EP0863976B1 - Glycine-n,n-diacetic acid derivatives used as organic co-builders in textile washing-agent formulations - Google Patents

Abstract

PCT No. PCT/EP96/04817 Sec. 371 Date May 18, 1998 Sec. 102(e) Date May 18, 1998 PCT Filed Nov. 5, 1996 PCT Pub. No. WO97/19159 PCT Pub. Date May 29, 1997A solid textile detergent formulation, comprising (A) 1-60% by weight of inorganic builders based on crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, carbonates and/or phosphates, (B) 0.1-25% by weight of one or more glycine-N,N'-diacetic acid derivatives I where R is an organic radical and M is hydrogen or a cation, as organic cobuilders, (C) 1-40% by weight of anionic surfactants and (D) 0.5-30% by weight of nonionic surfactants.

Description

The present invention relates to a solid phosphate-free textile detergent formulation from inorganic builders on silicate, aluminosilicate - And / or carbonate base, glycine-N, N-diacetic acid derivatives as organic cobuilders as well as anionic and nonionic Surfactants.

Conventional powder detergents for textiles contain large amounts on poorly or insoluble builders (framework substances) such as Zeolites or silicates, which are necessary to achieve a high primary and secondary washing ability to achieve. Because of this high Proportion of components insoluble in the wash liquor will also the overall solubility of the detergent formulation is severely impaired.

The task was to create a solid laundry detergent formulation with improved solubility of the builder system without disadvantageous To provide effects in particular on the primary washing ability.

WO-A 94/29421 (1) describes the use of glycine-N, N-diacetic acid derivatives as a biodegradable complexing agent for Alkaline earth and heavy metal ions, among others in the detergent and cleaning agent sector known. So it is mentioned there that such Glycine-N, N-diacetic acid derivatives generally as complexing agents or as a builder in powder detergent formulations for Textile laundry can be used.

In Japanese Laid-Open Publications 1980/157695 (2) and 1980/160099 (3) solid detergent compositions for the Textile laundry described which N, N-bis (carboxymethyl) amino acids such as N, N-bis (carboxymethyl) alanine, surfactants, sodium metasilicate and contain imidobissulfates as a further builder component.

(A) 1 bis 60 Gew.-% anorganische Builder auf Basis von kristallinen oder amorphen Alumosilicaten, kristallinen oder amorphen Silicaten und/oder Carbonaten,

(B) 0,1 bis 25 Gew.-% eines oder mehrerer Glycin-N,N-diessigsäure-Derivate der allgemeinen Formel I

in der

R

für C₁- bis C₃₀-Alkyl oder C₂- bis C₃₀-Alkenyl, welche zusätzlich als Substituenten bis zu 5 Hydroxylgruppen, Formylgruppen, C₁- bis C₄-Alkoxygruppen, Phenoxygruppen oder C₁-bis C₄-Alkoxycarbonylgruppen tragen und durch bis zu 5 nicht benachbarte Sauerstoffatome unterbrochen sein können, Alkoxylat-Gruppierungen der Formel -(CH₂)_k-O-(A¹O)_m-(A²O)_n-Y, in der A¹ und A² unabhängig voneinander 1,2-Alkylengruppen mit 2 bis 4 C-Atomen bezeichnen, Y Wasserstoff, C₁- bis C₁₂-Alkyl, Phenyl oder C₁- bis C₄-Alkoxycarbonyl bedeutet und k für die Zahl 1, 2 oder 3 sowie m und n jeweils für Zahlen von 0 bis 50 stehen, wobei die Summe aus m + n mindestens 4 betragen muß, Phenylalkylgruppen mit 1 bis 20 C-Atomen im Alkyl, einen fünf- oder sechsgliedrigen ungesättigten oder gesättigten heterocyclischen Ring mit bis zu drei Heteroatomen aus der Gruppe Stickstoff, Sauerstoff und Schwefel, welcher zusätzlich benzanelliert sein kann, wobei alle bei den Bedeutungen für R genannten Phenylkerne und heterocyclischen Ringe noch zusätzlich als Substituenten bis zu drei C₁- bis C₄-Alkylgruppen, Hydroxylgruppen, Carboxylgruppen, Sulfogruppen oder C₁ bis C₄-Alkoxycarbonylgruppen tragen können, oder einen Rest der Formel

steht, wobei A eine C₁- bis C₁₂-Alkylen-Brücke, vorzugsweise eine C₂- bis C₁₂-Alkylen-Brücke, oder eine chemische Bindung bezeichnet, und

