DE19829746A1 - Glycine-N, N-carboxylic acid derivatives with a side chain containing carbonyl groups, their preparation and their use in detergents and cleaning agents - Google Patents

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

The present invention relates to glycine-N, N-carboxylic acid deri vate with side chain containing carbonyl groups, process for their Manufacture and its use in washing and cleaning detergents, especially in textile detergents.

The use of glycine-N, N-diacetic acid derivatives in washing and cleaning agents is known. So describes the WO-A 94/29421 (1) their use as a biodegradable complex former for alkaline earth and heavy metal ions in Washing and cleaning process. In WO-A 97/19159 (2) are fixed Textile detergent formulations described, the glycine-N, N-dies Acetic acid derivatives as cobuilders to inhibit inorganic Contains tissue during washing. Out WO-A 97/27277 (3) and WO-A 97/27278 (4) are powder detergents Medium density formulations known to be glycine-N, N-dies contain acetic acid derivatives as a builder component. That patent The common focus is on short-chain applications Alkylglycine diacetic acids, especially methylglycine diacid acid, as clearly shown in the respective examples.

As the alkyl chain lengths increase, the water solubility of the Alkylglycinediacetic acids and their salts, especially in Presence of calcium and magnesium ions necessary for the water hardness are responsible. With increasing alkyl chain length however, the surface and interfacial activity of the alkyl also increases glycinediacetic acids, provided they are not water insoluble. These surfactant properties are in addition to complex-forming properties of special application technical interest. The incorporation of heteroatoms into the hydro phobic alkyl chain, as described in principle in (1) one measure, the water solubility of long chain alkylglycine to increase diacetic acids. This possibility is synthetic difficult to realize.

There was the task of biodegradable alkylglycine carbon acids for use in detergents and cleaning agents To provide a higher solubility even in hard Possess water, its complexing and surfactant at the same time  Can fully develop properties and also synthetically without big effort are accessible.

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

in the
R represents an organic radical having 3 to 30 carbon atoms, which has at least one functional group in its main chain which is a carbonyl function C = O or contains such a carbonyl function,
G ¹ and G ² independently of one another denote C ₁ 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 (COOM) _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-diestsacetic acid derivatives of the general formula Ia:

The compounds I or Ia are in the form of the free acids or their alkali metal, alkaline earth metal, ammonium and substituted th ammonium salts used. Such salts are suitable especially the sodium, potassium and ammonium salts, especially that Trisodium, tripotassium and triammonium salt and organic Triamine salts with a tertiary nitrogen atom.

As the bases on which the organic amine salts are based in particular tertiary amines such as trialkylamines with 1 to 6 carbon atoms men in alkyl, e.g. B. trimethyl and triethylamine, methyldiethylamine or tricyclohexylamine, and trialkanolamines with 2 or 3 carbon atoms in the alcohol residue, 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 or Ia and the two enantiomers with respect to the α-C atom in the glycine skeleton be used.

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

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

in which
X ₁ and X ₂ independently denote a chemical bond, an oxygen atom or a nitrogen atom carrying a hydrogen atom or a C ₁ to C ₄ alkyl group,
Z ^{1 represents} a C ₁ to C ₆ alkylene group and
Z ² for C ₁ - to C ₂₈ -alkyl or C ₂ - to C ₂₈ -alkenyl, which in addition Lich as substituents up to 5 hydroxyl groups, sulfate groups, sulfonate groups, formyl groups, C ₁ - to C ₄ -alkoxy groups, phenoxy groups or C Can carry ₁ to C ₄ alkoxycarbonyl groups or can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms, for 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 or C ₁ - to C ₄ - Alkoxycarbonyl mean and k represents the number 1, 2 or 3 and m and n each represent numbers from 0 to 14, where the sum of m + n must be at least 4, for phenyl or for phenylalkyl groups or alkylphenyl groups each with 1 to 20 Carbon atoms in the alkyl is, all of the phenyl nuclei mentioned in the meaning for Z ² additionally as Substituents up to three C ₁ - to C ₄ alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or C ₁ - to C ₄ alkoxycarbonyl groups can carry.

