EP1003826B1 - Solid textile detergent formulation based on glycin-n, n- diacetic acid derivatives with a highly reduced proportion of other anionic surfactants - Google Patents

Description

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.

The use of the above-mentioned glycine-N, N-diacetic acid derivatives in solid Textile detergent formulations is already out of the WO-A 97/19159 known. In this document there are solid textile detergent formulations described as an organic cobuilder up to 40% by weight of such glycine-N, N-diacetic acid derivatives contain; these also contain textile detergent formulations usual amounts of common anionic surfactants, i.e. approximately 10% by weight or more.

(A) 1 bis 30 Gew.-% anorganische Builder auf Carbonat Basis 0 bis 8 Gew.% anorgantsche Builder auf Basis von kristallinen oder amorphen Alumosilikaten und/oder kristallinen oder amorphen Silicaten und 0 bis 5 Gew.% anorganische Builder auf Phosphat Basis,

(B) 1 bis 40 Gew.-% eines oder mehrerer Glycin-N,N-diessigsäure-Derivate der allgemeinen Formel I

in der

R

für C₅- bis C₃₀-Alkyl oder C₅- bis C₃₀-Alkenyl, welche zusätzlich als Substituenten bis zu 5 Hydroxylgruppen, Sulfatgruppen, Sulfonatgruppen, Formylgruppen, C₁- bis C₄-Alkoxygruppen, Phenoxygruppen oder C₁-bis C₄-Alkoxycarbonylgruppen tragen und durch bis zu 5 nicht benachbarte Sauerstoffatome und/oder Stickstoffatome unterbrochen sein können, Alkoxylat-Gruppierungen der Formel -(CH₂)_k-O-(A¹O)_m-(A²O)_n-Y, in der A¹ und A² unabhängig voneinander 1,2-Alkylengruppen mit 2 bis 4 C-Atomen bezeichnen, Y Wasserstoff, C₁bis C₁₂-Alkyl, Phenyl, C₁- bis C₄-Alkoxycarbonyl oder Sulfo bedeutet und k für die Zahl 1, 2 oder 3 sowie m und n jeweils für Zahlen von 0 bis 50 stehen, wobei die Summe aus m + n mindestens 4 betragen muß, Phenylalkylgruppen mit 5 bis 20 C-Atomen im Alkyl, wobei die bei den Bedeutungen für R genannten Phenylkerne noch zusätzlich als Substituenten bis zu drei C₁- bis C₄-Alkylgruppen, Hydroxylgruppen, Carboxylgruppen, Sulfogruppen oder C₁ bis C₄-Alkoxycarbonylgruppen tragen können, oder einen Rest der Formel

steht, wobei A eine C₅- bis C₁₂-Alkylen-Brücke bezeichnet, und

M

Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium oder substituiertes Ammonium in den entsprechenden stöchiometrischen Mengen bedeutet,

(C) 0 bis 6 Gew.-% anionische Tenside mit einer oder mehreren Sulfat-Gruppen, einer oder mehreren Sulfonat-Gruppen, einer oder mehreren Phosphat-Gruppen oder einer oder zwei Carboxylat-Gruppen und

(D) 0,5 bis 50 Gew.-% nichtionische Tenside

enthält.In the sense of the present invention, a solid textile detergent formulation has now been found, which

(A) 1 to 30% by weight of inorganic builders based on carbonate 0 to 8% by weight of inorganic builders based on crystalline or amorphous aluminosilicates and / or crystalline or amorphous silicates and 0 to 5% by weight inorganic builders based on phosphate,

(B) 1 to 40% by weight of one or more glycine-N, N-diacetic acid derivatives of the general formula I

