EP0946695B1 - Cleaning composition comprising monoalkyl cationic surfactants - Google Patents

Cleaning composition comprising monoalkyl cationic surfactants Download PDF

Info

Publication number
EP0946695B1
EP0946695B1 EP97952956A EP97952956A EP0946695B1 EP 0946695 B1 EP0946695 B1 EP 0946695B1 EP 97952956 A EP97952956 A EP 97952956A EP 97952956 A EP97952956 A EP 97952956A EP 0946695 B1 EP0946695 B1 EP 0946695B1
Authority
EP
European Patent Office
Prior art keywords
surfactant
composition according
fatty alkyl
composition
mono
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
EP97952956A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0946695A1 (en
Inventor
Matthew James Leach
Yoshihisa Niwata
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0946695A1 publication Critical patent/EP0946695A1/en
Application granted granted Critical
Publication of EP0946695B1 publication Critical patent/EP0946695B1/en
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
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • 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
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • 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
    • 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 an alkaline cleaning composition for hard surfaces, wherein said composition comprises both a fatty alkyl cationic surfactant and a nonionic surfactant.
  • soil release agents including polymers, siloxanes and dialkyl quaternary cationic surfactants in cleaning compositions so as to provide a secondary cleaning benefit. It is believed that these soil release agents function by deposition of a layer of of polymer, siloxane or surfactant on the surface during cleaning. This layer of material is believed to facilitate further cleaning operations by reducing the extent to which soil adheres to the surface.
  • compositions are strongly alkaline, so as to assist cleaning.
  • quaternary, cationic surfactants are available at the lowest cost.
  • These quaternary salts generally comprise a quaternised nitrogen with one or two pendant fatty alkyl chains and three or two pendant lower alkyl chains.
  • dialkyl quaternary cationic surfactants it has been found difficult to stabilize the products against flocculation and or phase-separation due to the interaction of the components present.
  • the present invention provides an aqueous, hard-surface cleaning composition
  • a surfactant mixture comprising:
  • compositions of the present invention modify the surface energy of surfaces to which the composition is applied so as to raise the contact angle of soil subsequently deposited on the modified surface.
  • a range of cationic mono-fatty alkyl quaternary ammonium compounds find useful appliaction in the compositions of the present invention.
  • Particularly suitable cationic surfactants are of the general formula: [R 1 R 2 R 3 R 4 N] + X - wherein R 1 , R 2 and R 3 are independently C 1-6 alkyl, R 4 is a fatty alkyl chain and X is an monovalent anion equivalent, the distribution of chain lengths in the material being such that in at least 10%wt of the material the fatty alkyl chain comprises C18-26 carbon atoms. It is preferable that less than 60% of the material comprises mono-fatty alkyl quaternary ammonium compounds in which the fatty alkyl chain is C16 or shorter.
  • the fatty alkyl chain can be derived from synthetic or natural feedstocks. If the fatty alkyl chain is derived from natural feedstocks it will generally comprise a mixture of materials with a range of alkyl chain lengths in the fatty-alkyl chain. Preferably the fatty alkyl chains are fully saturated. It is envisaged that saturated alkyl chains will show effective properties due to packing of the alkyl chains at surfaces and interfaces.
  • Materials of this general nature, in which the lower alkyl groups are methyl groups are available in the marketplace.
  • a particularly preferred material is trimethyl behenyl ammonium bromide. We have determined that this material will flocculate over time in the presence of significant quantities of inorganic salts, including alkali's such as sodium hydroxide and sodium or potassium carbonate. As is further described herein, this difficulty is avoided in the compositions of the present invention.
  • Nonionic Surfactants :
  • compositions of the present invention comprise a nonionic surfactant.
