HK1106007A - Dressings which can be applied several times to textile fibres and textile fabrics - Google Patents

Description

Rechargeable finishing agent for textile fibers and fabrics

The invention relates to finishing formulations (finishes) and rechargeable finishes on textile fibers and fabrics, and to a method for applying such functional layers (functional layers) to textile fibers and fabrics. Likewise, the invention also relates to textile fibers and fabrics treated or obtained with the refillable finish based on the process of the invention.

The market for coated or finished textiles is probably the fastest growing market in the textile sector at present. The functional requirements of coated or finished textiles are becoming increasingly stringent, while at the same time more stringent environmental and consumer protection regulations limit the range of useful chemicals. Therefore, finishers (finishers) are required to produce new products with new and/or enhanced functionality using a limited range of raw materials. The literature and practice describes a variety of coatings which influence and improve the surface properties of textile fabrics against dust, water and/or oil, UV, abrasion and/or chemical attack. Among all these functions, emphasis is placed on protecting the wearer of the textile from certain external influences, i.e. keeping certain substances away from the wearer's body.

The term "smart textile" is a term that has been used to date and encompasses known, body-worn, textile products having a coating/finish that enables the provision of garments containing therapeutically or cosmetically active ingredients that are delivered to the skin of the wearer or released from the finish when such garments are worn. The range of economically significant active ingredients includes conceivable substances from cortisone in ointments for neurodermatitis patients and nicotine for abstaining tobacco users (smoking smokers) to anti-wrinkle agents in skin creams. It has been suggested to provide continuous analgesic, hormone, vitamin or sunscreen protection to the skin through such intelligent biological finishes. It is also known that antibacterial substances can be used in textiles, for example in underwear, socks, sportswear or shoes, to prevent the development of unpleasant sweat smells.

Hereinafter, unless otherwise indicated, active ingredients and active substances are considered as pharmaceutical and health (wellness) substances. Medical legislation defines the former as substances and compositions of substances administered to or in the human or animal body for the treatment, alleviation, prevention or detection of disease, pain, physical injury or symptoms of disease. A healthy substance is a substance for improving the overall sense of well-being of all physical and mental aspects of life and coordinating spirit, body and mood with nature. Healthy substances are also understood as cosmetics hereinafter. Several pharmaceutically active substances included in "natural drugs" and traditional drugs in the pharmaceutical products based on the above classification and their respective applications are summarized as follows:

motion sickness: scopolamine, cinnarizine, minoxidil;

smoking cessation: nicotine;

venous problems: heparin;

hay fever: antihistamines including cetirizine;

muscle/joint pain: diclofenac sodium; and

angina pectoris: glycerol trinitrate.

There are generally two different methods of making intelligent finishes in textile finishing. One method is to apply a loadable cage molecule (e.g. cyclodextrin or dendrimer) to the surface to be coated, and the other method is to apply a polymeric binder system (e.g. polyacrylate or polymhane) mixed with the active ingredients to the textile substrate. The layer functionalized with cage molecules can be repeatedly loaded, in contrast to a layer in which the coating substance consists of a preformed mixture of polymer binder and active substance and is applied as a finish during the finishing of the textile.

Both of the cited production methods are accompanied by disadvantages which are mainly associated with the targeted application, in particular with regard to the functionality of the finish layer to be produced.

The range of applications of layers made with cage molecules is limited to a large extent by the size and geometry of the molecules and the affinity for the substances to be bound and can therefore only be limited to a very narrow range. For example, cyclodextrin is an oligosaccharide consisting of 6 to 8 glucose units and having a hollow structure, which has polar OH groups on the outside and hydrophobic on the inside. Therefore, only small lipophilic actives can be incorporated, thereby placing great restrictions on the target of application and versatility of the cyclodextrin-containing finish. As a result, the cage molecules, which are usually already loaded with active substance, are mixed with the finishing liquor and applied to the textile by means of a textile finishing machine. Given the functionality obtained with such finished fabrics and the pre-programmed applications, only very limited quantities can be manufactured to reduce the sales risk. This makes the product very expensive and the range of products is narrow. The advantage of layers made with "caged molecules" over layers made with polymeric binder systems is related to their ability to be recharged after washing of the garment as described above, which is partly dependent on the finish used.

The application process of a polymeric binder system mixed directly with the active does not provide this recharging capability. In this case, the chemicals or active ingredients which determine the functionality are applied to the textile during the finishing process and then in most cases are thermally fixed. Most of the target function has been lost during this fixation process. In which the active ingredient is thermally decomposed or is altered, bonded or decomposed by reaction with the fixing means, or they are evaporated and dissipated together with the heating medium (for example with the exhaust air). The residual active substance remaining on the fabric determines its functionality only for a limited period of use of the respective garment, since the health layer produced by this method is not wash-durable and cannot be recharged. The result of the above-mentioned disadvantages is that the market for fabrics functionalized by this method is very limited and the risk of selling such textile finishing machines is high.

It is an object of the present invention to provide a finishing formulation, a rechargeable finishing agent, a finished textile fibre and fabric and a process for finishing textile fibres and fabrics which overcome the disadvantages inherent in the existing products and processes on the textile market.

This object is achieved with new finishing formulations, new finishing processes, new finishes, and textile fibers and fabrics treated with the new finishes. The specially selected chemicals, some of which are unusual for application in the textile industry, enable the following effects to be obtained, among others:

i) the novel finish can be applied several times with a multiplicity of substances, for example after prolonged use or after corresponding washing of the garments, and makes it possible to combine two independently controllable functionalities into one textile fabric finished according to the invention;

ii) a functional surface (guest/host system) is realized on the textile fabric, which makes it possible, depending on the intended application, to take up the predominantly lipophilic-dominant (lipophilic-mediated) active substance as guest substance and to release it again in an unoriented manner into the surrounding medium or in a directed manner by means of a locally directed (localized) substance flow into the directly adjacent layer.

