EP0598693A1 - Stabile, nichtionische Tensideemulsionen welche Viskositätskontrollmittel enthalten - Google Patents

Stabile, nichtionische Tensideemulsionen welche Viskositätskontrollmittel enthalten Download PDF

Info

Publication number
EP0598693A1
EP0598693A1 EP93870134A EP93870134A EP0598693A1 EP 0598693 A1 EP0598693 A1 EP 0598693A1 EP 93870134 A EP93870134 A EP 93870134A EP 93870134 A EP93870134 A EP 93870134A EP 0598693 A1 EP0598693 A1 EP 0598693A1
Authority
EP
European Patent Office
Prior art keywords
hydrophobic
nonionic surfactant
hydrophilic
ethylenediamine
disuccinic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93870134A
Other languages
English (en)
French (fr)
Other versions
EP0598693B1 (de
Inventor
Giulia Ottavia Bianchetti
Sergio Cardola
Stefano Scialla
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27545649&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0598693(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP92870188A external-priority patent/EP0598170B1/de
Priority claimed from EP93870104A external-priority patent/EP0629690B1/de
Priority claimed from EP93870103A external-priority patent/EP0629691B1/de
Priority to ES93870134T priority Critical patent/ES2125322T3/es
Priority to DE69322744T priority patent/DE69322744T2/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93870134A priority patent/EP0598693B1/de
Priority to AT93870134T priority patent/ATE174955T1/de
Priority to PCT/US1993/010444 priority patent/WO1994011099A1/en
Priority to AU55891/94A priority patent/AU5589194A/en
Publication of EP0598693A1 publication Critical patent/EP0598693A1/de
Publication of EP0598693B1 publication Critical patent/EP0598693B1/de
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers 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 which comprise a viscosity control system.
  • cleaning compositions have been described in the art.
  • 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.
  • 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.
  • cleaning compositions be more or less viscous. Indeed, viscous compositions do not run like thin liquids, and their pouring, dispensing, i.e. their overall handling is therefore easier to control. This aspect is particularly important when cleaning compositions are used to clean hard surfaces, especially on inclined or vertical surfaces such as toilet bowls, or in the context of laundry. In those instances, the cleaning compositions must be thick enough for a controlled application onto fabrics, and for a good cling onto surfaces.
  • thickening compounds are available for this purpose.
  • thickening compounds it is meant herein compounds whose sole function is to thicken the compositions.
  • Such compounds typically polymers, are however rather undesirable for a variety of reasons. Indeed, they can significantly increase formula cost without participating to the overall cleaning performance, they may involve processing issues, they may affect product stability, particularly in extreme acidic conditions, and they may affect the cleaning performance of the compositions.
  • Another advantage of the present invention is that it is only required to use a very small amount of ethylenediamine-N,N'-disuccinic acid in order to obtain the desired effect, which makes the present invention particularly cost-efficient.
  • ethylenediamine-N,N'-disuccinic acid also acts as a builder in the compositions of the present invention.
  • ethylenediamine-N,N'-disuccinic plays has a dual function in the compositions of the present invention.
  • Another advantage of the present invention is that it allows for the formulation of compositions which are thick and pseudoplastic, i.e. which are less viscous at higher shear stresses.
  • Pseudoplasticity compositions achieve the multiple and somewhat contradictory objects of being easy to dispense, i.e. rather less viscous, and providing good cling onto surfaces, i.e. rather more viscous.
  • Yet another advantage of the present invention is that ethylenediamine-N,N'-disuccinic acid has been found to provide additional stability to the preferred compositions herein which may comprise hydrogen peroxide as an optional but preferred compound.
  • Yet another advantage of the present invention is that it allows to achieve a given viscosity target with a lower surfactant level, compared to a composition without ethylenediamine-N,N'-disuccinic acid.
  • the present invention is a stable aqueous emulsion comprising a hydrophilic nonionic surfactant and a hydrophobic nonionic surfactant, said stable aqueous emulsion further comprising a viscosity-building amount of ethylenediamine-N,N'-disuccinic acid.
  • 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 two weeks at 20 °C, preferably at least six months.
  • 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 85%. 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, said two nonionic surfactants 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.
  • HLB values hydrophilic lipophilic balance
  • 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 (hydrophilic lipophilic balance).
  • HLB values of such alkoxylated nonionic surfactants depend essentially on the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a higher degree of alkoxylation, while hydrophobic surfactants tend to have a lower degree of alkoxylation.
  • Surfactants catalogs 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 70 % by weight of the total composition of said hydrophilic and hydrophobic nonionic surfactants, preferably from 3 % to 40 %, most preferably from 4 % 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 a viscosity-building amount of ethylenediamine-N,N'-disuccinic acid.
  • viscosity-building it is meant herein any amount of ethylenediamine-N,N'-disuccinic acid in a given composition which will provide an increase in viscosity compared to the same composition without ethylenediamine-N,N'-disuccinic acid, while maintaining acceptable stability.
  • compositions herein are not limited to any specific viscosity, and depending on the exact use envisioned, various viscosities may be achieved.
  • the addition of the dipicolinic acid or derivatives thereof to a given composition may produce a viscosity increase or decrease of from 5 cps to 2000 cps, preferably from 50 cps to 1000 cps, at a given shear rate, compared to the same composition without dipicolinic acid or derivatives thereof.
  • the decrease or increase is greater when measured at low shear rates (e.g. 12 rpm).
  • compositions according to the present invention may comprise from 0.01 % to 10 % by weight of the total composition of ethylenediamine-N,N'-disuccinic acid, preferably from 0.01 % to 1 %.
  • Ethylenediamine-N,N'-disuccinic acid can be synthesised, for example, from readily available, inexpensive starting materials such as maleic anhydride and ethylenediamine as follows.
  • the [S,S] isomer of ethylenediamine-N,N'-disuccinic acid can be synthesised from L-aspartic acid and 1,2-dibromoethane, as follows.
  • Ethylenediamine-N,N'-disuccinic acid can be used in the compositions of the present invention in its acid form or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred ethylenediamine-N,N'-disuccinic acid compounds for inclusion in the present compositions are the free acid form and the sodium or magnesium salt thereof.
  • Examples of such preferred sodium salts of ethylenediamine-N,N'-disuccinic acid include Mg ethylenediamine-N,N'-disuccinic acid and Mg2 ethylenediamine-N,N'-disuccinic acid.
  • the magnesium complexes are the most preferred for inclusion in compositions according to the invention. These complexes may be added to the compositions as such, or they may be formed during the process for making the composition by the reaction of an inert magnesium salt such as MgCl2 or Mg SO4 with an ethylenediamine-N,N'-disuccinic acid compound added as either the acid, or as a salt or complex. Where the ethylenediamine-N,N'-disuccinic acid compound is added in the making process, together with the inert magnesium salt, it is preferred that the molar ratio of magnesium to ethylenediamine-N,N'-disuccinic acid should be greater than 1:1, preferably greater than 3:1, to ensure formation of the desired magnesium complexes.
  • the pH of the formulation influences its stability.
  • bleaching ingredients being optional but preferred ingredients of the compositions herein, it is of course necessary, for chemical stability purposes to formulate the compositions herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5.
  • the pH of the can be trimmed by all means available to the man skilled in the art.
  • compositions according to the present invention comprise bleaches, i.e. hydrogen peroxide or water-soluble sources thereof.
  • Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate and persilicate 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 may further comprise a bleach activator as an optional ingredient.
  • bleach activator it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
  • Suitable bleach activators for use herein 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 co-pending European patent application No 91870207.7. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR 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 @ 23-2 and a hydrophilic nonionic surfactant with an HLB of 15, for instance a Dobanol @ 91-10.
  • Another suitable nonionic surfactant system comprises a Dobanol @ 23-6.5 (HLB about 12) and a Dobanol @ 23 (HLB below 6). All these Dobanol @ surfactants are commercially available from Shell.
  • compositions according to the present invention may further comprise the usual optional ingredients such as perfumes, dyes, optical brighteners, builders and chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and the like.
  • 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 toilet bowl cleaners, or as carpet cleaners to be used either by direct application onto the carpets or in carpet cleaning machines.
  • 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, ethylenediamine-N,N'-disuccinic acid, together with other, optional, 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.
  • 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 (weigh %).

