EP1710345A1 - Method for finishing textiles with active agents - Google Patents

Abstract

Method for finishing textiles with active agents (I), other than perfumes, comprises treating the textile with an amylose-containing substance (II), of amylose content at least 30wt.%, and at least one (I). An independent claim is included for a textile finished by the new method.

Description

The present invention relates to a process for finishing textile materials with active ingredients and to the textile materials obtainable by this process.

The equipment of textiles with active substances, ie substances which can cause a physiological effect directly or indirectly in living beings, are of interest in many respects. For example, textiles with biocidal finish can be used in the sanitary and medical sectors to prevent unwanted transmission of germs and resulting infections. In turn, the finishing of pharmaceutical grade organic textiles is of interest for therapeutic applications, such as the transdermal delivery of drugs. Recently, textiles have been reported which are equipped with so-called wellness additives, ie substances which promote well-being ( R. Breier "Megatrend Wellness - Innovative Ideas for Textile Equipment", 31st Aachener Textiltage November 2004 ). An insecticidal equipment in turn is in terms of material protection, such as equipment of the textile against moth feeding, etc., but especially for the defense against parasitic insects such as mosquitoes.

The fundamental problem in the finishing of textiles with active ingredients is the binding of the active ingredient to the textile carrier, which on the one hand must ensure the permanence of the equipment and on the other hand must be chosen so that the active ingredient does not lose its effect.

On various occasions cyclodextrins have been proposed for the attachment of active ingredients to textiles (see for example DE 19810951 and EP-A 392608 ). Cyclodextrins are cyclic oligosaccharides formed by enzymatic degradation of starch. The most common cyclodextrins are α-, β- and γ-cyclodextrins, which consist of six, seven and eight α-1,4-linked glucose units, respectively. A characteristic feature of the cyclodextrin molecules is their ring structure with largely invariable dimensions. The inner 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 able to trap guest molecules, in particular hydrophobic guest molecules, in varying amounts up to saturation.

However, cyclodextrins are so expensive that such equipment is a significant cost factor in the manufacture of textile materials. In addition, the textiles finished with cyclodextrins have disadvantageous tactile properties, especially a hard feel.

The European patent application EP 03023155.9 describes the finishing of textiles with fragrances wherein the fragrances are attached to the textile via an amylose-containing substance having an amylose content of at least 30%.

The present invention is therefore based on the object to provide a cheaper alternative for modifying the odor properties of textiles. In addition, this equipment should not adversely affect the properties of the tissue, in particular the tactile properties.

It has surprisingly been found that amylose-containing substances with an amylose content of at least 30% by weight make it possible to equip textiles with active ingredients in the same way as cyclodextrins.

Accordingly, the present invention relates to the use of amylose-containing substances having an amylose content of at least 30% by weight, based on the total weight of the substance, of finishing textiles with active ingredients, excluding fragrances.

The invention also provides a process for finishing textiles with active ingredients, which comprises treating the textile with amylose or an amylose-containing substance having an amylose content of at least 30% by weight and at least one active ingredient.

Due to the amylose content of the amylose-containing substance, the active substance is bound to the textile and released in a controlled manner, so that the effect is retained over a long period of time. It is assumed that the active substance is reversibly bound in the cavities formed by the helical conformation of the amylose in the sense of an inclusion compound similar to cyclodextrins, which on the one hand fixation of the active ingredient on the surface of the textile support is achieved and on the other hand, a controlled release is possible ,

In addition to amylose, all substances, in particular amylose-containing starches, ie native starches, modified starches and starch derivatives, whose amylose content is at least 30% by weight and in particular at least 40% by weight, are suitable for the finishing of textiles according to the invention. The starch may be native, for example corn starch, wheat starch, potato starch, sorghum starch, rice starch or marten starch, obtained by partial digestion of native starch or chemically modified. Also suitable is pure amylose as such, for example enzymatically obtained amylose, for. B. from sucrose won amylose. Also suitable are mixtures of amylose and starch, provided that the total content of amylose is at least 30% by weight on the total weight of the mixture. It is understood that here and below, all information in wt .-%, which relate to amylose or amylose-containing substances, in mixtures of amylose and starch are always based on the total weight of amylose + starch, unless expressly stated otherwise.

Particularly suitable 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 trademark Amylogel® and National Starch under the trade names HYLON® V and VII.

In order to achieve the binding of the active ingredient (s) to the textile, the textile containing the amylose-containing substance will generally be present in an amount of at least 0.5% by weight, preferably at least 1% by weight and in particular at least 2 Wt .-%, each based on the weight of the textile, equip. In general, the amylose-containing substance in an amount of not more than 25 wt .-%, often not more than 20 wt .-% and in particular not more than 15 wt .-%, based on the weight of the textile to use not to adversely affect the tactile properties of the textile.

In a first embodiment of the method according to the invention, the textile material will first be provided with the amylose-containing substance as such, and then the fabric treated in this way treated with a suitable preparation of the active ingredient. As a result, the amylose-containing substance present on the textile material is loaded with the active substance.

In a second embodiment of the method according to the invention, the amylose-containing substance will be used together with an active substance to provide the textile. In this case, the active substance and the amylose-containing substance can be used both as a mixture of separate components and in the already prefabricated form of the amylose active substance complex.

In general, one will use the active ingredient in an amount that is sufficient for the desired effect. The upper limit is determined by the maximum uptake capacity of the amylose units of the amylose-containing substance used and will generally not exceed 20% by weight and frequently 10% by weight, based on the amylose content of the substance. If desired, the active ingredient is usually incorporated in in an amount of 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, based on the amylose content of the amylose-containing substance.

