[go: up one dir, main page]

EP1236793B1 - Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel - Google Patents

Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel Download PDF

Info

Publication number
EP1236793B1
EP1236793B1 EP02004064A EP02004064A EP1236793B1 EP 1236793 B1 EP1236793 B1 EP 1236793B1 EP 02004064 A EP02004064 A EP 02004064A EP 02004064 A EP02004064 A EP 02004064A EP 1236793 B1 EP1236793 B1 EP 1236793B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
dye
acid
sodium
color
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
EP02004064A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1236793A3 (de
EP1236793A2 (de
Inventor
Frank-Peter Di. Lang
Helmut Dr. Berenbold
Michael Dr. Wessling
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
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 Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1236793A2 publication Critical patent/EP1236793A2/de
Publication of EP1236793A3 publication Critical patent/EP1236793A3/de
Application granted granted Critical
Publication of EP1236793B1 publication Critical patent/EP1236793B1/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
    • C11D3/39—Organic or inorganic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the invention relates to detergents and laundry treatment compositions containing at least 0.1% dye-transfer inhibiting dye fixing agents, these dye fixing agents being obtained by reacting polyamines with cyanamides and amidosulfuric acid.
  • polyamines in this case comprises e.g. Diamines, triamines, tetraamines, etc. Examples of these are ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine and higher polyamines. Particularly preferred is diethylenetriamine.
  • the cyanamides may be cyanamide or dicyandiamide.
  • color fixing agents are added to the detergents according to the invention to improve the wash fastness of textile dyes by reducing their bleeding.
  • these color fixing agents also have the effect of inhibiting dye transfer by binding residual amounts of bleeding dye in the wash liquor in the case of very poor wash fastnesses of the dyed textiles, thus preventing deposition on washed-on white or other-colored fabric.
  • the detergent formulations in which the dye transfer inhibiting dye fixing agents described can be used are powder, granular, paste, gel or liquid. Examples of these are heavy duty detergents, mild detergents, color detergents, wool detergents, curtain detergents, modular detergents, washing tablets, bar soaps, detergent formulations packaged in water-soluble films and stain salts.
  • Laundry treatment agents are e.g. Laundry starches and stiffeners as well as ironing aids.
  • color transfer-inhibiting dye fixing agents mentioned can be used in laundry pre- or laundry after-treatment agents which can be used before or after the actual wash cycle and which are used exclusively for laundry care and laundry conditioning, but not for cleaning the laundry.
  • the detergents according to the invention contain at least 0.1%, preferably between 0.1 and 10% and particularly preferably 0.5 to 5% of the dye transfer inhibiting dye fixing agents described.
  • Formulations used as laundry pre- and / or post-whitening agents may contain between 1 and 99% of the color fixing agents. Depending on their intended use, the formulations should be adapted in their composition to the type of textiles to be washed.
  • the total concentration of surfactants in the final detergent formulation may be from 1 to 99%, and preferably from 5 to 80% (all wt%).
  • the surfactants used may be anionic, nonionic, amphoteric and cationic. It is also possible to use mixtures of the surfactants mentioned.
  • Preferred detergent formulations contain anionic and / or nonionic surfactants and mixtures thereof with other surfactants.
  • Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof.
  • Suitable cations here are alkali metals, e.g. Sodium or potassium or alkaline earth metals, e.g. Calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.
  • the following types of anionic surfactants are particularly preferred: alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, alkanesulfonates and soaps, as described below.
  • Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by means of gaseous SO 3 as described in U.S. Pat. The Journal of the American Oil Chemists Society "52 (1975), pp. 323-329 is described. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature.
  • Preferred alkyl ester sulfonates are compounds of the formula wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl.
  • M stands for a cation, the one forming water-soluble salt with the alkyl ester sulfonate.
  • Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
  • R 1 is C 10 -C 16 -alkyl and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl.
  • Alkyl sulfates are here water-soluble salts or acids of the formula ROSO 3 M, wherein R is a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 -Alkgkomponente, more preferably a C 12 -C 18 alkyl or Hydroxyalkyl radical.
  • M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, eg methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine , Diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C 16 are preferred for low wash temperatures (eg below about 50 ° C) and alkyl chains with C 16 -C 18 for higher wash temperatures (eg above about 50 ° C).
  • Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, more preferably C 12 -C 18 represents alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy moiety
  • m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3
  • M is a hydrogen atom or a cation such as Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • Examples include C 12 - to C 18 called fatty alcohol ether sulfates wherein the content of EO is 1, 2, 2.5, 3, or 4 moles per mole of fatty alcohol ether sulfate, and in which M is sodium or potassium.
  • the alkyl group may be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
  • the sulfo group can be at any position of the C chain, with the primary methyl groups at the beginning and end of the chain having no sulfonate groups.
  • the preferred secondary alkanesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms, and more preferably about 13 to 17 carbon atoms.
  • the cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium, and mixtures thereof. Sodium as a cation is preferred.
  • the preferred alkyl chains and cations are the same as those of the secondary alkanesulfonates.
  • the preparation of primary alkanesulfonic acid, from which the corresponding surfactant sulfonates are obtained, is for example in EP 854 136-A1 described.
  • alkenyl or alkylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
  • the alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
  • magnesium is preferred as a cation
  • sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.
  • anionic surfactants also includes olefin sulfonates obtained by sulfonation of C 8 -C 24 , preferably C 14 -C 16, ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these Olefinsulfonate smaller amounts of Hydroxyalkansulfonaten and Alkandisulfonaten included. Specific mixtures of ⁇ -olefin sulfonates are in US 3,332,880 described.
  • Suitable anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants.
  • the soaps may be saturated or unsaturated and may contain various substituents such as hydroxyl groups or ⁇ -sulfonate groups.
  • Preferred are linear saturated or unsaturated hydrocarbon radicals as hydrophobic moiety with about 6 to about 30, preferably about 10 to about 18 carbon atoms.
  • acylaminocarboxylic acids which are acylsarcosinates formed by reaction of fatty acid chlorides with sodium sarcosinate in an alkaline medium; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, as described, for example, in US Pat GB 1,082,179 ; Alkyl and alkenyl glycerol sulfates such as oleyl glycerol sulfates, alkyl phenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N
  • Suitable nonionic surfactants are, for example, the following compounds: condensation products of aliphatic alcohols with from about 1 to about 25 mol of ethylene oxide.
  • the alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of C 10 - to C 20 -alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates may have a narrow range ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide (“Broad Range Ethoxylates").
  • nonionic surfactants of this type are Tergitol ® 15-S-9 (the condensation product of a linear secondary C 11 -C 15 alcohol with 9 moles ethylene oxide), Tergitol ® 24-L-NMW (the condensation product of a linear primary C 12 -C 14- alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution). Also included in this product class are Genapol ® brands from Clariant GmbH.
  • the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800.
  • the addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility.
  • the product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide.
  • Commercially available examples of this product class are the Pluronic ® brands from BASF and the ® Genapol PF brands from Clariant GmbH.
  • the hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000.
  • Commercially available Examples of this class of compounds are the ® Tetronic brands of BASF and the ® Genapol PN brands of Clariant GmbH.
  • This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides each having an alkyl group of about 10 to about 18 carbon atoms.
  • Semi-polar nonionic surfactants are also amine oxides of the formula R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms, R 2 is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof, each R 1 is an alkyl or hydroxyalkyl group having from about 1 to about 3 carbon atoms or a polyethylene oxide group having from about 1 to about 3 ethylene oxide units, and x represents a number from 0 to about 10.
  • the R 1 groups may be linked together via an oxygen or nitrogen atom and thus form a ring.
  • Amine oxides of this type are especially C 10 -C 18 -alkyldimethylamine oxides and C 8 -C 12 -alkoxyethyl-dihydroxyethylamine oxides.
  • Fatty acid amides have the formula
  • R is an alkyl group having from about 7 to about 21, preferably from about 9 to about 17 carbon atoms, and each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H, where x varies from about 1 to about 3.
  • C 8 -C 20 -amides, -monoethanolamides, -diethanolamides and -isopropanolamides are preferred.
  • nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettchurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or Mischformale, Alkyloligoglycoside, Alkenyloligoglycoside, fatty acid N-alkylglucamide, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.
  • Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
  • These compounds include the condensation products of alkylphenols having a C 6 to C 20 alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol.
  • Commercially available surfactants of this type include Igepal ® CO-630, Triton ® X-45, X-114, X-100 and X102, and the Arkopal N ® brands from Clariant GmbH. These surfactants are referred to as Alkylphenolalkoxilate, eg Alkylphenolethoxilate.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula wherein R 1 is C 8 -C 22 alkyl or alkenyl, R 2 is hydrogen or CH 2 CO 2 M, R 3 is CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CH 2 CO 2 M, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 COOM, Z CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.
  • Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples of these are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.
  • amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines having an alkyl group of about 8 to about 22 carbon atoms, which may be linear or branched, preferably having 8 to 18 carbon atoms and more preferably having about 12 to about 18 carbon atoms. These compounds are marketed, for example, by Clariant GmbH under the trade name ® Genagen LAB.
  • Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R 1 N (CH 3 ) 3 ⁇ X ⁇ , R 1 R 2 N (CH 3 ) 2 ⁇ X ⁇ , R 1 R 2 R 3 N (CH 3 ) ⁇ X ⁇ or R 1 R 2 R 3 R 4 N ⁇ X ⁇ .
  • the radicals R 1 , R 2 , R 3 and R 4 may preferably independently of one another unsubstituted alkyl having a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl having from about 1 to about 4 C Atoms, phenyl, C 2 - to C 18 -alkenyl, C 7 - to C 24 -aralkyl, (C 2 H 4 O) x H, where x is from about 1 to about 3, one or more ester groups-containing alkyl radicals or cyclic quaternary ammonium salts.
  • X is a suitable anion.
  • detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the degree of hardness of the water.
  • Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.
  • silicate builders are the alkali metal silicates, in particular those having a SiO 2 : Na 2 O ratio of between 1.6: 1 and 3.2: 1, and phyllosilicates, for example sodium layer silicates, as described in US Pat US 4,664,839 , available from Clariant GmbH under the trademark SKS® .
  • SKS- 6® is a particularly preferred phyllosilicate builder.
  • Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites of the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 is about 0.5, and x is an integer of about 15 to about 264.
  • Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced. Methods for the preparation of aluminosilicate-based ion exchangers are described in US Pat US 3,985,669 and US 4,605,509 , Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the designation zeolite A, zeolite P (B) (including those described in US Pat EP-A-0 384 070 aluminosilicate having a particle diameter between 0.1 and 10 ⁇ m.
  • Suitable organic builders include polycarboxylic compounds such as, for example, ether polycarboxylates and oxydisuccinates, such as, for example, in US Pat US 3,128,287 and US 3,635,830 described. Likewise on “TMS / TDS" equipment from US 4,663,071 to get expelled.
  • Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 , 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
  • Important organic builders are also polycarboxylates based on acrylic acid and maleic acid, such as the Sokalan CP brands from BASF.
  • Citric acid and its soluble salts, in particular the sodium salt are preferred polycarboxylic acid builders which can also be used in granulated formulations, in particular together with zeolites and / or sheet silicates.
  • phosphorus based builders can be used, and especially if hand soap bars are to be formulated by hand, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used.
  • phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those described in U.S. Pat US 3,159,581 . US 3,213,030 . US 3,422,021 . US 3,400,148 and US 3,422,137 are disclosed.
  • the detergents and laundry treatment compositions of the present invention may contain conventional adjuvants or other materials which enhance detergency, serve to treat or care for the fabric being washed, or alter the performance properties of the detergent composition.
  • Suitable adjuvants include those in US 3,936,537 substances, for example enzymes, in particular proteases, lipases, cellulases and amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or corrosion inhibitors, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropes, antioxidants, perfumes, solvents, solubilizers, anti-redeposition agents, dispersants, processing aids, plasticizers, antistatic agents and soil release polymers such as the TexCare brands / Fa. Clariant, the Repel-O-Tex brands / Fa. Rhodia or Sokalan SR-100 / Fa. BASF.
  • enzymes in particular proteases, lipases, cellulases and amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or corrosion inhibitors, suspending agents, dyes, fillers,
