WO2008083908A1 - Sheet materials with good breathing action and method for production thereof - Google Patents

Abstract

Sheet materials are disclosed, comprising a thermoplastic polyurethane film, coated with at least one protein and at least one textile material.

Description

 Layered materials with good breathability and process for their preparation

description

The present invention relates to layered materials comprising a thermoplastic polyurethane film coated with at least one protein and at least one textile material.

Furthermore, the present invention relates to a method for producing the layered materials according to the invention. Furthermore, the present invention relates to garments made of or using layered materials of the invention.

For many substrates, especially textile substrates, emphasis is placed on good breathability. On the one hand, water vapor should pass well through the substrate in question, and it should be avoided that condensed water accumulates on the inside of, for example, garments made from the respective substrates, and thus the garments inside feel wet. On the other hand, should liquid water, for example in the form of rain, not pass through the substrate in question, and made of the substrates in question clothing should be water and windproof. Such substrates should have good fastness properties, so for example, the wash fastness should be good. Finally, it should be ensured that the coating can be distributed as evenly as possible on the relevant substrate.

In many known from the prior art substrates, the above properties are only partially realized. Thus, WO 06/08163 proposes coating textile with spider silk proteins (claims 46, 47). However, a uniform coating of textiles with such a substance does not succeed in many cases. Instead, large accumulations of spider silk proteins are observed in a few places, for example in the gussets, and instead little or no coating on the fiber top.

No. 5,494,744 proposes coating films with amphiphilic proteins by first subjecting the film to be coated to a strong shearing force and thereby coating it. Such films are then modified hydrophilic. US 5,494,744 proposes to choose the films of thermoplastic polymers, in particular polyesters, polyamides or polyolefins (claims 29, 30). For the finishing of textiles such coated films are only slightly suitable. It turns out that coated polyolefin films, for example polyethylene films or polypropylene films, are not permeable to water vapor. Coated polyester films are uncomfortable to crunch when rubbed together, and polyamide films are economically unfavorable. In addition, For example, polyester films, polyamide films and polyolefin films do not have sufficient mechanical properties for many applications; for example, the recovery properties desired for textiles are not sufficient.

Macromolecular Bioscience 2005, 5, 1031-1021 describes immobilizing a protein (water-soluble chitosan and heparin) on a thermoplastic polyurethane surface. To achieve fastness, plasma activation of the surface of the thermoplastic polyurethane is necessary. Plasma activation is usually very expensive.

The object was, therefore, to provide a process by means of which textile substrates can be produced which have both permanently good thermo-physiological wearing comfort, for example characterized by breathability, heat insulation, perspiration transport, drying time, and good sensory wearing comfort, for example Skin, surface roughness / hairiness, contact surface textile / skin, stiffness. A further object was to provide textile substrates which are characterized both by permanently good thermophysiological wearing comfort, for example by breathability, thermal insulation, perspiration transport, drying time, and good sensory wearing comfort, for example textile / skin toning, surface roughness / hairiness, contact surface textile / Skin, stiffness.

Accordingly, the initially defined layered material was found.

The layered material defined at the outset comprises at least one textile material, which is preferably configured flat to form textile fabrics. Textile materials in the context of the present invention are textile semifinished and finished products and finished goods produced therefrom, which include, in addition to textiles for the clothing industry, for example, carpets and other home textiles as well as textile structures serving technical purposes. These include unshaped structures such as flakes and preferably area or body structures such as felts, fabrics, knitwear, nonwovens and wadding. Textile materials in the context of the present invention can be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blends, polyamide blends, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and glass fiber fabrics.

Textile materials in the sense of the present invention can be colored, for example dyed or printed, and they can be finished, for example equipped without ironing. In another embodiment of the present invention goes one from non-colored textile material. In another embodiment of the present invention is based on non-finished textile material.

The layered material defined at the beginning further comprises a thermoplastic polyurethane film. Thermoplastic polyurethanes (also referred to as TPUs for short) and films made therefrom are known as such.

Thermoplastic polyurethanes, preferably TPU elastomers are well known, are commercially available and generally consist of a soft phase of higher molecular weight polyhydroxyl compounds, e.g. from polyester or Polyetherseg- elements, and a urethane hard phase formed from low molecular weight chain extenders and di- or polyisocyanates.

Methods of making thermoplastic polyurethanes are well known. In general, thermoplastic polyurethanes by reaction of

(a) isocyanates, preferably diisocyanates with

(b) isocyanate-reactive compounds, usually having a molecular weight (Mw) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, more preferably 800 to 3,000 g / mol, and (c) chain extenders having a molecular weight of 50 to 499, if appropriate in the presence of

(d) catalysts

(e) and / or customary additives.

