DE19948670A1 - laundry detergent - Google Patents

Abstract

The invention relates to detergents, containing (a) anionic surfactants, non-ionic and/or amphoteric surfactants, (b) tetraalkyl ammonium compounds, and (c) phosphates, with the proviso that component (b) is present in quantities of between 1 and 20 % by weight.

Description

Field of the Invention

The invention is in the field of detergents and relates to preparations with an avi ending surfactant system.

State of the art

Detergents are available on the market that not only clean the laundry, but also soften it should give grip. Such preparations, which are often referred to as soft detergents, contain as finishing agents, as a rule, cationic surfactants of the tetraalkylammonium compound type, mostly together with layered silicates. Since the detergents are usually based on anionic surfactants, In the presence of cationic surfactants, undesirable salt formation easily occurs, which leads to Deactivation of some of the active washing components and also deposits on the company leads. As a result, there is a need for the manufacturer of soft dergents to find a balance to maintain and use only as much cationic surfactant in the recipe as this without significant salt balance is possible. As a rule, this amount is still less than 0.5% by weight. With such low stakes Concentrations is of course immediately clear why the soft detergents of the market have so far had little success are rich and usual liquid fabric softener, which is only in the rinse cycle, i.e. after the actual to be added to laundry, have so far not been able to displace.

Accordingly, the object of the present invention was to prefer new detergents to provide in the form of powders, granules, extrudates or agglomerates which the problem of salt formation between anionic and cationic surfactants is solved, so that with high washing performance, the use of larger amounts of cationic surfactants is possible and thus better fiber finish is achieved.

Description of the invention

The invention relates to detergents containing

• a) anionic surfactants, nonionic and / or amphoteric surfactants,
• b) tetraalkylammonium compounds, and
• c) phosphates

with the proviso that component (b) in amounts of 1 to 20, preferably 2 to 15, in particular whose 3 to 10 and particularly preferably 4 to 8 wt .-% is present.

Surprisingly, it was found that the detergents according to the invention have the ge meet the specified requirements in an excellent manner. In combination with non-ionic and / or Amphoteric surfactants not only show an improved tetraalkylammonium compound Soft handle, at the same time the tendency to salt formation with anionic surfactants is reduced, which the Her position of detergents makes possible that a higher Ka compared to the prior art have ionic surfactant content. In addition, in combination with phosphates as builders a special advantageous finishing effect observed by the addition of layered silicates and / or the use an anionic surfactant-free surfactant system based on nonionic and / or amphoteric surfactants, especially alk (en) yl oligoglycosides and / or betaines can be further improved.

Anionic surfactants

Typical examples of anionic surfactants which form component (a1) are soaps, alkylbenzene sulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl esters sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxyl mixtures ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, Fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as Acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. Provided the anionic surfactants contain polyglycol ether chains, these can be a conventional one but preferably have a narrow homolog distribution. Alkylbenes are preferred zolsulfonate, alkyl sulfates, soaps, alkanesulfonates, olefin sulfonates, methyl ester sulfonates and their Mixtures used.  

Preferred alkylbenzenesulfonates preferably follow the formula (I)

R-Ph-SO ₃ X (I)

in which R is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or Glucammonium stands. Of these, dodecylbenzene is particularly suitable sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in Form of sodium salts.

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II)

R ² O-SO ₃ Y (II)

in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols are Oxoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Finally, soaps are to be understood as meaning fatty acid salts of the formula (III)

R ³ CO-OX (III)

in which R ³ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, calcium prinic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid , Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Before preferably coconut or palm kernel fatty acid are used in the form of their sodium or potassium salts.

Nonionic surfactants

Typical examples of nonionic surfactants that can be used as component (a2) are fatty alcohols alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycols ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid-N-alkylglucamides, protein hydrolyzates (especially vegetable products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the contain nonionic surfactants polyglycol ether chains, these can be a conventional, preferably However, they have a narrow homolog distribution. Preferably fatty alcohol polygly colethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.

