[go: up one dir, main page]

EP1123375B1 - Eingedickte flüssige wasserstoffperoxydbleichmittelzusammensetzung - Google Patents

Eingedickte flüssige wasserstoffperoxydbleichmittelzusammensetzung Download PDF

Info

Publication number
EP1123375B1
EP1123375B1 EP99970679A EP99970679A EP1123375B1 EP 1123375 B1 EP1123375 B1 EP 1123375B1 EP 99970679 A EP99970679 A EP 99970679A EP 99970679 A EP99970679 A EP 99970679A EP 1123375 B1 EP1123375 B1 EP 1123375B1
Authority
EP
European Patent Office
Prior art keywords
bleaching composition
alkaline
hydrogen peroxide
composition
alkali metal
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
EP99970679A
Other languages
English (en)
French (fr)
Other versions
EP1123375A1 (de
Inventor
Hedeliza Malonzo Mercado
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive 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 Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP1123375A1 publication Critical patent/EP1123375A1/de
Application granted granted Critical
Publication of EP1123375B1 publication Critical patent/EP1123375B1/de
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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D1/75—Amino oxides
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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

Definitions

  • This invention relates to alkaline thickened liquid hydrogen peroxide bleaching compositions. More particularly, this invention relates to such alkaline thickened bleaching compositions which are highly stable in terms of providing a uniform and thickened viscosity which remains stable over time, concomitant with the ability to maintain a stable bleaching activity during extended periods of storage prior to use by the consumer.
  • Hydrogen peroxide compositions have been the focus of much attention in the patent literature in recent years as replacements for or as alternatives to halogen-containing bleaches, often motivated by environmental considerations.
  • interest has focused on alkaline hydrogen peroxide bleaches because of their greater reactivity and enhanced bleaching efficacy as compared to acidic hydrogen peroxide compositions.
  • One of the prime requirements of a bleach intended for domestic use is that the bleaching species remain sufficiently stable to insure good efficacy of the bleach product upon use by the consumer, typically many months after the products manufacture.
  • Hydrogen peroxide solutions are known to provide enhanced bleaching efficacy when used under alkaline conditions. However, stabilization of hydrogen peroxide is particularly troublesome at such alkaline conditions.
  • a thickened composition also serves to limit the rate at which the composition flows or drains from the surfaces to which it is applied.
  • a thickening agent or thickening system in the bleach composition presents problems in formulation: it is often incompatible with peroxide bleach stabilizers which are otherwise effective in non-thickened compositions, or the thickening agents themselves may provide an uneven viscosity to the liquid bleach product and, in general, adversely affect product appearance and flow characteristics depending on variables such as product pH or the non-bleach ingredients, such as electrolyte, present in the composition.
  • EP 376 704 describes hydrogen peroxide aqueous solutions which contain a combination of surfactant and electrolyte to provide thickening and bleach stability.
  • UK patent application GB 2 273 721 describes a thickened bleach composition which comprises an alkaline aqueous solution of hydrogen peroxide containing as the thickening system a mixture of a quaternary long chain alkyl ammonium compound together with a salt of an aromatic sulphonic acid hydrotrope.
  • U.S. Patent 5,736,498 is concerned with alkaline hydrogen peroxide compositions which are thickened with a polymeric thickener having a polyethylene backbone.
  • U.S. Patent 4,900,469 describes a thickened laundry composition comprising a surfactant thickening system, a hydrogen peroxide bleach and a stabilizing system consisting of a chelating agent and an antioxidant.
  • a C 6 -C 18 soap is optionally included to increase viscosity.
  • the present invention provides an alkaline thickened liquid bleaching composition with a viscosity in the range of 80 - 500 mPa.s (80 - 500 cps) comprising, by weight:
  • a method of bleaching fabrics comprising the step of contacting the fabrics to be bleached with an effective amount of the above-described alkaline thickened liquid bleaching composition.
  • the present invention is predicated on the discovery that thickening of a hydrogen peroxide bleach solution can be effectively provided with a surfactant mixture of alkyl dimethylamine oxide and soap as herein described in combination with a weak electrolyte such as an alkali metal sulfate, such that a stable commercially desirable viscosity in the range of from 80 ⁇ 10 -3 to 500 ⁇ 10 -3 m.sec/m 2 [80 to 500 cps] can be readily achieved, preferably from 100 ⁇ 10 -3 to 300 ⁇ 10 -3 m.sec/m 2 [100 to 300 cps] without adversely affecting the stability of the peroxide bleach.
  • a surfactant mixture of alkyl dimethylamine oxide and soap as herein described in combination with a weak electrolyte such as an alkali metal sulfate, such that a stable commercially desirable viscosity in the range of from 80 ⁇ 10 -3 to 500 ⁇ 10 -3 m.sec/m 2 [80 to 500 cps] can
  • the amount of hydrogen peroxide bleach present in the composition of the invention may vary from 0.1% to 10%, by weight, of the total composition.
  • Preferred compositions comprise from 2% to 6%, by weight.
  • the surfactant mixture which forms part of the thickening system is comprised of an alkyl dimethylamine oxide and a neutralized C 6 -C 18 fatty acid, such mixture being present in an amount of from 1.5 to 8%, by weight, preferably from 2% to 4%, by weight.
  • the alkyl group in the dimethylamine oxide surfactant contains from about 11 to 16 carbon atoms.
  • a preferred alkyl group is comprised of a mixture of carbon chain lengths comprising 33% to 43% of C 12 ; from 42% to 52% of C 14 ; and from 4% to 14% of C 16 .
  • Lauryl is a particularly preferred alkyl group.
  • the second component of the surfactant mixture is a C 6 -C 18 fatty acid which is neutralized in-situ by the alkali metal hydroxide in the liquid composition to form a C 6 -C 18 soap.
  • Typical fatty acids include capric acid, lauric acid, any myristic acid, but most preferred is coconut fatty acid which after neutralization forms the coconut lauryl soap.
  • the ratio of the described amine oxide surfactant to the fatty acid soap is generally from 1.5:1 to 6:1, and preferably from 2:1 to 4:1.
  • the third component of the thickening system which serves to stabilize the increased viscosity provided by the surfactant mixture is an alkali metal sulfate such as sodium or potassium or magnesium sulfate.
  • Sodium sulfate is preferred as a source of weak electrolyte which serves to stabilize the viscosity of the composition without adversely affecting the stability of the hydrogen peroxide in solution. It has been found that the presence of strong electrolyte in solution at a level to compliment the surfactant thickening such as Na 2 CO 3 , NaOH, NaHCO 3 cause decomposition of alkaline hydrogen peroxide solution and is, therefore, to be avoided in the present liquid bleaching compositions.
  • the peroxide bleach stabilizer used herein is a polyphosphonate sequestrant.
  • suitable phosphonate stabilizers include sodium or potassium salts of HEDP 1 and EDTMP 2 .
  • Most preferred is the pentasodium salt of diethylenetriamine penta (methylene phosphonic acid), which is available commercially under the trademark Dequest 2066 from the Monsanto Company.
  • An essential ingredient in the present bleaching composition is an alkali metal hydroxide such as sodium or potassium hydroxide, in an amount sufficient to neutralize in-situ the fatty acid ingredient present in the surfactant mixture so as to form the soap.
  • the alkali metal hydroxide also serves to provide an alkaline pH in the liquid bleach composition of from 8 to 9.5, and preferably from 8.2 to 9.2.
  • the amount of alkali metal hydroxide in the composition is generally from 0.10 to 0.5%.
  • the liquid bleach compositions may preferably include a pH buffer such as sodium benzoate which serves to stabilize the pH of the composition and thereby assists in stabilizing the peroxide bleach.
  • a pH buffer such as sodium benzoate which serves to stabilize the pH of the composition and thereby assists in stabilizing the peroxide bleach.
  • the sodium benzoate is present in an amount of from 0 to 2%, preferably from 0,2 to 1,5% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Claims (13)

