GB2442725A - Water-softening mixture - Google Patents
Water-softening mixture Download PDFInfo
- Publication number
- GB2442725A GB2442725A GB0511010A GB0511010A GB2442725A GB 2442725 A GB2442725 A GB 2442725A GB 0511010 A GB0511010 A GB 0511010A GB 0511010 A GB0511010 A GB 0511010A GB 2442725 A GB2442725 A GB 2442725A
- Authority
- GB
- United Kingdom
- Prior art keywords
- water
- mixture
- sodium
- water softening
- wash
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004744 fabric Substances 0.000 claims abstract description 18
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004900 laundering Methods 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000344 soap Substances 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- 239000003599 detergent Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 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 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000019351 sodium silicates Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 10
- 239000008233 hard water Substances 0.000 description 8
- 150000004760 silicates Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006173 Good's buffer Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000011160 magnesium carbonates Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/12—Carbonates bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A water softening mixture based on alkali carbonate and finely divided calcite. The mixture is for use to soften wash water first before laundering fabrics using a separate cleaning product based on anionic active.
Description
1 2442725 WATER SOFTENiNG FORMULATIONS CONTAINING ALKALI CARBOTATE AND
FINELY DWLDED CALCiTE The present invention pertains to the use of separate water softening mixtures, based on alkali carbonates and finely divided calcite, to soften hard water before laundering fabrics using soap based formulations, particularly formulations based on soap and fatty acid N-methyl glucamides.
The present invention is set against a background of change and urgency in society's attitude as to how the natural resources are used. There is a perception that it may be for the general good of society as well as environment to use natural and renewable feed stocks in consumer products such as laundry detergents. For sometime the detergent industry has been striving to achieve this.
Soaps of Cl 2 to Cl 8 alkyl chain lengths are very good laundry detergents when used in very soft water. Whereas lower alkyl chain fatty soaps-coco-are fairly soluble in water, longer chain -tallow-soaps are not very soluble.. It is these longer chain soaps that are generally preferred for laundry and textile cleaning applications. Therefore their solubiliiy needs to be improved by the addition of co-actives. Soaps are also very sensitive to water hardness ions with the loss of detergency. For many years, in the past, soap formulations built with alkaline materials such as carbonates, silicates, borax and orthophosphate had been produced for use in hard water with limited success and hence were superseded by superior built detergent compositions based on sulphonates and suiphates along with nonionics The drawback of soap-based formulations can be eliminated to some extent by softening the water prior to washing. Now a day washing machines can accommodate more than one product such as one for washing and one for softening. Also machines now are electronically * ** controlled and hence manufactures can be persuaded to incorporate other functional cycles such as water softening cycle if a case can be made.
* S. S *... Current environmentally conscious consumers can also be persuaded to soften hard water first, using a water softening product, if the process did not take more than 2-5 minutes with * :w: agitation, before wash fabrics and detergent products are added, if they can perceive environmental benefits.
In distilled water soaps, besides being good laundry detergents, generally show higher soil *..: suspending power than suiphonate and sulphate anionics and ethoxylated nonionics. In this * : respect soaps containing higher proportion ofCl8 saturated fatty acid are particularly good. ass..
* Soaps do not have the corrosive tendencies of more common synthetic detergents, and have good emulsi1'ing power As stated above sodium soaps, particularly Cl 4-C 18 range are not very soluble in water. The inclusion of more soluble Cl 2-C 14 fatty acid N-methyl glucamides will increase the dissolution and solubility of soaps in aqueous solutions, particularly under low temperature wash cycle conditions.
However the major drawback of soap is that hard water ion soaps are very insoluble in water and hence lost as detergents. Besides they deposit on fabrics making the fabric stiff and hydrophobic. This cannot be eliminated completely by using lime soap dispersing agents since some hard water ion soaps deposit in the interstices of the fabric The calcium and magnesium salts of conventional anionic detergents such as suiphonates and suiphates are relatively more water soluble compared to the corresponding chain length soaps.
Therefore when formulations based on such detergents built with sequestering builders are dissolved in water the equilibrium shifts towards sequestering builders side.
However, in the case of soap, since their hard water ion salts are very insoluble the equilibrium shifts towards soap precipitation side and hence soap based formulations cannot effectively be built with sequestering builders. Here only the precipitant builders such as alkali carbonates, silicates, orthophosphate and zeolites are useful. Even so certain amount of hard water ion soaps will precipitate in competition with precipitant builders when used together.
