EP1002046B1 - Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine - Google Patents

Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine Download PDF

Info

Publication number
EP1002046B1
EP1002046B1 EP98941364A EP98941364A EP1002046B1 EP 1002046 B1 EP1002046 B1 EP 1002046B1 EP 98941364 A EP98941364 A EP 98941364A EP 98941364 A EP98941364 A EP 98941364A EP 1002046 B1 EP1002046 B1 EP 1002046B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent formulation
alkyl
textile detergent
acid
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
EP98941364A
Other languages
German (de)
English (en)
Other versions
EP1002046A1 (fr
Inventor
Jürgen Detering
Richard Baur
Werner Bertleff
Rainer Rahm
Günter OETTER
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 DE1997132688 external-priority patent/DE19732688A1/de
Priority claimed from DE1998107104 external-priority patent/DE19807104A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1002046A1 publication Critical patent/EP1002046A1/fr
Application granted granted Critical
Publication of EP1002046B1 publication Critical patent/EP1002046B1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • 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
    • C11D3/04—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
    • 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

Definitions

  • the present invention relates to a solid textile detergent formulation from inorganic builders based on carbonate, where there is still a small proportion of silicate and phosphate builders can, glycine-N, N-diacetic acid derivatives as organic Builder components as well as surfactants and optionally other usual components.
  • Inorganic silicon-containing builders such as aluminosilicates (Zeolites) or silicates are essential components conventional phosphate-reduced or phosphate-free powder detergent. Their proportion is usually 10 to 45% by weight. Your primary job in the washing process is to reduce it the water hardness, which improves the washing performance of the anionic surfactants increases and at the same time the extent of tissue deposits (incrustations), consisting of insoluble calcium or magnesium salts, is reduced.
  • tissue deposits consisting of insoluble calcium or magnesium salts
  • Water-soluble inorganic silicate builders e.g. amorphous disilicate
  • zeolites zeolites
  • calcium and magnesium ions as poorly soluble silicates.
  • tissue incrustation given by silicates.
  • the insoluble bear Builder not insignificant to the sludge in the sewage treatment plant at.
  • the task was to create a solid laundry detergent formulation to provide in the proportion of inorganic builders Base of aluminosilicate and / or silicate is greatly reduced.
  • biodegradable glycine-N, N-diacetic acid derivatives allows the proportion of such inorganic Strongly reduce builders while maintaining washability to increase. Especially the build-up of tissue incrustations advantageously inhibited.
  • the total share increases biodegradable components in the detergent formulation as well as the total solubility of the detergent. Farther enables the amount of inorganic builders to be reduced Manufacture of particularly highly concentrated compact solid Detergent formulations with a significantly reduced volume.
  • Suitable inorganic builder substances (A) based on carbonate are carbonates and bicarbonates. These can take the form of their Alkali metal, alkaline earth metal or ammonium salts used become. Na, Li and Mg carbonates or - Hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, used.
  • Suitable inorganic builders (B) are primarily crystalline ones or amorphous aluminosilicates with ion-exchanging properties like especially zeolites.
  • Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially 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. ⁇ -Na 2 Si 2 O 5 or ⁇ -Na 2 Si 2 O 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 metasilicate, which has a polymeric structure, or amorphous disilicate (Britesil® H 20, manufacturer Akzo) can also be used.
  • Common phosphates as inorganic builders (C) are polyphosphates such as B. pentasodium triphosphate.
  • Component (A) lies in the textile detergent formulation according to the invention in an amount of 5 to 27 wt .-%, in particular 10 to 25% by weight.
  • Component (B) is preferably used in amounts of 0 to 10 wt .-%, in particular 0 to 8 wt .-%, used. Good results is achieved with amounts of 1.5 to 8% by weight, in particular 2 up to 6% by weight of component (B) in the detergent formulation. However, even in the absence or very small amounts of the component (B), i.e. a content of 0 to 0.5% by weight in the detergent formulation, you get the desired benefits and effects in the sense of the present invention.
  • Component (C) which is responsible for the effect of the invention Detergent formulation is less important, is preferably in amounts of 0.05 to 2% by weight, in particular 0.1 to 1 wt .-%, before or can be omitted entirely.
  • Such compounds I are used for component (D) in which R stands for a radical with at least 5 carbon atoms.
