DE102007007318A1 - Coating composition for bioactive textile materials, useful e.g. for producing wound dressings, comprises layer-forming inorganic nanoparticulate sol and active component, e.g. natural oil - Google Patents

Abstract

A coating composition (I) for bioactive textile materials comprises (A) a layer-forming nanoparticulate sol, formed by hydrolysis or cohydrolysis of silicon and/or metal compounds, and (B) a bioactive component, comprising one or more bioactive oil, viscous liquid or solid natural (or identical to natural) materials, in an aqueous or water-miscible organic solvent. An independent claim is included for a coating method for bioactiven textile materials using (I), involving: (1) preparing component (A) by hydrolysis or cohydrolysis of silicon and/or metal compounds in a water-miscible organic solvent (optionally mixed with an aqueous solvent); (2) adding the dissolved or suspended bioactive component (B); (3) optionally adding a soluble polymer (C); (4) applying the obtained composition to the textile surface; and (5) drying the layer.

Description

The The present invention relates to a coating agent for bioactive textile materials, which is a layer-forming nanoparticulate Sol, formed by hydrolysis or cohydrolysis of silicon or Metal compounds, as well as one or more bioactive oily, viscous or solid natural substances or nature-identical substances contains. The coating agent can be used to produce functional Textiles with biological effects, such. B. antimicrobial, anti-allergic, therapeutic or diagnostic properties, be used.

It is known that a lot of effort is currently being made to functionalize textile materials to their utility value to increase. Especially for the production of biofunctional Textiles, z. B. textiles with antimicrobial coating, textiles for hospital hygiene, textiles for allergy sufferers or Textiles with incorporated cosmetic or pharmaceutical Drug depots, there is an increasing need. The desired Properties are enhanced by the incorporation of chemical agents (eg. Silver for antimicrobial activity) or coatings achieved with them.

• i) Mikroverkapselungen erfordern einen hohen technologischen Aufwand und die Haftung der Kapseln auf der Faseroberfläche wird nur durch spezielle Haftvermittler erreicht. Problematisch ist auch die kontinuierliche Wirkstofffreisetzung aus den Mikrokapseln und ihre Steuerbarkeit.
• ii) Die direkte Einbettung natürlicher Wirkstoffe in die Fasern ist nur bei Nassspinnverfahren möglich und erfordert eine extreme Kompatibilität von Spinnlösung und natürlichen Wirkstoffen, die nur in speziellen Fällen erreicht wird.
• (iii) Die Einbettung der Wirkstoffe in polymere Harze führt bei der Schichtbildung häufig zu Entmischungen und einem Ausschwitzen der Öle und einer ungeregelten Wirkstoffabgabe. Da die eingebetteten Öle praktisch eine Weichmacherfunktion übernehmen, sind die Beschichtungen oft mechanisch sehr instabil.

So far, little is known about the use of natural active ingredients for the biofunctionalization of textiles, although they have considerable advantages in terms of availability, price and health safety. One of the main causes is that many bioactive natural active ingredients usually only occur in the form of oily (eg plant extracts) or viscous products (eg honey) whose application and fixation on textiles and the use value of these textiles causes problems , With the use of such natural active ingredients there is also the risk of a sticky surface and in the case of natural oils rapid volatilization, as z. B. in the direct textile impregnation with bioactive plant extracts ( EP0936299 . JP2001031516 . JP2004100083 ) or spraying with flavorings (cf. JP2003201669 ) the case is. There were therefore suggestions made, for. B. by microencapsulation of flavorings on the textile surface ( GB2385271 . KR20030006258 ) or by embedding directly into the textile fiber ( GB2329583 ) or in polymeric coatings ( JP8027624 ) to improve the fixation of natural substances on or in textiles. However, these methods also show a number of serious deficiencies:

• i) microencapsulations require a high technological effort and the adhesion of the capsules on the fiber surface is achieved only by special adhesion promoters. Also problematic is the continuous release of active ingredient from the microcapsules and their controllability.
• ii) The direct embedding of natural active ingredients in the fibers is only possible with wet-spinning processes and requires extreme compatibility of spinning solution and natural active ingredients, which is only achieved in special cases.
• (iii) Embedding the active ingredients in polymeric resins often causes segregation and exudation of the oils and uncontrolled drug delivery when layered. Since the embedded oils practically perform a softening function, the coatings are often very mechanically unstable.

