DE102016207835A1 - Knittedeigungsvermeidung in textiles - Google Patents

Abstract

The crease tendency of a cotton or other cellulosic textile should be reduced. This has been accomplished by contacting the fabric with a carboxylic acid group bearing substituent-bearing polymer which is amenable to reaction by reacting an aminopolysiloxane with a cyclic carboxylic anhydride and, if desired, subsequent ironing.

Description

The present invention relates to the use of aminopolysiloxanes having substituents carrying carboxylic acid groups for reducing the crease tendency of textiles made of cellulosic material, a process that can be carried out in the household for wrinkle-reducing finishing of textiles made of cellulosic material, and laundry or laundry care products containing such polymers.

Textiles made of cellulose, such as cotton or cellulose regenerated fibers (for example Modal or Lyocel) have from the consumer's point of view positive properties in terms of wearing comfort. However, a major disadvantage of these textiles is the slight creasing during wear, after washing and drying. This tendency to wrinkle is due to the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.

Therefore, it has long been common to iron cotton textiles or cellulosic textiles after washing and drying and thus to bring them into the desired shape. For the consumer, however, it would be advantageous to be able to reduce the formation of wrinkles in the context of textile care, which would ideally make ironing completely superfluous.

In the textile production one tries with the help of permanent textile equipment by a cross linking of the cellulose molecules among themselves to reduce their tendency to crease. The crosslinking of the cellulose molecules increases the elasticity of the material. The anti-crease equipment is carried out as part of the textile finishing on the raw material. However, crosslinkers used in the textile industry, such as formaldehyde-urea and formaldehyde-melamine combinations, because of their toxicity or the conditions under which they must be used, are not suitable for use in detergents or household use suitable.

Formaldehyde-free crosslinking processes for cellulose are also known, for example from US 2004/0043915 A1 a crosslinking process carried out with the aid of hydroxyl-bearing polymer and polycarboxylic acids, in particular butanetetracarboxylic acid (BTCA).

From the Article by CM Welch in Textile Research Journal, 1988, 480-486 , the use of tetracarboxylic acids for the crosslinking of cellulose fibers is known. These formaldehyde-free approaches of cellulose crosslinking with the aid of polycarboxylic acids are therefore also rather unsuitable for home use since, for example, BTCA in the Ames test shows a positive result and is therefore not toxicologically problematic.

In a different approach, such as from M. Hashem, P. Hauser and B. Smith in Textile Research Journal, 2003, 762-766 described, ion-pair bonds are exploited for the crosslinking of cellulose. Cotton usually has a content of carboxyl groups of about 10 ^-6 mol / g. To get as many ion pair contacts as possible, the cellulose can be treated with chloro or bromoacetic acid to increase the number of its carboxyl groups. Interaction of the carboxylated cellulose with polycations, such as cationized chitosan, can result in ionic crosslinks that reduce the tendency to crease. Without the carboxylation, the effect is too small and carboxylation of cotton fabrics with haloacetic acids is not considered for home use.

From the patent application DE 101 24 387 A1 For example, finishing agents for anti-cellulite finishing of cellulosic textiles are known which contain hydrophobically modified polyethyleneimines and / or polyvinylamines, the hydrophobic modification taking place by reaction of the polyethyleneimines and / or polyvinylamines with long-chain carboxylic acids, alkyl halides, alkyl epoxides, alkyl ketene dimers or cyclic dicarboxylic acid anhydrides.

The European patent application EP 0 095 676 A1 discloses the use of aminopolysiloxanes bearing carboxy-terminated substituents attached via amide bonds to the aminopolysiloxane backbone for fabric softening and water repellent treatment of textile materials.

From the US patent US Pat. No. 6,277,445 B1 are organopolysiloxanes with Carboxyalk (en) ylcarbonylgruppen known which can be used in the form of water-containing emulsions for waterproofing cardboard equipment.

The European patent application EP 1 108 765 discloses the use of carboxyl group-containing side chain polysiloxanes for the hydrophobization of leather and furs.