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

(Z ³ = hydrogen or C ₁ to C ₄ alkyl).

Particularly preferred are compounds I or Ia 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 O or NH or X ¹ and X ² each for a chemical bond Bond.

Suitable alkylene groups Z ¹ are in particular -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (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 ₂ -. Cyclic alkylene groups are also suitable for Z ¹ , e.g. B. cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene.

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-nonadece nyl. Mixtures can of course also occur for the Z ² radicals.

The C ₁ to C ₂₈ alkyl and C ₂ to C ₂₈ alkenyl groups for Z ² can carry up to 5, 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 -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 . Also of interest are substituted alk (en) yl groups of the formula -CH ₂ CH ₂ -OZ 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.

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 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 structures can also occur.

If possible substitution occurs on existing phenyl nuclei preferably two (same or different) or in particular a single substituent.

Such substitutions on phenyl nuclei are preferred serolizing groups such as hydroxyl groups, carboxyl groups or sulfo groups.

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 p-n-butylphenyl, p-n-hexylphenyl, p-n-octylphenyl, p-n-nonylphenyl, p-iso-nonylphenyl, p-n-decyl phenyl, p-n-undecylphenyl, p-n-dodecylphenyl, p-n-tridecylphenyl or p-iso-tridecylphenyl.

Compounds I or Ia in which Z ^{2 is} unsubstituted linear C ₅ to C ₂₀ 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 conventional synthesis methods. The compound I is conveniently prepared by:

• (a) reacting corresponding α-amino acids which already contain the radical R containing R with reagents suitable for generating the groups -G ¹ (COOM) _x and -G ² (COOM) _y ,
• (b) corresponding α-amino acids with reagents suitable for generating the groupings -G ¹ (COOM) _x and -G ² (COOM) _y and then the carbonyl group-containing radical R into the α-amino acid N, N-carboxylic acids thus obtained introduces or
• (c) corresponding α, β-unsaturated carbonyl compounds which already contain the radical R containing carbonyl groups, with a compound of the formula
  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), halogenous acetic acid such as bromo 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 generate -CH (CH ₃ ) -CH ₂ -COOM) and maleic acid, fumaric acid or corresponding reactive maleic or fumaric acid derivatives (for the generation of -CH (COOM) -CH ₂ -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 correspond to the carbonyl groups already containing radical R, with formaldehyde and Hydrogen cyanide or alkali metal cyanide or with halo implemented acetic acid,
• (ii) corresponding α-amino acids with formaldehyde and cyan hydrogen or alkali metal cyanide or with halogenes reacted acetic acid and then the carbonyl groups containing radical R into the α-amino acid N, N- introduces diacetic acid or
• (iii) corresponding α, β-unsaturated carbonylcer bonds with Iminodiacetic acid or a synthetic equivalent of Iminodiacetic acid (e.g. the corresponding Ni trilen, esters or amides).

The corresponding sub-steps in the embodiments (i) to (iii) are examples of "Strecker synthesis" in which generally aldehydes with ammonia or amines and hydrocyanic acid ("acidic" variant) or cyanides ("alkaline" variant) Amino acid or derivatives thereof can be implemented. The Reaction conditions for Strecker syntheses for the production of Glycine-N, N-diacetic acid derivatives are described in detail in (1)  described, this document should expressly refer to here be taken.

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 "hydro phobically modified" form, for example by esterification or amidation of a carboxyl group which is not α to the amino group, after which the carboxy methylation of the free ones takes place (L-amino groups by Strecker reaction; e.g .:

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

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. B .:

Aspartic and glutamic acid can be found in the literature Methods with long chain alcohols or alcohol mixtures or Alcohol alkoxylates on the β- or γ-standing carboxyl group ver be esters. This selective esterification reaction can occur after a procedure that was developed by Albert et al. in synthesis 1987, 7, 635. The catalyst used here is Di ethyl etherate of tetrafluoroboric acid used.

