EP1302531B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

Info

Publication number
EP1302531B1
EP1302531B1 EP02256296A EP02256296A EP1302531B1 EP 1302531 B1 EP1302531 B1 EP 1302531B1 EP 02256296 A EP02256296 A EP 02256296A EP 02256296 A EP02256296 A EP 02256296A EP 1302531 B1 EP1302531 B1 EP 1302531B1
Authority
EP
European Patent Office
Prior art keywords
alkylpolyglycoside
surfactant
range
sodium
alkyl
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.)
Revoked
Application number
EP02256296A
Other languages
German (de)
English (en)
Other versions
EP1302531A1 (fr
Inventor
Rudolfus J. H. Unilever R&D Vlaardingen Hafkamp
Rob Unilever R&D Vlaardingen Menting
David Martin Unilever R&D Colworth Reilly
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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=9923557&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1302531(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1302531A1 publication Critical patent/EP1302531A1/fr
Application granted granted Critical
Publication of EP1302531B1 publication Critical patent/EP1302531B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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 built laundry detergent compositions containing anionic sulphonate or sulphate surfactants, and ethoxylated alcohol nonionic surfactant and alkylpolyglycosides.
  • Heavy duty laundry detergent compositions have for many years contained an anionic sulphonate or sulphate surfactant, for example, linear alkylbenzene sulphonate (LAS) or primary alcohol sulphate (PAS), as the principal detergent-active ingredient.
  • anionic surfactants are frequently used in conjunction with ethoxylated alcohol nonionic surfactants which give improved detergency on hydrophobic soils.
  • the nonionic surfactants generally have alkyl chain lengths of C 12 -C 18 and degrees of ethoxylation of 1 to 10.
  • anionic and anionic/nonionic surfactant systems are robust and highly efficient on a wide range of soils and under a wide range of conditions, for example, temperature and water hardness. However, they are not noted for mildness to skin. These materials are designed to interact with fatty materials like body soil and protein residues on soiled laundry, and can therefore interact with the skin to give reactions such as dryness and erythema (redness).
  • the milder surfactants used to formulate products intended for prolonged skin contact, for example, shampoos and shower gels would not perform adequately in heavy duty laundry detergent compositions because of insufficient interaction with fatty materials occurring as soil.
  • Alkylpolyglycosides have been widely disclosed in the art as environmentally friendly carbohydrate-derived nonionic surfactants, and are used in various detergent and personal care products. Disclosures in the prior art include EP 75 994A, EP 75 995A and EP 75 996A (Procter & Gamble), EP 238 638B (Staley/Henkel), EP 487 262A (Unilever), EP 495 176 (Huels), EP 374 702A (Kao), WO 92 06150 (P&G), WO 94 26861A (Henkel), WO 94 24242 (P&G) and WO 96 29977 (Henkel). The use of APGs as detergency builders has been disclosed in EP 976 817A (Henkel).
  • WO 00 08129A discloses mild particulate laundry detergent compositions based on high-foaming anionic surfactant (for example linear alkylbenzene sulphonate) plus one or more milder cosurfactants, for example, amine oxide or cocoamidopropyl betaine.
  • high-foaming anionic surfactant for example linear alkylbenzene sulphonate
  • milder cosurfactants for example, amine oxide or cocoamidopropyl betaine.
  • CA 2 308 834 discloses a laundry detergent tablet containing anionic sulphonate and anionic sulfate surfactant, ethoxylated fatty alcohol nonionic surfactant and APG.
  • the APG is used to give a tablet with high hardness and disintegration rate. The mildness to skin of the tablet is not tested or mentioned.
  • the present invention provides the use of a an alkylpolyglycoside in an amount of from 1 to 3 wt% to increase the mildness to skin of a built particulate laundry detergent composition containing an anionic sulphonate or sulphate detergent.
  • the invention is based on the observation that use of alkylpolyglycoside (APG) at low levels to replace part of a conventional anionic/nonionic surfactant system results in a measurable increase in mildness to skin.
  • APG alkylpolyglycoside
  • the built particulate laundry detergent composition contains:
  • Detergent compositions utilising the invention contain a conventional anionic sulphonate or sulphate surfactant and a conventional nonionic surfactant, and also contain as an essential ingredient a low level of alkylpolyglycoside.
  • the built particulate laundry detergent composition comprises:
  • the skin-mild detergent compositions of the invention are free of enzymes, since enzymes can also cause skin irritation to sensitive individuals.
  • enzymatic compositions are also within the scope of the invention.
  • anionic sulphonate or sulphate surfactant (i)
  • Anionic sulphonate and sulphate surfactants are well-known to those skilled in the art. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • alkylbenzene sulphonates examples include alkylbenzene sulphonates, primary and secondary alkylsulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • the anionic surfactant is linear alkylbenzene sulphonate or primary alcohol sulphate. More preferably the anionic surfactant is linear alkylbenzene sulphonate.
