EP0629691B1 - Emulsions aqueuses stables d'agents tensioactifs non-ioniques - Google Patents

Emulsions aqueuses stables d'agents tensioactifs non-ioniques Download PDF

Info

Publication number
EP0629691B1
EP0629691B1 EP93870103A EP93870103A EP0629691B1 EP 0629691 B1 EP0629691 B1 EP 0629691B1 EP 93870103 A EP93870103 A EP 93870103A EP 93870103 A EP93870103 A EP 93870103A EP 0629691 B1 EP0629691 B1 EP 0629691B1
Authority
EP
European Patent Office
Prior art keywords
silicone compounds
emulsion according
hydrophobic
nonionic surfactant
emulsion
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.)
Expired - Lifetime
Application number
EP93870103A
Other languages
German (de)
English (en)
Other versions
EP0629691A1 (fr
Inventor
Stefano Scialla
Raffaele Scoccianti
Jean-Pol Boutique
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to SG1996002630A priority Critical patent/SG52309A1/en
Priority to ES93870103T priority patent/ES2121983T3/es
Priority to EP93870103A priority patent/EP0629691B1/fr
Priority to SG1996008330A priority patent/SG55157A1/en
Priority to DE69321711T priority patent/DE69321711T2/de
Priority to AT93870134T priority patent/ATE174955T1/de
Priority to ES93870134T priority patent/ES2125322T3/es
Priority to EP93870134A priority patent/EP0598693B1/fr
Priority to DE69322744T priority patent/DE69322744T2/de
Priority to DE69328900T priority patent/DE69328900T2/de
Priority to EP93870161A priority patent/EP0629694B1/fr
Priority to ES93870161T priority patent/ES2146606T3/es
Priority to AT93870161T priority patent/ATE194014T1/de
Priority to PT93870161T priority patent/PT629694E/pt
Priority to DK93870161T priority patent/DK0629694T3/da
Priority to PCT/US1993/010444 priority patent/WO1994011099A1/fr
Priority to AU55891/94A priority patent/AU5589194A/en
Priority to BR9406802A priority patent/BR9406802A/pt
Priority to CA002164815A priority patent/CA2164815A1/fr
Priority to PCT/US1994/006117 priority patent/WO1994029415A1/fr
Priority to RU96100545A priority patent/RU2132369C1/ru
Priority to PL94311878A priority patent/PL311878A1/xx
Priority to CN94192824A priority patent/CN1127521A/zh
Priority to JP7501893A priority patent/JPH08511575A/ja
Priority to AU69615/94A priority patent/AU693793B2/en
Priority to NZ267342A priority patent/NZ267342A/en
Priority to MA23531A priority patent/MA23218A1/fr
Publication of EP0629691A1 publication Critical patent/EP0629691A1/fr
Application granted granted Critical
Publication of EP0629691B1 publication Critical patent/EP0629691B1/fr
Priority to GR20000401149T priority patent/GR3033595T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/3703—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to cleaning compositions. More particularly, the cleaning compositions according to the present invention are stable aqueous emulsions of nonionic surfactants particularly suitable for the pretreatment of laundry or the cleaning of hard surfaces.
  • cleaning compositions have been described in the art.
  • European Patent Application EP-A-598170 a particular type of cleaning compositions is described which are aqueous emulsions of a nonionic surfactant system.
  • Such emulsions find a preferred application in the formulation of bleaching compositions comprising hydrogen peroxide or water soluble source thereof and a liquid hydrophobic bleach activator, or any other hydrophobic ingredient which needs to be separated from hydrogen peroxide.
  • bleaching compositions comprising hydrogen peroxide or water soluble source thereof and a liquid hydrophobic bleach activator, or any other hydrophobic ingredient which needs to be separated from hydrogen peroxide.
  • such emulsions can be used to formulate products which do not contain hydrogen peroxide.
  • such emulsions can be useful because they allow to keep a given hydrophobic ingredient separate from the aqueous phase, with which said hydrophobic ingredient could react, e.g., by hydrolysis.
  • Another advantage of such emulsions is that they provide a means to formulate ingredients with very low water solubility, without the need for using alcoholic or solvent mixtures, which are usually undesirable for aesthetic (odour) and toxicity reasons.
  • aqueous emulsions of nonionic surfactants In order to manufacture such aqueous emulsions of nonionic surfactants, it is necessary to vigorously mix the ingredients together. During this vigorous mixing, lots of air bubbles are generated which are detrimental both to the composition's aesthetics and stability. Indeed, surfactants tend to concentrate at the air/liquid interfaces generated by said air bubbles. Thus the more air bubbles a composition contains, the less surfactants will be available for the stabilisation of the droplets of the dispersed phase. This problem of air bubbles is aggravated in that aqueous emulsions of nonionic surfactants are pseudoplastic fluids, i.e. they have a higher viscosity at low shear rates. Consequently, the air bubbles generated upon mixing, i.e.