  • N-diacetic acid derivatives I are used in which R for straight-chain or branched unsubstituted C 5 to C 20 alkyl or C 5 to C 20 alkenyl Radicals that can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms; said nitrogen atoms can carry hydrogen or C 1 - to C 8 -alkyl groups.
  • the compounds I are in the form of the free acids or their Alkali metal, alkaline earth metal, ammonium and substituted Ammonium salts used.
  • Such salts are particularly suitable the sodium, potassium and ammonium salts, especially that Trisodium, tripotassium and triammonium salt and organic Triamine salts with a tertiary nitrogen atom.
  • the bases on which the organic amine salts are based come tertiary amines such as trialkylamines with 1 to 6 carbon atoms in alkyl, e.g. Trimethyl and triethylamine, methyldiethylamine or tricyclohexylamine, and trialkanolamines with 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine, tri-n-propanolamine or Triisopropanolamine.
  • trialkylamines with 1 to 6 carbon atoms in alkyl e.g. Trimethyl and triethylamine, methyldiethylamine or tricyclohexylamine
  • trialkanolamines with 2 or 3 carbon atoms in the alkanol radical preferably triethanolamine, tri-n-propanolamine or Triisopropanolamine.
  • the alkaline earth metal salts are, in particular, the calcium and Magnesium salts used.
  • straight-chain or branched alk (en) yl radicals are C 5 to C 30 alkyl and C 5 to C 30 alkenyl, in particular straight-chain radicals derived from saturated or unsaturated fatty acids.
  • individual radicals R are: n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, 3-heptyl (derived from 2-ethylhexanoic acid), n-octyl, iso-octyl (derived of iso-nonanoic acid), n-nonyl, n-decyl, n-undecyl, n-dodecyl, iso-dodecyl (derived from iso-tridecanoic acid), n-tridecyl, n-tetradecyl, n-pentadecyl, n
  • the C 1 - to C 12 -alkylene bridges A are primarily polymethylene groups of the formula - (CH 2 ) t -, in which t denotes a number from 2 to 12, in particular from 2 to 8, ie 1,2-ethylene, 1 , 3-propylene, 1,4-butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. Hexamethylene, octamethylene, 1,2-ethylene and 1,4-butylene are particularly preferred here.
  • branched C 1 - to C 12 -alkylene groups can also occur, for. B. -CH 2 CH (CH 3 ) CH 2 -, -CH 2 C (CH 3 ) 2 CH 2 -, -CH 2 CH (C 2 H 5 ) - or -CH 2 CH (CH 3 ) -.
  • the C 5 to C 30 alkyl and C 5 to C 30 alkenyl groups can carry up to 5, in particular up to 3, additional substituents of the type mentioned and by up to 5, in particular up to 3, non-adjacent oxygen atoms and / or Nitrogen atoms must be interrupted.
  • Examples of such substituted alk (en) yl groups are -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 3 or -CH 2 -OPh.
  • Suitable alkoxylate groups are in particular those in which m and n each represent numbers from 0 to 30, especially from 0 to 15.
  • a 1 and A 2 mean 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.
  • substitution on the phenyl nuclei preferably two occur (same or different) or especially one Substituent on.
  • phenylalkyl groups examples include benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, o-, m- or p-hydroxybenzyl, o-, m- or p-carboxybenzyl, o-, m- or p-sulfobenzyl, o-, m- or p-methoxy- or -ethoxycarbonylbenzyl.
  • Substitution on phenyl nuclei is preferably water-soluble making groups such as hydroxyl groups, carboxyl groups or sulfo groups on.
  • Component (D) lies in the textile detergent formulation according to the invention preferably in an amount of 2 to 30% by weight, in particular 5 to 25% by weight.
  • the presence of Component (B) in the solid textile detergent formulation according to the invention the weight ratio of (D) glycine-N, N-diacetic acid derivatives I to (B) aluminosilicates or silicates 50: 1 to 1: 5, preferably 40: 1 to 1: 2 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 C 1 - to C 30 -alkyl groups, especially branched and / or linear C 1 to C 15 alkyl groups are selected.
  • the glycine-N, N-diacetic acid derivatives I can be incorporated individually or identically into the textile detergent formulation as a prefabricated mixture.
  • Such a last-mentioned mixture of glycine-N, N-diacetic acid derivatives I can be produced by mixing the individual components, but it can also be obtained directly in the synthesis of the compound I. Examples of this are the products of the hydroformylation of ⁇ -olefin mixtures (oxosynthesis) with subsequent reaction of this mixture of linear and branched aldehydes of different C chain lengths to give the corresponding glycine-N, N-diacetic acid derivatives.
  • the described mixtures of glycine-N, N-diacetic acid derivatives not only in the invention solid textile detergent formulation are particularly effective, but generally in solid textile detergent formulations, for example in a formulation containing 1 to 60% by weight (preferably 10 to 45% by weight) based inorganic builders of crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, carbonates and / or phosphates, 0.1 to 25% by weight (preferably 3 to 10% by weight) of said mixture from glycine-N, N-diacetic acid derivatives I, 1 to 40% by weight (preferably 5 to 15% by weight) anionic surfactants, 0.5 to 30% by weight (preferably 3 to 12% by weight) of nonionic surfactants and optionally 0.5 to 20% by weight (preferably 1 to 12% by weight) of further organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids or Contains phosphonic acids or their salts.