M

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

als organische Cobuilder,

(C) 1 bis 40 Gew.-% anionische Tenside und

(D) 0,5 bis 30 Gew.-% nichtionische Tenside

enthält.Accordingly, a solid phosphate-free detergent formulation has been found which

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

(B) 0.1 to 25% by weight of one or more glycine-N, N-diacetic acid derivatives of the general formula I.

in the

R

C ₁ - to C ₃₀ -alkyl or C ₂ - to C ₃₀ -alkenyl, which up to 5 hydroxyl groups, formyl groups, C ₁ additionally carry as substituents - to C ₄ -alkoxy groups, phenoxy groups or C ₁ to C ₄ -alkoxycarbonyl wear and can be interrupted by up to 5 non-adjacent oxygen atoms, alkoxylate groups of the formula - (CH ₂ ) _k -O- (A ¹ O) _m - (A ² O) _n -Y, in which A ¹ and A ^{2 are} independent from each other denote 1,2-alkylene groups with 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 and m and n each represent numbers from 0 to 50, where the sum of m + n must be at least 4, phenylalkyl groups with 1 to 20 carbon atoms in the alkyl, a five- or six-membered unsaturated or saturated heterocyclic ring with up to three heteroatoms the group nitrogen, oxygen and sulfur, which may additionally be benzanellated, all of which are significant gene for R called phenyl nuclei and heterocyclic rings can additionally carry 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, or a radical of the formula

A is a C ₁ to C ₁₂ alkylene bridge, preferably a C ₂ to C ₁₂ alkylene bridge, or a chemical bond, and

M

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

as organic cobuilders,

(C) 1 to 40% by weight of anionic surfactants and

(D) 0.5 to 30% by weight of nonionic surfactants

contains.

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

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. SKS-6 (manufacturer: Hoechst). The Silicates can be in the form of their alkali metal, alkaline earth metal or ammonium salts are used, preferably as Na, Li and Mg silicates.

Amorphous silicates such as sodium metasilicate, which has a polymeric structure, or Britesil® H20 (manufacturer: Akzo) can also be used.

Suitable inorganic builders based on carbonate are Carbonates and hydrogen carbonates. These can be in the form of their alkali metal, Alkaline earth metal or ammonium salts can be used. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, used.

The components (A) mentioned can be used individually or in mixtures can be used with each other. Is of particular interest as inorganic builder component a mixture of aluminosilicate and carbonates, in particular from zeolites, especially zeolite A, and alkali metal carbonates, especially sodium carbonate, in the weight ratio from 98: 2 to 20:80, in particular from 85:15 to 40:60. In addition to this mixture, other components (A) may also be present.

steht.In a preferred embodiment, the compounds I used for component (B) are those in which R is C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ -alkenyl or a radical of the formula

stands.

In a particularly preferred embodiment, the compound I used is α-alanine-N, N-diacetic acid (R = CH ₃ ) and its alkali metal, ammonium and substituted ammonium salts.

Particularly suitable salts of this type are the sodium, potassium and ammonium salts, especially the trisodium, tripotassium and Triammonium salt and organic triamine salts with a tertiary Nitrogen atom.

In particular, the bases on which the organic amine salts are based come tertiary amines such as trialkylamines with 1 to 6 carbon atoms in alkyl, e.g. Trimethyl and triethylamine, methyldiethylamine or tricyclohexylamine, and trialkanolamines with 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine, tri-n-propanolamine or Triisopropanolamine.

