EP1743017B1 - Fabric care product containing a cellulose ether comprising amine groups - Google Patents

Abstract

The invention concerns a fabric care product containing an amine-modified cellulose ether, designed to protect the fabrics. The invention also concerns the use of said product to improve water absorption and resistance, to reduce lint, piling and folds, for smoothing, to obtain a softer feel, as well as for facilitating ironing.

Description

The invention relates to the use of an amine-modified cellulose ether for improving the water absorption and the shape retention of textile fabrics as well as the improvement of their ironing properties.

The modern textile cleaning makes high demands on the laundry to be cleaned. For example, the frequent washing of garments in a washing machine and the subsequent drying in a tumble dryer is associated with a high mechanical stress on the fabric. The frictional forces often lead to damage to the textile fabric, recognizable by a fluff and pilling. With each washing or drying cycle, but also by wearing the garments, a further abrasion and / or breakage of tiny fibers takes place on the surface of the textile surface fabrics. The conventional textile cleaners are unable to prevent this damage to the fabric or merely try to eliminate already incurred textile damage.

The international patent application WO 99/16956 A1 suggests the elimination of lint or pills through the use of cellulases. The cellulases thereby break off the microfibers protruding from the textile fabrics and thus ensure a smooth and therefore pilling-free textile surface.

Another major disadvantage of the mechanical stress on textile fabrics is the formation of unwanted wrinkled textile surfaces from the consumer and the formation of rough surfaces. Both the rough textile surfaces as well as the resulting creasing of the fabrics lead to a significant deterioration of the sliding properties of irons or other Textilplättungsvorrichtungen. The expense of flattening rough and crumpled textiles is not only a matter of greater effort, but also of considerable additional time. In the prior art, solutions for improving the ironing properties of laundered textiles are found mainly in the field of aftertreatment agents. For example, in the international patent application WO 00/77134 discloses the use of oxidized polyolefins in softener formulations to improve ironing properties.

The use of celluloses, hydrogels and acrylic acid polymers as lint reduction components in textile treatment agents is known from the German patent application DE 102 03 192 A1 known.

Out WO 99/14245 A1 Cellulosic polymers are known which are substituted with carboxyalkyl and Amidoalkylgruppen and optionally substituted with hydroxyalkyl groups. WO 98/29528 A2 relates to detergent, KOENEN in addition to surfactant and builder celluloses which a sealed with a C _8-24 alkyl end group Oligoalkyethersubstituenten, a sealed with an ammonium alkyl end group or Oligoalkyethersubstituenten transmits to C ₆ of the anhydroglucose monomeric unit at any point a carboxymethyl radical. The European patent application EP 0 017 120 A1 discloses finishing laundry detergents containing water-soluble quaternary ammonium group aminoethers of polysaccharides.

in der a und b unabhängig voneinander 2 oder 3, c 1, 2 oder 3, m und p unabhängig voneinander eine ganze Zahl von 0 bis 10, n eine ganze Zahl von 0 bis 3, q 0 oder 1, X- ein Anion, welches entsprechend seiner Ladung in einer solchen Anzahl vorhanden ist, dass es die positiven Ladungen der quaternären Stickstoffatome ausgleicht, und R' Wasserstoff, eine Carbonsäuregruppe oder eine Natrium-, Kalium- oder Ammoniumcarboxylatgruppe ist mit der Maßgabe, daß R' Wasserstoff ist, wenn q 0 ist. Die Verbindungen der Formel I können, wie dort beschrieben, durch Umsetzung üblicher oder zuvor speziell hergestellter nichtionischer Celluloseether mit quaternären Halogenhydrinen oder quaternären Epoxiden erhalten werden.The US patent US 3 472 840 describes quaternary nitrogen-containing cellulose ethers of the general formula (I),

