EP1003826A1 - Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques - Google Patents

Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques

Info

Publication number
EP1003826A1
EP1003826A1 EP98942573A EP98942573A EP1003826A1 EP 1003826 A1 EP1003826 A1 EP 1003826A1 EP 98942573 A EP98942573 A EP 98942573A EP 98942573 A EP98942573 A EP 98942573A EP 1003826 A1 EP1003826 A1 EP 1003826A1
Authority
EP
European Patent Office
Prior art keywords
groups
weight
detergent formulation
alkyl
textile detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98942573A
Other languages
German (de)
English (en)
Other versions
EP1003826B1 (fr
Inventor
Jürgen Detering
Richard Baur
Werner Bertleff
Rainer Rahm
Günter OETTER
Beate Ehle
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.)
BASF SE
Original Assignee
BASF SE
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
Priority claimed from DE1997132689 external-priority patent/DE19732689A1/de
Priority claimed from DE1998107105 external-priority patent/DE19807105A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1003826A1 publication Critical patent/EP1003826A1/fr
Application granted granted Critical
Publication of EP1003826B1 publication Critical patent/EP1003826B1/fr
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
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Solid textile detergent formulation based on glycine-N, N-diacetic acid derivatives with a greatly reduced proportion of other anionic surfactants
  • the present invention relates to a solid textile detergent formulation from inorganic builders, glycine-N, N-diacetic acid derivatives, optionally small amounts of further anionic surfactants, nonionic surfactants and optionally other conventional constituents.
  • surfactants represent the most important group of detergent ingredients. Their proportion in conventional phosphate-reduced or phosphate-free powder detergents is usually 10 to 25% by weight. Surfactants detach liquid (oily) and solid fiber stains during the washing process. However, the washing effect of the anionic surfactants in particular decreases with increasing water hardness. That is why builders such as zeolites are used, whose primary task is to increase the washing performance of the anionic surfactants by binding the calcium and magnesium ions responsible for the water hardness.
  • a number of solid soils contain alkaline earth metal ions, especially calcium ions.
  • the removal of calcium ions leads to a loosening of the dirt structure and thus to an easier removal of dirt from the fiber.
  • surfactants need the support of water-soluble complexing agents for calcium.
  • the object was to provide a solid textile detergent formulation in which the proportion of conventional anionic surfactants is drastically reduced and which contains a detergent (surface-active) substance which can bind calcium and magnesium ions.
  • Glycine-N, N-diacetic acid derivatives are such surface-active substances. They reduce the surface tension of the wash water and have a dirt-removing effect. They complex Ca and Mg ions, remove calcium soiling particularly well and additionally support the inorganic builders in their task of softening the wash water and preventing the build-up of tissue incrustation.
  • the use of the glycine-N, N-diacetic acid derivatives mentioned in solid textile detergent formulations is already known from WO-A 97/19159.
  • solid textile detergent formulations which, as organic co-builders, contain up to 40% by weight of such glycine-N, N-diacetic acid derivatives; these textile detergent formulations furthermore contain customary amounts of customary anionic surfactants, ie about 10% by weight or more.
  • Ci to C 4 alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or Ci to C 4 alkoxycarbonyl groups can carry, or a radical of the formula
  • M denotes hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts
  • Suitable inorganic builders (A) are, above all, crystalline or " amorphous aluminosilicates with ion-exchanging properties such as, in particular, zeolites.
  • zeolites Various types are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms, in which Na partly against others
  • Cations such as Li, K, Ca, Mg or ammonium are exchanged.
  • Suitable zeolites are described, for example, in EP-A 038591, EP-A 021491, EP-A 087035, US-A 4604224, GB-A 2013259, EP-A 522726, EP-A 384070 and WO-A 94/24251.
  • Suitable crystalline silicates are, for example, disilicates or layered silicates, e.g. B. ⁇ - aSi 2 0 5 or ß-Na Si 2 0 5 (SKS 6 or SKS 7, manufacturer: Hoechst).
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.