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

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

In addition to methyl, straight-chain or branched alk (en) yl radicals, in particular C ₂ - to C ₁₇ -alkyl and alkenyl, in particular straight-chain radicals derived from saturated or unsaturated fatty acids, are suitable for the radical R. 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 iso-nonanoic acid), n-nonyl, n-decyl, n-undecyl, n-dodecyl, iso-dodecyl (derived from iso-tridecanoic acid), n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and n-heptadecenyl (derived from oleic acid ). Mixtures can also occur for R, in particular those which are derived from naturally occurring fatty acids and from synthetically produced technical acids, for example by oxosynthesis.

The C ₁ - to C ₁₂ -alkylene bridges A are primarily polymethylene groups of the formula - (CH ₂ ) _t -, in which t denotes a number from 2 to 12, in particular from 2 to 8, ie 1,2-ethylene, 1 , 3-propylene, 1,4-butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. Hexamethylene, octamethylene, 1,2-ethylene and 1,4-butylene are particularly preferred here. In addition, branched C ₁ - to C ₁₂ -alkylene groups can also occur, for. B. -CH ₂ CH (CH ₃ ) CH ₂ -, -CH ₂ C (CH ₃ ) ₂ CH ₂ -, -CH ₂ CH (C ₂ H ₅ ) - or -CH ₂ CH (CH ₃ ) -.

The C ₁ to C ₃₀ alkyl and C ₂ to C ₃₀ alkenyl groups can have up to 5, in particular up to 3, additional substituents of the type mentioned and can be interrupted by up to 5, in particular up to 3, non-adjacent oxygen atoms. Examples of such substituted alk (en) yl groups are -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ -CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₃ , -CH ₂ -O-CH ₂ CH ₃ , -CH ₂ -O-CH ₂ CH ₃ -OH, -CH ₂ -CHO, -CH ₂ -OPh, -CH ₂ -COOCH ₃ or -CH ₂ CH ₂ -COOCH ₃ .

Suitable alkoxylate groups are in particular those in which m and n each represent numbers from 0 to 30, especially from 0 to 15. A ¹ and A ² mean groups derived from butylene oxide and especially from propylene oxide and from ethylene oxide. Pure ethoxylates and pure propoxylates are of particular interest, but ethylene oxide-propylene oxide block structures can also occur.

As five or six-membered unsaturated or saturated heterocyclic rings with up to three heteroatoms from the group Nitrogen, oxygen and sulfur, which additionally gasoline and can be substituted by the designated radicals, is being brought up for consideration: Tetrahydrofuran, furan, tetrahydrothiophene, thiophene, 2,5-dimethylthiophene, Pyrrolidine, pyrroline, pyrrole, isoxazole, oxazole, Thiazole, pyrazole, imidazoline, imidazole, 1,2,3-triazolidine, 1,2,3- and 1,2,4-triazole, 1,2,3-, 1,2,4- and 1,2,5-oxadiazole, tetrahydropyran, Dihydropyran, 2H- and 4H-pyran, piperidine, 1,3- and 1,4-dioxane, morpholine, pyrazane, pyridine, α-, β- and γ-picoline, α- and γ-picoline, pyrimidine, pyridazine, pyrazine, 1,2,5-oxathiazine, 1,3,5-, 1,2,3- and 1,2,4-triazine, benzofuran, thionaphthene, Indoline, indole, isoindoline, benzoxazole, indazole, benzimidazole, Chroman, isochroman, 2H and 4H chromene, quinoline, isoquinoline, 1,2,3,4-tetrahydroisoquinoline, cinnoline, quinazoline, quinoxaline, Phthalazine and benzo-1,2,3-triazine.

N-H groups in the heterocyclic rings mentioned should if possible in derivatized form, for example as an N-alkyl group, available.

With substitution on the phenyl nuclei or the heterocyclic ones Rings preferably occur two (same or different) or especially a single substituent.

