WO2000001661A2

WO2000001661A2 - Glycin-n,n-carboxylic acid derivatives with a lateral chain containing carbonyl groups, preparation thereof and their use in laundry and cleaning agents

Info

Publication number: WO2000001661A2
Application number: PCT/EP1999/004313
Authority: WO
Inventors: Jürgen Detering; Werner Bertleff; Alfred Oftring; Rainer Rahm
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-07-03
Filing date: 1999-06-22
Publication date: 2000-01-13
Also published as: WO2000001661A3; DE19829746A1

Abstract

The present invention relates to glycin-N,N-carboxylic acid derivatives of formula (I) in which R is an organic radical comprising from 3 to 30 carbon atoms and containing at least one carbonyl group in its main chain; G<1> and G<2> represent independently C1-C3 alkylene; x and y are 1 or 2; and M is hydrogen, an alkaline metal, an alkaline-earth metal, ammonium or substituted ammonium. The compounds of formula (I) can be used as components having surfactant and complex-building properties in textile detergent formulations.

Description

Glycine-N, N-carboxylic acid derivatives with a side chain containing carbonyl groups, their preparation and their use in detergents and cleaning agents

description

The present invention relates to glycine-N, N-carboxylic acid derivatives with a side chain containing carbonyl groups, processes for their preparation and their use in detergents and cleaning agents, in particular in textile detergents.

The use of glycine-N, N-diacetic acid derivatives in washing and cleaning agents is known. For example, WO-A 94/29421 (1) describes its use as a biodegradable complexing agent for alkaline earth and heavy metal ions in the washing and cleaning process, among other things. WO-A 97/19159 (2) describes solid textile detergent formulations which contain glycine-N, N-diacetic acid derivatives as cobuilders for inhibiting the inorganic fabric deposits during the washing process. Out

WO-A 97/27277 (3) and WO-A 97/27278 (4) powder-form detergent formulations of high density are known which contain glycine-N, N-diacetic acid derivatives as a builder component. Common to these patent applications is their focus on short-chain alkylglycinediacetic acids, in particular on methylglycinediacetic acid, as is clearly evident from the respective examples.

With increasing alkyl chain lengths, the water solubility of alkylglycinediacetic acids and their salts decreases, especially in the presence of calcium and magnesium ions, which are responsible for the water hardness. However, as the alkyl chain length increases, the surface and interfacial activity of the alkylglycinediacetic acids also increase, provided that they are not water-insoluble. In addition to the complex-forming properties, these surfactant properties are of particular technical interest. The incorporation of heteroatoms into the hydrophobic alkyl chain, as described in principle in (1), is a measure to increase the water solubility of long-chain alkylglycinediacetic acids. However, this possibility is difficult to implement synthetically.

The object was to provide biodegradable alkylglycine carboxylic acids for use in detergents and cleaning agents which have a higher solubility even in hard water, and at the same time their complexing and surfactant properties Can fully develop properties and are also accessible synthetically with little effort.

Accordingly, glycine-N, N-carboxylic acid derivatives of the general formula I

in the

R represents an organic radical with 3 to 30 carbon atoms, which has at least one functional group in its main chain which has a carbonyl function C = 0 or contains such a carbonyl function,

G ¹ and G ² independently of one another denote C _T. to C ₃ alkylene with two or three free valences, which may additionally carry a hydroxyl group,

x and y independently of one another represent the number 1 or 2 and

M denotes hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts.

The groups -G ¹ (COOM) _x and -G ² (CO0M) _y stand, independently of one another, for example for:

-CH ₂ -COOM

-CH ₂ CH ₂ -COOM

-CH ₂ CH ₂ CH ₂ -COOM -CH (COOM) -CH ₃

-CH ₂ -CH (COOM) -CH ₃

-CH (COOM) -CH ₂ -CH ₃

-CH (CH ₃ ) -CH ₂ -COOM

-CH (COOM) ₂ -CH (COOM) -CH ₂ -COOM

-CH ₂ -CH (COOM) ₂

-CH (COOM) -CH (COOM) -CH ₃

-CH (COOM) - CH ₂ - CH ₂ - COOM

- CH ₂ - CH (COOM) - CH ₂ - COOM -C (COOM) ₂ -CH ₃

-C (COOM) ₂ -CH ₂ -CH ₃

-CH ₂ -C (COOM) ₂ -CH ₃ -CH ₂ CH ₂ -CH (COOM) ₂ -CH (COOM) -CH (OH) -COOM -CH ₂ -CH (OH) -COOM -CH (OH) -CH ₂ -COOM -CH ₂ -C (OH ) (CH ₃ ) -COOM -CH (OH) -CH (CH ₃ ) -COOM -CH (CH ₃ ) -CH (OH) -COOM -C (OH) (CH ₃ ) -CH ₂ -COOM

The two or three free valences in G ¹ and G ² serve to bind the one or two carboxyl groups and the glycine nitrogen atom.

The groups -G ¹ (COOM) _x and -G ² (COOM) _y are preferably

-CH ₂ -COOM -CH ₂ CH ₂ -COOM -CH ₂ -CH (COOM) -CH ₃ -CH (CH ₃ ) -CH ₂ -COOM -CH (COOM) -CH ₂ -COOM

Of particular importance are those glycine-N, N-carboxylic acid derivatives I in which both groups -G ¹ (COOM) _x and -G ² (COOM) _y stand for -CH ₂ COOM, ie for the corresponding glycine-N, N-diacetic acid derivatives of the general formula Ia: j ¹ , CH ₂ COOM

MOOC-CH-Nv ^(Ia) H ₂ COOM

The compounds I or Ia are used in the form of the free acids or their alkali metal, alkaline earth metal, ammonium and substituted ammonium salts. Particularly suitable salts of this type are the sodium, potassium and ammonium salts, in particular the trisodium, tripotassium and triammonium salt, and also organic triamine salts with a tertiary nitrogen atom.

