EP0491553A2 - Composition détergente - Google Patents
Composition détergente Download PDFInfo
- Publication number
- EP0491553A2 EP0491553A2 EP91311703A EP91311703A EP0491553A2 EP 0491553 A2 EP0491553 A2 EP 0491553A2 EP 91311703 A EP91311703 A EP 91311703A EP 91311703 A EP91311703 A EP 91311703A EP 0491553 A2 EP0491553 A2 EP 0491553A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- composition
- detergent
- range
- weight
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 239000003599 detergent Substances 0.000 title claims abstract description 62
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 16
- 239000007844 bleaching agent Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 7
- 239000004927 clay Substances 0.000 claims abstract description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- -1 alkali metal tripolyphosphate Chemical class 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims 3
- 150000004679 hydroxides Chemical class 0.000 claims 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000007792 addition Methods 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Definitions
- This invention relates to detergent compositions and especially, but not exclusively to liquid detergent compositions for use in an automatic dishwasher.
- liquid automatic dishwasher detergent compositions have become available. These liquid products have a number of advantages when compared with the more traditional powdered products in that they have improved solubility, are easier to handle, dose and dispense, they are dust free and they do not cake in the machine dispenser.
- Liquid products pose a number of formulation problems which must be overcome if a viable, stable product is to be obtained.
- Liquid products contain high levels of solid ingredients which must be suspended in the composition so as to prevent physical separation. This may be achieved by producing a highly viscous composition. This also has the advantage in that it enables the liquid to be effectively retained within the detergent dispenser of the machine.
- ease of dispensing the composition is also important. It is therefore advisable to provide a composition with a high viscosity when not subjected to shear and a reduced viscosity when subjected to shear.
- Thixotropic dishwasher liquids have in the past comprised clays to modify their viscosity. However, the use of clay thickeners in these compositions has a number of disadvantages as indicated in EP 0323209.
- the present invention aims to provide a dishwasher detergent composition which avoids the use of clay thickeners.
- a detergent composition comprising detergent builder, bleach, silicate and a polymeric thickener comprising a copolymer of ethyl acrylic and methyl acrylic acids and at least one inorganic base, the said composition being free or substantially free of clay thixotropic thickeners.
- the inorganic base comprises a salt of an alkaline metal such as sodium hydroxide.
- the thickener comprises ACRYSOL ASE-108 (ACRYSOL ASE is a registered trade mark ).
- the composition preferably comprises from 1% to 5% of ACRYSOL ASE-108 by weight of the total composition, more preferably from 1.5% to 3%. In the most preferred embodiment of the invention the composition comprises from substantially 2% of ACRYSOL ASE-108 by weight of the total composition.
- ACRYSOL ASE-108 is a copolymer emulsion containing a cross linked copolymer of ethyl acrylic and methyl acrylic acids with a mean molecular weight in the order of 500,000.
- the ACRYSOL ASE-108 polymer comprise a number of polymer chains which are tightly wound to one another. Neutralisation with a suitable inorganic base such as sodium hydroxide causes the polymer chains to unwind. This produces an interwoven structure of polymer chains leading to viscosity increases and stabilisation of suspended solids with the system.
- a suitable inorganic base such as sodium hydroxide
- the silicate provides the composition with alkalinity for cleaning efficiency as well as acting as a corrosion inhibitor and providing protection for glazed surfaces of china ware.
- Preferred silicates include silicate solutions of suitable alkali or metals and especially sodium or potassium silicate.
- the incorporation of the silicate in a solution enhances ease of manufacture.
- Sodium silicate solution exists in a number of different grades with varying ratios of alkalinity to silicate content, varying total solid content and varying viscosities.
- the high alkalinity, high active grades of this material should be preferred such as with SiO2:Na2O ratios of 2:1 or less.
- SiO2:Na2O ratios of 2:1 or less.
- work conducted on neutral grades of silicate with SiO2:Na2O ratios at 3.3:1 or more has shown improvement in product viscosity but at the expense of alkalinity.
- the effect of blend of the two types of material have been studied and the preferred chemical and physical characteristics of the optimum blend established.