Examples of optionally substituted phenylalkyl groups and alkyl groups for R which carry heterocyclic rings are benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, o-, m- or p-hydroxybenzyl, o-, m- or p-carboxybenzyl, o-, m- or p-sulfobenzyl, o-, m- or p-methoxy- or -ethoxycarbonylbenzyl, 2-furylmethyl, N-methylpiperidin-4-ylmethyl or 2-, 3- or 4 - pyridinylmethyl.

With substitution on phenyl nuclei and also on heterocyclic ones Rings are preferably water-solubilizing groups such as hydroxyl groups, Carboxyl groups or sulfo groups.

The corresponding radicals for R listed above are also to be understood as examples of the C ₁ to C ₄ , C ₁ to C ₁₂ and C _{1 to} C ₂₀ alkyl groups mentioned.

Component (B) lies in the textile detergent formulation according to the invention preferably in an amount of 0.5 to 20 % By weight, in particular 1 to 15% by weight, especially 3 to 10% by weight in front.

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C9 to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by firstly using a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole 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 distribution can be obtained.

Other suitable anionic surfactants are alkane sulfonates such as C _{8 to} C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates and soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

Further suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) and alkyltoluenesulfonates.

Also suitable as anionic surfactants (C), C ₈ - to C ₂₄ olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkane sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol, fatty acid glycerol, alkylphenol polyglycol ether sulfates, paraffin sulfonates having approx. 20 to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids , Acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

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

Component (C) is preferably present in the textile detergent formulation according to the invention in an amount of 3 to 30% by weight, in particular 5 to 15% by weight. If C ₉ 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. Only one class of anionic surfactants can be used alone, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but mixtures of different classes can also be used, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Mixtures of different species can also be used within the individual classes of anionic surfactants.

Suitable nonionic surfactants (D) are, for example, alkoxylated C ₈ to C ₂₂ alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as surfactants. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. 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 distribution can be obtained.

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

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

Another class of nonionic surfactants are N-alkyl glucamides with C ₆ to C ₂₂ alkyl chains. Such compounds are obtained, for example, by acylation of reducing aminated sugars with corresponding long-chain carboxylic acid derivatives.

Block copolymers are also suitable as nonionic surfactants (D) from ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), polyhydroxy or Polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy- or N-aryloxy-polyhydroxy fatty acid amides, fatty acid amide ethoxylates, especially closed end groups, as well Fatty acid alkanolamide alkoxylates.

Component (D) is preferably present in the textile detergent formulation according to the invention in an amount of 1 to 20% by weight, in particular 3 to 12% by weight. Only one class of nonionic surfactants can be used alone, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but mixtures of different classes can also be used. Mixtures of different species can also be used within the individual classes of nonionic surfactants.

Because the balance between the types of surfactants mentioned is important for the effectiveness of the detergent formulation according to the invention is anionic surfactants (C) and nonionic surfactants (D) preferably in a weight ratio of 95: 5 to 20:80, in particular from 70:30 to 50:50.

In a preferred embodiment, the invention contains Textile detergent formulation in addition to component (B) 0.5 up to 20 wt .-%, in particular 1 to 12 wt .-% further organic Cobuilder (E) 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.

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

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

Aminopolycarbonsäuren wie z. B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure und Alkylethylendiamintriacetate;

Salze von Phosphonsäuren wie z. B. Hydroxyethandiphosphonsäure.

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

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, lactoboic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid and alkylethylenediamine triacetates;

Salts of phosphonic acids such. B. hydroxyethane diphosphonic acid.

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

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

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

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

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

can be polymerized.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, styrene, vinyl esters of C ₁ -C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ olefins, vinyl alkyl ethers having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) comprises (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ amines, N-vinylformamide and 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 4313909 known.

Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 100:90 bis 95:5, besonders bevorzugt solche im Gewichtsverhältnis 30:70 bis 90:10 mit Molmassen von 10000 bis 150000;

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

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

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

Copolymers of maleic acid and acrylic acid in a weight ratio of 100:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 10,000 to 150,000;

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

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

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623 and DE-A 4313909 are also suitable as components (E).