  • Suitable anionic surfactants (E) 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 C 11 alcohol sulfates, C 12 - to C 14 alcohol sulfates, C 12 - to C 18 alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 to C 22 alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by firstly using a C 8 - to C 22 -, preferably a C 10 - to C 18 alcohol, e.g. 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 C 8 to C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide.
  • the alkoxylated C 8 to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
  • alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.
  • alkane sulfonates such as C 8 to C 24 , preferably C 10 to C 18 alkane sulfonates and soaps such as the Na and K salts of C 8 to C 24 carboxylic acids.
  • LAS alkylbenzenesulfonates
  • LAS alkylbenzenesulfonates
  • anionic surfactants (E) are C 8 - to C 24 -olefin sulfonates and disulfonates, which can also be mixtures of alkene and hydroxyalkane sulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, paraffin phenol sulfate, alkylphenol sulfonate, alkylphenol sulfonate and alkylphenol sulfate polyols 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 in the detergent Form of salts added. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and Ammonium salts such as B. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Component (E) lies in the textile detergent formulation according to the invention preferably in an amount of 0.1 to 40% by weight, in particular 1 to 30% by weight, in particular from 5 to 20% by weight.
  • anionic surfactants can be used individually anionic surfactants or a combination of different ones Use anionic surfactants. There can be anionic surfactants from only one class, for example only Fatty alcohol sulfates or only alkyl benzene sulfonates, but you can also use surfactant mixtures from different classes, e.g. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
  • Glycine-N, N-diacetic acid derivatives I have additional surfactant character and can function as surfactants of anionic surfactants and take them in whole quantities or replace partially in the detergent formulation. It is so possible to produce even more concentrated formulations.
  • the solid laundry detergent formulation according to the invention contains in a further preferred embodiment as Component (E) only 0 to 6 wt .-%, in particular 0 to 4% by weight, especially 0.1 to 4% by weight, of anionic surfactants one or more sulfate groups, one or more sulfonate groups, one or more phosphate groups or one or two carboxylate groups (herewith are essentially the above anionic surfactants listed).
  • Suitable nonionic surfactants (F) are, for example, alkoxylated C 8 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. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as surfactants.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol.
  • Preferably used as the alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • alkoxylates with a broad or narrow alkylene oxide homolog distribution can be obtained.
  • alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 - to C 14 -alkyl chains and 5 to 30 moles of alkylene oxide units.
  • nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.
  • N-alkyl glucamides of the general structures wherein B 1 is C 6 to C 22 alkyl, B 2 is hydrogen or C 1 to C 4 alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups.
  • B 1 is preferably C 10 to C 18 alkyl
  • B 2 is CH 3
  • 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 10 to C 18 carboxylic acids.
  • Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C 8 - to C 18 -fatty acid methyl esters.
  • Block copolymers are also suitable as nonionic surfactants (F) from 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-aryloxypolyhydroxyfatty acid amides, fatty acid amide ethoxylates, especially closed end groups, as well Fatty acid alkanolamide.
  • F nonionic surfactants
  • Component (F) lies in the textile detergent formulation according to the invention preferably 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.
  • Nonionic surfactants from only one class can be used, in particular only alkoxylated C 8 to C 22 alcohols, but surfactant mixtures from different classes can also be used.
  • the invention contains Textile detergent formulation in addition to the builder component (D) 0.05 to 10 wt .-%, in particular 1 to 5 wt .-% organic Cobuilder (G) 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.
  • D builder component
  • G organic Cobuilder
  • Suitable unsaturated C 4 -C 8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated C 3 -C 8 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 olefins, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, vinyl esters of C 1 -C 8 carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C 2 -C 6 olefins, vinyl alkyl ethers with C 1 -C 4 alkyl groups, vinyl acetate and vinyl propionate.