  • Amorphous silicates such as sodium etasilicate, which has a polymeric structure, or amorphous disilicate (Britsil® H 20 manufacturer: Akzo) can also be used.
  • Suitable inorganic builder substances (A) based on carbonate are carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.
  • phosphates as inorganic builders are polyphosphates such as. B. pentasodium triphosphate.
  • the components (A) mentioned can be used individually or in mixtures with one another.
  • Component (A) is preferably present in the textile detergent formulation according to the invention in an amount of 5 to 50% by weight, isnesodnere 10 to 45% by weight.
  • those compounds I are used as component (B) in which R represents a radical having at least 7 C atoms.
  • N-diacetic acid derivatives I are used in which R is straight-chain or branched unsubstituted C - to C 3 o-alkyl or C 7 - to C 30 -alkenyl -Residues that can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms; said nitrogen atoms can carry hydrogen or Ci * to Cs alkyl groups.
  • the compounds I are substituted in the form of the free acids or their alkali metal, alkaline earth metal, ammonium and
  • Ammonium salts used are the sodium, potassium and ammonium salts, in particular the trisodium, tripotassium and triammonium salt, and also organic triamine salts with a tertiary nitrogen atom.
  • the bases on which the organic amine salts are based are, in particular, tertiary amines such as trialkylamines having 1 to 6 carbon atoms in the alkyl, for example triethylamine and triethylamine, methyldiethylamine or tricyclohexylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine, tri n-propanolamine or triisopropanolamine.
  • the calcium and magnesium salts are used as alkaline earth metal salts.
  • radical R straight-chain or branched alk (en) yl radicals C 5 - to C 3 o-alkyl and alkenyl, in particular straight-chain radicals derived from saturated or unsaturated fatty acids, are suitable.
  • individual radicals R are: n-pentyl, isopentyl, tert.
  • the C 5 - to -C 2 alkylene bridges A are mainly polymethylene groupings of the formula - (CH 2 ) t - > where t denotes a number from 5 to 12, in particular from 5 to 8, ie petethylene, hexa- methylene, heptarethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. Hexamethylene and octa-methylene are particularly preferred.
  • branched C 5 - to -C 2 alkylene groups can also occur, for. B.
  • the C 5 - to C 3 o-alkyl and alkenyl groups can have up to 5, in particular up to 3, additional substituents of the type mentioned and can be interrupted by up to 5, in particular up to 3, non-adjacent oxygen atoms and / or nitrogen atoms.
  • Examples of such substituted alk (en) yl groups are -CH 2 CH 2 -0-CH 2 CH 2 -0-CH 3 , -CH 2 -0- (CH 2 ) 4 -OH, -CH 2 CH 2 -N ( CH 3 ) CH 2 CH 2 CH 3 -, - (CH 2 ) 5 -N (CH 3 ) 2 or - (CH 2 ) 5 -COOCH 3 .
  • alkoxylate groups are those in which m and n each represent numbers from 0 to 30, especially from 0 to 15. The sum of m + n is preferably at least 6, in particular at least 8.
  • a 1 and A 2 groups derived from butylene oxide and especially from propylene oxide and from ethylene oxide. Pure ethoxylates and pure propoxylates are of particular interest, but ethylene oxide-propylene oxide block structures can also occur.
  • phenylalkyl groups are 5-phenylpentyl, 6-phenylhexyl, 8-phenyloctyl, 10-phenyldecyl or 12-phenyldodecy1.
  • water-solubilizing groups such as hydroxyl groups, carboxyl groups or sulfo groups preferably occur.
  • Component (B) is preferably present in the textile detergent formulation according to the invention in an amount of 2 to 30% by weight, in particular 3 to 20% by weight.
  • Anionic surfactants (C) are in principle all anionic surfactants which are structurally different from the compounds I.
  • the weight ratio of (B) glycine-N, N-diacetic acid derivatives I to the anionic surfactants (C) in the solid textile detergent formulation according to the invention is 50: 1 to 1: 2, preferably 20: 1 up to 1: 1 In this ratio range, the detergent formulation according to the invention is particularly effective.
  • the solid textile detergent formulation according to the invention contains two or more glycine-N, N-diacetic acid derivatives of the general formula I.
  • the present mixture of the glycine-N, N-diacetic acid derivatives I consists in particular of two or three or four or five components or major components.
  • Such mixtures are particularly effective in the solid textile detergent formulation according to the invention if they consist of glycine-N, N-diacetic acid derivatives I in which the radicals R consist of branched and / or linear Ci to C 3 o -alkyl groups, especially branched and / or linear Ci to Cis alkyl groups are selected.