In the following, by way of example, the starting components and processes for the preparation of the preferred polyurethanes are shown. The components (a), (b), (c) and optionally (d) and / or (e) usually used in the preparation of the polyurethanes are described below by way of example:

As isocyanates (a) it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate 1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 2, 6-cyclohexane diisocyanate and / or 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and / or 4.4 'Diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate. Preferably, 4,4'-MDI is used. Also preferred are aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI), and particular preference is given to aromatic diisocyanates such as 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and mixtures of the abovementioned isomers.

As isocyanate-reactive compounds (b) it is possible to use the generally known isocyanate-reactive compounds, for example polyesterols, polyetherols and / or polycarbonatediols, which are usually also grouped under the term "polyols", with molecular weights (M _w ) in the region of 500 and 8,000 g / mol, preferably 600 to 6,000 g / mol, in particular 800 to 3,000 g / mol, and preferably an average functionality to isocyanates of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2. Polyether polyols are preferably used, for example those based on generally known starter substances and customary alkylene oxides, for example ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (polyTHF), 1 , 2-propylene oxide and ethylene oxide.Polyetherols have the advantage that they have a higher hydrolytic stability than polyesterols, and are preferably as component (b).

Polyetherols are preferably by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, of diols such as ethylene glycol, 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 4-butanediol, 1, 3-propanediol, or at Triols such as glycerol, prepared in the presence of highly active catalysts. Such highly active catalysts include cesium hydroxide and dimetal cyanide catalysts, also referred to as DMC catalysts. A commonly used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyetherol after the reaction, preferably it is removed, for example by sedimentation or filtration.

Instead of a polyol, it is also possible to use mixtures of different polyols.

As chain extenders (c) known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol and at least two functional groups, preferably compounds having exactly two functional groups per molecule are used, for example Diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa- , Hepta-, octa, nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and / or polypropylene glycols, whereby mixtures of chain extenders (c) can be used. The components (a) to (c) are particularly preferably difunctional compounds, ie diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.

Suitable catalysts (d), which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the constituent components (b) and (c), are per se known tertiary amines, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) -octane ("DABCO") and similar tertiary amines, and especially organic metal compounds such as titanic acid esters Iron compounds such as iron (III) acetylacetonate, tin compounds, eg, tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, etc. The catalysts are usually used in amounts of from 0.0001 to 0 , 1 parts by weight per 100 parts by weight of component (b) used.

Besides catalyst (d), auxiliaries and / or additives (e) can also be added to components (a) to (c). Mention may be made, for example, of blowing agents, anti-block agents, surface-active substances, fillers, for example fillers based on nanoparticles, in particular fillers based on CaCO 3, furthermore nucleating agents, lubricants, dyes and pigments, antioxidants, for example against hydrolysis, light, heat or discoloration , inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators. In a preferred embodiment, component (e) also includes hydrolysis protectants such as, for example, polymeric and low molecular weight carbodiimides. Preferably, the thermoplastic polyurethane contains triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5 wt .-% based on the total weight of the relevant thermoplastic polyurethane. As antioxidants are generally suitable substances which inhibit or prevent unwanted oxidative processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers. Examples of sterically hindered phenols can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), pp. 98-107 and pp. 116-122. Examples of Aromatic Amines can be found in [1] pp. 107-108. Examples of thiosynergists are given in [1], p.104-105 and p.1 12-113. Examples of phosphites can be found in [1], p.109-112. Examples of hindered amine light stabilizers are given in [1], p.123-136. For use in the antioxidant mixture are preferably phenolic antioxidants. In a preferred embodiment, the antioxidants, in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, more preferably greater than 700 g / mol and a maximum molecular weight (M _w ) of at most 10,000 g / mol, preferably up to a maximum of 3,000 g / mol on. Furthermore, they preferably have a melting point of at most 180 ^° C. Furthermore, preference is given to using antioxidants which are amorphous or liquid. Also, as component (e), mixtures of two or more antioxidants may be used. In addition to the noble metal salts, inorganic and / or organic fillers which are not noble metal salts may preferably be present in the thermoplastic polyurethane films, preferably calcium carbonate.