  • aqueous emulsions of nonionic surfactants which comprise silicone compounds.
  • silicone compounds reduce the viscosity of aqueous emulsions comprising a nonionic surfactant system whatever the viscosity was before their addition and allow to substantially eliminate the air bubbles.
  • emulsions comprising silicone compounds are physically more stable than emulsions without said silicone compounds.
  • the present invention allows for greater flexibility in formulating and provides stable aqueous emulsions suitable to be used in the most efficient manner by the consumer.
  • silicone compounds are unexpected and beneficial as said silicone compounds are only known in the context of laundry compositions as sud-suppressing agents, see for instance US-A-4 076 648, US-A-4 021 365, US-A-4 749 740, US-A-4 983 316, EP-A-150 872, EP-A-217 501 and EP-A-499 364.
  • JP-A-63182008 discloses that a defoaming agent with superior foam breaking and persistent defoaming properties is obtained by adding liquid organopolysiloxane, fine silica powder, emulsifier and water and stirring/emulsifying this mixture into an emulsion.
  • the present invention allows to formulate aqueous activated bleaching emulsions, e.g. bleaching emulsions which comprise any hydrophobic liquid ingredient which needs to be kept separate from the hydrogen peroxide.
  • aqueous activated bleaching emulsions e.g. bleaching emulsions which comprise any hydrophobic liquid ingredient which needs to be kept separate from the hydrogen peroxide.
  • silicone compounds according to the present invention to the nonionic surfactant system used to emulsify hydrophobic liquid ingredients as for instance bleach activators improves the storage stability of hydrogen peroxide.
  • the present invention is a stable aqueous emulsion having a pH of from 0.5 to 6, comprising at least a hydrophilic nonionic surfactant and at least a hydrophobic nonionic surfactant, an effective amount of silicone compounds, hydrogen peroxide or a source thereof and a bleach activator wherein said bleach activator is emulsified by the nonionic surfactants.
  • compositions according to the present invention are stable aqueous emulsions of nonionic surfactants.
  • stable emulsion it is meant an emulsion which does not substantially separate into distinct layers, upon standing for at least 2 weeks at 50 °C.
  • compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 80%. Deionized water is preferably used.
  • compositions according to the present invention are emulsions of nonionic surfactants.
  • Said emulsions of nonionic surfactants comprise at least two nonionic surfactants.
  • Said two nonionic surfactants in order to form emulsions which are stable must have different HLB values (hydrophilic lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1, preferably at least 3.
  • nonionic surfactant used herein is a nonionic surfactant with an HLB above 11 (herein referred to as hydrophilic nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below 10 (herein referred to as hydrophobic nonionic surfactant).
  • Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values.
  • the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
  • Surfactants catalogues are available which list a number of surfactants including nonionics, together with their respective HLB values.
  • compositions according to the present invention comprise from 2 % to 50 % by weight of the total composition of said hydrophilic and hydrophobic nonionic surfactants, preferably from 5 % to 40 %, most preferably from 8 % to 30%.
  • compositions according to the present invention may further comprise other nonionic surfactants which should however not significantly alter the weighted average HLB value of the overall composition.
  • compositions according to the present invention further comprise as an essential element an effective amount of silicone compounds.
  • effective amount it is meant an amount of silicone compounds which is sufficient to reduce and substantially eliminate the air bubbles generated in the aqueous emulsions according to the present invention.
  • effective amount it is also meant an amount of silicone compounds which is sufficient to provide physically stable aqueous emulsions wherein the viscosity can be conveniently controlled.
  • the compositions according to the present invention comprise from 0.01 % to 5 % by weight of the total composition of said silicone compounds, more preferably from 0.1 % to 2 %.