  • the glycine-N, N-diacetic acid derivatives I can be incorporated individually or immediately into the textile detergent formulation as a ready-made mixture.
  • Such a last-mentioned mixture of glycine-N, N-diacetic acid derivatives I can be prepared by mixing the individual components, however, it can also be obtained directly in the synthesis of the compounds I. Examples of this are the products of hydroformylation of ⁇ -olefin mixtures (oxosynthesis) with subsequent conversion of this mixture of linear and branched aldehydes of different C chain lengths to the corresponding glycine-N, N-diacetic acid derivatives.
  • mixtures of glycine-N, N-diacetic acid derivatives described are particularly effective not only in the solid detergent formulation according to the invention, but generally in solid detergent formulations, for example in a formulation which is 1 to 60 % By weight (preferably 10 to 45% by weight) of inorganic builders based on crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, carbonates and / or phosphates, 0.1 to
  • Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols with 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C 9 - to Cn alcohol sulfates, C ⁇ 2 - to C 14 alcohol sulfates, C 12 -Ci 8 alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated CQ to C 22 alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by first using a C - to C 2 -, preferably a C ⁇ 0 - to Ci ⁇ -alcohol z.
  • B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated.
  • Ethylene oxide is preferably used for the alkoxylation, 1 to 50, preferably 1 to 20, mol of ethylene oxide being used per mol of alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • alkoxylated Cs to C 22 alcohols which are ethylene oxide and propylene oxide or ethylene oxide and Contain butylene oxide or ethylene oxide and propylene oxide and butylene oxide.
  • the alkoxylated Cs to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in a statistical distribution.
  • alkyl ether sulfate with a broad or narrow alkylene oxide homolog distribution can be obtained.
  • alkanesulfonates such as Cs to C 24 , preferably C 10 to Ciskansulfonate and soaps such as the Na and K salts of Cs to C 24 carboxylic acids.
  • anionic surfactants are linear Cs to C 0 "alkylbenzenesulfonates ("LAS "), preferably linear Cg to C 13 alkylbenzenesulfonates and alkyltoluenesulfonates.
  • anionic surfactants Cs to C 24 -01efinsulfonate and -disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids Alkylgly- cerinsulfonate, fatty acid glycerol, Alkylphenolpo- lyglykolethersulfate , Paraffin sulfonates with approx. 20 to approx.
  • alkyl phosphates based on paraffin or paraffin mixtures obtained from natural sources
  • alkyl phosphates based on paraffin or paraffin mixtures obtained from natural sources
  • alkyl phosphates based on paraffin or paraffin mixtures obtained from natural sources
  • acyl isethionates acyl taurates
  • acyl methyl taurates alkyl succinic acids
  • alkenyl succinic acids or their half esters or half amides alkyl sulfosuccinic acids or their amides
  • mono- and diesters of sulfosuccinic acids acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.
  • the anionic surfactants are preferably added to the detergent in the form of salts.
  • Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as e.g. B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Component (C) is preferably present in the textile detergent formulation according to the invention in an amount of 0 to 4% by weight, in particular 0.1 to 4% by weight. Examples of frequently used amounts are 0 to 0.3% by weight .%, 0.5% by weight, 1.5% by weight, 2% by weight, 2.5% by weight and 3.5 to 4.5% by weight.
  • anionic surfactants or a combination of different anionic surfactants can be used.
  • Anionic surfactants from only one class can be used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but one can also use surfactant mixtures from different classes, for example a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
  • the solid textile detergent formulation according to the invention contains a greatly reduced proportion of silicate builders, namely:
  • inorganic builders based on crystalline or amorphous aluminosilicates and / or crystalline or amorphous silicates and
  • inorganic builders based on phosphate 0 to 5% by weight, preferably 0.05 to 2% by weight, inorganic builders based on phosphate.
  • Suitable nonionic surfactants (D) are, for example, alkoxylated C ⁇ "to C 22 alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide.