  • the detergents and cleaners according to the invention containing dye-transfer-inhibiting dye-fixing agents may additionally contain the known and commercially available dye transfer inhibitors.
  • these color transfer inhibitors are polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
  • a significant disadvantage of the hitherto commercially available dye transfer inhibitors is that they not only bind the dye removed from the textiles and contained in the wash liquor, but additionally can also remove dyes from the textiles and thus promote a fading of the washed dye fabrics.
  • the dye transfer inhibiting color fixing agents By combining with the dye transfer inhibiting color fixing agents not only the color transfer inhibiting effect of the known dye transfer inhibitors can be improved, but it can additionally be counteracted by the fading of the color fabrics promoted by these products.
  • the detergent compositions of the present invention may optionally contain one or more conventional bleaching agents, as well as bleach activators, bleach catalysts and suitable stabilizers. In general, it must be ensured that the bleaching agents used are compatible with the detergent ingredients. Conventional test methods, such as the determination of the bleach activity of the final formulated detergent as a function of storage time, can be used for this purpose.
  • the peroxyacid may be either a free peroxyacid or a combination of an inorganic persalt, for example, sodium perborate or sodium percarbonate and an organic peroxyacid precursor, which is converted to a peroxyacid when the combination of the persalt and the peroxyacid precursor is dissolved in water.
  • the organic peroxyacid precursors are often referred to in the art as bleach activators. Examples of suitable organic peroxyacids are disclosed in US 4,374,035 . US 4,681,592 . US 4,634,551 . US 4,686,063 . US 4,606,838 and US 4,671,891 ,
  • compositions which are suitable for bleaching laundry and which contain perborate bleaches and activators are described in US Pat US 4,412,934 . US 4,536,314 . US 4,681,695 and US 4,539,130 ,
  • peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).
  • DPDA peroxydodecanedioic acid
  • NAPSA nonylamide of peroxysuccinic acid
  • NAPAA nonylamide of peroxyadipic acid
  • DDPSA decyldiperoxysuccinic acid
  • Bleach systems based on a persalt such as perborates or pecarbonates with the bleach activator tetraacetylethylenediamine (TAED) are particularly preferably used in the detergents and laundry treatment compositions according to the invention.
  • the described color fixing agents can also be used in commercial laundry conditioners for domestic use. These contain essentially plasticizing components, co-plasticizers, Emulsifiers, perfumes, dyes and electrolytes, and are adjusted to an acidic pH of below 7, preferably between 3 and 5, adjusted.
  • distearyldimethylammonium chloride ditallowalkyldimethylammonium chloride, ditallowalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride.
  • Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.
  • aminoglycerol derivatives such as, for example, dimethylaminopropanediol.
  • Alkylating or hydroxyalkylating agents are alkyl halides, preferably methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.
  • esterquats are compounds of the formulas: wherein RCO is derived from C 8 -C 24 fatty acids, which may be saturated or unsaturated. Examples of these are caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palminstearic acid, myristic acid and elaidic acid.
  • n is in the range of 0 to 10, preferably 0 to 3, particularly preferably 0 to 1.
  • tertiary amino group may additionally be a radical R 3 , which may be C 1 -C 4 alkyl, preferably methyl, and a counterion X, which may be chloride, bromide, iodide or methyl sulfate, are introduced.
  • R 3 which may be C 1 -C 4 alkyl, preferably methyl
  • a counterion X which may be chloride, bromide, iodide or methyl sulfate, are introduced.
  • Amidoaminooxethylates or their quaternized secondary products are available under the trade names ® Varisoft 510, ® Varisoft 512, ® Rewopal V 3340 and ® Rewoquat W 222 LM.
  • the preferred use levels of the color fixing agents in the fabric softener formulations are the same as those called for detergent formulations.
  • color transfer-inhibiting dye fixing agents used in the detergents according to the invention are:
  • Example 1 Reaction product of diethylenetriamine with dicyandiamide and amidosulfuric acid.
  • the dye transfer-inhibiting dye fixing agents were tested for their color-retaining effect in combination with standard detergents on various dye fabrics. At the same time, the test was for a color transfer inhibiting effect.
  • Tables 7 to 11 show average delta E values obtained on red, blue, green, violet and black colored fabrics. The lower these values are, the better is the color retention achieved with the dye fixing agents in the detergents according to the invention.
  • Detergent / additive ⁇ delta E-values Color differences to unwashed fabric after five washes IEC-A without additive 7.6 + Ex. 1 5.3
  • Detergent / additive ⁇ delta E-values Color differences to unwashed fabric after five washes IEC-A without additive 7.4 + Ex. 1 6.4