Suitable unsaturated carboxylic acids are, for example Maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, Methacrylic acid, crotonic acid and vinyl acetic acid and mixtures from acrylic acid and maleic acid, in quantities of 40 to 95 % By weight, based on the component to be grafted, grafted on become.

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

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein 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.

Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides are used, wherein 20 to 80 wt .-% monomers based on the graft component be used in the graft polymerization. For Grafting is preferably a mixture of maleic acid and Acrylic acid in a weight ratio of 90:10 to 10:90.

Examples of suitable polyglyoxylic acids as component (E) are described in EP-B 001004, US-A 5399286, DE-A 4106355 and EP-A 0656914. The end groups of the polyglyoxylic acids can be different Have structures.

Suitable as component (E) and modified polyamidocarboxylic acids Polyamidocarboxylic acids are known, for example, from EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.

Component (E) in particular also uses polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines. 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.

Suitable condensation products of citric acid as component (E) with hydroxycarboxylic acids or polyhydroxy compounds e.g. B. known from WO-A 93/22362 and WO-A 92/16493. Such Condensates containing carboxyl groups usually have molecular weights up to 10,000, preferably up to 5,000.

Also suitable as component (E) are ethylenediamine disuccinic acid, Oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.

Furthermore, in addition to components (B) and (E), oxidized Starches can be used as organic cobuilders.

In a further preferred embodiment, the Textile detergent formulation according to the invention additionally 0.5 up to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23 wt .-% bleach (F) in the form of percarboxylic acids, for. B. Diperoxododecanedicarboxylic acid or monoperoxophthalic acid, adducts of hydrogen peroxide on inorganic salts, e.g. Sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide to organic compounds, e.g. Urea perhydrate, or of inorganic peroxo salts, e.g. B. alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0 up to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 up to 8% by weight, bleach activators (G). With color detergents the bleach (F) (if available) usually without a bleach activator (G) used, otherwise bleach activators are usually used (G) with available.

• polyacylierte Zucker, z. B. Pentaacetylglucose;
• Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkalimetallsalze, z. B. Natrium-p-isononanoyloxy-benzolsulfonat oder Natrium-p-benzoyloxy-benzolsulfonat;
• N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, z. B. N,N,N',N' -Tetraacetyl-methylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z. B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mesyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z.B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetylhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z.B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z. B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhyrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, z.B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff;
• α-Acyloxy-polyacyl-malonamide, z. B. α-Acetoxy-N,N'-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• Benz-(4H) 1,3-oxazin-4-one mit Alkylresten, z. B. Methyl, oder aromatischen Resten z. B. Phenyl, in der 2-Position.

Suitable bleach activators (G) are:

• polyacylated sugars e.g. B. Pentaacetylglucose;
• Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;
• N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N' -Tetraacetyl-methylenediamine and -ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl -5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carbonamides, e.g. B. N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;
• N, N'-diacylsulfurylamide, e.g. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
• Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, e.g. B. benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, e.g. B. tetraacetylpropylene diurea;
• α-acyloxy polyacyl malonamides, e.g. B. α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromatic radicals such. B. phenyl, in the 2-position.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized ones Imines and sulfonimines, which are described for example in US-A 5 360 569 and EP-A 453 003. Particularly effective bleaching catalysts are manganese complexes, for example in the WO-A 94/21777 are described. Such connections are in If used in detergent formulations at most in amounts up to 1.5% by weight, in particular up to 0.5% by weight incorporated.

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

In a further preferred embodiment, the Textile detergent formulation according to the invention additionally 0.05 up to 4% by weight of enzymes (H). Preferably used in detergents Enzymes are proteases, amylases, lipases and cellulases. Of the Enzymes are preferably used in amounts of 0.1-1.5% by weight, in particular preferably 0.2 to 1.0% by weight of the made-up Enzyme added. Suitable proteases are e.g. B. Savinase and Esperase (Manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is z. B. Celluzym (manufacturer: Novo Nordisk). Also the Use of peroxidases to activate the bleaching system possible. One can use single enzymes or a combination of different ones Use enzymes. If necessary, the textile detergent formulation according to the invention also enzyme stabilizers, e.g. As calcium propionate, sodium formate or boric acids or their salts, and / or contain antioxidants.