It has surprisingly been found that the crease tendency of a cotton or other cellulosic textile (which for example consists of cellulose regenerated fibers or contains such) by contacting with a carboxylic acid group-bearing substituent containing polymer, which by reacting an aminopolysiloxane with a cyclic Carboxylic anhydride is accessible, and if desired, subsequent ironing can be reduced.

The invention therefore relates to the use of a polymer having carboxylic acid group-bearing substituent, which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic anhydride, to reduce the tendency of creases of textiles, which consist of cellulosic material or contain cellulose-containing material.

Another object of the invention is a feasible in the household process for wrinkle reducing equipment of textiles, which consist of cellulosic material or contain cellulosic material by contacting the textile with a carboxylic acid group-bearing substituent having polymer, which by reaction of an aminopolysiloxane with a cyclic carboxylic anhydride is accessible.

The materials from which the textiles to be treated are made include cotton, regenerated cellulose fibers such as Modal or Lyocel, and blended fabrics of cotton or regenerated cellulose with other fabrics commonly used in clothing such as polyester and polyamide.

In preferred embodiments of the invention, the textile is ironed following treatment with said polymer with a standard household iron.

The measures of the invention significantly reduce the creasing tendency of textiles made of cellulosic material compared to the untreated starting textiles or exclusive treatment with a noncarboxylic acid-substituted amino-containing polymer. Without wishing to be bound by this theory, it is conceivable that the reaction of carboxyl groups of the polymer with hydroxyl groups of the cotton leads to covalent bonds (ester bonds). In addition, the amino groups of the polymer may possibly interact electrostatically with carboxyl groups of the cotton (ionic crosslinking). Both covalent and ionic crosslinks could lead to an increased bounce of the textile and thus to crease reduction.

The evaluation of the wrinkle-free effect can be made by measuring the crease recovery angle (KEW) according to DIN 53890: 1972 respectively. Unfinished cotton generally has crease recovery angles of about 60 ° to 80 °. By applying the present invention, KEW values of well over 80 ° are obtained.

The polymer used in the context of the invention has amide bonds, which have entered into the amino function of the aminopolysiloxane, attached to the polymer backbone substituents which carry at least one carboxyl group, optionally a plurality of carboxyl groups. In addition to optionally present non-amidated amino groups and carboxyl groups, preferably no further nucleophilic units, such as, for example, hydroxyl groups, are present in the polymer essential to the invention.

Preferred polymers according to the invention are obtained by the reaction of aminopolysiloxanes of the general formula (I) R ¹ ₂ R ² Si-O- (SiR ¹ R ² -O-) _n SiR ¹ ₂ R ² (I) where n stands for a value of 10 to 2000 and each
R ^{1 represents} a straight-chain or branched or cyclic monovalent C ₁ to C ₁₈ hydrocarbon radical and
R ^{2 is} R ¹ or one of the groups -R ³ -NH ₂ or -R ³ -NH-R ³ -NH ₂ in which each
R ^{3 is} a straight-chain or branched or cyclic divalent C ₁ to C ₁₈ -carbon radical, in particular a C ₂ to C ₈ -carbon radical,
not all radicals R ¹ , not all radicals R ² , and not all radicals R ³ in the compound must be identical, with the proviso that at least 2 of the radicals R ^{2 are} not R ¹ ,
accessible with cyclic carboxylic anhydrides.

Examples of the monovalent C ₁ -C ₁₈ -hydrocarbon radicals R ¹ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, tert. Pentyl, n-hexyl, n-heptyl, n-octyl, trimethylpentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cycloalkyl, especially cyclopentyl or cyclohexyl, methylcyclohexyl, aryl, in particular Phenyl or naphthyl, alkaryl, in particular o-, m- or p-toluyl, xylyl or ethylphenyl; Aralkyl radicals, in particular benzyl, α- or ß-phenylethyl. The hydrocarbon radicals may optionally contain a C =C double bond. Examples are alkenyl radicals such as vinyl, allyl, 5-hexenyl, E-4-hexenyl, Z-4-hexen-1-yl, 2- (3-cyclohexenyl) -ethyl and cyclododeca-4,8-dienyl. Preferred radicals having aliphatic double bond are vinyl, allyl, and the 5-hexenyl radical. Preferably, however, at most 1% of the hydrocarbon radicals R ¹ contain a C =C double bond. Examples of the divalent C ₁ - to C ₁₈ -hydrocarbon radicals R ³ are saturated straight- or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and also propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and Octadecylene or unsaturated alkylene or arylene radicals such as the hexenylene radical and phenylene radical, wherein the n-propylene radical and the 2-methylpropylene radical are particularly preferred.