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)
EP02004064A 2001-03-03 2002-02-23 Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel Expired - Lifetime EP1236793B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10110338 2001-03-03
DE10110338 2001-03-03
DE10150724A DE10150724A1 (de) 2001-03-03 2001-10-13 Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel
DE10150724 2001-10-13
US10/085,712 US6858570B2 (en) 2001-03-03 2002-02-28 Laundry detergents and laundry treatment compositions comprising one or more dye-transfer-inhibiting dye fixatives

Publications (3)

Publication Number Publication Date
EP1236793A2 EP1236793A2 (de) 2002-09-04
EP1236793A3 EP1236793A3 (de) 2003-09-03
EP1236793B1 true EP1236793B1 (de) 2007-11-14

Family

ID=32045575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02004064A Expired - Lifetime EP1236793B1 (de) 2001-03-03 2002-02-23 Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel

Country Status (7)

Country Link
US (1) US6858570B2 (ja)
EP (1) EP1236793B1 (ja)
JP (1) JP4315634B2 (ja)
AT (1) ATE378392T1 (ja)
DE (2) DE10150724A1 (ja)
ES (1) ES2294053T3 (ja)
PT (1) PT1236793E (ja)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004018051A1 (de) * 2004-04-08 2005-11-10 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend Farbfixiermittel und Soil Release Polymere
ES2585181T3 (es) * 2004-05-05 2016-10-04 Unilever N.V. Procedimiento de limpieza
DE102004043728A1 (de) 2004-09-10 2005-06-30 Clariant Gmbh Flüssigwaschmittel enthaltend Farbfixiermittel
DE102004051011A1 (de) * 2004-10-20 2005-06-23 Clariant Gmbh Flüssigwaschmittel enthaltend sekundäres Alkansulfonat und Farbfixiermittel
DE102004051010A1 (de) * 2004-10-20 2005-06-23 Clariant Gmbh Flüssigwaschmittel enthaltend anionische Tenside und Farbfixiermittel
DE102004051714A1 (de) * 2004-10-23 2005-07-07 Clariant Gmbh Anionische Flüssigwaschmittel mit Farbfixiermitteln
DE102004051715A1 (de) * 2004-10-23 2005-06-30 Clariant Gmbh Flüssigwaschmittel enthaltend Farbfixiermittel
DE102004053970A1 (de) * 2004-11-09 2005-09-15 Clariant Gmbh Flüssigwaschmittel enthaltend anionische und kationische Tenside
DE102004053969A1 (de) * 2004-11-09 2005-09-15 Clariant Gmbh Flüssigwaschmittel enthaltend sekundäres Alkansulfonat und kationische Tenside
DE102005013780A1 (de) 2005-03-22 2006-09-28 Basf Ag Verwendung von kationischen Polykondensationsprodukten als farbfixierender und/oder farbübertragungsinhibierender Zusatz zu Waschmitteln und Wäschenachbehandlungsmitteln
ITTO20050321A1 (it) * 2005-05-11 2006-11-12 Loro Piana & C S P A Ing Procedimento per ottenere un effetto invecchiato o scolorito su capi in fibre proteiche quali, cachemire e seta e prodotto relativo.
GB0523634D0 (en) * 2005-11-21 2005-12-28 Reckitt Benckiser Nv Solid cleaning formulations
ITRE20060011A1 (it) * 2006-02-01 2007-08-02 Tintoria Emiliana S R L Procedimento per tingere in modo non uniforme prodotti tessili
JP4709693B2 (ja) * 2006-06-07 2011-06-22 株式会社東芝 電子機器
US20110021402A1 (en) * 2009-07-27 2011-01-27 The Procter & Gamble Company Detergent Composition
BR112017026459B1 (pt) 2015-06-11 2022-05-10 Unilever Ip Holdings B.V. Composição de detergente para lavagem de roupas e método de tratamento doméstico de um tecido
EP3307861B1 (en) * 2015-06-11 2019-04-03 Unilever PLC, a company registered in England and Wales under company no. 41424 of Laundry detergent composition
EP3421583A1 (en) 2017-06-26 2019-01-02 Basf Se Use of cationic vinylcarboxamide/vinylamine copolymers as a color care agent for laundering formulations
BR112023003008A2 (pt) 2020-08-28 2023-04-04 Unilever Ip Holdings B V Tensoativo de sulfonato de alcano secundário (sas), composição detergente e método de tratamento de um artigo têxtil
WO2022062753A1 (en) * 2020-09-28 2022-03-31 The Procter & Gamble Company Laundry detergent composition containing dye fixative and amine-based surfactant

