid and the like, or mixtures thereof.
- the compositions comprise from 0.5% to 20% by weight of the total composition of citric acid, preferably from 1% to 10%.
- citric acid it has been found there are many benefits obtainable from the addition of citric acid to the compositions according to the present invention, such as limescale removal performance and improved disinfesting properties.
- citric acid it is possible to form in situ the ammonium salts described herein above, in this case ammonium citrate by incorporating ammonium hydroxide.
- the presence of citric acid also helps to build the product's viscosity;
- compositions according to the invention further comprise from 0.01% to 0.5% by weight of the total composition of a capped 1,2- propylene terephthalate polyoxyethylene polyester of the formula: wherein n is an integer of from about 12 to 43 and u is an integer of from about 2 to 8, and mixtures thereof.
- the above polymers have a regulating effect on the viscosity of the compositions; indeed, the viscosity of a given product is typically very sensitive to temperature, and the compositions according to the present invention, although they remain phase-stable at all temperatures, tend to become more viscous when temperature drops. It has now been found that the above polymers make the composition's viscosity less sensitive to temperature; thus the compositions have less tendency to become thicker at low temperatures.
- the compositions according to the present invention further comprise from 1% to 15% by weight of the total composition, preferably from 2% to 10%, most preferably 3% to 8% of hydrogen peroxide.
- the addition of hydrogen peroxide leads to a severe drop in viscosity;
- another advantage of the compositions according to the present invention, i.e. comprising the stabilizing nonionic surfactant from the selected class, is that the addition of hydrogen peroxide has little effect on the product's viscosity.
- bleaching compositions can also be made according to the present invention.
- compositions according to the present invention may also comprise conventional ingredients such as solvents, chelating agents, fragrance and dyes, provided all these ingredients are compatible with the compositions.
- compositions according to the present invention can be made by any process where all ingredients are mixed together.
- the compositions comprise a substantial amount of citric acid
- the compositions also comprise hydrogen peroxide
- compositions according to the present invention can be useful in many different contexts where it is desirable to use a viscous product.
- hard surface cleaning compositions are advantageously formulated as viscous products in order to optimize their application to vertical surfaces, for instance baththubs or toilet bowls. Indeed, the product's viscosity prevents the product from running too quickly down said surface.
- compositions according to the present invention can also be used in the context of laundry cleaning.
- a laundry pretreatment composition can be advantageously formulated as a viscous product for a most convenient application to the laundry fabrics.
- the viscosity of the product allows for a better control of the dispensing of the product and prevents the spreading of the dispensed product beyond the fabric surface being pretreated.
- compositions which contain the listed ingredients in the listed proportions (weight %).
- Compositions 1 2 3 4 5 6 NaCnAS 3.5 3.5 3.5 4.0 2.4 3.5 Citric Acid 5.8 6.0 5.8 - 4.0 5.7 Ukanil R 1.5 1.5 1.0 1.0 2.0 - Dobanol R 23-3 - - - - - 0.9 Ammonia 0.6 0.6 0.7 - - 0.32 Ammonium Chloride - - - - 1.0 - Sodium Chloride - - - 4.0 - - Tri Ethanol Amine - - 1.5 - - 2.0 Hydrogen Chloride - - - 0.05 - - Hydrogen Peroxide - 6.0 - - - - Sodium Cumene Sulphonate 1.0 - - - - - - - Perfume 0.5 - - - 0.4 pH 4.1 4.0 4.5 2.5 2.2 3.6 Water & minors up to 100%
- compositions according to the present invention The following data illustrates the benefits obtained from the compositions according to the present invention.
- a composition is made which comprises, by weight of the total composition: Sodium coconut alkyl sulfate: 3.5% Ammonia: 0.75% Citric acid: 5.8 pH: 4.3 Water & minors: up to 100%
- An identical composition is also made, except it comprises in addition 1.5% of Ukanil R .