The preferred fatty alcohol polyglycol ethers follow the formula (IV)

R ⁴ O (CH ₂ CHR ⁵ O) _n H (IV)

in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{5 represents} hydrogen or methyl and n represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, Elaeo stearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)

R ⁶ CO- (OCH ₂ CHR ⁷ ) _m OR ⁸ (V)

in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and m is a number from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, calcium acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and behenic acid and behenic acid and behenic acid. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for. B. Calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI),

R ⁹ O- [G] _p (VI)

in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature, reference is made here to the documents EP-A1 0 301 298 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligo glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used: From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.1 2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, capric alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Amphoteric surfactants

Amphoteric surfactants that can be used as component (a3) are often referred to as betaines equated. It is known surfactants, mainly by carboxyalkylation, before preferably carboxymethylation of aminic compounds. Preferably who the starting materials with halocarboxylic acids or their salts, especially with sodium chlora acetate condensed, one mole of salt being formed per month of betaine. The addition of unsaturated carboxylic acids such as acrylic acid possible. To the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants is based on the contribution of U. Ploog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982). Further overviews of this Topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in Tens. Surf. Det. 23: 309 (1986), R. Bilbo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P. Ellis et al. in Euro Cosm. 1, 14 (1994).

Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (VII)

in which R ¹⁰ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ¹¹ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ¹² for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and Y for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, De cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C kyldimethylamin _12/14 -Kokosal, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl amine, oleyl dimethyl amine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

Carboxyalkylation products of amidoamines which follow the formula (VIII) are also suitable,

in which R ¹³ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ¹¹ , R ¹² , n and Y have the meanings given above. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, undoleic acid, arachene acid, arachene acid Erucic acid and its technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

The detergents can pre-comprise the surfactants which form component (a) in amounts of 1 to 50 preferably 5 to 25 and in particular 10 to 20 wt .-% - based on the detergent - contain.  

Tetraalkylammonium compounds

Tetraalkylammonium compounds used as component (b) are cationic surfactants in which the quaternary nitrogen is substituted by 4 alkyl radicals. The alkyl radicals can in turn also carry substituents, such as. B. hydroxyl groups or phenyl radicals. The quaternary nitrogen can also be part of a naphthenic ring system. Tetraalkylammonium connections that come into consideration in the sense of the invention preferably follow the formula (IX),

in which R ^{14 represents} a linear or branched, optionally hydroxyl-substituted alkyl radical having 6 to 22 carbon atoms or a benzyl radical, R ¹⁵ and R ¹⁶ independently of one another for an optionally hydroxyl-substituted alkyl radical having 1 to 22 carbon atoms, R ¹⁷ for an optionally hydroxyl-substituted alkyl radical having 1 up to 4 carbon atoms and Z represents halide, alkyl sulfate or alkyl phosphate. In view of the desired performance properties, it has proven to be particularly advantageous if the tetraalkylammonium compounds have one or two long-chain and two or three short-chain substituents, as is the case, for example, with dimethyldi stearylammonium chloride. Other particularly suitable compounds are cetyltrimethyl ammonium chloride (Dehyquart® A, Cognis Deutschland GmbH / Düsseldorf) and in particular hydroxy cetyl hydroxyethyl dimonium chloride (Dehyquart® E, Cognis Deutschland GmbH / Düsseldorf).

Phosphates

The detergents according to the invention can contain phosphates as builders (component c). Appropriate net are in particular the sodium salts of orthophosphates, pyrophosphates and in particular Tripolyphosphates. The phosphates in the ene preparations are preferably in amounts of 10 to 60, in particular 20 to 40 wt .-% - based on the agent - contain.

Auxiliaries and additives

Further preferred ingredients of the detergents according to the invention are additional inorganic and organic builder substances, the main inorganic builder substances being zeolites crystalline layered silicates and amorphous silicates are used. The amount of co-builder is there to count towards the preferred amounts of phosphates.  