Family Cites Families (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL132418C (ja) 1962-04-13
US3128287A (en) 1963-01-31 1964-04-07 Pfizer & Co C 2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
US3213030A (en) 1963-03-18 1965-10-19 Procter & Gamble Cleansing and laundering compositions
CA777769A (en) 1963-03-18 1968-02-06 H. Roy Clarence Substituted methylene diphosphonic acid compounds and detergent compositions
US3332880A (en) 1965-01-04 1967-07-25 Procter & Gamble Detergent composition
GB1082179A (en) 1965-07-19 1967-09-06 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof
US3400148A (en) 1965-09-23 1968-09-03 Procter & Gamble Phosphonate compounds
CA790610A (en) 1965-12-28 1968-07-23 T. Quimby Oscar Diphosphonate compounds and detergent compositions
US3635830A (en) 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
US4166845A (en) * 1970-11-16 1979-09-04 Colgate-Palmolive Company Antidandruff shampoo compositions containing an aminopolyureylene resin
US4605509A (en) 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
US3985669A (en) 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US3936537A (en) 1974-11-01 1976-02-03 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
US4374035A (en) 1981-07-13 1983-02-15 The Procter & Gamble Company Accelerated release laundry bleach product
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
GB8304990D0 (en) 1983-02-23 1983-03-30 Procter & Gamble Detergent ingredients
US4671891A (en) 1983-09-16 1987-06-09 The Procter & Gamble Company Bleaching compositions
US4539130A (en) 1983-12-22 1985-09-03 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
DE3413292A1 (de) * 1984-04-09 1985-10-17 Henkel KGaA, 4000 Düsseldorf Textil-waschmittel fuer farbige textilien
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
GB8415909D0 (en) 1984-06-21 1984-07-25 Procter & Gamble Ltd Peracid compounds
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
GB8422158D0 (en) 1984-09-01 1984-10-03 Procter & Gamble Ltd Bleach compositions
US4566984A (en) 1984-11-16 1986-01-28 The Procter & Gamble Company Ether polycarboxylates
US4606838A (en) 1985-03-14 1986-08-19 The Procter & Gamble Company Bleaching compositions comprising alkoxy substituted aromatic peroxyacids
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US4686063A (en) 1986-09-12 1987-08-11 The Procter & Gamble Company Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents
DE3814208A1 (de) * 1988-04-27 1989-11-09 Sandoz Ag Verwendung von ungefaerbten und/oder gefaerbten substraten
DE3816126A1 (de) * 1988-05-11 1989-11-23 Hoechst Ag Modifizierte blockpolymerisate, ihre herstellung und verwendung
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
