WO1997009405A2 - Composition detergente liquide contenant de la silice hydrophile dispersee - Google Patents

Composition detergente liquide contenant de la silice hydrophile dispersee Download PDF

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Publication number
WO1997009405A2
WO1997009405A2 PCT/EP1996/003659 EP9603659W WO9709405A2 WO 1997009405 A2 WO1997009405 A2 WO 1997009405A2 EP 9603659 W EP9603659 W EP 9603659W WO 9709405 A2 WO9709405 A2 WO 9709405A2
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WO
WIPO (PCT)
Prior art keywords
weight
composition
water
liquid
liquids
Prior art date
Application number
PCT/EP1996/003659
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English (en)
Other versions
WO1997009405A3 (fr
Inventor
Frederik Jan Schepers
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to EP96930057A priority Critical patent/EP0871694B1/fr
Priority to CA002230229A priority patent/CA2230229C/fr
Priority to AU69257/96A priority patent/AU6925796A/en
Priority to DE69613004T priority patent/DE69613004T2/de
Publication of WO1997009405A2 publication Critical patent/WO1997009405A2/fr
Publication of WO1997009405A3 publication Critical patent/WO1997009405A3/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the present invention relates to low or no water liquid detergent compositions comprising solid particles, and to a method of preparing such particles and such liquids.
  • Liquid detergent compositions with low water levels are known in the art and have been described in quite a number of patent publications, e.g. in US-A-4,316,812, US-A- 4,874,537 and EP-A-0,484,095 and provide a way of concentrating liquid detergents without giving in on washing performance.
  • Liquid detergent compositions with low or no water levels may comprise a liquid phase and a dispersion of solid detergent components and adjuncts depending on the purpose of use, primarily surfactants and builders.
  • the liquid phase often comprises a nonionic surfactant as major component, which apart from acting as carrier liquid for the detergent components, usually and preferably also has detergent-active properties, thereby preferably acting wholly or in part as the surfactant ingredient.
  • the liquid phase may comprise a nonionic surfactant and/or surfactant mixtures, such as mixtures of C13-C15 alcohols with an average of 3 ethoxy groups and C13-C15 alcohols with an average of 7 ethoxy groups and liquid phases as described in GB-A-1,462,134, WO 91/12313, WO 91/14765 and EP-A- 0,510,762.
  • the solid phase may for example comprises of builders, bleach, abrasives, dispersants, enzymes, solid surfactant material and/or minor ingredients such as fluorescers. It has been found very difficult to stably suspend solid particles in liquid compositions and various solutions have been proposed in the art.
  • Liquids with low or no water content comprising dispersed solid particles of the prior art generally contain high levels of solid material. Levels of 25% by weight or higher are generally used in order to arrive at stable dispersions of the solid particles in the liquid phase or to achieve the desired performance. High levels of solid particles may however lead to liquids with higher viscosity and/or poor dispersibility.
  • GB 1,205,711 discloses non-aqueous liquids comprising hydrophilic silica and solid dispersed silica.
  • liquids of the prior art may show setting, sedimentation, clear layer separation and/or poor dispersability.
  • Enzymatic liquid compositions with low or no water levels may be prepared by adding enzyme slurries to the liquid. These slurries require extra processing for preparation and consequently are more expensive. They are non-aqueous and viscous which means that they are more difficult to handle. Further, we have found that preparations with low water levels which are made with enzyme slurries may suffer from instability.
  • fluorescent agent and/or anti ⁇ redeposition agent can be incorporated in low or no water liquids with hydrophilic silica.
  • liquids comprising 0 to 20% by weight of water and enzymes can be prepared with good properties if the liquid comprises silicone and/or hydrophilic silica.
  • structured liquids with low water content with suspended enzyme particles can be prepared by precipitating the enzyme from an aqueous solution in the product. This is in particular surprising, as the skilled man would not be inclined to add water to low water containing liquids. Instead he would try to keep all ingredients and machinery as dry as possible.
  • liquids comprising enzymes can be prepared by mixing the enzyme with a liquid composition which comprises silica, from 0 to 20% by weight of water and further preferably comprises silicone.
  • the present invention is directed to liquid detergent composition
  • liquid detergent composition comprising from 0 to 20% by weight of water and a dispersed solid phase comprising hydrophilic silica material, wherein the composition comprises from 0.05 to 20% by weight of solid dispersed phase.
  • the present invention is further directed to liquid detergent composition
