EP1003826B1 - 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 Download PDF

Info

Publication number
EP1003826B1
EP1003826B1 EP98942573A EP98942573A EP1003826B1 EP 1003826 B1 EP1003826 B1 EP 1003826B1 EP 98942573 A EP98942573 A EP 98942573A EP 98942573 A EP98942573 A EP 98942573A EP 1003826 B1 EP1003826 B1 EP 1003826B1
Authority
EP
European Patent Office
Prior art keywords
weight
alkyl
detergent formulation
acid
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.)
Expired - Lifetime
Application number
EP98942573A
Other languages
German (de)
English (en)
Other versions
EP1003826A1 (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

  • 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, non-ionic surfactants and optionally further usual components.
  • Surfactants are the most important as surface-active substances Group of detergent ingredients. Their share in conventional phosphate-reduced or phosphate-free powder detergents is usually 10 to 25% by weight. Surfactants do that Detachment of liquid (oily) and solid fiber stains during the washing process. Especially the washing effect of the anionic surfactants however, decreases with increasing water hardness. Therefore be Builders (builders) such as the zeolites are used, their primary The task is to bind those responsible for water hardness Calcium and magnesium ions the washing performance of the anionic surfactants to increase.
  • 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 easier removal of dirt from the fiber.
  • Need surfactants here the support of water-soluble complexing agents for Calcium.
  • the task was to create a solid laundry detergent formulation provide in the proportion of conventional anionic surfactants is drastically reduced and the one wash-active (surface-active) Contains substance that contains calcium and magnesium ions can bind.
  • Glycine-N, N-diacetic acid derivatives are such surfactants Substances. They reduce the surface tension of the Wash water and have a dirt-removing effect. They complex Ca and Mg ions remove calcium-containing soiling particularly well and additionally support the inorganic builders in their Task to soften the wash water and build up tissue incrustations to prevent.
  • zeolites Different types 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 (A) 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.
  • 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 - Bicarbonates, especially sodium carbonate and / or Sodium bicarbonate used.
  • phosphates as inorganic builders are polyphosphates such as B. pentasodium triphosphate.
  • Component (A) lies in the textile detergent formulation according to the invention in a lot of 1 to 30% by weight.
  • component (B) those compounds I used in which R for a residue with is at least 7 carbon atoms.
  • N-diacetic acid derivatives I are used in which R for straight-chain or branched unsubstituted C 7 to C 30 alkyl or C 7 to C 30 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.
  • radical R straight-chain or branched alk (en) yl radicals C 5 -C 30 -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-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 5 - to C 12 -alkylene bridges A are primarily polymethylene groups of the formula - (CH 2 ) t -, in which t denotes a number from 5 to 12, in particular from 5 to 8, ie pentamethylene, hexamethylene, heptamethylene, octamethylene , Nonamethylene, decamethylene, undecamethylene and dodecamethylene. Hexamethylene and octamethylene are particularly preferred.
  • branched C 5 - to C 12 -alkylene groups can also occur, for. B.
  • the C 5 - to C 30 -alkyl and alkenyl groups can carry 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 -O-CH 2 CH 2 -O-CH 3 , -CH 2 -O- (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 .
  • Suitable alkoxylate groups are in particular 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 are 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 are 5-phenylpentyl, 6-phenylhexyl, 8-phenyloctyl, 10-phenyldecyl or 12-phenyldodecyl.
  • Substitution on phenyl nuclei is preferably water-soluble making groups such as hydroxyl groups, carboxyl groups or sulfo groups on.
  • Component (B) lies in the textile detergent formulation according to the invention preferably in an amount of 2 to 30% by weight, in particular 3 to 20% by weight.
  • anionic surfactants C
  • Compounds I meant structurally different anionic surfactants.
  • the execution is in the invention solid laundry detergent formulation the weight ratio of (B) Glycine-N, N-diacetic acid derivatives I to the anionic surfactants (C) 50: 1 to 1: 2, preferably 20: 1 to 1: 1 in this ratio range the detergent formulation according to the invention is special 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-NN-diacetic acid derivatives I in which the radicals R consist of branched and / or linear C 5 - to C 30 -alkyl groups, especially branched and / or linear C 5 to C 15 alkyl groups.
  • 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 prepared by mixing the individual components, but it can also be obtained directly in the synthesis of the compounds 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 43% by weight inorganic builders based of crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, carbonates and / or phosphates according to claim 1, 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.
  • inorganic builders based of crystalline or amorph
  • 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 C 11 alcohol sulfates, C 12 - to C 14 alcohol sulfates, C 12 -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 -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