In front It is an object of the invention to provide this background improved bioactive layers on textile substrates, the high mechanical stability with an efficient Drug immobilization and a controllable drug delivery combine.

Surprisingly could accomplish these tasks through the development of coating agents based on a combination of layer-forming nanoparticulate Brine (A) with a bioactive component (B) according to the Features of claim 1, in particular produced by the method according to claim 16, are solved. Advantageous embodiments and applications of the invention are the subject of the further claims.

• (Me = Metall, z. B. Si, Ti, Al, Zr; X = z. B. Alkoxyl, Acyl, Halogen;
• BN = bioaktiver öliger, dickflüssiger oder fester Naturstoff

The basic production process is shown in Scheme 1 below. For this purpose, by hydrolysis of silicon or metal alkoxides (I) or corresponding salts, stable metal oxide sols are prepared (II) which form thin metal oxide gel films on textile supports by concentration during drying (III). Scheme 1: Bioactive coating agent (MeO _n + BN) for textile materials

• (Me = metal, eg Si, Ti, Al, Zr, X = eg alkoxyl, acyl, halogen;
• BN = bioactive oily, viscous or solid natural product

In addition to the pure nanoparticulate sols (component A) in the form of z. As silicon, titanium, aluminum or zirconium oxide can be used by Cohydrolysen mixed metal oxide. For optimum immobilization of the biocomponents and / or to improve substrate adhesion and control wetting behavior, the silica sols (and other sols) may be organically modified, e.g. B. by cohydrolysis of 10 parts by weight of Si (OR ¹ ) ₄ and 0.1 to 10 parts by weight of R ² Si (OR ¹ ) ₃ and / or 0.1 to 5 parts by weight of R ³ ₂ Si (OR ¹ ) ₂ , wherein R ¹ and R ^{3 are} alkyl radicals having 1-4 C atoms and R ^{2 is} an alkyl radical having 1-18 C atoms or a fluoroalkyl radical having 1-18 C atoms or an epoxy- or amino-containing alkyl or cycloalkyl radical having 1-18 C Is -atoms. The hydrolysis is usually carried out in water-miscible organic solvents, for. As in low molecular weight alcohols, ketones, cyclic ethers, alkyl glycols or acetonitrile, or in a mixture of an aqueous solution with a water-miscible organic solvent. The preferred organic solvent is ethanol, which can be easily substituted by water after hydrolysis to z. B. to allow the introduction of honey-like substances.

One Advantage of the method consists in that you have solvent, concentration and composition of the sol can adapt to the nature of the bioactive component (B), so that virtually any bioactive oily, viscous or solid natural products can be integrated.

Some non-limiting example classes for the invention used bioactive natural substances or nature-identical substances are plant extracts, Vegetable oils or bee products (such as honey) or the corresponding nature-identical products (eg a synthetic oil or a synthetic sugar preparation). A "natural product" or "nature-identical substance", eg an "oil", as used here, can be made from a single chemical compound or a plurality of chemical compounds.

bioactive Natural or nature identical substances as used herein are all such substances having a biological effect, d. H. one direct or indirect effect on a living organism, z. B. on an animal or human body or on a microorganism.

For example may be used in the invention bioactive substances antimicrobial, antiallergic, therapeutic or have diagnostic properties.

A non-limiting special group of suitable bioactive Substances are oils and types of honey with biologically active by-products such as polyphenols, sesquiterpenes, triketones or flavonoids, e.g. B. various tea tree oils from the plant genera Leptospermum and melaleuca, especially manuka oil, perilla oil, enzyme- and active ingredient-rich honeys, such as heather honey or manuka honey. These are particularly suitable for antimicrobial coatings of wound dressings.

A another special group includes oils with proportions of omega-3 fatty acids and / or omega-6 fatty acids, eg. B. perilla oil, Evening primrose oil, chamomile oil, as well as tocopherol and Bisabolol, and is particularly suitable for the preparation antiallergic textiles.

A still other special group includes, but is not limited peppermint oil, menthol, eucalyptol, fennel oil, Caraway oil, camphor and capsaicin, in particular for therapeutic purposes for the relief of headache, Migraines, respiratory diseases and rheumatic pains.

