Method of modifying the adour properties of textiles

Abstract

The invention relates to a method of modifying the odour properties of textiles in which the textile is finished with an amylose-containing substance with an amylose content of at least 30% by weight. The invention also relates to textile materials which are obtainable by the method according to the invention.

Description

FIELD OF THE INVENTION

The present invention relates to a method of modifying the odour properties of textile materials, and to the textile materials obtainable by this method.

BACKGROUND OF THE INVENTION

Due to their fibre structure and the associated large specific surface area, textiles have a tendency to absorb odour-forming substances. In the case of textile clothing, for example, body sweat is adsorbed by the textile fibres and broken down to form substances which have an unpleasant odour. These are often so tightly bound in the textile materials that they can no longer be removed, or can be removed only with difficulty, even by washing or cleaning. On the other hand, they are released in small amounts, which are above the odour threshold, into the surrounding area meaning that even washed or cleaned textiles have an unpleasant sweat odour. Unpleasant odour substances from the atmosphere represent a further problem, for example food odours or cigarette smoke, which are firstly absorbed by textile clothing, but also by furnishing fabrics and then released again into the surroundings over a prolonged period, meaning that they exude an unpleasant odour over a relatively long period following contact with such odorants.

There have been various proposals to modify the odour properties of textiles with a finish based on cyclodextrins (see, for example, DE 40 35 378 and DE 10101294.2). Cyclodextrins are cyclic oligosaccharides which are formed by the enzymatic degradation of starch. The most common cyclodextrins are α-, β- and γ-cyclodextrins which consist of six, seven or eight, respectively, α-1,4 linked glucose units. A characteristic property of the cyclodextrin molecules is their ring structure with largely constant dimensions. The internal diameter of the rings is about 570 pm for α-cyclodextrin, about 780 pm for β-cyclodextrin and about 950 pm for γ-cyclodextrin. Due to their structure, cyclodextrins are in the position to be able to incorporate guest molecules, in particular hydrophobic guest molecules, in changing amounts to the point of saturation. In the case of the textiles finished with cyclodextrins, it is assumed that the odour-forming substances, for example sweat degradation products, are bound so firmly by the cyclodextrins that they are no longer released into the surroundings in an amount which can still be detected olefactorily. During washing or cleaning, the odour-forming substances are then displaced by the washing-active surfactant molecules which are present in large excess in the wash liquor, and discharged with the liquor. During subsequent rinsing, the surfactant molecules are rinsed out due to the dilution, meaning that the cyclodextrin molecules are again available to absorb odour-forming substances. It has also been proposed to charge the cyclodextrins with volatile fragrances in order to impart a pleasant odour to the textile finished in this way and simultaneously mask unpleasant odours.

However, cyclodextrins are so expensive that such a finishing represents a considerable cost factor in the manufacture of textile materials. In addition, the textiles finished with cyclodextrins have disadvantageous tactile properties, in particular a hard handle.

SUMMARY OF THE INVENTION

The object of the present invention was therefore to provide a more cost-effective alternative for modifying the odour properties of textiles. In addition, this finishing should not influence the properties of the fabric, in particular the tactile properties, in a disadvantageous way.

DETAILED DESCRIPTION OF THE INVENTION

Surprisingly, it has been found that amylose-containing substances with an amylose content of at least 30% by weight advantageously modify the odour properties of textiles in the same way as cyclodextrins. Accordingly, the present invention provides the use of amylose-containing substances with an amylose content of at least 30% by weight, based on the total weight of the substance, for modifying the odour properties of textiles.

The invention also provides a method of modifying the odour properties of textiles which is characterized in that the textile is finished with amylose or an amylose-containing substance with an amylose content of at least 30% by weight.

For the purposes of the invention, modification of the odour properties means both the reduction in unpleasant odours (odour-inhibiting effect) and the improvement in the odour of the textile with fragrances.

Besides amylose, suitable substances for modifying the odour properties are in principle all substances, in particular amylose-containing starches, i.e. native starches, modified starches and starch derivatives, whose amylose content is at least 30% by weight. The starch may be native, e.g. maize starch, wheat starch, potato starch, sorghum starch, rice starch or maranta starch, be obtained by partial digestion of native starch or be chemically modified. Also suitable is pure amylose as it is, e.g. enzymatically obtained amylose, e.g. amylose obtained from sucrose. Also suitable are mixtures of amylose and starch if the total content of amylose is at least 30% by weight, based on the total weight of the mixture. It goes without saying that here and below all data in % by weight which refers to amylose or amylose-containing substances, for mixtures of amylose and starch are always based on the total weight of amylose+starch, unless expressly stated otherwise.