in the

R

for C ₅ - to C ₃₀ -alkyl or C ₅ - to C ₃₀ -alkenyl, which additionally as substituents up to 5 hydroxyl groups, sulfate groups, sulfonate groups, formyl groups, C ₁ - to C ₄ -alkoxy groups, phenoxy groups or C _{1 to} C ₄ -alkoxycarbonyl groups and can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms, alkoxylate groups of the formula - (CH ₂ ) _k -O- (A ¹ O) _m - (A ² O) _n -Y, in which A ¹ and A ² independently denote 1,2-alkylene groups having 2 to 4 carbon atoms, Y is hydrogen, C ₁ to C ₁₂ alkyl, phenyl, C ₁ to C ₄ alkoxycarbonyl or sulfo and k is the number 1, 2 or 3 as well as m and n each represent numbers from 0 to 50, where the sum of m + n must be at least 4, phenylalkyl groups having 5 to 20 carbon atoms in the alkyl, where the meanings for R Phenyl nuclei mentioned additionally as substituents up to three C ₁ - to C ₄ alkyl groups, hydroxyl groups, carboxyl groups, sulfo group n or C ₁ to C ₄ alkoxycarbonyl groups can carry, or a radical of the formula

stands, wherein A denotes a C ₅ - to C ₁₂ alkylene bridge, and

M

Means hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts,

(C) 0 to 6% by weight of anionic surfactants with one or more sulfate groups, one or more sulfonate groups, one or more phosphate groups or one or two carboxylate groups and

(D) 0.5 to 50% by weight of nonionic surfactants

contains.

The sum of all detergent components listed above and below including residual amounts of water results in a maximum 100% by weight.

Suitable crystalline or are amorphous aluminosilicates with ion-exchanging properties 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 (A) are, for example, disilicates or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-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.

Common phosphates as inorganic builders (A) are polyphosphates such as B. pentasodium triphosphate.

The components (A) mentioned can be used individually or in mixtures are used with each other according to claim 1.

Component (A) lies in the textile detergent formulation according to the invention in a lot of 1 to 30% by weight.

In a preferred embodiment, component (B) those compounds I used in which R for a residue with is at least 7 carbon atoms.

In a particularly preferred embodiment, as component (B) those glycine-N, 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.

In particular, 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.

The alkaline earth metal salts are, in particular, the calcium and Magnesium salts used.

Both the racemates of the compounds I and the two enantiomers with respect to the α-C atom used in the glycine skeleton become.

For the 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. Examples of 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-hexadecyl, n -Heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and n-heptadecenyl (derived from oleic acid). Mixtures can also occur for R, in particular those which are derived from naturally occurring fatty acids and from synthetically produced technical acids, for example by oxosynthesis.

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. In addition, branched C ₅ - to C ₁₂ -alkylene groups can also occur, for. B. -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -, -CH ₂ C (CH ₃ ) ₂ CH ₂ -, -CH ₂ CH (C ₂ H ₅ ) CH ₂ - or -CH ₂ CH ₂ CH ( CH ₃ ) CH ₂ CH ₂ -.

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 . Substituted alk (en) yl groups of the formula -CH ₂ CH ₂ -O-R 'are also of interest, where R' has the meaning of R with the proviso that R 'has at least 3 C atoms.

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.

With substitution on the phenyl nuclei preferably two occur (same or different) or especially one Substituent on.

Examples of 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.

In principle, all of them are 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.

In a further preferred embodiment, 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. To produce the said mixture, 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 α-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.

It should be noted that 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. Besides that, of course other common components such as bleach, bleach activators, Enzymes etc. contained in the usual amounts for this his. Such solid laundry detergent formulations are described for example in WO-A 97/19159.

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.

Other 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. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are those 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. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are 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.

Further suitable anionic surfactants are linear C ₈ to C ₂₀ alkylbenzenesulfonates ("LAS"), preferably linear C _{9 to} C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants (C), 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. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, 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%.

One can use individual 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.

By using the biodegradable and additionally incrustation-inhibiting acting glycine-N, N-diacetic acid derivatives I. it is also possible to increase the proportion of inorganic builders (A) (in particular Alumosilicates, silicates) and thus more concentrated To provide detergent formulations that a contain a higher proportion of biodegradable components.

Accordingly, 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.

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. Here too, 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. Depending on the type of alkoxylation catalyst, alkoxylates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Another class of suitable nonionic surfactants are alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 moles of alkylene oxide units.

