EP0802971B1 - Waschmittel - Google Patents

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Publication number
EP0802971B1
EP0802971B1 EP96900948A EP96900948A EP0802971B1 EP 0802971 B1 EP0802971 B1 EP 0802971B1 EP 96900948 A EP96900948 A EP 96900948A EP 96900948 A EP96900948 A EP 96900948A EP 0802971 B1 EP0802971 B1 EP 0802971B1
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EP
European Patent Office
Prior art keywords
polymer
soil
composition
release
polymers
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EP96900948A
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English (en)
French (fr)
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EP0802971A1 (de
Inventor
Wilfried Blokzijl
Simon Unilever Research Lab. Veerman
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to EP96900948A priority Critical patent/EP0802971B1/de
Publication of EP0802971A1 publication Critical patent/EP0802971A1/de
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Publication of EP0802971B1 publication Critical patent/EP0802971B1/de
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition 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
    • 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
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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

Definitions

  • EP-A-272,033 discloses soil-release polymers comprising oxypropyleneoxy moieties.
  • US-A-3,962,152 (P&G) describes soil-release polymers containing polyethyleneglycol units having low molecular weight, wherein the molar ratio of terephthalate to polyethyleneglycol of 1.33 to 1.54 and wherein the molecular weight is in the range of 25,000 to 55,000. It is indicated that these polymers may be incorporated in solid detergent compositions.
  • EP-A-201,124 discloses soil-release polymers that contain two polyethyleneglycol units between which 3 to 5 ethylene-terephthalate units are positioned and the Examples further describe that the polymer mix is fractioned in ethanol to remove an ethanol-insoluble fraction, which method is also used in EP-A-199,403.
  • EP-A-253,567 discloses compositions comprising quaternary ammonium surfactant and soil-release polymers comprising a molar ratio of terephthalate to polyethyleneglycol of from 3:1 to 1.67:1.
  • WO-A-95/18207 discloses liquids with high levels of nonionic surfactant and soil-release polymers. These polymers are present in these isotropic liquids in a dissolved state.
  • Soil-release polymers that are commercially available include Permalose® (ex ICI), Repel-O-Tex® (ex Rhone Poulenc), Sokalan 9798X® (ex BASF) and Zelcon® 6126 (ex Dupont).
  • Soil-release polymers in particular commercially available soil release polymers, generally have only low solubility and dissolve and disperse slowly in the wash liquor, which may lead to the polymers being less effective in the wash. This is in particular true for soil-release polymers in granule form.
  • US-A-4,569,772 Coldgate
  • US-A-4,571,303 Coldgate
  • soil-release polymers tend to become less active upon storage, e.g the polymer itself, or the polymer in a liquid or solid detergent composition.
  • US-A-4,569,772 Coldgate
  • US-A-4,571,303 Coldgate
  • Liquid detergent compositions may become inhomogeneous, e.g. ingredients may separate and/or solid particles may sediment. Further, the number of interactions between the ingredients of liquid detergent compositions generally makes it difficult to prepare compositions which are chemically stable, especially upon storage. Even though its components have a more or less fixed position, soil-release polymer may also be chemically unstable in the solid detergent compositions, e.g. as a consequence of contact with moisture.
  • EP-A-199,403 (P&G) and EP-A-576,777 (P&G) describe isotropic liquid detergent compositions that comprise particular soil-release polymers. These polymers may however hydrolyse upon storage, resulting in low soil-release effectivity. Further, stabilising ingredients are required to stably incorporate the soil-release polymer in the isotropic liquid.
  • the present invention is directed to a liquid detergent composition
  • a liquid detergent composition comprising surfactant material, electrolyte material and soil-release polymer, characterised in that the composition has a structure and comprises precipitated soil-release polymer.
  • the present invention is further directed to a process for preparing a structured liquid detergent composition comprising surfactant material, electrolyte material and a soil-release polymer by blending the ingredients characterised in that the polymer is added to the detergent compositions at a temperature below the melting point of the polymer and a temperature about the cloud point of the polymer in the liquid.
  • compositions comprise a soil-release polymer composition, which may comprise one or more polymers of the following general formulae I or II: (I) HO-(CH2-CH2-O-CO-R1-CO-O)x-(CH2-CH2-O)n-H; (II) HO-(CH2-CH2-O-CO-R1-CO-O)y-(CH2-CH2-O)n-(CO-R1-CO-O)-(CH2 -CH2-O-CO-R1-CO-O)y-(CH2-CH2-O)n-H; wherein R1 is a phenyl, y is (independently) 0, 1 or 2, x is 1, 2 or 3 and wherein n is from 10 to 100.
  • the polymer of formula (I) is present in the polymer. composition at a level of from 20 to 100% by weight of the polyester material.
  • the polymer of formula (II) is present in the polymer composition at a level of from 20 to 100% by weight of the polyester composition. It is preferred to have at most 60% by weight of the total of polyester material of polymers I and/or II present in the polymer composition, more preferably 80%, most preferably substantially 100%, as it is preferred that the polymer composition is water-soluble.