  • Conventional nonionic detergent surfactants are ethoxylated alcohols of the formula R 1 -(-O-CH 2 -CH 2 ) m -OH wherein R 1 is a C 8 -C 20 hydrocarbyl chain, and the average degree of ethoxylation m is generally from 1 to 10, preferably from 3 to 8.
  • the alkyl chain length is preferably in the C 12 to C 15 range.
  • Alkylpolyglycosides may be represented by the general formula I RO(R'O) t (G) x in which R is a hydrocarbyl group containing from 10 to 20 carbon atoms, R' is an alkylene group containing from 2 to 4 carbon atoms, G is a saccharide residue containing 5 or 6 carbon atoms, t is in the range of from 0 to 25 and x is in the range of from 1 to 10.
  • the hydrophobic group R may be aliphatic, either saturated or unsaturated, notably linear or branched alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl. However, it may include an aryl group for example alkyl-aryl, alkenyl-aryl and hydroxyalkyl-aryl.
  • the preferred R group is an alkyl or alkenyl group having from 8 to 20 carbon atoms, more preferably from 8 to 16 carbon atoms.
  • the most preferred R group is an alkyl group having from 12 to 14 carbon atoms.
  • t in the general formula above is preferably zero, so that the -(RO) t - unit of the general formula is absent. In that case the general formula becomes RO(G) x
  • R'O is an ethylene oxide residue.
  • Other likely possibilities are propylene oxide and glycerol residues.
  • the value of t (which may be an average value) will preferably lie in the range of from 0.5 to 10.
  • the group G is typically derived from fructose, glucose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and/or ribose.
  • the group G is provided substantially exclusively by glucose units.
  • x which is an average, is usually termed the degree of polymerisation (dp). Desirably x is within the range of from 1 to 8. Preferred values of x lie within the range of from 1 to 3, especially from 1 to 1.8 and more especially from 1 to 1.6.
  • R is C 8 to C 14 alkyl or alkenyl.
  • R is C 8 to C 14 alkyl or alkenyl
  • t is zero
  • x is within the range of from 1 to 1.6.
  • Most preferably R is C 12 -C 14
  • t is zero
  • x is 1.4.
  • Commercially available products suitable for use in the compositions of the invention include the Plantacare (Trade Mark) and Glucopon (Trade Mark) ranges ex Cognis Germany; Lutensol (Trade Mark) GD 70 ex BASF; Marlosan (Trade Mark) 24 ex Hüls; and Atlas (Trade Mark) G73500 ex ICI.
  • compositions of the invention also contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder.
  • the quantity of builder is in the range of from 15 to 50% by weight.
  • the builder is selected from zeolite, sodium tripolyphosphate, sodium carbonate, sodium citrate, layered silicate, and combinations of these.
  • the zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders.
  • the zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever), and commercially available as Doucil (Trade Mark) A24 from Ineos Silicas Ltd, UK.
  • Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20. Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used.
  • phosphate builders especially sodium tripolyphosphate.
  • This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate.
  • inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
  • polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
  • polyaspartates monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl-
  • Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites.
  • Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%.
  • Builders, both inorganic and organic are preferably present in alkali metal salt, especially sodium salt, form.
  • compositions may optionally contain bleaching components and other active ingredients to enhance performance and properties.
  • optional ingredients may include, but are not limited to, any one or more of the following: soap, peroxyacid and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, proteases, lipases, cellulases, amylases, other detergent enzymes, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles, and perfume.
  • Detergent compositions according to the invention may suitably contain a bleach system.
  • the bleach system is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • sodium percarbonate having a protective coating against destabilisation by moisture Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • TAED N,N,N',N'-tetracetyl ethylenediamine
  • peroxybenzoic acid precursors in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate.
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
  • EDTA ethylenediamine tetraacetate
  • Dequest Trade Mark
  • EDTMP Dequest (Trade Mark)
  • enzymes are preferably absent, in other embodiments detergent enzymes may be present.
  • Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
  • detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
  • Antiredeposition agents for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present.
  • compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyviny
  • Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients.
  • “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.
  • Tablets may be prepared by compacting powders, especially "concentrated” powders.
  • Model formulation solutions were prepared containing the ingredients shown in the table below. The solutions were buffered to a pH of 10.5 which is typical for wash liquors. weight % Total surfactant 0, 0.7, 1.0 or 2.0 Zeolite MAP 0.18 Sodium carbonate 0.11 Sodium citrate 0.03 Water to 100%

