EP3487972B1 - Propylene glycol ester as fabric care constituents - Google Patents

Description

The present invention relates to detergents, laundry aftertreatment or laundry care products, in particular liquid detergents, which contain propylene glycol esters and their use to minimize the tendency to wrinkle and to facilitate ironing of textiles, in particular textiles made of cellulosic material, and a household process for making ironing easier and/or wrinkle-reducing finishing of textiles.

Textiles made of cellulose, such as cotton or regenerated cellulose fibers (e.g. Modal or Lyocel) have positive properties in terms of wearing comfort from the consumer’s point of view. However, a major disadvantage of these textiles is the easy crease formation during wear, after washing and drying. This wrinkling tendency is based on the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.

It has therefore long been customary to iron cotton or cellulosic textiles after washing and drying, in order to bring them into the desired shape. However, it would be advantageous for the consumer to be able to minimize the formation of creases in the context of fabric care, which would make the job of ironing easier or, ideally, eliminate the need for ironing altogether.

In the manufacture of textiles, attempts are made to reduce their tendency to wrinkle with the help of permanent textile finishes by cross-linking the cellulose molecules with one another. The cross-linking of the cellulose molecules increases the elasticity of the material. The crease-preventing finishes are carried out on the raw material as part of the textile finishing process. However, crosslinkers used in the textile industry, such as formaldehyde-urea and formaldehyde-melamine combinations, are not suitable for use in detergents or for household use because of their toxicity or the conditions under which they must be used suitable. Alternative formaldehyde-free crosslinking processes for cellulose using polycarboxylic acids are known, for example from U.S. 2004/0043915 A1 , but are not suitable for home use or for a consumer product.

There is therefore a continuing need for processes and products which reduce the wrinkling tendency of textiles.

Another problem when washing fabrics is that the fabrics lose their softness after several washes. For this reason, it is common to use fabric softener or to dry the laundry in a dryer. However, there are a number of consumers who do not (want to) use fabric softeners or dryers. It is therefore desirable to provide detergents which make the laundry pleasantly soft even during the normal washing process.

Surprisingly, it has now been found that the wrinkling tendency of cellulosic textiles, in particular textiles made of cotton and polyester/cotton fabrics, can be reduced by using detergents, laundry aftertreatment agents or laundry care agents which contain propylene glycol esters. Furthermore, it was found that the softness of the laundry after the washing process can also be advantageously influenced by means of this type. Certain propylene glycol esters have been used to date as viscosity regulators or to increase washing performance on oily soiling (cf. EP 0 845 523 A2 and JP 2005 002179 A ). EP 2404 591 discloses cosmetic preparations containing propylene glycol diester.

wobei

• X₁ -OH ist, und
• X₂
  
  ist,
• wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist. Ein weiterer Gegenstand der Erfindung ist die Verwendung eines Wasch-, Wäschenachbehandlungs- oder Wäschepflegemittels, insbesondere eines Flüssigwaschmittels, das bezogen auf das Gesamtgewicht 0,01 bis 30 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-% mindestens eines Propylenglykolesters gemäß Formel (I) enthält:
  
  
• wobei
• X₁ -OH oder ist,
• wobei R₁ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist;
• X₂ -OH oder
  
  ist,
• wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist, und
• wobei X₁ und X₂ nicht beide -OH sind, zur Minimierung der Knitterneigung und zur Erleichterung des Bügelns von Textilien.

The invention therefore relates in a first aspect to a detergent, laundry aftertreatment or laundry care product, in particular a liquid detergent, which, based on the total weight, contains 0.01 to 30% by weight, preferably 0.01 to 4% by weight, of at least one propylene glycol ester according to formula (I) contains:

whereby

• X ₁ is -OH, and
• _x2
  
  is,
• where R ₂ is an alkyl of 5-35 carbon atoms or an alkenyl of 5-35 carbon atoms. Another object of the invention is the use of a detergent, laundry aftertreatment or laundry care product, in particular a liquid detergent, based on the total weight 0.01 to 30 wt .-%, preferably 0.01 to 4 wt .-% of at least one propylene glycol ester Formula (I) contains:
  
  
• whereby
• X ₁ is -OH or
• wherein R ₁ is alkyl of 5-35 carbon atoms or alkenyl of 5-35 carbon atoms;
• X ₂ -OH or
  
  is,
• wherein R ₂ is an alkyl of 5-35 carbon atoms or an alkenyl of 5-35 carbon atoms, and
• where X ₁ and X ₂ are not both -OH to minimize wrinkling and ease of ironing of fabrics.

wobei

• X₁ -OH oder
  
  ist,
• wobei R₁ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist;
• X₂ -OH oder
  
  ist,
• wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist, und wobei X₁ und X₂ nicht beide -OH sind, zur Erhöhung der Weichheit von Textilien.