In principle, all organic compounds and mixtures of organic compounds which are known as active ingredients and which induce a physiological action in living beings such as humans and animals, including microorganisms, are suitable as active ingredients. Preference is given to those active substances which, as is known, can form inclusion compounds with cyclodextrins. Particularly suitable are active compounds which have hydrocarbon groups and in particular aliphatic, cycloaliphatic and / or aromatic structures. The molecular weight of the drugs is typically below 1000 daltons, and often in the range of 100 to 600 daltons. Also suitable are inorganic compounds such as hydrogen peroxide, which are known to be bound in cyclodextrins (see F. Vögtle, Supramolecular Chemistry, 2nd Edition, BG Teubner, Stuttgart 1992, Cyclodextrins and literature cited therein )

The active ingredients include, in particular, pharmaceutical active ingredients and active ingredients which promote the well-being of living beings, in particular of humans, and which are commonly referred to as "wellness additives". Unlike pharmaceutical ingredients, the wellness additives do not necessarily have a therapeutic effect. Rather, the well-being promoting effect can be based on a variety of factors such as nourishing, stimulating, cosmetic or other effects. Equally suitable are organic agents that act against parasitic organisms. These include, for example, active substances which act against fungi and / or microorganisms, for example fungicides and bactericides, or which act against animal pests such as snails, worms, mites, insects and / or rodents, for example nematicides, molluscicides, insecticides, acaricides, rodenticides and Reppellent Active substances, as well as active substances against grass weeds, ie herbicides. According to the invention, the active substances are not those in the EP 03023155.9 disclosed fragrances.

Preferred active pharmaceutical ingredients are those which are known to be absorbed through the skin. These include, for example, ibuprofen, flurbiprofen, acetylsalicylic acid, acetamidophen, apomorphine, butylated hydroxytoluene, chamulenes, gujaculas, chlorthalidone, cholecalciferol, dicumarol, digoxin, diphenylhydantoin, furosemide, hydroflumethiazide, indomethacin, ipronocidyl phosphate, nitroglycerin, nicotine, nicotinic acid amide, oubain, oxprenolol, Papaverine alkaloids such as papaverine, laudanosine, ethaverine and narcotin, as well as berberine, Retionl, trans-retinoic acid, pretinol, spironolactone, sulpiride, theophylline, theobromine, corticosteroids and derivatives such as testosterone, 17-methyltestosterone, cortisone, corticosterone, dexamethasone, triamcinolone, methylprednisolone , Fludrocortisone, fluocortolone, prednisone, prednisolone, progesterone, including estrogens and progestins such as estradiol, estriol, ethinylestradiol-3-methyl ether, norethisterone and ethisterone, as well as phenethylamine and derivatives such as tyramine, adrenaline, norepinephrine and dopamine.

Examples of active substances which are suitable according to the invention and have an action against parasitic organisms are the nematicides, bactericides, fungicides mentioned under www.reith-pfister.de/www.list.html and www.hclrss.demon.co.uk/class pesticides.html . Insecticides, insect repellents, acaricides and molluscicides.

• Antibiotioka, z.B. Cycloheximid, Griseofulvin, Kasugamycin, Natamycin, Polyoxin, Streptomycin, Penizillin oder Gentamycin;
• Organische Verbindungen und Komplexe biozider Metalle, z.B. Komplexe des Silbers, Kupfers, Zinns und/oder Zinks wie Bis-(tributyllzinn)oxid, Kupfer-, Zink- und Zinn-Naphthenate, Oxine-Kupfer wie Cu-8, Tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(Cyclohexyldiazeniumdioxy)-tributylzinn, Bis-N-(cyclohexyldiazeniumdioxy)-kupfer;;
• Quarternäre Ammoniumsalze, z.B. Benzyl-C₈-C₁₈-alkyldimethylammonium-halogenide, insbesondere Chloride (Benzalkoniumchloride);
• aliphatische Stickstofffungizide und Bactericide wie Cymoxanil, Dodin, Dodicin, Guazidine, Iminoctadin, Dodemorph, Fenpropimorph, Fenpropidin, Tridemorph,
• Substanzen mit Peroxidgruppen wie Wasserstoffperoxid, und organische Peroxide wie Dibenzoylperodid;
• Organische Chlorverbindungen wie z. B. Chlorhexidin;
• Triazolfungizide wie Azaconazol, Cyproconazol, Diclobutrazol, Difenoconazol, Diniconazol, Epoxiconazo, Fenbuconazol, Fluquinconazol, Flusilazol, Flutriafol, Hexaconazol, Metconazol, Propiconazol, Tetraconazol, Tebuconazol und Triticonazol;
• Strobilurine wie Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin und Trifloxystrobin
• Sulfonamide wie Tolylfluanid und Diclofluanid;
• lodverbindungen wie Diiodmethyl-p-tolylsulfon, , Napcocide 3-lod-2-propinylalkohol, 4-Chlorphenyl-3-iodpropargylformal, 3-Brom-2,3-diiod-3-propenylethylcarbonat, 2,3,3-Triiodallylalkohol, 3-lod-2-propinyl-n-hexylcarbamat, 3-Brom-2,3-diiod-2-propenylalkohol, 3-lod-2-propinylphenylcarbamat, 3-lod-2-propinyl-n-butylcarbamat, O-1-(6-lod-3-oxohex-5-inyl)phenylcarbamat, O-1-(6-Iod-3-oxohex-5-inyl)butylcarbamat;
• Isothiazolinone wie N-Methylisothiazolin-3-on, 5-Chloro-N-methylisothiazolin-3-on, 4,5-Dichloror-N-octylisothiazolin-3-on, 1,2-Benzisothiazol-3(2H)on, 4,5-Trimethytisothiazol-3-on und N-Octyl-isothiazolin-3-on.