The most environmentally friendly builders are sodium carbonate, sodium silicates and zeolites. However the problem with sodium carbonate is that the precipitated calcium carbonate fine particles, deposit in the interstices of the fabric and cannot, easily, be washed away. This causes encrustation, increasing the so-called ash content of the fabric, damaging the fabric after many laundering cycles. This can be eliminated to a great extent by the addition of calcite particles to the builder to act as nucleating agents in the aggregation of carbonate precipitates. Now the aggregates become particulate dirt, which can easily be washed away during, wash and rinse cycles. However the nucleating agent gets deactivated in the presence of anionic actives including soap, as disclosed in GB1424406 and US3957695, the disclosure of which is incorporated herein by way of reference. Since calcium and magnesium carbonates are insoluble in water they would not interact with sodium soap during the wash cycle time period.
Silicates also soften water by the formation of precipitates. Since the silicates are polymers the precipitates do not deposit on the fabric. They also suspend soil in solution and prevent their re- deposition on the cloth. Silicates are also good buffers. The best silicates are in the Na20:S 102 ratio of 1:1.6 to 1:2.4. Therefore a combination of alkali carbonates and silicates have good building property.
Description of the invention
A water softening mixture based on alkali carbonate and finely divided calcite when use to a... soften wash water, prior to laundering fabrics, using a product containing a mixture of soap and 25 % to 60% fatty acid N-methyl glucamides. The alkali carbonate is preferably sodium carbonate.
A method of laundering which comprising softening wash water first, using the water softening mixture of claim 1 before adding the wash fabrics.
It has now been realised that this is the best way to exploit the potential of sodium carbonate : *..: and finely divided calcite mixture as a water softener.
Auxiliary Surfactants The soap based detergent mixtures can further include an auxiliary surfactant component, to improve the performance further, which comprises anionic and non-ionic surfactants other than soap and N-methyl glucamides.
Such auxiliary surfactants include Cl 2-Cl 8 alkyl suiphates, coco alcohol E04-E0 12 ethoxylates coco alkyl polyglucosides, coco mono-and di -ethanolamides, their ethoxylates and mixtures thereof.
The formulations can be tailored and targeted to washing in waters at different hardness levels.
For water hardness <5dH the soap/gicamide formulation can be used as is, without any builders, where certain amount of soap will act as self builder and the small amount of calcium soap produced will be dispersed by the co-active present. However in such formulations the presence of alkaline builders would enhance detergency.
For use in water hardness <1 OdH small amount builders such as sodium carbonate or a combination of sodium carbonate and alkaline silicates, zeolite or mixtures thereof should be used.
However, in hard water wash, the water needs to be softened first before the detergents are added. Further advantages can be gained when both the fabrics and detergents are added after softening the water.
Other conventional ingredients such as lather suppressants, optical brighteners etc can be added to the active mixture.
Typical Formulations I.. Sodium carbonate 50%.
Finely divided calcite 30% Sodium silicate (Si02 Na20 2) 20%
Claims (4)
- LClaims 1. A water softening mixture, based on alkali carbonate and finely divided calcite, for use to soften wash water first before laundering fabrics using a separate cleaning detergent product based on anionic active.
- 2. A method of aundering, comprising softening wash water first using the water softening mixture of claim I before adding the wash fabrics and the detergent product.
- 3. A water softening mixture, as in claim 1, where the calcite particle size is below 20 microns.