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which is sold as VEGOBOND AX® (a commercial product from Condea Augusta S. p. A.) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from Is 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layer silicates are known for example from patent applications DE 23 34 899 A1, EP 0 026 529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Usable layered silicates are known, for example, from US 3,966,629, US 4,062,641, EP 0 026 529 A1 and EP 0 028 432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / compaction or by drying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 . The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202 A1, EP 0 427 349 A1, EP 0 472 042 A1 and EP 0 542 496 A1 and the international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0 150 930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029 wrote.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid). Suitable copolymeric poly Carboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous  Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 are described and as monomers preferably acrolein and acrylic have acidic acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups for example as described in European patent application EP 0 280 223 A1 can. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalalde hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. The preferred oil and fat dissolving components include for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Technology known polymers of phthalic acid and / or terephthalic acid or their deriva ten, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, ge rings contain amounts of neutral filler salts as well as colors and fragrances and the like.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADNT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0 525 239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0 446 982 B1 and EP 0 453 003 B1 known sulfonimines and / or bleach-boosting agents  transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0 272 030 A1 Complexes, the manganese complexes known from European patent application EP 0 693 550 A1, the manganese, iron, cobalt and copper known from European patent EP 0 392 592 A1 fer complexes and / or those in European Patent EP 0 443 651 B1 or the European Patent applications EP 0 0458 397 A1, EP 0 458 398 A1, EP 0 549 271 A1, EP 0 549 272 A1, EP 0 544 490 A1 and EP 0 544 519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glyco sylhydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially are particularly suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus ücheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic  acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Because the different cellulase types differ in their CMCase and avicelase activities the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme Granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. .

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. Here are what Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts poly merer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch ke or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Next Soluble starch preparations and starch products other than those mentioned above can be used the, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Prefers However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarb oxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 up to 5 wt .-%, based on the agent used.

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Next preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Wax-like compounds can be used as defoamers. As "waxy" sol che understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature temperature), preferably above 50 ° C and in particular above 70 ° C. The waxy Ent foaming agents are practically insoluble in water, d. H. at 20 ° C in 100 g of water solubility below 0.1% by weight. In principle, all known from the prior art wax-like defoamer substances can be included. Suitable wax-like compounds are in for example bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohol len as well as paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are used.

Suitable paraffin waxes are generally a complex mixture of substances without a sharp one Melting point. For characterization, one usually determines its melting range by Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or his Freezing point. This is the temperature at which the paraffin slowly slows down cooling changes from the liquid to the solid state. Thereby are complete at room temperature liquid paraffins, that is to say those with a solidification point below 25 ° C., are not according to the invention useful. For example, the Paraf known from EP 0 309 931 A1 can be used  finwax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax a solidification point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solid point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used, which in Solidify the range from 30 ° C to 90 ° C. It should be noted that it is solid even at room temperature Apparent paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C. Liquid content of less than 30% by weight, preferably from 5% by weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular from 40% by weight to 55% by weight, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached, is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. Appropriate nete fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as it is obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethy lendiamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Before pulled diamines are ethylenediamine and hexamethylenediamine. Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol portion of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol, and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, monostearate of glycerol, ethylene glycol and rat sorbitan, sorbitan Sorbitanmonolau, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax, which is a mixture of carnaubaic acid alkyl esters, often in combination with small amounts of free carnaubaic acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stea rinic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures as they are natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of be written fatty acids.

Dialkyl ethers may also be present as defoamers. The ethers can be asym be constructed metrically or symmetrically, d. H. two identical or different alkyl chains preferably contain 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i- octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point above Have 25 ° C, especially above 40 ° C.

Other suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained. One goes to their manufacture example of carboxylic acid magnesium salts, which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Publication DE 25 53 900 OS. Suitable fat ketones are those obtained by pyrolysis of the Ma magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid become.

Other suitable defoamers are fatty acid polyethylene glycol esters, preferably by ba sisch homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. In particular Ethylene oxide is added to the fatty acids in the presence of alkanolamines as catalyzes sators. The use of alkanolamines, especially triethanolamine, leads to an extremely selective one Ethoxylation of the fatty acids, especially when it comes to low ethoxylated verbin  to manufacture Within the group of fatty acid polyethylene glycol esters, those before moves that have a melting point above 25 ° C, especially above 40 ° C.