To achieve the inventive finish, both existing and new methods of textile finishing, such as UV curing of the finish formulation applied to the textile, can be used.

The finish of the invention may be designed and used as an active ingredient release layer, or so-called "drug delivery system", and/or as a harmful ingredient absorption layer.

An essential feature of the invention is that the finishing agent or finishing agent layer, which follows the host/guest principle, is applied to the textile fibers or fabrics and provides a host system which has the widest possible range of applications and which can be repeatedly and temporarily loaded with a plurality of active ingredients or guest molecules. The host layer applied by the textile finishing machine, which can be applied, for example, by the user himself, is the carrier for the guest molecules. Thus, typically a user (e.g., a manufacturer of ready-to-wear (ready-to-wear) garments, a chemical cleaner, or a wearer) may decide the functionality of each fabric or garment on their own. This is made possible by using: a crosslinkable polymer binder in combination with a crosslinkable spacer (spacer substance), a surfactant (emulsifier, dispersant or mixtures thereof), a conventional multifunctional crosslinking agent, and any catalyst. After the finish layer formed from the above chemicals is fixed to the surface of the fiber or fabric, the finish layer forms the host system necessary to accept the active.

The swelling capacity of the resulting finish is important for the understanding of the present invention. The use of preferred oleophilic modified polymer compounds and crosslinkable "antenna (tentacle)" or spacer molecules results in a polymer layer with a greater swelling capacity than can be achieved by polar-protic and/or polar-aprotic substances. When the polymer layer swells, random nano-pockets (spatial expansion dependent on the molecular size and depending on the spacer (spacer) used) are formed in the finish layer. These nanocapsules can accept one or more guest molecules, since their spatial structure and polarity can be adjusted according to the size of the molecule to receive the guest. The nanocapsule preferably has a maximum dimension of 500 nm. When the textile finished by this method is worn, the guest substance or substances, i.e. the accepted active substances, are released again and desorbed by means of body temperature, moisture, friction and movement. The active substance, depending on its kind, is absorbed transdermally or transdermally by the skin of the wearer and exerts the desired effect at the intended site.

The simultaneous use of a crosslinkable surfactant leads to a steric, thermodynamically induced self-organization (self-organization) of the finish components, which determines, on the one hand, the affinity of the finish layer for the lipophilic-dominant active substance and, on the other hand, the physiological behavior of the finish layer on the human skin.

Once the finish layer is created, nanocapsules are present in the unswollen finish layer in what is known as a collapsed form (collapsedform). The potential nanocapsules are shaped after the finish is set upon contact with: water and the substance to be absorbed or the mixture of substances to be absorbed, which in a preferred embodiment can be an aqueous emulsion of the active substance to be absorbed or a mixture of active substances. The ratio of the amounts of the chemicals forming the polymer layer and their selection represent the controlling parameters for receiving and precipitating the active substance through the finish layer.

In addition to nanocapsules, the finish layer of the present invention may have micropores and/or mesopores as additional structures. For this purpose, the finishing preparation can be produced simultaneously with, for example, incorporation of a compound capable of precipitating CO₂Or N₂And/or adding a non-reactive volatile solvent. During the drying and/or fixing process, the gases released or the escaping non-reactive solvents produce micro-or medium-scale capillary action (percolation cluster) in the finish layer, wherein the size of the micropores and mesopores ranges from 1 to 25 μm. The effective surface greatly enlarged in this way significantly influences the absorption behavior or desorption behavior of the active substance to be coated.

Another essential feature of the functional finish produced by this method is the ability to reload the finish and its dynamic formation of nanocapsules specific to the active substance. This function is determined firstly by the type and concentration of the spacer present in the finish layer.

Another functionality of the inventive finish is obtained by two means: the caged molecules are either incorporated into the finishing formulation or applied separately to the loadable textile of the present invention already provided with a polymer layer containing nanocapsules. In addition to the known cyclodextrins, particular mention should be made of beta-glucans and zeolites. Beta-glucan is a polymer of polysaccharide structure that forms as a waste product during the preparation of yeast.

After removal of the fat and protein from the glucan product, it should be ready to use as a cage molecule. Zeolites are silicates with an aqueous structure, which on the one hand can accommodate a plurality of cations in the lattice structure and on the other hand can accommodate guest molecules in the interstices between the zeolite particles.

The two host systems (dynamic formation of nanocapsules, which form nanocapsules by means of the component ratio of the finish layer, and cage molecules), which are based on the functionality and structure of the cage molecules used and their interaction with the finish components, differ in the mechanism of acceptance of the different active substances. For example, the dominant charge (anionic, nonionic, cationic) of the caged molecule, together with the finish component used, affects its ability to absorb actives. These parameters determine the properties that determine the adsorption or desorption priority of the guest molecule, such as polarity, affinity, geometry and steric structure, etc.

In addition to the correct choice of finish chemicals and their mixing ratios, drying and fixing conditions suitable for the host containing chemicals are also very important for the formation of nanocapsules in the host system. The chemicals that form the host are first mixed together to create a coating solution (curing liquid) or finishing formulation. To this end, a main component is provided in the form of at least one polymer compound, which is preferably cross-linkable, fat-modified (C)₂To C₁₈) Water emulsified acryl polymer, epoxy polymer or urethane polymer. Then, a chemical is added as a spacer, which on the one hand contains a molecular "antenna" with at least one terminal reactive group and on the other hand performs a spacer function. The chemical structure of the molecular "antenna" or spacer comprises a polyether chain, for example with a terminal hydroxyl, amino, carbonyl, carboxyl, amide, isocyanate, N-methylol or methoxy-N-methylol function (alpha-aminoalkylation product), preferably such as polyoxyethylene, polyoxypropylene, block polymer and/or C₂To C₁₈And (3) a chain.