  • Group (iii) comprises (meth) acrylic esters of C 1 to C 8 alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 amines, N-vinylformamide and N-vinylimidazole.
  • polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units are hydrolyzed.
  • Suitable cound Terpolymers are known, for example, from US-A 3887806 and DE-A 4313909 known.
  • 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 from acrylic acid and maleic acid, in quantities of 40 to 95 % By weight, based on the component to be grafted, grafted on become.
  • Suitable modifying Monomers are the above-mentioned monomers of groups (ii) and (Iii).
  • polyethylene glycols ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C 1 -C 22 alcohols, cf. US-A 5756456.
  • polyglyoxylic acids as component (G) are described in EP-B 001 004, US-A 5 399 286, DE-A 41 06 355 and EP-A 656 914.
  • the end groups of the polyglyoxylic acids can be different Have structures.
  • Suitable as component (G) and modified polyamidocarboxylic acids are known for example from EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.
  • Component (G) in particular also uses polyaspartic acids or cocondensates of aspartic acid with further 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 further amino acids C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono or diamines.
  • phosphorus-containing acids used prepared with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • component (G) iminodisuccinic acid, Oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, Aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified Citric acid such as Agaricic acid, poly- ⁇ -hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA-tallow amide.
  • Oxidized starches can also be used as organic cobuilders be used.
  • the Textile detergent formulation according to the invention additionally 0.5 up to 40% by weight, in particular 8 to 35% by weight, especially 13 to 30% by weight of bleach (H) in the form of percarboxylic acids, e.g. B. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or Monoperoxophthalic acid or terephthalic acid, adducts of hydrogen peroxide to inorganic salts, e.g. Sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate perhydrate or Sodium phosphate perhydrate, adducts of hydrogen peroxide organic compounds, e.g.
  • Urea perhydrate, or of inorganic Peroxo salts e.g. B. alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0.01 to 15 %
  • bleach activators (J) at Color detergents will turn the bleach (H) (if any) into usually used without bleach activator (J), otherwise are usually bleach activators (J) are also present.
  • the described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts.
  • Suitable bleaching catalysts are, for example, quaternized ones Imines and sulfonimines, which are described for example in US-A 5 360 569 and EP-A 453 003.
  • Particularly effective bleaching catalysts are manganese complexes, for example in the WO-A 94/21777 are described.
  • Such connections are in If they are used in the detergent formulations, at most in amounts up to 1.5% by weight, in particular up to 0.5% by weight, in In the case of very active manganese complexes in amounts up to 0.1 wt .-%, incorporated.
  • the Textile detergent formulation according to the invention additionally 0.05 up to 4% by weight of enzymes (K).
  • Enzymes are proteases, amylases, lipases and cellulases. Of the Enzymes are preferably used in amounts of 0.1 to 1.7% by weight, in particular preferably 0.2 to 1.2% by weight of the made-up Enzyme added.
  • Suitable proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is z. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is z. B. Celluzyme (manufacturer: Novo Nordisk).
  • the textile detergent formulation according to the invention is solid d. H. is usually powdered or granular or in Extrudate or tablet form.
  • the powder 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 low in adjusting agents and contain only up to 20 wt .-%, particularly preferably only up to 8% by weight of adjusting agents, especially for compact or Ultracompact detergents.
  • the solid detergents according to the invention can have different bulk densities in the range of 300 to 1300 g / l, especially from 550 to 1200 g / l, especially 650 to 1100 g / l.
  • Modern compact detergents have in the Usually high bulk densities and show a granulate build-up. to Desired compaction of detergents can be achieved in the art usual procedures are used.
  • the textile detergent formulation according to the invention is after Manufactured customary methods and optionally assembled.
  • compositions for compact heavy duty laundry detergents and color detergent are typical compositions for compact heavy duty laundry detergents and color detergent (the percentages relate to weight; the information in brackets for the Compositions (a) and (b) are preferred ranges):
  • the detergent formulations described in Table 1 were used to wash test fabrics made of cotton.
  • the washing conditions are shown in Table 2.
  • the number of washing cycles was 15. After this number of washes, the ash content of the test fabric was determined by ashing at 700 ° C.