  • liquid detergent composition comprising from 0 to 20% by weight of water and a dispersed solid phase comprising hydrophilic silica material, wherein the composition comprises silicone material.
  • the present invention is further directed to liquid detergent composition
  • liquid detergent composition comprising from 0 to 20% by weight of water and a dispersed solid phase comprising hydrophilic silica material, wherein the composition further comprises fluorescent agent at a level of from 0.01 to 10%, preferably from 0.02 to 2% by weight and/or anti- redeposition agent at a level of from 0.1% to 5% by weight of the composition.
  • the present invention is further directed to a process of preparing liquids comprising 0 to 20% by weight of water and enzymes, by adding enzyme to the liquid, wherein the liquid preferably comprises silicone and/or hydrophilic silica.
  • the present invention is further directed to a process for producing structured liquids with low water content with suspended enzyme particles, said process involving the precipitation of the enzyme from an aqueous solution in the product.
  • the present invention is further directed to a method of preparing liquids comprising enzymes by mixing the enzyme with a liquid composition which comprises silica, from 0 to 20% by weight of water and further preferably comprises silicone.
  • WO 94/29427 discloses liquids with high viscosity silicone droplets which may contain silica particles, and wherein the composition may further comprise hydrophobic silica particles.
  • WO 94/23009 discloses liquids with hydrophobic silica to which silicone oil may be added.
  • CA 2,066,008 discloses liquids with droplets of silicone oil which droplets may comprise silica, e.g. DB100 and Thompson-Hayward AF-IND-100.
  • EP 573,699 discloses silica particles (into which nonionic surfactant is absorbed) which are dispersed in silicone oil to produce antifoam particles. These particles may be included in liquids. The surfactant inside the silica prevents the silicone/silica droplets from co-agulating during storage.
  • EP 583,512 discloses the use of particles of silica with silicone, to protect sensitive ingredients, such as enzymes, in liquids.
  • GB 2,186,884 discloses particles (or droplets) of hydrophobic silica and silicone for use as enzyme stabilisers.
  • GB 1,205,711 discloses liquids with hydrophilic silica and enzymes.
  • hydrophilic silica allows for formulation of liquids comprising from 0 to 20% by weight of water and low levels of dispersed solid phase.
  • the liquids are stable and of low viscosity with no or low setting and low or no clear layer separation, whilst they have a good dispersibility.
  • silicone inclusion in liquids with hydrophilic silica and low or no water level enables stable suspending of solid particles, whilst the resulting liquid has low viscosity, low or no setting, low or no clear layer separation and good dispersibility.
  • liquids with fluorescent agent and/or anti-redeposition agent can be stable formulated with hydrophilic silica and low or now water.
  • no electrolyte is present and preferably the liquid contains some water.
  • Hydrophilic silica material The present invention requires the presence of hydrophilic silica, preferably present in dispersed form in the continuous phase of the liquid and forming a network which is able to disperse solid particles. Surprisingly, we have found that liquids of the invention with low solid levels, silicones, fluorescer and/or anti-redeposition agent do not suffer from the bad properties of liquids of the art comprising hydrophilic silica.
  • Hydrophilic silica material selected from amorphous silica, precipitated, fumed silica, gel-formation formed silica and mixtures thereof.
  • An example of such a silica material is Aerosil 200.
  • Mixtures of hydrophilic and hydrophobic silica e.g. Sypernat may also be used, e.g. on a 50:50 basis.
  • the silica level is higher than 0.5%, more preferably higher than 1.0%, most preferably higher than 2% by weight of the composition.
  • the level is lower than 8%, more preferably lower than 6%, most preferably lower than 4% by weight of the composition.
  • WO 93/24603, WO 94/01525 and WO 94/01524 disclose non ⁇ aqueous liquids with DB100, which is a commercially available silicone polymer material.
  • EP-A-515,418 and EP-A- 515,435 disclose the use of silicone material in non ⁇ aqueous liquids.
  • the silicone material is selected from polydialkylsiloxanes, wherein the alkyl may e.g. be C1-C6 and is preferably a methyl group.
  • Polydialkylsiloxanes may end blocking units, e.g. of a trimethylsilyl unit.
  • An example is DB100, ex Dow. Silicone may be added to the composition in the form of a mixture with silica material.
  • the silicone material is present at levels of from 0.01 to 1%, more preferably 0.05 to 0.5% by weight of the composition.
  • Liquids of the invention may not contain water.
  • the water content of liquid detergent products of the invention is from 0.05% to 20% by weight of the composition in order to provide high stability.