Examples of bactericidal and fungicidal substances include:

• Antibiotics, eg cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin, streptomycin, penicillin or gentamycin;
• Organic compounds and complexes of biocidal metals, eg complexes of silver, copper, tin and / or zinc such as bis (tributyltin) oxide, copper, zinc and tin naphthenates, oxine copper such as Cu-8, Tris-N- ( cyclohexyldiazeniumdioxy) -aluminum, N- (cyclohexyldiazeniumdioxy) -tributyltin, bis-N- (cyclohexyldiazeniumdioxy) -copper;
• Quaternary ammonium salts, for example benzyl C ₈ -C ₁₈ -alkyldimethylammonium halides, in particular chlorides (benzalkonium chlorides);
• aliphatic nitrogen fungicides and bactericides such as cymoxanil, dodin, dodicin, guazidines, iminoctadine, dodemorph, fenpropimorph, fenpropidine, tridemorph,
• Substances with peroxide groups such as hydrogen peroxide, and organic peroxides such as dibenzoyl peroxide;
• Organic chlorine compounds such. For example, chlorhexidine;
• Triazole fungicides such as azaconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, epoxiconazo, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, metconazole, propiconazole, tetraconazole, tebuconazole and triticonazole;
• Strobilurins such as dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin
• Sulfonamides such as tolylfluanid and diclofluanid;
• iodine compounds such as diiodomethyl-p-tolylsulfone,, napococide, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-3-propenylethylcarbonate, 2,3,3-triiodoallylalcohol, 3 iodo-2-propynyl-n-hexylcarbamate, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynylphenylcarbamate, 3-iodo-2-propynyl-n-butylcarbamate, O-1- (6 -Old-3-oxohex-5-ynyl) phenylcarbamate, O-1- (6-iodo-3-oxohex-5-ynyl) butylcarbamate;
• Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 1,2-benzisothiazol-3 (2H) one, 4, 5-trimethytisothiazol-3-one and N-octyl-isothiazolin-3-one.

• Organophosphate wie Acephate, Azamethiphos, Azinphos-methyl, Chlorpyrifos, Chlorpyriphos-methyl, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, O-xydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Triazophos, Trichlorfon;
• insbesondere Pyrethroide wie Acrinatrin, Allethrin, Bioallethrin, Barthrin, Bifenthrin, Bioethanomethrin, Cyclethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, gamma-Cyhalothrin, lambda-Cyhalothrin, Cypermethrin, α-Cypermethrin, β-Cypermethrin, λ-Cypermethrin, zeta-Cypermethrin, Cyphenothrin, Deltamethrin, Dimefluthrin, Dimethrin, Empenthrin, Fenfluthrin, Fenprithrin, Fenpropathrin, Fenvalerat, Esfenvalerat, Flucythrinat, Fluvinate, tau-Fluvinate, Furethrin, Permethrin, Biopermethrin, Trans-Permethrin, Phenothrin, Prallethrin, Profluthrin, Pyresmethrin, Resmethrin, Bioresmethrin, Cismethrin, Tefluthrin, Terallethrin, Tetramethrin, Tralomethrin, Transfluthrin, Etofenprox, Flufenprox, Halfenprox, Protrifenbute und Silafulfen.
• Pyrrol- und Pyrazol-Insektizide wie Acetoprole, Ethiprole, Fipronil, Tebufenpyrad, Tolfenpyrad, Chlorfenapyr und Vaniliprole.

Examples of insecticides and acaricides are

• Organophosphates such as acephates, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyriphos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoates, disulphoton, ethion, fenitrothion, fenthion, isoxathione, malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, O-xydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, phorates, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, triazophos, trichlorfon;
• especially pyrethroids such as acrinatrin, allethrin, bioallethrin, barthrin, bifenthrin, bioethanomethrin, cyclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, λ-cypermethrin, zeta Cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin, fenprithrin, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate, fluvinates, tau-fluvinates, furethrin, permethrin, biopermethrin, trans-permethrin, phenothrin, prallethrin, profluthrin, pyresmethrin, resmethrin , Bioresmethrin, Cismethrin, Tefluthrin, Terallethrin, Tetramethrin, Tralomethrin, Transfluthrin, Etofenprox, Flufenprox, Halfenprox, Protrifenbute and Silafulfen.
• Pyrrole and pyrazole insecticides such as acetoprole, ethiprole, fipronil, tebufenpyrad, tolfenpyrad, chlorfenapyr and vaniliprole.

Examples of repellent active ingredients are in particular anthraquinone, acridine bases, copper naphthenate, butopyronoxyl, dibutyl phthalate, dimethyl phthalate, dimethyl carbate, ethohexadiol, hexamides, methoquine-butyl, N-methyl neodecanamide, camphor, bergamot oil, pyrethrum, clove oil, geranium oil, thyme oil and in particular diethyl m-toluamide and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester (Picardin).

• Fette, vorzugsweise pflanzlichen Ursprungs, z.B. Lecithine,
• Pflanzenöle wie Jojoba-Öl, Teebaumöl, Nelkenöl, Nachtkerzenöl, Mandelöl, Kokosöl, Avocadoöl, Sojaöl und dergleichen,
• Fettsäuren, z.B. ω-6-Fettsäuren, Linolensäure, Linolsäure,
• Wachse tierischen oder planzlichen Ursprungs wie Bienenwachs, Candelillawachs, Sheabutter, Shoreabutter, Mangokernbutter, Japanwachs und dergleichen,
• Vitamine, insbesondere fettlösliche Vitamine, z. B. Tocopherole, Vitamin E, Vitamin A und dergleichen,
• Cortico-Steroide wie Cortison, Corticosteron, Dexamethason, Triamcinolon, Methylprednisolon, Fludrocortison, Fluocortolon, Prednison, Prednisolon, Progesteron,
• Aminosäuren, z.B. Arginin, Methionin,
• Pflanzenextrakte wie Algenextrakt, Rosskastanienextrakt, Mangoextrakt und dergleichen.

