EP0863976A1

EP0863976A1 - Glycine-n,n-diacetic acid derivatives used as organic co-builders in textile washing-agent formulations

Info

Publication number: EP0863976A1
Application number: EP96938087A
Authority: EP
Inventors: Birgit Potthoff-Karl; Beate Ehle; Angelika Funhoff; Dieter Kiessling; Richard Baur; Thomas Greindl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-11-18
Filing date: 1996-11-05
Publication date: 1998-09-16
Anticipated expiration: 2016-11-05
Also published as: DE59606967D1; US5994290A; AU7564996A; DE19543162A1; WO1997019159A1; JP4361604B2; ATE201439T1; EP0863976B1; ES2157465T3; JP2000500519A

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

GLYCIN-N, N-DI-ACETIC ACID DERIVATIVES AS ORGANIC COBUI LDER IN TEXTILE DETERGENT FORMULATIONS

5

description

The present invention relates to a solid textile detergent formulation from inorganic builders based on silicate, alumosilicate, carbonate and / or phosphate, glycine-N, N-diacetic acid derivatives as organic cobuilders and anionic and non-ionic surfactants .

Conventional powder detergents for textiles contain large amounts of poorly or insoluble builders (scent substances), such as zeolites or silicates, which are necessary in order to achieve a high primary and secondary washing power. This high proportion of components which are insoluble in the wash liquor also severely affects the overall solubility of the detergent formulation.

The object was to provide a solid textile detergent formulation with improved solubility of the builder system without adverse effects, in particular on the primary detergent capacity.

WO-A 94/29421 (1) describes the use of Glycm-N, N-dies - acetic acid derivatives as biodegradable complexing agents for alkaline earth and heavy metal ions and others. known in the washing and cleaning sector. So it is mentioned there that such

Glycιn-N, N-dιessigsaure derivatives can generally be used as complexing agents or as builders in powder detergent formulations for textile washing.

35 In Japanese Laid-Open Publications 1980/157695 (2) and

1980/160099 (3) describes solid detergent compositions for textile washing which contain N, N-bis (carboxymethyl) amino acids such as N, N-bis (carboxymethyl) alanine, surfactants, sodium metasilicate and, as a further bullder component, imidobissulfates.

40

Accordingly, a solid 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, carbonates and / or phosphates, (B) 0.1 to 25% by weight of one or more Glycm-N, N-diacid-acidic derivatives of the general formula I

CH ₂ COOM

MOOC CH N (I)

CH ₂ COOM

m the

additionally carry as substituents up to 5 hydroxyl groups, formyl groups, Ci to C ₄ alkoxy groups, phenoxy groups or Cχ-bιs C ₄ alkoxycarbonyl groups and can be interrupted by up to 5 non-adjacent oxygen atoms, alkoxylate groups of the formula - (CH ₂ ) _k -0- (A ¹ 0) _m - (A ² 0) _n -Y, in which A ¹ and A ² independently of one another have 1.2 alkylene groups

Denote 2 to 4 carbon atoms, Y denotes hydrogen, Ci to C ₂ alkyl, phenyl or Ci to C ₄ alkoxycarbonyl and k stands for the number 1, 2 or 3 and m and n each stand for numbers from 0 to 50, where the sum of m + n must be at least 4, phenyl alkyl groups with 1 to 20 C atoms in alkyl, a five- or six-membered unsaturated or saturated heterocyclic ring with up to three hetero atoms from the group nitrogen, oxygen and sulfur , which may be additionally be benzofused, all Phe in the meanings mentioned for R nylkerne and heterocyclic rings additionally to carry as substituents up to three Ci to C ₄ groups -Alkyl¬, groups hydroxyl, carboxyl, sulfo or Ci to C ₄ -alkoxycarbonyl can wear, or a residue of the formula

COOM

I CH ₂ COOM

A CH N

CH ₂ COOM stands, wherein A denotes a Ci to Cχ ₂ alkylene bridge, preferably a C ₂ to Cχ ₂ alkylene bridge, or a chemical bond, and

M denotes 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 JU wt. - ^ nonionic surfactants

included.