  1. Alkalische verdickte flüssige Bleichzusammensetzung mit einer Viskosität im Bereich von 80·10-3 bis 500·10-3 Ns/m2 (80 bis 500 cPs), die, bezogen auf das Gewicht, umfasst:
    (a) 0,1 % bis 10 % Wasserstoffperoxid,
    (b) 1,5 % bis 8 % einer Tensidmischung, die
    (i) Alkyldimethylaminoxid und
    (ii) Seife, die durch in situ-Neutralisation von C6bis C18-Fettsäure mit Alkalimetallhydroxid gebildet worden ist,
    wobei das Gewichtsverhältnis (i) und (ii) 1,5 : 1 bis 6 : 1 beträgt,
    (c) 0,5 % bis 5 % Alkalimetallsulfat als Elektrolyt,
    (d) 0,4 bis 1 % Phosphonatstabilisator für das Wasserstoffperoxid,
    (e) Akalimetallhydroxid in einer Menge, die ausreicht, um die in situ-Neutralisation der zuvor genannten C6- bis C18-Fettsäure zu bewirken, um die in (b) (ii) definierte Seife zu bilden, und außerdem einen pH-Wert im Bereich von 8 bis 9,5 für die verdickte Bleichzusammensetzung zu liefern,
    (f) 0 % bis 2 % Natriumbenzoat und
    (g) als Rest Wasser.
  2. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der die Menge an Wasserstoffperoxid 2 % bis 6 % beträgt.
  3. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der die Menge der Tensidmischung 2 % bis 4 Gew.-% der Zusammensetzung beträgt und das Verhältnis von (i) zu (ii) 2 : 1 bis 4 : 1 beträgt.
  4. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der die Alkylgruppe in dem Alkyldimethyl-aminoxid eine Mischung von Kohlenstoffkettenlängen umfasst, die im Wesentlichen aus 33 % bis 43 % C12, 42 % bis 52 % C14 und 4 % bis 14 % C16 bestehen.
  5. Alkalische verdickte Bleichzusammensetzung nach Anspruch 4, bei der das Aminoxidtensid Lauryldimethylaminoxid ist.
  6. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der die Seife eine Kokoslaurylseife ist, die durch Neutralisation von Kokosfettsäure mit dem Alkalimetallhydroxid gebildet worden ist.
  7. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der der Elektrolyt Natrium- oder Kaliumsulfat ist.
  8. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der der Phosphonatstabilisator das Pentanatriumsalz von Diethylentriaminpenta(methylenphosphonsäure) ist.
  9. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, bei der der pH-Wert der Zusammensetzung 8,2 bis 9,2 beträgt.
  10. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, die Natriumbenzoat in einer Menge von 0,2 % bis 1,5 Gew.-% enthält.
  11. Alkalische verdickte Bleichzusammensetzung nach Anspruch 1, die dadurch gekennzeichnet ist, dass sie im Wesentlichen frei von einem Elektrolyten ist, der von dem in (c) definierten verschieden ist.
  12. Verfahren zum Bleichen von Geweben, das den Schritt der Kontaktierung der zu bleichenden Gewebe mit einer wirksamen Menge der alkalischen verdickten flüssigen Bleichzusammensetzung gemäß Anspruch 1 umfasst.
  13. Verfahren nach Anspruch 12, bei dem die Seife eine Kokoslaurylseife ist, die durch Neutralisation von Kokosfettsäure mit dem Alkalimetallhydroxid gebildet worden ist.
EP99970679A 1998-10-22 1999-10-21 Eingedickte flüssige wasserstoffperoxydbleichmittelzusammensetzung Expired - Lifetime EP1123375B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17768898A 1998-10-22 1998-10-22
US177688 1998-10-22
PCT/US1999/024910 WO2000023555A1 (en) 1998-10-22 1999-10-21 Thickened liquid hydrogen peroxide bleach compositions