Of particular suitability according to the invention are amylose-containing substances, in particular amylose and amylose-containing starches, and amylose/starch mixtures whose amylose content is at least 40% by weight and in particular at least 45% by weight, based on the total weight of the substance. As a rule, the amylose content will not exceed 90% by weight and in particular 80% by weight. Such substances are known and commercially available. For example, amylose-containing starches are sold by the companies Cerestar under the trade mark Amylogel® and National Starch under the trade names HYLON® V and VII.

To achieve the odour-modifying effect, the textile will be finished with the amylose-containing substance generally in an amount of at least 0.5% by weight, preferably at least 1% by weight and in particular at least 2% by weight, in each case based on the weight of the textile. As a rule, the amylose-containing substance will be used in an amount of not more than 25% by weight, often not more than 20% by weight and in particular not more than 15% by weight, based on the weight of the textile so as not to adversely affect the tactile properties of the textile.

In a first embodiment of the invention, to improve the odour properties, the textile material will be finished with the amylose-containing substance as it is. In this way, odour inhibition is achieved, i.e. a reduction in or prevention of the release of unpleasant odours, when the textile was subjected beforehand to these odours or substances from which these odours can be formed. However, it is also possible to use the amylose-containing substance together with a fragrance in order to achieve a long-lasting pleasant odour, or scent of the textile. As a rule, the procedure will involve firstly treating the textile with the amylose-containing substance. The textile finished in this way will then be treated with the fragrance. As a result, the amylose-containing substance is charged with the fragrance.

As a rule, the fragrance will be used in an amount which suffices for the desired scent effect. The upper limit is determined by the maximum absorption capacity of the amylose units of the amylose-containing substance used and will generally not exceed 20% by weight and often 10% by weight, based on the amylose content of the substance. If desired, the fragrance is generally used in an amount of from 0.1 to 10% by weight and in particular 0.5 to 5% by weight, based on the amylose content of the amylose-containing substance.

Suitable fragrances are in principle all volatile organic compounds and mixtures of organic compounds which are known as fragrances. A review of fragrances is given in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. on CD Rom, Flavours and Fragrances, chapter 2, in particular chapters 2.1 to 2.4. Of particular suitability according to the invention are fragrances of aliphatic and cycloaliphatic nature. These include:

• • aliphatic C₄-C₁₂-alcohols, e.g. 3-octanol, cis-3-hexen-1-ol, trans-3-hexen-1-ol, 1-octen-3-ol, 2,6-dimethylheptan-2-ol, 1-octen-3-ol, 9-decen-1-ol, 10-undecen-1-ol, 2-trans-6-cis-nonadien-1-ol,
  • aliphatic C₆-C₁₃-aldehydes, e.g. hexanal, octanal, nonanal, decanal, undecanal, 2-methyldecanal, 2-methylundecanal, dodecanal and tridecanal, cis-4-heptenal and 10-undecenal,
  • esters of aliphatic C1-C6-carboxylic acids with aliphatic, optionally monounsaturated C1-C8-alcohols such as ethyl formate, cis-3-hexenyl formate, ethyl acetate, butyl acetate, isoamyl acetate, hexyl acetates, 3,5,5-trimethylhexyl acetate, trans-2-hexenyl acetate, cis-3-hexenyl acetate, ethyl propionate, ethyl butyrates, butyl butyrate, isoamyl butyrate, hexyl butyrate, cis-3-hexenyl isobutyrate, ethyl isovalerate, ethyl 2-methylbutyrate, ethyl hexanoate, 2-propenyl hexanoate, ethyl heptanoate, 2-propenyl heptanoate and ethyl octanoate,
  • acyclic terpene hydrocarbons and hydrocarbon alcohols, such as nerol, geraniol, tetrahydrogeraniol, linalool, tetrahydrolinalool, citronellol, lavandulol, myrcenol, farnesol, nerolidol, the formates, acetates, propionates, butyrates, valerates and isobutyrates of these alcohols, the aldehydes corresponding to the abovementioned alcohols, such as citral, citronellal, hydroxydihydrocitronellal, methoxydihydrocitronellal and the dimethyl- and diethylacetals of these aldehydes, such as diethylcitral, methoxydihydrocitronellal-dimethylacetal, also
  • cyclic terpene hydrocarbons, hydrocarbon alcohols and aldehydes.

These also include scents of natural provenance, such as rose oil, lemon oil, lavender oil and oil of cloves scent.