Another class of 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.

wobei B₁ ein C₆- bis C₂₂-Alkyl, B² Wasserstoff oder C₁- bis C₄-Alkyl und D ein Polyhydroxyalkyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise steht B¹ für C₁₀- bis C₁₈-Alkyl, B² für CH₃ und D für einen C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀- bis C₁₈-Carbonsäuren.Another class of nonionic surfactants 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. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

R¹

einen C₅- bis C₂₁-Alkyl- oder Alkenylrest bezeichnet,

R²

eine C₁- bis C₄-Alkylgruppe bedeutet,

A¹

für C₂- bis C₄-Alkylen steht,

y

die Zahl 2 oder 3 bezeichnet und

x

einen Wert von 1 bis 6 hat.

Other suitable nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225 R ¹ -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ² in the

R ¹

denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,

R ²

represents a C ₁ to C ₄ alkyl group,

A ¹

represents C ₂ -C ₄ -alkylene,

y

denotes the number 2 or 3 and

x

has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -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.

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.

Individual 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.

In a preferred embodiment, 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.

Phosphonsäuren wie z.B. 1-Hydroxyethan-1,1-diphosphonsäure, Aminotris(methylenphosphonsäure), Ethylendiamintetra(methylenphosphonsäure), Hexamethylendiamintetra(methylenphosphonsäure) und Diethylentriaminpenta (methylenphosphonsäure);

C₄- bis C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z. B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkenylbersteinsäuren mit C₂- bis C₁₆-Alkyl- bzw. -Alkenyl-Resten;

C₄- bis C₂₀-Hydroxycarbonsäuren wie z. B. Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, di- und tricarbonsäure;

Aminopolycarbonsäuren wie z. B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, Alkylethylendiamintriacetate, N,N-bis (Carboxymethyl)glutaminsäure, Ethylendiamindibernsteinsäure und N-(2-Hydroxyethyl)iminodiessigsäure, Methyl- und Ethylglycindiessigsäure.

Suitable low molecular weight carboxylic acids or phosphonic acids for (E) are for example:

Phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediamine tetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid);

C ₄ - to C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₁₆ -alkyl or -alkenyl radicals;

C ₄ - to C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediamine triacetates, N, N-bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and ethylenediacetic acid, methyl- and ethylacetic acid.

Oligomaleinsäuren, wie sie beispielsweise in EP-A 451508 und EP-A 396303 beschrieben sind;

Co- und Terpolymere ungesättigter C₄-C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere
aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%,
aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-% und
aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-%

einpolymerisiert sein können.Suitable oligomeric or polymeric carboxylic acids for (E) are, for example:

Oligomaleic acids as described, for example, in EP-A 451508 and EP-A 396303;

Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers
from group (i) in amounts of up to 95% by weight,
from group (ii) in amounts of up to 60% by weight and
from group (iii) in amounts of up to 20% by weight

can be polymerized.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids here 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.

If the 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.

Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10:90 bis 95:5, besonders bevorzugt solche im Gewichtsverhältnis 30:70 bis 90:10 mit Molmassen von 1000 bis 150000;

Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) :90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) :10 (Acrylsäure + vinylester), wobei das Gew.-Verhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann;

Copolymere von Maleinsäure mit C₂-C₈-Olef inen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, propylen oder Isobuten im Molverhältnis 50:50 besonders bevorzugt sind.

Suitable copolymers of dicarboxylic acids for component (E) are preferably:

Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150,000;

Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid for vinyl ester can vary in the range from 30:70 to 70:30;

Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623 and DE-A 4313909 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.

For modification, up to 30% by weight, based on the component to be grafted, further monoethylenically unsaturated Monomers are present in copolymerized form. Suitable modifying Monomers are the above group monomers (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or hydrated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols with molecular weights up to M _w = 5000 such as. B. 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.

Examples of suitable 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 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.

Also suitable as component (E) are iminosuccinic acid, Oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, Aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified Citric acid such as Agaricic acid, poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA-tallow amide.

Furthermore, oxidized starches can also be used as organic cobuilders be used.

In a further preferred embodiment, 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. 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 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% by weight, Bleach activators (G). With color detergents, the bleach is used (F) (if available) usually without bleach activator (G) otherwise bleach activators (G) are usually used with available.

