DE102007038456A1 - Use of polycarbonate, polyurethane and/or polyurea-polyorganosiloxane compounds or their acid addition compounds and/or salts to improve the cleaning efficiency of laundry detergents during washing textiles - Google Patents

Abstract

Use of polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds (I) or their acid addition compounds and/or salts to improve the cleaning efficiency of laundry detergents during washing textiles, is claimed. Use of polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds of formula (-Y 1>-A-(C=O)-A-) (I) or their acid addition compound and/or salts to improve the cleaning efficiency of laundry detergents during washing textiles, is claimed. Either A : S, O or NR 1>; and Y 1>bivalent to polyvalent, preferably tetravalent, optionally saturated or aromatic up to 1000C hydrocarbon containing one or more NR 2>, N +>R 2>R 3> (both preferred), O, (CO), NH, 2-1000 polyorganosiloxane unit with silicon atom (optionally substituted), preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); or Y 1>A : nitrogen containing heterocyclic ring; R 1>H, optionally saturated up to 40C aromatic hydrocarbon containing one or more O, (CO), NH, NR 2>, preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); R 2>optionally saturated up to 40C aromatic hydrocarbon containing one or more O, (CO), NH, preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000); and R 3>optionally saturated up to 100C aromatic hydrocarbon containing one or more O, (CO), NH, a bivalent residue, which forms cyclic structures within the Y 1>, preferably oligoethoxy and/or oligopropoxy (where its oligomerization degree is preferably 2-60) or oligoethylene imine (where its oligomerization degree is preferably 10-150000). Provided that: in formula (I) A, Y 1>, R 1>, R 2>, R 3> are not same when at least one of the remainders of Y 1> is polyorganosiloxane unit with 2-1000 silicon atom. Independent claims are included for: (1) use of dirt removing active agents comprising [1,3]-dioxolan-2-one compound of formula (IV) or [1,3]-diazepan-2-one compound of formula (V) and/or a polymer which is obtained by the reaction of a polymer substrate (that modifies the functional group of hydroxy-, primary and secondary amino- group) with (IV) or (V) to the cleaning efficiency of laundry detergents when washing textiles; (2) method for washing of textiles in detergents and the dirt removing active agents of polycarbonate-, polyurethane- and/or polyurea compound comprising at least a structural element of formula (-Y 1>-A-(C=O)-A-) (I) or their acid addition compound salts; and (3) method for washing of textiles in a detergents and the dirt removing active agents comprising [1,3]-dioxolan-2-one compound of formula (IV) or [1,3]-diazepan-2-one compound of formula (V) and/or the polymer. R : 1-12C-alky; X : CO-CH=CH 2, CO-C(CH 3)=CH 2, CO-O-aryl, 2-6C-alkylene-SO 2-CH=CH 2 or CO-NH-R1a; R1a : 1-30C-alkyl, 1-30C-haloalkyl, 1-30C-hydroxyalkyl, 1-6C-alkyloxy-1-30C-alkyl, 1-6C-alkylcarbonyloxy-1-30C-alkyl, amino-1-30C-alkyl, mono- or di(1-6C-alkyl)amino-1-30C-alkyl, ammonio-1-30C-alkyl, polyoxyalkylene-1-30C-alkyl, polysiloxanyl-1-30C-alkyl, (meth)acryloyloxy-1-30C-alkyl, sulfono-1-30C-alkyl, phosphono-1-30C-alkyl, di(1-6C-alkyl)-phosphono-1-30C-alkyl, phosphonato-1-30C-alkyl, di(1-6C-alkyl) phosphonato-1-30Calkyl or a saccharide; and k : greater than 0. Provided that: in formula (IV) when k is 1, X has the above variable or when k is greater than 1 X is: (i) polyamine bounded with ((CO)-NH) or (ii) polymer skeleton bounded with (CO)-, NH-2-6C-alkylene-O(CO)- or (CO)-O-2-6C-alkylene-O(CO)- or (iii) polymer skeleton bounded with (CO)-polysiloxanyl-1-30C-alkyl-groups. [Image] .

Description

The The present invention relates to the use of certain soil release agents Active ingredients to enhance the cleaning performance of detergents when washing textiles and especially bleach-containing Detergents and cleaning agents, which such soil release Contain active ingredients.

Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as "soil repellents". For example, from the US patent US 4,136,038 the soil release ability of methyl cellulose is known. The European patent application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose. From the European patent application EP 0 213 730 Textile treatment agents are known which contain cationic surfactants and nonionic cellulose ethers with HLB values of 3.1 to 3.8. The US patent US 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially consists of C ₁₀ - to C ₁₃ -alkyl sulfate and up to 5 wt .-% C ₁₄ alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C ₁₅ and higher. The US patent US 4,174,305 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially consists of C ₁₀ - to C ₁₂ -alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C ₁₃ and higher. The European patent EP 0 271 312 relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (having DS 1.5 to 2.7 and molecular weights of 2,000 to 100,000) such as methylcellulose and ethylcellulose, with weight ratio of peroxygen bleaching agent (based on the active oxygen content of the bleaching agent) of 10: 1 to 1 : 10 should be used. The European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives. Are explicitly disclosed with the latter only hydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose, as well as - in the examples - the methyl hydroxyethyl cellulose Tylose ^® MH50, the hydroxypropyl methyl cellulose Methocel ^® F4M, and hydroxybutyl methylcellulose. From the European patent EP 0 948 591 B1 For example, a detergent in liquid or granular form is known which imparts textile appearance benefits such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or enhanced softness to fabrics and textiles washed therewith, and from 1 to 80% by weight of surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether having a molecular weight of 10,000 to 2,000,000, wherein the modification in the presence of optionally oligomerized (degree of oligomerization up to 20 ) Ethyleneoxy or 2-propyleneoxy ether units and C _8-24 alkyl substituents and the alkyl substituents must be present in amounts of 0.1-5 wt .-%, based on the cellulose ether material.

Because of their chemical similarity to polyester fibers in textiles from this material particularly effective dirt removal wealthy Active ingredients are copolyesters, the dicarboxylic acid units, Include alkylene glycol units and polyalkylene glycol units.

Soil release Copolyester of the type mentioned as well as their use in detergents have been known for a long time.

For example, the German Offenlegungsschrift describes DT 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German patent application DT 22 00 911 relates to detergents containing nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German Offenlegungsschrift DT 22 53 063 are called acidic textile finishing agents containing a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units are molecular weights from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are in the German patent specification DE 28 57 292 described. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 be used in detergents. The European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 For example, methyl or ethyl group-end capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer are known. The European patent EP 241 984 relates to a polyester which in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units. From the European patent EP 241 985 are known polyester containing in addition to oxyethylene groups and terephthalic acid units 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and endgruppenverschlossen with C ₁ - to C ₄ alkyl groups are. The European patent EP 253 567 refers to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95. From the European patent application EP 272 033 are at least partially by C ₁₄ alkyl or acyl radicals end-capped polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units known. The European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C ₂₄ glycol units. The German patent application DE 26 55 551 describes the reaction of such polyesters with isocyanate group-containing polymers and the use of the polymers thus prepared against the repulping of dirt during the washing of synthetic fibers. From the German patent DE 28 46 984 Detergents are known which comprise, as a soil release polymer, a reaction product of a polyester having a terminal isocyanate group-containing prepolymer obtained from a diisocyanate and a hydrophilic nonionic macrodiol.

The have polymers known from the state of the art the disadvantage that they are especially for textiles that are not or at least not for the most part polyester exist, have no or only insufficient effectiveness. One However, a large part of today's textiles is made of cotton or cotton-polyester blends, so a need for greasy soiling on especially such textiles better effective soil release agents consists.

Surprisingly was found to accomplish this task through the use of certain polycarbonate, Polyurethane and / or polyurea-polyorganosiloxane compounds can be solved.

The invention relates to the use of a soil release agent selected from the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds containing at least one structural element of the formula (I): -YA- (C = O) -A- (I), where each A independently is selected from S, O and NR ¹ ,
Y is selected from bivalent to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (excluding the carbon atoms of any polyorganosiloxane unit optionally included) containing one or more May contain groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit having 2 to 1000 silicon atoms,
R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and having one or more groups selected from -O-, - (CO) -, -NH- and -NR ² - can contain
R ^{2 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and which may contain one or more groups selected from -O-, - (CO) - and -NH-,
R ^{3 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups selected from -O-, - (CO) - and -NH-, or is a divalent radical which forms cyclic structures within the radical Y, or one or both of which can form Y adjacent radicals A with the radical Y between them, a nitrogen-containing heterocyclic radical,
and in the entire compound not all radicals A or Y or R ¹ or R ² or R ³ given in formula (I) must be identical, with the proviso that in the entire compound at least one of the radicals Y is a polyorganosiloxane unit 2 to 1000 silicon atoms, or their acid addition compounds and / or salts to enhance the cleaning performance of detergents in the washing of textiles.