Yet another aspect of the invention is the use of the detergent, laundry aftertreatment or laundry care product described herein, in particular liquid detergent, which, based on the total weight, contains 0.01 to 30% by weight, preferably 0.01 to 4% by weight, of at least one Propylene glycol ester according to formula (I) contains:

whereby

• X ₁ -OH or
  
  is,
• wherein R ₁ is alkyl of 5-35 carbon atoms or alkenyl of 5-35 carbon atoms;
• X ₂ -OH or
  
  is,
• wherein R ₂ is an alkyl of 5-35 carbon atoms or an alkenyl of 5-35 carbon atoms, and wherein X ₁ and X ₂ are not both -OH, for increasing the softness of fabrics.

1. a) Bereitstellen einer Wasch- oder Reinigungslösung umfassend ein Wasch-, Wäschenachbehandlungs- oder Wäschepflegemittel, insbesondere Flüssigwaschmittel, das bezogen auf das Gesamtgewicht 0,01 bis 30 Gew.-%, vorzugsweise 0,01 bis 4 Gew.-% mindestens eines Propylenglykolesters gemäß Formel (I) enthält:
   
   wobei
   • X₁ -OH oder
     
     ist,
   • wobei R₁ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist
   • X₂ -OH oder
     
     ist,
   • wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist, und
   • wobei X₁ und X₂ nicht beide -OH sind, und
2. b) In Kontakt bringen eines Textils oder einer harten Oberfläche mit der Wasch- oder Reinigungslösung gemäß (a).

Finally, the invention also relates to a washing process that can be carried out in the household, comprising the process steps

1. a) Providing a washing or cleaning solution comprising a detergent, laundry aftertreatment or laundry care product, in particular liquid detergent, which, based on the total weight, contains 0.01 to 30% by weight, preferably 0.01 to 4% by weight, of at least one propylene glycol ester Formula (I) contains:
   
   whereby
   • X ₁ -OH or
     
     is,
   • wherein R ₁ is alkyl of 5-35 carbon atoms or alkenyl of 5-35 carbon atoms
   • X ₂ -OH or
     
     is,
   • wherein R ₂ is an alkyl of 5-35 carbon atoms or an alkenyl of 5-35 carbon atoms, and
   • where X ₁ and X ₂ are not both -OH, and
2. b) Bringing a textile or a hard surface into contact with the washing or cleaning solution according to (a).

The cellulosic materials from which the textiles to be treated are made include cotton, regenerated cellulosic fibers such as modal or lyocel, and blends of cotton or regenerated cellulosic fibers with other materials commonly used in clothing, such as polyester and polyamide.

The compositions herein comprise at least one propylene glycol monoester

The propylene glycol ester of the present invention may be propylene glycol laurate such as the Migoto Type BP compound from Riken. However, any other monoester of propylene glycol and fatty acids can also be used (e.g. propylene glycol isostearate, propylene glycol oleate and propylene glycol myristate). In the specialist literature, these monoesters are described as auxiliaries in the hair care sector, in the skin care sector and in the body care sector.

• X₁ -OH oder
  
  ist,
• wobei R₁ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist;
• X₂ -OH oder
  
  ist,
• wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen oder ein Alkenyl mit 5-35 Kohlenstoffatomen ist und wobei X₁ und X₂ nicht beide -OH sind, d.h. mindestens einer von X₁ und X₂ ist ein Rest der Formel -OOC-R₁/R₂.

In the above formula (I) a general representation of propylene glycol esters is given,
whereby

• X ₁ -OH or
  
  is,
• wherein R ₁ is alkyl of 5-35 carbon atoms or alkenyl of 5-35 carbon atoms;
• X ₂ -OH or
  
  is,
• wherein R ₂ is alkyl of 5-35 carbon atoms or alkenyl of 5-35 carbon atoms and wherein X ₁ and X ₂ are not both -OH, ie at least one of X ₁ and X ₂ is a group of the formula -OOC-R ₁ / _R2 .

wobei R₂ ein Alkyl mit 5-35 Kohlenstoffatomen, bevorzugt ein Alkyl mit 11 Kohlenstoffatomen ist.In certain embodiments, X ₁ is -OH and
_x2

wherein R ₂ is an alkyl of 5-35 carbon atoms, preferably an alkyl of 11 carbon atoms.

The term "alkenyl" as used herein refers to a monovalent straight or branched chain group containing at least one carbon-carbon double bond. The alkenyl groups can be optionally substituted.

The term "alkyl" as used herein refers to saturated, straight or branched chain hydrocarbon groups. Examples of alkylene include methyl, ethyl, propyl, iso -propyl, n -butyl, tert -butyl, neo -pentyl and n -hexyl. The alkyl groups can be optionally substituted.

"At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. "At least one propylene glycol ester" thus means at least one type of propylene glycol ester, i.e. one type of propylene glycol ester or a mixture of several different propylene glycol esters can be used. Together with weight information, the information refers to all compounds of the type specified that are contained in the composition/mixture, i.e. the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to % by weight, based in each case on the mixture in question.

As a result of the measures of the invention, the tendency of textiles made from cellulosic material to crease is significantly reduced compared to the untreated starting textiles.