  • nonionic surfactant is believed to contribute significantly to the cleaning effectiveness of the compositions of the invention.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Particular examples include the condensation product of aliphatic alcohols having from 6 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxy-ethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of
  • nonionic surfactants are the ethoxylated alcohols having 6-14 carbons and 2-9 moles of ethoxylation.
  • Suitable materials include IMBENTIN 91/35 OFA (TM), a C 9-11 nonionic having on average five moles of ethoxylation and NONIDET 91-6T (TM) a topped C 9-11 nonionic with an average of six moles of ethoxylation.
  • nonionic surfactants are known to the skilled worker, as set forth in M.J.Schick 'Nonionic Surfactants', Marcel Dekker (1967) and subsequent editions of the same work.
  • the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 1 to 30%wt, preferably from 2 to 20%wt, and most preferably from 5 to 10%wt.
  • the ratio of nonionic surfactant to anionic and cationic surfactant is such that > 75% of the total surfactant present in the composition is nonionic.
  • compositions of the present invention only comprise low levels of anionic detergent actives or that these actives are absent in so far as is practical. It is believed that the presence of anionic detergents will cause the formation of a complex between the cationic and anionic detergents which will reduce the effectiveness of the compositions.
  • the overall surfactant content of compositions according to the present invention will generally be 1 to 30%wt.
  • compositions of the invention comprise at least 0.5%wt of an organic amine, with a pK a of at least 8.0.
  • This component is believed to function as estercleavage agent which assists cleaning of recalcitrant soils such as the pyrolised soils which are produced when fatty and/or proteinaceous foodstuffs are heated at the surface.
  • organic amines with a lower pK a such as aniline are used they are ineffective in assisting cleaning.
  • inorganic alkali's are present at significant levels, the quaternary material described above flocculates, and the composition phase-separates.
  • composition comprises 1-10% of an alkanolamine, with levels of 2-6%wt being particularly preferred.
  • alkanolamines include: 2-amino-2-methyl-1-propanol, mono-ethanolamine and di-ethanolamine.
  • 2-amino-2-methyl-1-propanol is the most preferred organic amine.
  • compositions of the present invention comprise less than 1% of electrolyte salts, including sodium and/or potassium carbonates, bicarbonates and/or hydroxides.
  • compositions of the present invention can contain other ingredients which aid in their cleaning performance and/or improve the physical properties of the composition. These components are not essential to the functioning of the invention.
  • Hydrophobic oils are optional components of compositions according to the present invention. Suitable oils include oils which rapidly dissolve triglyceride. When oils are present preferred oils include limonene, para-cymene, di-butyl ether and butyl butyrate.
  • a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in those compositions according to the invention which have a tendency to produce excessive suds in use.
  • suds regulating materials are organic solvents, hydrophobic silica and silicone oils or hydrocarbons.
  • Solvents are optional components of compositions according to the present invention. Where solvents are present, preferred solvents are of the form R 1 -0-(E0) m -(PO) n -R 2 , wherein R 1 and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. More preferably, the solvent is selected from the group comprising di-ethylene glycol mono n-butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof.
  • Alternative solvents include the pyrrolid(in)ones, for example N-methyl pyrrolidinone.
  • a long-chain fatty alcohol particularly C16 or longer, more preferably C16-C20 such as tallow alcohol gives an improvement in cleaning performance.
  • these alcohols will be present at levels of 0.001-2%, and preferably less than 1%.
  • compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
  • various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
  • compositions according to the invention are packaged in a container adapted to produce a spray of 0.1-1.5ml of product per spraying operation, said spray having an average drop size in the range 30-300 microns.