  • alkyltoluenesulfonates alkyltoluenesulfonates
  • anionic surfactants C 8 - to C 24 olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol, fatty acid glycerol, alkylphenol polyglycol ether sulfates, paraffin sulfonates having 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 (C) lies in the textile detergent formulation according to the invention preferably in an amount of 0 to 4% by weight, in particular 0.1 to 4 wt .-%, before, examples of commonly used Quantities are 0 to 0.3% by weight, 0.5% by weight, 1.5% by weight, 2 wt%, 2.5 wt% and 3.5 to 4.5 wt%.
  • 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.
  • the solid textile detergent formulation according to the invention contains a greatly reduced proportion of silicate builders, namely: 1 to 30% by weight, preferably 5 to 27% by weight, inorganic builders based on carbonate, 0 to 8% by weight, in particular 2 to 6 wt .-%, or preferably 0 to 0.5 wt .-%, inorganic builders based on crystalline or amorphous aluminosilicates and / or crystalline or amorphous silicates and 0 to 5% by weight, preferably 0.05 to 2 wt .-%, inorganic builders based on phosphate.
  • silicate builders namely: 1 to 30% by weight, preferably 5 to 27% by weight, inorganic builders based on carbonate, 0 to 8% by weight, in particular 2 to 6 wt .-%, or preferably 0 to 0.5 wt .-%, inorganic builders based on crystalline or amorphous aluminosilicates and / or crystalline or
  • Suitable nonionic surfactants (D) 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 are N-alkyl glucamides. of the general structures where B 1 is a 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 and D is a C 5 or C 6 radical.
  • 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 -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 (D) 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.
  • D nonionic surfactants
  • 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.
  • Component (D) 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 inorganic Builders (A) 0.05 to 20% by weight, in particular 1 to 10% by weight organic cobuilders (E) in the form of low molecular weight, oligomeric or polymeric carboxylic acids, especially polycarboxylic acids, or phosphonic acids or their salts, in particular Na or K-salt.
  • 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) includes (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.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates are also suitable as components (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 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 group monomers (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 (E) are described in EP-B 001004, US-A 5399286, DE-A 4106355 and EP-A 656914.
  • the end groups of the polyglyoxylic acids can be different Have structures.
  • Suitable as component (E) and modified polyamidocarboxylic acids 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 further amino acids, C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono or diamines.
  • 6 -C 22 mono- or dicarboxylic acids are particularly preferred and used with C 6 -C 22 -mono- or -diamines in phosphorus-containing acids produced, with C.
  • component (E) is iminosuccinic 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 30% by weight, in particular 5 to 27% by weight, especially 10 to 23 wt .-% bleach (F) in the form of percarboxylic acids, for.
  • Urea perhydrate, or of inorganic Peroxo salts e.g. B. alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% by weight, Bleach activators (G).
  • the bleach is used (F) (if available) usually without bleach activator (G) otherwise bleach activators (G) are usually used with available.
  • 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 (H).
  • Enzymes are proteases, amylases, lipases and cellulases. Of the Enzymes are preferably used in amounts of 0.1 to 1.5% by weight, in particular preferably 0.2 to 1.0% 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. Celluzym (manufacturer: Novo Nordisk).
  • the Use of peroxidases to activate the bleaching system possible.
  • the textile detergent formulation according to the invention also enzyme stabilizers, z. As calcium propionate, sodium formate or boric acids or their salts, and / or contain antioxidants.
  • 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 detergents, especially for compact or ultra-compact detergents.
  • the solid detergents according to the invention can have different bulk densities in the range of 300 to 1300 g / l, in particular from 550 to 1200 g / l. Modern compact detergents usually have high bulk densities and show a granulate structure. For the desired compression of the detergent the methods customary in technology can be used.
  • the textile detergent formulation according to the invention is after Manufactured customary methods and optionally assembled.
  • the washed test fabrics were washed with a photometer from Measure Datacolor (Elrepho® 2000). The are given in each case Total reflectance values of all four tissue types in percent. The The higher the reflectance value, the better the primary washing power is.
  • the AGDA'S bind Ca and Mg ions and thus inhibit incrustation. Due to this ability, it is also possible to significantly reduce the proportion of inorganic silicate builders (eg zeolites, layered silicates, amorphous disilicates) by using AGDA's without any loss of performance.
  • inorganic silicate builders eg zeolites, layered silicates, amorphous disilicates