Examples of wellness additives are in particular the substances listed below and mixtures of substances, eg

• Fats, preferably of vegetable origin, eg lecithins,
• Vegetable oils such as jojoba oil, tea tree oil, clove oil, evening primrose oil, almond oil, coconut oil, avocado oil, soybean oil and the like,
• Fatty acids, eg ω-6 fatty acids, linolenic acid, linoleic acid,
• Waxes of animal or plant origin such as beeswax, candelilla wax, shea butter, shore butter, mango seed butter, Japan wax and the like,
• Vitamins, in particular fat-soluble vitamins, eg. As tocopherols, vitamin E, vitamin A and the like,
• Cortico-steroids such as cortisone, corticosterone, dexamethasone, triamcinolone, methylprednisolone, fludrocortisone, fluocortolone, prednisone, prednisolone, progesterone,
• Amino acids, eg arginine, methionine,
• Plant extracts such as algae extract, horse chestnut extract, mango extract and the like.

To improve the washing permanence of the equipment according to the invention, it has proven useful to fix the amylose-containing substance with a binder on the textile.

Suitable binders are on the one hand film-forming, water-insoluble polymers and, on the other hand, low molecular weight reactive substances which polymerize with heating.

In general, the binder will be used in an amount such that the weight ratio of amylose-containing substance to water-insoluble polymer is in the range of 1: 1 to 100: 1, preferably in the range of 1.5: 1 to 50: 1 and especially in the range of 2: 1 to 20: 1.

In general, the film-forming polymers are used in the form of an aqueous dispersion of finely divided polymer particles. The particle size is of secondary importance for the success of the invention. However, it is usually below 5 microns (weight average) and is usually 50 nm to 2 microns.

It is preferred if the film-forming polymer has a glass transition temperature T _G 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 component should have a glass transition temperature in this range. In particular, the glass transition temperature of the main component is in the range of -30 ° C to +60 ° C, and more preferably in the range of -20 ° C to +40 ° C. Preferably, all polymeric polymeric constituents have a glass transition temperature in these ranges. The glass transition temperatures given here refer to the "midpoint temperature" determined according to ASTM-D 3418-82 by means of DSC. In the case of crosslinkable binders, the glass transition temperature refers to the uncrosslinked state.

1. (1) Polyurethan-Harze
2. (2) Acrylatharze (Reinacrylate: Copolymere aus Alkylacrylaten und Alkylmethacrylaten);
3. (3) Styrolacrylate (Copolymere aus Styrol und Alkylacrylaten);
4. (4) Styrol/Butadien-Copolymerisate;
5. (5) Polyvinylester, insbesondere Polyvinylacetate und Copolymere des Vinylacetats mit Vinylpropionat;
6. (6) Vinylester-Olefin-Copolymere, z. B. Vinylacetat/Ethylen-Copolymere;
7. (7) Vinylester-Acrylat-Copolymere, z. B. Vinylacetat/Alkylacrylat-Copolymere sowie Vinylacetat/Alkylacrylat/Ethylen-Terpolymere;

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

1. (1) Polyurethane resins
2. (2) acrylate resins (pure acrylates: copolymers of alkyl acrylates and alkyl methacrylates);
3. (3) styrene acrylates (copolymers of styrene and alkyl acrylates);
4. (4) styrene / butadiene copolymers;
5. (5) polyvinyl esters, especially polyvinyl acetates and copolymers of vinyl acetate with vinyl propionate;
6. (6) vinyl ester-olefin copolymers, e.g. Vinyl acetate / ethylene copolymers;
7. (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, for. B. polymers of classes (2) to (7) in the form of aqueous dispersions under the names ACRONAL, STY-ROFAN, BUTOFAN (BASF AG), MOWILITH, MOWIPLUS, APPRETAN (Clariant), VINNAPAS, VINNOL (WACKER). Aqueous polyurethane dispersions (1) which are suitable for the process according to the invention are, in particular, those which are used for the coating of textiles (see, for example, US Pat. J. Hemmrich, Int. Text. Bull. 39, 1993, No.2, pp. 53-56 ; " Aqueous polyurethane coating systems "Chemiefasern / Textilind." 39 91 (1989) T149, T150 ; W. Schröer, Textilveredelung 22, 1987, pp. 459-467 ). Aqueous polyurethane dispersions are commercially available, for. B. under the trade names Alberdingk® the Fa. Alberdingk, Impranil® the Fa. BAYER AG, Permutex® the Fa. Steel, Waalwijk, Netherlands, the company BASF Aktiengesellschaft or can be prepared by known methods, as described for example in " Production Process for Polyurethanes "in Houben-Weyl," Methods of Organic Chemistry ", Volume E 20 / Macromolecular Substances, p. 1587 . D. Dietrich et al., Angew. Chem. 82 (1970), p. 53 et seq ., Angew. Makrom. Chem. 76, 1972, 85 et seq , and Angew. Makrom. Chem. 98, 1981, 133-165 . Progress in Organic Coatings, 9, 1981, pp. 281-240 , respectively. Römpp Chemielexikon, 9th edition, volume 5, p. 3575 to be discribed.

The film-forming polymers may be self-crosslinking, i. H. The polymers have functional groups (crosslinkable groups) which react when the composition is dried, if appropriate when heated, with one another, with the functional groups of the amylose or with a low molecular weight crosslinking agent to form bonds.