At least one multifunctional synthetic resin compound is preferably added as a further component to the coating liquid to act as a cross-linker (alpha-aminoalkylated products, such as methoxylated ethylene urea or melamine compounds), which plays an important role in helping to determine the wash resistance, swelling capacity and nanocapsule structure of the finish layer.

The catalyst is used as a substance which catalyzes the crosslinking reaction between the components, for example magnesium chloride, mono-and polycarboxylic acids or as an ester of an acid-evolving compound.

To control the substantivity and the physiological behaviour of the finish layer, a surfactant or a mixture of surfactants is added to the coating liquid. Surfactants are generally anionic and nonionic substances, such as glycerol citrate, glycerol laurate, fat-modified sorbitan derivatives (for example emulsifiers selected from the series sorbitol esters and polysorbates), cetamyl glucoside, polyglycerol oleate, polyglycerol stearate and silicone polyglycol ethers and/or silicone polyglucosides, having HLB values (hydrophilic-lipophilic balance) in the range from 3 to 15.

For special purposes, for example when large maximum loadings and high release rates are required, a gas evolved (CO) which has an expanding effect on the finish layer can optionally be used₂And N₂Used as a blowing gas). This objective is closely related to the absorption and desorption of malodorous emitting substances. The desired microporous/mesoporous percolation structure of the finish layer is obtained by adding: CO evolution₂And N₂CO is precipitated from organic substances (e.g., acetoacetic acid, 2 '-azobisisobutyronitrile, 2' -azobis- (2-methylpropane)) in the foaming gas₂Such as sodium bicarbonate together with a catalyst for the evolution of acid, and polar non-reactive swelling solvents with a boiling point of 60 to 200 c, preferably 120 c (such as ethyl acetate, ethylene glycol methyl ether acetate, diethylene glycol dimethyl ether).

In the second process step, the coating solution containing the host chemical is applied to the textile using standard industrial coating techniques, such as padding, coating or spraying. To improve the cleaning performance of the host system, especially for synthetic fiber materials, a binder layer containing reactive groups, also known as a primer layer, may be applied beforehand. Such primer layers are known, for example, from WO 01/75216. The application of the primer layer is a process step that precedes the application of the host layer. Depending on the intended application of the fabric with the host layer, a common coating system, such as a stop padding, may be used to coat the two host layers that serve different functions, such as different affinities (higher or lower lipophilicity).

The third process step, which is important for creating the nanocapsule structure, consists in drying the impregnated fabric (residual water content of at most 30%) and then in fixing the finish layer, which can be carried out by using a dry fixing process (at 120 to 180 ℃) and a wet fixing process (at 15 to 40 ℃). The finished fabric is dried using industrial equipment such as a tenter frame or a hot air dryer at a temperature of 50 to 150 ℃ for 30 to 180 seconds. In fixing the finish layer, it is preferred to use a thermal reaction device and/or a UV radiation reaction device, depending on the polymer/crosslinking system used. The heat-fixing takes place at a temperature of 120 to 200 ℃, preferably 140 to 160 ℃, and the reaction time is 1 to 5 minutes. When a UV-cured polymer is used, a reaction time of 0.5 to 60 seconds, preferably 1 to 3 seconds, is necessary depending on the type of polymer and the radiation power to the reactive aggregate (aggregate). One major advantage of using UV cured polymers is that the wash resistant layer can be anchored to the textile substrate at low temperatures. As a result, the functional layer can be filled with active substance during application of the layer chemical, even without thermal decomposition reactions and/or volatilization of the guest substance, which would otherwise occur.

The following examples illustrate examples selected from the preferred finish formulations of the present invention, methods of making the finish layer forming the nanocapsule, and illustrate their efficiency in terms of desired functionality.

Example 1: finish layer for producing percolating clusters of nanostructures

The weight per square meter is 210g/m²The pre-cleaned and bleached polycotton fabric (75% Co, 25% PES) was impregnated with a finishing liquor whose components formed nanocapsules, i.e. percolation clusters of nanostructures, during the drying of the fabric. The fabric coating containing nanocapsules can be used as both a rechargeable drug delivery system and as a simple absorbent layer, for exampleSuch as an absorbent layer that absorbs the substance that emits the odor.

The mass fraction of the finish applied to the surface of the fabric relative to the dry weight of the fabric was 11%. After the fabric was impregnated with the finishing liquor containing the finishing component, it was dried at 120 ℃ for 120 seconds.

The finishing formulation contained the following components:

table 1: finishing formulation of example 1

Finishing liquor component	Concentration of
		Water (W)	786.5
Dicrylan AS	150g/l
		Glucan P20	45g/l
Lyofix CHN	12.5g/l
		Magnesium chloride	6g/l

Dicrylan AS is a 40% acrylate aqueous dispersion sold by ERBA that, when combined with other formulation components, produces a soft, hypoallergenic coating.

Glucan P20 is a cross-linkable propoxylated glucose that acts as a spacer to form nanocags created by the host system for active agents (guests) that will be coated later.

Lyofix CHN is a synthetic resin (partially etherified hexamethylol-melamine resin) which crosslinks the finish components and reacts with other formulation components and catalysts (MgCl)₂) When combined, produces a permanent textile coating that is wash durable.