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

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 partly 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, di-silicates or layered silicates, e.g. B. SKS-6 (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 polymer structure, or Britesil® H20 (manufacturer: Akzo) can also be used.

Suitable carbonate-based inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, are preferably used. Common phosphates as inorganic builders are polyphosphates such as. B. pentasodium phosphate.

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

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

COOM

| CH ₂ COOM - A — CH— N ^

CH ₂ COOM

stands.

In a particularly preferred embodiment, the compound I used is α-alanine-N, N-dietic 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, in particular the trisodium, tin and triammonium salts, and organic triamm salts with a tertiary nitrogen atom.

The bases on which the organic amm salts are based are special tertiary ames such as trialkylamines with 1 to 6 carbon atoms in the alkyl, e.g. Trimethyl- and triethylamine, methyldiethylamm or tncyclohexylamm, and tπalkanolamm with 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine, tri-n-propanolamm or trnsopropanolamm, into consideration.

Calcium and magnesium salts are used in particular as alkaline earth metal salts. Both the racemates of the compounds I and the two enantiomers with respect to the α-C atom in the glycine framework can be used.

In addition to methyl, straight-chain or branched alk (en) yl radicals, in particular C ₂ - to Cχ- ₇ alkyl and alkenyl, in particular straight-chain radicals derived from saturated or unsaturated fatty acids, are suitable for the radical R. Examples of individual R radicals are: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, see. -Butyl, tert-butyl, n-pentyl, isopentyl, 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 derived from naturally occurring fatty acids and from synthetically produced technical acids, for example by oxo synthesis.

The ci to Cχ ₂ 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, hepta methylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. Hexamethylene, octamethylene, 1,2-ethylene and 1,4-butylene are particularly preferred here. Besides kön¬ but nen branched Cι ^~ to Cχ ₂ alkylene occur such. 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 Ci to C ₃ o-alkyl and C ₂ - to C ₃ o-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 his. Examples of such substituted alk (en) yl groups are -CH ₂ OH, -CH ₂ CH ₂ OH _, -CH ₂ CH ₂ -0-CH _3, -CH ₂ CH ₂ -0-CH ₂ CH ₂ -0-CH ₃ , -CH ₂ -0-CH ₂ CH _3, -CH ₂ -0-CH ₂ CH ₃ -0H, -CH ₂ -CHO, -CH ₂ -OPh, -CH ₂ -C00CH 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 ones are of particular interest Propoxylates, but also ethylene oxide-propylene oxide block structures can occur.

The following are considered as five- or six-membered unsaturated or saturated heterocyclic rings with up to three heteroatoms from the group nitrogen, oxygen and sulfur, which can additionally be benzene fused and substituted by the designated radicals:

Tetrahydrofuran, furan, tetrahydrothiophene, thiophene, 2, 5-dimethylthiophene, pyrrolidine, pyrroline, pyrrole, isoxazole, oxazole, thiazole, pyrazole, imidazole, imidazole, 1, 2, 3-tiazolidm, 1,2,3- and l, 2, 4 -Irid / üi, 1,2,3-, 1,2,4- and 1,2,3 üxcidictzoi, tetra hydropyran, dihydropyran, 2H and 4H pyran, piperidine, 1,3 and 1,4-dioxane , Morpholine, pyrazane, pyridm, α-, ß and γ-picolm, α- and γ-picoline, pyrimidine, pyridazm, pyrazine, 1,2,5 oxathiazm, 1,3,5, 1,2,3- and 1 , 2,4 triazine, benzofuran, thionaphthene, indolm, indole, isomdolm, benzoxazole, indazole, benzimidazole, chroman, isochroman, 2H and 4H chromium, chmolm, isochmolm, 1,2,3,4 tetrahydroisochmolm, cmnolm, quinazoline, quinoxaline , Phthalazm and benzo 1, 2, 3 - triazine.

N H groups in the heterocyclic rings mentioned should preferably be in de-derivatized form, for example as an N-alkyl group.

In the case of substitution on the phenyl nuclei or the heterocyclic rings, preferably two (identical or different) or in particular an individual substituent occur.