  • compositions obtained according to the present invention have a viscosity of from 100 cps to 3000 cps at 50 rpm shear rate at 25 °C, more preferably from 300 cps to 1500 cps, measured by a Brookfield DV II rotational viscosimeter.
  • said silicone compounds substantially reduce and preferably substantially eliminate the air bubbles generated either during the manufacture of said emulsions or when pouring or shaking said emulsions, thereby providing aqueous emulsions which are acceptable for aesthetics and stability.
  • silicone has become a generic term which encompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types.
  • silicone compounds have been extensively described in the art, see for instance US-A-4 076 648, US-A-4 021 365, US-A-4 749 740, US-A-4 983 316, EP-A-150 872, EP-A-217 501 and EP-A-499 364.
  • the silicone compounds disclosed therein are suitable in the context of the present invention.
  • the silicone compounds can be described as siloxanes having the general structure : wherein n is from 20 to 2.000, and where each R independently can be an alkyl or an aryl radical.
  • Preferred polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl endblocking units and having a viscosity at 25°C of from 5 x 10 -5 m 2 /s to 0.1 m 2 /s i.e. a value of n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost.
  • a preferred type of silicone compounds useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
  • the solid silica can be a fumed silica, a precipitated silica or a silica made by the gelformation technique.
  • the silica particles can be rendered hydrophobic by treating them with diaklylsilyl groups and/or trialkylsilane groups either bonded directly onto the silica or by means of silicone resin.
  • a preferred silicone compound comprises a hydrophobic silanated, most preferably trimethylsilanated silica having a particle size in the range from 10 mm to 20 mm and a specific surface area above 50 m 2 /g.
  • Silicone compounds employed in the compositions according to the present invention suitably have an amount of silica in the range of 1 to 30% (more preferably 2.0 to 15%) by weight of the total weight of the silicone compounds resulting in silicone compounds having an average viscosity in the range of from 2 x 10 -4 m 2 /s to 1m 2 /s.
  • Preferred silicone compounds may have a viscosity in the range of from 5 x 10 -3 m 2 /s to 0.1m 2 /s.
  • Particularly suitable are silicone compounds with a viscosity of 2 x 10 -2 m 2 /s or 4.5 x 10 -2 m 2 /s.
  • Suitable silicone compounds for use herein are commercially available from various companies including Rhone Poulenc, Fueller and Dow Corning.
  • An example of silicone compounds for use herein is Silicone DB R 100 commercially available from Dow Corning.
  • compositions according to the present invention in an acidic pH range contributes to the stability of the composition.
  • the compositions of the present invention have a pH as is of from 0.5 to 6, preferably of from 1 to 5.
  • the pH of the composition can be trimmed by all means available to the man skilled in the art.
  • compositions according to the present invention comprise hydrogen peroxide or a water-soluble source thereof.
  • Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate, persilicate and persulphate salts.
  • Hydrogen peroxide is most preferred to be used in the compositions according to the present invention.
  • the compositions according to the present invention comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide, preferably from 2% to 15%, most preferably from 3% to 10%.
  • compositions according to the present invention further comprise a bleach activator.
  • bleach activator it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
  • hydrophobic bleach activators typically belong to the class of esters, amides, imides, or anhydrides.
  • a particular family of bleach activators of interest in the present invention were disclosed in applicant's patent application WO-A-93/12067. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR-A-2 362 210.
  • Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol.
  • acetyl triethyl citrate has a good hydrolytical stability in the product upon storage and it is an efficient bleach activator.
  • the term bleach activator includes mixtures of bleach activators.