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

ω-Acyllysine derivatives are accessible, for example, through implementation of 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 conversion of such substituted α-amino acids into the desired N, N-biscarboximethylated forms can be obtained by Reaction with 2 equivalents of chloroacetic acid in a slightly alkali medium or through different variants of the Strecker-Reak tion with formaldehyde and hydrocyanic acid or alkali metal cyanides. These reactions are carried out based on (1) or to DE-A 42 11 713 (5), in which processes for the preparation of Aminodicarboxylic acid-N, N-diacetic acid are described.

Alternatively, those according to (5) and those already cited can also be used References available aspartic acid or glutamic acid re-N, N-diacetic acids in the corresponding amides or esters being transformed.

For the special case of aspartic acid-β-alkylamides or -ester another access opens up by adding Imi nodiacetic acid (IDA) or its alkali metal salts on malein acid half esters or monoamides. It's common knowledge that Maleic anhydride selectively ring to the desired half-esters can be opened, to which IDA can then be attached.  

The addition of IDA to β-alkylaroylacrylic acids, their preparation 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 suitable in excellent as a component with complex-forming and surfactant properties in detergents and cleaning agents Formulations, especially in laundry detergent formulations. The compounds I and Ib according to the invention are biological degradable.

The present invention also relates to a washing and Detergent formulation, especially a textile wash tel formulation, especially a solid detergent formulation lation, the 0.1 to 40 wt .-%, preferably 0.5 to 30 wt .-%, in particular 1 to 25 wt .-%, especially 2 to 20 wt .-%, the Compounds I or Ia according to the invention in addition to other conventional Contains components.

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

• (A) 1 to 60% by weight of inorganic builders based on crystalline NEN 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 various anionic surfactants and
• (C) 0.5 to 40% by weight of nonionic surfactants.

Suitable inorganic builders (A) are mainly crystalline ones or amorphous aluminosilicates with ion-exchanging properties like especially zeolites. Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially against others Cations such as Li, K, Ca, Mg or ammonium are exchanged. Suitable zeolites are described, for example, in EP-A 038591, EP-A 021491, EP-A 087035, US-A 4604224, GB-A 2013259, EP-A 522726, EP-A 384070 and WO-A 94/24251.

Suitable crystalline silicates (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 builders (A) based on carbonate are carbonates and bicarbonates. These can take the form of their Alkali metal, alkaline earth metal or ammonium salts used become. Na, Li and Mg carbonates or -Hydrogen carbonates, 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 can be used with each other.

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

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

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

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 builders based on carbonate,
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 wt .-%, preferably 0.05 to 2 wt .-%, inorganic builders based on phosphate.

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

In principle, all of them are anionic surfactants (B) Compounds I or Ia structurally different anionic Meant surfactants.

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 C ₁₁ alcohol sulfates, C ₁₂ - to C ₁₄ alcohol sulfates, C ₁₂ -C ₁₈ 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 -C ₂₂ -alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ -alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. 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 - 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 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.

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

Still further suitable anionic surfactants (B) 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 glycerinsulfonate, fatty acid glycerol polyglycol ether, alkylphenol, Paraffin sulfonates with approx. 20 to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isothioates, 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 sarcosates.

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 (hydroxy ethyl) aminonium 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 the C ₉ to C ₂₀ linear alkyl-benzenesulfonate (LAS) is 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-car Bonic acid derivatives I or Ia, it is also possible to increase the proportion anionic surfactants (B) clearly in the detergent formulation to reduce. Component (B) is in another preferred embodiment in an amount of 0 to 4% by weight, in particular 0.1 to 4% by weight.  

One can use single anionic surfactants or a combination use different anionic surfactants. It can be anionic Only one class of surfactants are used, for example only fatty alcohol sulfates or only alkyl benzene sulfonates, you can but also use surfactant mixtures from different classes, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzene sulfonates.

Suitable nonionic surfactants (C) 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. The alkylene oxide used is preferably 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 alkyl phenol alkoxylates such as alkyl phenol 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.

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

wherein 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.