Examples of crosslinkable functional groups include aliphatically bonded OH groups, NH-CH ₂ -OH groups, carboxylate groups, anhydride groups, capped isocyanate groups and amino groups. Often one will use a polymer that still has free OH groups as reactive groups. As a rule, the proportion of reactive functional groups is 0.1 to 3 mol / kg of polymer. Crosslinking can be effected within the polymer by reaction of complementary reactive functional groups. Preferably, the crosslinking of the polymer is effected by addition of a crosslinker having reactive groups which are complementary in their reactivity with the functional groups of the crosslinker. Suitable pairs of functional groups which have a complementary reactivity are those skilled in the art known. Examples of such pairs are OH / COOH, OH / NCO, NH ₂ / COOH, NH ₂ / NCO and M ²⁺ / COOH, where M ^{2+ is} a divalent metal ion such as Zn ²⁺ , Ca ²⁺ , or Mg ²⁺ stands. Examples of suitable crosslinkers are the di- or polyols mentioned below for the polyurethanes; primary or secondary diamines, preferably primary diamines, e.g. B. alkylenediamines such as hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N-bis [(aminopropyl) amino] ethane, 3,6-dioxaoctanediamine, 3,7-dioxanonandiamine, 3,6,9-Trioxaundecandiamin or Jeffamine, (4 , 4'-diaminodicyclohexyl) methane (4,4'-diamino-3,3-dimethyldicyclohexyl) methane; Amino alcohols 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 containing on average two or more, preferably three or more isocyanate groups or reversibly z. B. hydrogen sulfide blocked isocyanate groups. In this case, the ratio of crosslinker to polymeric binder is such that the molar ratio of the reactive groups in the polymeric binder (total amount of reactive groups in the polymers) to the reactive groups in the crosslinker is usually in the range from 1:10 to 10: 1 and preferably in the range of 3: 1 to 1: 3. Usually, the weight ratio of polymeric binder (calculated as solids) 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 fixation of the amylose-containing substance with water-insoluble polymers, the amylose or the amylose-containing substance can also be reacted with reactive compounds which have at least one group reactive with the OH groups of the amylose group and at least one further functional group which is opposite to the functional groups the fibers of the textile material, for example OH groups, NH ₂ groups or COOH groups, is reactive, fixate on the textile material. The reactive compounds include the above-mentioned crosslinkers as well as the in DE-A 40 35 378 for the fixation of cyclodextrins proposed substances, for example N-hydroxymethyl and N-alkoxymethyl derivatives of urea or urea-type compounds such as dimethylolurea (bis (hydroxymethyl) urea), di (methoxymethyl) urea, Dimethylolalkandioldiurethane such as N, N-dimethylolethyleneurea (N, N Bis (hydroxymethyl) imidazolin-2-one), N, N-dimethylol dihydroxyethylene urea (N, N-bis (hydroxymethyl) -4,5-dihydroxyimidazolin-2-one), dimethylolpropylene urea and the like. Such materials are commercially available in the form of aqueous formulations for the finishing of textiles, for example under the trade names Fixapret® and Fixapret®-eco of the BASF Aktiengesellschaft. Among the reactive materials that can be used to fix the amylose-containing substance on the textile material include in particular compounds having 2, 3, 4 or more (optionally reversibly blocked) isocyanate groups, especially those with bisulfite or CH-acidic compounds or Oximene, eg butanone oxime reversibly blocked polyisocyanate prepolymers based on polyether and polyester urethanes, which are available in DE 2837851 . DE 19919816 and the older one European Patent Application 03015121 to be discribed. Such products are also commercially available, for example under the trade names PROTOLAN®367 and PROTOLAN®357 of Rotta GmbH, Mannheim.

To fix the amylose-containing substance, the procedure known for the fixation of cyclodextrins can also be used in an analogous manner in which the cyclodextrin or, in the present case, the amylose-containing substance is provided with reactive anchors, for example by mixing with dicarboxylic acids or dicarboxylic acid anhydrides, such as maleic acid or fumaric acid , Maleic anhydride, succinic acid, succinic anhydride or adipic acid, with diisocyanates, e.g. As toluene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate or hexamethylene diisocyanate, or reacted with aminocarboxylic acids in a conventional manner such that only one of the functionalities present in these compounds reacts with the OH groups of the amylose-containing substance and the other for attachment to the reactive groups of the fiber material preserved. Reactive anchors can also be produced on the amylose-containing substance by reaction with 1,3,5-trichlorotriazine, 2,3-dichloroquinoxaline-5,6-carboxylic acid chloride and with chlorodifluoropyrimidine.

Furthermore, alkyoxysilanes, such as diethoxydimethylsilane, dimethoxydimethylsilane, triethoxyphenylsilane, tetraethoxysilane and dimeric, trimeric and higher condensation products of these compounds can also be used to fix the amylose. With the method according to the invention basically all textile materials can be equipped, i. not made-up goods as well as made-up goods. Textile materials here and below include woven, knitted, knitted and nonwoven fabrics. The textile materials can be constructed from natural fiber yarns, synthetic fiber yarns and / or blended yarns. In principle, all fiber materials commonly used for the production of textiles come into consideration as fiber materials. These include cotton, wool, hemp fiber, sisal fibers, flax, ramie, polyacrylonitrile fibers, polyester fibers, polyamide fibers, viscose fibers, silk, acetate fibers, triacetate fibers, aramid fibers and the like, and mixtures of these fiber materials.

Equipping or treating the textile materials with the amylose-containing substance can in a conventional manner, for example by means of in DE-A 4035378 for the finishing of textiles with cyclodextrins described procedures.

Examples include processes in which the amylose-containing substance, optionally as a complex with the active ingredient is already spun into the fiber, the filament and / or the yarn from which the fabric is made.

Often, however, the textile material will be treated before or after fabrication with the amylose-containing substance or a complex of amyl-containing substance and active ingredient. As a rule, the textile will be treated with an aqueous liquor which contains the amylose-containing substance and, if appropriate, the active ingredient in sufficient quantity. 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 especially in the range of 4 to 15% by weight.