In addition to the abovementioned components (a), (b) and (c) and, if appropriate, (d) and (e), it is also possible to use chain regulators (chain terminators), usually having a molecular weight of 31 to 3000 g / mol. Such chain regulators are compounds which have only one isocyanate-reactive functional group, e.g. monofunctional alcohols, monofunctional amines and / or monofunctional polyols. By means of such chain regulators, a flow behavior, in particular in the case of thermoplastic polyurethanes, can be adjusted in a targeted manner. Chain regulators can generally be used in an amount of from 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component (b), and fall by definition under component (c).

To adjust the hardness of the thermoplastic polyurethanes, the components (b) and (c) can be selected in relatively broad molar ratios. Proven molar ratios of component (b) to total used chain extenders (c) of 10: 1 to 1:10, in particular from 1: 1 to 1: 4, wherein the hardness of the thermoplastic polyurethanes with increasing content of (c) increases , The reaction for the preparation of the thermoplastic polyurethanes may be at a ratio of 0.8 to 1, 4: 1, preferably at a ratio of 0.9 to 1, 2: 1, more preferably at a ratio of 1, 05 to 1, 2 : 1. The index is defined by the ratio of the total isocyanate groups used in the reaction of component (a) to the isocyanate-reactive groups, i. the active hydrogens, components (b) and optionally (c) and, optionally, monofunctional isocyanate-reactive components as chain terminators such as e.g. Monoalcohols.

The production of thermoplastic polyurethanes can be carried out continuously by processes known per se, for example with reaction extruders or the belt process according to one-shot or the prepolymer process, or batchwise by the prepolymer process known per se. In these processes, the reacting components (a), (b), (c) and optionally (d) and / or (e) may be mixed together successively or simultaneously with the reaction starting immediately.

In the extruder process, the components (a), (b), (c) and optionally (d) and / or (e) are introduced into the extruder individually or as a mixture, for example at room temperature. ren of 100 to 280 ⁰ C, preferably 140 to 250 ⁰ C, and reacted. The resulting thermoplastic polyurethane is usually extruded, cooled and granulated. After the synthesis, the thermoplastic polyurethane can optionally be modified by formulation on an extruder.

Thereafter, the thermoplastic polyurethane is extruded according to methods known per se into a film, which is also referred to in the context of the present invention as a thermoplastic polyurethane film.

In one embodiment of the present invention, thermoplastic polyurethane films may have an average thickness in the range of 5 to 100 μm, preferably 10 to 50 μm, particularly preferably 15 to 40 μm.

The thermoplastic polyurethane film contained in layered materials according to the invention is coated with at least one protein on one side, specifically on the one which faces away from the textile material after completion of the process according to the invention. Layered materials according to the invention thus comprise at least one protein. If it is desired to produce garments from layered material according to the invention, the procedure is then such that protein-coated thermoplastic polyurethane film is on the inside of the garment in question. Advantageously, the protein coated side of the thermoplastic polyurethane film is directed to the body side of the wearer of such garment of the invention.

Suitable proteins are in particular those proteins which have hydrophilic and hydrophobic units and which may also be termed amphiphilic.

Suitable proteins are in particular silk proteins. For the purposes of the present application, these are understood as meaning proteins which contain repetitive amino acid sequences and are stored in an animal, for example an arthropod, in particular a spider or an insect, in a liquid form, for example in aqueous solution or aqueous dispersion, and fibers are formed on their secretion by shearing or spinning (see, for example, Craig, CL Evolution of arthropod silks, Annu Rev. Entomol 1997, 42, 231-267).

By highly repetitive amino acid sequences are meant amino acid sequences having a high number of repeating units consisting of particular amino acids.

In one embodiment of the present invention, layered materials of the invention comprise one or more spider silk proteins that have been isolated from spiders in their original form. In one embodiment of the present invention, layered materials of the invention comprise spider silk protein which can be isolated from the spider's "major ampullate" gland.

Particularly preferred spider silk proteins are ADF3 and ADF4 from the major ampullate gland of Araneus diadematus (Guerette et al., Science 272, 5258: 112-5 (1996)).

Further examples of suitable proteins are natural or synthetic proteins which are derived from natural silk proteins, in particular from natural spider silk proteins and which have been produced heterologously in prokaryotic or eukaryotic expression systems using genetic engineering working methods. Non-limiting examples of prokaryotic expression organisms are Escherichia coli, Bacillus subtilis, Bacillus megaterium, Corynebacterium glutamicum etc. Nonlimiting examples of eukaryotic expression organisms are yeasts such as Saccharomyces cerevisiae, Pichia pastoris and others, filamentous fungi such as Aspergillus niger, Aspergillus oryzae, Aspergillus nidulans and Trichoderma reesei , Acremonium chrysogenum and others, mammalian cells, such as Heia cells, COS cells, CHO cells and others, insect cells, such as Sf9 cells, MEL cells and others.