Examples of optionally substituted phenylalkyl groups and heterocyclic rings-bearing alkyl groups for R smd 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-methylpiperidm-4 -ylmethyl or 2, 3 or 4 pyridmylmethyl.

When substituted on phenyl nuclei and also on heterocyclic rings, water-solubilizing groups such as hydroxyl groups, carboxyl groups or sulfo groups preferably occur.

The corresponding radicals for R listed above are also to be understood as examples of the Ci to C ₄ -, Ci to C _X2 - and Ci to C ₂ o-alkyl groups mentioned. Component (B) is preferably present in the textile detergent formulation according to the invention in an amount of 0.5 to 20% by weight, in particular 1 to 15% by weight, especially 3 to 10% by weight.

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols with 8 to 22, preferably 10 to 18 carbon atoms, e.g. B. Cg to Cn alcohol sulfates, Cι ₂ - to Cχ ₄ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated Cg DIS c ₂₂ AiKonoie (AlKyietnerbuirace) DZW αeren losli ehe salts. Compounds of this type are prepared, for example, by firstly using a Cg. to C ₂₂ -, preferably a Cio to Ciβ alcohol z. 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 with all propylene oxide and, if appropriate, butylene oxide. Also suitable are those alkoxylated Cs to C ₂₂ -AI alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated C _ß - to C ₂₂ alcohols can

Containing ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or 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 alkanesulfonates such as Cs to C ₂₄ , preferably Cχo to Cig alkanesulfonates and soaps such as the Na and K salts of Cs to C ₂₄ carboxylic acids.

Other suitable anionic surfactants are C ₉ to C ₂ linear AI alkylbenzenesulfonates (LAS) and alkyltoluenesulfonates

Also suitable as anionic surfactants (C), Cβ to _C24 olefin sulfonates and disulfonates, which ken mixtures of AI and hydroxyalkane sulfonates or disulfonates represent kon NEN, alkyl ester sulfonates, sulfonated polycarboxylic acids, Alkylgly cermsulfonate, Fettsaureglycermestersulfonate, Alkylphenolpo lyglykolethersulfate, paraffin sulfonates with about 20 to approx. 50 C atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl amber acid, alkenyl amber stone acids or their half esters or half amides, alkyl sulfo succinic 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 added to the detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as e.g. B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Component (C) is preferably present in the textile detergent formulation according to the invention in an amount of 3 to 30% by weight, in particular b to 1b% 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 can also be distinguished within the individual classes of anionic surfactants. species are used.

Examples of suitable nonionic surfactants (D) are alkoxylated Cg-bis C ₂₂ alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added can be used as tenides. 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 alkyl phenol alkoxylates such as alkyl phenol ethoxylates with C 6 to C ₄ alkyl chains and 5 to 30 moles of alkylene oxide units. Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.

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

Also suitable as nonionic surfactants (D) are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, especially end-capped, and 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 are used alone, in particular only alkoxylated Cg - C ~ ₂₂ alcohols, but one can also use mixtures of verεchiedenen classes. Mixtures of different species can also be used within the individual classes of nonionic surfactants.

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

In a preferred embodiment, the textile detergent formulation according to the invention contains, in addition to component (B), 0.5 to 20% by weight, in particular 1 to 12% by weight, of further organic cobuilders (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.

Suitable low molecular weight carboxylic acids or phosphonic acids for (E) are for example: C ₄ - to C ₂ o-Dι / -Tri and -Tetracarbonsauren such as. B. amber acid, propane carboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ to Cie alkyl or alkenyl radicals;

C ₄ to C ₂ o-hydroxycarboxylic acids such as. B. malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactoboic acid and sucrose mono-, di- and tπcarbonsaure;

Aminopolycarboxylic acids such as. B. Nitπlotπessigsaure, ß Alanin diestsigsaure, ethylenediammetetraacetic acid, Sermdiessigsaure, Isosermdieεsigεaure and Alkylethylenediammtriacetate;

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

Suitable oligomeric or polymeric carboxylic acids for (E) smd, for example:

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

Co and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers

from group (1) m amounts of up to 95% by weight from group (11) m amounts of up to 60% by weight and from group (111) m amounts of up to 20% by weight

can be polymerized.