- 4. A method of laundering which comprising prior softening wash water using the mixture of claim 1, before adding the wash fabrics4. A water softening mixture, as in claim 1, where the calcite particle size is preferably between 0.01 and 5 microns.5. A water softening mixture, as in claim 1, where the alkali carbonate is sodium carbonate.6. A water softening mixture as in claim I which further contains from I to 30% other builder materials such as sodium bicarbonate, sodium sesquicarbonare, sodium silicat; ze olite or mixtures thereof.Amendments to the claims have been filed as follows Chflms I. A water softening mixture, based on alkali carbonate and finely divided calcite when *. *** used to soften wash water prior to laundering fabrics, using a product containing soap and 25% to 60% fatty acid N-methyl glucamides 2. The alkali carbonate in claim 1 is sodium cabonate 3. The water softening mixture, as in claim 1, which further contains from 1% to 30% other builder materials such as sodium silicates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0511010A GB2442725B (en) | 2004-07-03 | 2004-07-03 | Water softening formulation containing alkali carbonate and finely divided calcite |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0511010A GB2442725B (en) | 2004-07-03 | 2004-07-03 | Water softening formulation containing alkali carbonate and finely divided calcite |
| GB0414997A GB2415964B (en) | 2004-07-03 | 2004-07-03 | Detergent formulations based on soap and fatty acid N-methyl glucamides |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0511010D0 GB0511010D0 (en) | 2005-07-06 |
| GB2442725A true GB2442725A (en) | 2008-04-16 |
| GB2442725B GB2442725B (en) | 2008-12-17 |
Family
ID=32843565
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0414997A Expired - Fee Related GB2415964B (en) | 2004-07-03 | 2004-07-03 | Detergent formulations based on soap and fatty acid N-methyl glucamides |
| GB0511010A Expired - Fee Related GB2442725B (en) | 2004-07-03 | 2004-07-03 | Water softening formulation containing alkali carbonate and finely divided calcite |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0414997A Expired - Fee Related GB2415964B (en) | 2004-07-03 | 2004-07-03 | Detergent formulations based on soap and fatty acid N-methyl glucamides |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB2415964B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1437950A (en) * | 1972-08-22 | 1976-06-03 | Unilever Ltd | Detergent compositions |
| GB2138439A (en) * | 1983-04-22 | 1984-10-24 | Unilever Plc | Detergent composition |
| EP0246896A1 (en) * | 1986-05-23 | 1987-11-25 | Unilever Plc | Detergent compositions |
| EP0292193A1 (en) * | 1987-05-14 | 1988-11-23 | Unilever Plc | Detergent composition |
| US4908159A (en) * | 1985-05-10 | 1990-03-13 | Lever Brothers Company | Detergent granules containing simple sugars and a seed crystal for calcium carbonate |
| DE4122490A1 (en) * | 1991-07-06 | 1993-01-07 | Henkel Kgaa | Liq. water softener compsns. - contg. alkali metal or poly:carboxylate salt, water-soluble alcohol and surfactant opt. with phosphonic acid |
| GB2386381A (en) * | 2002-03-14 | 2003-09-17 | Darren Keats | Water softener for a washing machine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254281A (en) * | 1991-01-29 | 1993-10-19 | The Procter & Gamble Company | Soap bars with polyhydroxy fatty acid amides |
| DE4331297A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Bar soaps |
| WO1998005752A1 (en) * | 1996-08-07 | 1998-02-12 | The Procter & Gamble Company | Laundry bar compositions |
-
2004
- 2004-07-03 GB GB0414997A patent/GB2415964B/en not_active Expired - Fee Related
- 2004-07-03 GB GB0511010A patent/GB2442725B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1437950A (en) * | 1972-08-22 | 1976-06-03 | Unilever Ltd | Detergent compositions |
| GB2138439A (en) * | 1983-04-22 | 1984-10-24 | Unilever Plc | Detergent composition |
| US4908159A (en) * | 1985-05-10 | 1990-03-13 | Lever Brothers Company | Detergent granules containing simple sugars and a seed crystal for calcium carbonate |
| EP0246896A1 (en) * | 1986-05-23 | 1987-11-25 | Unilever Plc | Detergent compositions |
| EP0292193A1 (en) * | 1987-05-14 | 1988-11-23 | Unilever Plc | Detergent composition |
| DE4122490A1 (en) * | 1991-07-06 | 1993-01-07 | Henkel Kgaa | Liq. water softener compsns. - contg. alkali metal or poly:carboxylate salt, water-soluble alcohol and surfactant opt. with phosphonic acid |
| GB2386381A (en) * | 2002-03-14 | 2003-09-17 | Darren Keats | Water softener for a washing machine |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2415964B (en) | 2008-04-16 |
| GB0414997D0 (en) | 2004-08-04 |
| GB0511010D0 (en) | 2005-07-06 |
| GB2442725B (en) | 2008-12-17 |
| GB2415964A (en) | 2006-01-11 |
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| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20150703 |