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)

Claims (10)

  1. Formulation détergente solide pour textiles contenant
    (A) des adjuvants inorganiques à base de carbonates, à raison de 5% à 27% en poids,
    (B) des adjuvants inorganiques à base d'aluminosilicates cristallins ou amorphes et/ou de silicates cristallins ou amorphes, à raison de 0% à 12% en poids,
    (C) un ou plusieurs dérivés de l'acide glycine-N,N-diacétique, à raison de 1% à 40% en poids, de formule générale I
    Figure 00380001
       dans laquelle
    R
    représente un groupe alkyle en C5 à C30 ou alcényle en C5 à C30 qui présentent en plus, en tant que substituants, jusqu'à 5 groupes hydroxyle, groupes sulfate, groupes sulfonate, groupes formyle, groupes alcoxy en C1 à C4, groupes phénoxy ou groupes alcoxy(en C1 à C4)carbonyle et qui sont éventuellement interrompus par jusqu'à 5 atomes d'azote et/ou atomes d'oxygène non vicinaux, un groupement alcoxylate de formule -(CH2)k-O-(A1O)m-(A2O)n-Y dans laquelle A1 et A2 représentent, indépendamment l'un de l'autre, un groupe 1,2-alcène possédant 2 à 4 atomes de C, Y représente un atome d'hydrogène, un groupe phényle, alkyle en C1 à C12, sulfo ou alcoxy(en C1 à C4)carbonyle, et k représente le nombre 1, 2 ou 3, et m et n représentent chacun un nombre allant de 0 à 50, la somme de m + n étant d'au moins 2, des groupes phénylalkyle possédant 1 à 20 atomes de C dans le groupe alkyle, tous les noyaux phényle mentionnés dans la définition de R portant éventuellement en plus, en tant que substituants, jusqu'à trois groupes alkyle en C1 à C4, groupes hydroxyle, groupes carboxyle, groupes sulfo, ou groupes alcoxy(en C1 à C4)carbonyle, ou un groupe de formule
    Figure 00390001
    dans laquelle A représente un pont alcène en C1 à C12 ou une liaison chimique, et
    M
    représente un atome d'hydrogène, de métal alcalin ou de métal alcalino-terreux, un groupe ammonium ou ammonium substitué, en quantité stoechiométrique appropriée,
    en tant que composant adjuvant organique,
    (E) des tensio-actifs anioniques à raison de 0% à 40% en poids, et
    (F) des tensio-actifs non ioniques à raison de 0,5% à 50% en poids.
  2. Formulation détergente solide pour textiles selon la revendication 1, contenant en plus
    (G) des coadjuvants organiques, à raison de 0,05% à 10% en poids, sous la forme d'acides phosphoniques ou d'acides carboxyliques à faible masse moléculaire, oligomères ou polymères, ou de leurs sels.
  3. Formulation détergente solide pour textiles selon la revendication 1 ou 2, contenant en plus
    (H) des agents de blanchiment, à raison de 0,5% à 40% en poids, sous la forme d'acides percarboxyliques, de produits d'addition du peroxyde d'hydrogène avec des sels inorganiques ou des composés organiques, ou de sels peroxo inorganiques, ainsi qu'éventuellement
    (J) des activateurs de blanchiment à raison de 0,01% à 15% en poids.
  4. Formulation détergente solide pour textiles selon les revendications 1 à 3, contenant en plus
    (K) des enzymes à raison de 0,05% à 4% en poids.
  5. Formulation détergente solide pour textiles selon les revendications 1 à 4, contenant
    (B) des adjuvants inorganiques à base d'aluminosilicates et/ou de silicates, à raison de 1,5% à 8% en poids.
  6. Formulation détergente solide pour textiles selon les revendications 1 à 4, contenant
    (B) des adjuvants inorganiques à base d'aluminosilicates et/ou de silicates, à raison de 0% à 0,5% en poids.
  7. Formulation détergente solide pour textiles selon les revendications 1 à 6, présentant, en présence du composant (B), un rapport pondéral de (D) dérivés d'acide glycine-N,N-diacétique I à (B) aluminosilicates ou les silicates, allant de 50:1 à 1:5.
  8. Formulation détergente solide pour textiles selon les revendications 1 à 7, contenant, en tant que composant (D), les dérivés d'acide glycine-N,N-diacétique I, dans lesquels R représente un groupe alcényle en C5 à C20 ou alkyle en C5 à C20 non substitué à chaíne linéaire ou ramifiée, groupe qui est éventuellement interrompu par jusqu'à 5 atomes d'azote et/ou atomes d'oxygène non vicinaux.
  9. Formulation détergente solide pour textiles selon les revendications 1 à 8, contenant
    (E) des tensio-actifs anioniques, à raison de 0% à 6% en poids, présentant un ou plusieurs groupes sulfate, un ou plusieurs groupes sulfonate, un ou plusieurs groupes phosphate ou un ou deux groupes carboxylate.
  10. Formulation détergente solide pour textiles selon les revendications 1 à 9, présentant une masse volumique apparente allant de 300 g/L à 1 300 g/L.
EP98941364A 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine Expired - Lifetime EP1002046B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1997132688 DE19732688A1 (de) 1997-07-30 1997-07-30 Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten als Buildern mit stark reduziertem Anteil an Silicat-Buildern
DE19732688 1997-07-30
DE1998107104 DE19807104A1 (de) 1998-02-20 1998-02-20 Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten als Buildern mit stark reduziertem Anteil an Silicat-Buildern
DE19807104 1998-02-20
PCT/EP1998/004484 WO1999006524A1 (fr) 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine comme adjuvants a teneur fortement reduite en adjuvants au silicate