• kationische Tenside, üblicherweise in einer Menge bis 25 Gew.-%, vorzugsweise 3 bis 15 Gew.-%, beispielsweise C₈- bis C₁₆-Alkyl-dimethylammoniumhalogenide oder langkettige Alkoxydimethylammoniumhalogenide;
• ampholytische Tenside, üblicherweise in einer Menge bis 15 Gew.-%, beispielsweise Derivate von sekundären oder tertiären Aminen, Alkyldimethylaminoxide oder Alkyl- oder Alkoxy-methylaminoxide;
• Vergrauungsinhibitoren und Soil-Release-Polymere, beispielsweise Polyester aus Polyethylenoxiden mit Ethylenglykol und/ oder Propylenglykol und aromatischen und/oder aliphatischen Dicarbonsäuren, Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder höherwertigen Alkoholen und Dicarbonsäuren, amphiphile Pfropf- oder Copolymere von Vinyl- und/oder Acrylestern auf Polyalkylenoxide oder modifizierte Cellulosen wie z. B. Methylcellulose, Hydroxypropylmethylcellulose oder Carboxymethylcellulose (CMC);
• Farbübertragungsinhibitoren, beispielsweise Homo- und Copolymerisate des Vinylpyrrolidons, des Vinylimidazols, des Vinyloxazolidons oder des 4-Vinylpyridin-N-oxids mit Molmassen von 15.000 bis 100.000 sowie vernetzte feinteilige Polymere auf Basis dieser Monomere;
• nichttensidartige Schaumdämpfer oder Schauminhibitoren, beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure;
• Komplexbildner (auch in der Funktion von organischen Cobuildern) ;
• optische Aufheller;
• Polyethylenglykole;
• Parfüme oder Duftstoffe;
• Füllstoffe;
• anorganische Stellmittel, z. B. Natriumsulfat;
• Konfektionierhilfsmittel;
• Löslichkeitsverbesserer;
• Trübungs- und Perlglanzmittel;
• Farbstoffe;
• Korrosionsinhibitoren;
• Peroxidstabilisatoren;
• Elektrolyte.

In addition to the main components (A) to (H) mentioned, the textile detergent formulation according to the invention can also contain the following further customary additives in the 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 -C ₁₆ -alkyldimethylammonium halides or long-chain alkoxydimethylammonium halides;
• ampholytic surfactants, usually in an amount of up to 15% by weight, for example derivatives of secondary or tertiary amines, alkyldimethylamine oxides or alkyl or alkoxymethylamine oxides;
• Graying inhibitors and soil release polymers, for example polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic and / or aliphatic dicarboxylic acids, polyesters from polyethylene oxides which are end group-capped with di- and / or higher-quality alcohols and dicarboxylic acids, amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides or modified celluloses such as. B. methyl cellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose (CMC);
• Color transfer inhibitors, for example homopolymers and copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone or 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000, and crosslinked, finely divided polymers based on these monomers;
• 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.

The textile detergent formulation according to the invention is solid, d. H. is usually powdered or granular or in Extrudate or tablet form.

The powder or granular detergents according to the invention can contain up to 60% by weight of inorganic adjusting agents. Sodium sulfate is usually used for this. Preferably however, the detergents according to the invention are low in adjusting agents and contain only up to 20 wt .-%, particularly preferably only up to 8% by weight of detergents, especially in the case of compact or ultra-compact detergents. The solid detergents according to the invention can have different bulk densities in the range of 300 to 1300 g / l, in particular from 550 to 1200 g / l. Modern compact detergents usually have high bulk densities and show a granulate structure. For the desired compression of the detergent the methods customary in technology can be used.

The textile detergent formulation according to the invention is after Manufactured customary methods and assembled if necessary.