((RO-) ₃ R _Cell ) _y (I)

in the R _{cell is} an anhydroglucose residue (C ₆ H ₁₀ O ₅ ), the degree of polymerization y is a number from 50 to 20 000 and each of the radicals R corresponds to the general formula (II),

in the a and b are independently 2 or 3, c is 1, 2 or 3, m and p are independently an integer from 0 to 10, n is an integer from 0 to 3, q is 0 or 1, X is an anion, which is present, according to its charge, in such number as to balance the positive charges of the quaternary nitrogen atoms, and R 'is hydrogen, a carboxylic acid group or a sodium, potassium or ammonium carboxylate group, provided that R' is hydrogen when q 0 is. As described there, the compounds of the formula I can be obtained by reacting customary or previously custom-made nonionic cellulose ethers with quaternary halohydrins or quaternary epoxides.

Analogously, from cellulose ethers by reaction with haloalkylamines, epoxyalkylamines or by reaction with epoxyalkyl halides (for example epichlorohydrin) and subsequent reaction with amines, corresponding amine-substituted derivatives in which the nitrogen atoms in the substituent are not quaternized are obtained.

Surprisingly, it has now been found that the use of the last-mentioned amine-substituted derivatives without a quaternary nitrogen atom in the washing process leads to a significant improvement in the fiber and textile properties.

in denen a und b unabhängig voneinander 2 oder 3, c 1, 2 oder 3, m und p unabhängig voneinander eine ganze Zahl von 0 bis 10, n eine ganze Zahl von 0 bis 3, q 0 oder 1, R¹ und R² unabhängig voneinander Wasserstoff oder ein C_1-4-Alkylrest und R³ Wasserstoff, -NR¹R², eine Carbonsäuregruppe oder eine Natrium-, Kalium- oder Ammoniumcarboxylatgruppe ist mit der Maßgabe, dass R³ Wasserstoff ist, wenn q 0 ist, und mit der weiteren Maßgabe, dass in mindestens einem der Reste R die Zahl n größer als 0 ist oder in mindestens einem der Reste R die Gruppierung -R³ für -NR¹R² steht, in einem Textilpflegemittel zur Verbesserung der Wasseraufnahme oder zur Verbesserung des Formerhalts oder zur Bügelerleichterung textiler Flächengebilde.The present invention therefore provides the use of a nitrogen-containing cellulose ether of the general formula (I),

((RO-) ₃ R _Cell ) _y (I)

in the R _{cell is} an anhydroglucose radical (C ₆ H ₁₀ O ₅ ), the degree of polymerization y is a number from 80 to 65 000 and each of the radicals R corresponds to the general formula (II),

in which a and b are independently 2 or 3, c is 1, 2 or 3, m and p are independently an integer from 0 to 10, n is an integer from 0 to 3, q is 0 or 1, R ¹ and R ² independently of one another are hydrogen or a C _1-4 -alkyl radical and R ^{3 is} hydrogen, -NR ¹ R ² , a carboxylic acid group or a sodium, potassium or ammonium carboxylate group with the proviso that R ^{3 is} hydrogen when q is 0, and with the further proviso that in at least one of the radicals R, the number n is greater than 0 or in at least one of the radicals R is the group -R ^{3 is} -NR ¹ R ² , in a textile care agent to improve the water absorption or to improve the Formerhalt or for ironing relief textile fabrics.

As stated above, such amine-modified cellulose ethers can be prepared in a simple manner by reaction of at least one hydroxyl group of cellulose and / or hydroxyl-containing cellulose ethers, for example alkyl, hydroxyalkyl or Alkylhydroxyalkylcelluloseethers, with halogenated alkylamines, epoxyalkylamines or first with Epoxyalkylhalogeniden (eg epichlorohydrin) and subsequent reaction with amines, are obtained. Particularly suitable halogenoalkylamines are trialkylamines in which an alkyl group carries a halogen atom, in particular chlorine. Among them, 1-diethylamino-2-chloroethane is particularly preferred. As Epoxyalkylhalogenid is in particular epichlorohydrin into consideration, in which case the subsequent reaction with diethylamine is particularly preferred. In order to avoid a nucleophilic reaction of the amine-nitrogen when using halogenated alkylamines or epoxy-alkylamines, this may be in the usual way in salt form, for example as hydrochloride, so that a neutralization must follow, before the free amines of the general Formula (I) receives.