  • Suitable polymers include polyvinyl pyrrolidone, available in the marketplace as Polymer PVP K-90.
  • Suitable levels of PVP polymer range upwards from 50ppm. Levels of 300-2000ppm are particularly preferred.
  • compositions have a pH of >10 and comprise, in admixture with water,:
  • Aqueous compositions comprising nonionic surfactant, and a relatively low level of cationic surfactant were prepared as in Tables 1 below: using the following materials (all compositions are given in terms of wt% unless otherwise stated) :
  • the required amounts of all of the ingredients were mixed at room temperature.
  • examples 2 & 5 VBM was added to hot water at 80C and stirred using a Heidolph mixer at 80C for 2 hours, to give a 15.5% solution by weight.
  • the required amount of this solution was then added to the required amount of a solution containing all the remaining ingredients, at room temperature, and the solution stirred for a further 10 minutes.
  • equal amounts of nonionic surfactant (NONI) and dihardened tallow dimethyl ammonium chloride were melted together at 60C.
  • the required amount of this comelt was added (still at 60C) to the required amount of a solution containing all the remaining ingredients, at room temperature, and the solution stirred for a further 30 minutes.
  • the required amounts of all of the ingredients were mixed at room temperature. The solution was then warmed briefly to 60 C to homogenise.
  • Tiles were cleaned by hand using damp J-cloths and the compositions listed in Table 1. The effort required to clean the tiles was determined as 'ETh' in Table 1. ETh measurements are expressed in Newton seconds, higher values indicate that more effort was required to clean the tile.
  • Stability was determined by placing samples on storage at 5, 25 an 37 Celcius for three months. In the cases indicated as unstable in Table 1 a cloudy precipitate was formed under one or more of the storage conditions.
  • Example 2 shows that the lowest effort cleaning score were obtained with example 2, which is an embodiment of the invention using the longer chain fatty alkyl containing quaternary cationic VBM.
  • Examples 3 and 4 also showed an improvement over the control formulation provide as example 1. It can be seen that this improvment was either slight, as with the shorter fatty alkyl chain (CTAB: as used in example 4) or that product stability on storage was lost, as with the di fatty alkyl material (2HT: as used in example 3).
  • Example 5 shows that the combination of an alkaline salt with VBM did not lead to a stable product.
  • This mixture was then sprayed using a Humbrol [RTM] airbrush paint sprayer onto the cleaned tiles, using a circular mask, to give 5.5cm diameter patches of soil.
  • the acetone was allowed to evaporate to give 0.04-0.05g of soil per tile.
  • the soiled tiles were heated at 175 Celcius for 34 minutes and left overnight prior to cleaning.
  • the soil tile was placed in the 'WIRA' tester and 0.5ml of test product applied.
  • the tile was then cleaned using a 'J-cloth' [RTM] (ex. Johnson and Johnson, UK), folded to give eight layers, at a head pressure of 657g/cm 2 , for one full cycle (17 passes of the head).
  • CB is the contact angle on glass which has been contacted with the composition according to the example, using bromonaphthalene.
  • EXAMPLE 6-11 Ex: 6 7 8 9 10 11 NONI 10% 10% 10% 10% 10% 10% 10% DIGOL 8% 8% 8% 8% 8% AMP 4% - 4% - 4% DEA - 4% - - - - CARB - - - - 1.25% 1.25% VBM 1 1 0 1 1 1 0 CTAB 0 0 1 0 0 0 ETh 185 474 1383 336 742 2919 WIRA 88 84 83 57 85 89 CB 27 31.8 23.6 29 30 20.1
  • Example 6 is in accordance with the invention, whereas the remaining examples are comparative.
  • Example 11 is a commercially successful kitchen cleaner.
  • CB data demonstrates that the compositions of the invention modify the surface energy (which may be calculated from the contact angle) as compared with a known kitchen cleaning formulation (example 11) which contains no quaternary cationic.
  • examples 6 and 7 with clean a surface with reduced effort and leave the surface energy modified so as to prevent or reduce re-soiling.
  • Example 8 is less effective especially as regards thermally aged soils.
  • the formulation of example 9 will attack the thermally aged soil used to determine ETh but is poor as a general cleaner.
  • Example 10 is acceptable but it is preferable that carbonate is absent.