By using the glycine-N, N-diacetic acid derivatives I as component (B) it is possible to reduce the amount of insoluble constituents in the builder system consisting of one or more inorganic Builders and one or more organic cobuilders, to reduce and thereby the solubility of the whole Buildersystems and thus also to improve the detergent, whereby the application properties (primary and Secondary washing capacity) can be maintained or even improved.

Typical compositions for compact heavy duty detergents and color detergents are given below (the percentages in the following and in the examples relate to the weight; the information in brackets for compositions (a) and (b) are preferred ranges):
(a) Composition of compact heavy duty detergent (powder or granular) 1-60% (8-30%) at least one anionic (C) and one nonionic surfactant (D) 5-50% (10-45%) at least one inorganic builder (A) 0.1-20% (0.5-15%) at least one organic cobuilder (B) and if necessary (E) 5-30% (10-25%) an inorganic bleaching agent (F) 0.1-15% (1-8%) a bleach activator (G) 0-1% (maximum 0.5%) a bleaching catalyst 0.05-5% (0.2-2.5%) a color transfer inhibitor 0.3-1.5% of a soil release polymer 0.1-4% (0.2-2%) Enzyme or enzyme mixture (H)

Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers
(b) Color detergent composition (powder or granular) 3 - 50% (8 - 30%) at least one anionic (C) and one nonionic surfactant (D) 10 - 60% (20 - 55%) at least one inorganic builder (A) 0 - 15% (0 - 5%) an inorganic bleaching agent (F) 0.05-5% (0.2-2.5%) a color transfer inhibitor 0.1-20% (1-8%) at least one organic cobuilder (B) and possibly (E) 0.2-2% Enzyme or enzyme mixture (H) 0.2-1.5% Soil release polymer

Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners, Perfume oils, foam attenuators, graying inhibitors, bleach stabilizers

Examples

In Table 2 are examples of compositions of modern compact detergent formulations A to M compiled. The Application test results refer to those in the Table 2 contained laundry detergent formulations A to C.

To test the application properties, the Detergent formulations A, B, and C are used. Formulations B and C contained the organic cobuilder of the invention α-D, L-alanine-N, N-diacetic acid (methylglycine-N, N-diacetic acid, MGDA). For comparison, the formulations analogous to B and C were used B and C, respectively, which did not contain an organic cobuilder.

Washing experiments were carried out with these formulations and both primary washability and incrustation inhibition certainly.

Washing conditions Primary washing power

Device: Launder-o-meter from Atlas, Chicago, U.S.A. Wash liquor: 250 ml Washing time: 30 minutes at 60 ° C Detergent dosage 4.5 g / l Water hardness: 3 mmol Ca: Mg 3: 1 Fleet ratio 1: 12.5 Test fabric: WFK 10D, WFK 20D (WFK-Testgewebe GmbH, D-41379 Brüggen-Bracht) EMPA 101, EPMA 104 (Eidgenössische Materialprüfanstalt, St. Gallen, Switzerland)

The washed test fabrics were washed with a photometer from Measure Datacolor (Elrepho® 2000). The are given in each case Total values of those on the individual test fabrics by multiple measurements average remission values obtained.

Washing conditions incrustation

Device: Launder-o-meter from Atlas, Chicago, U.S.A. Wash liquor: 250 ml Washing time: 30 minutes at 60 ° C Wash cycles: 15 Detergent dosage 4.5 g / l Water hardness: 4 mmol Ca: Mg 4: 1 Fleet ratio 1: 12.5 Test fabric: Cotton nettle fabric

The detergent formulations described in the table were each used to wash test fabrics made of cotton. The number of wash cycles was 15. After this number of washes, the ash content of the fabric was determined by ashing the test fabric at 700 ° C. in each case. Washing results Example No. formulation Zeolite A as a builder in [%] Na ₂ CO ₃ as a builder in [%] MGDA as cobuilder in [%] Ash [%] Primary washing capacity total remission in [%] 1 B 28.5 9.5 5 1.84 189.7 2 C. 24th 8th 8th 1.86 206.1 V1 A 36 12th - 2.86 178.7 V2 B 28.5 9.5 - 3.15 176.1 V3 C. 24th 8th - 3.80 166.7