The process can be carried out, for example, by bringing textiles made of cellulose-containing material into contact with an aqueous preparation which contains 0.01 to 30% by weight, preferably 0.1 to 4% by weight, of at least one propylene glycol ester according to the invention. This can be done as part of a standard washing process, which can be carried out using a domestic washing machine or by hand. The propylene glycol ester in an aqueous liquor is preferably used in the washing step, but can also be used in the rinsing step, for example. The propylene glycol ester can be a component of detergents or laundry aftertreatment agents such as fabric softeners that are usually used in such washing processes. The concentration of propylene glycol ester in aqueous treatment liquor is in particular in the range from 0.01 g/l to 2.7 g/l, particularly preferably 0.01 g/l to 0.4 g/l. However, the propylene glycol ester can also be part of a laundry care product, which can be present in particular as a liquid spray product which, after dilution with water or preferably undiluted, is applied, in particular sprayed, to a textile made of cellulosic material, without a washing process having to follow or the application of a washing process must have immediately preceded it.

Detergents, laundry aftertreatment or laundry care products which contain the active ingredient to be used according to the invention or are used together with them or are used in the method according to the invention are preferably liquid and can also be present, for example, as a single dose (for example in the form of a sachet pack). Examples of specific agents in which the propylene glycol esters can be used are liquid detergents and fabric softeners.

All of the detergents, laundry aftertreatment agents or laundry care agents mentioned above can contain customary other components of such agents which do not interact in an undesirable manner with the propylene glycol ester essential to the invention.

Such a composition preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 35% by weight, in particular from 0.1% by weight to 25% by weight, based in each case on the composition as a whole. Synthetic anionic surfactants which are particularly suitable for use in such agents are the alkyl and/or alkenyl sulfates having 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion as counter cation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, 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 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulphoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, deriving sulfonation products, and the sulfofatty acids resulting from these by formal hydrolysis. The anionic surfactants that can be used also include the salts of sulfosuccinic acid esters, which are also known as alkyl sulfosuccinates or dialkyl sulfosuccinates are referred to, and represent the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain _C8 to _C18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol residue, which in itself represents a nonionic surfactant. In this context, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Alkyl benzene sulfonate is a further synthetic anionic surfactant.

A further embodiment of the agent 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 products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and/or fatty acid amides and their Mixtures, especially in an amount ranging from 2% to 25% by weight.

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 carbon atoms, preferably 12 to 18 carbon 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. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used for the preparation of useful alkoxylates. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. The ethylene oxide and/or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides also come into consideration. So-called alkyl polyglycosides suitable for incorporation into the agents 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 carbon atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) _n is an oligomer or polymer of naturally occurring aldose or ketose monomers, including in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose belong. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain but also by their number, the so-called degree of oligomerization. The degree of oligomerization n, as a variable to be determined analytically, generally assumes fractional numerical values; it is between 1 and 10, in the case of the glycosides preferably used it is below one value of 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because it is readily available. The alkyl or alkenyl part R ¹² of the glycosides also preferably originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof can be used in particular. Particularly preferred alkyl glycosides contain a coconut fat alkyl radical, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is present in the compositions described preferably in amounts of 1% by weight to 30% by weight, in particular 1% by weight to 25% by weight, with amounts in the upper part of this range being more likely to be found in liquid compositions and particulate compositions preferably contain rather minor amounts of up to 5% by weight.

Other optional surfactant ingredients are soaps, with 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, being suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight 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, particularly in liquid agents which contain an active ingredient used according to the invention, higher amounts of soap, generally up to 20% by weight, can also be present.

If desired, the agents can also contain betaines and/or cationic surfactants, which—if present—are preferably used in amounts of 0.01% by weight to 7% by weight. Among these, ester quats are particularly preferred.

If desired, the detergents can contain bleaching agents based on peroxygen, especially in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, especially in amounts ranging from 0.5% by weight to 10% by weight, contain. The bleaches that come into consideration are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperoic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which can be in the form of tetrahydrate or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Bleaching agents of this type are present in detergents which contain a propylene glycol ester used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on entire Medium, available, with percarbonate being used in particular. The optionally present component of the bleach activators includes the N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides , In particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators may have been coated and/or granulated in a known manner with encapsulating substances, granulated tetraacetylethylenediamine having an average grain size of 0.01 mm to 0.8 mm, granulated 1, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammoniumacetonitrile formulated in particulate form is particularly preferred. Such bleach activators are preferably present 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 detergent as a whole.

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

The water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which also may contain small proportions of polymerizable substances without carboxylic acid functionality as polymerized units. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g/mol and 200,000 g/mol, and 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 relative molecular weight of 50,000 g/mol to 100,000 g/mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, especially 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. In this case, the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol. In particular, preference is given to vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 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% to 40% by weight, preferably 10% to 30% by weight, 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 substituted in the 2-position with an alkyl radical, preferably a C ₁ -C ₄ alkyl radical, or an aromatic radical, preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 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% by weight, preferably 15% by weight to 25% by weight, of methallyl sulfonic acid and/or methallyl sulfonate and, as a third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight. % of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred. Presumably, the use of the third monomer incorporates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular mass of 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 the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid compositions. All of 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. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions.