  • alkoxylated alcohols containing at least two molecules can be used as surfactants block polymers of ethylene oxide, propylene oxide and / or butylene oxide or adducts which contain the alkylene oxides mentioned in a statistical distribution are used, 2 to 50, preferably 3 to 20, mol at least being used per mol of alcohol
  • An alkylene oxide is preferably used as the alkylene oxide, and the alcohols preferably have 10 to 18 carbon atoms, depending on the type of alkoxylation catalyst, alkoxylates with a broad or narrow alkylene oxide homolog distribution can be obtained.
  • nonionic surfactants are alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 to C 4 alkyl chains and 5 to 30 moles of alkylene oxide units.
  • alkyl polyglucosides having from 8 to 22, preferably 10 to 18 carbon atoms in the A Tomen lkylkette. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • N-alkyl glucamides of the general structures
  • Bi is a C 6 to C 22 alkyl
  • B 2 is hydrogen or C 1 to C 4 alkyl
  • D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups.
  • B 1 is Cio to Cis alkyl
  • B 2 is CH
  • D is a C 5 or C 6 radical.
  • such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C I Q to cis carboxylic acids.
  • nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225
  • R 1 denotes a C 5 -C 2 -alkyl or alkenyl radical
  • R 2 denotes a C 1 -C 4 -alkyl group
  • a 1 represents C 4 -C 4 -alkylene
  • y denotes the number 2 or 3 and x has a value from 1 to 6.
  • Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -0) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyl tetraglycol-a in the formula H 2 N- (CH 2 -CH 2 -0) 4 -C 2 H 5 with a commercially available mixture of saturated Cs to Cis fatty acid methyl esters.
  • nonionic surfactants are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, Fatty acid- amide ethoxylates, especially end group-capped, and fatty acid alkanolamide alkoxylates.
  • Pluronic® and Tetronic® brands from BASF
  • polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, Fatty acid- amide ethoxylates, especially end group-capped, and fatty acid alkanolamide alkoxylates.
  • Component (D) is preferably present in the textile detergent formulation according to the invention in an amount of 1 to 40% by weight, in particular 3 to 30% by weight, especially 5 to 25% by weight.
  • nonionic surfactants or a combination of different nonionic surfactants can be used. It may be nonionic surfactants from only one class be employed, in particular only alkoxylated Cs to C lkohole 22 _A, but you can also blends surfactant mixtures from different classes.
  • the textile detergent formulation according to the invention contains, in addition to the inorganic builders (A), 0.05 to 20% by weight, in particular 1 to 10% by weight, of organic cobuilders (E) in the form of low molecular weight, oligomeric or polymeric carboxylic acids, especially polycarboxylic acids, or phosphonic acids or their salts, especially Na or K salts.
  • organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids, especially polycarboxylic acids, or phosphonic acids or their salts, especially Na or K salts.
  • Suitable low molecular weight carboxylic acids or phosphonic acids for (E) are for example:
  • Phosphonic acids such as 1-hydroxyethane-l, 1-diphosphonic acid, aminotris (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid);
  • C 4 - to C 2 Q-di-, tri- and tetracarboxylic acids such as.
  • hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
  • Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, ß-alanine-diacetic acid, ethylenediaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid, alkylethylenediamine triacetates, N, N- bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and methyldiacetic acid.
  • Suitable oligomeric or polymeric carboxylic acids for (E) are, for example:
  • Suitable unsaturated C 4 -Cs dicarboxylic acids are maleic acid, fu aric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated C 3 -Cs monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
  • Group (ii) includes monoethylenically unsaturated
  • C 2 -C 22 -01efins vinyl alkyl ethers with Ci-Cs-alkyl groups, styrene, vinyl esters of Ci-C ⁇ "carboxylic acids, (meth) acrylamide and vinylpyrrolidone.
  • Group (iii) includes (meth) acrylic esters of Ci- to Cs-alcohols, (meth) acrylonitrile, (meth) acrylamides of Ci-Cs-amines, N-vinylformamide and N-vinylimidazole.
  • polymers of group (ii) contain vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to form vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are known for example from US-A 3887806 and DE-A 4313909.
  • Suitable copolymers of dicarboxylic acids for component (E) are preferably: Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150,000;
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates are also suitable as component (E).
  • Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted,
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose,
  • a ls component (E) suitable polyglyoxylic acids are described for example in EP-B 001004, US-A 5,399,286, DE-A 4106355 and EP-A 656,914th
  • the end groups of the polyglyoxylic acids may have various structures.
  • Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as component (E) are known, for example, from EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.
  • Component (E) in particular also uses polyaspartic acids or cocondensates of aspartic acid with other amino acids, C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines.
  • polyaspartic acids or cocondensates of aspartic acid with other amino acids C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines.
  • phosphorus-containing acids prepared with C 6 -C 22 - used ONO or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • component (E) is iminosuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acid such as e.g. Agaricic acid, poly- ⁇ -hydroxyacrylic acid, N-acylethylene diamine triacetates such as lauroyl ethylene diamine triacetate and alkylamides of ethylene diamine tetraacetic acid such as EDTA tallow amide.
  • citric acid such as e.g. Agaricic acid, poly- ⁇ -hydroxyacrylic acid
  • N-acylethylene diamine triacetates such as lauroyl ethylene diamine triacetate
  • alkylamides of ethylene diamine tetraacetic acid such as EDTA tallow amide.
  • Oxidized starches can also be used as organic cobuilders.
  • the textile detergent formulation according to the invention additionally contains 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight, of bleaching agent (F) in the form of percarboxylic acids, for .
  • bleaching agent (F) in the form of percarboxylic acids, for .
  • bleach activators (G) are:
  • polyacylated sugars e.g. B. Pentaacetylglucose
  • N, N-diacylated and N, N, N ', N' - tetraacylated amines e.g. B. N, N, N ', N' -Tetraacetylmethylenediamine and -ethylenediamine
  • TESS N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
  • N-alkyl-N-sulfonylcarbonamides e.g. B. N-methyl-N-mesylacetamide or N-methyl -N-mesylbenzamide;
  • N-acylated cyclic hydrazides acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
  • N-trisubstituted hydroxylamines e.g. 0-benzoyl-N, N-sucinylhydroxylamine, 0-acetyl-N, N-succinylhydroxylamine or 0, N, N-triacetylhydroxylamine;
  • N N '-diacylsulfurylamides, e.g. B. N, N '-dimethyl-N, N' -diacetyl-sulfurylamide or N, N '-diethyl-N, N' -dipropionylsulfuryla id;
  • acylated lactams such as, for example, acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam;
  • Anthranil derivatives such as 2-methylanthranil or 2-phenyl-anthranil
  • Triacylcyanurates e.g. Triacetylcyanurate or tribenzoylcyanurate
  • Oxime esters and bisoxime esters such as O-acetylacetone oxime or bisisopropyliminocarbonate;
  • Carboxylic anhydrides e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
  • enol esters such as isopropenyl acetate; 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl -4,5-diacetoxyimidazoline;
  • diacylated 2,5-diketopiperazines e.g. 1,4-diacetyl-2,5-dike-topiperazine;
  • ammonium substituted nitriles such as N-methylmorpholinium acetonitrile methyl sulfate;
  • Diacyl-dioxohexahydro-1, 3, 5-triazines e.g. B. 1,5 -diacetyl -2, 4 -dioxohexahydro- 1, 3, 5-triazine;
  • alkyl radicals e.g. B. methyl
  • aromatic radicals such. B. phenyl
  • the described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts.
  • Suitable bleaching catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat. Nos. 5,360,569 and EP-A 453,003.
  • Particularly effective bleaching catalysts are manganese complexes, which are described, for example, in WO-A 94/21777. When used in the detergent formulations, such compounds are used in amounts of up to 1.5% by weight, in particular up to 0.5% by weight, in the case of very active manganese complexes in amounts of up to 0.1% by weight. -%, incorporated.
  • bleaching system consisting of bleaching agents, bleach activators and optionally bleaching catalysts
  • bleaching catalysts it is also possible to use systems with enzymatic peroxide release or photoactivated bleaching systems for the textile detergent formulation according to the invention.
  • the textile detergent formulation according to the invention additionally contains 0.05 to 4% by weight of enzymes (H).
  • Enzymes that are preferably used in detergents are proteases, amylases, lipases and cellulases. Quantities of 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.0% by weight, of the enzymes are preferably packaged Enzyme added.
  • Suitable proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk).