To improve the washing permanence of the finishing according to the invention, it has proven useful to use the amylose-containing substance together with a film-forming, water-insoluble polymer. As a rule, the film-forming polymer will be used in an amount such that the weight ratio of the amylose-containing substance to water-insoluble polymer is in the range from 1:1 to 100:1, preferably in the range from 1.5:1 to 50:1 and in particular in the range from 2:1 to 20:1.

As a rule, the film-forming polymers will be used in the form of an aqueous dispersion of finely divided polymer particles. The particle size is of minor importance for success according to the invention. It is, however, usually below 5 μm (weight-average) and is generally 50 nm to 2 μm.

It is preferred if the film-forming polymer has a glass transition temperature TG in the range from −40 to 100° C., preferably −30 to +60° C., in particular −20 to +40° C. If the polymeric binder comprises a plurality of polymer components, at least the main constituent should have a glass transition temperature in this range. In particular, the glass transition temperature of the main constituent is in the range from −30° C. to +60° C. and particularly preferably in the range from −20° C. to +40° C. Preferably, all of the polymeric constituents have a glass transition temperature in these ranges. The glass transition temperatures given refer to the midpoint temperature determined in accordance with ASTM-D 3418-82 by means of DSC. In the case of crosslinkable binders, the glass transition temperature refers to the uncrosslinked state.

Examples of suitable film-forming polymers are based on the following classes of polymer:

• (1) polyurethane resins
• (2) acrylate resins (straight acrylates: copolymers of alkyl acrylates and alkyl methacrylates);
• (3) styrene acrylates (copolymers of styrene and alkyl acrylates);
• (4) styrene/butadiene copolymers;
• (5) polyvinyl esters, in particular polyvinyl acetates and copolymers of vinyl acetate with vinyl propionate;
• (6) vinyl ester-olefin copolymers, e.g. vinyl acetate/ethylene copolymers;
• (7) vinyl ester-acrylate copolymers, e.g. vinyl acetate/alkyl acrylate copolymers, and vinyl acetate/alkyl acrylate/ethylene terpolymers;

Such polymers are known and commercially available, e.g. polymers from classes (2) to (7) in the form of aqueous dispersions under the names ACRONAL, STYROFAN, BUTOFAN (BASF AG), MOWILITH, MOWIPLUS, APPRETAN (Clariant), VINNAPAS, VINNOL (WACKER). Aqueous polyurethane dispersions (1) suitable for the method according to the invention are, in particular, those which are used for the coating of textiles (see e.g. J. Hemmrich, Int. Text. Bull. 39, 1993, No. 2, pp. 53-56; “Wässrige Polyurethan-Beschichtungssysteme” [Aqueous polyurethane coating systems] Chemiefasern/Textilind. [Chemistry Fibres/Textile Ind.] 39 91 (1989) T149, T150; W. Schröer, Textilveredelung [Textile finishing] 22, 1987, pp. 459-467). Aqueous polyurethane dispersions are commercially available, e.g. under the trade names Alberdingk® from Alberdingk-Boley Inc. NC, Impranil® from BAYER Material Science AG, Leverkusen, Permutex® from Stahl, Waalwijk, The Netherlands, Perapret® PU from BASF Aktiengesellschaft or can be prepared by known processes, as are described, for example, in “Hersteliverfahren für Polyurethane” [Preparation processes for polyurethanes] in Houben-Weyl, “Methoden der organischen Chemie” [Methods of organic chemistry], volume E 20/Makromolekulare Stoffe [Macromolecular substances], p. 1587, D. Dietrich et al., Angew. Chem. 82 (1970), p. 53 ff., Angew. Makrom. Chem. 76, 1972, 85 ff. and Angew. Makrom. Chem. 98, 1981, 133-165, Progress in Organic Coatings, 9, 1981, pp. 281-240, and Römpp Chemielexikon [Chemistry lexicon], 9th edition, volume 5, p. 3575.

The film-forming polymers may be self-crosslinking, i.e. the polymers have functional groups (crosslinkable groups) which, upon drying the composition, if appropriate upon heating, react with one another, with the functional groups of the amylose or with a low molecular weight crosslinker with bond formation.