In particular, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed.

Among these, the crystalline detergent grade aluminosilicates, particularly zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. In particular, suitable aluminosilicates do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Your calcium binding capacity, according to the information in the German patent specification DE 24 12 837 can be determined is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders in the agents 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 can be present in amorphous or crystalline form. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na ₂ O:SiO ₂ ratio of 1:2 to 1:2.8. Amorphous alkali metal silicates of this type are commercially available, for example, under the name ^Portil® . Those with a molar ratio of Na ₂ O:SiO ₂ of 1:1.9 to 1:2.8 are preferably added as a solid and not in the form of a solution during production. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _2x+1 · yH ₂ O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 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 layered silicates are those in which x has the value 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in the compositions described herein. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced 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. Their content of alkali metal silicates is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali metal silicate content 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, based in each case on anhydrous active substances, is then preferably 4:1 to 10:1. In compositions 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 in particular 1:1 to 2:1.

In addition to the inorganic builder mentioned, other water-soluble or water-insoluble inorganic substances can be used together with it in the compositions or in the compositions according to the invention Procedures are used to be included. The alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable in this context. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents can contain other components that are customary in detergents, laundry aftertreatment agents, laundry care agents, or cleaning agents. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, builders, bleaches, builders, electrolytes, non-aqueous solvents, pH adjusters, odor absorbers, deodorizing substances, perfume, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, Graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellent and impregnating agents, swelling and non-slip agents, softening components and UV absorbers.

In addition to water, solvents which can be used in particular in the case of liquid agents are preferably non-aqueous solvents which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.

In a preferred embodiment, the washing or cleaning agent according to the invention also comprises at least one enzyme.

Optional enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. Protease obtained from microorganisms such as bacteria or fungi is primarily considered. It can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available, for example, under the names ^BLAP® , ^Savinase® , ^Esperase® , ^Maxatase® , ^Optimase® , ^Alcalase® , ^Durazym® or ^Maxapem® . The lipase that 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 commercially available, for example, under the names ^Lipolase® , ^Lipozym® , ^Lipomax® , ^Lipex® , ^Amano® lipase, Toyo- ^Jozo® lipase, ^Meito® lipase and ^Diosynth® lipase. Suitable amylases are commercially available, for example, under the names ^Maxamyl® , ^Termamyl® , ^Duramyl® and ^Purafect® OxAm. The cellulase that can be used can be an enzyme that can be obtained from bacteria or fungi and has a pH optimum, preferably in the weakly acidic to weakly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme ^® , Carezyme ^® and Ecostone ^® . Suitable pectinases are, for example, under the names ^Gamanase® , Pektinex ^AR® , X- ^Pect® or ^Pectaway® from Novozymes, under the name Rohapect ^UF® , Rohapect ^TPL® , Rohapect ^PTE100® , Rohapect ^MPE® , Rohapect MA plus HC, Rohapect DA12L ^® , Rohapect 10L ^® , Rohapect B1L ^® from AB Enzymes and available under the name Pyrolase ^® from Diversa Corp., San Diego, CA, USA.

In preferred embodiments, the agent according to the invention contains at least one enzyme selected from protease, amylase, cellulase, mannanase, lipase, pectate lyase as the enzyme.

In general, the enzymes contained in the agent according to the invention can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation.

The enzymes obtained can be added to agents according to the invention in any form established according to the prior art. These include, in particular, the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and/or mixed with stabilizers. In an alternative dosage form, the enzymes can also be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel, or in those from Core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and/or chemicals. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their optimum pH is usually in the clearly alkaline range.

Examples of the subtilisin-type proteases preferably used in detergents and cleaning agents are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but no longer the subtilisins in the narrower sense of the enzymes Thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned which have an amino acid sequence which is altered compared to the starting protease. Proteases are modified in a targeted or random manner using methods known from the prior art and are thus optimized, for example, for use in detergents and cleaning agents. These include point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein parts. These modified protease variants can also be contained in the agents according to the invention.

In preferred embodiments, the agent according to the invention can contain an amylase, more preferably an alpha-amylase. Alpha amylases are among the technically important enzymes. An alpha-amylase is an enzyme that catalyzes the hydrolysis of the internal α(1-4) glycosidic bonds of amylose but not the cleavage of terminal or α(1-6) glycosidic bonds. Alpha amylases therefore represent a group of esterases (EC 3.2.1.1.). Alpha-amylases catalyze the cleavage of starch, glycogen, and other oligo- and polysaccharides that contain an α(1-4) glycosidic linkage. In this respect, alpha-amylases act against starch residues in the laundry and catalyze their hydrolysis (endohydrolysis). The alpha-amylases used in the detergents or cleaning agents known from the prior art are usually of microbial origin and usually come from bacteria or fungi, for example of the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma or Trichosporon, in particular Bacillus . Alpha-amylases are usually produced by suitable microorganisms, for example by transgenic expression hosts of the genus Bacillus or by filamentous fungi, using biotechnological methods known per se.