Yet another specific group includes, but is not limited to, lavender oil, ginger extract, lemon balm oil, thyme oil and peppermint oil, especially for the preparation of therapeutic textiles Drug delivery for the treatment of headache, migraine, insomnia, back pain and rheumatism.

advantageously, should the ratio of the inorganic matrix (component A) and the bioactive agent (component B) equal to 1 or greater be.

to Control drug release and improve wash stability can be soluble in the coating solution Polymers up to 50 wt .-%, based on A, are added. Especially suitable are soluble polymers such as polyacrylates, polymethacrylates, Polyalkylene oxides, dextranes, hydroxyalkyl starches, hydroxyalkyl celluloses and / or polysiloxanes. The addition of these polymers requires no special steps or reaction conditions.

The thus obtained Begusslösungen can by the technically common coating techniques such as padding, Dipping, spraying, watering on the textile material (For example, fibers, fabrics, nonwovens) are applied and dried. Drying usually takes place under moderate heat at a temperature which is chosen such that the bioactive agent is not significantly volatilized, typically at a temperature below 60 ° C.

The textile substrate is not particularly limited. In which textile substrate may be, for example, fibers, fabrics or nonwovens made of all known natural (eg silk, Cotton, linen etc.) or synthetic (eg polyamide, polyacryl, Polyester, viscose, etc.) textile materials. In principle are also coatings of medical devices, of paper, cardboard or other substrates possible.

• (1) Herstellen der Komponente A durch Hydrolyse oder Cohydrolyse von Silicium- und/oder Metallverbindungen in einem mit Wasser mischbaren organischen Lösungsmittel oder in einer Mischung einer wässrigen Lösung mit einem mit Wasser mischbaren organischen Lösungsmittel;
• (2) Zugeben der gelösten oder suspendierten bioaktiven Komponente B;
• (3) fakultativ Zugabe eines löslichen Polymers;
• (4) Aufbringen des Beschichtungsmittels auf textile Flächen;
• (5) Trocknen der Schicht.

The process for the bioactive coating of textile materials using the coating composition according to one of claims 1-15 is characterized by the following process steps:

• (1) preparing component A by hydrolysis or cohydrolysis of silicon and / or metal compounds in a water-miscible organic solvent or in a mixture of an aqueous solution with a water-miscible organic solvent;
• (2) adding the dissolved or suspended bioactive component B;
• (3) optionally adding a soluble polymer;
• (4) applying the coating agent to textile surfaces;
• (5) drying the layer.

• – als textile Wundauflagen
• – als textile Kleidungsstücke mit antiallergischen Eigenschaften
• – als textile Träger (Auflagen, Kompressen, Binden, Bandagen, Strümpfe u. a. Kleidungsstücke) mit therapeutischen bzw. diagnostischen Eigenschaften, z. B. zur Linderung von Kopfschmerzen, Migräne, Schlaflosigkeit, Atemwegserkrankungen und Rheumaschmerzen, Hauterkrankungen, Schäden der Haut z. B. Ulcus cruris, Ulzerationen bei Diabetikern, Dekubitusprophylaxe und -behandlung.

The bioactive textile materials produced according to the invention have z. As antimicrobial, anti-allergic, therapeutic or diagnostic properties, resulting in many new applications, such. B .:

• - as textile wound dressings
• - as textile garments with antiallergic properties
• - As a textile carrier (pads, compresses, bandages, bandages, stockings and other garments) with therapeutic or diagnostic properties, eg. As for the relief of headache, migraine, insomnia, respiratory diseases and rheumatism, skin diseases, skin damage z. As leg ulcers, ulcerations in diabetics, decubitus prophylaxis and treatment.

• – selbst bei Einsatz flüchtiger oder fetter Öle erhält man trockene, glatte Oberflächen;
• – die anorganische Schichtmatrix, die aus den anorganischen Nanosolen gebildet wird, führt zu einer wirksamen Immobilisierung der Biokomponente und bietet eine hinreichende Auswaschstabilität;
• – die rezepturmäßig variierbare Porosität der Schichtmatrix, z. B. durch den Polymerzusatz, ermöglicht eine steuerbare Freisetzung des bioaktiven Wirkstoffs
• – die Beschichtungsmittel bieten vollkommen neue Möglichkeiten, Textilien mit antimikrobiellen, antiallergischen, therapeutischen oder diagnostischen Eigenschaften herzustellen.