The coating was fixed at 150 ℃ for 3 minutes.

The coating produced by the above method is capable of forming a percolating cluster of nanostructures loaded with active substance(s) when immersed in an aqueous emulsion containing active substance(s).

Example 2: nano pocket dynamically adjusted according to guest substance

A finishing formulation, also referred to below as coating material, and which represents the host system for the guest substance (i.e. active substance) to be applied after the fabric has been made, is applied by dipping to a boiled and bleached blend fabric consisting of 30% cotton and 70% polyamide weighing 165g per square meter. The mass fraction of finish fixed to the surface of the fibres relative to the dry weight of the untreated fabric was 8%. After the blended fabric was impregnated with the finishing liquor containing the coating material, it was dried at 130 ℃ for 60 seconds and the finishing agent layer containing the nanocapsules formed during the drying process was set at 150 ℃ for 180 seconds. The impregnation liquid contains the following components:

table 2: finishing formulation of example 2

Finishing liquor component	Concentration of
		Water (W)	799.4g/l
Subitol ES	3g/l
		Dicrylan AS	104g/l
Ethyl-hydroxyethyl cellulose	7g/l
		Pluriol P 600	30g/l
Lauryl sorbitan	10.6g/l
		Lyofix MLF	36g/l
Magnesium chloride	8g/l
		Citric acid	2g/l

Subitol ES (Bezema AG) is a crosslinking and blocking aid based on anionic surfactants.

DICRYLAN AS is a chemically/thermally crosslinkable nonionic polyacrylate dispersion for aqueous coating of textile fibre materials.

Pluriol P600 (BASF) is a polypropylene glycol with an average molar mass of about 600g/ml that is used to suppress foaming, impart solubility, change polarity and consistency.

LYOFIX MLF (ERBA) is a partially etherified nonionic hexamethylolmelamine resin with a relatively low formaldehyde content that is used as a dimensionally stable finish for cellulose and mixtures of cellulose and synthetic fibers. Compared with conventional crosslinkers based on melamine, it has a lower formaldehyde content and very good buffering effect and achieves good washing and ironing/water reducing values (shrinkage value), good basic effects and very good properties.

After 12 hours of exposure to an aqueous emulsion containing 20% isooctanol, a model substance of lipophilic health substances (modelsubstance), the octanol of the finish layer produced by the finish absorbs up to 16% of the layer mass. After loading and extracting the finish layer three times with a 50% water/ethanol solution, the initial measured 16% octanol uptake was reproducible.

This test shows that even the end user can repeatedly load the finish layer with lipophilic substance, in which case he can freely choose the functionality of the finish layer to reflect his needs.

Example 3: functional finishing agent with nano pocket for nervous leather patients

A knitted fabric composed of polyester and lycra and having a weight of 230g per square meter was chemically cleaned to remove the fiber preparation before dyeing, and then dyed. A coating system is used which coats the backside of the knitted fabric (intermittent padding) followed by the outer layer to apply a coating material to the dyed and dried knitted fabric, wherein the coating material serves as a host system capable of absorbing a lipophilic active substance as a guest, such as phenolic carbonic acid, farnesol or gamma-linolenic acid (evening primrose oil) of a root extract of oregano or burdock. The functionality of the finish layer is determined only by the person wearing the garment by the choice of the active ingredient to be applied. The root extracts of origanum and Arctium have antifungal and antibacterial effects, while farnesol has antibacterial effect, and evening primrose oil can relieve skin pruritus caused by neurodermatitis. The coating containing the nanocapsule is prepared by the following method: the knitted fabric was impregnated with the following finishing liquor, then allowed to dry at 120 ℃ for 80 seconds and set at 160 ℃ for 180 seconds. The mass of the applied finish layer was 12% of the dry weight of the knitted fabric. The composition of the finish layer and its concentration are listed below.

Table 3: finishing formulation of example 3

Finishing liquor component	Concentration of
		Water (W)	717.5g/l
Invadin PBN	2.5g/l
		Perapret HVN	120g/l
Ethyl-hydroxyethyl cellulose	10g/l
		Pluronic PE 3100	39g/l
Drapal GE 202	42g/l
		Lyofix MLF	54g/l
Magnesium chloride	15g/l

Invadin PBN (ERBA) is a surface-active preparation composed of ethoxylated fatty alcohols and aliphatic ether alcohols that is used as a special crosslinker for water and oil repellent finishes.

The Perapret HVN is a thermally crosslinkable anionic polyacrylate dispersion supplied by BASF for the finishing of woven and knitted fabrics composed of cellulose and mixtures of cellulose and synthetic fibers.

Pluronic PE 3100 is a product of BASF made by copolymerizing propylene oxide and ethylene oxide, which is used as a low foaming surfactant.

Drapal GE 202(Akzo Chemie) is a partially esterified branched carbonic acid copolymer containing hydrophobic alkyl and hydrophilic ether groups and having emulsifying properties.

LYOFIX MLF (ERBA) is a partially etherified nonionic hexamethylolmelamine resin with a relatively low formaldehyde content that is used as a dimensionally stable finish for cellulose and mixtures of cellulose and synthetic fibers. Compared with conventional crosslinkers based on melamine, it has a lower formaldehyde content and very good buffering effect and achieves good washing and ironing/shrinkage values, good basic effects and very good properties.

The finishing agent layer produced using the above formulation was filled with an aqueous emulsion of a root extract of oregano or burdock and farnesol by spraying one side of the knitted fabric containing the coating layer from one side. After twelve hours of exposure, a piece of the knitted fabric was gently washed and allowed to dry. One piece of washed knitted fabric containing the active ingredient was then placed on a mould-attacked agar gel together with one piece of untreated knitted fabric and placed in a 30 ℃ conditioned cabinet for three days.