The agents preferably additionally contain at least one cellulase. A cellulase is an enzyme. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethyl cellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase , celludextrinase or avicelase. The decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-β-D-glucosidic bonds in cellulose.

Cellulases (endoglucanases, EG) which can be prepared according to the invention include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the company Novozymes under the trade name ^Celluzyme® . The products Endolase ^® and Carezyme ^{® ,} which are also available from the company Novozymes, are based on the 50 kD EG or the 43 kD EG from Humicola insolens DSM 1800. Other usable commercial products from this company are Cellusoft ^® , Renozyme ^® and Celluclean ^® . Also usable are, for example, cellulases from the company AB Enzymes, Finland under the tradenames ^Ecostone® and ^Biotouch® and which are based at least in part on the 20 kD EG from Melanocarpus. Other cellulases from the company AB Enzymes are Econase ^® and Ecopulp ^® . Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp. CBS 670.93 is available from the Danisco/Genencor company under the tradename ^Puradax® . Other usable commercial products from the company Danisco/Genencor are “Genencor detergent cellulase L” and ^IndiAge® Neutra.

Variants of these enzymes obtainable by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants described in International Laid-Open Specification WO 98/12307 are disclosed, cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in International Offenlegungsschrift WO 97/14804 are disclosed, EGIII-type cellulases from Trichoderma reesei, which are disclosed in European patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those disclosed in the European patent applications EP1240525 and EP1305432 , as well as cellulases disclosed in the International Laid-Open Specifications WO1992006165 , WO 96/29397 and WO 02/099091 . Reference is therefore expressly made to their respective disclosure or their relevant disclosure content is therefore expressly included in the present patent application.

It is preferred according to the invention if the agents according to the invention additionally contain at least one lipase. Lipase enzymes preferred according to the invention are selected from at least one enzyme from the group formed by triacylglycerol lipase (EC 3.1.1.3) and lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).

The area of use preferred according to the invention for the agents according to the invention is the cleaning of textiles. Because detergents and cleaning agents for textiles have predominantly alkaline pH values, lipases in particular are used for this purpose, which are active in an alkaline medium.

Furthermore, the lipase preferably contained in a composition according to the invention is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus or is derived from the aforementioned naturally present lipases by mutagenesis.

According to the invention, preferred lipases are the lipase enzymes available from Amano Pharmaceuticals under the names Lipase M- ^AP10® , Lipase ^LE® and Lipase ^F® (also Lipase ^JV® ). For example, the lipase F ^® is naturally present in Rhizopus oryzae. For example, the lipase M- ^AP10® is naturally present in Mucor javanicus.

Compositions of a most preferred embodiment of the invention contain at least one lipase selected from at least one or more polypeptides having an amino acid sequence that is at least 90% (and more preferably at least 81%, 82%, 83%, 84%, 85% %, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 .5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%) to the wild-type lipase from the strain DSM 4109 Thermomyces lanuginosus is identical. It is again preferred if, starting from said wild-type lipase from strain DSM 4109, at least the amino acid change N233R is present.

A highly preferred lipase is commercially available under the trade name ^Lipex® from the company Novozymes (Denmark) and can be used advantageously in the cleaning compositions according to the invention. The lipase ^Lipex® 100 L (ex Novozymes A/S, Denmark) is particularly preferred here. Preferred compositions are characterized in that said lipase enzyme from Lipex ^® 100 L is present in a total amount of from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight, based on the total weight of the composition. %, is included.

The agents according to the invention can additionally contain at least one mannanase as an enzyme. A mannanase contained in the composition according to the invention (in particular in a detergent and cleaning agent preferred according to the invention for textiles) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans as part of its mannanase activity. According to the enzyme nomenclature, said mannanase enzymes according to the invention are referred to as E.C. 3.2.1.78 classified.

Suitable compositions according to the invention contain, for example, the mannanase which is marketed under the name ^Mannaway® by the Novozymes company.

The customary enzyme stabilizers that may be present, especially in liquid agents, include amino alcohols, for example mono-, di-, triethanolamine 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 sulphur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, as well as microfine, optionally silanated or otherwise hydrophobic silica may contain. For use in particulate compositions, 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. The preferably used dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR ¹¹ -) _a OH, which can also be used as a polymeric diol H-(O-(CHR ₁₁ -) _a ) _b OH may be present. Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl 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. The polyesters obtainable from these preferably contain both monomer diol units -O-(CHR ₁₁ -) _a O- and polymer diol units --( O-(CHR ¹¹ -) _a ) _b O- before. 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. The degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-removing polyesters is in the range from 250 g/mol to 100,000 g/mol, in particular from 500 g/mol to 50000 g/mol. The acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulphoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester. These include, for example, alkylene and alkenylenedicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO-(CHR ¹¹ -) _a OH include those in which R ¹¹ is hydrogen and a is from 2 to 6 and those in which a is 2 and R ¹¹ is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH, in which R ¹¹ has the meaning given above, 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. Especially preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 g/mol to 6000 g/mol. If desired, the polyesters can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bonded via ester bonds 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, lauroleic 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, eleostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid . The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present more than once in an end group. The number of hydroxymonocarboxylic acid units per end group, i.e. their degree of oligomerization, is preferably 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 active ingredient essential to the invention. The soil-removing polymers are preferably water-soluble, the term "water-soluble" meaning 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, polymers which are preferably used 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, the laundry care agents used as aftertreatment agents in particular can contain additional softener components, preferably cationic surfactants. Examples of fabric-softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as are used in hair care products and also in fabric conditioners.