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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Colloid Chemistry (AREA)
EP93870134A 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten Expired - Lifetime EP0598693B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT93870134T ATE174955T1 (de) 1992-11-16 1993-07-12 Stabile, nichtionische tensidemulsionen, welche viskositätskontrollmittel enthalten
EP93870134A EP0598693B1 (de) 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten
ES93870134T ES2125322T3 (es) 1992-11-16 1993-07-12 Emulsiones acuosas estables de tensioactivos no ionicos con un agente de control de la viscosidad.
DE69322744T DE69322744T2 (de) 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten
PCT/US1993/010444 WO1994011099A1 (en) 1992-11-16 1993-10-29 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
AU55891/94A AU5589194A (en) 1992-11-16 1993-10-29 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
EP92870188 1992-11-16
EP92870188A EP0598170B1 (de) 1992-11-16 1992-11-16 Reinigungs- und Bleichmittelzusammensetzungen
EP93870104 1993-06-09
EP93870103A EP0629691B1 (de) 1993-06-09 1993-06-09 Stabile wässrige nichtionische Tensideemulsionen
EP93870104A EP0629690B1 (de) 1993-06-09 1993-06-09 Stabile wässrige nichtionische Tensidemulsionen
SG1996008330A SG55157A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870103 1993-06-09
SG1996002630A SG52309A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870134A EP0598693B1 (de) 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten

Publications (2)

Publication Number Publication Date
EP0598693A1 true EP0598693A1 (de) 1994-05-25
EP0598693B1 EP0598693B1 (de) 1998-12-23

Family

ID=27545649

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93870134A Expired - Lifetime EP0598693B1 (de) 1992-11-16 1993-07-12 Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten

Country Status (6)

Country Link
EP (1) EP0598693B1 (de)
AT (1) ATE174955T1 (de)
AU (1) AU5589194A (de)
DE (1) DE69322744T2 (de)
ES (1) ES2125322T3 (de)
WO (1) WO1994011099A1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006908A1 (en) * 1994-08-26 1996-03-07 The Procter & Gamble Company Ethylenediamine disuccinate as detergent builder
EP0779357A1 (de) * 1995-12-16 1997-06-18 The Procter & Gamble Company Stabile Emulsionen enthaltend einen hydrophobischen flüssigen Bestandteil
WO1999000478A1 (en) * 1997-06-27 1999-01-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing enzyme particles
EP0906950A1 (de) * 1997-10-03 1999-04-07 The Procter & Gamble Company Persäurestoffbleichmittel enthaltende Zusammensetzungen, die ein besonders Chelatierungsmittelsystem enthalten
WO2001046377A1 (de) * 1999-12-21 2001-06-28 Henkel Kommanditgesellschaft Auf Aktien Mittel zur behandlung von substraten
EP1233055A1 (de) * 2001-02-15 2002-08-21 Givaudan SA Bleichmittelzusammensetzung

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5928384A (en) * 1994-11-10 1999-07-27 The Procter & Gamble Company Method of cleaning carpets
CA2204631C (en) * 1994-11-10 2001-02-06 Stefano Scialla Method of cleaning carpets
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US5733858A (en) * 1995-08-30 1998-03-31 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thererof
WO1997008288A1 (en) * 1995-08-30 1997-03-06 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
AU2002303139B2 (en) 2001-03-20 2005-06-30 Noxell Corporation Compositions suitable for the treatment of hair comprising chelants and methods for reducing oxidative hair damage
KR101615431B1 (ko) * 2014-05-15 2016-04-25 코오롱인더스트리 주식회사 폴리이미드 및 이를 이용한 필름

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3907131A1 (de) * 1989-03-06 1990-09-13 Henkel Kgaa Bleichmittelsuspension
TW291496B (de) * 1991-02-01 1996-11-21 Hoechst Ag
ES2113421T3 (es) * 1992-11-16 1998-05-01 Procter & Gamble Composiciones de limpieza y blanqueo.
EP0629691B1 (de) * 1993-06-09 1998-10-21 The Procter & Gamble Company Stabile wässrige nichtionische Tensideemulsionen
ES2137245T3 (es) * 1993-06-09 1999-12-16 Procter & Gamble Emulsiones acuosas estables de tensioactivos no ionicos.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006908A1 (en) * 1994-08-26 1996-03-07 The Procter & Gamble Company Ethylenediamine disuccinate as detergent builder
EP0779357A1 (de) * 1995-12-16 1997-06-18 The Procter & Gamble Company Stabile Emulsionen enthaltend einen hydrophobischen flüssigen Bestandteil
EP0910465A1 (de) * 1995-12-16 1999-04-28 The Procter & Gamble Company Stabile emulsionen, die einen hydrophoben flüssigen bestandteil enthalten
EP0910465A4 (de) * 1995-12-16 1999-04-28
WO1999000478A1 (en) * 1997-06-27 1999-01-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing enzyme particles
EP0906950A1 (de) * 1997-10-03 1999-04-07 The Procter & Gamble Company Persäurestoffbleichmittel enthaltende Zusammensetzungen, die ein besonders Chelatierungsmittelsystem enthalten
WO1999018180A1 (en) * 1997-10-03 1999-04-15 The Procter & Gamble Company Peroxygen bleach-containing compositions comprising a particular chelating agent system
WO2001046377A1 (de) * 1999-12-21 2001-06-28 Henkel Kommanditgesellschaft Auf Aktien Mittel zur behandlung von substraten
EP1233055A1 (de) * 2001-02-15 2002-08-21 Givaudan SA Bleichmittelzusammensetzung