Preferred examples of suitable proteins are synthetic proteins which are based on repeating units of natural silk proteins, so-called repetitive silk protein sequences. In addition to the synthetic repetitive silk protein sequences, these synthetic proteins may additionally contain one or more natural non-repetitive silk protein sequences (see, for example, Winkler and Kaplan, J. Biotechnol., 2000, 74, 85).

In one embodiment of the present invention, suitable proteins are selected from synthetic spider silk proteins based on repeating units of natural spider silk proteins. In addition to the synthetic repetitive spider silk protein sequences, these synthetic spider silk proteins may additionally contain one or more natural non-repetitive spider silk protein sequences.

Among the synthetic spider silk proteins, preference is given to the so-called C16 protein (Huemmerich et al., Biochemistry 2004, 43, 13604-13612). C16 protein has the polypeptide sequence shown in SEQ ID NO: 1. In addition to the polypeptide sequence shown in SEQ ID NO: 1, particularly functional equivalents, functional derivatives and salts of this sequence are also preferred. In the context of the present application, functional equivalents also include, in particular, mutants which, in at least one sequence position of the abovementioned amino acid sequences, have a different amino acid than the one specifically mentioned, but nevertheless have one of the abovementioned biological properties. Functional equivalents within the meaning of the present invention thus include the mutants obtainable by one or more amino acid additions, substitutions, deletions and / or inversions, wherein said changes can occur in any sequence position, as long as they correspond to a mutant with the o ben designated property profile lead. Functional equivalence is especially given when the reactivity patterns between mutant and unmodified protein are qualitatively consistent. Functional equivalents in the above sense are also precursors of the described proteins as well as functional derivatives and salts of the aforementioned proteins.

Precursors are natural or synthetic precursors of the aforementioned proteins.

Examples of suitable amino acid substitutions are shown in Table 1.

Table 1: Amino acid substitutions for functional equivalents of synthetic proteins used according to the invention

Wässrige Lösungen von vorstehend genannten Proteinen lassen sich bevorzugt durch das im Folgenden beschriebene Verfahren herstellen. Das Protein wird in einem ersten Lösungsmittel gelöst. Als Lösungsmittel können beispielsweise wässrige Salzlösungen verwendet werden. Insbesondere eignen sich hochkonzentrierte Salzlösungen mit ei- ner Konzentration größer 2 mol/l Salz, insbesondere größer 4 mol/l und besonders bevorzugt größer 5 mol/l. Besonders gut eignen sich Salzlösungen, deren Ionen stärker ausgeprägte chaotrope Eigenschaften aufweisen als Natriumionen und Chloridionen. Ein Beispiel für eine solche Salzlösung ist 6 M Guanidiniumthiocyanat oder 9 M Lithiumbromid. Des Weiteren können organische Lösungsmittel zum Lösen der Protei- ne verwendet werden. Insbesondere eignen sich fluorierte Alkohole oder zyklische Kohlenwasserstoffe. Beispiele dafür sind Hexafluorisopropanol und Cyclohexan. Um wässrige Proteinlösungen zu erhalten, kann das erste Lösungsmittel durch ein weiteres Lösungsmittel, z. B. Wasser oder niedrig konzentrierte Salzlösungen (c < 0,5 M) durch Dialyse oder Verdünnung ersetzt werden. Die Endkonzentration des gelösten Proteins sollte im Bereich von 0,1 bis 100 g/l betragen. Die Temperatur, bei der das Verfahren durchgeführt wird, beträgt üblicherweise 0 bis 80 ⁰C, bevorzugt 5 bis 50 ⁰C und besonders bevorzugt 10 bis 40 ⁰C.

Aqueous solutions of the above-mentioned proteins can preferably be prepared by the method described below. The protein is dissolved in a first solvent. As the solvent, for example, aqueous salt solutions can be used. In particular, highly concentrated salt solutions with a concentration greater than 2 mol / l of salt, in particular greater than 4 mol / l and particularly preferably greater than 5 mol / l are suitable. Saline solutions are particularly well suited whose ions have more pronounced chaotropic properties than sodium ions and chloride ions. An example of such a saline solution is 6 M guanidinium thiocyanate or 9 M lithium bromide. Furthermore, organic solvents can be used to dissolve the proteins. In particular, fluorinated alcohols or cyclic hydrocarbons are suitable. Examples are hexafluoroisopropanol and cyclohexane. To obtain aqueous protein solutions, the first solvent may be replaced by another solvent, e.g. As water or low-concentration salt solutions (c <0.5 M) can be replaced by dialysis or dilution. The final concentration of the dissolved protein should be in the range of 0.1 to 100 g / l. The temperature at which the process is carried out is usually 0 to 80 ^° C., preferably 5 to 50 ^° C., and particularly preferably 10 to 40 ^° C.