wobei in (II) 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 (II) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Suitable examples are quaternary ammonium compounds of the formulas (II) and (III),

where in (II) R and R ¹ are 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 the same as R, R ¹ or R ² or is one aromatic residue. X ^- represents either a halide, methosulfate, methophosphate, or phosphate ion, and mixtures thereof. Examples of cationic compounds of the formula (II) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of the formula (III) are so-called esterquats. Esterquats are notable for 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 represents H, OH or O(CO)R ⁷ , R ⁶ independently of R ⁵ represents H, OH or O(CO)R ⁸ , where R ⁷ and R ⁸ each independently represent an aliphatic alkyl radical having 12 bis 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently have the value 1, 2 or 3. X ^- can be either a halide, methosulfate, methophosphate or phosphate ion, and mixtures of these. Preference is given to compounds which contain the group O(CO)R ⁷ for R ⁵ and alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Compounds in which R ⁶ is also OH are particularly preferred. Examples of compounds of the formula (III) 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 additional plasticizer components in amounts of up to 35% by weight, preferably from 0.01 to 25% by weight, particularly preferably from 0.01 to 15% by weight and in particular from 0.01% up to 10% by weight, in each case based on the total agent.

In addition to the aforementioned components, the agents may contain pearlescent agents. Pearlescent agents give the textiles an additional shine and are therefore preferably used in mild detergents. Examples of suitable pearlescent agents are: alkylene glycol esters; fatty acid alkanolamides; partial glycerides; esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of 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 can also contain thickeners. The use of thickeners, particularly in the case of liquid detergents in gel form, has proven effective in increasing consumer acceptance. Polymers derived from nature that can be used as thickeners are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatine and casein, cellulose derivatives such as carboxymethylcellulose hydroxyethyl - and -propyl cellulose, and polymeric polysaccharide thickeners such as xanthan gum; fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable. In a preferred embodiment, the textile care agents according to the invention contain thickeners, preferably in amounts of up to 10% by weight, particularly preferably up to 5% by weight, in particular from 0.1 to 1% by weight, based in each case on the agent as a whole .

Furthermore, the agents can additionally contain odor absorbers and/or color transfer inhibitors. In a preferred embodiment, the agents optionally contain 0.1% by weight to 2% by weight, preferably 0.2% by weight to 1% by weight, of color transfer inhibitor which, in a preferred embodiment of the invention, is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these. Both, for example, polyvinylpyrrolidones with molecular weights of 15,000 to 50,000 and polyvinylpyrrolidones with molecular weights above 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole/N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers can be used and carboxylic acid amides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids. However, enzymatic systems can also be used, comprising a peroxidase and hydrogen peroxide or a substance that supplies 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, it also being possible to use the above-mentioned polymeric dye transfer inhibitor active ingredients. For use in agents according to the invention, polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 to 60,000, in particular in the range from 25,000 to 50,000. Among the copolymers, preference is given to those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average molar mass in the range from 5,000 to 50,000, in particular from 10,000 to 20,000.

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 resin 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 resin acid is abietic acid. Preferred metals are the transition metals and the lanthanides, in particular the transition metals from Groups VIIIa, Ib and IIb of the Periodic Table and lanthanum, cerium and neodymium, particularly preferably cobalt, nickel, copper and zinc, extremely preferably zinc. Although the cobalt, nickel and copper salts and the zinc salts are similarly effective, the zinc salts are to be preferred for toxicological reasons. One or more metal salts of ricinoleic acid and/or abietic acid, preferably zinc ricinoleate and/or zinc abietate, in particular zinc ricinoleate, are advantageous and therefore particularly preferred as deodorizing substances. Cyclodextrins and mixtures of the aforementioned 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: 3 to 3:1. The term "cyclodextrin" includes all known cyclodextrins, i.e. both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and their mixtures and/or their derivatives and/or their mixtures.

Liquid or pasty agents in the form of solutions containing customary solvents, in particular water, are generally produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.