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 (7)

  1. Formulation solide de détergent pour textiles contenant
    (A) 1% à 30% en poids d'adjuvants inorganiques à base de carbonate, 0% à 8% en poids d'adjuvants inorganiques à base d'aluminosilicates cristallins ou amorphes et/ou de silicates cristallins ou amorphes et 0% à 5% en poids d'adjuvants organiques à base de phosphate,
    (B) 1% à 40% en poids d'un ou de plusieurs dérivés d'acide glycine-N,N-diacétique de formule générale I
    Figure 00360001
    dans laquelle
    R
    représente un groupe alkyle en C5 à C30 ou alcényle en C5 à C30, lesquels peuvent porter 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 alcoxycarbonyle en C1 à C4, et peuvent être interrompus par jusqu'à 5 atomes d'oxygène et/ou d'azote non vicinaux,
    des groupements alcoxylate de formule - (CH2)-k-O-(A1O)m-(A2O)n-Y, dans laquelle A1 et A2 représentent, indépendamment l'un de l'autre, des groupes 1,2-alcényle possédant 2 à 4 atomes de C, Y représente un atome d'hydrogène, un groupe alkyle en C1 à C12, phényle, alcoxycarbonyle en C1 à C4 ou sulfo, et k vaut 1, 2 ou 3 et m et n valent de 0 à 50, la somme de m + n devant être égale à au moins 4,
    des groupes phénylalkyle possédant 5 à 20 atomes de C dans le groupe alkyle, tous les noyaux phényle mentionnés pour les significations de R pouvant contenir en plus, en tant que substituants, jusqu'à trois groupes alkyle en C1 à C4, groupes hydroxyle, groupes carboxyle, groupes sulfo ou groupes alcoxycarbonyle en C1 à C4,
    ou représente un groupe de formule
    Figure 00370001
    dans laquelle A représente des ponts alkylène en C5 à C12, et
    M
    représente un atome d'hydrogène, un métal alcalin, un métal alcalino-terreux, un groupe ammonium ou un groupe ammonium substitué dans les quantités stoechiométriques appropriées,
    (C) 0% à 6% en poids de tensio-actifs anioniques comprenant un ou plusieurs groupes sulfate, un ou plusieurs groupes sulfonate, un ou plusieurs groupes phosphate ou un ou deux groupes carboxylate,
    (D) 0,5% à 50% en poids de tensio-actifs non ioniques,
    dans laquelle le rapport pondéral de (B) dérivés d'acide glycine-N,N-diacétique I à (C) tensio-actifs anioniques va de 50:1 à 1:1, dans le cas où des tensio-actifs anioniques (C) sont présents dans la formulation de détergent pour textiles.
  2. Formulation solide de détergent pour textiles selon la revendication 1, contenant en plus
    (E) 0,05% à 20% en poids de co-adjuvants organiques sous la forme d'acides phosphoniques ou d'acides carboxyliques oligomères ou polymères de faible masse moléculaire, ou de leurs sels.
  3. Formulation solide de détergent pour textiles selon la revendication 1 ou 2, contenant en plus
    (F) 0,5% à 30% en poids d'agents de blanchiment sous la forme d'acides percarboxyliques, de produits d'addition de peroxyde d'hydrogène avec des sels organiques ou des composés organiques, ou de sels peroxo inorganiques, ainsi qu'éventuellement
    (G) 0,01% à 15% en poids d'activateurs de blanchiment.
  4. Formulation solide de détergent pour textiles selon les revendications 1 à 3, contenant en plus
    (H) 0,05% à 4% en poids d'enzymes.
  5. Formulation solide de détergent pour textiles selon les revendications 1 à 4 contenant, en tant que composant (B), les dérivés d'acide glycine-N,N-diacétique I dans lesquels R représente un groupe possédant au moins 7 atomes de carbone.
  6. Formulation solide de détergent pour textiles selon la revendication 5 contenant, en tant que composant (B), les dérivés d'acide glycine-N,N-diacétique I dans lesquels R représente des groupes alkyle en C7 à C30 ou alcényle en C7 à C30 linéaires ou ramifiés non substitués qui peuvent être interrompus par jusqu'à 5 atomes d'oxygène et/ou d'azote non vicinaux.
  7. Formulation solide de détergent pour textiles selon les revendications 1 à 6 présentant une masse volumique apparente allant de 300 g/L à 1300 g/L.
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 EP1003826A1 (fr) 2000-05-31
EP1003826B1 true 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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11034875B2 (en) 2017-02-03 2021-06-15 Saudi Arabian Oil Company Enhanced filtration control packages, wellbore servicing fluids utilizing the same, and methods of maintaining the structure of a wellbore