The type of treatment is of minor importance and may be described, for example, as a minimum order, e.g. by spray application, as a normal job in the padder or as a high-moisture application. Here, the textile material is impregnated with the aqueous liquor. Optionally, one can then remove excess liquor, e.g. by squeezing to a liquor pick-up of about 30 to 120%.

Another possibility for the treatment of the textile with amylose-containing substance or complex of amylose-containing substance and active ingredient, a liquor is to be prepared with water, in which the desired amount of amylose-containing substance and optionally active ingredient is contained, e.g. 0.5 to 20% by weight (based on the weight of the textile to be finished). The textile material is left over a period of time, e.g. Soaked with the treatment liquor for 10-60 minutes in equipment sets suitable for this purpose (for example reel skid, roller skid, paddle, etc.) and then squeezed and / or spun off as indicated above. The liquor ratio is usually in the range of 1: 2 to 1:50 and in particular in the range of 1: 3 to 1:20.

Such methods are known to the person skilled in the art, for example from HK Rouette, Lexicon of Textile Finishing, Laumann-Verlag, Dülmen 1995, p. 669 ff ,

As a rule, the treatment with the liquor is followed by a drying process. The temperatures are usually in the range of 100 to 200 ° C and preferably in the range of 120 to 180 ° C. The drying can be carried out in customary apparatuses, in the case of ready-made goods, for example by dry-bluing at the temperatures indicated above. In the case of non-ready-made goods, the textile material will usually be guided over one or more tenter frames following the order.

If the amylose-containing substance is used together with a film-forming polymer, the drying leads to a fixation of the amylose-containing substance on the textile fibers. In general, then the drying temperature will not fall below 100 and is preferably in the range of 120 to 200 ° C and in particular in Range from 140 to 180 ° C. In general, the drying is carried out for a period of 1 to 10 minutes, in particular 1 to 2 minutes, longer drying times are also suitable.

For the treatment with an aqueous liquor, it has proved to be advantageous if the aqueous liquor contains, in addition to the amylose-containing substance and optionally the active ingredient, at least one surface-active substance (or surfactant) which is used to disperse the amylose-containing substance and the active ingredient in the aqueous Fleet is suitable. Preferably, the surfactant is an oligomeric or polymeric dispersant. The term oligomeric or polymeric dispersant, unlike low molecular weight surfactants, includes those dispersants whose number average molecular weight is typically at least 2000 daltons, e.g. 2000 to about 100,000 daltons and in particular in the range of about 3000 to 70,000 daltons.

In general, the aqueous liquor contains the polymeric or oligomeric dispersant in an amount of 0.5 to 20 wt .-%, preferably 1 to 18 wt .-% and in particular 5 to 15 wt .-%, based on the amylose-containing substance.

Suitable oligomeric or polymeric dispersants are water-soluble and include both neutral and amphoteric water-soluble polymers and cationic and anionic polymers, the latter being 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 sulfonic acid groups and are usually used as salts, e.g. be used as alkali metal salts or ammonium salts.

Preferred anionic dispersants are, for example, carboxylated derivatives of cellulose such as carboxymethyl cellulose, homopolymers of ethylenically unsaturated C ₃ -C ₈ mono- and C ₄ -C ₈ dicarboxylic acids, for example of acrylic acid, methacrylic acid, maleic acid, itaconic acid, copolymers of at least two different ethylenic unsaturated C ₃ -C ₈ mono- and C ₄ -C ₈ dicarboxylic acids as mentioned above, and copolymers of at least one of the aforementioned ethylenically unsaturated C ₃ -C ₈ mono- or C ₄ -C ₈ dicarboxylic acid with at least one neutral comonomer , Examples of neutral comonomers are N-vinyllactams such as N-vinylpyrrolidone, vinyl esters of aliphatic C ₂ -C ₁₆ -carboxylic acids such as vinyl acetate, vinyl propionate, amides of the abovementioned ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and the like, hydroxy-C ₁ -C ₄ -alkyl (meth) acrylates such as hydroxyethyl acrylate and methacrylate, esters of ethylenically unsaturated C ₃ -C ₈ mono- or C ₄ -C ₈ dicarboxylic acids with Polyethers, for example esters of acrylic acid or methacrylic acid with polyethylene oxides or ethylene oxide / propylene oxide block copolymers, vinylaromatics such as styrene and C ₂ -C ₁₆ -olefins such as ethylene, propene, 1-hexene, 1-octene, 1-decene, 1-dodecene and like. Further preferred are homopolymers of ethylenically unsaturated sulfonic acids such as styrenesulfonic acid and acrylamidopropanesulfonic acid and their copolymer with the abovementioned comonomers. In the copolymers, the proportion of the ethylenically unsaturated acid will generally be at least 20% by weight and not exceed a value of 90% by weight and in particular 80% by weight, based in each case on the total weight of all 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 available commercially, for example the copolymers of acrylic acid and maleic acid as Sokalan grades from BASF AG.

Also preferred anionic dispersants are phenolsulfonic acid-formaldehyde condensates and naphthalenesulfonic acid-formaldehyde condensates (e.g., the Tamol and Setamol brands of BASF) and lignosulfonates.

Useful dispersants 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 C ₈ -C ₁₈ -alkyl sulfates, such as sodium lauryl sulfate; C ₈ -C ₁₈ alkyl sulfonates, such as dodecyl sulfonate; C ₈ -C ₁₈ alkyl ether sulfates; and C ₈ -C ₁₈ alkyl ethoxylates; polysorbate; C ₈ -C ₁₈ alkyl glycinates; C ₈ -C ₁₈ -alkyldimethylamine oxides; Betaines etc. Preferred are the alkyl sulfates and alkyl sulfonates.