Embodiments of the present invention include all solid, powdery, liquid, gel-like or pasty forms of administration of the agents described herein, which may also consist of several phases and may be in compressed or non-compressed form. The agent can be in the form of a free-flowing powder, in particular with a bulk density of 300 g/l to 1200 g/l, in particular 500 g/l to 900 g/l or 600 g/l to 850 g/l. The solid dosage forms of the agent also include extrudates, granules, tablets or pouches. Alternatively, the agent can also be liquid, gel-like or pasty, for example in the form of a non-aqueous liquid detergent or dishwashing detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or dishwashing detergent or an aqueous paste. Furthermore, the agent can be in the form of a one-component system. Such funds consist of one phase. Alternatively, a remedy can also consist of several phases. Such a remedy is therefore divided into several components.

In principle, the agents can have different states of aggregation. In a preferred embodiment, the detergents or cleaning agents are liquid or gel-like agents.

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

The funds can be packed in foil bags, for example. Pouch packaging made from water-soluble film eliminates the need for the consumer to tear open the packaging. In this way, a single portion measured for a wash cycle can be conveniently dosed by placing the bag directly in the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, bowl or hand wash basin. The film bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

There are numerous processes in the prior art for the production of water-soluble detergent portions, which in principle can also be used within the scope of the present invention. The best-known methods are the tubular film method with horizontal and vertical sealing seams. The thermoforming process (deep-drawing process) is also suitable for the production of film bags or dimensionally stable detergent portions. However, the water-soluble envelopes do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules from polyvinyl alcohol or gelatin are known, which in principle offer the possibility of providing capsules with a high degree of filling. The processes are based on the water-soluble polymer being introduced into a shaping cavity. The capsules are filled and sealed either synchronously or in sequential steps, in which case the capsules are filled through a small opening. The capsules are filled, for example, by a filling wedge which is arranged above two counter-rotating drums which have spherical hemispheres on their surface. The drums carry polymer tapes that cover the cavities of the hemispheres. Sealing takes place at the positions where the polymer tape of one drum meets the polymer tape of the opposite drum. At the same time, the filling material is injected into the capsule that is being formed, with the injection pressure of the filling liquid pressing the polymer strips into the cavities of the hemisphere. A process for the production of water-soluble capsules, in which first the filling and then the Sealing is based on the so-called Bottle-Pack ^® process. Here, a tube-like preform is fed into a two-part cavity. The cavity is closed, with the lower tube section being sealed, the tube is then inflated to form the capsule shape in the cavity, filled and finally sealed.

The casing material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly 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 the materials mentioned, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark ^Mowiol® (Clariant). In the context of 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 produce the portion can optionally also contain 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 is 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 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 lies. It is also preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight the water-soluble polymeric thermoplastic.

Any methods known from the prior art are suitable for producing the detergents or cleaning agents described herein.

Washing or cleaning processes, ie in particular processes for cleaning textiles, are generally characterized in that active cleaning substances are applied to the items to be cleaned in one or more process steps and washed off after the exposure time, or that the items to be cleaned are otherwise treated with a detergent or cleaning agent or a solution of this agent.

In the washing or cleaning methods described, in particular washing methods, temperatures of up to 95° C. or less, 90° C. or less, 60° C. or less, 50° C. or less, 40° C. or less are used in various embodiments of the invention , 30°C or less or 20°C or less. These temperature specifications relate to the temperatures used in the washing or cleaning steps.

In further aspects, the present invention is also aimed at the use of the agent according to the invention for minimizing the tendency to wrinkle and/or for facilitating the ironing of textiles; and to increase the softness of fabrics after laundering as described above.

The present invention is also directed to methods of finishing textiles to reduce the tendency to wrinkle and/or make them easier to iron, and methods of increasing the softness of textiles as described above, and a washing method as described above.

All facts, objects and embodiments that are described for the agents according to the invention are also applicable to the subject invention of the uses, methods and the washing method. Therefore, at this point, reference is expressly made to the disclosure at the appropriate point, with the indication that this disclosure also applies to the above uses, methods and the washing method according to the invention.

examples Composition of the detergent

Different textiles (cotton fabrics and polyester/cotton fabrics) were washed with a liquid detergent (recipe 1) and once with a liquid detergent with the addition of 1.0% of a propylene glycol ester (recipe 2).

The different fabrics were each washed separately at 40°C (in the easy-care program) and 5 wash cycles were carried out. After 3 washes, intermediate drying was carried out overnight. After 5 washes the fabric was dried again. ingredients recipe 1 Recipe 2 (according to the invention) Standard (in % by weight) Standard with 1.0% propylene glycol ester (in % by weight) anionic surfactant 5.7 5.7 nonionic surfactant 3.3 3.3 Builders (citric acid and phosphonates) 0.43 0.43 caustic soda 0.6 0.6 palm kernel oil fatty acid 0.5 0.5 glycerin 0.5 0.5 sodium chloride 1.8 1.8 Enzymes (protease, amylase, cellulase, lipase) 0.4 0.4 boric acid 0.5 0.5 propylene glycol laurate; Migoto type BP (propylene glycol ester) - 1.0 Other additives (preservatives, defoamers, optical brighteners, dyes, perfume) 0.49 0.49 Water to 100 to 100

The Migoto type BP compound from Riken was used as the propylene glycol ester. Surprisingly, it has now been found that these compounds can improve the surface of textiles in detergents. The esters can be easily incorporated into the liquid detergent.

measurement method

• (Zuvor wurden die 3 Einzelproben jeweils 5mal auf der gleichen Bügelstrecke hintereinander gebügelt.)
• Messung 1 erfolgt auf der ungebügelten Probe = statische Reibung
• Messung 2 auf der bereits gebügelten Probe = dynamische Reibung
• Die Berechnung der Ergebnisse erfolgte wie in den Tests zuvor in Anlehnung an DIN EN ISO 13937-2:2000.