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Utilisation d'un alkylpolyglycoside pour augmenter la douceur pour la peau d'une composition détergente pour le linge particulaire additivée qui comprend :
    (i) de 5 à 25 % en poids d'un tensioactif anionique sulfonate ou sulfate,
    (ii) de 1 à 10 % en poids d'un tensioactif non-ionique de type alcool éthoxylé,
    (iii) de 1 à 3 % en poids de l'alkylpolyglycoside,
    (iv) de 10 à 80 % en poids d'un adjuvant de détergence et
    (v) éventuellement d'autres ingrédients détergents jusqu'à 100 % en poids.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'alkylpolyglycoside répond à la formule générale I : RO (R'O)t (G)x dans laquelle R est un groupe hydrocarbyle contenant de 10 à 20 atomes de carbone, R' est un groupe alkylène contenant de 2 à 4 atomes de carbone, G est un résidu de saccharide contenant 5 ou 6 atomes de carbone, t est situé dans la plage allant de 0 à 25 et x est situé dans la plage allant de 1 à 10.
  3. Utilisation selon la revendication 2, caractérisée en ce que l'alkylpolyglycoside répond à la formule générale I dans laquelle R est un alkyle ou alcényle en C8 à C14, t vaut zéro et x est situé dans la plage allant de 1 à 1,6.
  4. Utilisation selon la revendication 3, caractérisée en ce que l'alkylpolyglycoside répond à la formule générale I dans laquelle R est un alkyle en C12 à C14, t vaut zéro et x vaut 1,4.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition détergente est exempte d'enzymes.
EP02256296A 2001-10-10 2002-09-11 Compositions détergentes Revoked EP1302531B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0124306.2A GB0124306D0 (en) 2001-10-10 2001-10-10 Detergent compositions
GB0124306 2001-10-10

Publications (2)

Publication Number Publication Date
EP1302531A1 EP1302531A1 (fr) 2003-04-16
EP1302531B1 true EP1302531B1 (fr) 2005-12-28

Family

ID=9923557

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02256296A Revoked EP1302531B1 (fr) 2001-10-10 2002-09-11 Compositions détergentes

Country Status (5)

Country Link
EP (1) EP1302531B1 (fr)
AT (1) ATE314449T1 (fr)
DE (1) DE60208290T2 (fr)
ES (1) ES2252397T3 (fr)
GB (1) GB0124306D0 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0228354D0 (en) 2002-12-05 2003-01-08 Unilever Plc Detergent compositions