Suitable unsaturated C ₄ - Cg dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

The group (1) includes monoethylenically unsaturated C ₃ C _ß -monocarboxylic acids such as. B. acrylic acid, methacrylic acid, Crotonεaure and vinyl acetic acid. Acrylic acid and methacrylic acid from group (1) are preferably used.

Group (11) includes monoethylenically unsaturated

C ₂ -C ₂₂ olefins, Vmylalkylether with C _τ C ₈ alkyl groups, styrene, Vmyleεter of Ci-Cs carboxylic acids, (meth) acrylamide and Vmyl pyrrolidone. From group (11), preference is given to using C ₂ -C ₆ olefins, methyl alkyl ethers with C ₁ -C ₄ alkyl groups, vinyl acetate and methyl propionate. The group (m) includes (meth) acrylic esters of C _± to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of Ci-Cs amines, N vinylformamide and vmylimidazole.

5 If the polymers of group (ii) contain Vmyl ester in an empolymerized form, they can also be partially or completely hydrolyzed to Vmyl alcohol structural units. Suitable co and terpolymers are known, for example, from US A 3887806 and DE A 4313909. 10

Copolymers of dicarboxylic acids are preferably suitable for component (E):

Copolymers of maleic acid and acrylic acid in a weight ratio of 15 100: 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 methyl ester emer Ci C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 20 (acrylic acid + methyl ester) to 95 (maleic acid): 10 (acrylic acid + methyl ester), the weight ratio of acrylic acid to vinyl esters can vary in the range from 30:70 to 70:30;

Copolymers of maleic acid with C ₂ -Cs olefins in a molar ratio of 25 40:60 to 80:20, copolymers of maleic acid with ethylene,

Propylene or isobutene in a molar ratio of 50:50 particularly preferably smd.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, see US Pat. No. 5,227,446, DE-A 4415623 and DE-A 4313909, are also suitable as component (E).

Suitable unsaturated carboxylic acids include, for example, 35 maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid as well as mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted. 0

For modification, up to 30% by weight, based on the component to be grafted, of additional monoethylenically unsaturated monomers can also be present in polymerized form. Suitable modifying monomers are the above-mentioned monomers of groups 5 (ii) and (m). Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulms or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, amino sorbitol and N-alkyl glucam 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 Ci C ₂₂ alcohols, cf. US A 5756456.

From this group, grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used, 20 to 80% by weight of monomers based on the graft component being used in the graft polymerization. A mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used for the grafting.

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

Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as component (E) 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 diams. Polyaspartic acids which are prepared in acids containing phosphorus and modified with Ce C ₂₂ mono or dicarboxylic acids or modified with C ₆ -C ₂₂ mono or diams are particularly preferably used.

As component (E) suitable condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds smd z. B. known from WO-A 93/22362 and WO-A 92/16493. Such condensates containing carboxyl groups usually have molar masses of up to 10,000, preferably up to 5,000.

Also suitable as component (E) are ethylenediammdiberns, rock acid, oxydibernstemsaic acid, ammopolycarboxylates, aminopolyalkylenephosphates and polyglutamates. In addition to components (B) and (E), oxidized starches can also be used as organic cobuilders.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight, of bleaching agent (F) in the form of percarboxylic acids, for . B. di-peroxododecanedicarboxylic acid or monoperoxophthalic acid, adducts of hydrogen peroxide with inorganic salts, e.g. Sodium perboate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide with organic compounds, e.g. Urea perhydrate, or from anorgamsciien peroxosalzen, e.g. B. alkali metal persulfates, or peroxodisulfates, optionally in combination with 0 to 15 wt.%, Preferably 0.1 to 15 wt.%, In particular 0.5 to 8 wt.%, Bleach activators (G). In the case of color laundry detergents, the bleach (F) (if present) is generally used without a bleach activator (G), otherwise bleach activators (G) are usually present.