It is preferred if, in the aminopolysiloxane, the number-average ratio of the radicals R ² which are not R ¹ to the radicals R ^{1 is} in the range from 1:99 to 50:50, in particular in the range from 6:94 to 20:75.

The aminopolysiloxane from which the polymer essential to the invention is obtainable preferably has an average molar mass in the range from 2000 g / mol to 30 000 g / mol, in particular from 4000 g / mol to 20000 g / mol. The mean molecular weights given here and optionally for other polymeric ingredients are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, wherein the measurement is expediently carried out against an external standard.

in der R⁴ für einen zweibindigen aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, vorzugsweise einen linearen Alkylenrest mit 2 bis 6 Kohlenstoffatomen wie beispielsweise einen Ethylenrest, Ethenylenrest, Propylenrest oder Butylenrest, oder einen 1,2-Phenylenrest oder einen 1,2-Naphthylenrest, steht, R⁵ für H, OH oder R⁶(COOX)_p und Mischungen aus diesen steht, wobei jedes C-Atom in R⁴ je nachdem ob es sich um eines in einer C-C-Dreifachbindung, einer C-C-Doppelbindung oder aromatischen Bindung oder um eines in einer C-C-Einfachbindung handelt, keinen, einen oder zwei Reste R⁵ trägt, R⁶ für einen zweibindigen aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise einen Methylenrest, X für H, ein Atom eines Alkalimetalls wie insbesondere Natrium oder Kalium, oder eine Ammoniumgruppe und p für eine Zahl von 0 bis 3, insbesondere 1 oder 2, steht, erhältlich. Vorzugsweise ist das cyclische Anhydrid ein fünf-, sechs- oder siebengliedriger Ring. Zu den bevorzugten cyclischen Anhydriden gehören Bernsteinsäureanhydrid, Maleinsäureanhydrid, Glutarsäureanhydrid, Adipinsäureanhydrid, Tricarballylsäureanhydrid, Zitronensäureanhydrid, BTCA-Mono- oder Dianhydrid, Phthalsäureanhydrid, Trimellitsäureanhydrid (1,2,4-Benzoltricarbonsäureanhydrid), Naphthalin-2,3-dicarbonsäureanhydrid und deren Mischungen. Es werden vorzugsweise solche molaren Mengen an cyclischem Anhydrid bezogen auf Aminopolysiloxan eingesetzt, dass im Zahlenmittel 80 % bis 100 %, insbesondere 95 % bis 100 % der Stickstoffatome des Aminopolysiloxans amidiert werden. Polymers which can be used according to the invention are, in particular, by reacting an abovementioned aminopolysiloxane or mixtures of different aminopolysiloxanes of this type with cyclic carboxylic anhydrides of the general formula (II),