  • the water level is less than 15% by weight, more preferably less than 12% by weight, most preferably less than 10% and preferably more than 2%, 0%, more preferably more than 5% by weight of the composition.
  • Enzymes As indicated aboves, we have found that use of aqueous enzyme preparations leads to stable enzyme liquids, e.g. as compared to use of enzyme slurries which may e.g. contain salt crystals.
  • compositions according to the invention contain enzyme material.
  • Enzymes may be selected from lipases, amylases, proteases (10-1,000 GU/mg) , cellulases and mixtures thereof.
  • enzyme levels are from 0.1- 20%, more preferably from 1 to 5% by weight of the composition.
  • Enzymes often contain propyleneglycol/water mixtures or the like to stabilise them.
  • the enzyme solution contains no more than 10% by weight of water-soluble electrolyte material.
  • the liquid phase of the detergent composition of the present invention may comprise water, surfactant material and solvent material.
  • Liquids of the invention often and preferably comprise a liquid nonionic surfactant as major component and normally consist of a water-solubilising polyalkoxylene or a ono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived from, for example, fatty alcohols with from 9 to 15 carbon atoms (optionally branched, e.g.
  • alkylphenols preferably from 12 to 20 carbon atoms
  • dialkylphenols in which each alkyl group contains from 6 to 2 carbon atoms
  • primary, secondary or tertiary aliphatic alcohols or alkyl-capped derivatives thereof
  • monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
  • C10-20 fatty acid mono- and dialkanolamides wherein the alkyloyl group has from 1 to 3 carbon atoms are also common .
  • polyalkoxylene containing surfactants the polyalkoxylene moiety usually consists of an average of from 2 to 20 groups of ethylene oxide, propylene oxide groups or mixtures thereof.
  • the latter class includes those described in European Patent Specification EP-A-0,225,654, especially for use as all or part of the liquid phase.
  • ethoxylated nonionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 7 moles of ethylene oxide.
  • condensation products of Cll-13 alcohols with 3 or 7 moles of ethylene oxide may be used as the sole nonionic surfactant or in combination with those described in EP-A-0,225,654.
  • alkyl saccharides polyglycosides/oligosaccharides
  • alkyl saccharides polyglycosides/oligosaccharides
  • EP-A-0,092,355 EP-A-0,099,183
  • EP-A-0,070,074 EP-A-0,070,075
  • EP-A-0,070,075 EP-A-0,070,075
  • EP-A-0,070,076 EP-A-0,070,077
  • EP-A-0,075,994 EP-A-0,075,995 and EP-A-0,075,996.
  • a typical blend of surfactants includes a nonionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactant. Mixtures of different nonionic detergent surfactants may be used and also mixtures with other detergent surfactants such as anionic, cationic or ampholytic surfactants and soaps may also be used.
  • compositions of the invention comprise from 50 to 99% by weight of surfactant material, preferably the level is at most 97%, more preferably at most 95%, most preferably at most 94% and preferably, at least 70%, more preferably at least 80% by weight.
  • Solvent material may be included in compositions according to the present invention and in particular esters of Cl-6 carboxylic acid and/or poly-carboxylic acid and an alcohol selected from dihydric alcohols, ether alcohols and sterically hindered alcohols.
  • the ester is present in amounts of from 0.01 to 50% by weight of the composition.
  • a preferred ester material is propylene glycol di-acetate.
  • liquid detergent compositions are defined as being in a liquid to paste form, preferably in a liquid form.
  • the viscosity of the compositions is preferably at most 2,500 mPa.s, more preferably at most 1,500 mPa.s, most preferably at most 1,000 mPa.s at 21s-l at 25°C.
  • liquids of the invention have a physical stability of no or minimal phase separation after 2 months at 37°C. More preferably, the phase separation is less than 2mm per month at 37°C.
  • compositions according to the invention comprise from 0.1 to 20% by weight of a solid phase.
  • the level of the solid phase is at least 0.2%, more preferably at least 0.5% and, preferably, at most 15%, more preferably less than 10%, most preferably at most 9%, in particular preferred at most 5% by weight of the composition.
  • these low levels of solid particles are beneficial not only to the viscosity of the liquid, but also to the physical stability, whilst it would be expected that higher of dispersed solid particles would be required.
  • compositions of the invention may comprise electrolyte material.
  • electrolyte may affect the properties of the compositions of the invention, in particular upon storage. Therefore, compositions of the invention preferably comprise electrolyte at a concentration of lower than 1% by weight of the composition.
  • the composition preferably comprise electrolyte, more particular soluble electrolyte at a concentration of lower than 1% by weight, more preferably lower than 0.3% most preferably lower than 0.2% by weight of the composition.