In the context of this invention, textile care products are understood as meaning both washing and cleaning agents and pretreatment agents and agents for conditioning textile fabrics, such as mild detergents and post-treatment agents, such as fabric softeners. Conditioning is to be understood as the avivating treatment of textile fabrics, fabrics, yarns and fabrics. The purpose of the conditioning is to impart positive properties to the textiles, such as, for example, improved softness, increased gloss and color brilliance, refreshment of fragrance, and reduction of creasing behavior and static charge.

When using agents containing said cellulose ether, in particular the wrinkling of textiles is prevented by the washing and / or drying process, the ironing properties of the textile are improved and the "leaching" of the textiles during washing is considerably reduced. In addition, especially with synthetic fibers, which are otherwise usually unable to absorb moisture such as sweat, the water absorption capacity is significantly increased by the use of such agents and thereby the feel of the textiles much more pleasant.

The textile care agents may be either in solid form, for example as a powder, granules, extrudate, pressed and / or molten molded articles such as tablets, or in liquid form, for example as dispersion, suspension, emulsion,

Solution, microemulsion, gel or paste. In a preferred embodiment of the invention, they are liquid. The compositions preferably contain 0.1% by weight to 5% by weight, in particular 0.1% by weight to 1% by weight, of amine-modified cellulose ether of the general formula (I). In the compounds of the formula (I), y is preferably in the range from 200 to 35 000, in particular in the range from 800 to 30 000. Per anhydroglucose unit R _Cell , n is preferably 0.01 to 1, in particular 0.1 to 0, 8, or corresponding numbers of R ³ radicals corresponding to the grouping -NR ¹ R ² , are present, that is to say averaged over the total cellulose ether, preferably one to one in every 10th to every 10th to 10th of the anhydroglucose units Substituted nitrogen atom-bearing group. The sum of m, n, p and q per anhydroglucose unit R _Cell is preferably 0.01 to 4, in particular 0.1 to 2 and more preferably 0.8 to 2 as average.

In addition to the groups bearing the nitrogen atom, the cellulose ethers to be used according to the invention preferably contain methyl, ethyl, propyl, hydroxyethyl and / or hydroxypropyl groups. These groups represent part of the radicals R and / or are part of the group carrying the nitrogen atom as a subgroup - (C _b H _2b -O) _p - (C _c H ₂ ) _q -R ³ .

The average molecular weight M w of the cellulose ethers to be used according to the invention is preferably above 5000, more preferably above 10 000, in particular between 30 000 and 1 000 000, advantageously between 50 000 and 800 000 g / mol and most preferably between 200 000 and 600 000 g / mol. The molecular weight can be determined by gel permeation chromatography against normalized polyacrylic acid standards.

In a preferred embodiment, the fabric care agents contain complexing agents in addition to the amine-modified cellulose ether. It has surprisingly been found that, in particular, organic, advantageously water-soluble, complexing agents can be incorporated particularly well into the textile care compositions and in particular together with the cellulose ether to be used according to the invention gives the textile care product, in particular the liquid preparations, increased stability. The complexing agents improve the stability of the agents and protect, for example, against the heavy metals catalyzed decomposition of certain ingredients of washing active formulations. Together with the cellulose ethers to be used according to the invention, they contribute to the inhibition of incrustations. The group of complexing agents includes, for example, the salts, in particular the alkali metal salts of nitrilotriacetic acid (NTA) and derivatives thereof, and alkali metal salts of anionic polyelectrolytes, such as polymaleates and polysulfonates. Furthermore, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and their derivatives as well as mixtures of these are suitable. Particularly preferred compounds include organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Particularly preferred in the context of the present invention is the citric acid and / or its alkali metal salts, for example sodium citrate and / or potassium citrate. In a preferred embodiment, the fabric care agents contain complexing agents in an amount of up to 20 wt .-%, preferably from 0.01 to 15 wt .-%, particularly preferably from 0.1 to 10 and in particular from 0.3 to 5.0 wt. -%, Advantageously from 1.5 to 3 wt .-%, each based on the total agent.