  • the nonionic surfactant system to be chosen to emulsify said bleach activator depends on the HLB value of said bleach activator. Accordingly, a suitable way to proceed is to determine the HLB value of the hydrophobic liquid ingredient (bleach activator), then select both the hydrophobic nonionic surfactants which have HLB values below said HLB value of said hydrophobic liquid ingredient and the hydrophilic nonionic surfactants which have HLB values above said HLB value of said hydrophobic liquid ingredient, wherein the difference in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is preferably at least 3.
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with an HLB from 1 to 10, and a hydrophilic nonionic surfactant with an HLB of above 11.
  • a particularly suitable system comprises a hydrophobic nonionic surfactant with an HLB of 6, for instance a Dobanol R 23-2 and a hydrophilic nonionic surfactant with an HLB of 15, for instance a Dobanol R 91-10.
  • Another suitable nonionic surfactant system comprises a Dobanol R 23-6.5 (HLB about 12) and a Dobanol R 23 (HLB below 6). All these Dobanol R surfactants are commercially available from Shell.
  • compositions according to the present invention are free of other surfactant types, especially anionic surfactants.
  • compositions according to the present invention may further comprise a variety of other ingredients such as perfumes, dyes, optical brighteners, builders and chelants, pigments, enzymes, dye transfer inhibitors, solvents and buffering agents.
  • compositions according to the present invention are particularly useful as laundry pretreaters, i.e compositions which are dispensed and left to act onto fabrics before they are washed, or as laundry additives to be used together with detergents to boost their performance, or as dishwashing compositions to be used either in the dishwashing machines or by hand, or as hard surface cleaners, or as carpet cleaners to be used either by direct application onto the carpets or as detergent for carpet cleaning machines or also alone without detergents.
  • the compositions according to the present invention are also particularly adapted to be used for delicate items.
  • the present invention further encompasses a process for the manufacture of the composition described herein.
  • the process according to the present invention comprises at least three steps:
  • a hydrophobic mixture which comprises said hydrophobic nonionic surfactant and silicone compounds together with other hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers.
  • a hydrophilic mixture which comprises at least said water, and said hydrophilic nonionic surfactant.
  • Said hydrophilic mixture preferably further comprises other hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, chelants, hydrogen peroxide and buffering agents.
  • hydrogen peroxide is preferably added last, after said buffering agent has been added.
  • first and said second steps can be performed in any order, i.e second step first is also suitable.
  • said hydrophobic mixture and said hydrophilic mixture are mixed together.
  • compositions are made which comprise the listed ingredients in the listed proportions (weight %).
  • I II III Dobanol R 45-7 6 6 6
  • Dobanol R 23-2 6 6 Hydrogen peroxide 7.5 7.5 7.5
  • Brightener 49 R 0.20 0.20 0.20 S,S-ethylene diamino disuccinic acid 0.10 0.10 0.10 0.10
  • Silicone DB R 100 - 0.10 0.50 Deionized water ---------balance----------------
  • compositions I to III are each made by preparing two mixtures.
  • a hydrophilic mixture is prepared which comprises the water, the brightener, S,S-EDDS, poly(4-vinylpyridine-N-oxide), the Dobanol R 91-10 and the Dobanol R 45-7. Hydrogen peroxide is added in said hydrophilic mixture as last step.
  • a hydrophobic mixture is prepared which comprises the acetyl triethyl citrate, Silicone DB R 100 and the Dobanol R 23-2.
  • hydrophobic mixture is poured into said hydrophilic mixture, while mixing.
  • the compositions II and III which comprise Silicone DB R 100 have a density which is higher than the density of the composition I which is free of any silicone compounds.
  • the compositions II and III contain less air bubbles than the composition I.
  • by visual inspection it is also established that the compositions II and III contain less air bubbles than the composition I and are therefore more acceptable from a consumer viewpoint for aesthetic reasons.
  • compositions II and III (with silicone compounds) have a lower viscosity than the composition I which is free of any silicone compounds.
  • compositions according to the present invention reduces and substantially eliminates the air bubbles and also reduces the viscosity of said compositions. Additionally, the compositions according to the present invention which comprise silicone compounds are physical stable emulsions, even more stable than analogous compositions without silicone compounds.