in the R ^{4 is} a divalent aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 20 carbon atoms, preferably a linear alkylene radical having 2 to 6 carbon atoms such as an ethylene radical, ethenylene radical, propylene radical or butylene radical, or a 1,2-phenylene radical or a 1, 2-naphthylene radical, R ⁵ is H, OH or R ⁶ (COOX) _p, and mixtures stands thereof, wherein each carbon atom in R ⁴ depending on whether it is one of a carbon-carbon triple bond, a carbon-carbon double bond or aromatic bond or is one in a CC single bond, none, one or two R ⁵ carries, R ^{6 is} a divalent aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 6 carbon atoms, preferably a methyl radical, X is H, an atom an alkali metal such as in particular sodium or potassium, or an ammonium group and p is a number from 0 to 3, in particular 1 or 2, available. Preferably, the cyclic anhydride is a five, six or seven membered ring. Preferred cyclic anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, tricarballylic anhydride, citric anhydride, BTCA mono- or dianhydride, phthalic anhydride, trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride), naphthalene-2,3-dicarboxylic anhydride, and mixtures thereof. Preferably, such molar amounts of cyclic anhydride are used based on aminopolysiloxane, that in the number average 80% to 100%, in particular 95% to 100% of the nitrogen atoms of the aminopolysiloxane are amidated.

Preferably, the textile of cellulosic material at temperatures in the range of 10 ° C to 100 ° C, in particular from 20 ° C to 60 ° C, with said aminopolysiloxane with carboxylic acid-bearing substituents, said substituents are bonded via amide bonds to the polymer backbone , brought in contact. Further preferably, the textile of cellulosic material over a period of 10 minutes to 180 minutes, in particular from 30 minutes to 60 minutes, with the polymer brought into contact. The observance of at least one of these conditions presumably leads - without wishing to be bound by this theory - to a chemical reaction of the cellulose with the polymer having substituents carrying carboxylic acid groups to such an extent that a particularly high reduction in the tendency to crease is observed.

The implementation of the invention can be carried out, for example, by bringing textiles consisting of cellulosic material or containing cellulose-containing material into contact with a surfactant-containing aqueous preparation which contains said polymer. This can be done as part of a conventional washing process, which can be carried out by means of a household washing machine or by hand. In this case, the polymer essential to the invention is preferably used in the rinsing step, that is to say after the actual washing step. But also possible is the joint use of essential to the invention polymer and detergent in the washing step. The polymer essential to the invention may be a constituent of agents used in such washing processes, or it may be added separately to such agents or aqueous formulations containing them.

Another object of the present invention is therefore a laundry or laundry care containing a carboxylic acid group-bearing substituent-containing polymer which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic anhydride.

Said polymer may be present as such, but also in the use of the user-friendly form of preparation, for example in admixture or granulated with vehicles, binders, wrapping materials, extrusion aids, free-flow improvers, stabilizers, solvents, rheology modifiers and / or emulsifiers. This embodiment of the invention makes it possible for the consumer in a simple manner, the advantages of the invention by using said polymer in addition to conventional washing and / or laundry aftertreatment only to bear, if they are desirable.

Said polymer may be present in a liquid or solid agent, whereby the single dosage (pouch packaging, Pouch) of the agent is possible.

The said polymer can also be present in a liquid spray product which, after dilution with water or, in particular, undiluted, can be sprayed onto a textile. In a preferred embodiment of the invention said polymer is applied to it, in particular by spraying in the form of a liquid spray product, after washing and drying the textile.

In preferred embodiments of the invention, the polymer essential to the invention is formulated as an aqueous microemulsion. Emulsifiers, in particular nonionic emulsifiers and among these preferably alkyl polyglycol ethers, may be present if desired.

In further preferred embodiments of the invention, the polymer essential to the invention is formulated as a solution. Preferred solvents are isopropanol and ethanol, but also ethyl acetate is readily possible.

The content of polymer essential to the invention in compositions according to the invention, including the mentioned microemulsions and solutions, is preferably 0.1% by weight to 5% by weight, in particular 0.5% by weight to 1% by weight, if the agent intended for direct contact with the textile. In agents according to the invention, including the mentioned microemulsions and solutions which are to be dissolved or diluted before use, the content of polymer essential to the invention is preferably 5% by weight to 30% by weight, in particular 15% by weight. to 25% by weight.

After the use of said polymer, it is preferable to iron the fabric once or a few times under ordinary household conditions. In particular, a particularly high effect is achieved, which particularly increases the elasticity and bounce of the textile and this particular fixed in the desired shape. In the ironing subsequent washes using said polymer creasing is particularly reduced. In addition, the formation of Trageknittern is reduced when using the textiles.