GB9013784D0 (en) 1990-06-20 1990-08-08 Unilever Plc Process and composition for treating fabrics
JPH04312502A (ja) * 1991-04-08 1992-11-04 Mitsubishi Gas Chem Co Inc 洗浄方法
EP0918836A1 (en) 1996-05-03 1999-06-02 The Procter & Gamble Company Liquid detergent compositions comprising specially selected modified polyamine polymers
EP0811679B1 (en) 1996-06-03 2003-05-21 The Procter & Gamble Company Fabric softening compositions
AU7162796A (en) 1996-09-19 1998-04-14 Procter & Gamble Company, The Color care compositions
DE19643281A1 (de) * 1996-10-21 1998-04-23 Basf Ag Verwendung von polykationischen Kondensationsprodukten als farbfixierenden Zusatz zu Waschmitteln und Wäschenachbehandlungsmitteln
EP0841391A1 (en) 1996-11-07 1998-05-13 The Procter & Gamble Company Perfume compositions
DE69711925D1 (de) 1996-12-06 2002-05-16 Innovations L L C Outdoor Spinnerköder, draht und kabel vorfach zum angeln
US6140292A (en) * 1996-12-31 2000-10-31 The Procter & Gamble Company Laundry detergent compositions with polyamide-polyamines
JP3981430B2 (ja) 1997-01-20 2007-09-26 株式会社Ａｄｅｋａ 純粋なアルカンスルホン酸の製造方法
US5827813A (en) 1997-02-28 1998-10-27 Procter & Gamble Company Detergent compositions having color care agents
EP0978556B1 (en) * 1998-08-03 2004-10-06 The Procter & Gamble Company Wrinkle resistant composition
EP0979861B1 (en) * 1998-08-03 2004-12-15 The Procter & Gamble Company Fabric care compositions
US6008316A (en) * 1998-09-03 1999-12-28 National Starch And Chemical Investment Holding Corporation Functionalized polyamines
US6228783B1 (en) * 1998-12-31 2001-05-08 National Starch And Chemical Investment Holding Corporation Laundry article which attracts soil and dyes
AR023155A1 (es) * 1999-03-25 2002-09-04 Procter & Gamble Composiciones para el mantenimiento de la tela que comprenden ciertos polimeros para el tratamiento de la tela, cargados cationicamente
AU6056200A (en) * 1999-06-29 2001-01-31 Procter & Gamble Company, The Fabric enhancement compositions having improved color fidelity
EP1254204A1 (en) * 2000-02-10 2002-11-06 The Procter & Gamble Company Laundry detergent compositions with a combination of a cyclic amine polymer and a dye transfer inhibitor
US6596678B2 (en) * 2000-05-09 2003-07-22 The Procter & Gamble Co. Laundry detergent compositions containing a polymer for fabric appearance improvement
GB2366304A (en) * 2000-09-01 2002-03-06 Unilever Plc Fabric care composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
PT1236793E (pt) 2008-02-12
US6858570B2 (en) 2005-02-22
DE50211176D1 (de) 2007-12-27
EP1236793A3 (de) 2003-09-03
JP2002338995A (ja) 2002-11-27
JP4315634B2 (ja) 2009-08-19
DE10150724A1 (de) 2003-04-17
ES2294053T3 (es) 2008-04-01
US20030171249A1 (en) 2003-09-11
EP1236793A2 (de) 2002-09-04
ATE378392T1 (de) 2007-11-15