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- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91870095 | 1991-06-14 | ||
EP91870095 | 1991-06-14 | ||
EP92870025 | 1992-02-14 | ||
EP92870025 | 1992-02-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0518401A1 true EP0518401A1 (de) | 1992-12-16 |
EP0518401B1 EP0518401B1 (de) | 1995-11-02 |
Family
ID=26130362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92201412A Expired - Lifetime EP0518401B1 (de) | 1991-06-14 | 1992-05-19 | Reinigungsmittelzusammensetzungen mit eigener Selbstverdickungsfähigkeit |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0518401B1 (de) |
JP (1) | JPH06508393A (de) |
AT (1) | ATE129742T1 (de) |
AU (1) | AU667481B2 (de) |
BR (1) | BR9206153A (de) |
CA (1) | CA2110413C (de) |
DE (1) | DE69205730T2 (de) |
DK (1) | DK0518401T3 (de) |
ES (1) | ES2079138T3 (de) |
GR (1) | GR3018145T3 (de) |
IE (1) | IE921922A1 (de) |
MX (1) | MX9202883A (de) |
NZ (1) | NZ243138A (de) |
TR (1) | TR25965A (de) |
WO (1) | WO1992022628A1 (de) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995033024A1 (en) * | 1994-05-31 | 1995-12-07 | The Procter & Gamble Company | Cleaning compositions |
EP0875551A1 (de) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Selbstverdickende saure Reinigungsmittel |
US6150320A (en) * | 1994-07-21 | 2000-11-21 | 3M Innovative Properties Company | Concentrated cleaner compositions capable of viscosity increase upon dilution |
US6849589B2 (en) | 2001-10-10 | 2005-02-01 | 3M Innovative Properties Company | Cleaning composition |
WO2006055788A1 (en) * | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Acidic laundry detergent compositions |
WO2012104159A1 (en) * | 2011-01-31 | 2012-08-09 | Unilever Plc | Alkaline liquid detergent compositions |
WO2012172367A1 (en) * | 2011-06-17 | 2012-12-20 | Reckitt Benckiser N.V. | Composition |
WO2014190133A1 (en) * | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Low ph detergent composition comprising nonionic surfactants |
US9840681B2 (en) | 2013-05-24 | 2017-12-12 | The Procter & Gamble Company | Concentrated surfactant composition |
US10519400B2 (en) | 2013-05-24 | 2019-12-31 | The Procter & Gamble Company | Low PH detergent composition |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5656580A (en) * | 1992-12-04 | 1997-08-12 | The Procter & Gamble Company | Acidic cleaning compositions self-thickened by a mixture of cationic and nonionic surfactants |
CA2150914C (en) * | 1992-12-04 | 1999-07-13 | Michel Jean Carrie | Self-thickened acidic cleaning composition |
ES2146254T3 (es) * | 1993-03-30 | 2000-08-01 | Minnesota Mining & Mfg | Composiciones de limpieza multi-superficie y metodo de uso. |
EP0623671A1 (de) * | 1993-05-06 | 1994-11-09 | The Procter & Gamble Company | Zugabe der Mischungskomponenten in einer bestimmten Reihenfolge zur Herstellung von wässrigen klaren Reinigungsmittelzusammensetzungen |
EP0839898A1 (de) * | 1996-11-04 | 1998-05-06 | The Procter & Gamble Company | Selbstverdickende Reinigungszusammensetzungen |
US6617293B2 (en) | 2001-08-06 | 2003-09-09 | 3M Innovative Properties Company | Thickening on dilution liquid soap |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969282A (en) * | 1974-12-23 | 1976-07-13 | Basf Wyandotte Corporation | Acidic surfactant composition, stock surfactant solution prepared therefrom, and method of washing soiled substrates employing the same |