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Colloid Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (11)

  1. Emulsion aqueuse stable ayant un pH de 0,5 à 6, comprenant au moins un tensioactif non ionique hydrophile et au moins un tensioactif non ionique hydrophobe, une quantité efficace de composés de silicone, du peroxyde d'hydrogène ou une source de peroxyde d'hydrogène et un activateur de blanchiment, dans laquelle ledit activateur de blanchiment est émulsionné par les tensioactifs non ioniques.
  2. Emulsion selon la revendication 1, dans laquelle lesdits composés de silicone sont choisis parmi les siloxanes de structure générale:
    Figure 00200001
    dans laquelle n vaut de 20 à 2 000 et dans laquelle chaque R peut être indépendamment un radical alkyle ou un radical aryle.
  3. Emulsion selon la revendication 2, dans laquelle lesdits composés de silicone sont un mélange desdits siloxanes et de silice solide.
  4. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle la proportion des composés de silicone est de 0,01% à 5% du poids total de l'émulsion, de préférence de 0,1% à 2%.
  5. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle la proportion de tensioactif non ionique est de 2% à 50% du poids de l'émulsion totale, de préférence de 5% à 40%, tout particulièrement de 8% à 30%.
  6. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif non ionique hydrophile possède une BHL supérieure à 11 et dans laquelle le tensioactif non ionique hydrophobe possède une BHL inférieure à 10.
  7. Emulsion selon la revendication 6, dans laquelle la différence entre la BHL des composés non ioniques hydrophiles et la BHL des composés non ioniques hydrophobes est d'au moins 1, de préférence d'au moins 3.
  8. Emulsion selon l'une quelconque des revendications précédentes, qui comprend de 0,5% à 20%, en poids de l'émulsion totale, dudit peroxyde d'hydrogène.
  9. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle l'activateur de blanchiment est le citrate d'acétyle et de triéthyle.
  10. Emulsion selon l'une quelconque des revendications précédentes, qui possède une viscosité dans la gamme de 100 cP à 3 000 cP, à une vitesse de cisaillement de 50 tours/min à 25°C, mieux encore de 300 à 1 500 cP.
  11. Composition détergente comprenant une émulsion selon l'une quelconque des revendications précédentes.
EP93870103A 1992-11-16 1993-06-09 Emulsions aqueuses stables d'agents tensioactifs non-ioniques Expired - Lifetime EP0629691B1 (fr)

Priority Applications (28)