Similar Documents

Publication Publication Date Title
EP1236793B1 (de) Waschmittel und Wäschebehandlungsmittel enthaltend ein oder mehrere farbübertragungsinhibierende Farbfixiermittel
EP1035194B1 (de) Verwendung von Kammpolymeren als Schmutzablösepolymere
EP0964015B1 (de) Schmutzablösevermögende Oligoester
DE102004018051A1 (de) Wasch- und Reinigungsmittel enthaltend Farbfixiermittel und Soil Release Polymere
EP2276824B1 (de) Additive für wasch- und reinigungsmittel
EP1966273B1 (de) Anionische soil release polymere
DE102007013217A1 (de) Anionische Soil Release Polymere
EP1239025A2 (de) Waschmittel und Wäschebehandlungsmittel enthaltend farbübertragungsinhibierend Farbfixiermittel
DE102007005532A1 (de) Wässrige Oligo- und Polyesterzubereitungen
EP3489338A1 (en) Detergent compositions containing renewably sourced soil release polyesters
DE19701896A1 (de) Granulares sekundäres Alkansulfonat
DE102005039580A1 (de) Farbschützendes Waschmittel
DE102004029310A1 (de) Hochkonzentrierte, wässrige Formulierungen von Oligo-und Polyestern
EP2732015B1 (de) Verwendung einer kombination von sekundärem paraffinsulfonat und amylase zur erhöhung des reinigungsvermögens von flüssigen waschmitteln
WO2007023087A1 (de) Flüssigwaschmittelformulierung
DE10150723A1 (de) Waschmittel und Wäschebehandlungsmittel enthaltend farbübertagungsinhibierende Farbfixiermittel
DE102007012581A1 (de) Flüssigwaschmittel mit Bleichwirkung
DE69532955T2 (de) Waschmittel
DE69413987T2 (de) Amidoferoxocarbonsäuren als bleichmittel
EP1050575B1 (de) Alkalische Wasch- und Reinigungsmittelzusammensetzung enthaltend Alkylbenzolsulfonate und Alkanolamine
CH678678B5 (ja)
DE102023205588A1 (de) Biotensidhaltige Tensidmischungen
DE3812455A1 (de) Bleichmittelersatz fuer waschmittel
DE19620094A1 (de) Einsatz von Schmutzlösepolymeren in Wasch- und Reinigungsmitteln

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: A2

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

AX Request for extension of the european patent

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 11D 3/37 A

AK Designated contracting states

Kind code of ref document: A3

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

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17P Request for examination filed

Effective date: 20040303

AKX Designation fees paid

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

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

17Q First examination report despatched

Effective date: 20060816

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WESSLING, MICHAEL, DR.

Inventor name: BERENBOLD, HELMUT, DR.

Inventor name: LANG, FRANK-PETER, DI.

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL PT TR

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 DE ES FR GB GR IT LI NL PT TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 50211176

Country of ref document: DE

Date of ref document: 20071227

Kind code of ref document: P

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20080130

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20080204

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20080400073

Country of ref document: GR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2294053

Country of ref document: ES

Kind code of ref document: T3

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

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed

Effective date: 20080815

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

Ref country code: PT

Payment date: 20081120

Year of fee payment: 8

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

Ref country code: AT

Payment date: 20081215

Year of fee payment: 8

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

Ref country code: GR

Payment date: 20081120

Year of fee payment: 8

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

Ref country code: TR

Payment date: 20090217

Year of fee payment: 8

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

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

Effective date: 20100823

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: 20100223

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 NON-PAYMENT OF DUE FEES

Effective date: 20100823

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

Ref country code: TR

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

Effective date: 20100223

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCOW

Free format text: NEW ADDRESS: PATENT MANAGEMENT INDUSTRIEPARK HOECHST / G 860, 65926 FRANKFURT AM MAIN (DE)

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

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

Ref country code: NL

Payment date: 20180223

Year of fee payment: 17

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

Ref country code: ES

Payment date: 20180322

Year of fee payment: 17

Ref country code: GB

Payment date: 20180227

Year of fee payment: 17

Ref country code: CH

Payment date: 20180223

Year of fee payment: 17

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

Ref country code: BE

Payment date: 20180223

Year of fee payment: 17

Ref country code: FR

Payment date: 20180227

Year of fee payment: 17

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

Ref country code: DE

Payment date: 20180430

Year of fee payment: 17

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

Ref country code: IT

Payment date: 20190221

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50211176

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20190301

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

Effective date: 20190223

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190228

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: 20190228

Ref country code: CH

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

Effective date: 20190228

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: 20190301

Ref country code: DE

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

Effective date: 20190903

Ref country code: GB

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

Effective date: 20190223

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 NON-PAYMENT OF DUE FEES

Effective date: 20190228

Ref country code: FR

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

Effective date: 20190228

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200331

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: 20190224

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: 20200223