Examples of crosslinkable functional groups include aliphatically bonded OH groups, NH—CH2-OH groups, carboxylate groups, anhydride groups, capped isocyanate groups and amino groups. A polymer will often be used that also has free OH groups as reactive groups. As a rule, the fraction of the reactive functional groups is 0.1 to 3 mol/kg of polymer. The crosslinking can be effected within the polymer by the reaction of complementary-reactive functional groups. Preferably, the crosslinking of the polymer is effected by adding a crosslinker which has reactive groups which are complementary to the functional groups of the crosslinker with regard to their reactivity. Suitable pairs of functional groups which have complementary reactivity are known to the person skilled in the art. Examples of such pairs are OH/COOH, OH/NCO, NH2/COOH, NH2/NCO and M2+/COOH, where M2+ is a divalent metal ion, such as Zn2+, Ca2+, or Mg2+. Examples of suitable crosslinkers are the diols or polyols specified above for the polyurethanes; primary or secondary diamines, preferably primary diamines, e.g. alkylenediamines, such as hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N,N-bis[(aminopropyl)amino]ethane, 3,6-dioxaoctanediamine, 3,7-dioxanonanediamine, 3,6,9-trioxaundecanediamine or jeffamines, (4,4′-diaminodicyclohexyl)methane (4,4′-diamino-3,3-dimethyldicyclohexyl)methane; aminoalcohols, such as ethanolamine, hydroxypropylamine; ethoxylated di- and oligoamines; dihydrazides of aliphatic or aromatic dicarboxylic acids, such as adipic dihydrazide; dialdehydes, such as glyoxal; partially or completely O-methylated melamines, and compounds or oligomers which have two or more, preferably three or more, isocyanate groups or reversibly e.g. hydrogensulphite blocked isocyanate groups. In this case, the quantitative ratio of crosslinker to polymeric binder is such that the molar ratio of the reactive groups in the polymeric binder (total amount of the reactive groups in the polymers) to the reactive groups in the crosslinker is generally in the range from 1:10 to 10:1 and preferably in the range from 3:1 to 1:3. Usually, the weight ratio of polymeric binder (calculated as solid) to crosslinker is in the range from 100:1 to 1:1 and in particular in the range from 50:1 to 5:1.

As an alternative to fixing the amylose-containing substance with water-insoluble polymers, the amylose or the amylose-containing substance can also be fixed to the textile material with reactive compounds which have at least one group which is reactive towards the OH groups of the amylose, and at least one further functional group which is reactive towards the functional groups on the fibres of the textile material, e.g. OH groups, NH2 groups or COOH groups. The reactive compounds include the abovementioned crosslinkers, and the substances proposed in DE-A 40 35 378 for the fixing of cyclodextrins, e.g. N-hydroxyl or N-alkoxyl derivatives of urea or urea-like compounds, such as dimethylolurea, dimethoxymethylurea, dimethylolalkanediol diurethanes, dimethylolethyleneurea, dimethylolethyleneurea, dimethylolpropyleneurea and the like. The reactive materials which can be used for fixing the amylose-containing substance to the textile material include, in particular, also compounds with 2, 3, 4 or more (optionally reversibly blocked) isocyanate groups, specifically the bisulphite-reversibly blocked polyisocyanate prepolymers based on polyether urethanes and polyester urethanes which are described in DE 2837851, DE 19919816 and the earlier European patent application 03015121.1. Such products are also commercially available, for example under the trade names PROTOLAN®367 and PROTOLAN®357 from Rotta GmbH, Mannheim.

To fix the amylose-containing substance, the procedure known for the fixing of cyclodextrins can also be used in an analogous way, in which the cyclodextrin or in the present case the amylose-containing substance is provided with reactive anchors, for example by reacting them with dicarboxylic acids or dicarboxylic anhydrides, such as maleic acid, fumaric acid, maleic anhydride, succinic acid, succinic anhydride or adipic acid, with diisocyanates, e.g. toluene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate or hexamethylene diisocyanate, or with amino carboxylic acids in a manner known per se in such a way that only one of the functionalities present in these compounds reacts with the OH groups of the amylose-containing substance and the other is retained for binding to the reactive groups of the fibre material. Reactive anchors can be generated on the amylose-containing substance also by reaction with 1,3,5-trichlorotriazine, 2,3-dichloroquinoxaline-5,6-carboyl chloride, and with chlorodifluoropyrimidine.

To fix the amylose it is also possible to use alkoxysilanes, such as diethoxydimethylsilane, dimethoxydimethylsilane, triethoxyphenylsilane, tetraethoxysilane, and dimeric, trimeric and higher condensation products of these compounds.