In a preferred embodiment, the fabric care agents additionally contain nonionic surfactants. The use of nonionic surfactants not only increases the washing performance of the compositions, but additionally supports the dispersion and homogeneous distribution of the cellulose ether to be used according to the invention.

Furthermore, in a preferred embodiment, the fabric care agents may additionally contain enzymes.

Enzymes support the washing processes in a variety of ways, especially in the removal of poorly bleachable contaminants, such as protein stains. The incorporation of enzymes in detergent formulations, especially in liquid fabric care products, however, often causes problems because it can lead to incompatibilities with other detergent ingredients, which in turn can cause a loss of activity of the enzymes. Surprisingly, it has been found that the stability of the enzymes in wash liquor or textile care formulation, in particular in liquid fabric care formulations, can be improved by the use of the copolymers to be used according to the invention.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. As different cellulase types through their Differentiate CMCase and avicelase activities, the desired activities can be adjusted by targeted mixtures of cellulases.

The enzymes may be adsorbed or coated on carriers to protect against premature degradation.

The textile care agents in a preferred embodiment contain enzymes, preferably selected from the group of proteases and / or amylases and / or cellulases.

If the textile care agents are present as mild detergents or after-treatment agents, for example as fabric softeners, they can, in a preferred embodiment, comprise cellulase, preferably in an amount of from 0.005 to 2% by weight, particularly preferably from 0.01 to 1% by weight, in particular of 0.02 to 0.5 wt .-%, each based on the total agent included.

In a preferred embodiment, the textile care agents are in liquid form and advantageously have a viscosity of from 50 to 5000 mPas, more preferably from 50 to 3000 mPas and in particular from 500 to 1500 mPas (measured at 20 ° C. with a rotational viscometer (Brookfield RV, spindle 2 ) at 20 rpm (rpm: revolutions per minute)).

Preferred liquid fabric care agents in one preferred embodiment contain one or more nonaqueous, water-miscible solvents.

The fabric care products, if they are in liquid form, in a preferred embodiment, up to 95 wt .-%, particularly preferably 20 to 90 wt .-% and in particular 50 to 80 wt .-% of one or more solvents, preferably water-soluble solvents and especially water.

In a preferred embodiment, the fabric care agents additionally contain plasticizer components, preferably cationic surfactants. In particular, when the textile care agents as a mild detergent or textile aftertreatment agent, for example as a fabric softener, are present, the use of additional plasticizer components has proven to be extremely advantageous. Especially when washing sensitive textiles, such as silk, wool or linen, which are washed and ironed at low temperatures, has proven the use of plasticizer components. In addition to the cellulose ethers to be used according to the invention, the plasticizer components additionally facilitate the ironing of the textiles and reduce the static charge of the textile materials.

Examples of fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.

In addition to the aforementioned components, the fabric care agents may contain pearlescing agents. Pearlescing agents give the textiles an extra gloss and are therefore preferably used in fine detergents according to the invention.

Examples of suitable pearlescing agents are: 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 textile care products may additionally contain thickeners. The use of thickeners in the textile care agents according to the invention which are to find use as liquid detergents has proven particularly advantageous. To increase consumer acceptance, the use of thickening agents has proven particularly useful in gel-type liquid detergents. The thickened consistency of the agent simplifies the application of the agent directly to the spots to be treated. A bleeding, as usual with thin liquids, is thereby prevented.