links of the general formula (I) can be obtained by reacting diisocyanates, Bis-chloroformates or amides or Phosgene containing the structural element Y thiols, alcohols or amines. To obtain polymeric structures have these structural element Y having starting compounds at least 2 of the said functional groups. As end groups compounds come into consideration that are otherwise the structural element Y, but only monofunctional.

Among the preferred polycarbonate and / or polyurethane-polyorganosiloxane compounds are those which contain at least one structural element of the formula (II) or (III): -AYA- (CO) -OZ- (CHORO) -ZO- (CO) - (II), -AYA- (CO) -O- (CHCH ₂ OH) -ZO- (CO) - (III), in which A and Y have the meanings mentioned above and
Z is selected from the divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon radicals having 1 to 12 carbon atoms. These structural elements can be obtained by ring opening of cyclic carbonates (carbonic acid esters of vicinal diols) with the thiols, alcohols or amines containing the structural element Y.

The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound preferably has the structural element of the formula (I) several times in succession, the multiply occurring in each case corresponding radicals A or Y or Z or R ¹ or R ² or R ^{3 may be the} same or different.

Of the Term acid addition compound means a salt type Compound formed by protonation of basic groups in the molecule, in particular the optionally present amino groups, for example by reaction with inorganic or organic acids can be obtained. The acid addition compounds can used as such or under conditions of use optionally form the compounds defined above.

If the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound contains moieties - (N ⁺ R ² R ³ ) -, common counter anion ions, such as halide, hydroxide, sulfate, carbonate, are present in order to ensure charge neutrality.

When in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds present polyorganosiloxane structural element is preferably the structure - (SiR ⁴ ₂ O) _p - (SiR ⁴ ₂₎ -, wherein R ⁴ is a straight chain, cyclical or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 20 carbon atoms, and p = 1 to 999. The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds preferably contain on average at least two, in particular at least three, of said polyorganosiloxane structural elements. R ⁴ is preferably a straight-chain or cyclic or branched, saturated or unsaturated or aromatic C ₁ - to C ₂₀ -, in particular C ₁ - to C ₉ -hydrocarbon radical, particularly preferably methyl or phenyl, and p is especially 1 to 199, particularly preferred 1 to 99. In a preferred embodiment, all radicals R ^{4 are the} same.

preferred polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds are linear, that is, there are all Y units in the structural element of the formula (I) each divalent radicals. According to the invention but also includes branched compounds wherein at least one Y is trivalent or polyvalent, preferably tetravalent, then that branched structures with linear repeating structures form from structural elements of the formula (I).

In a further embodiment, in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound used according to the invention, at least one of the Y units according to the structural element of the formula (I) has a grouping -NR ² - and / or at least one of the Y units according to structural element of the formula (I) a grouping - (N ⁺ R ² R ³ ) - on. R ² and R ³ are preferably methyl groups.

A further embodiment relates to the multiple regular occurrence of -O-groupings in at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I), preferably in the form of oligoethoxy and / or oligopropoxy groups their degrees of oligomerization are preferably in the range of 2 to 60.

In a further preferred embodiment, at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I) contains oligoethylenimine groups whose degrees of oligomerization are in particular in the range from 10 to 15 000.

The preparation of compounds having structural elements of the formula (I) starting from diisocyanates is disclosed in a German Patent Application filed on the same day by Momentive Performance Materials. Reactive cyclic carbonates and ureas, processes for their preparation and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described.

One Another object of the invention is a method for washing of textiles containing a detergent and a soil release agent Active ingredient used. This procedure can be manual or preferably by means of a conventional household washing machine be executed. It is possible, in particular bleach-containing detergents and soil release agents To use active ingredient simultaneously or in succession. The simultaneous Application can be particularly advantageous the use of a detergent, which the dirtablösevermögenden Contains active substance.