When aqueous solutions of suitable protein are used, they may also be mixed with a buffer, preferably with a pH in the range from 4 to 10, particularly preferably 5 to 9, very particularly preferably 6 to 8.5.

The term salts of the abovementioned proteins means both salts of carboxyl groups and acid addition salts of amino groups of the proteins used in the process according to the invention. Salts of carboxyl groups can be prepared in a manner known per se and include inorganic salts such as sodium, calcium, ammonium, iron and zinc salts, as well as salts with organic bases such as amines such as triethanolamine, arginine, lysine and piperidine. Acid addition salts such as, for example, salts with mineral acids such as hydrochloric acid or sulfuric acid and salts with organic acids such as acetic acid and oxalic acid can also be used in the process according to the invention.

Functional derivatives of suitable proteins may also be prepared at functional amino acid side groups or at their N- or C-terminal end using known techniques. Such functional derivatives include, for example, aliphatic esters of carboxylic acid groups, amides of carboxylic acid groups obtainable by reaction with ammonia or with a primary or secondary amine, N-acyl derivatives of free amino groups prepared by reaction with acyl groups; or O-acyl derivatives of free hydroxy groups, prepared by reaction with acyl compounds such as, for example, acid chlorides or anhydrides of carboxylic acids. Layered materials according to the invention have a good breathability. To estimate the breathability one can use various methods known per se. For example, ASTM D-6701 is suitable.

In order to determine the improvement in the moisture transport, it is possible, for example, to use the contact angle, in particular the static contact angle, with water. The static contact angle with water of the present invention layer-shaped materials can be, for example, according to methods known per se determined and is, for example up to 50 °, preferably in the range of 10 to 35 °, measured at 20 ⁰ C. The contact angle of numerous uncoated thermoplastic polyurethane Films with water is in many cases at 75 to 80 ⁰ C, measured at 20 ⁰ C.

It is observed that layered materials according to the invention are strongly hydrophilized on the side coated with protein in the thermoplastic polyurethane film. Moisture, especially water, no longer separates in the form of separate drops, but as a thin film.

It is further observed that the moisture transport of layered materials of the present invention is greatly improved compared to materials comprising a textile material and a thermoplastic polyurethane film, but no protein. The drying time is usually significantly shorter, which leads to a significantly improved thermophysiological comfort.

Inventive layered materials furthermore have very good fastness properties, for example rub fastnesses, wash fastnesses and wet rub fastnesses. For this purpose, no plasma activation of the thermoplastic polyurethane film is required as a rule.

Another object of the present invention is a process for the preparation of layered materials according to the invention, also called production process according to the invention. The terms protein, thermoplastic polyurethane film and textile material are as defined above.

In garments made from layered materials made in accordance with the present invention, it is then preferred that the coated thermoplastic polyurethane film is on the inside of the garment in question. Advantageously, the protein coated side of the thermoplastic polyurethane film is directed to the body side of the wearer of such garment of the invention.

As a rule, the production method according to the invention can be carried out without plasma activation of the surface of the thermoplastic polyurethane film. In one embodiment of the production process according to the invention, the procedure is to join a textile material with a thermoplastic polyurethane film which is coated with at least one protein on the side facing away from the textile material.

In another embodiment of the production method according to the invention, the procedure is to coat a thermoplastic polyurethane film, which is connected to a textile material, with at least one protein.

In one embodiment of the present invention, the coating of thermoplastic polyurethane film with protein is carried out by treating the thermoplastic polyurethane film with a preferably aqueous formulation of protein.

In one embodiment of the present invention, when coating the thermoplastic polyurethane film, optionally in combination with textile, no shear forces are exerted which lead to an elongation of the thermoplastic polyurethane film, in particular no shear forces which are so considerable that lead to irreversible stretching of the thermoplastic Polyurethane film lead.

Such a treatment can be carried out, for example, by spraying with preferably aqueous formulation or by immersion in a preferably aqueous formulation of protein. When spraying or immersing it is important to ensure that only one side of the film concerned with preferably aqueous formulation of protein in contact.

In a preferred embodiment of the present invention, by knife coating.