• polyacylierte Zucker, z. B. Pentaacetylglucose;
• Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkalimetallsalze, z. B. Natrium-p-nonanoyloxybenzolsulfonat oder Natrium-p-benzoyloxybenzolsulfonat;
• N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, z. B. N,N,N',N'-Tetraacetylmethylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonylcarbonamide, z. B. N-Methyl-N-mesylacetamid oder N-Methyl-N-mesylbenzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetylmaleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z.B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinylhydroxylamin oder O,N,N-Triacetylhydroxylamin:
• N,N'-Diacylsulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionylsulfurylamid:
• acylierte Lactame wie beispielsweise Acetylcaprolactam, Octanoylcaprolactam, Benzoylcaprolactam oder Carbonylbiscaprolactam;
• Anthranilderivate wie z.B. 2-Methylanthranil oder 2-Phenylanthranil;
• Triacylcyanurate, z.B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Oximester und Bisoximester wie z.B. O-Acetylacetonoxim oder Bisisopropyliminocarbonat;
• Carbonsäureanhydride, z. B. Essigsäureanhydrid, Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• Enolester wie z.B. Isopropenylacetat;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, z.B. 1,4-Diacetyl-2,5-diketopiperazin;
• ammoniumsubstituierte Nitrile wie z.B. N-Methylmorpholiniumacetonitrilmethylsulfat;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff;
• α-Acyloxypolyacylmalonamide, z. B. α-Acetoxy-N,N-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• Benz-(4h)1,3-oxazin-4-one mit Alkylresten, z. B. Methyl, oder aromatischen Resten z. B. Phenyl, in der 2-Position.

Suitable bleach activators (G) are:

• polyacylated sugars e.g. B. Pentaacetylglucose;
• Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;
• N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N'-tetraacetylmethylene diamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5 , 5-dimethylhydantoin;
• N-alkyl-N-sulfonylcarbonamides, e.g. B. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine:
• N, N'-diacylsulfurylamides, e.g. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide:
• acylated lactams such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonyl biscaprolactam;
• Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil;
• Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;
• Oxime esters and bisoxime esters such as O-acetylacetone oxime or bisisopropyliminocarbonate;
• Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• Enol esters such as isopropenyl acetate;
• 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine;
• ammonium substituted nitriles such as N-methylmorpholinium acetonitrile methyl sulfate;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, e.g. B. tetraacetylpropylene diurea;
• α-acyloxypolyacylmalonamides, e.g. B. α-acetoxy-N, N-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• Benz- (4h) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromatic radicals such. B. phenyl, in the 2-position.

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.

In addition to the bleaching system described, consisting of bleaching agents, bleach activators and optionally bleaching catalysts is for the Textile detergent formulation according to the invention also the Use of systems with enzymatic peroxide release or photo-activated bleaching systems possible.

In a further preferred embodiment, the Textile detergent formulation according to the invention additionally 0.05 up to 4% by weight of enzymes (H). Preferably used in detergents 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). Also the Use of peroxidases to activate the bleaching system possible. One can use single enzymes or a combination of different ones Use enzymes. If necessary, 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.