The coating compositions for bioactive textile materials according to the invention thus show considerable advantages over the prior art:
the use of the inorganic nanoparticulate sols ensures good film formation and adhesion to the textile substrates;

• - Even with the use of volatile or fatty oils to get dry, smooth surfaces;
• The inorganic layer matrix, which is formed from the inorganic nanosols, leads to an effective immobilization of the biocomponent and offers a sufficient leaching stability;
• - The recipe variable porosity of the layer matrix, z. B. by the polymer additive, allows a controllable release of the bioactive agent
• The coating agents offer completely new possibilities for producing textiles with antimicrobial, antiallergic, therapeutic or diagnostic properties.

embodiments

1. Preparation of the SiO ₂ sol A

20 ml of tetraethoxysilane and 84 ml of acetone are stirred at room temperature with 4 ml of 0.01 N Hydrochloric acid and stirred for 20 h. The result is a SiO ₂ sol with about 6 wt .-% SiO ₂ .

2. Preparation of the SiO ₂ sol B

560 ml of tetraethoxysilane and 350 ml of acetone are mixed with stirring at room temperature with 90 ml of 0.01 N hydrochloric acid and stirred for 20 h. The result is a SiO ₂ sol with about 17 wt .-% SiO ₂ .

3. Preparation of the SiO ₂ sol C

560 ml of tetraethoxysilane and 350 ml of 96% ethanol are mixed with stirring at room temperature with 90 ml of 0.01 N hydrochloric acid and stirred for 20 h. The result is a SiO ₂ sol with about 17 wt .-% SiO ₂ .

4. Preparation of the SiO ₂ sol D

300 ml of tetraethoxysilane, 420 ml of acetone are mixed with stirring at room temperature with 60 ml of 0.01 N hydrochloric acid and stirred for 20 h. The result is a SiO ₂ sol with about 12 wt .-% SiO ₂ .

Example 1: Bioactive antimicrobial Coatings by immobilization of manuka oil and honey

• 1) Spezifische antimikrobielle Aktivität a = log KBE (unbeschichtet, 24 h) – log KBE (beschichtet, 24 h); KBE = koloniebildende Einheiten

The alcoholic sol C was admixed with 5% polyacrylate according to the following table. Subsequently, the amounts indicated in the table new moon manuka oil or New Zealand Active Manuka Honey UMF 25+ (MegaVitalShop Gablingen) were solved in the sol. Viscose (20 × 20 cm ² ) was dip-coated with this solution. The textiles were predried at room temperature for 3 hours and then tempered at 60 ° C. for 30 minutes. The antimicrobial efficacy of the coatings was compared to E. coli and Bac. tested subtilis. The following table shows the variants and efficiencies produced. variant spec. antimicrobial activity a ¹⁾ E. coli Bacillus subtilis Sol C + 5% Manuka oil 1.9 4.7 Sol C + 10% manuka oil 0.7 4.7 Sol C + 5% polyacrylate + 5% manuka oil 5.0 4.7 Sol C + 5% polyacrylate + 10% manuka oil 5.0 4.7 Sol C + 10% H ₂ O + 10% Manuka honey 1.1 -

• 1) Specific antimicrobial activity a = log CFU (uncoated, 24 h) - log CFU (coated, 24 h); KBE = colony forming units

Example 2: Bioactive antimicrobial Coatings by immobilization of perilla oil

Sol B was mixed with polyacrylate as needed. Then, according to the following table, perilla oil (Chendu Deyuantang Industry Commerce Co., LTD, China) was dissolved in the sol. Viscose (20 × 20 cm ² ) was dip-coated with this solution. The textiles were predried at room temperature for 3 hours and then tempered at 60 ° C. for 30 minutes. To determine the washing resistance washing was done in a commercial washing machine at 40 ° C with ECE detergent and Beiladung. The spec. antimicrobial activities were compared to Bac. determined subtilis test germs. The following table shows the determined activity values. Bacillus subtilis spec. antimikr. activity 5 × ECE unwashed 40 ° C Sol B + 5% perilla oil 5.0 0 Sol B + 10% perilla oil 5.0 0 Sol B + 5% polyacrylate + 5% perilla oil 5.0 1.9 Sol B + 5% polyacrylate + 10% perilla oil 5.0 4.5