The bases on which the organic amine salts are based are, in particular, tertiary amines such as trialkylamines with 1 to 6 carbon atoms in alkyl, for example trimethylamine and triethylamine, methyldiethylamine or tricyclohexylamine, and trialkanolamines with 2 or 3 carbon atoms in the alcohol radical, preferably triethanolamine, tri -n-propanolamine or triisopropanolamine. In particular, the calcium and magnesium salts are used as alkaline earth metal salts.

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

The organic radical R contains 3 to 30, preferably 6 to 24, carbon atoms and has in its main chain at least one C = 0 group (keto group) or one C = 0-containing functional group (in particular amide or ester group). Because of the balance between the hydrophilic and hydrophobic structural elements in the radical R, it is important that this carbonyl function is built into the main chain and not as a substituent on the periphery of the radical R.

In a preferred embodiment, R in the compounds I or Ia represents a radical of the formula

0 z ¹ -x ¹ -cx ² -z ²

in which

Xi and X ₂ independently denote a chemical bond, an oxygen atom or a nitrogen atom carrying a hydrogen atom or a Cj_ to C - alkyl group,

Z ^{1 represents} a Ci to C ₆ alkylene group and

Z ² for Ci to C ₂₈ "alkyl or C ₂ to C ₂₈ alkenyl, which additionally as substituents up to 5 hydroxyl groups, sulfate groups, sulfonate groups, formyl groups, Ci to C alkoxy groups, phenoxy groups or Ci to C can carry alkoxycarbonyl groups or can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms, for alkoxyla groups of the formula - (CH ₂ ) _k -0- (A ¹ 0) _m - (A ² 0) _n -Y, in which A ¹ and A ² independently denote 1, 2 -alkylene groups having 2 to 4 carbon atoms, Y is hydrogen, Ci to -C ₂ alkyl, phenyl or Ci to C alkoxycarbonyl and k is the number 1 , 2 or 3 as well as m and n each represent numbers from 0 to 14, the sum of m + n must be at least 4, represent phenyl or phenylalkyl groups or alkylphenyl groups each having 1 to 20 carbon atoms in the alkyl, all of the phenyl nuclei mentioned in the meaning for Z ² additionally as a substitute up to three Ci to C ₄ -alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or Ci - to C -alkoxycarbonyl groups.

Examples of combinations of X ¹ and X ² in such a radical R are:

0 -Z ⁱ -CZ ²

0

-Z ⁱ -OCZ ²

0

-z ^x -coz ²

Z ³ 0 -Z ⁱ -NCZ ²

0 z ³

-Z ¹ -CNZ ²

0 Z ³ -Z ⁱ -OCNZ ²

Z ³ 0 -Z ⁱ -NCOZ ²

0 -Z ⁱ -OCOZ ² Z 0 z ³ - Z ^x - N - C - N - Z ²

(Z ³ = hydrogen or Cχ to C ₄ alkyl)

Compounds I or Ia are particularly preferred in which in such a radical X ¹ for NH and X ² for a chemical bond or X ¹ for a chemical bond and X ² for 0 or NH or X ¹ and X ² each for a chemical bond Bond.

Suitable alkylene groups Z ¹ are primarily -CH -, -CHCH ₂ -, - (CH ₂ ) 3-, - (CH ₂ ) -, - (CH ₂ ) 5- and - (CH ₂ ) ₆ - / but also -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH ₂ CH ₂ -, - CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH (C ₂ H ₅ ) -CH ₂ - , -CH {CH ₂ CH ₂ CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH ₂ CH ₂ CH ₂ -, -CH ₂ -CH (CH ₃ ) -CH ₂ CH ₂ and -CH ₂ - CH (C ₂ H ₅ ) -CH -. Cyclic alkylene groups, for example cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene, are also suitable for Z ¹ .

For the radical Z ² , linear or branched alk (en) yl radicals are, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n Pentyl, iso-pentyl, tert. -Pentyl, neo-pentyl, n-hexyl, n-heptyl, 3-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n -Undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tride-cyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-oc-tadecyl, n-nonadecyl, n-eicosyl , n-heptadecenyl and n-nonadecenyl. Mixtures can of course also occur for the Z ² radicals.

The Ci to C ₂₈ alkyl and C to C ₂₈ alkenyl groups for Z ² can carry up to b, in particular up to 3, additional substituents of the type mentioned and through up to 5, in particular up to 3, non-adjacent oxygen atoms and / or nitrogen atoms are interrupted. Examples of such substituted alk (en) yl groups are -CH ₂ CH ₂ -0-CH ₂ CH -0-CH ₃ , -CH ₂ -0- (CH ₂ ) ₄ -OH, -CH ₂ CH ₂ -N (CH ₃ ) CH ₂ CH ₂ CH ₃ , - (CH ₂ ) ₅ "N (CH ₃ ) ₂ or - (CH ₂ ) ₅ " CO0CH ₃ . Also of interest are substituted alk (en) yl groups of the formula -CH ₂ CH ₂ -0-Z ⁴ , where Z ^{4 has} the meaning of Z ² with the proviso that Z ^{4 has} at least 3 C atoms and at most 26 C atoms having.