Other suitable nonionic surfactants are the end-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 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 -O) ₃ -C ₄ H ₉ with methyl dodecane or the reaction products of ethyl tetraglycol amine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

Also suitable as nonionic surfactants (C) are blocks 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) is in the laundry detergent according to the invention tel formulation preferably in an amount of 1 to 30 wt .-%, 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. Non-ionic 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 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 B. 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, butane tetracarboxylic acid, cyclopentane tetracarboxylic 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-alanine, diacetic acid, ethylenediaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid, alkylethylenediamine triacetates, N, N- bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and ethyl-acetic 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) acrylic acid and methacrylic acid are preferably used.

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 having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

The group (iii) comprises (meth) acrylester of C ₁ - to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ -amines, N-Vinylfor mamid 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 co- and terpolymers are known, for example, from US-A 3887806 and DE-A 43 13 909 known.

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 molecular weights 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 to the 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 44 15 623 and DE-A 43 13 909 are also suitable as organic cobuilder.  

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 amounts 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 unsung saturated monomers are present in copolymerized form. Suitable modifi decorative monomers are the above-mentioned monomers of the 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 C ₁ -C ₂₂ alcohols, cf. US-A 5756456.

Polyglyoxylic acids suitable as organic cobuilders are described for example in EP-B 001004, US-A 5399286, DE-A 41 06 355 and EP-A 656914. The end groups of the polyglyoxyl acids can have different structures.

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

The organic cobuilders used include, in particular, 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. 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.

Iminodibernstein is also suitable as an organic cobuilder acid, oxydisuccinic acid, aminopolycarboxylates, alkyl polyamino carboxylates, aminopolyalkylene phosphonates, polyglutamates, hydro phobmodified citric acid such as B. agaricinic 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 be used.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally, especially in addition to the inorganic builders (A) 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, has no functional group in its Main chain, which is a carbonyl function C = O or contains such carbonyl function. In (2) such glycine-N, N- diacetic acid derivatives described.

In the case of the glycine-N, N-diacetic acid derivatives from (2), in addition to methyl, the radicals R are straight-chain or branched alk (en) yl radicals, in particular C ₂ - to C ₁₇ -alkyl and alkenyl, in particular straight-chain, residues derived from saturated or unsaturated fatty acids. Examples of individual radicals R are: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neo pentyl, n-hexyl, n-heptyl, 3-heptyl (derived from 2-ethylhexanoic acid), n-octyl, iso-octyl (derived from iso-nonanoic acid), n-no nyl, 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 0.5 up to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight bleach in the form of percarboxylic acids, e.g. B. Diper oxododecanedicarboxylic acid, phthalimidopercaproic acid or monoper oxophthalic acid or terephthalic acid, adducts of hydrogen peroxide to inorganic salts, e.g. B. sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate perhydrate or Sodium phosphate perhydrate, adducts of hydrogen peroxide organic compounds, e.g. B. urea perhydrate, or from anor ganic 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. With color detergents it will Bleach (if present) usually without a bleach activator otherwise bleach activators are usually used available.

Suitable bleach activators are:

• - polyacylated sugars, e.g. B. Pentaacetylglucose;
• - Acyloxybenzenesulfonic acids and their alkali and alkaline earths 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 ethylene diamine (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. B. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
• - N-acylated cyclic hydrazides, acylated triazoles or ura zole, e.g. B. monoacetyl maleic acid hydrazide;
• - O, N, N-trisubstituted hydroxylamines, e.g. B. O-Benzoyl-N, N-suc cinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, 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 acetylcaprolactam, Octanoylcaprolactam, benzoylcaprolactam or carbonylbisca prolactam;
• - Anthranil derivatives such as B. 2-methylanthranil or 2-phenyl anthranil;
• - Triacylcyanurate, e.g. B. triacetyl cyanurate or Tribenzoylcya nurat;
• - Oxime esters and bisoxime esters such as. B. O-acetylacetone oxime or Bisisopropyliminocarbonate;  
• - Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic acid anhydride, m-chlorobenzoic anhydride or phthalic acid anhydride;
• - enol esters such as B. 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. B. 1,4-diacetyl-2,5-dike topiperazine;
• - Ammonium substituted nitriles such as. B. N-methylmorpholinium acetonitrile methyl sulfate;
• - acylation products of propylene diurea and 2,2-dimethyl propylene diurea, e.g. B. tetraacetylpropylene diurea;
• - α-Acyloxypolyacylmalonamide, 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 residues z. B. phenyl, in the 2-position.