6 individual samples are each ironed twice at different points, which means that an increased sample size is generated for each measurement. 12 individual values are generated per measurement. 2 measurements are evaluated.

• (Before, the 3 individual samples were each ironed 5 times in a row on the same ironing section.)
• Measurement 1 takes place on the unironed sample = static friction
• Measurement 2 on the already ironed sample = dynamic friction
• The results were calculated as in the previous tests based on DIN EN ISO 13937-2:2000.

Measurement results

Fabric: SAM Fabric 65% Polyester / 35% Cotton
The differences in cN versus formulation 1 are shown in each case, taking into account the standard deviations and assuming a significance of 10 cN, x > or = 10cN
Dark means significant value and light means equal to the standard.
Fabric: SAM Fabric 65% Polyester / 35% Cotton Formulation 2 (standard with 1% propylene glycol laurate) Static Friction - 17.3 dynamic friction - 18.6
It can be seen that formulation 2 with the addition of propylene glycol laurate results in significantly better static and dynamic friction on the blended fabric.

Claims (9)

1. A laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, characterized in that the composition contains, based on the total weight, from 0.01 to 30% by weight, preferably from 0.1 to 4% by weight, of at least one propylene glycol ester corresponding to formula (I):

   

   where

   X₁ is -OH and

   X₂ is

   

   where R₂ is an alkyl having 5-35 carbon atoms or an alkenyl having 5-35 carbon atoms.
2. Laundry detergent, laundry after-treatment or laundry care composition, in particular liquid detergent, according to claim 1, characterized in that R₂ is an alkyl having 11 carbon atoms.
3. Laundry detergent, laundry after-treatment or laundry care composition, in particular liquid detergent, according to one of Claims 1 to 2, characterized in that the composition further comprises at least one further constituent selected from the group consisting of surfactants, enzymes, enzyme stabilizers, complexing agents for heavy metals, builders, bleaching agents, builders, electrolytes, non-aqueous solvents, pH-adjusting agents, odor absorbers, deodorizing substances, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, other anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, softening components and UV absorbers.
4. Use of a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, characterized in that the composition contains, based on the total weight, from 0.01 to 30% by weight, preferably from 0.1 to 4% by weight, of at least one propylene glycol ester corresponding to formula (I):

   

   where

   X₁ is -OH and

   X₂ is

   

   wherein R₂ is an alkyl having 5-35 carbon atoms or an alkenyl having 5-35 carbon atoms, to minimize the tendency to wrinkle and / or facilitate the ironing of textiles.
5. Use of a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, characterized in that the composition contains, based on the total weight, from 0.01 to 30% by weight, preferably from 0.1 to 4% by weight, of at least one propylene glycol ester corresponding to formula (I):

   

   where

   X₁ is -OH and

   X₂ is

   

   wherein R₂ is an alkyl having 5-35 carbon atoms or an alkenyl having 5-35 carbon atoms, to increase the softness of textiles after washing.
6. A process for the crease-reducing and/or easy-ironing finishing of textiles by bringing them into contact with a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, characterized in that the composition contains, based on the total weight, from 0.01 to 30% by weight, preferably from 0.1 to 4% by weight, of at least one propylene glycol ester corresponding to formula (I):

   

   where

   X₁ is -OH and

   X₂ is

   

   wherein R₂ is an alkyl having 5-35 carbon atoms or an alkenyl having 5-35 carbon atoms,

   and subsequent washing of the textile in the presence of the laundry detergent, laundry aftertreatment or laundry care composition.
7. A process for increasing the softness of textiles by bringing them into contact with a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid detergent, characterized in that the composition contains, based on the total weight, from 0.01 to 30% by weight, preferably from 0.1 to 4% by weight, of at least one propylene glycol ester corresponding to formula (I):

   

   where

   X₁ is -OH and

   X₂ is

   

   wherein R₂ is an alkyl having 5-35 carbon atoms or an alkenyl having 5-35 carbon atoms,

   and subsequent washing of the textile in the presence of the laundry detergent, laundry aftertreatment or laundry care composition.
8. Washing process comprising the process steps

   a) Providing a washing or cleaning solution comprising a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, according to any one of claims 1 to 3, and

   b) Bringing a textile or hard surface into contact with the washing or cleaning solution according to (a).
9. Use or method according to any one of claims 4-7, characterized in that the laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, is a laundry detergent, laundry aftertreatment or laundry care composition, in particular a liquid laundry detergent, according to any one of claims 1-3.