Suitable alkoxylate groups for Z ² are, in particular, those in which m and n each represent numbers from 0 to 10, especially from 0 to 8. The sum of m + n is preferably at least 5, in particular at least 6. A ¹ and A ² mean groups derived from butylene oxide and especially from propylene oxide and from ethylene oxide. Pure are of particular interest Ethoxylates and pure propoxylates, but also ethylene oxide-propylene oxide block structures can occur.

In the event of possible substitution on existing phenyl nuclei, preferably two (identical or different) or in particular a single substituent occur.

In such substitutions on phenyl nuclei, water-solubilizing groups such as hydroxyl groups, carboxyl groups or sulfo groups preferably occur.

Examples of phenylalkyl groups are 5-phenylpentyl, 6-phenyl-hexyl, 8-phenyloctyl, 10-phenyldecyl or 12-phenyldodecyl.

Examples of alkylphenyl groups are o-, m- or p-methylphenyl, m- or p-ethylphenyl, m- or pn-butylphenyl, pn-hexylphenyl, pn-octylphenyl, pn-nonylphenyl, p-iso-nonylphenyl, pn-decyl- phenyl, pn-undecylphenyl, pn-dodecylphenyl, pn-tridecylphenyl or p-iso-tridecylphenyl.

Compounds I or Ia in which Z ^{2 is} unsubstituted linear C ₅ to co-alkyl or alkenyl or phenyl or alkylphenyl groups having 1 to 20 C atoms in the alkyl are particularly preferred.

The compounds I and Ia can be prepared using customary synthetic methods; the compound I is advantageously prepared by

(a) reacting corresponding amino acids, which already contain the radical R containing carbonyl groups, with reagents suitable for generating the groups -G ¹ (C00M) _X and -G (COOM) _y ,

(b) reacting corresponding α-amino acids with reagents suitable for generating the groups -G ¹ (COOM) _x and -G ² (C00M) _y and then introducing the carbonyl group-containing radical R into the α-amino acid N, N-carboxylic acids thus obtained or

(c) corresponding α, β-unsaturated carbonyl compounds, which already contain the carbonyl group R, with a compound of the formula

G COOM) ,, HN

"~ ^ G ² (COOM) _y or a synthesis equivalent thereof (for example the corresponding carboxylic acid nitriles, esters or amides).

Suitable reagents for generating the groups -G ¹ (COOM) _x and -G ² (COOM) _y are, for example, formaldehyde / hydrogen cyanide or alkali metal cyanide (for generating -CH ₂ COOM), haloacetic acid such as bromine or chloroacetic acid (for generating -CH ₂ COOM), acrylic acid (to produce -CH ₂ CH ₂ -COOM), methacrylic acid (to produce -CH ₂ -CH (COOM) -CH ₃ ), crotonic acid (to produce -CH (CH ₃ ) - CH ₂ -COOM) and maleic acid, fumaric acid or corresponding reactive maleic or fumaric acid derivatives (to produce -CH (COOM) -CH -COOM). In this context, reactive maleic or fumaric acid derivatives are in particular maleic anhydride, halogenated (in particular brominated or chlorinated) succinic acids and epoxysuccinic acid. In principle, groups G ¹ and G ² contain a hydroxyl group when reacting with such epoxidized reagents.

The glycine-N, N-diacetic acid derivatives Ia are prepared - in accordance with the general synthesis routes (a) to (c) - in particular by

(i) corresponding α-amino acids which already contain the radical R containing carbonyl, reacted with formaldehyde and hydrogen cyanide or alkali metal cyanide or with haloacetic acid,

(ii) reacting corresponding α-amino acids with formaldehyde and cyano-hydrogen or alkali metal cyanide or with haloacetic acid and then introducing the radical R containing carbonyl into the α-amino acid-N, N-diacetic acid thus obtained or

(iii) corresponding α, β-unsaturated carbonylcer bonds are reacted with iminodiacetic acid or a synthetic equivalent of iminodiacetic acid (for example the corresponding nitriles, esters or amides).

The corresponding substeps in the embodiments (i) to (iii) represent examples of the "Strecker synthesis", in which aldehydes with ammonia or amines and hydrocyanic acid ("acid" variant) or cyanides ("alkaline" variant) in general to give amino acid or derivatives thereof. The reaction conditions for Strecker syntheses for the preparation of glycine-N, -diacetic acid derivatives are described in detail in (1) described, reference is expressly made here to this document.

Typical production routes for the compounds Ia are described in more detail below:

Corresponding bi - or oligofunctional α-amino acids such as aspartic acid, glutamic acid or lysine can be converted into a "hydrophobically modified" form, for example by esterification or amidation of a carboxyl group which is not α to the amino group, followed by carboxymethylation of the free α-amino groups by Strecker reaction; e.g .:

MOOC-Z ¹ -

(X ² = 0 or NH)

Furthermore, α-amino acid-N, N-diacetic acids which also carry further derivatizable functional groups can be correspondingly “hydrophobically modified”; e.g .:

(χ2 = 0 or NH)

Iminodiacetic acid (IDA), its alkali metal salts or its methyl or ethyl ester can also be added to appropriately functionalized α, β-unsaturated carbonyl compounds; e.g .:

(X ² = 0 or NH) (IDA)

Aspartic acid and glutamic acid can be prepared using long-chain alcohols or alcohol mixtures or alcohol alkoxylates on the ß- or. γ- carboxyl group are esterified. This selective esterification reaction can be carried out according to a procedure described by Albert et al. in Synthesis 1987, 7, 635. The diethyl etherate of tetrafluoroboric acid is used here as the catalyst.