Suitable bleach activators (G) are:

polyacylated sugars e.g. B. Pentaacetylglucose;

- Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for. B. sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;

N, N-diacylated and N, N, N ', N' - tetraacylated ames, e.g. B. N, N, N ', N' -Tetraacetyl-methylenediamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidm or 1, 3 -diacylated hydantoins such as 1, 3 -diacetyl- 5, 5 -dimethylhydantantom;

- 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;

0, N, N-tπε-substituted hydroxylammes, e.g. O-benzoyl -N, N-suc-cmylhydroxylamine, O-acetyl-N, N-succmyl-hydroxylamine or 0, N, N-triacetylhydroxylamine;

- N, N '-diacyl-sulfurylamide, e.g. B. N, N '-dimethyl-N, N' -diacetyl-εulfurylamide or N, N '-diethyl -N, N'-dipropionyl-εulfurylamide; Triacylcyanurates, for example triacetylcyanurate or tnbenzoylcyanurate;

Carbonεaureanhydπde, z. B. benzoic anhydride, m-chlorobenzoic anhydride or Phthalsaureanhyπd;

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

Tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2.5 diketopiperazms, e.g. 1.4 diacetyl 2.5 dike topiperazm;

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

α-acyloxy polyacyl malonamides, e.g. B. α acetoxy-N, N 'diacetyl malonamide;

Diacyl-dioxohexahydro 1, 3, 5-triazines, e.g. B. 1,5-diacetyl 2,4 dioxohexahydro-1,3,5 triazine;

Benz- (4H) 1, 3-oxazm-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 bleaching activators can optionally also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized inks and sulfonimme, which are described, for example, in US Pat. No. 5,360,569 and EP-A 453,003. Particularly effective bleaching catalysts in manganese complexes, which are described, for example, in WO-A 94/21777. When used in the detergent formulations, such compounds are incorporated at most in amounts of up to 1.5% by weight, in particular up to 0.5% by weight.

In addition to the described bleaching system comprising bleaching agents, bleach activators and, if appropriate, bleaching catalysts, this is also the case for the textile detergent formulation according to the invention

Use of systems with enzymatic peroxide release or photo-activated bleaching systems is conceivable.

In a further preferred embodiment, the textile detergent formulation according to the invention additionally contains 0.05 to 4% by weight of enzymes (H). Enzymes preferably used in detergents, such as proteases, amylases, lipases and cellulases. Of the Enzymes are preferably added in amounts of 0.1-1.5% by weight, in particular preferably 0.2-1.0% by weight, of the prepared enzyme. Suitable proteases are e.g. B. Savmase and Es perase (manufacturer: Novo Nordisk). A suitable lipase is e.g. B. Lipolaεe (manufacturer: Novo Nordisk). A suitable cellulose is e.g. B. Celluzym (manufacturer: Novo Nordisk). Peroxidases can also be used to activate the bleaching system. You can use single enzymes or a combination of different enzymes. If necessary, the textile detergent formulation according to the invention can also enzyme stabilizers, e.g. As calcium propionate, Natπumformiat or boric acids or their salts, and / or Oxidationsverhmderer contain.

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 m an amount up to 25 wt%, preferably 3 to 15 wt%, for example C _s to C ₁₅ alkyl or dimethylammoniumhalogenide dimethylammoniumhalogenide long-chain alkoxy..;

ampholytic surfactants, usually in an amount of up to 15% by weight, for example derivatives of secondary or tertiary amines, alkyldimethylammoxides or alkyl or alkoxy methylammoxides;

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 one-end-capped polyethylene oxides with di- and / or high-quality alcohols and dicarboxylic acids, amphiphilic graft or copolymers and / or acrylic esters on polyalkylene oxides or modified celluloses such. B. methyl cellulose, hydroxypropyl methyl cellulose or carboxymethyl cellulose (CMC);

Dye transfer inhibitors, for example homo and copolymeates of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone or 4-vinyl pyridm-N-oxide with molar masses from 15,000 to 100,000 and cross-linked polymer particles based on these monomers;

non-surfactant-like foam steamers or foam inhibitors, for example organopolysiloxanes and their mixtures with rrikrofemer, 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;

ruiiscoffe;

inorganic adjusting agents, e.g. B. sodium sulfate;

Assembly aids;

Solubility enhancer;

Opacifying and pearlescent agents;

Dyes;

- corrosion inhibitors;

Peroxide stabilizers;

Electrolytes.