  • soil-release polymers which are copolymers of ethylene glycol, polyoxyethylene glycol and terephthalic acid are described in GB-A-2 137 652.
  • the present invention is further directed to a method of washing with a composition according to claim 1, wherein the wash liquor has a pH of at least 6 and at most 10.
  • EP-A-576,777(P&G) describes the use of PVP to keep the soil-release polymer in solution.
  • EP-A-401, 123 discloses soil-release polymer containing iso-terephthalate units that may be included in liquid detergent compositions.
  • a further complication for preparing detergent compositions comprising soil-release polymer is that the polymers may hydrolyse under influence of alkaline material.
  • the electrolyte precipitates or salts out the polymer.
  • the resulting polymer particles or droplets are thought not to be subject to hydrolysis during storage.
  • the precipitated soil-release polymer remains effective during the wash, even after incorporation in the liquid.
  • Soil-release polymers can also be precipitated or salted-out in other ways, e.g. by raising the temperature (preferably in the absence of water-insoluble polymers) or by evaporating the reaction mixture after preparation of the polymer (preferably in the absence of water-insoluble polymer particles).
  • precipitated, salted out and emulsions of soil-release polymer are all considered as precipitated soil-release polymer.
  • the effectiveness of the precipitated soil-release polymer is even more surprising as we have found that water-insoluble polymer components that may be present in polymer compositions may adversely influence the soil-release performance of the polymer composition. This problem applies in particular to polymer compositions that are incorporated in detergent compositions. Without wishing to be bound by any theory, it has been found that water-insoluble polymer components are not effective as soil-release agent, e.g. due to their low solubility in the wash liquor. It is however believed that, e.g. as a consequence of temperature changes, the water-insoluble polymer components, or more in particular the polyoxyethylene groups, may melt and become pasty or liquid, e.g. during polymer preparation or during detergent preparation.
  • the water-insoluble polymer components may blend with active soil-release polymer material. If the temperature subsequently drops below the melting temperature of the water-insoluble polymer components, then the active soil-release polymer material may be trapped inside the water-insoluble polymer component. This may lead to an overall decrease in soil-release activity.
  • the weight average particle size of soil-release polymer particles in the liquid is from 1 to 500 ⁇ m.
  • the liquid detergent composition according to this aspect of the invention comprises a polymer mixture that comprises one or more polymers of the formulae I and II as defined below.
  • the total level of electrolyte is from 1 to 60% by weight of the composition, more preferably from 5 to 45% by weight, most preferably from 10 to 30% by weight.
  • compositions according to the invention comprise salting-out electrolyte having a lyotropic value of less than 9.5 and preferably less than 9.0.
  • Salting-out electrolyte has the meaning ascribed in specification EP-A-0,079 646.
  • Preferred salting-out electrolytes are selected from alkali metal and ammonium salts of phosphates (including pyro, ortho and poly phosphates), silicates, borates, carbonates, sulphates, citrates, NTA and succinates.
  • the liquid compositions contain at least 1% by weight of a salting-out electrolyte, more preferably at least 2%, most preferably at least 5% by weight and preferably at most 20% by weight, more preferably at most 15% by weight of a salting-out electrolyte.
  • some salting-in electrolyte (as defined in the latter specification) may also be included.
  • hydrotrope material may break up the structure of the liquids and may lead to dissolvign of the soil-release polymer in the liquid composition, it is preferred only to use levels of hydrotrope material of lower than 10%, more preferably lower than 5%, most preferably lower than 3%.
  • the invention is in particular useful for liquids with contain material with alkaline surfaces. Such surfaces tend to deactivate soil-release polymers, whereas we have surprisingly found that the deactivation is far lower in liquids according to the present invention. Therefore, preferably the liquids comprise alkaline material selected from zeolite, carbonate, silicate and clay material.
  • soil release polymers of the invention do not only show good soil-release activity, but we have also found that they may be used in preparing detergent compositions comprising the specific polymer composition wherein the compositions are stable upon storage and remain effective in soil-release in the wash after storage.
  • the polymer mixture that is incorporated into detergent compositions comprises low levels of water-insoluble polymer material, preferably less than 40% by weight of the polyester of water-insoluble polyester material when the mixture is dissolved at 1% in water at a temperature of 25°C. More preferably, less than 30% by weight is water-insoluble, most preferably less than 20%, in particular less than 10%, e.g. substantially 0% by weight of the polyester. It is noted that the structured liquids of the invention are in particular useful as they also allow suspending of the insoluble fraction of the polymer, which could not be achieved by liquids of the prior art.