In one embodiment of the present invention, the coating is carried out at temperatures in the range from 5 to 95 ^° C., preferred are 10 to 50 ^° C., particularly preferably 10 to 30 ^° C.

The preferably aqueous formulation used for coating contains in an embodiment of the present invention in the range of 0.1 to 20 wt .-%, preferably 0.5 to 5 wt .-% protein.

In one embodiment of the present invention, the preferably aqueous formulation used for coating, apart from water and protein, contains no further constituents. In another embodiment of the present invention, the aqueous formulation used for coating may contain one or more further ingredients, for example one or more surfactants or one or more surfactants, for example one or more surfactants selected from anionic or cationic or nonionic surfactants, nonionic surfactants being preferred. Examples of nonionic surfactants are, in particular, polyalkoxylated fatty acids, polyalkoxylated fatty acid amides, polyalkoxylated non-quaternized fatty acid amines, polyalkoxylated mono- and diglycerides, optionally polyalkoxylated alkyl polyglycosides, preferably selected from alkyl polyglucosides and sugar ester alkoxylates, and polyethoxylated fatty amines, in particular 2- to 20-fold alkoxylated C8-C30 fatty amines, saturated or mono- or polyunsaturated.

Specific examples of nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C12) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36). Examples are the Lutensol ^® brands of BASF Aktiengesellschaft.

Examples of suitable wetting agents are, in particular, polyvinyl alcohol and partially saponified polyvinyl acetates, which are commercially available, for example, as Mowiol® grades. For the most part, saponified polyvinyl acetates are preferred, for example having up to 40 mol% residual acetyl content, in particular having up to 15 mol% residual acetyl content, in each case based on the non-hydrolyzed polyvinyl acetate in question.

In one embodiment of the present invention, the preferably aqueous formulation of protein is allowed to act on the thermoplastic polyurethane film, for example, over a period of time ranging from 5 minutes to 2 hours, preferably 10 to 45 minutes, prior to further passing the coated polyurethane film processed, for example by thermal treatment or by bonding with textile material.

In one embodiment of the present invention, the coating of the thermoplastic polyurethane film is fixed after treatment with preferably aqueous formulation of protein, for example by thermal treatment.

The thermal treatment can be, for example, at temperatures ranging from 20 to 140 ⁰ C, preferably 50 to 130 ⁰ C, particularly preferably by lead 80 to 125 ° C. Suitable devices for the thermal treatment are, for example, drying cabinets and tenter frames. The thermal treatment can be carried out in one or more steps, for example two or three steps, wherein the temperature in the respective subsequent steps is preferably increased in each case.

In one embodiment of the present invention, the average layer thickness of protein on thermoplastic polyurethane film in the range of 5 nm to 5 microns, preferably in the range of 10 nm to 2 microns and more preferably in the range of 20 nm to 1 micron. The layer thickness is determined in each case on a over a period of 10 minutes at 100 ⁰ C and a further 10 minutes at 125 ° C dried polyurethane film, for example by microscopic determination or by weighing. It is also possible to determine a theoretical layer thickness by determining the wet layer thickness and calculating, taking into account the protein concentration, the layer thickness of protein on thermoplastic polyurethane film. Furthermore, it is possible to determine the enzymatic activity of the protein layer by methods known per se, for example by antibody reaction.

Following the coating and, if appropriate, the thermal treatment, the thermoplastic protein-coated polyurethane film, if appropriate coated with protein, is bonded to a textile material, for example by gluing or by lamination.

In one embodiment of the present invention, the treatment of thermoplastic polyurethane film with preferably aqueous formulation of protein is carried out such that a composite body comprising a thermoplastic polyurethane film and a carrier material to which the relevant thermoplastic polyurethane film is applied, coated with protein, in such a way that the coating is applied to the thermoplastic polyurethane film. After that you can treat thermally. Thereafter, the protein-coated thermoplastic polyurethane film is separated from the carrier material and bonded to the textile material. The composite can also be referred to as a layered material in the context of the present invention.

As support materials, basically all materials are suitable which give the composite a greater mechanical rigidity (stiffness). In the context of the present invention, carrier materials are preferably sheet-like materials, in particular film-like materials, for example polymer films such as, for example, polyolefin films or polyester films. The thickness of the carrier material may be greater or smaller than the thickness of the thermoplastic polyurethane film to be coated, preferably the thickness of the carrier material is in the range of 1, 1 to 10 times as large as the relevant thermoplastic polyurethane film. In another embodiment of the present invention, the thickness of thermoplastic polyurethane film and substrate to be coated is the same. If a composite body is used to carry out the production process according to the invention, which comprises, inter alia, a carrier material, in many cases an even more uniform coating with protein succeeds.