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 working step. Preferably, the treatment is carried out together with the amylose-containing substance. Accordingly, a preferred embodiment of the invention relates to a process 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 so that the weight ratio of amylose-containing substance to water-insoluble polymer in the range of 1: 1 to 100: 1, preferably in the range of 1.5: 1 to 50: 1 and in particular in the range of 2: 1 to 20: 1.

The equipment of the textile with the active ingredient may be made in a separate operation or in one operation together with the equipment containing the amylose-containing substance.

If one equips the textile in a separate operation with the active ingredient, it is advisable to treat the textile also with an aqueous liquor of the active ingredient. For this purpose, as a rule, the active compound, which is usually insoluble in water, is emulsified or dispersed in water, if appropriate using suitable surface-active substances. Suitable surface-active substances are, in particular, the abovementioned low molecular weight surfactants and preferably the nonionic surfactants, in particular polyoxyethylene sorbitan esters, esters of mono- or oligosaccharides with C ₆ -C ₁₈ -fatty acids and particularly preferably C ₈ -C ₁₈ -alkyl ethoxylates, in particular those having an ethoxylation degree in the range of 6 to 50. As a rule, the aqueous liquor contains the active ingredient in an amount of 0.1 to 10 wt .-% and in particular in an amount of 0.2 to 5 wt .-%. The amount of surface-active substance is usually in the range of 0.5 to 50 wt .-% and in particular in the range of 3 to 30 wt .-%, based on the active ingredient. The application of the active ingredient from aqueous liquor can be carried out using the methods customary for this purpose, for example by means of a padder.

But you can also carry out the equipment with active ingredient and amylose-containing substance in one operation. In principle, it is possible to proceed as described for the equipment containing the amylose-containing substance, the aqueous liquor of the amylose-containing substance now additionally containing the at least one active substance. The active ingredient may be added separately to the liquor or in the form of an inclusion compound, i. in the form of a host-guest complex with the amylose-containing substance.

The process of the present invention can be used to finish any type of fabric including fabrics, knits, nonwovens, and the like. The type of textile material depends primarily on the desired application.

The textiles to be finished may be ready-made products such as clothing, including underwear and outerwear, outdoor, trekking and military equipment, roofs, tents, nets, e.g. Insect nets and curtains, as well as used in water sports textiles such as sails, Boortabdeckungen, tarpaulins and the like. Particularly suitable is the equipment for use in textile construction materials.

In the same way, the equipment can be made on the raw material in bale or roll form.

The textiles treated with active substances against parasitic organisms such as insects and acarids are, in addition to the protection of humans, also particularly suitable for animal protection for protection against ticks, mites, fleas and the like.

The textile materials may be composed of natural fiber yarns, synthetic fiber yarns and / or blended yarns, wherein the fabrics usually have a basis weight in the range of 10 to 500 g / m ^2, preferably 20 to 250 g / m ² . In principle, all fiber materials commonly used for the production of textiles come into consideration as fiber materials. These include cotton, wool, hemp fiber, sisal fibers, flax, ramie, polyacrylonitrile fibers, polyester fibers, polyamide fibers, viscose fibers, silk, acetate fibers, triacetate fibers, aramid fibers and the like, and mixtures of these fiber materials. Also suitable are glass fibers and mixtures of the aforementioned fiber materials with glass fibers z. For example, fiberglass / kevlar blends.

The process according to the invention surprisingly results in textiles having an active ingredient composition whose properties are at least comparable to those of equipment based on cyclodextrins. The active ingredients remain even after several washes in the textiles equipped with it In addition, the so-equipped textiles are characterized by a pleasant feel, which is particularly for the comfort of made of these textiles clothing advantage.

The following examples serve only to illustrate the invention.

A Equipment containing the amylose substance

• Konservierungsmittel: Mergal K 9N (Troy-Chemie, Seelze)
• Carboxymethylcellulose: Phricolat RT 20 (Fa. MTPC GmbH, Siegen)
• Stärke mit 50 % Amyloseanteil: Amylogel 03001 (Fa. Cerestar)
• Stärke mit 70 % Amyloseanteil: Amylogel 03003 (Fa. Cerestar)
• Nichtionogene Polyurethandispersion: Cromelastik NI 77, Fa. Cromogena Units SA, Barcelona
• Nichtionisches Tensid 1: Lutensol TO8
• Nichtionisches Tensid 2: Lutensol ON 30

The following feedstocks were used:

• Preservatives: Mergal K 9N (Troy-Chemie, Seelze)
• Carboxymethylcellulose: Phricolat RT 20 (from MTPC GmbH, Siegen)
• Starch with 50% amylose content: Amylogel 03001 (Cerestar)
• Starch with 70% amylose content: amylogel 03003 (Cerestar)
• Nonionic polyurethane dispersion: Cromelastik NI 77, Cromogena Units SA, Barcelona
• Nonionic surfactant 1: Lutensol TO8
• Nonionic surfactant 2: Lutensol ON 30

I. Preparation of Aqueous Slurries of Amylose-Containing Starch Slurry S-1

570 g of deionized water were mixed with 10 g of a commercial preservative. Here, 20 g of carboxymethyl cellulose was dissolved, followed by the addition of 400 g of an amylose-containing starch having an amylose content of 50% by weight, and a slurry was prepared with stirring.

Slurry S-2

In an analogous manner to S-1, an aqueous slurry of an amylose-containing starch having an amylose content of 70% by weight was prepared.

Slurry S-3

In an analogous manner to S-1, an aqueous slurry of an amylose-containing starch having an amylose content of 50% by weight was prepared, except that 60 g of carboxymethylcellulose were used as a departure from S-1.