The described bleaching system consisting of bleaching agents and bleaching stock vatoren 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 that are used, for example, in the WO-A 94/21777 are described. Such connections are in If used in the detergent formulations, the maximum least 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% by weight.

In addition to the bleaching system described from 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. Preferably used in detergents Enzymes are proteases, amylases, lipases and cellulases. Of the Enzymes are preferably amounts of 0.1 to 1.5 wt .-%, ins particularly preferably 0.2 to 1.0% by weight of the compound Enzyme added. Suitable proteases are e.g. B. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellu lase is e.g. B. Celluzym (manufacturer: Novo Nordisk). Also the Use of peroxidases to activate the bleaching system possible. One can use single enzymes or a combination different enzymes. If necessary, the Textile detergent formulation according to the invention still enzyme stabilizer lisators, e.g. As calcium propionate, sodium formate or boric acids or their salts, and / or contain 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 ₁₆ dialkyldimethylammonium halides, dialkoxydimethylam monium halides or imidazolinium salts with a long-chain alkyl radical;
• - Amphoteric surfactants, usually in an amount up to 15 wt .-%, preferably 2 to 10 wt .-%, for example derivatives of secondary or tertiary amines such as. B. C ₁₂ -C ₁₈ alkyl betaines or C ₁₂ -C ₁₈ alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides;
• - Graying inhibitors and soil release polymers (han is it z. B. to polyester from polyethylene oxides Ethylene glycol and / or propylene glycol and aromatic Dicarboxylic acids or aromatic and aliphatic dicarbon acids or polyester from one end group-capped Polyethylene oxides with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US-A-5 142 020. Other suitable Soil-Re lease polymers are amphiphilic graft or copolymers of Vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-37 11 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126, or  modified celluloses such as B. methyl cellulose, hydroxyl propyl cellulose or carboxymethyl cellulose. Graying inhi Bitterns and soil release polymers are in the detergent formulations of 0.1 to 2.5 wt .-%, preferably 0.2 to Contain 1.5% by weight, particularly preferably 0.3 to 1.2% by weight Soil-release polymers used with preference are those of U.S. Patent 4,746,456 to graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in weight ratio 1.2: 1 to 3.0: 1, as well as commercially available polyethylene terephthalate / polyoxyethylene terephthalate with a molecular weight of 3000 up to 25,000 from polyethylene oxides with a molecular weight of 750 to 5,000 Terephthalic acid and ethylene oxide and a molar ratio of 8: 1 polyethylene terephthalate to polyoxyethylene terephthalate up to 1: 1 and the block poly known from DE-A-44 03 866 condensates, the blocks of (a) ester units made of poly alkylene glycols with a molecular weight of 500 to 7500 and aliphati Dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) Ester units from aromatic dicarboxylic acids and contain polyhydric alcohols. These amphiphiles Block copolymers have molecular weights from 1500 to 25,000.);
• - Color transfer inhibitors, for example homo- and copoly merisates of N-vinylpyrrolidone, N-vinylimidazole, N- With vinyl oxazolidone or 4-vinyl pyridine-N-oxide Molar masses from 15,000 to 100,000 and crosslinked fine particles Polymers based on these monomers with a particle size from 0.1 to 500, preferably 0.1 to 250 µm;
• - non-surfactant foam dampers or foam inhibitors, for example organopolysiloxanes and mixtures thereof microfine, optionally silanized silica and Paraffins, waxes, microcrystalline waxes and mixtures thereof 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;
• - opacifying and pearlescent agents;
• - dyes;
• - corrosion inhibitors;
• - peroxide stabilizers;
• - electrolytes.