Options for the preparation of γ-alkylamides of glutamic acid can be found in J. Pharm. 1980, 69, 553 (Murphy et al.) And of β-alkylamides of aspartic acid in Can. J. Chem. 1966, 44, 2348 (Walter et al.).

ω-Acyllysine derivatives are accessible, for example, by reacting lysine with N-hydroxysuccinimidyl esters (Popovitz -Biro et al., J. Am. Chem. Soc. 1990, 112, 2498; A. Paquet, Can. J. Biochem. 1980 , 58, 573).

The α-amino acids substituted in this way can be converted into the desired N, N-biscarboximethylated forms by reaction with 2 equivalents of chloroacetic acid in a slightly alkaline medium or by various variants of the Strecker reaction with formaldehyde and hydrocyanic acid or alkali metal cyanides. These reactions can be carried out in accordance with (1) or with DE-A 42 11 713 (5), which describes processes for the preparation of aminodicarboxylic acid N, N-diacetic acid.

Alternatively, the aspartic acid or glutamic acid N, N-diacetic acids obtainable according to (5) and the literature references already cited can also be converted into the corresponding amides or esters.

For the special case of aspartic acid -ß-alkylamides or

-ester opens up a further approach by adding iminodiacetic acid (IDA) or its alkali metal salts to maleic acid semiesters or monoamides. It is generally known that maleic anhydride can be selectively ring-opened to the desired half-esters, to which IDA can then be attached. The addition of IDA to ß-alkylaroylacrylic acids, the preparation of which in J. Am. Oil Chem. Soc. 1972, 254, leads analogously to 2-alkylphenyl-2-oxoethylglycinediacetic acids.

The compounds I and Ia according to the invention are outstandingly suitable as a component with complexing and surfactant properties in detergents and cleaning compositions - formulations, in particular in textile detergent formulations. The compounds I and Ib according to the invention are biodegradable.

The present invention also relates to a detergent formulation, in particular a textile detergent formulation, especially a solid textile detergent formulation, which contains 0.1 to 40% by weight, preferably 0.5 to 30% by weight. %, in particular 1 to 25% by weight, especially 2 to 20% by weight, of the compounds I or Ia according to the invention in addition to other customary constituents.

The textile detergent formulation according to the invention generally contains other common constituents

(A) 1 to 60% by weight of inorganic builders based on crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, carbonates or phosphates,

(B) 0.5 to 40% by weight of the glycine-N, N-carboxylic acid derivatives I or Ia different anionic surfactants and

(C) 0.5 to 40% by weight of nonionic surfactants.

Suitable inorganic builders (A) are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as, in particular, 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 replaced by other cations such as Li, K, Ca, Mg or ammonium. 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 0 ₅ or ß-Na ₂ Si ₂ 0 ₅ (SKS 6 or SKS 7, manufacturer: Hoechst). The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicates such as sodium 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 hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.

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

The components (A) mentioned can be used individually or in mixtures with one another.

Component (A) is preferably present in the textile detergent formulation according to the invention in an amount of 5 to 50% by weight, in particular 10 to 45% by weight.

In a preferred embodiment, the textile detergent formulation according to the invention contains no phosphate-based builders or such only up to a maximum of 5% by weight, in particular only up to a maximum of 2% by weight.

By using the biodegradable and additionally incrustation-inhibiting glycine-N, -carboxylic acid derivatives I or Ia, it is also possible to reduce the proportion of inorganic builders (A) (especially aluminosilicates, silicates) and thus to provide more concentrated detergent formulations. which contain a higher proportion of biodegradable components.

Accordingly, the (preferably solid) textile detergent formulation according to the invention in a further preferred embodiment contains a greatly reduced proportion of silicate builders, namely:

1 to 30% by weight, preferably 5 to 27% by weight, inorganic

Carbonate-based builder,

0 to 12% by weight, preferably 0.5 to 8% by weight, in particular 1 to 6% by weight, of 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% by weight, inorganic

Phosphate-based builder.

In a further preferred embodiment, the (preferably solid) textile detergent formulation according to the invention contains two or more glycine-N, N-carboxylic acid derivatives of the general formulas I or Ia. The present mixture of the glycine-N, N-carboxylic acid derivatives I or Ia consists in particular of two or three or four or five components or main components. To produce the said mixture, the glycine-N, N-carboxylic acid derivatives I or Ia can be incorporated individually or as a ready-made mixture into the textile detergent formulation. Such a last-mentioned mixture of glycine-N, N-carboxylic acid derivatives I or Ia can be produced by mixing the individual components, but it can also be obtained directly in the synthesis of the compounds I or Ia.

Anionic surfactants (B) are in principle all anionic surfactants structurally different from compounds I or Ia.

Suitable anionic surfactants (B) 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 Cu alcohol sulfates, Cι ₂ - to Cι ₄ alcohol sulfates, Cι ₂ -Cι ₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, 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 first using a C ₈ - to C ₂₂ - 'preferably a Cio to C ₈ 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. Such alkoxylated C ₈ are suitable also - to C ₂₂ alcohols, the 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 alkanesulfonates such as C ₈ to C ₂₄ , preferably C ₀ to C ₈ alkanesulfonates and soaps such as, for example, the Na and K salts of C ₈ to C carboxylic acids.