Furthermore, the textile care agents may additionally contain odor absorbers and / or color transfer inhibitors. Especially for the Textile care products as fine. Aftertreatment and liquid detergents are present, the use of Farbübertragungsinhibtoren has proven. The use of odor absorbers has proven to be very useful for deodorizing foul-smelling constituents of formulations, for example amine-containing components, but also for the sustainable deodorization of the washed textiles.

The textile care agents may additionally contain other surfactants, for example amphoteric surfactants.

The textile care agents may additionally comprise further detergent additives, for example from the group of builders, bleaches, bleach activators, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, grayness inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , UV absorbers, optical brighteners, anti-redeposition agents, viscosity regulators, anti-shrinkage agents, corrosion inhibitors, preservatives, repellents and impregnating agents.

The funds may contain builders. All builders conventionally used in detergents and cleaning agents can be incorporated into the compositions according to the invention, in particular zeolites, silicates, carbonates, organic cobuilders and, if there are no ecological prejudices against their use, also the phosphates.

The agents of the invention may contain bleaching agents.

The agents may contain bleach activators.

The agents may contain electrolytes.

The agents may contain pH adjusters.

The agents may contain dyes and perfumes.

Dyes and fragrances are added to the compositions in order to improve the aesthetic appearance of the products and to provide the consumer, in addition to the washing or cleaning performance, a visually and sensory "typical and unmistakable" product. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, α-isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The agents may contain UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers and / or the lightfastness of the other ingredients of the formulation. UV absorbers are understood as meaning organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivation compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable. Of particular importance are biphenyl and especially Stilbenderivate as described for example in the EP 0728749 A are described and commercially available as Tinosorb FD ^® or Tinosorb FR ^® are available ex Ciba. As UV-B absorber are 3-benzylidene camphor or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1 described; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, as described in U.S. Pat EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives as described in U.S.P. EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenrnethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S. Pat DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV light protection filters can be found in the review by P. Finkel in SÖFW Journal 122, 543 (1996). UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

The agents may contain additional anti-wrinkle agents to support the corresponding effect of the cellulose ether to be used according to the invention, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are resistant to bending, buckling, pressing and crushing transversely to the fiber direction are sensitive. These include, for example, synthetic products based on fatty acids, Fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

The agents may contain grayness inhibitors. These have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-raising of the dirt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to anionic or nonionic cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and / or methylcarboxymethylcellulose.

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

The textile care agents can be packed in foil bags, for example. 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 inserting the bag into a certain amount of water, for example in a bucket, a bowl or in Handwasch- or -spülbecken, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature. Detergents packaged in bags of water-soluble film are described in large numbers in the prior art. So revealed the German patent application DE 198 31 703 a portioned detergent or cleaner preparation in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 wt .-% of the particles of the detergent or cleaning preparation particle sizes> 800 microns ,

Numerous processes for the preparation of water-soluble detergent portions, which are basically also useful in the context of the present invention, already exist in the prior art. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Further suitable for the production of film bags or dimensionally stable detergent portions is the Thermoformverrfahren (thermoforming method), as for example in the WO-A1 00/55068 is described. 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. A known process for the preparation of water-soluble injection molded hollow bodies containing detergents and / or cleaning agents, is for example in the WO-A1 01/36290 described.

Furthermore, processes for the preparation of water-soluble capsules of polyvinyl alcohol or gelatin are known in the prior art, 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. Processes in which the filling and sealing are parallel, for example, in the WO 97/35537 described. The filling of the capsules is carried out 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, the injection pressure of the Filling fluid presses the polymer bands in the ball half-shell cavities. A process for the preparation of water-soluble capsules, in which first the filling and then the sealing takes place, is in the WO 01/64421 disclosed. The manufacturing process is based on the so-called Bottle-Pack ^® method, as described for example in the German Offenlegungsschrift DE 14 114 69 is described. 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.