A solid textile detergent formulation according to the invention lies usually in powder or granular form or in extrudate or Tablet form.

Powder or granular detergents according to the invention can contain up to 60% by weight of inorganic adjusting agents. More common Sodium sulfate is used for this. Preferably, the detergents according to the invention but low in adjusting agents and ent hold only up to 20% by weight, particularly preferably only up to 8 % By weight of adjusting agents, in particular in the case of compact or ultracom compact detergents. The solid detergents according to the invention can different bulk densities in the range from 300 to 1300 g / l, in particular from 550 to 1200 g / 1. Modern compact detergents generally 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 assembled if necessary.

Typical compositions for compact full detergents and color detergents are given below (the percentages relate to the weight; the information 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 glyine-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% (0.5-10%) of an organic cobuilder
  5-30% (10-25%) of an inorganic bleach
  0.1-15% (1-8%) of a bleach activator
  0-1% (maximum of a bleaching catalyst 0.5%)
  0.05-5% (0.2-2.5%) of a color transfer inhibitor
  0.3-1.5% of a soil release polymer
  0.1-4% (0.2-2%) enzyme or enzyme mixture.

Other common additives:
Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers.

• (b) Color detergent composition (powder, granule or tablet form)
  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 (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% (0.5-10%) 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.

Other common additives:
Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers.

Manufacturing examples example 1

65.6 g (0.2 mol) of ε-lauroyl lysine were dissolved in 200 at room temperature ml of water suspended, with a pH of about 8 posed. After adding 5.9 g (0.04 mol) of a 33% by weight aqueous sodium cyanide solution was heated to 80 ° C before the same a further 53.5 g (0.36 mol) of NaCN solution within 1 h and 40 g (0.4 mol) of a 30% by weight formaldehyde solution were added dropwise. The now clear reaction solution was still Stirred for 3 hours at the same temperature, the at the hydrolysis released ammonia by means of nitrogen stripping was removed. According to the residual cyanide content according to Liebig 1.45 g (0.01 mol) of aqueous formaldehyde were added in equimolar amounts before saponifying at 95 ° C for 3 hours. To Cooling to room temperature was done with concentrated hydrochloric acid adjusted to pH 2, the precipitate formed is suction filtered and washed a little cold water. After drying, 98.7 g were obtained an almost colorless crystal powder that binds calcium of 1.77 mmol / g. The yield determined in this way N, N-biscarboximethyl-ε-lauroyl lysine of those given below Structural formula was 87.3%. For the application engineering Un The free acid was tested with sodium hydroxide solution in the tri sodium salt transferred.

Example 2

66.5 g (0.5 mol) of iminodiacetic acid were suspended in 75 g of water diert and with 50 wt .-% aqueous sodium hydroxide solution pH adjusted to 10. After adding 25 g of soda a temperature of 10 to 15 ° C 100.1 g (0.5 mol) of maleic acid mo slowly added nohexyl ester within 30 min, the pH was kept at 10 with the addition of sodium hydroxide solution. The mixture was then stirred at room temperature for a further 2 hours. The yield of tri-Na salt determined via the calcium binding capacity of the ω-hexyl ester of α-aspartic acid-N, N-diacetic acid below structural formula given was 83.2%.  

Example 3

51.9 g (0.2 mol) of γ-monooctyl glutamic acid were added vigorous stirring suspended in 100 g of water and with 20% by weight sodium hydroxide solution was adjusted to a pH of 9. Then it was heated to 50 ° C. and a saturated aqueous solution of 78.8 g (0.4 mol) of 2-bromosuccinic acid were added within 1 h drips. The pH was ver by adding appropriate amounts thin sodium hydroxide solution kept at 9. It was still 2 hours at the same temperature before stirring after cooling the reak tion solution with conc. Hydrochloric acid was acidified to pH 2. The Almost colorless precipitate formed was suction filtered, with little washed cold water and dried. The isolated yield was 87.1 g (88.6%) of product of the structure given below formula.