The present invention is therefore also a method in which a cotton or other cellulosic material consisting of or containing this textile with a carboxylic acid group-bearing substituent having polymer, which by reaction of an aminopolysiloxane accessible with a cyclic carboxylic anhydride, brought into contact and then fixed with a household iron in the desired shape. Ironing temperatures preferably occur in the range from 50 ° C. to 220 ° C., in particular from 100 ° C. to 160 ° C.

A preferred embodiment of the method consists in bringing the polymer essential to the invention into contact with the textile in a rinsing step, preferably the last rinsing step, of a manually or mechanically carried out washing process. For this, the polymer essential to the invention may be part of a laundry care product used in the final rinse cycle.

It is preferred according to the invention to apply the polymer essential to the invention in an amount in the range from 1% by weight to 2% by weight, based on the weight of the textile to be treated, on the latter. This can be achieved by applying the method according to the invention once or several times.

A cumulative effect of the invention results in some, for example 1 to 5, repeated applications. The textile does not need to be ironed after each application of the polymer according to the invention. Crease recovery angle improves from application to application. This cumulative effect allows the use of lower concentrations of the active ingredient according to the invention. Furthermore, it reduces the danger of damaging a textile by ironing in an undesired shape (for example a fold); Ironing errors can be corrected at the next application. For this reason, a dosage of the active substances essential to the invention which brings about a cumulative effect is preferred. The concentration of polymer having carboxylic acid group-bearing substituents which is obtainable by reacting an aminopolysiloxane with a cyclic carboxylic anhydride in a liquid, especially aqueous, preparation which comes into contact with the textile to be treated is preferably in the range of 0.1 g / 1 to 50 g / l, in particular from 0.2 g / l to 20 g / l. Such preparations may be a liquid agent according to the invention. If desired, the agents may also be dissolved or diluted prior to use.

Detergents or laundry detergents which contain the active ingredient to be used according to the invention or are used together or used in the process according to the invention may contain all customary other constituents of such agents which do not undesirably interact with the active ingredient essential to the invention.

Such an agent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based on the total agent. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, 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 sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. The anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Another synthetic anionic surfactant is alkylbenzenesulfonate in question.

A further embodiment of the compositions comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation 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 wt .-% to 25 wt .-%.

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 the alcohols is generally 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 contain an active ingredient according to the invention or used in the context of the use according to the invention or the method according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid agents and particulate preferably contain lower amounts of up to 5 wt .-%.

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. In particular, in liquid agents containing an active ingredient according to the invention, however, higher amounts of soap can be contained, usually up to 20 wt .-%.

If desired, the compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight. Among these, esterquats are particularly preferred.

If desired, the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents which have a Active ingredient used according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on the total agent, present, in particular Percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts. In order to avoid interaction with the peroxygen compounds, the bleach activators may have been coated and / or granulated in a known manner with coating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

In a further embodiment, the agent may be water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60% Wt .-%, contained.

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble organic and / or inorganic builder, if present. The water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol. 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. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. 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 may 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 from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate 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 and / or (meth) acrylate to maleic acid and / 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. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may 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 and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / 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 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50000 g / mol and in particular between 3000 g / mol and 10000 g / mol. 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 builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

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, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. 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 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. 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 metal 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 of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 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. 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.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents or cleaners. 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 contain an active ingredient used according to the invention, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brightener, in particular compounds from 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 agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, the weight proportions in each case referring to the total agent.

Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents 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 in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and 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® ^®. Suitable pectinases for example, under the name Gamanase ^®, Pektinex AR ^®, X-Pect ^® or Pectaway ^® from Novozymes, UF under the name Rohapect ^®, Rohapect TPL ^®, Rohapect PTE100 ^®, Rohapect MPE ^®, Rohapect MA plus HC, Rohapect DA12L ^®, Rohapect 10L ^®, Rohapect B1L ^® AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA.