• kationische Tenside, üblicherweise in einer Menge bis 25 Gew.-%, vorzugsweise 3 bis 15 Gew.-%, beispielsweise C₈- bis C₁₆-Dialkyldimethylammoniumhalogenide, Dialkoxydimethylammoniumhalogenide oder Imidazoliniumsalze mit langkettigem Alkylrest;
• amphotere Tenside, üblicherweise in einer Menge bis 15 Gew.-%, vorzugsweise 2 bis 10 Gew.-%, beispielsweise Derivate von sekundären oder tertiären Aminen wie z.B. C₁₂-C₁₈-Alkylbetaine oder C₁₂-C₁₈-Alkylsulfobetaine oder Aminoxide wie Alkyldimethylaminoxide;
• Vergrauungsinhibitoren und Soil-Release-Polymere (Dabei handelt es sich z.B. um Polyester aus Polyethylenoxiden mit Ethylenglykol und/oder Propylenglykol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren oder Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäuren. Derartige Polyester sind bekannt, vgl. beispielsweise US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 und US-A-5 142 020. Weitere geeignete Soil-Release-Polymere sind amphiphile Pfropf- oder Copolymere von Vinyl- und/oder Acrylester auf Polyalkylenoxiden, vgl. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 und US-A-4 849 126, oder modifizierten Cellulosen wie z.B. Methylcellulose, Hydroxylpropylcellulose oder Carboxymethylcellulose. Vergrauungsinhibitoren und Soil-Release-Polymere sind in den Waschmittelformulierungen zu 0,1 bis 2,5 Gew.-%, vorzugsweise zu 0,2 bis 1,5 Gew.-%, besonders bevorzugt zu 0,3 bis 1,2 Gew.-% enthalten. Bevorzugt eingesetzte Soil-Release-Polymere sind die aus der US-A-4 746 456 bekannten Pfropfpolymeren von Vinylacetat auf Polyethylenoxid der Molmasse 2500 - 8000 im Gewichtsverhältnis 1,2:1 bis 3,0:1, sowie handelsübliche Polyethylenterephthalat/Polyoxyethylenterephthalate der Molmasse 3000 bis 25000 aus Polyethylenoxiden der Molmasse 750 bis 5000 mit Terephthalsäure und Ethylenoxid und einem Molverhältnis von Polyethylenterephthalat zu Polyoxyethylenterephthalat von 8:1 bis 1:1 und die aus der DE-A-44 03 866 bekannten Blockpolykondensate, die Blöcke aus (a) Ester-Einheiten aus Polyalkylenglykolen einer Molmasse von 500 bis 7500 und aliphatischen Dicarbonsäuren und/oder Monohydroxymonocarbonsäuren und (b) Ester-Einheiten aus aromatischen Dicarbonsäuren und mehrwertigen Alkoholen enthalten. Diese amphiphilen Blockcopolymerisate haben Molmassen von 1500 bis 25000.);
• Farbübertragungsinhibitoren, beispielsweise Homo- und Copolymerisate des N-Vinylpyrrolidons, des N-Vinylimidazols, des N-Vinyloxazolidons oder des 4-Vinylpyridin-N-oxids mit Molmassen von 15.000 bis 100.000 sowie vernetzte feinteilige Polymere auf Basis dieser Monomere mit einer Teilchengröße von 0,1 bis 500, vorzugsweise 0,1 bis 250 µm;
• nichttensidartige Schaumdämpfer oder Schauminhibitoren, beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure;
• Komplexbildner (auch in der Funktion von organischen Cobuildern);
• optische Aufheller;
• Polyethylenglykole;
• Parfüme oder Duftstoffe;
• Füllstoffe;
• anorganische Stellmittel, z. B. Natriumsulfat;
• Konfektionierhilfsmittel;
• Löslichkeitsverbesserer;
• Trübungs- und Perlglanzmittel;
• Farbstoffe;
• Korrosionsinhibitoren;
• Peroxidstabilisatoren;
• Elektrolyte.

In addition to the main components (A) to (H) mentioned, the textile detergent formulation according to the invention can also contain the following further customary additives in the usual amounts:

• cationic surfactants, usually in an amount of up to 25% by weight, preferably 3 to 15% by weight, for example C ₈ to C ₁₆ dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical;
• Amphoteric surfactants, usually in an amount of up to 15% by weight, preferably 2 to 10% by weight, for example derivatives of secondary or tertiary amines such as C ₁₂ -C ₁₈ alkyl betaines or C ₁₂ -C ₁₈ alkyl sulfobetaines or amine oxides such as alkyldimethylamine;
• Graying inhibitors and soil release polymers (these are, for example, polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids or polyesters from polyethylene oxides which are end-capped with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, see for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A- 0 272 033 and US Pat. No. 5,142,020. Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, see US Pat. No. 4,746,456, US Pat. No. 4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126, or modified celluloses such as methyl cellulose, hydroxylpropyl cellulose or carboxymethyl cellulose. Graying inhibitors and soil Release polymers are in the detergent formulations at 0.1 to 2.5 wt .-%, preferably may also contain 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight. Soil-release polymers used with preference are the graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, known from US Pat. No. 4,746,456, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates of the molecular weight 3000 to 25000 from polyethylene oxides with a molecular weight of 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate of 8: 1 to 1: 1 and the block polycondensates known from DE-A-44 03 866, the blocks of (a) ester -Units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block copolymers have molecular weights from 1500 to 25000.);
• Color transfer inhibitors, for example homopolymers and copolymers of N-vinylpyrrolidone, N-vinylimidazole, N-vinyloxazolidone or 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000, and crosslinked, finely divided polymers based on these monomers with a particle size of 0. 1 to 500, preferably 0.1 to 250 µm;
• non-surfactant-like foam attenuators or foam inhibitors, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica;
• Complexing agents (also in the function of organic cobuilders);
• optical brighteners;
• Polyethylene glycols;
• Perfumes or fragrances;
• fillers;
• inorganic adjusting agents, e.g. B. sodium sulfate;
• formulation aids;
• solubility;
• Opacifiers and pearlescent agents;
• dyes;
• Corrosion inhibitors;
• peroxide stabilizers;
• Electrolytes.