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5834417A (en) * 1996-06-13 1998-11-10 Colgate Palmolive Co. Light duty liquid cleaning compositions
GB9707718D0 (en) * 1997-04-16 1997-06-04 Unilever Plc Light duty cleaning composition
US5780417A (en) * 1997-07-31 1998-07-14 Colgate-Palmolive Company Light duty liquid cleaning compositions
US5929024A (en) * 1997-11-20 1999-07-27 Colgate Palmolive Company Cleaning compositions
CN1085726C (zh) * 1998-12-22 2002-05-29 黎原寿 无毒洗衣粉
US6387870B1 (en) * 1999-03-29 2002-05-14 Ecolab Inc. Solid pot and pan detergent
DE19944544A1 (de) * 1999-09-17 2001-03-29 Cognis Deutschland Gmbh Tensidgemische
DE19960766A1 (de) * 1999-12-16 2001-06-21 Beiersdorf Ag Verfahren zur Herstellung besonders hautverträglicher kosmetischer oder dermatologischer Reinigungszubereitungen
CA2308834A1 (fr) * 2000-06-08 2000-08-21 Henkel Kommanditgesellschaft Auf Aktien Detergent sous forme solide ayant des proprietes de desagregation ameliorees

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VON RYBINSKI; HILL: "Alkylpolyglycoside...", ANGEW. CHEM, vol. 110, 1998, pages 1394 - 1412 *

Also Published As

Publication number Publication date
DE60208290T2 (de) 2006-07-06
ES2252397T3 (es) 2006-05-16
DE60208290D1 (de) 2006-02-02
EP1302531A1 (fr) 2003-04-16
GB0124306D0 (en) 2001-11-28
ATE314449T1 (de) 2006-01-15

Similar Documents

Publication Publication Date Title
EP1558717B1 (fr) Composition de detergent de lessive
US6794349B2 (en) Detergent compositions
EP1470213B2 (fr) Compositions detergentes
US7033984B2 (en) Detergent compositions
CA2431979C (fr) Detergent a lessive comportant un agent tensio-actif non ionique hautement ethoxyle
US6235703B1 (en) Surfactant blends, processes for preparing them and particulate detergent compositions containing them
EP1434839B1 (fr) Compositions detergentes
EP1302531B1 (fr) Compositions détergentes
EP1254202B1 (fr) Compositions detergentes
US7033983B2 (en) Detergent compositions
EP1254201A1 (fr) Compositions d tergentes
EP1527155B2 (fr) Compositions detergentes

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

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17P Request for examination filed

Effective date: 20030813

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

17Q First examination report despatched

Effective date: 20040303

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

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

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: 20051228

Ref country code: LI

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: 20051228

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: 20051228

Ref country code: CH

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: 20051228

Ref country code: FI

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: 20051228

Ref country code: CZ

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: 20051228

Ref country code: NL

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: 20051228

Ref country code: SK

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: 20051228

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60208290

Country of ref document: DE

Date of ref document: 20060202

Kind code of ref document: P

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

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: 20060328

Ref country code: BG

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: 20060328

Ref country code: SE

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: 20060328

Ref country code: GR

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: 20060328

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2252397

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: 20060529

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

Effective date: 20060429

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

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

Effective date: 20060911

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

Ref country code: MC

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

Effective date: 20060930

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

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

Ref country code: EE

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: 20051228

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: 20060911

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

Ref country code: CY

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: 20051228

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

Ref country code: ES

Payment date: 20100927

Year of fee payment: 9

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

Ref country code: FR

Payment date: 20100930

Year of fee payment: 9

Ref country code: IT

Payment date: 20100923

Year of fee payment: 9

Ref country code: TR

Payment date: 20100819

Year of fee payment: 9

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

Ref country code: GB

Payment date: 20100927

Year of fee payment: 9

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

Ref country code: DE

Payment date: 20100929

Year of fee payment: 9

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

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

Effective date: 20110911

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

Effective date: 20110911

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60208290

Country of ref document: DE

Effective date: 20120403

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: 20120403

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: 20110911

Ref country code: FR

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

Effective date: 20110930

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20110713