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture . The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminum silicates, water-soluble sheet silicates, alkali metal silicates, alkali metal sulfates, for example sodium sulfate, and alkali metal phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios of 80:20 to 40:60, in particular 75: 25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is called native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. As carrier materials, one or more of the compounds mentioned above can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.

Suitable silicones are conventional organopolysiloxanes, which contain finely divided silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0 496 510 A1. Are particularly preferred Polydiorganosiloxanes, which are known from the prior art. But it can also use siloxane cross-linked compounds are used, as they are known to the person skilled in the art under the name of silicon har ze are known. As a rule, the polydiorganosiloxanes contain finely divided silica, which is also sila can be kidneyed. Silica-containing dimethylpolysiloxanes are particularly suitable. Advantageously the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range of 5000 mPas up to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably on Trä germ materials applied. Suitable carrier materials are already in connection with the Par affine. The carrier materials are generally in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries. If desired, the final preparations can also contain inorganic salts as fillers or fillers contain, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular whose 1 to 5 wt .-% - based on agent - is included.  

Production of detergents

The detergents obtainable using the additives according to the invention can be in the form of Powders, extrudates, granules or agglomerates are produced or used. It can both universal and fine or color detergents, possibly in the form of com act compact or super compact. For the production of such agents, the corresponding ones are out methods known in the art. This means that the funds are preferred represents that various particulate components containing detergent ingredients are mixed together. The particulate components can be easily dried by spray drying Mixing or complex granulation processes, for example fluidized bed granulation become. It is particularly preferred that at least one surfactant-containing component by Wir granulation is produced. It can also be particularly preferred if aqueous Preparations of alkali silicate and alkali carbonate together with other detergents ingredients are sprayed in a drying device, with a drying at the same time Granulation can take place.

The drying device into which the aqueous preparation is sprayed can be any Act drying equipment. In a preferred procedure, drying is sprayed drying carried out in a drying tower. The aqueous preparations are in be Known way exposed to a drying gas stream in finely divided form. In patent publications The Henkel company developed an embodiment of spray drying with superheated steam described. The principle of work disclosed there is hereby expressly also the subject of present invention disclosure made. Reference is made here in particular to the following Relevant publications: DE 40 30 688 A1 and the further publications according to DE 42 04 035 A1; DE 42 04 090 A1; DE 42 06 050 A1; DE 42 06 521 A1; DE 42 06 495 A1; DE 42 08 773 A1; DE 42 09 432 A1 and DE 42 34 376 A1. This procedure has already been used in connection with the manufacturer of the defoamer grain presented.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step. The compacting the ingredients take place in a preferred embodiment of the invention in a press agglomerate process. The press agglomeration process to which the solid premix (dried base detergent) can be realized in various devices. Depending on The type of agglomerator used different press agglomeration divorced. The four most common press agglomes preferred in the context of the present invention ration processes are extrusion, roller pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred pressag within the scope of the present invention  Glomeration processes Extrusion, roll compacting, pelleting or tableting processes are.

All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced be liable. The tools can be used in all processes (with tableting with restrictions) heat up to higher temperatures or dissipate the shear forces Cool heat.

In all processes, one or more binders can be used as an aid to compaction. However, it should be made clear that the use of several different ones is always inherent Binders and mixtures of different binders is possible. In a preferred out embodiment of the invention, a binder is used that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C already completely as a melt lies. The binder must therefore be selected depending on the process and process conditions or the process conditions, especially the process temperature, - if a be correct binder is desired - be adapted to the binder.

The actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not so even correspond to the temperature of the melting point of the binder. In a preferred out In the embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, it is be prefers that the process temperature in the compression step is not more than 20 ° C above the melt temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or the softening temperature of the binder of 20 ° C is generally quite sufficient and even higher temperatures are no additional advantages effect parts. Therefore - especially for energy reasons - it is particularly preferred above, but as close as possible to the melting point or the upper temperature limit of the melting range of the binder. Such a temperature control has the white ter advantage that thermally sensitive raw materials, such as peroxy bleach such as Perbo Rat and / or percarbonate, but also enzymes, increasingly without serious loss of active ingredient ver can be worked. The possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between the mixing / homogenization of the Premix and the shape, allows an energetically very favorable and for the temperatu sensitive components of the premix extremely gentle process management, because the pre mixture is only exposed to the higher temperatures for a short time. In preferred press agglomerati  the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process ren temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. The duration is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more precise description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12,000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, can be used and such combinations advantageously more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a relative molecular weight between 3500 and 5000 sen. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular weight of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular mass ranges between 3000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as the sole binder, but in combination with others, especially in combination with polyethylene glycols.

The compacted material preferably has temperature immediately after it leaves the production apparatus temperatures do not exceed 90 ° C, with temperatures between 35 and 85 ° C especially before are moving. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment, the detergent according to the invention is extruded prepared, as for example in the European patent EP 0 486 592 B1 or interna tional patent applications WO 93/02176 and WO 94/09111 and WO 98112299 who described the. Here, a solid premix is extruded under pressure and the extrudate after exiting drawn from the hole shape by means of a cutting device to the predeterminable granule dimension cut. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastic under the pressure or under the entry of specific work softens and becomes extrudable. Preferred plasticizers and / or lubricants are surfactants and / or Po polymers. To explain the actual extrusion process, we hereby expressly refer to the above referenced patents and patent applications. The premix is preferably used preferably a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and Extruder pelletizing head can be heated to the predetermined extrusion temperature. Under the The premixing is sheared by the extruder screws under pressure, which is preferably at least is at least 25 bar, with extremely high throughputs depending on the device used but can also lie below, compressed, plasticized, in the form of fine strands through the perforated nozzles plate extruded in the extruder head and finally the extrudate by means of a rotating tee knife preferably reduced to approximately spherical to cylindrical granules. The hole The diameter of the perforated nozzle plate and the length of the strand cut are based on the selected granulate dimension matched. In this way, the production of granules is essentially uniform Predeterminable particle size, with the absolute particle sizes being specific may be adapted to the intended purpose. In general, particle diameters are up to maximum at least 0.8 cm preferred. Important embodiments see the production of uniform gra nulates in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio of the chipped primary granule latex is preferably in the range from about 1: 1 to about 3: 1. It is further preferred that to supply still plastic primary granulate to a further shaping processing step; there edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. At this stage, if desired, small Amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines. It is important to ensure that in only small amounts of fine grain are produced at this stage. A drying, which in the above called prior art documents is described as a preferred embodiment  subsequently possible, but not mandatory. It may just be preferred after Compaction step no longer drying. Alternatively, extrusions / grouting solutions in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the extruder of the Bepex. The temperature control in the transition region is preferred Screw, the pre-distributor and the nozzle plate designed so that the melting temperature of the bin at least the upper limit of the melting range of the binder is reached, preferably wise but is exceeded. The duration of the temperature influence lies in the compression area range of extrusion preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The detergents according to the invention can also be produced by means of roller compaction become. Here, the premix is deliberately defined between two smooth or with wells Formed rollers metered in and between the two rollers under pressure to form a sheet gene compactate, the so-called Schülpe, rolled out. The rollers practice on the premix high line pressure and can be additionally heated or cooled as required. In the Use of smooth rollers gives you smooth, unstructured sash bands, while through that Using structured rollers correspondingly structured slugs can be generated in which, for example, certain forms of the later detergent particles can be specified nen. The cuff band is subsequently cut into small pieces by a knock-off and crushing process broken pieces and can be processed in this way to granules, which by white Tere known surface treatment processes refined, especially in approximately spherical can be shaped. The temperature of the roller compaction is also pressing tools, i.e. the rollers, preferably at a maximum of 150 ° C., preferably at a maximum 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work in roller compacting with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the bandage by lying. It is further preferred that the duration of the temperature exposure in the compressor area of the smooth rollers or with recesses of a defined shape maximum 2 mi grooves and is in particular in a range between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by pelleting. Here the premix is applied to a perforated surface and by means of a pressure-giving body pressed through the holes with plasticization. In conventional embodiments of pellet presses the premix is compressed under pressure, plasticized, using a rotating roller in the form of finer Strands pressed through a perforated surface and finally with a knock-off device to Gra crushed granules. Here are the most varied configurations of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well concave or convex ring matrices through which the material by means of one or more pressure rollers  is pressed through. The press rollers can also be conical in the plate devices, in the annular devices can die and press roller (s) in the same or opposite direction have. An apparatus suitable for carrying out the method is described, for example, in German described in DE 38 16 842 A1. The ring matrices disclosed in this document The press consists of a rotating ring die with penetrating press channels and at least one with the inner surface of the press roller, which supplies the die space Presses material through the press channels into a material discharge. Here are ring die and press roll can be driven in the same direction, resulting in reduced shear stress and thus lower temperatures increase of the premix is feasible. Of course, it can also be used for pelleting heatable or coolable rollers are worked to a desired temperature of the premix adjust. The pelleting temperature is also the temperature of the pressing tools Pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work with the whale zenkompaktierung with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the binder.