In one embodiment of the invention, the wrapping material may consist entirely or partially of the cellulose ethers to be used according to the invention in the textile care agent.

The polyvinyl alcohols described above 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 is 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%. More preferably, the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , more preferably 12,000 to 80,000 gmol ^{-1 1,} and most preferably 13,000 to 70,000 gmol ^-1 is located. 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. The polymeric thermoplastics may contain plasticizing aids to improve their machinability. This may be advantageous in particular if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries. It is advantageous if the polymeric thermoplastics plasticizing in amounts of at least> 0 wt .-%, preferably from = 10 wt .-%, particularly preferably from = 20 wt .-% and in particular of = 30 wt .-%, each based on the weight of the wrapping material.

Surprisingly, it has also been found that the cellulose ethers to be used according to the invention not only reduce wrinkling and provide a smooth textile surface, but also significantly improve the soft feel of the treated textiles.

A conditioning substrate, which is a substrate which is impregnated and / or impregnated with the cellulose ether-containing textile care agent used according to the invention, is conceivable.

The substrate material is made of porous materials capable of reversibly feeding and dispensing an impregnating liquid. In question come for it both three-dimensional structures, such as sponges, but preferably porous, sheet-like cloths. They may consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient amounts of impregnating or coating agent to effectively condition fabrics without significant bleeding or bleeding of the composition during storage he follows. These wipes include cloths of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.

Preferably, conventional cloths of nonwoven material (nonwovens) are used here. Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed. The fibers may be of natural origin, such as wool, silk, jute, hemp, cotton, linen, sisal or ramie; or synthetically produced, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides, viscose or polyester. In general, any fiber diameter or titer is suitable for the present invention. Preferred conditioning substrates according to the invention consist of a nonwoven material which contains cellulose. The nonwoven fabrics employed herein tend not to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material which impart excellent strength in all directions when used, for example, in a household tumble dryer. Examples of nonwoven fabrics suitable as substrates in the present invention include, for example WO 93/23603 known. Preferred porous and Flat conditioning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these. The conditioning substrates in fabric form preferably have an area of from 0.2 to 0.005 m ² , preferably from 0.15 to 0.01 m ² , in particular from 0.1 to 0.03 cm ² and particularly preferably from 0.09 to 0, 06 m ² up. The grammage of the material is usually between 20 and 500 g / m ² , preferably from 25 to 200 g / m ² , in particular from 30 to 100 g / m ² and particularly preferably from 40 to 80 g / m ² .

Also conceivable is a conditioning method for conditioning wet textiles by means of the conditioning substrate.

The conditioning process is carried out by using the conditioning substrate in a textile drying process together with wet textiles obtained, for example, from a previous washing process. The textile drying process usually takes place in a device for drying textiles, preferably in a household tumble dryer.

The fabric care agents can be added in their conditioning aspect directly with the wet laundry in a household dryer and / or a washing machine.

The fabric care agents can be prepared by simple, familiar to the expert mixing together and stirring of the individual components. The cellulose ethers to be used according to the invention can be admixed as a solution or slurry, preferably in aqueous form, to a particular liquid agent and / or can be compounded or granulated, mixed or tabletted or pelletized as a dried powder, preferably as a carrier on a detergent component.

Examples Example 1: Composition

Table 1 shows the liquid formulation M1 containing a cellulose derivative to be used according to the invention and the comparative formulation V1. All information is given in weight percent, in each case based on the total mean. <u> Table 1 </ u> M1 V1 C _12-14 sodium alkyl ether sulfate 5 5 C ₁₂ -C ₁₈ fatty alcohol + 7 EO 12 12 C _14-16 -Alkylglukosid 2 2 C _12-18 soap (Na salt) 5 5 trisodium citrate 2 2 glycerin 5 5 Cellulose ethers ^[a] 1 - water on 100 on 100 ^[a] Hydroxyethyl cellulose reacted with diethylaminoethylene chloride

The test textiles indicated in Table 2 below were washed with 120 g of the respective composition [water hardness: 16 ° dH] (Miele W308, standard program 40 ° C.) and then dried (hanging for 2 days on a line in a climatic chamber at 20 ° C.) 65% humidity).