Other suitable anionic surfactants are linear C ₈ - to C ₂₀ -alkylbenzenesulfonates ("LAS"), preferably linear Cg to Cι- ₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants (B) are C ₈ -C ₂ -olefin sulfonates and disulfonates, which can also be mixtures of alkene and hydroxyalkane sulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol sulfonates polyglycol ether sulfates, paraffin sulfonates with about 20 to about 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 or alkyl sulfosuccinic acids, their Mono- and diesters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as e.g. B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Component (B) is preferably present in the textile detergent formulation according to the invention in an amount of 1 to 30% by weight, especially 3 to 25% by weight, in particular 5 to 15% by weight. If Cg to C ₂₀ "linear alkylbenzenesulfonates (LAS) are also used, these are usually used in an amount of up to 10% by weight, in particular up to 8% by weight.

By using the surface- and surface-active glycine-N, N-carboxylic acid derivatives I or Ia, it is also possible to significantly reduce the proportion of anionic surfactants (B) in the detergent formulation. In a further preferred embodiment, component (B) is then present in an amount of 0 to 4% by weight, in particular 0.1 to 4% by weight. Individual anionic surfactants or a combination of different anionic surfactants can be used. Anionic surfactants from only one class can be used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use surfactant mixtures from different classes, for example a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.

Examples of suitable nonionic surfactants (C) are 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 abovementioned alkylene oxide added 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. Ethylene oxide is preferably used as the alkylene 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 alkyl phenol alkoxylates such as alkyl phenol ethoxylates with C ₆ to C ₄ 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.

Another class of nonionic surfactants are N-alkyl glucamides of the general structures

B ¹ CNDB ¹ NCD

OB ² B ² 0

wherein Bi 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 hydroxyl groups. Preferably B ^{1 is} C _I Q to Ciβ alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such connections are obtained through the Acylation of reducing aminated sugars with acid chlorides from C o to C ₈ carboxylic acids.

Other suitable nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ⁱ -CO-NH- (CH ₂ ) _y -0- (A ⁱ Ol _x -R ²

in the

R ¹ denotes a C ₅ -C ₂ -alkyl or alkenyl radical,

R ^{2 represents} a C 1 to C ₄ alkyl group,

A ^{1 represents} C ₂ to C ₄ alkylene, y denotes the number 2 or 3 and x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -0) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycol amine of the formula H ₂ N- ( CH ₂ -CH ₂ -0) -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to -C ₈ fatty acid methyl esters.

Also suitable as nonionic surfactants (C) are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, Fatty acid amide ethoxylates, especially end group capped, and fatty acid alkanolamide alkoxylates.

Component (C) in the textile detergent formulation according to the invention is preferably in an amount of 1 to 30% by weight. in particular 3 to 25% by weight, especially 5 to 20% 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 textile detergent formulation according to the invention contains, in addition to the inorganic builders (A), 0.05 to 20% by weight, in particular 1 to 10% by weight, organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids, especially polycarboxylic acids, or phosphonic acids or their salts, especially Na or K salts.

Examples of low molecular weight carboxylic acids or phosphonic acids suitable as organic cobuilders are:

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 Co-di-, tri- and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₆ -alkyl or -alkenyl radicals;

C - to C ₂ o-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, ß-alanine diestsigsäure, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediaminetriacetates, N, N- bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid,.

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:

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 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 "01efins, vinyl alkyl ethers with Cχ-C ₈ alkyl groups, styrene, vinyl esters of Cχ-C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. Preferred from the group (ii) C ₂ -C ₆ -01efins, vinyl alkyl ethers with C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate are used.

Group (iii) comprises (meth) acrylic esters of C 1 -C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C ₈ amines, N-vinyl formamide and N-vinyl imidazole.

If the polymers of group (ii) contain vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known for example from US-A 3887806 and DE-A 4313909.

Suitable copolymers of dicarboxylic acids as organic cobuilders 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): lo (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 _θ -01efins 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 organic cobuilders. 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 as well as mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted.

For modification, up to 30% by weight, based on the component to be grafted, of additional monoethylenically unsaturated monomers can be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates 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 with 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 Cχ-C ₂₂ alcohols, see. US-A 5756456.

Polyglyoxylic acids suitable as organic cobuilders are described, for example, in EP-B 001004, US-A 5399286, DE-A 4106355 and EP-A 656914. The end groups of the polyglyoxylic acids can have different structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as organic cobuilders are known, for example, from EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.

Organic cobuilders used include, in particular, polyaspartic acids or cocondensates of aspartic acid with further amino acids, C -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ ono- or diamines. Are particularly preferred in phosphorus-containing acids used prepared with C ₆ -C ₂₂ -mono- or -dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Also suitable as organic cobuilders are iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkylpolyamino carboxylates, aminopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid such as e.g. Agaricic acid,

Poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as Lauroylethylenediamine triacetate and alkylamides of ethylenediamine tetraacetic acid such as EDTA tallow amide.

Oxidized starches can also be used as organic cobuilders.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally, in particular in addition to the inorganic builders (A), contains the anionic surfactants (B) and / or the nonionic surfactants

(C), 0.5 to 20% by weight, in particular 1 to 10% by weight, glycine-N, N-diacetic acid derivatives of the type of the general formula Ia, in which the organic radical R, however, does not contain any functional group has its main chain, which is a carbonyl function C = 0 or contains such a carbonyl function. (2) describes such glycine-N, N-diacetic acid derivatives.