Application Number Priority Date Filing Date Title
SG1996002630A SG52309A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
ES93870103T ES2121983T3 (es) 1993-06-09 1993-06-09 Emulsiones acuosas estables de tensioactivos no ionicos.
EP93870103A EP0629691B1 (fr) 1993-06-09 1993-06-09 Emulsions aqueuses stables d'agents tensioactifs non-ioniques
SG1996008330A SG55157A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
DE69321711T DE69321711T2 (de) 1993-06-09 1993-06-09 Stabile wässrige nichtionische Tensideemulsionen
ES93870134T ES2125322T3 (es) 1992-11-16 1993-07-12 Emulsiones acuosas estables de tensioactivos no ionicos con un agente de control de la viscosidad.
EP93870134A EP0598693B1 (fr) 1992-11-16 1993-07-12 Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrÔle de la viscosité
DE69322744T DE69322744T2 (de) 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten
AT93870134T ATE174955T1 (de) 1992-11-16 1993-07-12 Stabile, nichtionische tensidemulsionen, welche viskositätskontrollmittel enthalten
DK93870161T DK0629694T3 (da) 1993-06-09 1993-08-03 Fremgangsmåde til tæpperensning
EP93870161A EP0629694B1 (fr) 1993-06-09 1993-08-03 Procédé de nettoyage de tapis
ES93870161T ES2146606T3 (es) 1993-06-09 1993-08-03 Metodo para limpiar alfombras.
AT93870161T ATE194014T1 (de) 1993-06-09 1993-08-03 Verfahren zur reinigung von teppichen
PT93870161T PT629694E (pt) 1993-06-09 1993-08-03 Metodo para limpar carpetes
DE69328900T DE69328900T2 (de) 1993-06-09 1993-08-03 Verfahren zur Reinigung von Teppichen
AU55891/94A AU5589194A (en) 1992-11-16 1993-10-29 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
PCT/US1993/010444 WO1994011099A1 (fr) 1992-11-16 1993-10-29 Emulsions aqueuses stables de tensio-actifs non ioniques comprenant un agent regulant la viscosite
AU69615/94A AU693793B2 (en) 1993-06-09 1994-05-31 Stable aqueous emulsions of nonionic surfactants
PCT/US1994/006117 WO1994029415A1 (fr) 1993-06-09 1994-05-31 Emulsions aqueuses stables de tensioactifs non ioniques
RU96100545A RU2132369C1 (ru) 1993-06-09 1994-05-31 Водная эмульсия для предварительной стирки или очистки твердых поверхностей и включающая ее моющая композиция
PL94311878A PL311878A1 (en) 1993-06-09 1994-05-31 Stable aqueous emulsions of non-ionic surfactants
CN94192824A CN1127521A (zh) 1993-06-09 1994-05-31 非离子表面活性剂的稳定水乳液
JP7501893A JPH08511575A (ja) 1993-06-09 1994-05-31 非イオン界面活性剤の安定な水性乳濁液
CA002164815A CA2164815A1 (fr) 1993-06-09 1994-05-31 Emulsions aqueuses stables de surfactifs non ioniques
BR9406802A BR9406802A (pt) 1993-06-09 1994-05-31 Emulsoes aquosas estáveis de tensoativos nao-ionicos
NZ267342A NZ267342A (en) 1993-06-09 1994-05-31 Stable aqueous emulsions of nonionic surfactants and silicones
MA23531A MA23218A1 (fr) 1993-06-09 1994-06-08 Emulsions aqueuses stables de tensio-actifs non ioniques
GR20000401149T GR3033595T3 (en) 1993-06-09 2000-06-22 Method of carpet cleaning.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SG1996002630A SG52309A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
SG1996008330A SG55157A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870103A EP0629691B1 (fr) 1993-06-09 1993-06-09 Emulsions aqueuses stables d'agents tensioactifs non-ioniques

Publications (2)

Publication Number Publication Date
EP0629691A1 EP0629691A1 (fr) 1994-12-21
EP0629691B1 true EP0629691B1 (fr) 1998-10-21

Family

ID=27235603

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93870103A Expired - Lifetime EP0629691B1 (fr) 1992-11-16 1993-06-09 Emulsions aqueuses stables d'agents tensioactifs non-ioniques

Country Status (14)

Country Link
EP (1) EP0629691B1 (fr)
JP (1) JPH08511575A (fr)
CN (1) CN1127521A (fr)
AU (1) AU693793B2 (fr)
BR (1) BR9406802A (fr)
CA (1) CA2164815A1 (fr)
DE (1) DE69321711T2 (fr)
ES (1) ES2121983T3 (fr)
MA (1) MA23218A1 (fr)
NZ (1) NZ267342A (fr)
PL (1) PL311878A1 (fr)
RU (1) RU2132369C1 (fr)
SG (2) SG55157A1 (fr)
WO (1) WO1994029415A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2125322T3 (es) * 1992-11-16 1999-03-01 Procter & Gamble Emulsiones acuosas estables de tensioactivos no ionicos con un agente de control de la viscosidad.
US5929012A (en) * 1995-02-28 1999-07-27 Procter & Gamble Company Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage
DE69625471T2 (de) * 1995-02-28 2003-11-06 Procter & Gamble Wäschevorbehandlung mit peroxybleichmitteln enthaltend komplexbildner für eisen, kupfer oder mangan für reduzierten gewebeschaden
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US5759439A (en) * 1996-06-14 1998-06-02 The Procter & Gamble Company Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
US6828290B1 (en) 1996-05-03 2004-12-07 The Procter & Gamble Company Hard surface cleaning compositions
DE19635070A1 (de) * 1996-08-30 1998-03-05 Clariant Gmbh Flüssige Bleichmittelsuspension
US6808701B2 (en) 2000-03-21 2004-10-26 Johnson & Johnson Consumer Companies, Inc. Conditioning compositions
DE102005034752A1 (de) * 2005-07-21 2007-01-25 Henkel Kgaa Reinigungs- und Pflegemittel mit verbesserter Emulgierfähigkeit
JP5243522B2 (ja) * 2007-04-13 2013-07-24 イーコラブ インコーポレイティド 発泡性が低減された床クリーニング用組成物
EP2435547A1 (fr) 2009-05-26 2012-04-04 The Procter & Gamble Company Composition liquide aqueuse pour un prétraitement de vaisselle souillée