Example 3 Embedding Bisabolol and Determination of washout stabilities of textile coatings

The active ingredient bisabolol (Fluka) was dissolved in Sol A according to the following table. If necessary, a certain amount of polyacrylate has previously been added to the sol. With these solutions, cotton textiles (120 g / m ² ) were dip-coated and dried at room temperature in air.

to Determination of the washing resistance carried out washing operations in a commercial washing machine at 30 ° C with ECE detergent and additional charge. The residual content of active ingredient the samples (which at the same time is a measure of washout stability the sol-gel layer is) after extraction with acetone (90 min, 40 ° C, Ultrasonic bath) determined by gas chromatography.

The table shows the determined bisabolol concentrations. composition Bisabolol content [g / m ² ] before washing test 1 × ECE 3 × ECE 5 × ECE Sol A + 0.5% bisabolol 4.4 0.5 0.3 - Sol A + 2% polyacrylate + 0.5% bisabolol 2.9 0.8 0.3 - Sol A + 4% polyacrylate + 0.5% bisabolol 3.3 1.5 0.6 0.4 Sol A + 6% polyacrylate + 0.5% bisabolol 2.9 1.7 1.0 0.4

Example 4: Embedding Evening Primrose Oil and determining the washout stabilities of the textile coatings

Sol B was added according to the following table with polyacrylate. Subsequently, evening primrose oil (Roth) in Sol solved. With this solution was cotton fabric (20 × 20 cm) dip-coated. The textiles were added Room temperature predried for 3 h and then at 60 ° C for 30 min annealed. To determine the wash resistance took place Washing processes in a commercial washing machine at 30 ° C with ECE detergent and additional charge. The γ-linolenic acid content of the evening primrose oil was subsequently transesterified determined by gas chromatography.

The following table contains the determined concentrations of γ-linolenic acid. composition γ-linolenic acid content [g / m ² ] before washing test 1 × ECE 3 × ECE 5 × ECE 10 × ECE Sol B + 4% polyacrylate + 8% evening primrose oil 38.7 29.4 36.9 27.4 8.4 Sol B + 8% evening primrose oil 34.9 23.7 6.3 3.7 3.0

Example 5 Embedding Eucalyptol, Menthol and camphor for the relief of respiratory diseases

To prepare the coating solution, 100 g of Sol D were first admixed with 2 g of polyacrylate, and 5.5 g of eucalyptol, 2.5 g of menthol, 0.4 g of camphor and 2 g of evening primrose oil were dissolved therein. As substrate, cotton fabric (120 g / m ² with polymer interlayer as barrier layer) was used. The coating was machined on a small-scale plant. The textiles were continuously coated in a width of 22 cm by one-sided application by means of extrusion casters. The drying was carried out by a downstream circulating air dryer at 60 ° C. The active substance content of the textiles was determined by gas chromatography after extraction in acetone (90 min, 40 ° C., ultrasonic bath). The total active substance concentration was 7.3 g / m ² .

The Determination of drug concentrations in the air of volunteers resulted after applying coated textile samples of size 10 × 20 cm in the back and then Absorption through the skin after a maximum drug concentration after 90 min.

• – eine kontinuierlichere Freisetzung der Wirkstoffe
• – eine längere Wirkdauer
• – ein größeres subjektives Wohlbefinden der Probanden.

A test subject to compare the bioactive coating with the conventional method of ointment application in comparable concentrations showed the benefits of the coated textile:

• - a more continuous release of the active ingredients
• - a longer duration of action
• - a greater subjective well-being of the subjects.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• EP 0936299 [0003]
• - JP 2001031516 [0003]
• - JP 2004100083 [0003]
• - JP 2003201669 [0003]
• GB 2385271 [0003]
• - KR 20030006258 [0003]
• GB 2329583 [0003]
• - JP 8027624 [0003]

Claims (21)