Using the method according to the invention it is in principle possible to finish all textile materials, i.e. non-made-up goods and also made-up goods. Textile materials include here and below wovens, weft knits, warp knits and nonwovens. The textile materials can be constructed from natural fibre yarns, synthetic fibre yarns and/or mixed yarns. Suitable fibre materials are, in principle, all of the fibre materials customarily used for producing textiles. These include cotton, wool, hemp fibres, sisal fibres, flax, ramie, polyacrylonitrile fibres, polyester fibres, polyamide fibres, viscose fibres, silk, acetate fibres, triacetate fibres, aramid fibres and the like, and mixtures of these fibre materials.

The finishing of the textile materials with the amylose-containing substance can be carried out in a manner known per se, e.g. by means of the method described in DE-A 4035378 for the finishing of textiles with cyclodextrins.

Mention may be made, for example of methods in which the amylose-containing substance has already been spun into the fibre, the filament and/or the yarn from which the fabric is produced.

However, the textile material will often be treated with the amylose-containing substance before or after making-up. For this purpose, the textile will as a rule be treated with an aqueous liquor which comprises the amylose-containing substance in an adequate amount. Depending on the type of application and the desired amount in which the amylose-containing substance is to be applied, the concentration of amylose-containing substance in the liquor is in the range from 1 to 40% by weight, in particular in the range from 2 to 20% by weight and specifically in the range from 4 to 15% by weight.

The type of treatment is of minor importance and can be carried out, for example, as minimal application, e.g. by spray application, as standard application in the padder or as high-moisture application. In this process, the textile material is saturated with the aqueous liquor. If necessary, excess liquor can then be removed, e.g. by squeezing off to a liquor pick-up of about 30 to 120%.

Another way of treating the textile with amylose-containing substance is to prepare a liquor with water in which the desired amount of amylose-containing substance is present, e.g. 0.5 to 20% by weight (based on the mass of the textile to be finished). The textile material is drenched through over a certain period, e.g. 10-60 min with the treatment liquid in suitable finishing assemblies (e.g. winch beck; roller beck; paddle; etc.) and then squeezed off and/or spun off as stated above. The liquor ratio here is usually in the range from 1:2 to 1:50 and in particular in the range from 1:3 to 1:20.

Such methods are known to the person skilled in the art, for example from H. K Rouette, Lexikon der Textilveredlung [Lexicon of textile finishing], Laumann-Verlag, Dülmen 1995, p. 669 et seq.

The treatment with the liquor is generally followed by a drying operation. The temperatures here are usually in the range from 100 to 200° C. and preferably in the range from 120 to 180° C. Drying can be carried out in the equipment customary for this purpose, in the case of made-up goods for example by dry-tumbling at the temperatures given above. In the case of goods which are not made-up, following application, the textile material will usually be guided over one or more tenters. If the amylose-containing substance is used together with a film-forming polymer, drying leads to a fixing of the amylose-containing substance on the textile fibres. As a rule, the drying temperature will not drop below 100° C. and is preferably in the range from 120 to 200° C. and in particular in the range from 140 to 180° C. In general, drying takes place over a period of from 1 to 10 min, in particular 1 to 2 min, with longer drying times likewise being suitable.

For the treatment with an aqueous liquor, it has proved advantageous if the aqueous liquor comprises at least one surface-active substance (or interface-active substance) which is suitable for dispersing the amylose-containing substance in the aqueous liquor, in addition to the amylose-containing substance. The surface-active substance is preferably an oligomeric or polymeric dispersant. The term oligomeric or polymeric dispersant includes, in contrast to low molecular weight surface-active substances, those dispersants whose number-average molecular weight is generally at least 2000 daltons, e.g. 2000 to about 100 000 daltons and in particular is in the range from about 3000 to 70 000 daltons.

As a rule, the aqueous liquor comprises the polymeric or oligomeric dispersant in an amount of from 0.5 to 20% by weight, preferably 1 to 18% by weight and in particular 5 to 15% by weight, based on the amylose-containing substance.

Suitable oligomeric or polymeric dispersants are soluble in water and include both neutral and amphoteric water-soluble polymers and also cationic and anionic polymers, where the latter are preferred.

Examples of neutral polymeric dispersants are polyethylene oxide, ethylene oxide/propylene oxide copolymers, preferably block copolymers, polyvinylpyrrolidone, and copolymers of vinyl acetate with vinylpyrrolidone.

The preferred anionic oligomeric or polymeric dispersants are characterized in that they have carboxyl groups and/or sulphonic acid groups and are usually used in the form of salts, e.g. in the form of alkali metal salts or ammonium salts.