In one embodiment of the present invention, in a further working step, a textile material is applied to the protein-coated thermoplastic polyurethane film, preferably on the side which is coated with protein. This gives a layered material composed of a textile material, a protein-coated film and another textile material, which may be different from or equal to the first textile material.

Another object of the present invention are layered materials comprising a thermoplastic polyurethane film coated with at least one protein, and a carrier material.

Another object of the present invention is the use of layered materials according to the invention, in particular one which comprises a thermoplastic polyurethane film which is coated with at least one protein, and at least one textile material, as or for the production of clothing pieces. Another object of the present invention is a process for the production of garments using at least one layered material according to the invention, in particular at least one comprising a thermoplastic polyurethane film coated with at least one protein, and at least one textile material. Another object of the present invention are garments made using at least one layered material according to the invention, in particular at least one comprising a thermoplastic polyurethane film coated with at least one protein, and at least one textile material.

Examples of suitable clothing items include: shoes, in particular those with textile parts such as hiking and sports shoes, furthermore jackets, coats, trousers, pullovers, stockings, belts, workwear, protective clothing, smocks and overalls, in particular sportswear. Other suitable clothing items are protective suits for high-temperature workplaces, for example for the fire brigade or for steel cookers.

Garments according to the invention are characterized by great thermophysiological and sensory wearing comfort, in particular good breathability, good moisture transport and short drying times of perspiration and condensate, with at the same time good fastnesses, in particular washing and rubbing fastness. The invention will be explained by working examples.

I. Preparation of an aqueous spider silk protein solution

The following method was used to prepare aqueous solution of the spider silk protein C16: lyophilized C16 protein (C16 spider silk protein), prepared according to Hümmerich et al. Biochemistry 2004, 43, 13604, Sequence Listing s. Appendix) was dissolved in 6 M aqueous solution of guanidinium thiocyanate (GdmSCN) to a final concentration of 20 g protein / L. Subsequently, the GdmSCN was removed by dialysis against 5 mM potassium phosphate with a pH of 8.0. During the dialysis incurred protein aggregates were then separated by centrifugation. The protein concentration in solution was determined photometrically at 276 nm using the calculated extinction coefficient (Hümmerich et al., Biochemistry 2004, 43, 13604). Thereafter, if necessary, a pH of 8.0 was established by dilution with 5 mM potassium phosphate solution.

II. Coating of thermoplastic polyurethane films and production of textile substrates according to the invention

The contact angle of the employed uncoated thermoplastic polyurethane film with water was in each case 78 °, determined at 20 ⁰ C.

When the contact angles are within the scope of the present invention, each static contact angle, measured at 20 ⁰ C with a drop weight of 0.0061 g. The contact angle measurements were each measured with a contact angle measuring device from Kröss, type G1.

11.1 Production of Inventive Layered Material S.1

An aqueous 2% by weight C16 spider silk protein solution (20 g / l) from I. was prepared with a spiral doctor from Erichsen (20 μm wet layer thickness) onto a composite of a thermoplastic polyurethane film, thickness 20 μm MDI, 1, 4-butanediol and polyethylene glycol, and a polypropylene film, thickness 50 microns, aufgerakelt. After 30 minutes contact time at room temperature the film for 10 minutes at 100 ⁰ C and 10 minutes at 125 ° C was dried in the oven. A layered material of the invention was obtained from a coated thermoplastic polyurethane film which had a very thin (0.4 μm), homogeneous-looking protein coating under the microscope, and a polypropylene film. The contact angle with water was 27 °, determined at 20 ⁰ C. This invention layered material was subjected to the side of the coated thermoplastic polyurethane film a 20- minutigen shower test, ie according to the invention sheet-shaped material was on the side of the coated thermoplastic polyurethane film under an angle of 45 ° for 20 minutes, a powerful jet of water from a shower head exposed. After showering, the contact angle at 20 ⁰ C was measured again. The contact angle was 26 °.

After stripping off the polypropylene film, the water vapor permeability of the coated thermoplastic polyurethane film was measured (ASTM D-6701). The water vapor permeability of the coated thermoplastic polyurethane film was 8,000 g / m ² / day.