DE3718896A1 (de) * | 1987-06-05 | 1988-12-22 | Wintershall Ag | Verwendung von alkoxylierten alkoholen als viskositaetsregler fuer hochviskose alkylbenzolsulfonat-konzentrate |
EP0303187A2 (de) * | 1987-08-13 | 1989-02-15 | Henkel Kommanditgesellschaft auf Aktien | Wässrige Zubereitungen ionischer Tenside mit erhöhter Viskosität |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5036646B2 (de) * | 1971-09-09 | 1975-11-26 | ||
GB1538747A (en) * | 1975-07-17 | 1979-01-24 | Shell Int Research | Detergent compositions |
EP0000224A1 (de) * | 1977-06-29 | 1979-01-10 | THE PROCTER & GAMBLE COMPANY | Flüssiges Waschmittel zur verbesserten Beseitigung von fetthaltigem Schmutz |
JPS54157110A (en) * | 1978-06-01 | 1979-12-11 | Lion Corp | Liquid detergent composition having excellent rinsability |
ATE14453T1 (de) * | 1981-11-13 | 1985-08-15 | Unilever Nv | Stabile fluessige detergenssuspensionen. |
ATE39126T1 (de) * | 1982-07-27 | 1988-12-15 | Procter & Gamble | Fluessige reinigungsmittelzusammensetzungen, eine koazervatmischung aus alkylcellulose enthaltend und carboxymethylcellulose und verfahren zu deren herstellung. |
US4681704A (en) * | 1984-03-19 | 1987-07-21 | The Procter & Gamble Company | Detergent composition containing semi-polar nonionic detergent alkaline earth metal anionic detergent and amino alkylbetaine detergent |
DE3585505D1 (de) * | 1984-12-21 | 1992-04-09 | Procter & Gamble | Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen. |
GB8508010D0 (en) * | 1985-03-27 | 1985-05-01 | Unilever Plc | Liquid bleaching compositions |
US4661267A (en) * | 1985-10-18 | 1987-04-28 | The Procter & Gamble Company | Fabric softener composition |
US4671895A (en) * | 1985-11-15 | 1987-06-09 | Colgate-Palmolive Company | Liquid detergent compositions |
DE3541535A1 (de) * | 1985-11-25 | 1987-05-27 | Henkel Kgaa | Verwendung von polyglykoldialkylethern als viskositaetsregler fuer waessrige aniontensidloesungen |
US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
DE3730179A1 (de) * | 1987-09-09 | 1989-03-23 | Henkel Kgaa | Verdickte waessrige tensidloesungen, insbesondere fuer deren einsatz auf dem gebiet kosmetischer praeparate |
DE3817415A1 (de) * | 1988-05-21 | 1989-11-30 | Henkel Kgaa | Verdickte waessrige tensidloesungen |
US4997641A (en) * | 1990-04-09 | 1991-03-05 | Colgate-Palmolive Company | Hair conditioning shampoo containing C6 -C10 alkyl sulfate or alkyl alkoxy sulfate |
JP2602557B2 (ja) * | 1989-09-01 | 1997-04-23 | 花王株式会社 | 液体漂白剤組成物 |
JP2602563B2 (ja) * | 1989-12-15 | 1997-04-23 | 花王株式会社 | 液体酸素系漂白剤組成物 |
-
1992
- 1992-05-19 ES ES92201412T patent/ES2079138T3/es not_active Expired - Lifetime
- 1992-05-19 DK DK92201412.1T patent/DK0518401T3/da active
- 1992-05-19 DE DE69205730T patent/DE69205730T2/de not_active Expired - Fee Related
- 1992-05-19 EP EP92201412A patent/EP0518401B1/de not_active Expired - Lifetime
- 1992-05-19 AT AT92201412T patent/ATE129742T1/de not_active IP Right Cessation
- 1992-06-08 JP JP5500950A patent/JPH06508393A/ja active Pending
- 1992-06-08 BR BR9206153A patent/BR9206153A/pt not_active Application Discontinuation
- 1992-06-08 AU AU23364/92A patent/AU667481B2/en not_active Ceased
- 1992-06-08 CA CA002110413A patent/CA2110413C/en not_active Expired - Fee Related
- 1992-06-08 WO PCT/US1992/004772 patent/WO1992022628A1/en active Application Filing