To the optionally present in particular liquid agents usual enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal 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.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The known polyester-active soil release polymers 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, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ¹¹ -) _a O- and also polymeric diol units - ( O- (CHR ¹¹ -) _a ) _b O-. 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 of the molecular weight distribution of preferred soil release polyester is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. 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 their mixtures selected. 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 from 1000 g / mol to 6000 g / mol. If desired, the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with an essential ingredient of the invention. The soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean 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. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

In one embodiment of the invention, in particular the laundry care compositions used as aftertreatment agent with the polymer essential to the invention having substituents carrying carboxylic acid groups may comprise textile softening components, preferably cationic surfactants. Examples of softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile care agents.

wobei in (V) R und R¹ für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R² für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R³ entweder gleich R, R¹ oder R² ist oder für einen aromatischen Rest steht. X^– steht entweder für ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (V) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid. Suitable examples are quaternary ammonium compounds of the formulas (V) and (VI),

wherein in (V) R and R ^{1 is} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² or is a aromatic residue stands. X ^- is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (V) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (VI) are so-called ester quats. Esterquats are characterized by their good biodegradability and are preferred in the context of the present invention. Here, R ^{4 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is independently of R ^{5 is} H, OH or O (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preference is given to compounds which contain the group O (CO) R ⁷ for R ⁵ and to alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of the formula (VI) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl-oxyethyl) ammonium methosulfate, bis (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.

In a preferred embodiment, the agents contain the plasticizer components in amounts of up to 35% by weight, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 15% by weight and in particular from 1 to 10% by weight .-%, in each case based on the total agent.

In addition to the aforementioned components, the agents may contain pearlescing agents. Pearlescing agents give the textiles an extra shine and are therefore preferably used in mild detergents. As pearlescing agents are for example in question:
alkylene glycol esters; fatty acid; partial glycerides; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Furthermore, liquid agents may additionally contain thickeners. To increase consumer acceptance, the use of thickening agents has proven particularly useful in gel-type liquid detergents. Naturally derived polymers that can be used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, Hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan; In addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes come into question. In a preferred embodiment, the textile care agents according to the invention comprise thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total composition ,

Furthermore, the agents may additionally contain odor absorbers and / or color transfer inhibitors. In a preferred embodiment, the agents optionally contain from 0.1% to 2%, preferably from 0.2% to 1%, by weight of color transfer inhibitor which in a preferred embodiment of the invention comprises a vinylpyrrolidone polymer, Vinylimidazole, vinylpyridine N-oxide or a copolymer of these. Useful are, for example, polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 as well as polyvinylpyrrolidones having molecular weights above 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, copolymers based on vinyl monomers and carboxylic acid amides, pyrrolidone group-containing polyesters and polyamides, grafted polyamidoamines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Preferred deodorizing substances are metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any mixtures thereof. A particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid. A particularly preferred rosin acid is abietic acid. Preferred metals are the transition metals and the lanthanides, in particular the transition metals of Groups VIIIa, Ib and IIb of the Periodic Table, and lanthanum, cerium and neodymium, more preferably cobalt, nickel, copper and zinc, most preferably zinc. The cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred. It is advantageous and therefore particularly preferred to use as deodorizing substances one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate. Cyclodextrins, as well as mixtures of the abovementioned metal salts with cyclodextrin, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also turn out to be further suitable deodorizing substances within the meaning of the invention. 3 to 3: 1. The term "cyclodextrin" includes all known cyclodextrins, ie both unsubstituted cyclodextrins having 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and also their mixtures and / or their derivatives and / or mixtures thereof.

The preparation of solid agents used according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, wherein, for example, enzymes and possibly other thermally sensitive ingredients such as bleaching agents are optionally added separately later. For the preparation of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.

Particularly in the case of multilayer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are predominantly introduced via the metering device, for example the washing machine, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) × (34 to 40 mm), in particular of 26 × 36 mm or of 24 × 38 mm.

Liquid or pasty compositions in the form of common solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

In a particularly preferred embodiment, the agents are present, preferably in liquid form, as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.

The funds can be packed, for example, in foil bags. Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.