  • a suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk).
  • a suitable cellulase is e.g. B. Celluzym (manufacturer: Novo Nordisk).
  • the V SE OF peroxidases to activate the bleach system is possible. You can use single enzymes or a combination of different enzymes.
  • the textile detergent formulation according to the invention can also contain enzyme stabilizers, e.g. B. calcium propionate, sodium formate or boric acids or their salts, and / or antioxidants.
  • the textile detergent formulation according to the invention can also contain the following further customary additives in the amounts customary for this:
  • cationic surfactants usually in an amount of up to 25% by weight, preferably 3 to 15% by weight, for example Cs to C 6 -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with long-chain alkyl radical;
  • Amphoteric surfactants usually in an amount of up to 15% by weight, preferably 2 to 10% by weight, for example derivatives of secondary or tertiary amines such as, for example, C 2 -C -alkyl betaine or C 2 -C alkylsulfobetaines or amine oxides, Alkyldimethylamine oxides;
  • Graying inhibitors and soil release polymers are, for example, polyesters made of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic
  • polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020.
  • Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299,
  • Graying inhibitors and soil release polymers are in the detergent formulations to 0.1 to 2.5 wt .-%, preferably 0.2 to 1.5 wt .-%, particularly preferably 0.3 to 1.2 % By weight included.
  • Soil release polymers used with preference are those of the US-A-4,746,456 known graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates of molecular weight 3000 to 25000 made of polyethylene oxides Molar mass 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-44 03 866, the blocks of (a) ester units from polyalkylene glycols a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols.
  • These amphiphilic block copolymers have mo
  • Color transfer inhibitors for example homopolymers and copolymers of N-vinylpyrrolidone, N-vinylimidazole, N-vinyloxazolidone or 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000, and crosslinked, finely divided polymers based on these monomers with a Particle size of 0.1 to 500, preferably 0.1 to 250 microns;
  • non-surfactant-like foam dampers or foam inhibitors for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica;
  • inorganic adjusting agents e.g. B. sodium sulfate
  • the textile detergent formulation according to the invention is solid, i. H. is usually in powder or granule form or in extrudate or tablet form.
  • the powdered or granular detergents according to the invention can contain up to 60% by weight of inorganic fillers. Sodium sulfate is usually used for this.
  • the detergents according to the invention are preferably low in detergents and contain only up to 20% by weight, particularly preferably only up to 8% by weight, of detergents, especially in the case of compact or ultra-compact detergents.
  • the solid detergents according to the invention can have different bulk densities in the range from 300 to 1300 g / 1, in particular from 550 to 1200 g / 1. Modern compact detergents generally have high bulk densities and show a granular structure. The processes customary in the art can be used for the desired compression of the detergents.
  • the textile detergent formulation according to the invention is produced by customary methods and, if appropriate, made up.
  • compositions for compact full detergents and color detergents are given below (the percentages relate to the weight; the details in brackets for compositions (a) and (b) are preferred ranges):
  • TAED tetraacetylethylenediamine
  • the washed test fabrics were measured with a photometer from Datacolor (Elrepho® 2000). The total remission values of all four tissue types are given in percent. The higher the reflectance value, the better the primary washing power.
  • the AGDA's bind Ca and Mg ions and thus have an incrustation-inhibiting effect. Because of this ability, it is also possible to significantly reduce the proportion of inorganic silicate builders (eg zeolites, layered silicates, amorphous disilicates) by using AGDAs without any loss of performance.
  • inorganic silicate builders eg zeolites, layered silicates, amorphous disilicates
  • Table 4 shows an example of compositions [in%] of modern compact detergent formulations A to S according to the invention
  • Incrustation inhibitor acrylic acid / maleic acid copolymer soil-release additive 1: polyethylene terephthalate / polyoxyethylene terephthalate in a molar ratio of 3: 2;