Especially pronounced is the washing performance enhancing Effect of the active ingredients to be used according to the invention for multiple use, that is especially for removal of soiling of corresponding textiles already at Presence of the active ingredient has been washed and / or aftertreated were before they were stained. In connection with the aftertreatment it should be pointed out that the designated positive aspect can also be realized by a washing process, in which the textile after the actual washing process, with the help a detergent containing a said active ingredient can, but in this case also be free of this, is running, with an aftertreatment medium, for example in the context of a Softening step, which according to the invention to containing active ingredient is brought into contact. Even with this procedure occurs at the next wash, even if desired, again a detergent without an active ingredient to be used according to the invention is used, the washing performance enhancing effect of Active ingredients to be used according to the invention. This one is significantly higher than one is when using a conventional SRP drug.

The Active ingredients used in the invention are as portrayed easy to produce and ecological as well as toxicologically harmless. They lead to a significant better detachment of especially grease and cosmetics soiling on textiles, including those made of cotton or cotton-containing Tissue than this when used previously for this purpose known compounds is the case. Alternatively you can at constant fat removal capacity significant Saving amounts of surfactants.

The Use according to the invention can be carried out as part of a Washing process carried out such that the active ingredient of a detergent-containing Fleet added or preferably the active ingredient as part of a Bring detergent into the fleet. Another object of the The invention is therefore a detergent which has one described above Active ingredient containing the structural element of Fornel (I).

The Use according to the invention in the context of a laundry aftertreatment process can be done in such a way that the active ingredient of the rinse separately added, after using a particular Bleach-containing detergent was used for washing or as part of the laundry treatment agent, especially a softener, brings. In this aspect According to the invention, said detergent can also be used according to the invention but can also be free of this be.

Laundry detergent, the an active ingredient to be used according to the invention contained or used together with this or in the inventive methods are used, can all the usual ingredients of such Contain agents that are not undesirable with Interact with the active substance essential to the invention. Preferably the active substance defined above is added in amounts of 0.01% by weight to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% incorporated in detergent.

Surprisingly has been found that such agents have the effect of certain influence other detergent and cleaning agent ingredients positively and that, conversely, the effect of the soil-release agent by certain other detergent ingredients in addition is reinforced. These effects occur especially with bleaches, in enzymatic agents, in particular proteases and lipases, at water-soluble inorganic and / or organic builders, in particular based on oxidised carbohydrates or polymeric polycarboxylates, in synthetic anionic surfactants of the sulfate and sulfonate type, and in Dye transfer inhibitors, for example vinylpyrrolidone, Vinylpyridine or vinylimidazole polymers or copolymers or corresponding Polybetainen, on, which is why the use at least one of the said further ingredients together with according to the invention the active ingredient is preferred.

One Agent which is to be used according to the invention Contains or is used together with active ingredient or in the process according to the invention is used, preferably contains bleach Peroxygen base, in particular in quantities of 5% by weight to 70 wt .-%, and optionally bleach activator, in particular in amounts ranging from 2% to 10% by weight. The considered The bleaching agents which are used are preferably those in detergents usually used peroxygen compounds such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, Hydrogen peroxide, alkali perborate, as tetra- or monohydrate may be present, percarbonate, perpyrophosphate and persilicate, the usually present as alkali salts, especially as sodium salts. Such bleaching agents are in detergents which are used in accordance with the invention Active ingredient, preferably in amounts up to 25 wt .-%, in particular up to 15% by weight and more preferably from 5% by weight to 15% by weight, in each case based on total resources, available, in particular Percarbonate is used. The optional component the bleach activator usually includes used N- or O-acyl compounds, for example several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated Hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can to avoid the interaction with the per compounds in the Storage coated in a known manner with hell substances or granulated, with the aid of carboxymethyl cellulose granulated tetraacetylethylenediamine with average particle sizes from 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or particulate form trialkylammonium acetonitrile is particularly preferred. In detergents are such bleach activators preferably in amounts of up to 8% by weight, in particular of 2% by weight to 6 wt .-%, each based on the total agent included.

In a preferred embodiment includes a according to the invention used according to the invention or used in the process according to the invention Nonionic surfactant selected from fatty alkyl polyglycosides, Fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, Fettsäurepolyhydroxyamiden and / or ethoxylation and / or Propoxylation products of fatty alkylamines, vicinal diols, Fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2% by weight to 25% by weight.