Publications (2)

Publication Number Publication Date
EP1002046A1 EP1002046A1 (fr) 2000-05-24
EP1002046B1 true EP1002046B1 (fr) 2003-04-16

Family

ID=26038664

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98941364A Expired - Lifetime EP1002046B1 (fr) 1997-07-30 1998-07-20 Formulation detergente solide pour textiles a base de derives d'acide n,n-diacetique de glycine

Country Status (5)

Country Link
US (1) US6235704B1 (fr)
EP (1) EP1002046B1 (fr)
JP (1) JP4210427B2 (fr)
DE (1) DE59807982D1 (fr)
WO (1) WO1999006524A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0131055D0 (en) * 2001-12-28 2002-02-13 Unilever Plc Detergent compositions
US7605116B2 (en) * 2004-08-11 2009-10-20 The Procter & Gamble Company Highly water-soluble solid laundry detergent composition that forms a clear wash liquor upon dissolution in water
GB0522659D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Delivery cartridge
EP1918362A1 (fr) * 2006-10-16 2008-05-07 The Procter & Gamble Company Composition de lessive détergente solide de faible densité, hautement hydrosoluble et à faible teneur en adjuvant
DE102007062518A1 (de) * 2007-12-20 2009-06-25 Henkel Ag & Co. Kgaa Waschmittel enthaltend stickstoffhaltige Cotenside
WO2010076291A1 (fr) * 2008-12-29 2010-07-08 Akzo Nobel N.V. Particules de chélateur enrobées
EP2454296B1 (fr) 2009-07-15 2015-11-11 Basf Se Copolymères, leur utilisation comme épaississants et procédé pour leur production
MX341385B (es) 2010-07-01 2016-08-18 Basf Se Copolimeros de acidos monocarboxilicos y acidos dicarboxilicos, su preparacion y uso.
JP6063748B2 (ja) * 2012-07-27 2017-01-18 花王株式会社 固体洗浄剤
CN105555931B (zh) 2013-09-16 2018-11-16 巴斯夫欧洲公司 改性聚天冬氨酸在洗碗洗涤剂中的用途
US10233286B2 (en) 2013-09-16 2019-03-19 Basf Se Methods for producing polyaspartic acids in the presence of methanesulfonic acid
CN105793289A (zh) 2013-12-16 2016-07-20 巴斯夫欧洲公司 用于洗衣洗涤剂中和用作抗泛灰剂的改性多糖
WO2016091654A1 (fr) 2014-12-12 2016-06-16 Basf Se Procédé de production d'acide polyaspartique à l'aide d'un précondensat
US9828571B2 (en) 2015-06-05 2017-11-28 Illinois Tool Works, Inc. Heavy duty laundry detergent
CA2995901A1 (fr) 2015-09-08 2017-03-16 Basf Se Procedes de production d'acide polyaspartique par chauffage a reflux
CN107177429A (zh) * 2016-03-11 2017-09-19 华北制药秦皇岛有限公司 一种便于携带、使用方便的洗衣片及其制备工艺
KR20190039192A (ko) 2016-08-08 2019-04-10 바스프 에스이 액체 세탁 제형
EP3421583A1 (fr) 2017-06-26 2019-01-02 Basf Se Utilisation de copolymères vinylamine/vinylcarboxamide cationiques comme agent de protection des couleurs pour formulations de blanchissage
BR112021004413A2 (pt) 2018-09-11 2021-07-20 Basf Se composição para cuidado de tecido, método para prover um efeito de cuidado da cor melhorado, e, uso da composição para cuidado de tecido
CN114727599A (zh) 2019-11-14 2022-07-08 巴斯夫欧洲公司 包含疏水改性聚亚烷基亚胺和生物杀伤剂的织物护理组合物
BR112022020071A2 (pt) 2020-04-07 2022-11-22 Basf Se Composição de polímero aquosa, processo para produzir uma composição de polímero, uso de uma composição de polímero aquosa, e, formulação de detergente para roupa
WO2024022962A1 (fr) * 2022-07-29 2024-02-01 Unilever Ip Holdings B.V. Composition de détergent textile
EP4574955A1 (fr) * 2023-12-22 2025-06-25 Henkel AG & Co. KGaA Composition détergente à haute concentration présentant une stabilité au stockage améliorée

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994029421A1 (fr) * 1993-06-16 1994-12-22 Basf Aktiengesellschaft Utilisation de derives de glycine-n,n-acide diacetique comme agents complexants biodegradables pour des ions de metaux lourds et alcalino-terreux, et leur procede de preparation
EP0882786A1 (fr) * 1996-01-22 1998-12-09 Kao Corporation Composition de detergent pulverulente haute densite