After three days, the untreated piece of knitted fabric was heavily topped up with mould cultures, whereas the piece of knitted fabric containing the finishing agent and loaded with burdock root extract and farnesol completely prevented the mould growth on the agar layer covered by the sample by desorption of the active substance.

This example shows that in this example the loading of the host layer and the desorption of the guest substance exert a fungicidal and bacteriostatic effect depending on the intended application.

Example 4: finishing agent with odor-absorbing effect

The blended fabric consisting of 30% cotton and 70% polyester was previously washed, dyed and dried. The fabric surface was functionalized by applying a finish layer having the following composition:

table 4: finishing formulation of example 4

Finishing liquor component	Concentration of
		Water (W)	747g/l
Subitol LS-N	3g/l
		Dicrylan AS	120g/l
Methocell 311	12g/l
		Polypropylene glycol	30g/l
Siloxane polyglycol ether	8g/l
		Knittex FPC	55g/l
Knittex catalyst MOF	10g/l
		Azobisisobutyronitrile	15g/l

Subitol LS-N is a low foaming anionic crosslinker based on a synergistic surfactant mixture, which is sold by the CHT company of Tubingen.

Methocell 311 is a cellulose ether produced by DOW Europe s.a.

Knittex FPC (ERBA) is a non-ionic reactant crosslinker based on a modified glyoxal crosslinker for low formaldehyde, boil-off resistant, easy care finishing of cellulosic products and blends thereof.

Knittex catalyst mof (erba) is a magnesium salt based liquid acid donor (acid donor) that is preferably used to apply advanced finishes to cellulosic articles.

Azodiisobutyronitrile as a precipitate of N₂The swelling agent of (1).

The chemicals contained in the finishing liquor ensure, on the one hand, the formation of a nanocapsule structure and a polarity suitable for the absorption of lipophilic substances and, on the other hand, the porosity of the layer required for the rapid absorption and desorption of the adsorbent. To produce the functional layer, the fabric was impregnated with the above-mentioned finishing liquor (80% liquid adsorption) and dried at 110 ℃ for 180 seconds. The functional layer was then fixed by coagulation with a tenter at 150 ℃ for 3 minutes. To prevent exposure of the adsorbed species to bacterial attack, which otherwise often occurs, a small amount of farnesol (about 2% by weight of the finish layer) is loaded into the finish layer.

After loading with farnesol, the finish described in example 4 was used to adsorb substances which give off strong odours, such as those encountered in restaurants or restaurant kitchens. After the finish of example 4 was applied to the workwear of restaurant workers, the workwear or men's and women's garments of this type were no longer affected by any odor, even after three days of wear. The odor-absorbing properties of the farnesol are maintained even after repeated washing of the garments, wherein the garment or finish layer has to be filled with farnesol after each washing.

Example 5: bi-component finish with nanocapsules and caged molecules

The knitted fabric consisting of 100% polyamide is dyed and dried after removal of the fiber softener. The knitted fabric was then impregnated with nanocag forming chemicals in a first process step and dried at 120 ℃ for 2 minutes. In a second process step, the coating is carried out by means of one-sided batch padding with a suspension containing carboxylation-modified anionic dextrans (cage molecules) which are pre-loaded with silver complexes. Subsequently, drying is carried out and the two host systems (nanocapsule and caged molecule) are chemically immobilized, the functionality of which differs due to the difference in the dominant charges (nanocapsule host is non-ionic and caged molecule host is anionic). The mass of the nanocag-forming finish applied to the knitted fabric was 10%, while the mass of the dextran-containing finish was 1%, both relative to the mass of the unfinished knitted fabric. The composition of the coating liquid coated in the first process step with a residual moisture of 72% is as follows:

table 5: first finishing formulation of example 5

Finishing liquor component	Concentration of
		Water (W)	780g/l
Subitol ES	2.5g/l
		Dicrylan AS	140g/l
Bermocoll E 230 FQ	5g/l
		Pluronic P 3500	23g/l
Lyofix MLF	30g/l
		Drapal GE 202	10g/l
Magnesium chloride 6H2O	8g/l
		Citric acid	1.5g/l

BERMOCOLL E230 fq (akzo nobel) is a non-ionic water-soluble cellulose ether (low viscosity grade ethyl hydroxyethyl cellulose) that improves consistency and stability of water-based products.

Pluronic P3500 (BASF) is a block copolymer of polypropylene glycol and ethylene oxide and is essentially used as a nonionic surfactant.

In a second process step, the glucose suspension applied from one side to the subsequent loading side (bearing side) of the garment by intermittent padding consists of the following components:

table 6: second finishing formulation of example 5 containing dextran

Finishing liquor component	Concentration of
		Water (W)	964g/l
Beta-glucan (anionically modified and loaded with silver complexes)	25g/l
		Glutaraldehyde	8g/l
Acetic acid 80%	1g/l
		Subitol ES	2g/l

The finish reflects a multifunctional layer for a body-worn garment in which the wearer has dry, scaly or otherwise susceptible skin. The finishing agent has a remarkable bactericidal effect of the glucan cage-like molecules filled with silver, and the skin is lubricated and moisturized again through active ingredients filled in the nano pockets to generate a bacteriostatic effect. For this purpose, the functional layer containing the nanocapsule was filled with an aqueous emulsion containing linseed oil, urea, gamma-linolenic acid and farnesol for 12 hours and the precipitation was examined on a gel simulating human skin for several days. After four days of desorption of the above active substance in the Franz diffusion cell, only about 17% of the mass of the active substance originally present in the nanocapsule structure could be detected. As expected, the remaining 83% of the active mass was present in a diffusion gel simulating human skin.