  • Polymer compositions with low levels of water-insoluble polymers can be prepared by various ways including centrifuging and altering the processing route, e.g. by using lower levels of terephthalate and/or using higher molecular weight PEG.
  • polyethyleneglycol units in the polymer composition of the invention that contain 10 to 100 units of ethyleneglycol.
  • they have a molecular weight of higher than about 1500, more preferably higher than about 2000, most preferably higher than about 2200, in particular higher than about 2500 and preferably at most about 5000, more preferably at most about 4000, most preferably at most about 3000.
  • the number average molecular weight of the polymers in said polymer composition is between 500 and 10,000, preferably more than 1,000, more preferably more than 2,000, most preferably more than 3,000. But preferably less than 9,000, more preferably less than 8,000.
  • Molecular weight can be determined by various methods, e.g. NMR-spectroscopy, Matrix Assisted Laser Desorption Ionisation - time of flight- Mass Spectrometry (MALDI-tof-MS) or Gel Permeation Chromatography (GPC).
  • the terephthalate unit that is used for the preparation of polymer compositions of the invention may be selected from ortho, meta and preferably para phenyyl-dicarboxylates.
  • detergent compositions comprising the polymer composition according to the above aspect of the invention show excellent soil-release activity.
  • water-insoluble polymer components in the polymer composition may adversely influence the soil-release performance of detergent compositions comprising the polymer composition.
  • Structured liquids can either be internally structured, whereby the structure is formed by primary ingredients (e.g. surfactant material) and/or by providing a three dimensional matrix structure using secondary additives (e.g. polymers, clay and/or silicate material).
  • primary ingredients e.g. surfactant material
  • secondary additives e.g. polymers, clay and/or silicate material
  • the surfactant can exist as a molecular solution, or as a solution of spherical micelles, both of these solutions being isotropic, i.e. they are not structured. With the addition of further surfactant and/or electrolyte structures of surfactant material may form.
  • lamellar structures are lamellar droplets of surfactant material in which the dispersed structuring phase is generally believed to consist of an onion-like configuration comprising concentric bilayers surfactant molecules, between which water is trapped, the aqueous phase.
  • Liquids with a lamellar droplets structure are preferred as systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties, i.e. low viscosity with stability.
  • Such liquids have for example been described in A. Jurgens, Microstructure and Viscosity of Liquid Detergent, Tenside Surfactants Detergent 26 (1989) 222 and J.C.
  • a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and sometimes, electron microscopy.
  • soil-release polymers can be stably incorporated in liquid detergent compositions, whilst remaining its soil-releasing activity, by adding the polymer at a temperature below the melting point of the polymer and above the cloud point of the polymer in the liquid.
  • the melting point of the polyoxyethylene parts in the soil-release polymer illustrates the melting point of the polymer well.
  • the melting point of at least 80% by weight (preferably 90% by weight) of the polyoxyethylene of the polymer is at least 30°C, more preferably at least 40°C, most preferably at least 50°C and preferably at most 110°C.
  • the cloud point of the polymer in the liquid is at most 25°C, more preferably at most 22°C, most preferably at most 20°C, in particular at most 17°C.
  • the cloud point will preferably be higher than 0°C.
  • Solid and Liquid compositions of the invention also comprise surfactant materials, preferably at a level of at least 1% by weight of the composition, more preferred at least 5% by weight, most preferred at least 10% by weight of the composition; and preferably at a level of at most 70% by weight, more preferably at most 40%, most preferably at most 35% by weight.
  • the surfactant material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • an alkali metal soap of a C12-C18 carboxylic acid Preferably the level of soap is from 1 to 35% by weight of the composition, more preferred from 5 to 25%.
  • compositions according to the invention may comprise electrolyte material, some or all of which may be builder material. It is noted that for the purpose of the invention, the term electrolytes includes builder material.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • detergency builder material some or all of which may be electrolyte.
  • surfactant materials such as for example soaps, also have builder properties.
  • Liquid detergent compositions preferably comprise a deflocculating polymer, e.g. as described in WO-A-91/06622, WO-A-91/06623, GB-A-2,237,813, WO-A-91/09109, PCT Application No. WO 94/03575 and/or EP-A-0,346,995.
  • the deflocculating polymer will be used at levels of from 0.01 to 5% by weight of the composition, more preferably from 0.1 to 3.0% especially preferred from 0.25 to 2.0%.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and usually, present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), enzyme stabilisers, anti-redeposition agents, germicides and colorants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic
  • Detergent compositions according to the present invention are liquid. Preferably, the compositions of the present invention are concentrated.
  • Liquid compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 s-1, more preferred less than 1,500 mPas, most preferred less than 1,000 mPas and preferably higher than 100, more preferably higher than 500 mPas at 21 s-1.
  • Liquid compositions according to the invention are physically stable, i.e. they will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • the pH, as provided to the wash liquor, preferably by a liquid, is at least 6, more preferably at least 7.5, most preferably at least 8.
  • the pH is at most 10, more preferably at most 9.
  • Polymers were dispersed in water at 1% by weight. Insoluble fractions were separated from the soluble fractions using ultracentrifugation and subsequent freeze drying. To obtain information about the monomer distribution, molecular weight and monomer ratio, chemical composition of the polymer fractions were studied using 1 H and 13 C NMR-spectroscopy, Matrix Assisted Laser Desorption Ionisation - time of flight- Mass Spectrometry (MALDI-tof-MS), UV-spectroscopy, IR-spectroscopy and Gel Permeation Chromatography (GPC). The Malditof has been described in M. Karas, U. Bahr, U. Giesmann, Mass Spectrometry Review 10 (1991) 335 and can be used in combination with NMR to determine the type of polymers.
  • MALDI-tof-MS Matrix Assisted Laser Desorption Ionisation - time of flight- Mass Spectrometry
  • UV-spectroscopy UV-spectroscopy
  • IR-spectroscopy IR-spectroscopy
  • Polyester swatches were prewashed several times under standard European conditions with the liquid to be tested.
  • the prewashed polyester swatches were contaminated with a heptane stock solutions containing oleic-acid, mono-oleate, squalane, squalene, wax-ester, di-olein and tri-olein.
  • the contaminated swatches were washed under model conditions with a non-enzyme liquid optionally containing soil-release polymer.
  • the swatches were dried and extracted with THF after addition of an internal standard.
  • the THF extracts were added to a GC-Vial and the THF was evaporated using a Reactie-Vap evaporating unit under a Nitrogen flow.
  • the cloud temperature decreases dramatically when electrolytes are present. Stronger salting-out electrolytes, such as sodium citrate are more effective in bringing about a decrease of cloud temperature.
  • the cloud temperature increases with increasing molecular weight of the polyoxyethylene moieties as well as with decreasing weight percentage of ethyleneterephthalate.
  • Polymer A which is completely soluble in water, comprises 23% ethylene-terephthalate groups and 77% polyoxyethylene groups.
  • the polymer is dispersed at a level of 0.5% by weight in a liquid detergent composition, as given in Table 3.
  • the polymer was added under the melting point and stored above its clouding point, i.e. the polymer was precipitated.
  • the liquid showed good stability.
  • Polymer A* i.e. composition of polymer A with also present the water-insoluble fraction, was also dispersed in the above liquid formulation, at a percentage of 0.5%. This formulation showed acceptable storage stability and gave less good %detergency (due to the lower level of active soil-release polymer as compared with polymer A).
  • Polymer B that is not according to the present invention gave a % removal of only 40%.
  • composition was prepared by adding the ingredients in the order listed. The formulation was cooled after addition of the active premix to a temperature of about 30°C at which point the minors were added. Ingredients by weight % Water to 100 Fluorescer 0.1 KOH 9.8 Citric acid 8.2 Glycerol 2 Borax 1.5 Zeolite 15 Stabilising Polymer A11 1 Active Premix 30 Minors 1.4
  • Soil-Release Polymer Permalose TM, ex ICI
  • Composition 1 the SRP polymer was added at the end of the preparation process at room temperature.
  • composition A the SRP polymer was added to the water at the beginning of the process.
  • composition B the SRP polymer was added before the addition of the active premix.
  • composition C the SRP polymer was added after addition of the premix, but before cooling.
  • composition 1 showed both good formulation viscosity and good washing results.
  • the melting points of the polymers were measured by Differential Scanning Calorimetry as peak value:
  • the Tc (cloud points) of the water-soluble fraction were determined by UV turbidity measurements at 500 nm of a 1% solution in water.
  • the % water-insoluble components of the polymer mixtures were: Polymer 1 29% insol Polymer 2 20% insol Polymer 3 35% insol Polymer 4 22% insol
  • Polymers 1, 2, 3 and 4 of example 5 were added to the liquid of Table 3 at a level of 0.5% and a temperature of between 25-30°C. Liquids were also prepared with polymer X (a polymer with an insoluble fraction of 65%) and without a soil-release polymer. The liquids were tested according to the washing performance method identified above. Removal of each individual component was determined quantitatively. Shown is the removal (in %) of the triglyceride component: Composition with: % removal of triglyceride component Polymer 1 50.2 Polymer 2 38.5 Polymer 3 50.4 Polymer 4 42.2 Polymer X # 30.0 No polymer 26.0 #: Polymer X has 65% of insoluble material.
  • Soil release polymer 3 of Example 4 was added to both liquids at a temperature of lower than 30°C and precipitated. The resulting liquids were stable and showed improved washing performance.