Slurry S-4

405 g of deionized water were mixed with 10 g of a commercial preservative. This was dissolved in 14 g of carboxymethylcellulose, then gave 357 g of an amylose-containing starch having an amylose content of 50 wt .-% and 214 g of a 30 wt .-% aqueous polyurethane dispersion (non-ionic) and made with stirring a slurry ago.

II. Preparation of aqueous liquors with amylose-containing starch:

• Method 1: The respective slurry S-1 to S4 are adjusted to a starch content of 5 or 15% by weight by dilution with water.
• Method 2: The respective slurry S-1 to S-3 are first diluted with water to a starch content of 5 or 15 wt .-% and then with 30 g / l of a 30 wt .-%, aqueous polyurethane dispersion (not ionogenic).

The preparation and composition of the aqueous liquors F1 to F11 are given in Table 1 Table 1: fleet slurry method Starch content [% by weight] Polyurethane content * g / l F1 S-1 1 5 0 F2 S-2 1 5 0 F3 S-3 1 5 0 F4 S-4 1 5 10 F5 S-1 1 15 0 F6 S-2 1 15 0 F7 S-1 2 5 9 F8 S-2 2 5 9 F9 S-3 2 5 9 F10 S-1 2 15 9 F11 S-1 2 15 9 * based on polyurethane in fleet

For comparison purposes, a liquor VF1 was prepared with 36 g / l hydroxypropylcyclodextrin (CAVASOL W7 HPTL from Wacker, Burghausen). 9 g / l of a nonionic polyurethane in the form of an aqueous dispersion (Cromelastic NI 77) were added thereto.

For comparison purposes, an aqueous liquor with 6% by weight potato starch (amylose content 25%) was prepared by dissolving the potato starch at 80 ° C. in water (liquor VF2).

III. Equipment of textiles: a) General regulation on equipment containing amylose starch:

Cotton fabric samples having a basis weight of 124 g / m ² are each treated with the aqueous liquors F1 to F11 and the comparative liquors VF1 and VF2 by means of a padder to a liquor pick-up of 80% by weight, based on the weight of the fabric. It is then dried for 2 min at 120 ° C.

This gives the tissue samples G1 to G11 as well as the comparative tissue samples VG1 and VG2. In addition, the properties of an untreated tissue sample VG3 are examined for comparison purposes.

b) General requirement for equipment containing amylose starch and active substance:

First, cotton fabric samples are prepared as described under a). Subsequently, the tissue samples thus treated are treated with an aqueous active ingredient formulation by padding an aqueous emulsion / suspension of an active substance with an active ingredient content of 1 to 7% by weight up to a liquor pick-up of 79-80% by weight onto the fabric sample. Subsequently, the thus treated fabric samples are dried in a household dryer to a residual moisture content of 15%. Then the samples are packed in polyethylene film and stored for 3 h at 50 ° C in a drying oven.

In the same way, the following aqueous active compound formulations can be used.

5% aqueous emulsion of diethyl m-toluamide (Autan from Johnson & Johnson)

5% aqueous dispersion of Bayrepel, (1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester of Lanxcess, D-Leverkusen)

3% aqueous solution of a water-soluble vitamin E acetate (Covitol 700 WD from Cognis Deutschland GmbH + Co. KG, Henkelstr. 67, 40589 Dusseldorf)

7% aqueous emulsion of a natural D-alpha tocopherol (Covitol F 1300, Cognis) emulsified with 12g / l Eumulgin RO 35 PH (Cognis)

5 wt .-% aqueous formulation of permethrin (Butox 50 Fa. Intervet Germany).

Claims (16)

A process for finishing textiles with active ingredients, excluding fragrances, characterized in that treating the textile with an amylose-containing substance having an amylose content of at least 30 wt .-% and at least one active ingredient which is different from perfumes. Method according to one of the preceding claims, characterized in that one uses the amylose-containing substance together with a film-forming, water-insoluble polymers. Method according to one of the preceding claims, characterized in that one uses the amylose-containing substance in an amount of 0.5 to 25 wt .-%, based on the weight of the textile. Method according to one of the preceding claims, characterized in that the textile is treated with the amylose-containing substance in an aqueous liquor. A method according to claim 4, characterized in that the aqueous liquor additionally contains a surface-active substance which is suitable for dispersing the amylose-containing substance. Method according to one of claims 4 or 5, characterized in that the aqueous liquor contains the polymeric or oligomeric dispersant in an amount of 0.5 to 20 wt .-%, based on the amylose-containing substance Method according to one of claims 4 to 6, characterized in that the aqueous liquor contains the amylose-containing substance in a concentration of 1 to 40 wt .-%, based on the weight of the liquor. Method according to one of the preceding claims, characterized in that the treatment with the amylose-containing substance and the treatment with the active ingredient takes place simultaneously. The method of claim 8, wherein the textile is treated with an aqueous liquor containing the amylose-containing substance and the at least one active ingredient. Method according to one of claims 8 or 9, wherein the active ingredient is used in the form of a complex with the amylose-containing substance. Method according to one of the preceding claims, wherein the active substance is a well-being promoting human substance or drug mixture. The method of claim 11, wherein the active ingredient or the active ingredient mixture are selected from fats, vegetable oils, fatty acids, waxes of animal or vegetable origin, vitamins, cortico-steroids, amino acids and mixtures thereof. A method according to any one of claims 1 to 11, wherein the active ingredient is a pharmaceutical organic active ingredient. A method according to any one of claims 1 to 10, wherein the active ingredient is selected from agents which effect control of parasitic organisms. Textile material obtainable by a process according to any one of the preceding claims. Use of amylose-containing substances with an amylose content of at least 30% by weight for the binding of active substances to textiles.