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)
  • Cosmetics (AREA)
EP97952956A 1996-12-20 1997-12-15 Cleaning composition comprising monoalkyl cationic surfactants Expired - Lifetime EP0946695B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9626610 1996-12-20
GBGB9626610.1A GB9626610D0 (en) 1996-12-20 1996-12-20 Cleaning composition comprising monoalkyl cationic surfactants
PCT/EP1997/007152 WO1998028391A1 (en) 1996-12-20 1997-12-15 Cleaning composition comprising monoalkyl cationic surfactants

Publications (2)

Publication Number Publication Date
EP0946695A1 EP0946695A1 (en) 1999-10-06
EP0946695B1 true EP0946695B1 (en) 2001-08-22

Family

ID=10804833

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97952956A Expired - Lifetime EP0946695B1 (en) 1996-12-20 1997-12-15 Cleaning composition comprising monoalkyl cationic surfactants

Country Status (16)

Country Link
EP (1) EP0946695B1 (es)
JP (1) JP2001506694A (es)
KR (1) KR20000069596A (es)
AR (1) AR009668A1 (es)
AU (1) AU719564B2 (es)
BR (1) BR9713967A (es)
CA (1) CA2272607A1 (es)
DE (1) DE69706314T2 (es)
ES (1) ES2163209T3 (es)
GB (1) GB9626610D0 (es)
HU (1) HUP0000687A3 (es)
SK (1) SK81199A3 (es)
TR (1) TR199901318T2 (es)
TW (1) TW374798B (es)
WO (1) WO1998028391A1 (es)
ZA (1) ZA9710996B (es)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6849589B2 (en) * 2001-10-10 2005-02-01 3M Innovative Properties Company Cleaning composition
DE102006006765A1 (de) 2006-02-13 2007-08-16 Schülke & Mayr GmbH Alkalisches Desinfektions- und Reinigungsmittel mit verbesserter Reinigungsleistung
CN106701351A (zh) * 2015-11-12 2017-05-24 艺康美国股份有限公司 低起泡器皿清洗清洁剂,含增强含油污垢除去的混合的阳离子/非离子表面活性剂体系
JP6585145B2 (ja) * 2016-12-13 2019-10-02 アース製薬株式会社 水洗トイレ用洗浄組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH17340A (en) * 1980-03-11 1984-08-01 Unilever Nv Detergent composition
JPS5876477A (ja) * 1981-10-30 1983-05-09 Lion Corp 陶磁器、ガラス表面のケイ酸スケールによる汚れを防止する方法
DE69422081T2 (de) * 1993-04-19 2000-07-20 Reckitt & Colman Inc Allzweckreinigungsmittelzusammensetzung
DK0730636T3 (da) * 1993-11-22 2001-08-13 Colgate Palmolive Co Flydende universalrengøringssammensætninger af mikroemulsionstypen
EP0811053B1 (en) * 1995-02-23 1999-05-06 Unilever Plc Process and composition for cleaning surfaces

Also Published As

Publication number Publication date
BR9713967A (pt) 2000-04-11
ES2163209T3 (es) 2002-01-16
HUP0000687A2 (hu) 2000-08-28
CA2272607A1 (en) 1998-07-02
TW374798B (en) 1999-11-21
KR20000069596A (ko) 2000-11-25
WO1998028391A1 (en) 1998-07-02
DE69706314T2 (de) 2002-01-03
AR009668A1 (es) 2000-04-26
GB9626610D0 (en) 1997-02-05
TR199901318T2 (xx) 1999-08-23
ZA9710996B (en) 1999-06-08
JP2001506694A (ja) 2001-05-22
HUP0000687A3 (en) 2003-02-28
DE69706314D1 (de) 2001-09-27
SK81199A3 (en) 1999-12-10
AU5663898A (en) 1998-07-17
AU719564B2 (en) 2000-05-11
EP0946695A1 (en) 1999-10-06

Similar Documents

Publication Publication Date Title
KR101350353B1 (ko) 경질 표면을 세정하기 위한 저향 에스테르-기재마이크로에멀션
US5741765A (en) Cleaning composition comprising quaternised poly-dimethylsiloxane and nonionic surfactant
AU699687B2 (en) Aerosol cleaning compositions
JP6781513B2 (ja) 硬質表面洗浄剤
JPH02289697A (ja) 硬質表面洗浄用組成物
US20030073602A1 (en) Non-foaming cleaning compositions and a method for their use
US4140647A (en) Detergent composition
EP0946695B1 (en) Cleaning composition comprising monoalkyl cationic surfactants
WO2000052128A1 (en) Hard surface cleaning composition
CA2211346C (en) Cleaning composition comprising saturated dialkyl cationic surfaces
EP0866115A2 (en) Cleaning composition comprising fluoro-surfactants
US20230058960A1 (en) Oven cleaning compositions and methods of making and using same
JP3396283B2 (ja) クリーナー組成物
CZ9902226A3 (cs) Čisticí prostředek
JPS5943516B2 (ja) ガラスクリ−ナ−
JP3306327B2 (ja) 硬質表面用洗浄剤組成物
KR20070091747A (ko) 백색 액체 세정제 조성물

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: 19990602

AK Designated contracting states

Kind code of ref document: A1

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

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20001020

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

AK Designated contracting states

Kind code of ref document: B1

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

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: 20010822

REF Corresponds to:

Ref document number: 69706314

Country of ref document: DE

Date of ref document: 20010927

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20011213

Year of fee payment: 5

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2163209

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: FR

Payment date: 20021119

Year of fee payment: 6

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

Ref country code: GB

Payment date: 20021211

Year of fee payment: 6

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: 20021216

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

Ref country code: DE

Payment date: 20021230

Year of fee payment: 6

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: 20031215

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: 20040701

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

Effective date: 20031215

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021216

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: 20040831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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: 20051215