The washing and drying cycles were repeated 9 times each (ie a total of 10 wash / dry cycles).

The textile to be tested was stretched in a dynamometer (Hounsfield H5KS) for 1 minute by 80% of the original length, then relaxed for 3 minutes and then measured the remaining residual strain. Table 2 below shows the residual elongation of the non-washed textile (U) and the residual elongation determined by the use of the agent M1 or V 1. Table 2: residual strain [%] Textile U V1 M1 Sweater (100% cotton) 19 42 33 Sweater (76% cotton finished / 19% PA / 5% spandex) 10 14 7

It can be seen that the use of the agent containing the active ingredient according to the invention leads to a significant improvement in the elasticity.

Example 2: Determination of water absorption capacity of textiles

Table 3 shows the universal detergent formulation M2 containing a cellulose derivative to be used according to the invention and the comparative formulation V2. All information is given in weight percent, in each case based on the total mean. <u> Table 3 </ u> M2 V2 esterquat 4 4 C _12-14 Sodium Alkyl Sulfate 0.5 0.5 C ₁₂ -C ₁₈ fatty alcohol + 7 EO 14 14 C _14-16 alkyl glucoside 3 3 ethanol 2 2 Cellulose ethers ^[a] 1 - water on 100 on 100 ^[a] Hydroxyethyl cellulose reacted with diethylaminoethylene chloride

Textiles of the material indicated in Table 4 below were washed with 120 g of the respective composition [water hardness: 16 ° dH] (Miele W918, single-lobe cooking / color program 40 ° C.) and then dried (hanging on a leash in the climatic chamber for 2 days) at 20 ° C and 65% humidity). The washing and drying cycles were repeated 9 times each (ie a total of 10 wash / dry cycles). Thereafter, the absorbency of the textiles was measured by measuring the rise height according to DIN 53924. <u> Table 4: Rising height [mm] </ u> test fabric M2 V2 cotton 92 46 Cotton / polyester (55/45) 71 48 polyester 125 88

For the formulation M2 containing a cellulose derivative to be used according to the invention, there is a markedly improved absorbency of the textiles treated therewith in comparison to their treatment with V2.

Claims (14)

1. Use of a nitrogenous cellulose ether of the general formula (I),
   
           ((R-O-)₃R_Cell)_y     (I)
   
   in which R_Cell is an anhydroglucose residue (C₆H₁₀O₅), the degree of polymerisation y is a number from 80 to 65,000 and each of the residues R corresponds to the general formula (II),

   

   in which a and b are mutually independently 2 or 3, c is 1, 2 or 3, m and p are mutually independently an integer from 0 to 10, n is an integer from 0 to 3, q is 0 or 1, R¹ and R² are mutually independently hydrogen or a C_1-4 alkyl residue and R³ is hydrogen, -NR¹R², a carboxylic acid group or a sodium, potassium or ammonium carboxylate group with the proviso that R³ is hydrogen if q is 0, and with the further proviso that in at least one of the residues R the number n is greater than 0 or in at least one of the residues R the grouping -R³ denotes -NR¹R², in a textile care agent for improving the water absorption of textile fabrics.
2. Use of a nitrogenous cellulose ether of the general formula (I),
   
           ((R-O-)₃R_Cell)_y     (I)
   
   in which R_Cell is an anhydroglucose residue (C₆H₁₀O₅), the degree of polymerisation y is a number from 80 to 65,000 and each of the residues R corresponds to the general formula (II),