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4604224A (en) 1975-12-15 1986-08-05 Colgate Palmolive Co. Zeolite containing heavy duty non-phosphate detergent composition
ES472603A1 (es) 1977-08-22 1979-10-16 Monsanto Co Un procedimiento para preparar un polimero de carboxilato deacetal
DE2902236A1 (de) 1978-01-25 1979-07-26 Kao Corp Bleichmittelmischung
EP0021491A1 (fr) 1979-06-18 1981-01-07 THE PROCTER & GAMBLE COMPANY Composition détergente contenant un mélange non-ionique et cationique d'agents tensioactifs et un mélange d'agents renforçateurs
US4265777A (en) 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap
DE3360741D1 (en) 1982-02-08 1985-10-17 Union Carbide Corp Zeolite-containing detergent compositions and process for preparing same
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
JPH02229849A (ja) 1989-03-03 1990-09-12 Asahi Chem Ind Co Ltd ジアセチレン化合物の成形用組成物
JPH02229894A (ja) * 1989-03-03 1990-09-12 Kao Corp 高密度粉粒状非イオン洗剤組成物
DE4003172A1 (de) 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
IT1240684B (it) 1990-04-26 1993-12-17 Tecnopart Srl Poliamminoacidi quali builders per formulazioni detergenti
DE4106354A1 (de) 1991-02-28 1992-09-03 Basf Ag Polyacetale, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
DE4106355A1 (de) 1991-02-28 1992-09-03 Basf Ag Verfahren zur herstellung von polyglyoxylaten
FR2675153B1 (fr) 1991-04-15 1994-07-22 Rhone Poulenc Chimie Composition detergente contenant un biopolymere polyimide hydrolysable en milieu lessiviel.
GB9113674D0 (en) 1991-06-25 1991-08-14 Unilever Plc Detergent compositions
US5266237A (en) 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
DE4228159A1 (de) 1992-08-25 1994-03-03 Basf Ag Verfahren zur Herstellung von Polyacetalen, ihre Verwendung und neue Polyacetale
US5307837A (en) 1992-10-27 1994-05-03 Woltz Robert L Water valve apparatus
GB9308047D0 (en) 1993-04-19 1993-06-02 Unilever Plc Particulate detergent,bleaching or cleaning compositions containing aluminosilicates
DE4313909A1 (de) 1993-04-28 1994-11-03 Huels Chemische Werke Ag Wasserenthärtende Formulierungen
DE4415623A1 (de) 1994-05-04 1995-11-09 Basf Ag Verwendung von Pfropfpolymerisaten von monoethylenisch ungesättigten Dicarbonsäuren auf hydrierten Sacchariden als Zusatz zu Wasch- und Reinigungsmitteln
US5770567A (en) 1994-11-14 1998-06-23 Genentech, Inc. Sensory and motor neuron derived factor (SMDF)
US5481018A (en) 1995-03-31 1996-01-02 The Dow Chemical Company Amino nitrile intermediate for the preparation of alanine diacetic acid
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
WO1997048773A1 (fr) * 1996-06-19 1997-12-24 Unilever N.V. Composition de traitement des sols
JPH108094A (ja) * 1996-06-20 1998-01-13 Kao Corp 食器洗浄機用洗浄剤組成物
JPH1053799A (ja) * 1996-08-09 1998-02-24 Kao Corp 粉末洗剤組成物
US5968884A (en) * 1997-04-07 1999-10-19 Basf Corporation Concentrated built liquid detergents containing a biodegradable chelant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994029421A1 (fr) * 1993-06-16 1994-12-22 Basf Aktiengesellschaft Utilisation de derives de glycine-n,n-acide diacetique comme agents complexants biodegradables pour des ions de metaux lourds et alcalino-terreux, et leur procede de preparation