Based on the above-mentioned versatility of the finish layer, its use in close-fitting clothing is absolutely ideal for neurodermatitis patients.

Example 6: other bicomponent finishes with nanocapsules and caged molecules

The knitted fabric consisting of 100% polyamide is dyed after pre-cleaning, washed and post-treated with tannin. The dried knitted fabric was first finished with the nanocag forming chemicals, similar to example 5. In the next process step, spraying is carried out with a suspension of silver zeolite. Subsequent drying and coagulation anchored the two host systems (nanocag and silver zeolite) to the knitted fabric. The coating amounts selected were similar to those described in example 5. The chemicals coated in the first process step have a residual moisture content of 75% after coating. The finishing liquor containing silver zeolite sprayed onto the knitted fabric consisted of the following components:

table 7: finishing formulation of example 6 containing silver zeolite

Finishing liquor component	Concentration of
		Water (W)	956.5g/l
Silver zeolite	30g/l
		Acryl polymer	12g/l
Subitol ES	1.5g/l

The functionality of the finish layer consisting of the two host systems can be used for the intended application mentioned in example 5. The use of zeolites that are not loaded or loaded with other substances (other than silver) enables other functionalities to be created.

In the case of thermal and/or UV or blue-light curable finishes, the host system which receives the active ingredient and the active substance (guest or drug) consists of a thermal and/or UV or blue-light curable prepolymer or monomer and at least one component with a spacer function and a surfactant. The host system constructed by this method can be swelled by an aqueous emulsion containing an active ingredient and an active substance, and can adsorb the active ingredient and the active substance contained in the emulsion and release them again.

The surfactants are monomers and/or polymers containing reactive groups, the HLB value of which fluctuates between 3 and 16, preferably between 8 and 12. Typical surfactants include sorbitol laurate or stearate, mono-and diglycerides, ethoxylated and/or propoxylated C having 10 to 30 EO units₈To C₂₀Compounds or vinyl or allyl ether alkoxylates (alkoxylates) which form addition or condensation products with nucleophilically predominant reactive groups such as amino and hydroxyl functional groups.

The spacer material, which helps to determine the swelling of the finish layer, is typically of the type RG-RS-RG. RG corresponds to a reactive group that is UV or blue light curing or a functional group that crosslinks with such a reactive group, and RS corresponds to a residue that characterizes the spacer, such as a polyether, polyester, or vinylogous chain:

[-CH₂-CH₂-O-]_n，

[-CH(CH₃)-CH₂-O-]_n，

[-CH₂-CO-O-(CH₂)_x-O-]_n，

[-CH(CO-O-(CH₂)_x-CH₃)-CH₂-]_nor is or

The chain length of the residues RS determining the hydrophilicity or hydrophobicity of the spacer is defined by n and x, wherein n is preferably greater than 5 and less than 30 and x is preferably between 2 and 4.

Example 7: UV-cured bacteriostatic finishing agent

A fabric consisting of cotton and polyester and weighing 170g per square meter was pretreated (desized and bleached), dyed and dried. The fabric is then impregnated with the healthy active ingredient and the "micro pocket" forming coating component, the chemical fixation of which occurs only after the fabric has been dried by UV curing. The use of UV-cured nanocapsule-forming finish components enables the use of health actives while making the finish layer without fear of chemical alteration or heat-induced material loss.

The following formulation of a finishing agent with bacteriostatic action illustrates this example:

table 8: UV-curable bacteriostatic finishing formulation of example 7

Finishing liquor component	Concentration of
		Water (W)	77.7％
Emulsoge R109	1.5％
		Dicrylan AS(40％)	10％
OTA 480	6％
		Octadecyl methacrylate	4％
2-hydroxy-2-methyl-1-phenyl-1-propanone	0.3％
		Farnesol	0.5％

The finish was applied to the fabric with a mangle, with a shrink effect (ping-off effect) of 75%, and dried with a tenter at 110 ℃ for 2 minutes.

The finish layer was UV cured immediately after passing through the tenter. Curing of the finish layer was continued in a UV tunnel under a protective atmosphere for 2.5 seconds.

The textiles finished with this method are characterized by weak hydrophobicity and bacteriostatic action. After the clothes made of the fabric are washed, the farnesol can be used for regenerating the bacteriostatic action.

Example 8: UV-curable, rechargeable finish coating

The weight per square meter is 180g/m²The previously cleaned dyed polyamide fabric is impregnated with a 5g/l solution of Rewin RT (BEZEMA AG) to improve the fastness of dyeing. In the second step, the pretreated and dried fabric is impregnated with a finishing formulation in the form of an aqueous emulsion using a tenter mangle. The preparation and composition of the emulsion will be described below.

The emulsion was prepared from the following components:

table 9: UV-curable finishing formulation of example 8

Finishing liquor component	Concentration (% w/w)
		Water (W)	93.0
Superonic PE/F 108	1.40
		OTA 480	2.10
UVR 6105	1.61
		Pluronic PE 6200	1.05
Ethyl hydroxyethyl cellulose	0.21
		Sorbitol monolaurate	0.35
2-hydroxy-2-methyl-1-phenyl-1-propanone	0.28

OTA 480 is propoxylated trimethylolpropane triacrylate sold by UCB.

Superonic PE/F108 is a vinyl ether alkoxylate of Unicema (about 14,000 g/mol).

UVR 6105 represents Dow epoxy.