Also Published As

Publication number Publication date
WO1994011099A1 (en) 1994-05-26
DE69322744T2 (de) 1999-07-22
ES2125322T3 (es) 1999-03-01
AU5589194A (en) 1994-06-08
EP0598693B1 (de) 1998-12-23
DE69322744D1 (de) 1999-02-04
ATE174955T1 (de) 1999-01-15

Similar Documents

Publication Publication Date Title
EP0598170B1 (de) Reinigungs- und Bleichmittelzusammensetzungen
EP0598693B1 (de) Stabile, nichtionische Tensidemulsionen, welche Viskositätskontrollmittel enthalten
JPH01156399A (ja) ジエチレングリコール モノヘキシルエーテル溶剤を含む水性洗剤組成物
EP0634476B1 (de) Stabile, wässrige Emulsionen aus nichtionischen oberflächenaktiven Mitteln mit einem viskositätskontrollierendem Mittel
JPH0625697A (ja) パーオキシカルボン酸の水性懸濁液
EP0735133A1 (de) Flüssige aktivierte Bleichmittelzusammensetzungen
JPH11501576A (ja) 疎水性液体成分を含む安定な乳濁液
US5759989A (en) Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
LU85391A1 (fr) Composition detergente liquide a une seule phase,stabilisee,chargee d'adjuvant de detergence et contenant des enzymes,et procede de lavage utilisant cette composition
JPH03210399A (ja) 塩素を含まない液体自動皿洗い組成物
AU706186B2 (en) Bleaching compositions
EP0629691B1 (de) Stabile wässrige nichtionische Tensideemulsionen
KR930003938B1 (ko) 농축 증강된 단일상의 액상 세제 조성물
LU86525A1 (fr) Composition detergente liquide renforcee stabilisee contenant des enzymes,et procede de lavage mettant en oeuvre
US6303564B1 (en) Detergents, cleaning compositions and disinfectants comprising chlorine-active substances and fatty acid alkyl ester ethoxylates
JPH03210400A (ja) 懸濁性液体洗剤組成物
US5880079A (en) Bleaching compositions
CA1255182A (en) Concentrated single-phase built liquid detergent composition
US5132053A (en) Concentrated single-phase built liquid detergent composition and laundering method
JPH08511291A (ja) 洗剤組成物
WO1992002611A1 (en) Manufacture of solid, cast non-swelling detergent compositions
EP0506874A1 (de) Konzentrierte wässrig-flüssige bleichmittel

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): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19941031

17Q First examination report despatched

Effective date: 19970325

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

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

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2121983

Country of ref document: ES

Kind code of ref document: T3

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

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

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19981223

Ref country code: GR

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

Effective date: 19981223

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

REF Corresponds to:

Ref document number: 174955

Country of ref document: AT

Date of ref document: 19990115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT

REF Corresponds to:

Ref document number: 69322744

Country of ref document: DE

Date of ref document: 19990204

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2125322

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990323

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990323

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

Ref country code: LU

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

Effective date: 19990712

Ref country code: IE

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

Effective date: 19990712

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

Ref country code: LI

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

Effective date: 19990731

Ref country code: CH

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

Effective date: 19990731

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 19990908

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2137245

Country of ref document: ES

Kind code of ref document: T3

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KGAA

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: 20000201

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 93870134.9

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

Effective date: 20000201

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20011210

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

Ref country code: GB

Payment date: 20020613

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20020702

Year of fee payment: 10

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

Ref country code: ES

Payment date: 20020724

Year of fee payment: 10

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

Ref country code: DE

Payment date: 20020731

Year of fee payment: 10

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: 20030712

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: 20030714

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: 20040203

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

Effective date: 20030712

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: 20040331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030714

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: 20050712