The examples V1, V2 and V3 show that by reduction of the builder percentage by 10 to 16% the incrustation clearly increases and at the same time the primary washing power of the formulation worsens. You replace half of the reduced builder percentage by the Cobuilder MGDA according to the invention (Example 1 by 5% MGDA, Example 2 by 8% MGDA), then the incrustation inhibition and significantly improves the primary washing ability, one even surpasses that formulated with the complete builder system Comparative detergent A (V1).

The cobuilder according to the invention thus allows the insoluble fractions of the detergent formulations to be reduced, improvements in the primary detergent capacity and the incrustation inhibition being obtained at the same time.

Claims (8)

1. A solid phosphate-free textile detergent formulation, comprising

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

   (B) 0.1-25% by weight of one or more glycine-N,N-diacetic acid derivatives of the general formula I

   

   where

   R

   is C₁-C₃₀-alkyl or C₂-C₃₀-alkenyl, each of which may additionally carry as substituents up to 5 hydroxyl groups, formyl groups, C₁-C₄-alkoxy groups, phenoxy groups or C₁-C₄-alkoxycarbonyl groups and be interrupted by up to 5 non-adjacent oxygen atoms, or alkoxylate groups of the formula - (CH₂)_k-O- (A¹O)_m- (A²O)_n-Y, where A¹ and A² are, independently of one another, 1,2-alkylene groups having 2 to 4 carbon atoms, Y is hydrogen, C₁-C₁₂-alkyl, phenyl or C₁-C₄-alkoxycarbonyl, and k is 1, 2 or 3, and m and n are each from 0 to 50, where the total of m + n must be at least 4, or phenylalkyl groups having from 1 to 20 carbon atoms in the alkyl, a five- or six-membered unsaturated or saturated heterocyclic ring which has up to three hetero atoms from the group consisting of nitrogen, oxygen and sulfur and which can additionally be benzo-fused, it being possible for all the phenyl nuclei and heterocyclic rings mentioned in the meanings of R additionally to carry as substituents up to three C₁-C₄-alkyl groups, hydroxyl groups, carboxyl groups, sulfo groups or C₁-C₄-alkoxycarbonyl groups, or a radical of the formula

   

   where A is a C₁-C₁₂-alkylene bridge or a chemical bond, and

   M

   is hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium in the appropriate stoichiometric amounts,

   as organic cobuilders,

   (C) 1-40% by weight of anionic surfactants and

   (D) 0.5-30% by weight of nonionic surfactants.
2. A solid textile detergent formulation as claimed in claim 1, additionally comprising
   (E) 0.5-20% by weight of other organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids or phosphonic acids or salts thereof.
3. A solid textile detergent formulation as claimed in claim 1 or 2, additionally comprising

   (F) 0.5-30% by weight of bleaches in the form of percarboxylic acids, adducts of hydrogen peroxide onto inorganic salts or organic compounds or of inorganic peroxo salts and, where appropriate,

   (G) 0.1-15% by weight of bleach activators.
4. A solid textile detergent formulation as claimed in any of claims 1 to 3, additionally comprising
   (H) 0.05-4% by weight of enzymes.
5. A solid textile detergent formulation as claimed in any of claims 1 to 4, comprising as an inorganic builder component (A) a mixture of zeolite A and sodium carbonate in the ratio from 85:15 to 40:60 by weight.
6. A solid textile detergent formulation as claimed in any of claims 1 to 5, comprising as glycine-N,N-diacetic acid derivatives I for (B) those where R is C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl or a radical of the formula

   
7. A solid textile detergent formulation as claimed in any of claims 1 to 6, where the ratio of components (C) and (D) is from 95:5 to 20:80 by weight.
8. A solid textile detergent formulation as claimed in any of claims 1 to 7 with an apparent density of from 300 to 1,300 g/l.