In the case of the glycine-N, N-diacetic acid derivatives from (2), in addition to methyl, the radical R as straight-chain or branched alk (en) yl radicals are, in particular, C ₂ -C 1 -alkyl and alkenyl, in particular straight-chain, from residues derived from saturated or unsaturated fatty acids. Examples of individual radicals R are: ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, tert. -Pentyl, neopentyl, n-hexyl, n-heptyl, 3-heptyl (derived from 2-ethylhexanoic acid), n-octyl, iso-octyl (derived from iεo-nonanoic acid), n-nonyl, n -Decyl, n-undecyl, n-dodecyl, iso-dodecyl (derived from iso-tridecanoic acid), n-tridecyl, n-tetradecyl, n-pentadecyl, n-He-xadecyl, n-heptadecyl, n-octadecyl, n- Nondecyl, n-eicosyl and n-heptadecenyl (derived from oleic acid). Mixtures can also occur for radicals R, in particular those which are derived from naturally occurring fatty acids and from synthetically produced technical acids, for example by oxosynthesis.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight, of bleaching agent in the form of percarboxylic acids, for. B. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or - terephthalic acid, adducts of hydrogen peroxide with inorganic salts, for example sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide, such as hydrogen peroxide , 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. In the case of color detergents, the bleach (if present) is generally used without a bleach activator, otherwise bleach activators are usually also present.

Suitable bleach activators 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' -Tetraacetylmethylenediamine and -ethylenediamine

(TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethyl-hydantoin;

- N-alkyl-N-sulfonylcarbonamides, e.g. N-methyl-N-mesylacetamide or N-methyl -N-mesylbenzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;

0, N, N-substituted hydroxyamines, e.g. 0-benzoyl-N, N-sucinylhydroxylamine, O-acetyl -N, N-succinylhydroxylamine or 0, N, -triacetylhydroxylamine;

- N, N '-diacylsulfurylamides, e.g. B. N, N '-dimethyl -N, N' -diacetyl-sulfurylamide or N, N '-diethyl-N, N' -dipropionylsulfurylamide;

acylated lactams such as, for example, acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam;

Anthranil derivatives such as 2-methylanthranil or 2-phenyl-anthranil;

Triacylcyanurates, e.g. Triacetylcyanurate or tribenzoylcyanurate;

Oxime esters and bisoxime esters such as O-acetylacetone oxime or bisisopropyliminocarbonate; Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;

- enol esters such as Isopropenyl acetate;

1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl -4,5 -diacetoxyimidazoline;

- tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2,5-diketopiperazines, e.g. 1,4-diacetyl -2,5-dike topiperazine;

ammonium substituted nitriles such as N-methylmorpholinium acetonitrile methyl sulfate;

Acylation products of propylene diurea and 2,2-dimethyl propylene diurea, e.g. B. tetraacetylpropylene diurea;

α-acyloxypolyacylmalonamides, e.g. B. α-acetoxy-N, N '-diacetylma-lonamid;

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 imines and sulfonimines, which are described, for example, in US Pat. No. 5,360,569 and EP-A 453,003. Manganese complexes which are described, for example, in WO-A 94/21777 are particularly effective. When used in the detergent formulations, such compounds are used in amounts of up to 1.5% by weight, in particular up to 0.5% by weight, in the case of very active manganese complexes in amounts of up to 0.1% by weight. -%, incorporated.

In addition to the described bleaching system comprising bleaching agents, bleach activators and, if appropriate, bleaching catalysts, it is also possible for the textile detergent formulation according to the invention to use systems with enzymatic peroxide release or photoactivated bleaching systems. In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.05 to 4% by weight of enzymes. Enzymes that are preferably used in detergents are proteases, amylases, lipases and cellulases. Amounts of 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.0% by weight, of the compounded enzyme are preferably added. Suitable proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellulose is e.g. B. Celluzym (manufacturer: Novo Nordisk). Also the

Peroxidases can be used to activate the bleaching system. You can use single enzymes or a combination of different enzymes. If appropriate, the textile detergent formulation according to the invention can also contain enzyme stabilizers, e.g. B. calcium propionate, sodium formate or boric acids or their salts, and / or antioxidants.

The textile detergent formulation according to the invention can contain, in addition to the main components mentioned above, the following further customary additives in the amounts customary for this:

cationic surfactants, usually in an amount of up to 25% by weight, preferably 3 to 15% by weight, for example C ₈ to C ₆ -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 -alkyl-betaines or C ₂ -C ₈ -alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides ;

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-A-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 -A-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, hydroxypropyl cellulose or carboxymethyl cellulose. Graying inhibitors and soil release polymers are in the detergent formulations at 0.1 to 2.5% by weight, preferably 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 with a molecular weight of 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 from 8: 1 to 1: 1 and the block polycondensates known from DE-A-44 03 866, the blocks from (a) ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) containing 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 homo- 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 dampers or foam inhibitors, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica;

- 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; Assembly aids;

Solubility enhancer;

Opacifiers and pearlescent agents;

Dyes;

Corrosion inhibitors;

Peroxide stabilizers;

Electrolytes.

A solid textile detergent formulation according to the invention is usually in powder or granule form or in extrudate or tablet form.

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. However, the detergents according to the invention are preferably low in detergents and contain only up to 20% by weight, particularly preferably only up to 8% by weight, of detergents, in particular in the case of compact or ultra-compact detergents. The solid detergents according to the invention can have different bulk densities in the range from 300 to 1300 g / 1, in particular from 550 to 1200 g / 1. Modern compact detergents generally have high bulk densities and show a granular structure. The processes customary in the art can be used for the desired compression of the detergents.

The textile detergent formulation according to the invention is produced by customary methods and, if appropriate, is made up.