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)

Abstract

L'invention concerne une formulation détergente solide pour textiles, contenant (A) 1 à 60 % en poids d'adjuvants organiques à base de silicates d'aluminium cristallins ou amorphes, de silicates cristallins ou amorphes, de carbonates et/ou de phosphates, (B) 1 à 40 % en poids d'un ou de plusieurs dérivés d'acide N,N-diacétique de glycine de formule (I), dans laquelle R désigne un reste organique et M désigne hydrogène et un cation, (C) 0 à 6 % en poids de tensioactifs anioniques avec 1 ou plusieurs groupes sulfate, un ou plusieurs groupes sulfonate, un ou plusieurs groupes phosphate ou bien un ou deux groupes carboxylate et (D) 0,5 à 50 % en poids de tensioactifs non ioniques.
EP98942573A 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques Expired - Lifetime EP1003826B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1997132689 DE19732689A1 (de) 1997-07-30 1997-07-30 Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
DE19732689 1997-07-30
DE19807105 1998-02-20
DE1998107105 DE19807105A1 (de) 1998-02-20 1998-02-20 Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
PCT/EP1998/004486 WO1999006513A1 (fr) 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques

Publications (2)

Publication Number Publication Date
EP1003826A1 true EP1003826A1 (fr) 2000-05-31
EP1003826B1 EP1003826B1 (fr) 2004-02-25

Family

ID=26038665

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98942573A Expired - Lifetime EP1003826B1 (fr) 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques

Country Status (5)

Country Link
US (1) US6225278B1 (fr)
EP (1) EP1003826B1 (fr)
JP (1) JP2001512174A (fr)
DE (1) DE59810854D1 (fr)
WO (1) WO1999006513A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2383329A1 (fr) * 2010-04-23 2011-11-02 The Procter & Gamble Company Particule
EP2380962B1 (fr) 2010-04-23 2016-03-30 The Procter and Gamble Company Particule
ES2682051T3 (es) 2010-04-23 2018-09-18 The Procter & Gamble Company Composición detergente
JP6063748B2 (ja) * 2012-07-27 2017-01-18 花王株式会社 固体洗浄剤
US9828571B2 (en) 2015-06-05 2017-11-28 Illinois Tool Works, Inc. Heavy duty laundry detergent
US10266745B2 (en) 2017-02-03 2019-04-23 Saudi Arabian Oil Company Anti-bit balling drilling fluids, and methods of making and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4319935A1 (de) * 1993-06-16 1994-12-22 Basf Ag Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen
DE19518987A1 (de) * 1995-05-29 1996-12-05 Basf Ag Verfahren zur Herstellung von Glycin-N,N-diessigsäure-Derivaten durch Umsetzung von Glycinderivaten oder deren Vorstufen mit Formaldehyd und Alkalimetallcyanid in wäßrig-alkalischem Medium
DE19543162A1 (de) * 1995-11-18 1997-05-22 Basf Ag Feste Textilwaschmittel-Formulierung aus anorganischen Buildern, Glycin-N,N-diessigsäure-Derivaten als organische Cobuilder sowie anionischen und nichtionischen Tensiden
JP3810847B2 (ja) * 1996-01-22 2006-08-16 花王株式会社 高密度粉末洗剤組成物
JP3810854B2 (ja) * 1996-01-22 2006-08-16 花王株式会社 高密度粉末洗剤組成物
WO1997048773A1 (fr) * 1996-06-19 1997-12-24 Unilever N.V. Composition de traitement des sols
US5968884A (en) * 1997-04-07 1999-10-19 Basf Corporation Concentrated built liquid detergents containing a biodegradable chelant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9906513A1 *