- a detergent composition comprising a detergent builder, a bleach, a thickener, an inorganic base and sodium silicate characterised in that the sodium silicate has a SiO2:Na2O ratio within the range from substantially 2.3 to 2.6:1 and an active solid content within the range from 42% to 44% of the total composition.
- the preferred thickener is an ACRYSOL ASE polymer thickener and preferably ACRYSOL ASE-108 in combination with an inorganic base.
- the preferred sodium silicate grade has a SiO2:Na2O ratio of substantially 2.5:1 and an active solids content of substantially 43.6%.
- the amount of silicate used is preferably in the range from 2.5% to 22% by weight of the total composition, more preferably from 15% to 22% and still more preferably from 18% to 20%.
- a detergent composition comprising water, the copolymer emulsion of ethyl acrylic and methyl acrylic acids known as ACRYSOL ASE-108 and at least one inorganic base, wherein the ratio by weight of the ACRYSOL ASE-108 to the water to the base is in the range from 1:3.5:1.5 to 1:5:1.5
- the ratio of ACRYSOL ASE-108 to water to base is substantially 1:4:1.5
- a suitable builder may be used such as an an alkali metal tripolyphosphate, sodium tripolyphosphate being particularly preferred.
- the amount of builder used is preferably in the range from 5% to 35% by weight of the total composition, more preferably from 20% to 33% by weight of the total composition and especially in the range from 25% to 27% by weight of the total composition.
- the main purpose of the builder is to soften hard water and to emulsify and/or to peptise soils.
- the preferred grade is partially moisturised having approximately 3% water content corresponding to a degree of hydration in the order of 1, and having fine granular particle size distribution.
- hypochlorites such as alkali metal hypochlorites preferably sodium hypochlorite. This bleach is the source of the available chlorine within the formulation.
- the compound should provide at least 0.2% available chlorine in the final product although substantially 0.7% to 1.5% available chlorine is preferred.
- composition may optionally include further constitutents such as alkali metal carbonates, perfumes or anti foaming agents.
- the hydroxide such as sodium hydroxide is preferably included in the range from 2% to 4% and preferably substantially 3% by weight of the total composition.
- the carbonate such as sodium carbonate is preferably included in the range from 0% to 9% and more preferably substantially 2% by weight of the composition.
- the composition preferably comprises from 8.0% to 10% by weight of water (excluding water content of raw materials) and more preferably in the order of 8% water.
- compositions generally do not comprise clay thickeners.
- compositions of the invention are aqueous thixotropic detergent compositions with particular application as automatic dishwasher detergent compositions.
- This example was successfully provided both at laboratory scale (up to 10kg) and on a pilot plant (up to 120 kg).
- a method of making a detergent composition comprising the addition of a polymeric thickener to water followed by the addition in order of the following components to the mixture: inorganic base, silicate solution, bleach and builder.
- the inorganic base comprises sodium hydroxide
- the silicate solution comprises sodium silicate
- the bleach comprises sodium hypochlorite
- the builder comprises sodium tripolyphosphate
- compositions may be included in the composition.
- example 1 was subjected to various tests to ensure that the physical properties of the composition were acceptable to the consumer.
- Unstable compositions will separate into a clear liquor and high solids content lower phase. This is undesirable to the consumer and also adversely affects the performance of the composition.
- polycarboxylate polymer ACRYSOL ASE-108 enhances the stability of the composition whilst also improving the rheology of the composition.
- the stability modifying effect of the polymer can be measured in a number of ways for example as follows:-
- the standard test conditions were as follows: - Centrifuges used: - M.S.E. Centaur 2 Model. 4 samples filled to 100g Rotated at 3,500 r.p.m. for 150 minutes.
- Products are placed on test under a variety of conditions in both final packaging (when appropriate) and glass bottles, for at least a 3 month period.
- Typical conditions for testing are refrigerated (5°C), ambient temperature (20°C), elevated temperature (37 to 40°C) and when appropriate light exposure testing and testing under conditions of high humidity.
- a series of physical and chemical parameters are checked on a monthly basis, these are
- the initial data on viscosity is as follows: -
- Viscosity was measured with a Brookfield RV8 Viscometer at quoted speeds using spindle 6 at 20°C.