There are numerous processes in the prior art for producing water-soluble detergent portions, which are basically also useful in the context of the present invention. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Furthermore suitable for the production of film bags or dimensionally stable detergent portions is the thermoforming process (thermoforming process). However, the water-soluble envelopes need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules of polyvinyl alcohol or gelatin are known, which in principle offer the possibility to provide capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling of the capsules takes place through a small opening in the latter case. The filling of the capsules takes place, for example, by a Befüllkeil, which is above two mutually rotating drums, which have ball half shells on its surface, is arranged. The drums carry polymer bands that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten. A process for the preparation of water-soluble capsules, in which initially the filling and then the sealing takes place, is based on the so-called Bottle-Pack ^® method. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648. The water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 lies. It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic.

Examples

Example 1: Polymer production

• a) To a solution of 10 g of aminopropylmethylsiloxane-dimethylsiloxane copolymer (manufactured by Gellest Inc .; 20-25% aminopropylmethylsiloxane monomer content) in 80 ml of pyridine (absolute), a solution of 2.6 g of succinic anhydride in 20 ml of pyridine was added rapidly with stirring. The reaction was stirred for 20 h at room temperature and then concentrated on a rotary evaporator under reduced pressure. To remove pyridine residues, the residue was repeatedly mixed with 50 ml of ethyl acetate and concentrated. The residue was subsequently dried in a vacuum drying oven (10 mbar, 50 ° C.). 12.6 g of the succinic acid monoamide derivative P1 were obtained.
• b) 11.2 g Tricarballylsäure were mixed with 12 ml of acetic anhydride and stirred for 24 h at room temperature. Subsequently, excess acetic anhydride was evaporated on a rotary evaporator under reduced pressure. The residue was taken up in a little ethyl acetate, stirred briefly and then filtered off with suction. The solid was washed with a little ethyl acetate and dried in a vacuum drying oven (10 mbar, 50 ° C.). 7 g of tricarballylic anhydride were obtained.

To a solution of 10 g of aminopropylmethylsiloxane-dimethylsiloxane copolymer (manufactured by Gellest Inc, 6-7% aminopropylmethylsiloxane monomer content) in 80 ml of pyridine (absolute) a solution of 4.11 g of the tricarballylic anhydride thus obtained in 20 ml of pyridine was rapidly absorbed Stirring added. The reaction was stirred for 20 h at room temperature and then concentrated on a rotary evaporator under reduced pressure. To remove pyridine residues, the residue was repeatedly mixed with 50 ml of ethyl acetate and concentrated. The residue was subsequently dried in a vacuum drying oven (10 mbar, 50 ° C.). 14 g of the tricarballylic monoamide derivative P2 were obtained.

Example 2: Wrinkling production test

Test textiles of a size of about 12 × 18 cm were cut out of pressed cotton fabric (type "Stella Royal" of the manufacturer Brenneth) and ironed. Solutions of the polymers P1 and P2 prepared in Example 1 (E1: 1% by weight P1 in isopropanol, E2: 2% by weight P1 in isopropanol, E3: 1% by weight P1 in ethyl acetate, E4: 1% by weight of P2 in isopropanol, E5: 2% by weight of P2 in isopropanol, E6: 1% by weight of P2 and 0.02% by weight of sodium hypophosphite in isopropanol), so that a degree of soaking of 100% is achieved. of the textile weight. The patches were dried for 45 minutes at 25 ° C and then with a household iron (Rowenta ^®, Model DE634B) ironed (temperature two points). The wrinkle recovery angles were measured on the lobes treated in this way. For comparison, lobes of the untreated textile (V1) were also measured.