A further embodiment of such means the presence of synthetic anionic surfactant from the sulfate and / or Sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, Sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range of 2% by weight to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates, in which the alkyl or alkenyl group 8 to 22, in particular 12 has up to 18 C atoms. These are usually not individual substances, but cuts or mixtures. Of these, those are preferred whose proportion of compounds with longer-chain residues in the range of 16 to 18 carbon atoms 20 wt .-% is.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of Alko Hole is usually between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

nonionic Surfactant is in agents which use a according to the invention Soilrelease contain active ingredient used in the invention or used in the process according to the invention are, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 wt .-%, with amounts in the upper part This area is more likely to be found in liquid detergents and particulate detergents are more preferable contain lower amounts of up to 5 wt .-%.

The Means may instead or additionally Surfactants, preferably synthetic anionic surfactants of the sulfate or Sulfonate type, such as alkylbenzenesulfonates, in quantities preferably not more than 20% by weight, in particular of 0.1 wt .-% to 18 wt .-%, each based on the total agent included. As particularly suitable for use in such agents Synthetic anionic surfactants are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which is an alkali, ammonium or alkyl or Carry hydroxyalkyl-substituted ammonium ion as a counter cation, to call. Preference is given to the derivatives of the fatty alcohols in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional one Sulfation reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl- or hydroxyalkyl-substituted ammonium bases getting produced. Among the usable surfactants of the sulfate type Also include the sulfated alkoxylation of the mentioned alcohols, so-called ether sulfates. Preferably included such ether sulfates 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule. To the suitable anionic surfactants of the sulfonate type belong by the conversion of fatty acid esters α-sulfoester obtainable with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 to 6 C atoms, preferably 1 to 4 C atoms, derivative sulfonation products, and the sulfo fatty acids resulting from formal saponification thereof.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

If desired, the agents may also contain betaines and / or cationic surfactants which, if present, preferably in amounts of 0.5 wt .-% to 7 wt .-% are used. Under these For example, the esterquats discussed below are particularly preferred.

In Another embodiment includes the means water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline Alkali silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, especially in amounts in the range of 2.5% to 60% by weight.

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, especially citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and Mischpoly mers of these, the may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

such Organic builders are preferably in amounts up to 40 wt .-%, in particular up to 25 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%. Quantities close to the stated upper limit are preferably in pasty or liquid, especially water-containing agents used.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these are the detergent-quality crystalline aluminosilicates, in particular zeolite NaA and optionally NaX. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Amorphous alkali metal silicates are available, for example under the name Portil ^® commercially. Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

additionally To said inorganic builder may be further water-soluble or water-insoluble inorganic substances in the compositions, which is an active ingredient to be used according to the invention contained, used together with this or in accordance with the invention Be used method be included. Suitable in this Connection the alkali carbonates, alkali hydrogen carbonates and alkali sulfates as well as their mixtures. Such additional inorganic Material may be present in amounts up to 70% by weight.

additionally the agents may be more common in detergents and cleaners Contain ingredients. These optional ingredients include in particular enzymes, enzyme stabilizers, complexing agents for heavy metals, for example, aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, Polyphosphonic acids and / or aminopolyphosphonic acids, Foam inhibitors, for example organopolysiloxanes or paraffins, Solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which are used in accordance with the invention Active ingredient, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brightener, in particular compounds of the Class of substituted 4,4'-bis (2,4,6-triamino-s-triazinyl) stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, in particular Aminoalkylenphosphonsäuren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors contain, wherein said weight fractions refer to total funds.

Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or suspended Form before.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP ^®, Savinase ^®, Esperase ^®, Maxatase ^®, Optimase.RTM ^®, Alcalase ^{®, ®} or Durazym Maxapem ^®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are for example available under the names Lipolase ^®, Lipozym ^®, Lipomax® ^®, Lipex ^{®, ®} Amano lipase, Toyo Jozo ^® lipase, Meito ^® lipase and Diosynth lipase ^® commercially. Suitable amylases are commercially available for example under the name Maxamyl ^®, Termamyl ^®, Duramyl ^® and Purafect ^® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the name Celluzyme ^{®, ®} and Carezyme Ecostone® ^®.