The textile detergent formulation according to the invention is solid, i. H. is usually in powder or granule form 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. However, the detergents according to the invention are preferably low in detergents and contain only up to 20% by weight, particularly preferably only up to 8% by weight of detergents, in particular in the case of compact or ultra-compact detergents. The solid detergents according to the invention can have different rubble densities in the range from 300 to 1300 g / l, in particular from 550 to 1200 g / l. Modern compact laundry detergents generally have high rubble densities and show a granular structure. The processes customary in the art can be used for the desired compression of the detergents. The textile detergent formulation according to the invention is produced by customary methods and, if appropriate, is made up.

By using the glycine N, N-diacetic acid derivatives I 5 as component (B) it is possible to reduce the amount of insoluble constituents in the builder system, consisting of one or more organic builders and one or more organic cobuilers thereby improving the solubility of the entire builder system and thus also of the detergent, with the application properties (primary and

Secondary washing capacity) can be maintained or even improved.

Typical compositions for compact full detergents and color detergents are given below (the percentages 15 in the following and in the examples relate to the weight; the details in brackets for the compositions (a) and (b) and preferred ranges):

(a) Composition compact heavy duty detergent (powder or granular 20 lat)

1 60% (8 30%) of at least one anionic (C) and one non-ionic surfactant (D)

25 5 50% (10 45%) of at least one inorganic builder (A)

0.1-20% (0.5 15% of at least one organic cobuilder (B) and possibly (E)

30 5 30% (10 25%) of an inorganic bleaching agent (F)

0.1 15% (1-8%) of a bleach activator (G)

0 1% (at most 0.5%) of a bleaching catalyst

35

0.05 5% (0.2 2.5%) of a color transfer inhibitor

0.3 1.5% of a soil release polymer

40 0.1 4% (0.2-2%) enzyme or enzyme mixture (H)

Other common additives:

Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfumes, foam vaporizers, graying inhibitors, bleach stabilizers (b) Color detergent composition (powder or granular for

3 - 50% (8 30%) of at least one anionic (C) and one nonionic surfactant (D)

10 60% (20 - 55%) of at least one inorganic builder (A)

0 15% (0 5%) of an inorganic bleaching agent (F)

0.05-5% (0.2 2.5%) of a color transfer inhibitor

0.1 20% tl 6-s) at least one organic cobuilder (B) and if necessary (E)

0.2 2% enzyme or enzyme mixture (H)

0.2 1.5% soil release polymer

Other usual additives

Sodium sulfate, complexing agents, phosphonates, optical brighteners, perfumes, foam vaporizers, graying inhibitors, bleach stabilizers

Examples

In Table 2, examples of compositions of modern granular detergent formulations A to M are compiled. The application test results relate to the textile detergent formulations A to C contained in Table 2.

Detergent formulations A, B and C were used to test the application properties. Formulations B and C contained the organic cobuilder according to the invention α D, L alanine N, N-diacetic acid (methylglycine-N, N-diacetic acid, MGDA). For comparison, the formulations B and C, which did not contain any organic cobuilder, were prepared analogously to B and C.

Washing experiments were carried out with these formulations, and both the primary washing capacity and the incrustation mixing were determined.

Washing conditions Primary washability

Device: Launder-o meter from Atlas, Chicago,

United States Waεchf soldered: 250 ml washing time: 30 min. At 60 ° C.

Detergent dosage 4.5 g / l

Water hardness: 3 mmol Ca: Mg 3: 1 liquor ratio 1: 12.5 test fabric: WFK IOD, WFK 20D (WFK-Teεtgewebe GmbH,

D-41379 Brüggen-Bracht)

EMPA 101, EPMA 104 (Federal Material Testing Institute, St. Gallen, Switzerland)

The washed test fabrics were measured with a photometer from Datacolor (Elrepho® 2000). The sum values of the individual püfy fabrics obtained by multiple measurements are given in each case by means of remission mean values obtained by multiple measurements.