Examples of use 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. The washing conditions are shown in Table 2. The number the wash cycles were 15. After this number of washes was carried out the ash content of the test fabric by ashing at 700 ° C determined, the results are given in Table 3.  

Table 2 Washing conditions incrustation

Device: Launder-o-meter from Atlas, Chicago, USA
Wash liquor: 250 ml
Washing time: 30 min at 60 ° C
Wash cycles: 15
Detergent dosage: 4.5 g / l
Water hardness: 4 mmol / l Ca: Mg = 4: 1
Fleet ratio: 1: 12.5
Test fabric: Cotton fabric EMPA 211 (Swiss Federal Laboratory, St. Gallen, Switzerland)

Table 3

The results show that additives I and II are the tissues Inhibit crusting very effectively. In effect, they are the comparison substances III and IV, which are used as cobuilders in her conventional detergents are used, and the comparison Substantially superior to substance V. The low ash values of the Bei  games 6 and 9 in comparison to example 1 reveal the Builder character of additives I and II. You can at least partially replace zeolite A without loss of effectiveness. The tenside cha The character of additives I and II can be seen in the very good primary washability of those made with these additives Formulations (Examples 4 to 9).

Table 4 shows exemplary compositions of modern com Compact detergent formulations A to R.  

Claims (12)

1. Glycine-N, N-carboxylic acid derivatives of the general formula I
in the
R represents an organic radical having 3 to 30 carbon atoms, which has at least one functional group in its main chain which has a carbonyl function C = O or contains such a carbonyl function,
G ¹ and G ² independently of one another denote C ₁ to C ₃ alkylene with two or three free valences, which can 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. 2. Glycine-N, N-carboxylic acid derivatives of the general formula Ia according to claim 1
in which R and M have the meanings mentioned in claim 1. 3. Glycine-N, N-carboxylic acid derivatives I or Ia according to claim 1 or 2, in which R represents a radical of the formula
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 C ₁ - to C ₄ -alkyl group,
Z ^{1 represents} a C ₁ to C ₆ alkylene group and
Z ² for C ₁ - to C ₂₈ or C ₂ - to C ₂₈ -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 Can carry ₄ alkoxycarbonyl groups or can be interrupted by up to 5 non-adjacent oxygen atoms and / or nitrogen atoms, for alkoxide 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 or C ₁ - to C ₄ -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 having to be at least 4, represents phenyl or phenylalkyl groups or alkylphenyl groups each having 1 to 20 carbon atoms in the alkyl, where all phenyl nuclei mentioned in the meaning for Z ² additionally as substituents can carry up to three C ₁ - to C ₄ -alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or C ₁ - to C ₄ -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} O or NH. 6. Glycine-N, 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 ₂₀ 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) reacting corresponding α-amino acids which already contain the radical R containing R with reagents suitable for generating the groups -G ¹ (COOM) _x and -G ² (COOM) _y ,
• (b) corresponding α-amino acids with reagents suitable for generating the groups -G ¹ (COOM) _x and -G ² (COOM) _y and then the radical R containing carbonyl groups in the α-amino acid N, N-carboxylic acids thus obtained introduces or
• (c) corresponding α, β-unsaturated carbonyl compounds which already contain the radical R containing carbonyl groups, with a compound of the formula
  or a synthesis equivalent thereof.

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

• (i) corresponding α-amino acids, which already contain the carbonyl group-containing radical R, are reacted with formaldehyde and hydrogen cyanide or alkali metal cyanide or with haloacetic acid,
• (ii) corresponding α-amino acids with formaldehyde and hydrogen cyanide or alkali metal cyanide or with halogen acetic acid and then introducing the carbonyl group-containing radical R into the α-amino acid N-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 at the same time complexing and surfactant properties in washing and  Detergent formulations, especially in textiles detergent formulations. 11. Detergent and cleaning agent formulation, in particular Textile detergent formulation containing 0.1 to 40% by weight 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. 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 or amorphous silicates, carbonates or phosphates,
• (B) 0.5 to 40 wt .-% 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.