   

   in which a and b are mutually independently 2 or 3, c is 1, 2 or 3, m and p are mutually independently an integer from 0 to 10, n is an integer from 0 to 3, q is 0 or 1, R¹ and R² are mutually independently hydrogen or a C_1-4 alkyl residue and R³ is hydrogen, -NR¹R², a carboxylic acid group or a sodium, potassium or ammonium carboxylate group with the proviso that R³ is hydrogen if q is 0, and with the further proviso that in at least one of the residues R the number n is greater than 0 or in at least one of the residues R the grouping -R³ denotes -NR¹R², in a textile care agent for improving the shape retention of textile fabrics.
3. Use of a nitrogenous cellulose ether of the general formula (I),
   
           ((R-O-)₃R_Cell)_y     (I)
   
   in which R_Cell is an anhydroglucose residue (C₆H₁₀O₅), the degree of polymerisation y is a number from 80 to 65,000 and each of the residues R corresponds to the general formula (II),

   

   in which a and b are mutually independently 2 or 3, c is 1, 2 or 3, m and p are mutually independently an integer from 0 to 10, n is an integer from 0 to 3, q is 0 or 1, R¹ and R² are mutually independently hydrogen or a C_1-4 alkyl residue and R³ is hydrogen, -NR¹R², a carboxylic acid group or a sodium, potassium or ammonium carboxylate group with the proviso that R³ is hydrogen if q is 0, and with the further proviso that in at least one of the residues R the number n is greater than 0 or in at least one of the residues R the grouping -R³ denotes -NR¹R², in a textile care agent for facilitating the ironing of textile fabrics.
4. Use according to any one of claims 1 to 3, characterised in that the agent contains 0.1 wt.% to 5 wt.%, in particular 0.1 wt.% to 1 wt.% of amine-modified cellulose ether of the general formula (I).
5. Use according to any one of claims 1 to 4, characterised in that, in the compounds according to formula (I), y is in the range from 200 to 35,000, in particular in the range from 800 to 30,000.
6. Use according to any one of claims 1 to 5, characterised in that, in the compounds according to formula (I) per anhydroglucose unit R_Cell, n is on average 0.01 to 1, in particular 0.1 to 0.8 or corresponding numbers of residues R³, which correspond to the grouping -NR¹R², are present.
7. Use according to any one of claims 1 to 6, characterised in that, in the compounds according to formula (I), the sum of m, n, p and q per anhydroglucose unit R_Cell amounts on average to 0.01 to 4, in particular 0.1 to 2 and particularly preferably 0.8 to 2.
8. Use according to any one of claims 1 to 7, characterised in that, in the compounds according to formula (I), in addition to the groups bearing the tertiary nitrogen atom, methyl, ethyl, propyl, hydroxyethyl and/or hydroxypropyl groups are present.
9. Use according to any one of claims 1 to 8, characterised in that the compound according to formula (I) has an average molecular weight Mw of above 10,000, in particular of above 30,000 g/mol.
10. Use according to claim 9, characterised in that the compound according to formula (I) has an average molecular weight Mw of between 50,000 and 800,000, in particular between 200,000 and 600,000 g/mol.
11. Use according to any one of claims 1 to 10, characterised in that the agent contains complexing agents, in particular organic, advantageously water-soluble, complexing agents, particularly preferably complexing agents comprising acid groups, extremely preferably citric acid and/or the alkali metal salts thereof.
12. Use according to any one of claims 1 to 11, characterised in that the agent is present in solid form, preferably as a powder, granular product, extrudate, pressed and/or fused moulding or as a tablet, particularly preferably in liquid form, in particular as a dispersion, suspension, emulsion, solution, microemulsion, gel or paste.
13. Use according to any one of claims 1 to 12, characterised in that the agent contains enzymes, preferably selected from the group of proteases and/or amylases and/or cellulases.
14. Use according to any one of claims 1 to 13, characterised in that the agent is present as a portion in a completely or partially water-soluble casing.