Preferred anionic dispersants are, for example, carboxylated derivatives of cellulose, such as carboxymethylcellulose, homopolymers of ethylenically unsaturated C3-C8-mono- and C4-C8-dicarboxylic acids, e.g. of acrylic acid, of methacrylic acid, of maleic acid, of itaconic acid, copolymers of at least two different ethylenically unsaturated C3-C8-mono- and C4-C8-dicarboxylic acids as specified above, and copolymers of at least one of the above-mentioned ethylenically unsaturated C3-C8-mono- or C4-C8-dicarboxylic acid with at least one neutral comonomer. Examples of neutral comonomers are N-vinyllactams, such as N-vinylpyrrolidone, vinyl esters of aliphatic C2-C16-carboxylic acids, such as vinyl acetate, vinyl propionate, amides of the abovementioned ethylenically unsaturated carboxylic acids, such as acrylamide, methacrylamide and the like, hydroxy-C1-C4-alkyl (meth)acrylates, such as hydroxyethyl acrylate and methacrylate, esters of ethylenically unsaturated C3-C8-mono- or C4-C8-dicarboxylic acids with polyethers, e.g. esters of acrylic acid or of methacrylic acid with polyethylene oxides or ethylene oxide/propylene oxide block copolymers, vinyl aromatics, such as styrene and C2-C16-olefins such as ethylene, propene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Preference is also given to homopolymers of ethylenically unsaturated sulphonic acids, such as styrenesulphonic acid and acrylamidopropanesulphonic acid and copolymers thereof with the abovementioned comonomers. In the copolymers, the content of the ethylenically unsaturated acid will usually be at least 20% by weight and not exceed a value of 90% by weight and in particular 80% by weight, in each case based on the total weight of all of the monomers constituting the polymer.

Copolymers of at least one of the abovementioned acids and at least one comonomer are known for this purpose and are commercially available, for example the copolymers of acrylic acid and maleic acid as Sokalan grades from BASF AG.

Likewise preferred anionic dispersants are phenolsulphonic acid-formaldehyde condensates and naphthalenesulphonic acid-formaldehyde condensates (for example the Tamol and Setamol grades from BASF) and lignosulphonates.

Dispersants which can be used are also low molecular weight anionic, nonionic, cationic, ampholytic and zwitterionic surfactants. Suitable surfactants are, for example, the alkali metal, ammonium or amine salts of C8-C18-alkyl sulphates, such as sodium lauryl sulphate; C8-C18-alkylsulphonates, such as dodecylsulphonate; C8-C18-alkyl ether sulphates; and C8-C18-alkyl ethoxylates; polyoxyethylene sorbitan esters; C8-C18-alkyl glycinates; C8-C18-alkyldimethylamine oxides; betaines, etc. Preference is given to the alkyl sulphates and alkylsulphonates.

If the amylose-containing substance is used together with a film-forming, water-insoluble polymer, the textile can be treated with the polymer in a separate processing step. The treatment preferably takes place together with the amylose-containing substance. Accordingly, a preferred embodiment of the invention provides a method in which the aqueous liquor additionally comprises a dispersed, film-forming, water-insoluble polymer of the type described above. The amount of film-forming polymer is chosen such that the weight ratio of amylose-containing substance to water-insoluble polymer is in the range from 1:1 to 100:1, preferably in the range from 1.5:1 to 50:1 and in particular in the range from 2:1 to 20:1.

If the textile is to be finished with a fragrance, this preferably takes place in a separate operation. However, it is in principle also possible to finish the textile material with amylose-containing substance and fragrance in one operation.

If the textile is finished with the fragrance in a separate operation, said fragrance will likewise expediently be applied from an aqueous liquor. For this purpose, the fragrance, which is usually not soluble in water, will usually be emulsified in water, where appropriate using suitable surface-active substances. Suitable surface-active substances are, in particular, the abovementioned low molecular weight surfactants and, of these, preferably the nonionic surfactants, polyoxyethylene sorbitan esters, esters of mono- or oligosaccharides with C6-C18-fatty acids and particularly preferably C8-C18-alkyl ethoxylates, in particular those with a degree of ethoxylation in the range from 6 to 50. As a rule, the aqueous liquor comprises the fragrance in an amount of from 0.1 to 10% by weight and in particular in an amount of from 0.2 to 5% by weight. The amount of surface-active substance is generally in the range from 0.5 to 50% by weight and in particular in the range from 3 to 30% by weight, based on the fragrance. The fragrance can be applied from aqueous liquor using the methods customary for this purpose, e.g. by means of a padder.