EP0882786A1 (fr) * 1996-01-22 1998-12-09 Kao Corporation Composition de detergent pulverulente haute densite

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JAKOBI ET AL.: "Detergents and Textile Washing", 1987, VCH, WEINHEIM *
JP-A-55/157695 (DEUTSCHE ÜBERSETZUNG) *
JP-A-55/160099 (DEUTSCHE ÜBERSETZUNG) *

Also Published As

Publication number Publication date
JP2001512179A (ja) 2001-08-21
EP1002046A1 (fr) 2000-05-24
WO1999006524A1 (fr) 1999-02-11
JP4210427B2 (ja) 2009-01-21
DE59807982D1 (de) 2003-05-22
US6235704B1 (en) 2001-05-22

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
DE10243361A1 (de) Alkoxylatgemische und diese enthaltende Waschmittel
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
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
EP1599435B1 (fr) Produits issus de la reaction de 2-propylheptanol, de 1-halogene-2,3-epoxypropanes et de 1-hydroxy-2,3-epoxypropane
EP0964912B1 (fr) Formulations detergentes et nettoyantes comprenant un systeme de blanchiment et un melange d'amines et d'agents complexants
WO1997009409A1 (fr) Utilisation d'acides polyaspartiques modifies dans des agents de lavage
DE19732689A1 (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
WO1997035950A1 (fr) Renforçateur de pouvoir de blanchiment pour compositions d'agents de blanchiment et de detergents textiles
DE19807105A1 (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
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
DE19647636A1 (de) Hydroxyfettsäureamide und deren Verwendung als oberflächenaktive Substanzen, nichtionische Tenside oder Emulgatoren
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: 20000111

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 20010503

RTI1 Title (correction)

Free format text: SOLID TEXTILE DETERGENT FORMULATION BASED ON GLYCIN-N,N-DIACETIC ACID DERIVATIVES

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

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: 59807982

Country of ref document: DE

Date of ref document: 20030522

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
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: 20040119

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

Ref country code: FR

Payment date: 20140731

Year of fee payment: 17

Ref country code: GB

Payment date: 20140729

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: 20140728

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: 20140930

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59807982

Country of ref document: DE

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

Effective date: 20150720

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: 20150720

Ref country code: DE

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

Effective date: 20160202

Ref country code: GB

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

Effective date: 20150720

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160331

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: 20150731