Examples Examples 1 to 12, comparative examples V1 to V4

In a washing machine (Miele W 918) 3.5 kg of standard laundry and a terry towel (which is pre-treated twice with a Univer sal detergent was washed) in a full wash at 90 ° C. 84 g each Detergents of the composition according to Table 1 were immediately in the Ein given washing chamber. After the wash, the terry towel was left at room temperature for 24 hours dried and then subjected to a panel test of 20 people. Each person awarded one Grade between 1 and 4 (1 = hard; 4 = very soft). The rating for the products, which can also be found in Table 1.

Table 1

Detergent composition and soft handle

Claims (10)

1. Detergent containing

• a) anionic surfactants, nonionic and / or amphoteric surfactants,
• b) tetraalkylammonium compounds, and
• c) phosphates with the proviso that component (b) is present in amounts of 1 to 20% by weight.

2. Detergent according to claim 1, characterized in that they contain anionic surfactants, selected from the group consisting of alkylbenzenesulfonates, alkylsulfates, Soaps, alkanesulfonates, olefin sulfonates and methyl ester sulfonates. 3. Detergent according to claims 1 and / or 2, characterized in that it is nonionic Contain surfactants that are selected from the group that is formed from fatty alcohol polygly colethers, alkoxylated fatty acid lower alkyl esters and alkyl and / or alkenyl oligoglycosides. 4. Detergent according to at least one of claims 1 to 3, characterized in that it contain amphoteric surfactants which are selected from the group formed by Alkylbe taines, alkylamido betaines and imidazolinium betaines. 5. Detergent according to at least one of claims 1 to 4, characterized in that it the surfactants which form component (a) in amounts of 1 to 50% by weight, based on the Detergent - included. 6. Detergent according to at least one of claims 1 to 5, characterized in that it contains tetraalkylammonium compounds of the formula (IX),
in which R ^{14 represents} a linear or branched, optionally hydroxy-substituted alkyl radical having 6 to 22 carbon atoms or a benzyl radical, R ¹⁵ and R ¹⁶ independently of one another an optionally hydroxyl-substituted alkyl radical having 1 to 22 carbon atoms, R ¹⁷ for a possibly hydroxy-substituted alkyl radical having 1 up to 4 carbon atoms and Z represents halide, alkyl sulfate or alkyl phosphate. 7. Detergent according to at least one of claims 1 to 6, characterized in that it contain as tetraalkylammonium compounds hydroxycetyl hydroxyethyl dimmonium chloride. 8. Detergent according to at least one of claims 1 to 7, characterized in that it the tetraalkylammonium compounds in amounts of 0.1 to 10% by weight, based on the composition, contain. 9. Detergent according to at least one of claims 1 to 8, characterized in that it Contain tripolyphosphates. 10. Detergent according to at least one of claims 1 to 9, characterized in that it the phosphates in amounts of 10 to 60 wt .-% - based on the agent - contain.