  • the preferred weight ratio of water:electrolyte in the compositions of the invention is more than 1:0.03, more preferably more than 1:0.02 and preferably 1:0 or less.
  • Other ingredients comprise those remaining ingredients which may be used in liquid detergent products, such as fabric conditioning agents, abrasive material, bleaches, builders, enzymes, enzyme stabilising agents (if necessary), fluorescers, perfumes (including deoperfumes), micro-biocides, soil-suspending agents, anti-redeposition agent, corrosion inhibitors, and lather depressants.
  • Enzymes which can be used in liquids according to the present invention include proteolytic enzymes (protease) , amylolytic enzymes (amylase) , lipolytic enzymes (lipases) and cellulolytic enzymes (cellulase) .
  • proteolytic enzymes proteolytic enzymes
  • amylolytic enzymes amylolytic enzymes
  • lipolytic enzymes lipolytic enzymes
  • cellulolytic enzymes cellulase
  • Various types of proteolytic enzymes and amylolytic enzymes are known in the art and are commercially available. They may be incorporated as “prills", “marumes” or suspensions e.g.
  • the preferred level of enzyme materials is from 0.01 to 5% by weight of the composition.
  • Enzyme stability is preferably higher than 50% after 3 months storage at 37°C, more preferably higher than 80%, most preferably higher than 90%.
  • the total amount of the fluorescent agent or agents used in a detergent composition is preferably from 0.1 to 10%, more preferably 0.02 to 2% by weight.
  • anti-redeposition agents When it is desired to include anti-redeposition agents in the liquid detergent products, the amount thereof is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the total liquid composition.
  • Preferred anti-redeposition agents include carboxy derivatives of sugars and celluloses, e.g. sodium carboxyalkyl (e.g. methyl) cellulose, anionic poly- electrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates. Processing
  • the present invention further relates to a method of preparing liquids comprising 0 to 20% by weight of water and enzymes, by adding enzyme to the liquid.
  • the liquid further comprises silicone and/or hydrophilic silica.
  • the enzyme is added in the form of an aqueous solution.
  • a further embodiment of the present invention is that the enzyme can be included in a structured liquid composition comprising 0 to 20% by weight of water by precipitation the enzyme from an aqueous solution in the composition.
  • a further embodiment is a method of preparing liquids comprising enzymes by mixing the enzyme with a liquid composition comprising silica and 0 to 20% by weight of water and preferably silicones.
  • the enzymes are added after silica and silicones dispersal is complete and at temperatures of 30°C or lower.
  • the enzyme is in-situ precipitated.
  • composition A 1 Composition A 1
  • Nonionic 1 57.2 56.7
  • Nonionic 2 35.9 35.4
  • Composition 1 was prepared by dispersing the silica and silicones in the mixture of nonionic surfactants and water. Thereafter, the aqueous enzyme solution was added and the enzyme was in-situ precipitated at a temperature under 30°C.
  • composition A is instable, whereas composition 1 according to the present invention is stable, shows no setting, no sediment, no clear layer separation and good dispersability.
  • Example 2
  • Composition 1 2 3 4 B Ingredients (% by weight)
  • Nonionic 1 56.7 56.7 56.7 56.7 56.7
  • Nonionic 2 35.4 35.4 35.4 35.4 35.4
  • Aerosil 200 3 3 3 3 3 3
  • compositions 1, 2, 3 and 4 showed good stability upon storage, whereas composition B containing higher levels of electrolyte, showed instability after 2 days of storage.
  • Example 3
  • Nonionic 1 1) 56.7 56.7 56.7 56.7 Nonionic 2 2) 35.4 35.4 35.4 35.4 Water 1.8 1.8 1.8 1.8 Aerosil 200 3 3 3 3 Silicone 3) 0.1 0.1 0.1 0.1 Enzyme 4) 3 3 3 3 SCMC 5) 0.5 2.0 3.0 4.0 Total water 10 10 10 Total electrolyte 0.07 0.10 0.12 0.14 Viscosity 6) ⁇ thin liquids >
  • the four compositions showed good stability after 3 weeks storage at 37°C.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Cette composition liquide détergente comprend de 0 à 20 % en poids d'eau, ainsi que des particules dispersées, la phase solide consistant en un matériau hydrophile à base de silice. On décrit également un procédé consistant à inclure des enzymes dans cette composition, ainsi qu'un procédé de préparation de tels liquides.
PCT/EP1996/003659 1995-09-05 1996-08-20 Composition detergente liquide contenant de la silice hydrophile dispersee WO1997009405A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP96930057A EP0871694B1 (fr) 1995-09-05 1996-08-20 Composition detergente liquide contenant de la silice hydrophile dispersee
CA002230229A CA2230229C (fr) 1995-09-05 1996-08-20 Composition detergente liquide contenant de la silice hydrophile dispersee
AU69257/96A AU6925796A (en) 1995-09-05 1996-08-20 Liquid detergent composition comprising dispersed hydrophilic silica
DE69613004T DE69613004T2 (de) 1995-09-05 1996-08-20 Flüssige waschmittelzusammensetzung enthaltend dispergierte hydrophile kieselsäure.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95202403.2 1995-09-05
EP95202403 1995-09-05