11.2 Production of Inventive Layered Material S.2

An aqueous C16 spider silk protein solution (10 g / l) was coated with a spiral blade from Erichsen (20 μm wet layer thickness) onto a layered material comprising a thermoplastic polyurethane film applied to a polyester fabric (basis weight 210 g / m ² ) was laminated, hereinafter also called laminate, geräkelt on the polyurethane side of the laminate. After 30 minutes contact time at room temperature, the laminate for 10 minutes at 100 ⁰ C and 10 minutes was dried at 125 ° C in the oven. A layered material S.2 according to the invention was obtained which had a very thin (0.2 μm), protein-homogeneous coating under the microscope. The contact angle with water was 44 °, measured at 20 ⁰ C. The layered material S.2 according to the invention was washed five times in the washing machine with a mild detergent at 40 ⁰ C, then the contact angle with water was measured again. The contact angle with water was 44 °, measured at 20 ° C.

II.3 Detection of C16 Spider Silk Protein on Inventive Layered Material S.2 by Antibody Reaction

From inventive layered material S.2 several pieces (1 cm ² ) were cut. The pieces were treated for 30 minutes with Western Blocking Reagent (Roche, 10 x conc.) And then twice with TTBS buffer (20 mM tris (hydroxymethyl) aminomethane; 150 mM NaCl, pH 7.5, 0.05 % Polyoxyethylene (20) sorbitan monolaurate) and once with TBS buffer (20 mM Tris (hydroxymethyl) aminomethane, 150 mM NaCl, pH 7.5) for 5 minutes each. The pieces were then incubated with an antibody directed against the T7 tag of the C16 spider silk protein used (anti-T7-POD antibody, Sigma) which was diluted 1: 1000 in 20 ml TBS buffer. Subsequently, the batches were washed twice with TTBS buffer and once with TBS buffer for 5 minutes each. The reaction of the peroxidase coupled to the antibody was started by adding 5 ml peroxidase substrate. To prepare the peroxidase substrate, 1 TMB tablet (Sigma) was dissolved in 100 μl of DMSO in an ultrasound bath and treated with 10 ml of substrate buffer (0.1 M sodium acetate, pH 4.9) and 14.7 μl of H ₂ O. ₂ (3 wt .-%). The reaction mixtures were then incubated until blue (60-120 seconds) and then stopped by adding 200 μl 2 M H2SO4. The reaction supernatant was measured by absorption photometry at 405 nm, wherein the absorption strength conclusions on the enzyme activity and thus the amount of bound antibody and indirectly on the amount of the existing C16 spider silk protein allows. In the illustrated assay it was found that layered material S.2 according to the invention has a significantly greater peroxidase enzyme activity than the similarly treated blank test (Table 2).

TABLE 2 Absorption photometric detection of C16 spider silk protein on layered material according to the invention S.2

Claims

claims A layered material comprising a thermoplastic polyurethane film coated with at least one protein and at least one textile material. 2. Layered material according to claim 1, characterized in that at least one protein is a silk protein. 3. A layered material according to claim 1 or 2, characterized in that at least one protein is a spider silk protein. 4. Layer-shaped material according to one of claims 1 to 3, characterized in that it is a flat textile material in textile material. 5. A process for the production of layered materials according to any one of claims 1 to 4, characterized in that at least one textile material with a thermoplastic polyurethane film connects, which is coated on the side facing away from the textile material with at least one protein. 6. A process for the production of layered materials according to any one of claims 1 to 4, characterized in that one coats a thermoplastic polyurethane film, which is connected to a textile material, with at least one protein. 7. The method according to claim 5 or 6, characterized in that the optionally coated thermoplastic polyurethane film is laminated to the textile material. 8. The method according to any one of claims 5 to 7, characterized in that first coated a thermoplastic polyurethane film, which is applied to a carrier material with at least one protein, then the coated thermoplastic polyurethane film separates from the carrier material and with the textile material connects. 9. The method according to any one of claims 5 to 8, characterized in that in a further step, a textile material is applied to the protein-coated thermoplastic polyurethane film. 10. The method according to any one of claims 5 to 9, characterized in that exerts no shear forces during coating of the thermoplastic polyurethane film, which lead to an elongation of the thermoplastic polyurethane film. 1 1. A method according to any one of claims 5 to 10, characterized in that treating the thermoplastic polyurethane film with an aqueous formulation containing at least one protein. 12. The method according to any one of claims 5 to 1 1, characterized in that thermally treated after coating the thermoplastic polyurethane film with protein. 13. A layered material comprising a thermoplastic polyurethane film coated with at least one protein and a support material. 14. Use of layered materials according to any one of claims 1 to 4 or 13 as or for the production of clothing. 15. A process for the production of garments using at least one layered material according to one of claims 1 to 4 or 13. 16. Clothing pieces, produced by a method according to claim 15.