Washing conditions incrustation

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

U.S. washing liquor: 250 ml washing time: 30 min at 60 ° C washing cycles: 15

Detergent dosage 4.5 g / l

Water hardness: 4 mmol Ca: Mg 4: 1 liquor 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 washing 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.

Table 1

Washing results

Examples VI, V2 and V3 show that by reducing the proportion of builder by 10 to 16%, the incrustation increases significantly and at the same time the primary washing power of the formulation deteriorates. If one replaces half of the reduced proportion of the builder with the Cobuilder MGDA according to the invention (example 1 with 5% MGDA, example 2 with 8% MGDA), then the increment inhibition and the primary washing power are significantly improved, and even that is exceeded with complete Buildersystem formulated comparative detergent A (VI).

The cobuilder according to the invention thus makes it possible to reduce the insoluble proportions of the detergent formulations, while at the same time improving the primary washing ability and the incrustation inhibition.

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Claims

1. Solid detergent formulation containing

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

(B) 0.1 to 25% by weight of one or more Glycm-N, N-dιessig- εäure derivatives of the general formula I.

R

I CH ₂ C00M

MOOC CH N ^(i;

CH ₂ COOM

m the

R for Ci to C ₃ o-alkyl or C _{2 to} C ₃ o alkenyl, which additionally as substituents up to 5 hydroxyl groups, formyl groups, Ci to C ₄ alkoxy groups, phenoxy groups or Ci to C ₄ -alkoxycarbonyl groups and can be interrupted by up to 5 non-adjacent oxygen atoms, alkoxylate groups of the formula in which A ¹ and A ² independently denote 1,2 -alkylene groups with 2 to 4 carbon atoms, Y hydrogen, Ci bis

Cχ ₂ alkyl, phenyl or Ci to C ₄ alkoxycarbonyl means and k stands for the number 1, 2 or 3 and m and n each stand for numbers from 0 to 50, the sum of m + n being at least 4 must, phenyl - alkyl groups with 1 to 20 C atoms in the alkyl, a five- or six-membered unsaturated or saturated heterocyclic ring with up to three hetero atoms from the group nitrogen, oxygen and sulfur, which can additionally be benzanellated, where all phenyl nuclei and heterocyclic rings given the meanings for R additionally as substituents up to three C 1 -C ₄ -alkyl

groups, hydroxyl groups, carboxyl groups, sulfo groups or Ci to C ₄ alkoxycarbonyl groups, or a radical of the formula COOM i CH ₂ COOM A CH N CH ₂ COOM

ε stands, where A denotes a Ci-bi-C ₂ alkylene bridge or a chemical bond, and

as organic cobuilders,

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

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

2. Solid textile detergent formulation according to claim 1, additionally containing

(E) 0.5 to 20% by weight of further organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids or phosphonic acids or their salts.

3. Solid textile detergent formulation according to claim 1 or 2, additionally containing

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

(G) 0.1 to 15% by weight bleach activators.

Solid textile detergent formulation according to claims 1 to 3, additionally containing

(H) 0.05 to 4% by weight of enzymes.

5. Solid textile detergent formulation according to claims 1 to 4, containing as an inorganic builder component (A) a mixture of zeolite A and sodium carbonate in a weight ratio of 85:15 to 40:60. 6. Solid textile detergent formulation according to claims 1 to 5, containing as glycine-N, N-diacetic acid derivatives I for (B) those in which R for Ci to C ₂ cralkyl, C ₂ - to C ₂ o- Alkenyl or a radical of the formula

COOM

I CH ₂ COOM A CH N CH ₂ COOM

stands..

7. Solid textile detergent formulation according to claims 1 to 6, in which the components (C) and (D) are in a weight ratio of 95: 5 to 20:80.

8. Solid textile detergent formulation according to claims 1 to 7 with a bulk density of 300 to 1300 g / l.