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. Preferably however, 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.

(a) Zusammensetzung Kompakt-Vollwaschmittel (pulver- oder granulatförmig) 1-40% (2-30%) mindestens eines Glycin-N,N-diessigsäure-Derivats (B) mind 5% (10%) mindestens eines anorganischen Builders (A) in Zusammensetzung und Mengen gemäß Anspruch 1 0-6% (0,1-4%) mindestens eines anionischen Tensids (C) 0,5-50% (1-40%) mindestens eines nichtionischen Tensids (D) 0-20% (0,5-10%) mindestens eines organischen Cobuilders (E) 5-30% (10-23%) eines anorganischen Bleichmittels (F) 0,01-15% (0,5-8%) eines Bleichaktivators (G) 0-1,5% (0-0,5%) eines Bleichkatalysators 0-5 % (0,2-2,5%) eines Farbübertragungsinhibitors 0-2,5% (0,2-1,5%) eines Soil-Release Polymers 0,05-4% (0,1-1,5%) Enzym oder Enzymmischung (H) Weitere übliche Zusätze:

Natriumsulfat, Komplexbildner, Phosphonate, optische Aufheller,

Parfümöle, Schaumdämpfer, Vergrauungsinhibitoren, Bleichstabilisatoren

(b) Zusammensetzung Color-Waschmittel (pulver- oder granulatförmig) 1-40% (2-30%) mindestens eines Glycin-N,N-diessigsäure-Derivats (B) mind. 5% (10%) mindestens eines anorganischen Builders (A) in Zus.setzung und Mengen gemäß Anspruch 1 0-6% (0,1-4%) mindestens eines anionischen Tensids (C) 0,5-50% (1-40%) mindestens eines nichtionischen Tensids (D) 0-20% (0-10%) mindestens eines organischen Cobuilders (E) 0-15% (0-5%) eines anorganischen Bleichmittels (F) 0-5% (0-2,5%) eines Farbübertragungsinhibitors 0,1-2% (0,2-1%) Enzym oder Enzymmischung (H) 0-2,5% (0-1,5%) Soil-Release-Polymer Weitere übliche Zusätze:

Natriumsulfat, Komplexbildner, Phosphonate, optische Aufheller, Parfümöle, Schaumdämpfer, vergrauungsinhibitoren, Bleichstabilisatoren

Typical compositions for compact heavy-duty detergents and color detergents are given below (the percentages are based on weight; the information in brackets for compositions (a) and (b) are preferred ranges):

(a) Composition of compact heavy-duty detergent (powder or granular) 1-40% (2-30%) at least one glycine-N, N-diacetic acid derivative (B) at least 5% (10%) at least one inorganic builder (A) in composition and amounts according to claim 1 0-6% (0.1-4%) at least one anionic surfactant (C) 0.5-50% (1-40%) at least one nonionic surfactant (D) 0-20% (0.5-10%) at least one organic cobuilder (E) 5-30% (10-23%) an inorganic bleaching agent (F) 0.01-15% (0.5-8%) a bleach activator (G) 0-1.5% (0-0.5%) a bleaching catalyst 0-5% (0.2-2.5%) a color transfer inhibitor 0-2.5% (0.2-1.5%) of a soil release polymer 0.05-4% (0.1-1.5%) Enzyme or enzyme mixture (H) Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners,