Typical compositions for Kompak heavy-duty detergents and color detergents are given below (the percentages relate to the weight; the details in brackets for compositions (a) and (b) are preferred ranges):

(a) Composition of compact heavy-duty detergent (powder, granule or tablet)

0.5-25% (1-15) of at least one glycine-N, N-carboxylic acid

Derivative I or Ia

5-50% (10-45%) of at least one inorganic builder

(A)

0.5-30% (3-25%) of at least one anionic surfactant (B) 0.5 - 30% (3 - 25%) of at least one nonionic surfactant (C)

0-20%: 0.5-0%) of an organic cobuilder 5-30%; i0-25%) of an inorganic bleaching agent 0.1-15%: ι-8%) of a bleach activator 0-1% (at most one Bleaching catalyst 0.5%)

0.05-5% (0.2-2.5%) of a color transfer inhibitor 10 0.3-1.5% of a soil release polymer

0.1-4% (0.2-2%) enzyme or enzyme mixture

Other common additives:

15 sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers.

(b) Color detergent composition (powder, granule or 20 tablets)

0.5-25% (1-15%) of at least one glyine-N, N-carboxylic acid

Derivative I or Ia

"-. 10-60% (15-55%) of at least one inorganic builder ²⁵ (A)

0.5-30% (3-25%) of at least one anionic surfactant (B)

0.5-30% (3-25%) of at least one nonionic surfactant

(C)

_3Q 0-20% (0.5-10%) of an organic cobuilder

0-15% (0-5%) of an inorganic bleach

0.05-5% (0.2-3.0%) of a color transfer inhibitor

0.2-2% enzyme or enzyme mixture

0.2-1.5% soil release polymer

35

Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners,

Perfume oils, foam attenuators, graying inhibitors, bleaching 40

Stabilizers.

45 Manufacturing examples

example 1

5 65.6 g (0.2 mol) of ε-lauroyl lysine were suspended in 200 ml of water at room temperature, a pH of about 8 being established. After the addition of 5.9 g (0.04 mol) of a 33% by weight aqueous sodium cyanide solution, the mixture was heated to 80 ° C. before a further 53.5 g (0.36 mol) of NaCN solution were added within 1 h

10 and 40 g (0.4 mol) of a 30 wt. % formaldehyde solution were added dropwise. The now clear reaction solution was stirred for a further 3 hours at the same temperature, the ammonia released during the hydrolysis being removed by means of nitrogen stripping. According to the residual cyanide content according to Liebig

15 equimolar 1.45 g (0.01 mol) of aqueous formaldehyde were added before saponification was continued at 95 ° C. for 3 hours. After cooling to room temperature, the pH was adjusted to 2 with concentrated hydrochloric acid, the precipitate formed was suction filtered and washed with a little cold water. After drying, 98.7 g were obtained

20 of an almost colorless crystal powder which had a calcium binding capacity of 1.77 mmol / g. The yield of N, N-biscarboximethyl-ε-lauroyl lysine in the structural formula given below was 87.3%. For the technical application studies, the free acid was added to the tri-

25 sodium salt transferred.

Example 2

66.5 g (0.5 mol) iminodiacetic acid were suspended in 75 g water and 35 wt. -% aqueous sodium hydroxide solution was adjusted to a pH of 10. After 25 g of soda had been added, 100.1 g (0.5 mol) of maleic acid monohexyl ester were slowly metered in at a temperature of 10 to 15 ° C., the pH being kept at 10 with the addition of sodium hydroxide solution. 40 The mixture was then stirred at room temperature for a further 2 hours. The yield of tri-Na salt of the ω-hexyl ester of α-aspartic acid N, -diacetic acid of the structural formula given below, determined via the calcium binding capacity, was 83.2%.

45

Example 3

51.9 g (0.2 mol) of glutamic acid-γ-monooctyl ester were suspended in 100 g of water with vigorous stirring and mixed with

A pH of 9 was set at 20% by weight sodium hydroxide solution. The mixture was then heated to 50 ° C. and a saturated aqueous solution of 78.8 g (0.4 mol) of 2-succinic acid was added dropwise over the course of 1 h. The pH was kept at 9 by adding appropriate amounts of dilute sodium hydroxide solution. It was still 2 hours at the

15 stirred the same temperature before, after cooling the reaction solution with conc. Hydrochloric acid was acidified to pH 2. The almost colorless precipitate formed was suction filtered, washed with a little cold water and dried. The isolated yield was 87.1 g (88.6) of product of the structure given below

20 formula.

COOH

Examples of use

30

Determination of inorganic tissue deposits (incrustation)

The detergent formulations described in Table 1 (WM 1 to 6) were used to wash test fabrics made of cotton, 35 The washing conditions are shown in Table 2. The number of washing cycles was 15. After this number of washes, the ash content of the test fabric was determined by ashing at 700 ° C., the results are shown in Table 3.

40

45

The abbreviations in table 1 have the following meaning:

TAED: tetraacetylethylenediamine SKS 6: layered silicate

The following additives were used:

Additive IN, N-biscarboximethyl -ε-lauroyllysine (trisodium salt) according to Production Example 1 additive II trisodium salt of the hexyl ester of aspartic acid N, N-diacetic acid according to Production Example 2 additive III sodium citrate as comparative substance additive IV copolymer of acrylic acid and maleic acid in a ratio of 70:30 with M _w = 70000 (sodium salt) as reference substance additive V methylglycine-N, N-diacetic acid (trisodium salt) as reference substance

Table 2

Washing conditions incrustation

Device: Launder-o-meter from Atlas, Chicago, USA

Wash liquor: 250 ml wash time: 30 min at 60 ° C wash cycles: 15 detergent dosage 4.5 g / 1 water hardness: 4 mmol / 1 Ca: Mg = 4: 1 liquor ratio: 1: 12.5 test fabric: cotton fabric EMPA 211 ( Federal

Materials Testing Institute, St. Gallen, Switzerland)

Table 3

The results show that additives I and II inhibit tissue incrustation very effectively. In their effect, they are clearly superior to the comparison substances III and IV, which are used as cobuilders in conventional detergents, and the comparison substance V. The low ash values of the games 6 and 9 in comparison to example 1 reveal the builder character of additives I and II. They can at least partially replace zeolite A without loss of activity. The surfactant character of additives I and II is evident in the very good primary washability of the formulations prepared with these additives (examples 4 to 9).