The water and Superonic PE/F108 were mixed together thoroughly. To this mixture was added a mixture of OTA 480, UVR 6105, Pluronic PE 6200, ethyl hydroxyethyl cellulose, sorbitol monolaurate and 2-hydroxy-2-methyl-1-phenyl-1-propanone in small portions.

Subsequently, a tenter frame follard will be used with the liquid at an application rate of 80% relative to the dry weight of the textileThe impregnated fabric was dried at 120 ℃ for 2 minutes and after drying passed through a UV tunnel to set the finish layer. The reaction time in the UV channels was 5.5kW/m²Is 2.5 seconds at the specific radiation power of (2). The UV channels are preferably filled with a protective gas, e.g. nitrogen, CO₂Or argon, in order to avoid any unwanted oxidation processes during the free-radical curing of the acrylate on the one hand and to prevent the formation of ozone on the other hand.

Textile finishes produced in this way differ by excellent host properties which are in turn characterized by a good swelling capacity of the host layer and a high affinity for lipophilic substances. The layer produced in this way exhibits a specific substance absorption of 23mg of isooctanol (model substance for therapeutically and/or cosmetically active substances) per gram of host layer. Another basic criterion for host performance is recharging of the host layer after each garment has been washed. The ability of the finish layer to recharge was still 82% of the original isooctanol absorption capacity after five washes.

In addition to the properties associated with the functionality of the UV-curable finish layer, mention must also be made of its cost-effective production process, since the high-temperature fixing action that normally occurs is omitted. The use of a UV-curable finish component enables the use or addition of the desired active substances while the finish layer is being manufactured without fear of chemical changes or thermally induced material loss.

Claims (45)

1. A finishing formulation for the manufacture of finishes on textile fibres and fabrics, comprising a cross-linkable polymer binder, a surfactant and a versatile multifunctional cross-linking agent, characterized in that the composition comprises a cross-linkable spacer and that it, after combination with a preferably oleophilic modified polymer binder, is capable of producing a polymer finish layer repeatedly filled with active substance having nanocapsules swellable by polar-protic and/or polar-aprotic substances.

2. The finishing formulation of claim 1, characterized in that the polymeric binder is selected from the group consisting of crosslinkable, fat-modified, water-emulsified C₂To C₁₈Acryl polymers, epoxy polymers, vinyl acetate polymers, vinyl pyrrolidone polymers and block polymers thereof or urethane polymers.

3. The finishing formulation according to claim 1 or 2, characterized in that the polymeric binder is present in a percentage of 40 to 80%, preferably 50 to 65%, relative to the dry matter content of the finishing layer to be produced.

4. Finishing formulation according to one of claims 1 to 3, characterized in that a multifunctional synthetic resin compound, preferably an alpha-amino alkylated product, such as methylolated and/or methoxylated ethylene urea or melamine compound, is added as a crosslinking agent.

5. The finishing formulation according to one of claims 1 to 4, characterized in that the crosslinker is present in a percentage of 5 to 40%, preferably 10 to 20%, relative to the dry matter content of the finishing layer to be produced.

6. The finishing formulation according to one of claims 1 to 5, characterized in that the spacer is selected from the group consisting of: polyether chains, preferably polyoxyethylene, polyoxypropylene, block polymers, and/or C₂To C₁₈A chain, preferably with terminal hydroxyl, amino, carbonyl, carboxyl, amide, isocyanate, N-methylol or methoxy-N-methylol functional groups.

7. The finishing formulation according to one of claims 1 to 6, characterized in that the spacer is present in a percentage of 5 to 40%, preferably 10 to 25%, relative to the dry matter content of the finishing layer to be produced.

8. The finishing formulation according to one of claims 1 to 7, characterized in that substances selected from the group consisting of: magnesium chloride, mono-and poly-carbonic acids or esters which precipitate compounds as acids.

9. The finishing formulation according to one of claims 1 to 8, characterized in that the crosslinking catalyst is present in a percentage of 1 to 8%, preferably 2 to 4%, relative to the dry matter content of the finishing layer to be produced.

10. The finishing formulation according to one of claims 1 to 9, characterized in that anionic and nonionic substances having an HLB value in the range of 3 to 15 are added as surfactants, wherein the surfactants are selected from: glycerol citrate, glycerol laurate, fat-modified sorbitan derivatives, preferably selected from emulsifiers of the sorbitol ester and polysorbitol ester series, cetaryl glucoside, polyglycerol oleate, polyglycerol stearate and silicone polyglycol ethers and/or silicone polyglucosides.

11. The finishing formulation according to one of claims 1 to 10, characterized in that the surfactant is present in a percentage of 2 to 25%, preferably 5 to 8%, relative to the dry matter content of the finishing layer to be produced.

12. Finishing preparation according to one of claims 1 to 11, characterized in that the addition of a layer capable of CO evolution is carried out simultaneously with the production of the finishing preparation layer₂And/or N₂And/or a non-reactive swelling substance to control the creation and spatial expansion of the percolated structure in the finish layer-fiber composite.

13. Finishing preparation according to claim 12, characterised in that CO is evolved₂And/or N₂The substance of the foaming gas comprises an organic substance selected from the group consisting of acetoacetic acid, 2 '-azobisisobutyronitrile and 2, 2' -azobis- (2-methylpropane), and/or is combined with a catalyst for precipitating acid to precipitate CO₂Sodium bicarbonate is the inorganic substance of (2).

14. The finishing formulation according to claim 12, characterized in that ethyl acetate, ethylene glycol-methyl ether acetate and/or diethylene glycol dimethyl ether with a boiling point of 60 to 200 ℃, preferably 120 ℃, are preferably added as polar non-reactive swelling solvents.