Perfume oils, foam attenuators, graying inhibitors, bleach stabilizers

(b) Color detergent composition (powder or granular) 1-40% (2-30%) at least one glycine-N, N-diacetic acid derivative (B) at least 5% (10%) at least one inorganic builder (A) in addition and amounts according to claim 1 0-6% (0.1-4%) at least one anionic surfactant (C) 0.5-50% (1-40%) at least one nonionic surfactant (D) 0-20% (0-10%) at least one organic cobuilder (E) 0-15% (0-5%) an inorganic bleaching agent (F) 0-5% (0-2.5%) a color transfer inhibitor 0.1-2% (0.2-1%) Enzyme or enzyme mixture (H) 0-2.5% (0-1.5%) Soil release polymer Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers

Examples

The examples in Table 1 and A-O and Q in Table 4 do not fall under the claimed range.

Unless otherwise stated, all refer Percentages by weight.

Determination of primary washing power

The primary washing tests were carried out with the detergent formulations described in Table 1 (WM 1 to 5). Table 2 lists the washing conditions. WM1 [%] WM 2 [%] WM 3 [%] WM 4 [%] WM 5 [%] lin. alkylbenzenesulfonate 10.00 5.00 C ₁₂ -C ₁₈ alkyl sulfate 5.00 1.50 C ₁₃ -C ₁₅ oxo alcohol x 7 EO 10.00 10.00 10.00 10.00 6.00 AGDA, Na salt 10.00 6.00 6.00 Soap 0.50 0.50 0.50 0.50 Zeolite A 36,00 36,00 36,00 36,00 36,00 Sodium metasilicate x 5 H ₂ O 3.50 3.50 3.50 3.50 3.50 sodium 12,00 12,00 12,00 12,00 12,00 carboxymethylcellulose 1.50 1.50 1.50 1.50 1.50 sodium perborate 15.00 15.00 15.00 15.00 15.00 TAED 3.50 3.50 3.50 3.50 3.50 sodium sulphate 4.00 4.00 4.00 4.00 4.00 water to 100 to 100 to 100 to 100 to 100

The abbreviations in table 1 have the following meaning: TAED tetraacetylethylenediamine AGDA Alkylglycine-N, N-diacetic acid of formula I with R = linear C ₇ -alkyl to C ₁₅ -alkyl Washing conditions Primary washing ability device Launder-o-meter from Atlas, Chicago, USA wash liquor 250 ml washing time 30 minutes at 60 ° C detergent dosage 4.0 g / l water hardness 3 mmol / l Ca: Mg = 4: 1 liquor ratio 1: 12.5 Test fabric WKF 10D, WKF 20D (WKF-Testgewebe GmbH, D-41379 Brüggen-Bracht)
EMPA 101, EMPA 104 (Federal Material Testing Institute, St. Gallen, Switzerland)

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.

Results (primary washing power): example laundry detergent AGDA Total remission [%] 1 WM 1 178.8 2 WM 2 184.7 3 WM 3 C ₇ AGDA 200.9 4 WM 3 C ₈ AGDA 205.3 5 WM 3 C ₁₀ AGDA 194.5 6 WM 3 C ₁₃ AGDA 192.2 7 WM 4 C ₇ AGDA 199.1 8th WM 4 C ₁₁ AGDA 193.6 9 WM 4 C ₁₅ AGDA 189.1 10 WM 5 C ₇ AGDA 200.0 11 WM 5 C ₉ AGDA 194.3 12 WM 5 C ₁₃ AGDA 185.1

The results show that the detergent formulations according to the invention WM 3 to 5, in which the proportion of the usual anionic surfactants (C) is greatly reduced compared to that conventional standard compact detergent formulations WM 1 and 2 (for comparison) have a much better primary wash.

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.