Also Published As

Publication number Publication date
DE59810854D1 (de) 2004-04-01
US6225278B1 (en) 2001-05-01
EP1003826B1 (fr) 2004-02-25
WO1999006513A1 (fr) 1999-02-11
JP2001512174A (ja) 2001-08-21

Similar Documents

Publication Publication Date Title
EP1002046B1 (fr) Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine
EP0863976B1 (fr) Derives glycine-n,n-acide diacetique utilises comme co-adjuvants organiques dans des formulations d'agents de lavage de textiles
EP0934385B1 (fr) Utilisation dans des detergents et des nettoyants, de composes contenant de l'azote, reticules, solubles ou dispersibles dans l'eau
EP0826025B1 (fr) Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques
EP0941299B1 (fr) Formulation de produit de lavage pour textiles a base de glycine-nitriles quaternises, d'agents blanchissants, de tensioactifs non ioniques et/ou anioniques et de composes sequestrant les ions calcium et/ou magnesium
EP0891411B1 (fr) Renfor ateur du pouvoir lavant de detergents
EP1599435B1 (fr) Produits issus de la reaction de 2-propylheptanol, de 1-halogene-2,3-epoxypropanes et de 1-hydroxy-2,3-epoxypropane
EP1003826B1 (fr) Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine a teneur fortement reduite en autres tensioactifs anioniques
EP0964912B1 (fr) Formulations detergentes et nettoyantes comprenant un systeme de blanchiment et un melange d'amines et d'agents complexants
DE19650537A1 (de) Verwendung von endgruppenverschlossenen Fettsäureamidalkoxylaten in Wasch- und Reinigungsmitteln
DE19732689A1 (de) Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
DE10218752A1 (de) Alkoxylatgemische und diese enthaltende Waschmittel
DE19807105A1 (de) Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
WO2000001661A2 (fr) Derives de glycine-acide n,n-carboxylique a chaine laterale contenant des groupes carbonyle, leur preparation et leur utilisation dans des detergents et des nettoyants
DE19807104A1 (de) Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten als Buildern mit stark reduziertem Anteil an Silicat-Buildern
DE19732688A1 (de) Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten als Buildern mit stark reduziertem Anteil an Silicat-Buildern
WO1998022431A1 (fr) Hydroxyamides d'acides gras et leur utilisation comme substances a activite de surface, comme agents tensioactifs non ioniques ou comme emulsifiants
DE19650151A1 (de) Alkoxylierte Amide und ihre Verwendung in Wasch-, Reinigungs- und Körperpflegemitteln
DE19624701A1 (de) Phosphatfreie Waschmittel, enthaltend Hydroxyalkyl- und/oder Hydroxyalkenyl(oxy)aminocarbonsäurederivate als anionische Tenside

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: 19991221

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 20021223

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): DE FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59810854

Country of ref document: DE

Date of ref document: 20040401

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20040708

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20040714

Year of fee payment: 7

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

Ref country code: DE

Payment date: 20040729

Year of fee payment: 7

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: 20041126

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: 20050720

Ref country code: GB

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

Effective date: 20050720

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 THE APPLICANT RENOUNCES

Effective date: 20050813

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

Effective date: 20050720

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: 20060331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060331