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63182008A (ja) * 1987-01-21 1988-07-27 Shin Etsu Chem Co Ltd エマルジヨン型シリコ−ン消泡剤の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1562801A (en) * 1976-01-02 1980-03-19 Procter & Gamble Liquid detergent composition
EP0019315B1 (fr) * 1979-05-16 1983-05-25 Procter & Gamble European Technical Center Compositions détergentes liquides contenant un acide gras très concentré
EP0091802B1 (fr) * 1982-04-13 1987-09-30 The Procter & Gamble Company Compositions à mousse controlée comme additifs à des détergents et leur utilisation dans des compositions détergentes
US5106609A (en) * 1990-05-01 1992-04-21 The Procter & Gamble Company Vehicle systems for use in cosmetic compositions
US5100657A (en) * 1990-05-01 1992-03-31 The Procter & Gamble Company Clean conditioning compositions for hair

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63182008A (ja) * 1987-01-21 1988-07-27 Shin Etsu Chem Co Ltd エマルジヨン型シリコ−ン消泡剤の製造方法

Also Published As

Publication number Publication date
RU2132369C1 (ru) 1999-06-27
EP0629691A1 (fr) 1994-12-21
ES2121983T3 (es) 1998-12-16
SG55157A1 (en) 1998-12-21
AU693793B2 (en) 1998-07-09
BR9406802A (pt) 1996-03-19
CA2164815A1 (fr) 1994-12-22
AU6961594A (en) 1995-01-03
DE69321711D1 (de) 1998-11-26
DE69321711T2 (de) 1999-06-10
NZ267342A (en) 1998-01-26
SG52309A1 (en) 1998-09-28
PL311878A1 (en) 1996-03-18
JPH08511575A (ja) 1996-12-03
WO1994029415A1 (fr) 1994-12-22
MA23218A1 (fr) 1994-12-31
CN1127521A (zh) 1996-07-24

Similar Documents

Publication Publication Date Title
RU2135558C1 (ru) Водная композиция для очистки и отбеливания
AU755029B2 (en) Stable alkaline emulsion cleaners
EP0629691B1 (fr) Emulsions aqueuses stables d'agents tensioactifs non-ioniques
JP5543490B2 (ja) 高粘性洗剤エマルジョン
EP0634476B1 (fr) Emulsions stables aqueuses de surfactants non-ioniques avec un agent controlant la viscosité
EP0598693B1 (fr) Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrÔle de la viscosité
EP0875556A2 (fr) Agent de rinçage pour vaisselle en plastique
JPH07507588A (ja) シリコーン及びシリカを含む起泡抑制組成物
US5759989A (en) Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
EP0638634B1 (fr) Composition détergente sous forme de microémulsion stable
EP0687726B1 (fr) Compositions de blanchiment
AU623371B2 (en) Thixotropic aqueous automatic dishwashing detergent compositions
EP0997524B1 (fr) Détergents liquides contenant des compositions demoussantes et compositions demoussantes utilisables dans de tels détergents
US5830841A (en) Suds controlling compositions comprising silicone and silica
KR950007721B1 (ko) 소포제 조성물과 그 제조방법 및 이를 함유하는 세정제 조성물
GB2148926A (en) Detergent composition
MXPA97003106A (en) Stable liquid detergent compositions comprising fatty acid and sili oil

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB GR IT NL

17P Request for examination filed

Effective date: 19950610

17Q First examination report despatched

Effective date: 19970417

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): BE DE ES FR GB GR IT NL

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB GR IT NL

REF Corresponds to:

Ref document number: 69321711

Country of ref document: DE

Date of ref document: 19981126

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000320

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20000426

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000502

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000602

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000614

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000630

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000714

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010609

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010611

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20010630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010609

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020228

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020403

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050609

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1013307

Country of ref document: HK