The abbreviations in table 4 have the following meaning: TAED tetraacetylethylenediamine AGDA Alkylglycinediacetic acid of formula I with R = linear C ₇ alkyl to C ₁₅ alkyl or mixture of two or three alkyl diacetic acids of formula I, for example R = methyl / tridecyl (molar ratio approx. 1: 2). R = α-ethylpentyl / tridecyl (molar ratio approx. 1: 1), R = heptyl / decyl / pentadecyl (molar ratio approx. 1: 1: 1) or R = dodecyl / tetradecyl (molar ratio approx. 2: 1) EO ethylene oxide Color transfer inhibitor Polyvinlypyrrolidone, poly-4-vinylpyridine-N-oxide or vinylimidazole / vinylpyrrolidone copolymer encrustation Acrylic acid / maleic acid copolymer Soil release additive 1 Polyethylene terephthalate / polyoxyethylene terephthalate in a molar ratio of 3: 2; Molecular weight of the condensed polyethylene glycol 4000, molecular weight of the polyester 10000 Soil release additive 2 Graft polymer of vinyl acetate on polyethylene glycol with a molecular weight of 8000

Claims (7)

1. A solid textile detergent formulation, comprising

   (A)

   from 1 to 30% by weight of carbonate-based inorganic builders,

   from 0 to 8% by weight of inorganic builders based on crystalline or amorphous alumosilicates and/or crystalline or amorphous silicates and

   from 0 to 5% by weight of phosphate-based inorganic builders,

   (B) from 1 to 40% by weight of one or more glycine-N,N-diacetic acid derivatives of the formula I

   

   where

   R

   is C₅- to C₃₀-alkyl or C₅- to C₃₀-alkenyl, each of which is unsubstituted or substituted by up to 5 hydroxyl, sulfate, sulfonate, formyl, C₁- to C₄-alkoxy, phenoxy or C₁- to C₄-alkoxycarbonyl groups, and may be interrupted by up to 5 nonadjacent oxygen and/or nitrogen atoms,
   alkoxylate of the formula -(CH₂)_k-O-(A¹O)_m-(A²O)_n-Y, where A¹ and A², independently of one another, are 1,2-alkylene having from 2 to 4 carbon atoms, Y is hydrogen, C₁- to C₁₂-alkyl, phenyl, C₁- to C₄-alkoxycarbonyl or sulfo, k is 1, 2 or 3, and m and n are each from 0 to 50, where the sum m + n must be at least 4,
   phenylalkyl having from 5 to 20 carbon atoms in the alkyl moiety, where all phenyl rings given in the meanings for R are unsubstituted or substituted by up to three C₁- to C₄-alkyl, hydroxyl, carboxyl, sulfo or C₁- to C₄-alkoxycarbonyl groups,
   or R is a radical of the formula

   

   where A is a C₅- to C₁₂-alkylene bridge and

   M

   is hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric quantities,

   (C) from 0 to 6% by weight of anionic surfactants having one or more sulfate groups, one or more sulfonate groups, one or more phosphate groups or one or two carboxylate groups and

   (D) from 0.5 to 50% by weight of nonionic surfactants.

   in which the weight ratio of (B) glycine-N,N-diacetic acid derivatives I to (C) anionic surfactants is from 50:1 to 1:1, if anionic surfactants (C) are present in the textile detergent formulation.
2. A solid textile detergent formulation as claimed in claim 1, additionally comprising

   (E) from 0.05 to 20% by weight of organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids or phosphonic acids or salts thereof.
3. A solid textile detergent formulation as claimed in claim 1 or 2, additionally comprising

   (F) from 0.5 to 30% by weight of bleaching agents in the form of percarboxylic acids, adducts of hydrogen peroxide with inorganic salts or organic compounds or of inorganic peroxo salts and also, if desired,

   (G) from 0.01 to 15% by weight of bleach activators.
4. A solid textile detergent formulation as claimed in any of claims 1 to 3, additionally comprising

   (H) from 0.05 to 4% by weight of enzymes.
5. A solid textile detergent formulation as claimed in any of claims 1 to 4, comprising, as component (B), glycine-N,N-diacetic acid derivatives I in which R is a radical having at least 7 carbon atoms.
6. A solid textile detergent formulation as claimed in claim 5, comprising, as component (B), glycine-N,N-diacetic acid derivatives I in which R is a linear or branched unsubstituted C₇- to C₃₀-alkyl or C₇- to C₃₀-alkenyl radical, which may be interrupted by up to 5 nonadjacent oxygen and/or nitrogen atoms.
7. A solid textile detergent formulation as claimed in any of claims 1 to 6 having a bulk density of from 300 to 1300 g/l.