The method according to the invention surprisingly gives textiles with an odour-inhibiting finish, the odour-inhibiting effect of which is at least comparable with that of a finish based on cyclodextrins. In addition, the textiles can also be finished with fragrances which give the textiles a long-lasting pleasant odour/scent. With regard to this property too, the textile materials obtainable according to the invention are at least comparable, if not superior, to those with a finish based on cyclodextrins. In addition, the textiles finished in this way are characterized by a pleasant handle, which is advantageous particularly for the wear comfort of clothing produced from these textiles.

The examples below serve exclusively to illustrate the invention.

The following feed materials were used:

• • preservative: Mergal K 9N (Troy-Chemie, Seelze)
  • carboxymethylcellulose: Phricolat RT 20 (MTPC GmbH, Siegen)
  • starch with 50% amylose content: Amylogel 03001 (Cerestar)
  • starch with 70% amylose content: Amylogel 03003 (Cerestar)
  • nonionogenic polyurethane dispersion: Cromelastik NI 77, Cromogena Units SA, Barcelona
  • nonionic surfactant 1: Lutensol TO8
  • nonionic surfactant 2: Lutensol ON 30
  • fragrance 1: lavender oil Bontoux 1421, Duellberg Konzentra GmbH, Hamburg,
  • fragrance 2: rose scent Rosato, Haarmann and Reimer, Holzminden,
  • fragrance 3: lily of the valley scent, Aromaland Röttingen
  • fragrance 4: carnation scent, Aromaland Röttingen

I. Preparation of Aqueous Slurries of Amylose-Containing Starch

Slurry S-1

570 g of deionized water were admixed with 10 g of a standard commercial preservative. 20 g of carboxymethylcellulose were dissolved therein, then 400 g of an amylose-containing starch with an amylose content of 50% by weight were added, and a slurry was prepared with stirring.

Slurry S-2

An aqueous slurry of an amylose-containing starch with an amylose content of 70% by weight was prepared in a manner analogous to S-1.

Slurry S-3

An aqueous slurry of an amylose-containing starch with an amylose content of 50% by weight was prepared in a manner analogous to S-1, but, in contrast to S-1, 60 g of carboxymethylcellulose.

Slurry S4

405 g of deionized water were admixed with 10 g of a standard commercial preservative. 14 g of carboxymethylcellulose were dissolved therein, then 357 g of an amylose-containing starch with an amylose content of 50% by weight and 214 g of a 30% strength by weight aqueous polyurethane dispersion (nonionogenic) were added and a slurry was prepared with stirring.

II. Preparation of Aqueous Liquors with Amylose-Containing Starch:

Method 1: The particular slurry S-1 to S-4 are adjusted to a starch content of 5 or 15% by weight by dilution with water.

Method 2: The particular slurry S-1 to S-3 are firstly diluted to a starch content of 5 or 15% by weight with water and then admixed with 30 g/l of a 30% strength by weight aqueous polyurethane dispersion (nonionogenic).

The preparation and composition of the aqueous liquors L1 to L11 is given in Table 1

TABLE 1
				Polyurethane
			Starch content	content*
Liquor	Slurry	Method	[% by wt.]	g/l
L1	S-1	1	5	0
L2	S-2	1	5	0
L3	S-3	1	5	0
L4	S-4	1	5	10
L5	S-1	1	15	0
L6	S-2	1	15	0
L7	S-1	2	5	9
L8	S-2	2	5	9
L9	S-3	2	5	9
L10	S-1	2	15	9
L11	S-1	2	15	9
*based on polyurethane in liquor

For comparison purposes, a liquor CL1 was prepared with 36 g/l of hydroxypropylcyclodextrin (CAVASOL W7 HPTL from Wacker, Burghausen). To this were added 9 g/l of a nonionic polyurethane in the form of an aqueous dispersion (Cromelastic NI 77).

For comparison purposes, an aqueous liquor with 6% by weight of potato starch (amylose content 25%) was prepared by dissolving potato starch in water at 80° C. (liquor CL2).

III. Finishing of Textiles:

a) General Procedure for Finishing with Amylose-Containing Starch:

Cotton fabric samples with a mass per unit area of 124 g/m² is treated in each case with the aqueous liquors L1 to L11 and also the comparison liquors CL1 and CL2 using a padder to a liquor pick-up of 80% by weight, based on the weight of the fabric. Drying is then carried out for 2 min at 120° C.

This gives the fabric samples F1 to F11 and also the comparison fabric samples CF1 and CF2. In addition, for comparison purposes, the properties of an untreated fabric sample CF3 are analysed.