Publications (2)

Publication Number Publication Date
EP1123375A1 EP1123375A1 (de) 2001-08-16
EP1123375B1 true EP1123375B1 (de) 2005-04-20

Family

ID=22649583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99970679A Expired - Lifetime EP1123375B1 (de) 1998-10-22 1999-10-21 Eingedickte flüssige wasserstoffperoxydbleichmittelzusammensetzung

Country Status (8)

Country Link
EP (1) EP1123375B1 (de)
AT (1) ATE293675T1 (de)
AU (1) AU1226800A (de)
BR (1) BR9914702A (de)
CA (1) CA2347430A1 (de)
DE (1) DE69924859T2 (de)
DK (1) DK1123375T3 (de)
WO (1) WO2000023555A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10039031A1 (de) * 2000-08-10 2002-02-28 Henkel Ecolab Gmbh & Co Ohg Pastenförmige Persäuren
DE102005000955B4 (de) * 2005-01-07 2007-08-30 Henkel Kgaa Flüssige Bleichmittelzusammensetzung
DE102006029344A1 (de) * 2006-06-23 2007-12-27 Henkel Kgaa Zahnbehandlungsmittel mit verstärkter Bleichwirkung

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900469A (en) * 1986-10-21 1990-02-13 The Clorox Company Thickened peracid precursor compositions
GB8830296D0 (en) * 1988-12-28 1989-02-22 Unilever Plc Bleaching composition
DE3906044A1 (de) * 1989-02-27 1990-08-30 Henkel Kgaa Bleichendes fluessigwaschmittel
JPH04372695A (ja) * 1991-06-20 1992-12-25 Kao Corp 漂白剤および漂白洗浄剤組成物
JP2896724B2 (ja) * 1991-12-19 1999-05-31 日本パーオキサイド株式会社 漂白用組成物
GB2273721B (en) * 1992-12-24 1996-05-01 Jeyes Group Plc Bleaches
GB9319943D0 (en) * 1993-09-28 1993-11-17 Solvay Interox Ltd Thickened compositions
GB9804068D0 (en) * 1998-02-27 1998-04-22 Mcilroy Andrew Bleach stabiliser