- Example 2 The composition of Example 2 was prepared by the method previously described. Three formulations were prepared each with a different grade of sodium silicate solution.
- Formulation 2A comprises a neutral grade (crystal 79)
- formulation 2B comprises an intermediate grade (crystal 100S)
- formulation 2C comprises an alkaline grade of sodium silicate solution (Crystal 120A) supplied by Crosfield Chemicals .
- T.I. is the Thixotropic Index and is defined as the ratio of the viscosity of the composition at 5 rpm to the viscosity at 50 rpm.
- the products final viscosity and the thixotropic index are seen to vary with the grade of silicate used.
- the most preferred grade of silicate has been found to be 2.5:1 SiO2:Na2O.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909027372A GB9027372D0 (en) | 1990-12-18 | 1990-12-18 | Detergent composition |
| GB9027372 | 1990-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0491553A2 true EP0491553A2 (fr) | 1992-06-24 |
| EP0491553A3 EP0491553A3 (en) | 1993-06-30 |
Family
ID=10687154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19910311703 Withdrawn EP0491553A3 (en) | 1990-12-18 | 1991-12-17 | Detergent composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0491553A3 (fr) |
| AU (1) | AU8984391A (fr) |
| GB (1) | GB9027372D0 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046659A1 (fr) * | 1996-05-31 | 1997-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Agents de blanchiment aqueux |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE626321A (fr) * | 1961-12-20 | |||
| US3671440A (en) * | 1970-01-16 | 1972-06-20 | Chemed Corp | Process of cleaning |
| US4116849A (en) * | 1977-03-14 | 1978-09-26 | The Procter & Gamble Company | Thickened bleach compositions for treating hard-to-remove soils |
| US4252665A (en) * | 1979-06-13 | 1981-02-24 | Monsanto Company | Disinfectant cleaning compositions |
| NZ203036A (en) * | 1982-01-18 | 1986-04-11 | Colgate Palmolive Co | Aqueous automatic dishwasher composition with thixotropic properties |
| US4597889A (en) * | 1984-08-30 | 1986-07-01 | Fmc Corporation | Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers |
| US5064553A (en) * | 1989-05-18 | 1991-11-12 | Colgate-Palmolive Co. | Linear-viscoelastic aqueous liquid automatic dishwasher detergent composition |
| NZ226174A (en) * | 1987-09-23 | 1991-03-26 | Colgate Palmolive Co | Aqueous cleaning composition; no- or low-phosphorus built mixture |
| NZ226709A (en) * | 1987-11-05 | 1990-10-26 | Colgate Palmolive Co | Al 2 o 3 or tio 2 and polyacrylic acid polymer in thixotropic dishwashing compositions |
| US4867896A (en) * | 1988-02-17 | 1989-09-19 | Lever Brothers Company | Cleaning compositions containing cross-linked polymeric thickeners and hypochlorite bleach |
| US4859358A (en) * | 1988-06-09 | 1989-08-22 | The Procter & Gamble Company | Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection |
| EP0439878A1 (fr) * | 1990-01-30 | 1991-08-07 | Union Camp Corporation | Détergent sous forme de gel clair pour machines à laver la vaisselle |
| NZ237301A (en) * | 1990-03-13 | 1992-09-25 | Colgate Palmolive Co | Aqueous automatic dishwasher detergent compositions comprising potassium tripolyphosphate, cross-linked polycarboxylate-type thickener and sodium ions |
-
1990
- 1990-12-18 GB GB909027372A patent/GB9027372D0/en active Pending
-
1991
- 1991-12-17 EP EP19910311703 patent/EP0491553A3/en not_active Withdrawn
- 1991-12-18 AU AU89843/91A patent/AU8984391A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046659A1 (fr) * | 1996-05-31 | 1997-12-11 | Henkel Kommanditgesellschaft Auf Aktien | Agents de blanchiment aqueux |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9027372D0 (en) | 1991-02-06 |
| AU8984391A (en) | 1992-06-25 |
| EP0491553A3 (en) | 1993-06-30 |
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