• • b) General Procedure for Finishing with Amylose-Containing Starch and Fragrance:

Firstly, a cotton fabric sample was finished as described under a). The fabric samples finished in this way were then treated with aqueous scent oil formulation by padding the aqueous scent oil emulsion onto the fabric sample to a liquor pick-up of 79-80% by weight. The fabric samples treated in this way were then dried in a domestic dryer to a residual moisture of 15%. The samples were then packed in polyethylene film and stored in a drying cabinet for 3 h at 50° C. The samples were then unwrapped and, to remove the unbound fragrances, treated in a circulatory air drying cabinet for 3 min at 120° C. The samples were then transferred to a climatically controlled area and sprayed with water to release the fragrances. The odour was assessed by a team of 6 people smelling the sample and evaluating it compared with an untreated reference sample. The results are given in Table 2.

As scent oil formulation, use is made of aqueous emulsion of the particular fragrances 1, 2, 3 or 4 with a fragrance content of 0.7 g/l and a content of 0.1 g/l of emulsifier 1 and 0.15 g/l of emulsifier 2.

	TABLE 2
	Fragrance No.
	Sample	Liquor	1	2	3	4
	F9	L9	++	++	++	+
	CF1	CL-1	++	++	0	0
	CF3	Water	0	0	0	0
	++ odour strongly detectable
	+ odour detectable
	0 odour not detectable

IV. Investigation of the Absorption Capacity for Fragrances.

The fabric samples F1 to F11 prepared as in III.a, and the comparison sample CF1 (with cyclodextrin), CF2 (with normal starch) and CF3 (untreated) were investigated.

a) In a first experimental arrangement, an untreated cotton cloth (10×10 cm) was placed into a 1 l screw-cap bottle. To this was added 0.5 g of the particular fragrance in order to distribute it uniformly within the glassware. After moistening to a water content of 15%, the fabric sample in each case is then placed into the respective bottle and the bottle is closed. The bottle is then stored in a drying cabinet for 3 h at 50° C. After cooling, the bottle is opened and the fabric sample is transferred to a circulatory air drying cabinet heated to 120° C. to remove nonbound fragrance for 2 min. The fabric sample is left to cool and sprayed with water, and then the odour impression is assessed in accordance with the scale given above. The results are given in Table 3.

Sample	Scent
	Liquor No.	Propyl propionate	Lemon oil	Citrus terpene
F1	L1	++	++
F2	L2	++	+
F5	L5	++	++	++
F6	L6	++	++	++
F7	L7	++	+	++
F8	L8	++	+	++
F10	L10	++	++	++
F11	L11	++	++	++
CF1	CL1	0	0	0
CF3	Water	++	++	+

b) Analogously to the experimental arrangement described under a), various fragrances were left to act on the fabric samples, although, in contrast to a), the contact temperature was 120° C. The fabric samples treated in this way were assessed with regard to their odour and with regard to their handle in accordance with a grading scale from 1 to 3, where 1 means a soft handle and 3 means a hard and stiff handle. The properties of the fabric samples are given in Table 4:

	TABLE 4
	Sample		Fragrance
		Liquor	Handle	No. 3	No. 4
	CF3	Water	1	0	0
	F9	L9	1	++	++
	CF1	CL1	2	+	+
	CF2	CL2	3	0	0

Claims

1. Method of modifying the odour properties of textiles, characterized in that the textile is treated with an amylose-containing substance with an amylose content of at least 30% by weight.

2. Method according to claim 1, characterized in that the textile is additionally treated with a fragrance.

3. Method according to claim 1, characterized in that the amylose-containing substance is used together with a film-forming, water-insoluble polymer.

4. Method according to claim 1, characterized in that the amylose-containing substance is used in an amount of from 0.5 to 25% by weight, based on the weight of the textile.

5. Method according to claim 1, characterized in that the textile is treated with the amylose-containing substance in aqueous liquor.

6. Method according to claim 5, characterized in that the aqueous liquor additionally comprises an interface-active substance which is suitable for dispersing the amylose-containing substance.

7. Method according to claim 5, characterized in that the aqueous liquor comprises the polymeric or oligomeric dispersant in an amount of from 0.5 to 20% by weight, based on the amylose-containing substance.

8. Method according to claim 5, characterized in that the aqueous liquor comprises the amylose-containing substance in a concentration of from 1 to 40% by weight, based on the weight of the liquor.

9. Textile material obtainable by a method according to claim 1.

10. Use of amylose-containing substances with an amylose content of at least 30% by weight for modifying the odour properties of textiles.