To the customary, especially in liquid resources existing Enzyme stabilizers include amino alcohols, for example Mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower Carboxylic acids, boric acid or alkali borates, Boric acid-carboxylic acid combinations, boric acid esters, Boronic acid derivatives, calcium salts, for example, Ca-formic acid combination, Magnesium salts, and / or sulfur-containing reducing agents.

To the suitable foam inhibitors include long-chain soaps, especially behen soap, fatty acid amides, paraffins, waxes, Microcrystalline waxes, organopolysiloxanes and mixtures thereof In addition, microfine, optionally silanated or may otherwise contain hydrophobized silica. For use in particulate agents are such Foam inhibitors preferably on granular, water-soluble Bound carrier substances.

In A preferred embodiment is a means into which incorporated according to the invention to be used is, particulate and contains up to 25 wt .-%, in particular from 5% by weight to 20% by weight of bleaching agent, in particular alkali percarbonate, up to 15% by weight, in particular 1% by weight to 10% by weight, of bleach activator, From 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2 wt .-% to 8 wt .-% of water-soluble organic Builder, 10% to 25% by weight synthetic anionic surfactant, 1% by weight to 5 wt .-% of nonionic surfactant and up to 25 wt .-%, in particular 0.1% by weight to 25% by weight of inorganic salts, in particular alkali metal carbonate and / or bicarbonate.

In Another preferred embodiment is a means in the active ingredient to be used according to the invention is incorporated, liquid and contains 10 wt .-% to 25 wt .-%, in particular 12 wt .-% to 22.5 wt .-% nonionic Surfactant, 2% by weight to 10% by weight, in particular 2.5% by weight to 8% by weight synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 4.5% by weight to 12.5% by weight of soap, 0.5% by weight to 5% by weight, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight to 1% by weight Complexing agent for heavy metals, such as phosphonate, and beside optionally contained enzyme, enzyme stabilizer, color and / or Perfume water and / or water-miscible solvent.

Possible is also the use of a combination of an invention essential Dirt-releasing active substance with a dirt-removing wealthy Polymer of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of Detergents when washing textiles. Also within the scope of the invention Agent and the method according to the invention are such combinations with a particular polyester-active soil release wealthy Polymer possible.

The known polyester-active soil release polymers which can be used in addition to the active compounds of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ₁₁ -) _a ) _b OH may be present. Therein, Ph represents an o-, m- or p-phenylene radical containing 1 to 4 substituents selected from Al Cyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyester obtainable from these, both monomer diol units -O- (CHR ₁₁ -) _a O- and also polymeric diol units - (O- (CHR ¹¹ -) _a ) _b O- are present. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH in which R ^{11 has} the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.

If desired, These may be polyester as described above also be endgruppenverschlossen, with alkyl groups as end groups with 1 to 22 carbon atoms and esters of monocarboxylic acids in Question come. The ester groups bound by end groups may be alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 C-atoms, in particular 5 to 18 C-atoms, based. These include valeric acid, caproic acid, enanthic acid, Caprylic acid, pelargonic acid, capric acid, Undecanoic acid, undecenoic acid, lauric acid, Lauroleic acid, tridecanoic acid, myristic acid, Myristoleic acid, pentadecanoic acid, palmitic acid, Stearic acid, petroselinic acid, petroselaidic acid, oleic acid, Linoleic acid, linoleic acid, linolenic acid, Peoic acid, arachidic acid, gadoleic acid, Arachidonic acid, behenic acid, erucic acid, brassidic acid, Clupanodonic acid, lignoceric acid, cerotic acid, Melissinic acid, benzoic acid containing 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms can carry, for example, tert-butylbenzoic acid. The End groups can also hydroxymonocarboxylic acids with 5 to 22 C atoms on which, for example, hydroxyvaleric acid, Hydroxycaproic acid, ricinoleic acid, its hydrogenation product Hydroxystearic acid and o-, m- and p-hydroxybenzoic acid belong. The hydroxymonocarboxylic acids can in turn via their hydroxyl group and their carboxyl group be connected to each other and thus several times in an end group available. Preferably, the number of hydroxymono carboxylic acid units per end group, ie their degree of oligomerization, in the Range from 1 to 50, especially from 1 to 10. In a preferred Embodiment of the invention are polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units Have molecular weights of 750 to 5000 and the molar ratio from ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, in combination with combination with one essential to the invention used active ingredient.