Table 4 shows an example of the compositions of modern compact detergent formulations A to R.

Table 4

TAED: tetraacetylethylenediamine

EO: ethylene oxide

Color transfer inhibitor: polyvinylpyrrolidone, poly-4-vinylpyridine-N-oxide or

Vinyl imidazole / vinyl pyrrolidone copolymer

Incrustation inhibitor: acrylic acid / maleic acid copolymer soil release additive 1: polyethylene terephthalate / polyoxyethylene terephthalate in

Molar ratio 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 of molecular weight 8000

Claims

claims

1. Glycine-N, N-carboxylic acid derivatives of the general form

2. Glycine-N, N-carboxylic acid derivatives of the general formula Ia according to claim 1

0

-z ⁱ -xcx -z ²

stands where

X ¹ and X ² independently of one another denote a chemical bond, an oxygen atom or a nitrogen atom carrying a hydrogen atom or a Ci to ^" C alkyl group,

Z ^{1 represents} a Cχ ~ to C ₆ alkylene group and

Z ² for Ci to C ₂₈ or C to C ₂ β-alkenyl, which additionally bear as substituents up to 5 hydroxyl groups, sulfate groups, sulfonate groups, formyl groups, Ci to C alkoxy groups, phenoxy groups or Ci to C ₄ alkoxycarbonyl groups can or can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms, for alkoxylate groups of the formula - (CH ^^ - O- (A ¹ 0) _m - (A ² 0) _n -Y, in the A ¹ and A ² independently denote 1, 2 -alkylene groups having 2 to 4 carbon atoms, Y is hydrogen, Ci to C ₁₂ alkyl, phenyl or Ci to C alkoxycarbonyl and k is the number 1, 2 or 3 and m and n each represent numbers from 0 to 14, the sum of m + n must be at least 4, phenyl or phenylalkyl groups or alkylphenyl groups each having 1 to 20 carbon atoms in the alkyl, all of which have the meaning of Z ² phenyl nuclei mentioned additionally as substituents up to three C. i to C alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or Ci to C alkoxycarbonyl groups.

4. Glycine-N, N-carboxylic acid derivatives I or Ia according to claim 3, in which X ^{1 is} NH and X ^{2 is} a chemical bond.

5. Glycine-N, N-carboxylic acid derivatives I or Ia according to claim 3, in which X ^{1 represents} a chemical bond and X ^{2 represents} 0 or NH.

6. Glycine-N, -carboxylic acid derivatives I or Ia according to claim 3, in which X ¹ and X ² each represent a chemical bond.

7. Glycine-N, N-carboxylic acid derivatives I or Ia according to claims 3 to 5, in which Z ² for unsubstituted linear C ₅ - to C ₂ o-alkyl or alkenyl or for phenyl or alkylphenyl groups with 1 to 20 C. -Atoms stands.

8. A process for the preparation of glycine-N, N-carboxylic acid derivatives I according to claim 1, characterized in that

(a) Corresponding α-amino acids, which already contain the radical R containing carbonyl groups, for generating the

Implement groups -G ¹ (COOM) _x and -G ² (COOM) _y suitable reagents,

(b) reacting corresponding α-amino acids with reagents suitable for generating the groups -G COOM ^ and -G ² (COOM) _y and then introducing the carbonyl group-containing radical R into the α-amino acid-N, N-carboxylic acids thus obtained or

G COOMJx HN

^ G ² (COOM) _y

or a synthesis equivalent thereof.

9. A process for the preparation of glycine-N, N-carboxylic acid derivatives Ia according to claim 2, characterized in that according to claim 8

(i) corresponding α-amino acids, which already contain the radical R containing carbonyl groups, with

Formaldehyde and hydrogen cyanide or alkali metal cyanide or with haloacetic acid,

(ii) reacting corresponding α-amino acids with formaldehyde and cyano-hydrogen or alkali metal cyanide or with haloacetic acid and then introducing the carbonyl group-containing radical R into the α-amino acid-N, N-diacetic acids thus obtained or

(iii) corresponding α, β-unsaturated carbonyl compounds are reacted with iminodiacetic acid or a synthetic equivalent of iminodiacetic acid.

10. Use of glycine-N, N-carboxylic acid derivatives I or Ia according to claims 1 to 7 as a component with complexing and surfactant properties in washing and Detergent formulations, especially in textile detergent formulations.

11. Detergent and cleaner formulation, in particular 5 textile detergent formulation, containing 0.1 to 40% by weight of one or more glycine-N, N-carboxylic acid derivatives I or Ia according to claims 1 to 7 in addition to the other usual Components.

10 12. Textile detergent formulation according to claim 11, containing as other usual ingredients

(A) 1 to 60% by weight of inorganic builders based on crystalline or amorphous aluminosilicates, crystalline

15 or amorphous silicates, carbonates or phosphates,

20 (C) 0.5 to 40 wt% nonionic surfactants.

25

30

35

40

45