- 1992-06-09 TR TR92/0529A patent/TR25965A/xx unknown
- 1992-06-15 MX MX9202883A patent/MX9202883A/es not_active IP Right Cessation
- 1992-06-15 NZ NZ243138A patent/NZ243138A/xx unknown
- 1992-07-01 IE IE192292A patent/IE921922A1/en not_active Application Discontinuation
-
1995
- 1995-11-21 GR GR950403264T patent/GR3018145T3/el unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969282A (en) * | 1974-12-23 | 1976-07-13 | Basf Wyandotte Corporation | Acidic surfactant composition, stock surfactant solution prepared therefrom, and method of washing soiled substrates employing the same |
DE3718896A1 (de) * | 1987-06-05 | 1988-12-22 | Wintershall Ag | Verwendung von alkoxylierten alkoholen als viskositaetsregler fuer hochviskose alkylbenzolsulfonat-konzentrate |
EP0303187A2 (de) * | 1987-08-13 | 1989-02-15 | Henkel Kommanditgesellschaft auf Aktien | Wässrige Zubereitungen ionischer Tenside mit erhöhter Viskosität |
Non-Patent Citations (2)
Title |
---|
DATABASE WPIL Derwent Publications Ltd., London, GB; DATABASE WPIL, accession no. 91-158447, week 9122; & JP - A - 3091597 (KAO CORP) 17.04.1991 * |
PATENT ABSTRACTS OF JAPAN vol. 4, no. 19 (C-73), 16 February 1980; & JP - A - 54157110 (LION YUSHI KK) 12.11.1979 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995033024A1 (en) * | 1994-05-31 | 1995-12-07 | The Procter & Gamble Company | Cleaning compositions |
US6150320A (en) * | 1994-07-21 | 2000-11-21 | 3M Innovative Properties Company | Concentrated cleaner compositions capable of viscosity increase upon dilution |
EP0875551A1 (de) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Selbstverdickende saure Reinigungsmittel |
US6849589B2 (en) | 2001-10-10 | 2005-02-01 | 3M Innovative Properties Company | Cleaning composition |
WO2006055788A1 (en) * | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Acidic laundry detergent compositions |
WO2012104159A1 (en) * | 2011-01-31 | 2012-08-09 | Unilever Plc | Alkaline liquid detergent compositions |
WO2012172367A1 (en) * | 2011-06-17 | 2012-12-20 | Reckitt Benckiser N.V. | Composition |
WO2014190133A1 (en) * | 2013-05-24 | 2014-11-27 | The Procter & Gamble Company | Low ph detergent composition comprising nonionic surfactants |
CN105209587A (zh) * | 2013-05-24 | 2015-12-30 | 宝洁公司 | 包含非离子表面活性剂的低ph洗涤剂组合物 |
US9267095B2 (en) | 2013-05-24 | 2016-02-23 | The Procter & Gamble Company | Low pH detergent composition comprising nonionic surfactants |
US9840681B2 (en) | 2013-05-24 | 2017-12-12 | The Procter & Gamble Company | Concentrated surfactant composition |
US10519400B2 (en) | 2013-05-24 | 2019-12-31 | The Procter & Gamble Company | Low PH detergent composition |
Also Published As
Publication number | Publication date |
---|---|
CA2110413C (en) | 1997-12-09 |
JPH06508393A (ja) | 1994-09-22 |
GR3018145T3 (en) | 1996-02-29 |
DE69205730D1 (de) | 1995-12-07 |
DK0518401T3 (da) | 1996-03-04 |
AU667481B2 (en) | 1996-03-28 |
DE69205730T2 (de) | 1996-05-30 |
WO1992022628A1 (en) | 1992-12-23 |
NZ243138A (en) | 1995-07-26 |
EP0518401B1 (de) | 1995-11-02 |
IE921922A1 (en) | 1992-12-16 |
ATE129742T1 (de) | 1995-11-15 |
BR9206153A (pt) | 1994-12-27 |
AU2336492A (en) | 1993-01-12 |
TR25965A (tr) | 1993-11-01 |
MX9202883A (es) | 1993-03-01 |
ES2079138T3 (es) | 1996-01-01 |
CA2110413A1 (en) | 1992-12-23 |
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