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  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (7)

  1. Flüssige Waschmittel-Zusammensetzung, enthaltend Tensid-Material, Elektrolyt-Material und schmutzfreisetzendes Polymeres, dadurch gekennzeichnet, daß die Zusammensetzung eine Struktur hat und ausgefälltes schmutzfreisetzendes Polymeres enthält.
  2. Zusammensetzung gemäß Anspruch 1, worin der Elektrolyt einen lyotropen Wert von weniger als 9,5 hat.
  3. Zusammensetzung gemäß den Ansprüchen 1-2, worin die durchschnittliche Teilchengröße der schmutzfreisetzenden Polymer-Teilchen im Bereich von 1 bis 500 µm liegt.
  4. Zusammensetzung gemäß den Ansprüchen 1-3, worin zumindest 60 Gewichtsprozent des Polymeren sich in einer 1%-Lösung in Wasser auflöst.
  5. Verfahren zur Herstellung einer strukturierten flüssigen Waschmittel-Zusammensetzung, enthaltend Tensid-Material, Elektrolyt-Material und ein schmutzfreisetzendes Polymeres durch Mischen der Bestandteile, dadurch gekennzeichnet, daß das Polymere zu der Waschmittel-Zusammensetzung bei einer Temperatur unterhalb des Schmelzpunkts des Polymeren und einer Temperatur oberhalb des Trübungspunkts des Polymeren in der Flüssigkeit zugesetzt wird.
  6. Verfahren gemäß Anspruch 5, worin der Schmelzpunkt zumindest 30°C und der Trübungspunkt höchstens 25°C ist.
  7. Verfahren des Waschens mit einer Zusammensetzung gemäß Anspruch 1, worin die Waschflüssigkeit einen pH-Wert von zumindest 6 und höchstens 10 hat.
EP96900948A 1995-01-12 1996-01-04 Waschmittel Expired - Lifetime EP0802971B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96900948A EP0802971B1 (de) 1995-01-12 1996-01-04 Waschmittel