Publications (2)

Publication Number Publication Date
WO1997009405A2 true WO1997009405A2 (fr) 1997-03-13
WO1997009405A3 WO1997009405A3 (fr) 1997-05-09

Family

ID=8220612

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003659 WO1997009405A2 (fr) 1995-09-05 1996-08-20 Composition detergente liquide contenant de la silice hydrophile dispersee

Country Status (7)

Country Link
EP (1) EP0871694B1 (fr)
AU (1) AU6925796A (fr)
CA (1) CA2230229C (fr)
DE (1) DE69613004T2 (fr)
ES (1) ES2158341T3 (fr)
WO (1) WO1997009405A2 (fr)
ZA (1) ZA967448B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111019777A (zh) * 2019-12-17 2020-04-17 广州立白企业集团有限公司 一种颗粒型浓缩洗涤剂组合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997460A (en) * 1975-04-10 1976-12-14 The Clorox Company Liquid abrasive cleaner
EP0460810A1 (fr) * 1990-05-07 1991-12-11 Colgate-Palmolive Company (a Delaware corporation) Composition détergente à base liquide non-aqueuse pour lave vaisselle automatique
EP0573699A1 (fr) * 1992-06-06 1993-12-15 The Procter & Gamble Company Compositions pour le contrôle de la mousse
EP0666301A1 (fr) * 1994-02-04 1995-08-09 The Procter & Gamble Company Compositions détergentes liquides stables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997460A (en) * 1975-04-10 1976-12-14 The Clorox Company Liquid abrasive cleaner
EP0460810A1 (fr) * 1990-05-07 1991-12-11 Colgate-Palmolive Company (a Delaware corporation) Composition détergente à base liquide non-aqueuse pour lave vaisselle automatique
EP0573699A1 (fr) * 1992-06-06 1993-12-15 The Procter & Gamble Company Compositions pour le contrôle de la mousse
EP0666301A1 (fr) * 1994-02-04 1995-08-09 The Procter & Gamble Company Compositions détergentes liquides stables

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111019777A (zh) * 2019-12-17 2020-04-17 广州立白企业集团有限公司 一种颗粒型浓缩洗涤剂组合物

Also Published As

Publication number Publication date
EP0871694A2 (fr) 1998-10-21
WO1997009405A3 (fr) 1997-05-09
EP0871694B1 (fr) 2001-05-23
ES2158341T3 (es) 2001-09-01
CA2230229A1 (fr) 1997-03-13
AU6925796A (en) 1997-03-27
ZA967448B (en) 1998-03-03
DE69613004T2 (de) 2001-10-25
CA2230229C (fr) 2008-01-08
DE69613004D1 (de) 2001-06-28

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