Coating agent for bioactive textile Materials containing (A) a layer-forming nanoparticulate Sol, formed by hydrolysis or cohydrolysis of silicon and / or Metal compounds, and (B) a bioactive component comprising one or more bioactive oily, viscous or solid natural substances or nature-identical substances, in an aqueous or water-miscible organic solvents. Coating composition according to claim 1, wherein the component A by hydrolysis or cohydrolysis of silicon alkoxides or alkoxides or salts of titanium, aluminum or zirconium was formed. Coating composition according to claim 1 or 2, wherein component A is obtained by cohydrolysis of 10 parts by weight of Si (OR ¹ ) ₄ and 0.1 to 10 parts by weight of R ² Si (OR ¹ ) ₃ and / or 0.1 to 5 parts by weight of R ³ ₂ Si (OR ¹ ) _{2 was} formed, wherein R ¹ and R ^{3 are} alkyl radicals having 1-4 C atoms and R ^{2 is} an alkyl radical having 1-18 C atoms or a fluoroalkyl radical having 1-18 C atoms or an epoxy or amino-containing alkyl or cycloalkyl radical having 1-18 C atoms. Coating composition according to one of the claims 1-3, wherein the component B from bioactive oily, viscous or solid natural or nature-identical substances with antimicrobial, antiallergic or therapeutic properties. Coating composition according to one of the claims 1-4, wherein component B consists of bioactive plant extracts, Vegetable oils, bee products or the corresponding nature-identical Substances. Coating composition according to claim 5, wherein the component B from oils or honey with biologically active by-products, z. Polyphenols, sesquiterpenes, triketones or flavonoids, consists. Coating composition according to claim 6, wherein the component B from the group consisting of a tea tree oil, in particular Manuka oil or the oil of the Australian tea tree (Melaleuca alternifolis), heather honey and manuka honey is. Coating composition according to claim 5, wherein the component B from oils containing omega-3 fatty acids and / or omega-6 fatty acids. Coating composition according to claim 5 or 8, wherein component B from the group consisting of perilla oil, Evening primrose oil, tocopherol and bisabolol is. Coating composition according to claim 5, wherein the component B from the group consisting of peppermint oil, menthol, Eucalyptol, fennel oil, caraway oil, evening primrose oil, Capsaicin and camphor, is selected. Coating composition according to claim 5, wherein the component B from the group consisting of lavender oil, ginger extract, Lemon balm oil, thyme oil and peppermint oil, is selected. Coating composition according to one of the claims 1-11, wherein the weight ratio A: B is the same 1 or greater. Coating composition according to one of the claims 1-12, wherein the organic solvent is one with water miscible solvent is that consisting of the group from low molecular weight alcohols and ketones, cyclic ethers, Alkyl glycols or acetonitrile. Coating composition according to one of the claims 1-13, which additionally soluble polymers up to 50 wt .-%, based on A, contains. Coating composition according to one of the claims 1-14, the soluble polymers being polyacrylates, Polymethacrylates, polyalkylene oxides, dextrans, hydroxyalkyl starches, Hydroxyalkylcellulosen and / or polysiloxanes. Process for coating bioactive textile materials using the coating composition according to one of Claims 1-15, characterized by the following process steps: (1) preparing component A by hydrolysis or cohydrolysis of silicon and / or metal compounds in a water-miscible organic solvent or in a mixture of an aqueous Lö (2) adding the dissolved or suspended bioactive component B; (3) optionally adding a soluble polymer; (4) applying the coating agent to textile surfaces; (5) drying the layer. Use of the coating composition according to one of Claims 1-15 for the production of biofunctional textile materials with antimicrobial, anti-allergic, therapeutic or diagnostic properties. Use according to claim 17, wherein the coating agent Heath-honey, Manuka honey or other natural or nature-identical Contains sugar preparations or honeys with polyphenol components, for the production of textile wound dressings. Use according to claim 17, wherein the coating agent Perilla oil, bisabolol, tocopherol and / or evening primrose oil contains, for the production of antiallergic textiles. Use according to claim 17, wherein the coating agent Eucalyptol, menthol and / or camphor contains for manufacturing therapeutic textiles with drug delivery for the treatment of Headaches, migraines, respiratory diseases and rheumatism. Use according to claim 17, wherein the coating agent Lavender oil, ginger extract, lemon balm oil, thyme oil and / or peppermint oil for manufacturing therapeutic textiles with drug delivery for the treatment of Headache, migraine, insomnia, back pain and rheumatism.