Families Citing this family (5)

* 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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0882786A1 (fr) * 1996-01-22 1998-12-09 Kao Corporation Composition de detergent pulverulente haute densite

Family Cites Families (6)

* 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
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0882786A1 (fr) * 1996-01-22 1998-12-09 Kao Corporation Composition de detergent pulverulente haute densite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11034875B2 (en) 2017-02-03 2021-06-15 Saudi Arabian Oil Company Enhanced filtration control packages, wellbore servicing fluids utilizing the same, and methods of maintaining the structure of a wellbore

Also Published As

Publication number Publication date
DE59810854D1 (de) 2004-04-01
US6225278B1 (en) 2001-05-01
EP1003826A1 (fr) 2000-05-31
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
EP0934385B1 (fr) Utilisation dans des detergents et des nettoyants, de composes contenant de l'azote, reticules, solubles ou dispersibles dans l'eau
EP1501775B9 (fr) Melanges d'alkoxylate et lessives les contenant
EP0863976B1 (fr) Derives glycine-n,n-acide diacetique utilises comme co-adjuvants organiques dans des formulations d'agents de lavage de textiles
DE10243361A1 (de) Alkoxylatgemische und diese enthaltende Waschmittel
EP0826025B1 (fr) Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques
DE102005011608A1 (de) Veresterte Alkylalkoxylate als schaumarme Tenside
EP1718606A1 (fr) Sulfates déthers d alkyles
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
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
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
EP0964912B1 (fr) Formulations detergentes et nettoyantes comprenant un systeme de blanchiment et un melange d'amines et d'agents complexants
DE19732689A1 (de) Feste Textilwaschmittel-Formulierung auf Basis von Glycin-N,N-diessigsäure-Derivaten mit stark reduziertem Anteil an weiteren anionischen Tensiden
JP2006504708A (ja) 補助界面活性剤としてのアルキルグリシドールカーボネート
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

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