After a crease recovery time of 30 minutes, the values given in the table below for the crease recovery angle (mean values of 5-fold determinations) were obtained. Table: Crease recovery angle E1 92 ° E2 98 ° E3 106 ° E4 94 ° E5 106 ° E6 109 ° V1 72 °

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• US 2004/0043915 A1 [0005]
• DE 10124387 A1 [0008]
• EP 0095676 A1 [0009]
• US 6277445 B1 [0010]
• EP 1108765 [0011]
• DE 2412837 [0050]

Cited non-patent literature

• Article by CM Welch in Textile Research Journal, 1988, 480-486 [0006]
• M. Hashem, P. Hauser and B. Smith in Textile Research Journal, 2003, 762-766 [0007]
• DIN 53890: 1972 [0018]

Claims (10)

 Use of a carboxylic acid group-bearing substituent-containing polymer which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic anhydride, for reducing the tendency of creases of textiles consisting of cellulosic material or contain cellulosic material.  A process for anti-wrinkle finishing of textiles comprised of cellulosic material or containing cellulosic material by contacting the textile with a carboxylic acid group-bearing substituent-bearing polymer obtainable by reacting an aminopolysiloxane with a cyclic carboxylic acid anhydride. Use or method according to one of the preceding claims, characterized in that the textile of cellulose-containing material at temperatures in the range of 10 ° C to 100 ° C, in particular from 20 ° C to 60 ° C, and / or over a period of 10 minutes to 180 minutes, especially from 30 minutes to 60 minutes, with the polymer which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic acid anhydride. Use or method according to one of the preceding claims, characterized in that the textile is ironed after treatment with the polymer, which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic anhydride, with a conventional household iron. Use or method according to claim 4, characterized in that ironing temperatures in the range of 50 ° C to 220 ° C, in particular from 100 ° C to 160 ° C occur.  Laundry or laundry care compositions containing a carboxylic acid group-bearing substituent-containing polymer which is accessible by reacting an aminopolysiloxane with a cyclic carboxylic anhydride. Composition according to Claim 6, characterized in that it is a liquid spray product which, after dilution with water or, in particular, undiluted, can be sprayed onto a textile. Use, method or means according to any one of the preceding claims, characterized in that the polymer by the reaction of aminopolysiloxanes of the general formula (I) R ¹ ₂ R ² Si-O- (SiR ¹ R ² -O-) _n SiR ¹ ₂ R ² (I) in which n is from 10 to 2000 and each R ^{1 is} a straight-chain or branched or cyclic monovalent C ₁ to C ₁₈ hydrocarbon radical and R ^{2 is} R ¹ or one of the groups -R ³ -NH ₂ or -R ³ -NH-R ³ -NH ₂ in which each R ^{3 is} a straight-chained or branched or cyclic divalent C _{1 to} C ₁₈ -carbon radical, where not all radicals R ¹ , not all radicals R ² , not all radicals R ³ in the compound must be the same, with the proviso that at least 2 of the radicals R ^{2 are} not R ¹ , is accessible with cyclic carboxylic anhydrides. Use, method or means according to any one of the preceding claims, characterized in that the polymer by the reaction of an aminopolysiloxane or mixtures of different aminopolysiloxanes with cyclic carboxylic anhydrides of the formula (II),

in the R ^{4 is} a divalent aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 20 carbon atoms, preferably a linear alkylene radical having 2 to 6 carbon atoms as for example, an ethylene radical, ethenylene radical, propylene radical or butylene radical, or a 1,2-phenylene radical or a 1,2-naphthylene radical, R ^{5 is} H, OH or R ⁶ (COOX) _p and mixtures thereof, where each C Atom in R ^4, depending on whether it is one in a CC triple bond, a CC double bond or aromatic bond or one in a CC single bond, bears no, one or two radicals R ⁵ , R ^{6 is} a divalent aliphatic , aromatic or araliphatic hydrocarbon radical having 1 to 6 carbon atoms, preferably a methyl radical, X is H, an atom of an alkali metal such as in particular sodium or potassium, or an ammonium group and p is a number from 0 to 3, in particular 1 or 2, available is .. Use, processes or compositions according to one of the preceding claims, characterized in that the aminopolysiloxane from which the polymer is accessible has a mean molecular weight in the range from 2000 g / mol to 30,000 g / mol, in particular from 4000 g / mol to 20,000 g / mol.