The soil release polymers are preferred water-soluble, where by the term "water-soluble" a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water at room temperature and pH 8 to be understood. Preferably used polymers have among these Conditions, however, a solubility of at least 1 g per liter, in particular at least 10 g per liter.

Preferred laundry aftertreatment compositions which comprise an active substance to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol. These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, passing air through and then quaternizing with dimethyl sulfate or ethylene oxide. The production of solid ester quats is also known in which the quaternization of triethanolamine esters in the presence of suitable dispersants ren, preferably fatty alcohols, performs.

in der R¹ CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1:1 bis 3:1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2:1 bis 2,2:1, vorzugsweise 1,5:1 bis 1,9:1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (I), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (IV),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. Preferably, technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also elaidic acid-rich C _16/18 fatty acid cuts are used. To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil fatty acid (iodine value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R ¹ CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, suitable esterquats are quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ and R ^{5 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R¹ CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI) should be mentioned as a further group of suitable esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimum degree of esterification, the exemplary data given for (IV) apply mutatis mutandis to the esterquats of the formulas (V) and (VI). Typically, the esterquats are in the form of 50 to 90 weight percent alcoholic solutions in the Trade, which can also be easily diluted with water, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

esterquats are preferably in amounts of 5 wt .-% to 25 wt .-%, in particular 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent, used. If desired, the inventively used Laundry aftertreatment agent additionally listed above detergent ingredients unless they are unreasonably negative with the Esterquat interact. It is preferably a liquid, hydrous agent.

Examples

a) Washing conditions Washer: Miele W 918 Wash program: Single-leach cooking-colorful program Washing temperature: 40 ° C Fleet size: 17 l Water hardness: 16 ° dH filling laundry: 3.5 kg clean linen incl. Test fabric (pillow, jersey, tableware, barley grain towels)

b) Implementation:

The test fabrics were washed with a detergent containing one of the above-described ingredients under the conditions given above 3 times and air-dried after washing. This was followed by the application of standardized greasy / pigment-containing stains and an aging of soiling of 7 days. The textiles thus prepared were washed again with the detergent under the conditions mentioned above. The evaluation was color-colorimetric. Detergent compositions [wt%]: E1 E2 E3 C _12-14 fatty alcohol with 7 EO 5 4 10 C _9-13 alkyl benzene sulphonate, Na salt 10 10 10 Sodium lauryl ether sulfate with 2 EO - - 8th active substance 1 1 1 polyacrylate - - 1 sodium 15 18 - TAED 3 3 - C _12-18 fatty acid, Na salt 1 1.5 7.5 PVA / maleic acid copolymer 4.5 2 - Citric acid, Na salt 2.5 - 2 Phosphonic acid, Na salt 0.5 0.5 1 sodium 10 20 - propanediol - - 6.5 Zeolite A 25 25 - Boric acid, Na salt - - 1.2 Silicone antifoam 2.5 1.3 0.1 Enzymes (amylase, protease, cellulase) + + + dye + + + Perfume 0.5 0.2 0.8 water - - Ad 100 sodium sulphate - Ad 100 - sodium bicarbonate Ad 100 - -

The Detergent with an inventively used Active ingredient showed a significantly better washing performance than otherwise equally composed means that lacked this.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

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Claims (13)