15. The finishing formulation according to one of claims 1 to 14, characterized in that the swelling substance is present in a percentage of 1 to 15%, preferably 2 to 5%, relative to the dry matter content of the finishing layer to be produced.

16. The finishing formulation according to one of claims 1 to 15, characterized in that it comprises a cage-like molecule selected from the group consisting of cyclodextrins, dendrimers and/or dextrans.

17. The finishing formulation according to one of claims 1 to 16, characterized in that the cage-like molecules are present in a percentage of 1 to 20%, preferably 8 to 15%, relative to the dry matter content of the finishing layer to be produced.

18. The finishing formulation according to one of the preceding claims, characterized in that it can be crosslinked with light in the UV range from 100nm to 400nm or in the visible range from 400nm to 800 nm.

19. The finishing formulation according to claim 18, characterized in that it comprises thermally and/or UV or blue curable prepolymers or monomers and at least one component with a spacing function and a surfactant.

20. Finishing agent for textile fibres and fabrics, characterized in that it is manufactured using a finishing formulation according to one of the preceding claims and is swellable by polar-protic and/or polar-aprotic substances and in that it has nanocapsules which can be repeatedly filled with active substances in the swollen state.

21. The finish of claim 20, characterized in that the nanocapsules exhibit a random distribution with respect to their spatial expansion.

22. The finish of claim 20, characterized in that the upper limit of the nanocag size is 500 nm.

23. The finish of claim 20, characterized in that it exhibits micron-scale or medium-scale capillarity, wherein the micropores and mesopores range in size from 1 to 25 μm.

24. The finishing agent according to one of claims 20 to 23, characterized in that it comprises a cage molecule selected from the group consisting of cyclodextrins, dendrimers or dextrans or mixtures thereof.

25. The finishing agent according to one of claims 20 to 24, characterized in that it comprises silver zeolite.

26. Process for the manufacture of finishes on textile fibres and fabrics according to one of claims 20 to 25, characterised in that at least one finish formulation according to one of claims 1 to 19 is used.

27. A process for the manufacture of finishes on textile fibres and fabrics according to claim 26 characterised in that the finish is applied to the textile fibres and fabrics using standard industrial application techniques such as padding, coating or spraying, followed by drying and fixing.

28. A process for the manufacture of finishes on textile fibres and fabrics according to claim 27 characterised in that the finished textile fibres and fabrics are dried at a temperature of 50 to 150 ℃ for 30 to 180 seconds using conventional industrial equipment such as tenter frames or hot air dryers.

29. Process for the manufacture of finishes on textile fibres and fabrics according to claim 27 or 28, characterised in that, in the fixing of the finish layer, preferably a thermal reaction device and/or a reaction device for UV or blue radiation is used, depending on the polymer/crosslinking system used.

30. Process for the manufacture of finishes on textile fibres and fabrics according to claim 29 characterised in that the heat fixing takes place at a temperature of 120 to 200 ℃, preferably 140 to 160 ℃.

31. A process for the manufacture of a finish on textile fibres and fabrics according to claim 29 characterised in that the chemical fixing takes place after the fabric has been dried by UV or blue light curing.

32. Process for the manufacture of finishes on textile fibres and fabrics according to claim 31 characterised in that light in the UV range of 100nm to 400nm or light in the visible range of 400nm to 800nm is used for fixing.

33. A method according to claim 31 or 32, characterized in that the acrylate-based finish layer is fixed under a protective atmosphere.

34. Process according to one of claims 31 to 33, characterized in that the active substance is added to the finish component before fixing.

35. Process for the manufacture of finishes on textile fibres and fabrics according to one of claims 26 to 34, characterised in that the application of a primer layer is carried out prior to the application of a finish layer, wherein a primer layer containing reactive groups is applied to enhance the wash performance of the host system, especially in synthetic fibre materials.

36. Process for the manufacture of finishes on textile fibres and fabrics according to one of claims 26 to 35, characterised in that cage molecules are also applied to the textile to be finished.

37. Process for the manufacture of finishes on textile fibres and fabrics according to one of claims 26 to 36, characterised in that the fully anchored finish layer is swollen by polar-protic and/or polar-aprotic substances, preferably by aqueous emulsions of active substances, during which the micro pockets in the finish layer are filled with active substances.

38. Textile product consisting of a carrier material selected from the group consisting of textile fibers and fabrics and a finish according to one of claims 20 to 25 applied to the carrier material.

39. Textile product according to claim 38, characterized in that it is designed as a textile and has a finish according to one of the preceding claims 20 to 25 on at least one side.

40. The textile product of claim 39, characterized in that the second side has a finish comprising a cage molecule selected from the group consisting of: cyclodextrin, dendrimer or dextran or mixtures thereof.

41. The textile article of claim 40, characterized in that the second side has a finish comprising silver zeolite.

42. Textile product according to one of claims 38 to 41, characterized in that it can be repeatedly loaded with at least one active substance, preferably an oleophilic active substance.

43. Textile product according to one of claims 38 to 42, characterized in that it is loaded with at least one active substance, preferably a lipophilic active substance.

44. A textile product according to claim 42 or 43, characterized in that said at least one active substance is selected from the group consisting of: phenolic carbonic acid, farnesol or gamma-linolenic acid (evening primrose oil) of origanum or Arctium root extract, lipophilic analgesic, hormone or vitamin, scopolamine, cinnarizine, minoxidil, nicotine, heparin, antihistamine, diclofenac sodium, and glyceryl trinitrate.

45. Textile product according to one of the preceding claims, characterized in that the mass of the applied finish layer is between 1 and 10%, preferably between 2 and 4%, relative to the dry weight of the textile product.