Also Published As

Publication number Publication date
WO2000023555A1 (en) 2000-04-27
DE69924859T2 (de) 2006-02-23
DK1123375T3 (da) 2005-08-15
DE69924859D1 (de) 2005-05-25
EP1123375A1 (de) 2001-08-16
BR9914702A (pt) 2001-07-10
AU1226800A (en) 2000-05-08
ATE293675T1 (de) 2005-05-15
CA2347430A1 (en) 2000-04-27

Similar Documents

Publication Publication Date Title
FI89721B (fi) Flytande tvaettmedelkomposition innehaollande fast peroxiblekningsmedel
AU2007317613B2 (en) Liquid detergent formulation with hydrogen peroxide
US4642198A (en) Liquid bleaching compositions
US5869440A (en) Peroxide activation method and peroxide composition
CA2015728C (en) Thickened hypochlorite bleach solution and method of use
EP0737242B1 (de) Verdickte alkalimetallhypochloritzubereitungen
EP0845526A2 (de) Reinigungs-, Desinfektions- und Bleichmittelzusammensetzung
US4828747A (en) Suspending system for insoluble peroxy acid bleach
JPH0558480B2 (de)
GB2286603A (en) Thickened alkaline peroxide bleaches
US5559090A (en) Stable, hydrogen peroxide-containing bleaching compositions
JPH04214800A (ja) 水性液体漂白剤組成物
JPH02227498A (ja) 漂白組成物
CA1228453A (en) Bleaching compositions
CA1303453C (en) Cleaning compositions
CA2159821A1 (en) Lavatory blocks containing active oxygen
AU2615295A (en) Aqueous bleaching compositions comprising peroxy carboxylic acids
US5804545A (en) Stable alkaline chlorine compositions
EP1123375B1 (de) Eingedickte flüssige wasserstoffperoxydbleichmittelzusammensetzung
AU9411998A (en) Detergents, cleaning compositions and disinfectants comprising chlorine-active substances and fattyacid alkyl ester ethoxylates
MXPA97003841A (en) Thickening compositions thickenes, method of use and procedure to make mys
JP2663180B2 (ja) 粘度低下防止剤及び該防止剤を含有する液体漂白剤組成物
WO2023213524A1 (en) Detergent composition
US5914304A (en) Bleaching compositions
MXPA01003982A (en) Thickened liquid hydrogen peroxide bleach compositions

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

17P Request for examination filed

Effective date: 20010420

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO PAYMENT 20010420;SI

17Q First examination report despatched

Effective date: 20030729

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 CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Extension state: RO

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050420

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;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: 20050420

Ref country code: ES

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: 20050420

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: 20050420

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: 69924859

Country of ref document: DE

Date of ref document: 20050525

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20050402270

Country of ref document: GR

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: 20050920

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: 20051021

Ref country code: GB

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

Effective date: 20051021

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: 20051021

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: 20051031

Ref country code: LU

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

Effective date: 20051031

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

ET Fr: translation filed
26N No opposition filed

Effective date: 20060123

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

Effective date: 20051021

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: COLGATE-PALMOLIVE COMPANY

Free format text: COLGATE-PALMOLIVE COMPANY#300 PARK AVENUE#NEW YORK, N.Y. 10022 (US) -TRANSFER TO- COLGATE-PALMOLIVE COMPANY#300 PARK AVENUE#NEW YORK, N.Y. 10022 (US)

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

Ref country code: DK

Payment date: 20140924

Year of fee payment: 16

Ref country code: GR

Payment date: 20140929

Year of fee payment: 16

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

Ref country code: DE

Payment date: 20141028

Year of fee payment: 16

Ref country code: SE

Payment date: 20141007

Year of fee payment: 16

Ref country code: CH

Payment date: 20141027

Year of fee payment: 16

Ref country code: FR

Payment date: 20140924

Year of fee payment: 16

Ref country code: FI

Payment date: 20141002

Year of fee payment: 16

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

Ref country code: AT

Payment date: 20140925

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69924859

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20151031

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 293675

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151021

REG Reference to a national code

Ref country code: GR

Ref legal event code: ML

Ref document number: 20050402270

Country of ref document: GR

Effective date: 20160506

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

Ref country code: CH

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

Effective date: 20151031

Ref country code: GR

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

Effective date: 20160506

Ref country code: LI

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

Effective date: 20151031

Ref country code: DE

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

Effective date: 20160503

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160630

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

Ref country code: AT

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

Effective date: 20151021

Ref country code: SE

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

Effective date: 20151022

Ref country code: FR

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

Effective date: 20151102

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 NON-PAYMENT OF DUE FEES

Effective date: 20151031

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

Ref country code: FI

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

Effective date: 20151021