Use of a polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound containing at least one structural element of the formula (I): -YA- (C = O) -A- (I), wherein each A independently is selected from S, O and NR ¹ , Y is selected from bi- to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (the Not counting carbon atoms of an optionally contained polyorganosiloxane unit) containing one or more groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and having one or more groups selected from -O-, - (CO) -, -NH-, and -NR ² - may contain, R ² is a straight, cyclic or branched, saturated, unsaturated or aromatic Kohlenwasserstoffre st having up to 40 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, R ^{3 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or a bivalent radical which forms cyclic structures within the radical Y, or one or both of which are adjacent to Y. Residues A with the radical Y between them can form a nitrogen-containing heterocyclic radical, and in the entire compound not all of the radicals A or Y or R ¹ or R ² or R ³ indicated in formula (I) must be identical with the proviso that in the entire compound at least one of the radicals Y comprises a polyorganosiloxane unit having 2 to 1000 silicon atoms, or their acid addition compound and / or salt for enhancing the cleaning performance of detergents b when washing textiles. Use according to claim 1 in the washing of textiles, that already in the presence of the soil removal wealthy Drugs were washed and / or post-treated before they were stained. Use of a combination of soil release agent selected from the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds containing at least one structural element of the formula (I): -YA- (C = O) -A- (I), wherein each A independently is selected from S, O and NR ¹ , Y is selected from bi- to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (the Not counting carbon atoms of an optionally contained polyorganosiloxane unit) containing one or more groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and having one or more groups selected from -O-, - (CO) -, -NH-, and -NR ² - may contain, R ² is a straight, cyclic or branched, saturated, unsaturated or aromatic Kohlenwasserstoffre st having up to 40 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, R ^{3 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or a bivalent radical which forms cyclic structures within the radical Y, or one or both of which are adjacent to Y. Residues A with the radical Y between them can form a nitrogen-containing heterocyclic radical, and in the entire compound not all of the radicals A or Y or R ¹ or R ² or R ³ indicated in formula (I) must be identical the proviso that in the total The compound of at least one of the radicals Y comprises a polyorganosiloxane unit having 2 to 1000 silicon atoms, or their acid addition compounds and / or salts, and a soil release polymer of a dicarboxylic acid and an optionally polymeric diol for enhancing the cleaning performance of detergents in the washing of textiles. Use according to one of Claims 1 to 3, characterized in that the polyorganosiloxane structural element present in the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds is the structure - (SiR ⁴ ₂ O) _p - (SiR ⁴ ₂ ) - wherein R ^{4 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 20 carbon atoms, and p = 1 to 999. Use according to one of claims 1 to 4, characterized in that the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound on average at least two, in particular at least three of said polyorganosiloxane structural elements contains. Use according to one of claims 1 to 5, characterized in that in the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compound at least one of the Y units according to the structural element of the formula (I) is a grouping -NR ² - and / or at least one of the Y units according to the structural element of the formula (I) has a grouping - (N ⁺ R ² R ³ ) -. Use according to one of Claims 1 to 6, characterized in that oligoethoxy and / or oligopropoxy groups are present in at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I) whose degrees of oligomerization are in particular Range from 2 to 60 are. Use according to one of claims 1 to 7, characterized in that in at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I) Oligoethylenimingruppen are present whose degrees of oligomerization, in particular in the range of 10 to 15 0000 lie. A process for laundering textiles comprising a detergent and a soil release agent selected from the polycarbonate, polyurethane and / or polyurea compounds containing at least one structural element of formula (I): -YA- (C = O) -A- (I), wherein each A is independently selected from S, O and -NR ¹ -, Y is selected from bi- to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms ( wherein the carbon atoms of an optionally contained polyorganosiloxane unit are not counted) which contain one or more groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms which contains one or more groups selected from -O-, - (CO) -, -NH-, and -NR ² - may contain, R ² is a straight, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms, one or more groups selected from -O-, - and may contain -NH-, R ³ is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to - (CO) 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or a bivalent radical which forms cyclic structures within the radical Y, or one or both of which are adjacent to Y. Residues A with the radical Y between them can form a nitrogen-containing heterocyclic radical, and in the entire compound not all of the radicals A or Y or R ¹ or R ² or R ³ indicated in formula (I) must be identical with the proviso that in the entire compound of at least one of the radicals Y comprises a Polyorganosiloxaneinheit having 2 to 1000 silicon atoms, or their acid addition compounds and / or salts are used. A method according to claim 9, characterized in that the textile after the actual washing process, which is carried out with the aid of a particular bleach-containing detergent, with an after treatment agent containing the active ingredient is brought into contact. Method according to claim 10, characterized in that that one uses a laundry treatment agent, which the soil release agent and ester quat contains. Method according to one of claims 9 to 11, characterized in that the agent in amounts from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 2% by weight contains. Use or process according to one of the preceding claims, characterized in that the compound of formula (I) is a polycarbonate and / or polyurethane-polyorganosiloxane compounds containing at least one structural element of the formula (II) or formula (III): -AYA- (CO) -OZ- (CHORO) -ZO- (CO) - (II), -AYA- (CO) -O- (CHCH ₂ OH) -ZO- (CO) - (III), in which A and Y have the meanings given for formula (I) and Z is selected from the divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon radicals having 1 to 12 carbon atoms.