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP95300175 1995-01-12
EP95300175 1995-01-12
PCT/EP1996/000123 WO1996021720A1 (en) 1995-01-12 1996-01-04 Detergent composition
EP96900948A EP0802971B1 (de) 1995-01-12 1996-01-04 Waschmittel

Publications (2)

Publication Number Publication Date
EP0802971A1 EP0802971A1 (de) 1997-10-29
EP0802971B1 true EP0802971B1 (de) 1999-08-11

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EP96900948A Expired - Lifetime EP0802971B1 (de) 1995-01-12 1996-01-04 Waschmittel

Country Status (9)

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EP (1) EP0802971B1 (de)
AR (1) AR000664A1 (de)
AU (1) AU713996B2 (de)
BR (1) BR9606911A (de)
CA (1) CA2208343A1 (de)
DE (1) DE69603702T2 (de)
ES (1) ES2136382T3 (de)
WO (1) WO1996021720A1 (de)
ZA (1) ZA96217B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8900328B2 (en) 2009-03-16 2014-12-02 The Procter & Gamble Company Cleaning method
DE102015003483A1 (de) * 2015-03-19 2016-09-22 Henkel Ag & Co. Kgaa Polymere Ester aromatischer Dicarbonsäuren als schmutzablösevermögende Wirkstoffe

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1049367A (en) * 1974-06-25 1979-02-27 The Procter And Gamble Company Liquid detergent compositions having soil release properties
US3959230A (en) * 1974-06-25 1976-05-25 The Procter & Gamble Company Polyethylene oxide terephthalate polymers
US3962152A (en) * 1974-06-25 1976-06-08 The Procter & Gamble Company Detergent compositions having improved soil release properties
NZ207692A (en) * 1983-04-04 1986-04-11 Colgate Palmolive Co Soil-release promoting liquid detergent containing terephthalate polymers

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Publication number Publication date
WO1996021720A1 (en) 1996-07-18
EP0802971A1 (de) 1997-10-29
AU4486196A (en) 1996-07-31
AU713996B2 (en) 1999-12-16
DE69603702D1 (de) 1999-09-16
CA2208343A1 (en) 1996-07-18
AR000664A1 (es) 1997-07-10
ES2136382T3 (es) 1999-11-16
DE69603702T2 (de) 2000-01-27
ZA96217B (en) 1997-07-11
BR9606911A (pt) 1997-10-21

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