DE10037983B4 - Polymer composition and molded articles containing it containing alkaloid - Google Patents

Abstract

Polymer compositions comprising a biodegradable polymer selected from the group consisting of cellulose, carboxyethyl cellulose, nitrate cellulose, Copper cellulose, viscanthogenate and cellulose carbamate, and at least an alkaloid or at least one material containing at least one alkaloid.

Description

The The invention relates to a polymer composition containing a biological includes degradable polymer, and their use for the production of a shaped article from the polymer composition molded body, a process for its preparation and its use as well as a garment that the shaped body in the form of fibers.

polymer compositions with various additives for the production of moldings known.

So For example, US-A-5,766,746 describes a nonwoven web of cellulosic fibers, which contain a flame-retardant, phosphorus-containing component.

The US-A-5,565,007 describes modified rayon fibers with a modifier to improve the dyeing properties the fibers.

Further U.S. Patent 4,055,702 describes melt spun cold drawn fibers from a synthetic, organic polymer with additives. These Additives can Receptors, flame retardants, antistatic agents, stabilizers, Mildew inhibitors or antioxidants.

From "Lenzinger Reports ", 76/97, Page 126 is also a lyocell fiber made of a cellulose solution in N-methylmorpholine N-oxide (hereinafter "NMMNO") was spun, 0.5 to 5% by weight, based on the weight of the cellulose, on crosslinking agents for improvement of wet scrub value can be incorporated. Furthermore is described lyocell fibers carboxymethyl chitin, carboxymethyl chitosan or polyethyleneimine for improving the fungicidal properties, Polyethyleneimine for metal ion adsorption and dye uptake, hyaluronic acid for improving bactericidal properties, xanthan gum, guar gum, Carubin, Bassorin or Strength to improve the hydrophilicity, water absorption and water vapor permeability or strength for accelerated enzymatic hydrolysis.

The WO 98/58015 further describes a composition which is fine Contains solid particles, for Admixture to a moldable solution of cellulose in an aqueous tertiary Amine oxide. The composition consists of solid particles, tertiary amine oxide, Water and at least one other substance. This further substance may be a stabilizer or a dispersant. The solid Particles can Be pigments.

Known but it is also that high Concentrations of iron and transition metals the stability a cellulose pulp, NMMNO and water. High concentrations of iron lower the decomposition temperature the solution so strong, that explosive ongoing decomposition reactions of the solution may occur. In "The Paper", F. A. Buitenhuijs, Volume 40, Volume 12, 1986 is the decomposition and stabilization of cellulose, dissolved in NMMNO. At the same time the influence of iron (III) on these cellulose solutions explained. With an addition of 500 ppm iron (III) over 40% of the NMMNO is converted into the decomposition product N-methylmorpholine (hereinafter "NMM") The addition of copper (II) cations has also been reported to be the Solution stability reduced. The decomposition temperature (Tonset ° C) was at the addition of Copper to a NMMNO cellulose solution without copper of 175 ° C at 114 ° C lowered in the presence of 900 mg copper / kg mass. Furthermore is the positive effect of stabilizers, such as propyl gallate and ellagic acid described.

At the Addition of additives to fibers, however, presents difficulties the necessary in practice properties of the fibers, such as mechanical Strengths, fiber elongations, loop strengths, abrasiveness and dyeability to obtain.

Indeed are just due to the strong development of so-called functional Fibers or garments straight fibers with specific additives are in high demand. there It is important that the difficulties described above are overcome so that not only functionalized fibers are obtained, but these fibers also the demands normally placed on them, just in mechanical terms, meet. The most interesting ones Additives are additives that have an effect on the organism can.

Therefore, it is an object of the present invention to provide a polymer composition containing an additive having good stability and processability and a molded article produced therefrom and to provide a method for its production.

The solution This object is a polymer composition that is a biological degradable polymer and at least one alkaloid or at least one an alkaloid-containing material, a material prepared therefrom moldings and a method for its production.

preferred embodiments each result from the dependent claims.

The at least one alkaloid or containing at least one alkaloid Material will hereinafter also be referred to as "inventive additive".

The Biodegradable polymer is preferably selected from the group consisting of cellulose, modified cellulose, latex, Vegetable protein and of animal origin, in particular cellulose, and mixtures from that. Polycondensation and polymerization polymers, polyurethanes, Polyesters and blends of these materials can also be used as far as they are biodegradable. The polymer composition according to the invention preferably contains or the molded articles produced therefrom are not non-biological degradable polymers or mixtures of such polymers.

Indeed it is not excluded that polymer compositions according to the invention also contain non-biodegradable polymers. Examples of it are aromatic polyamides (aramids), polyacrylonitrile (PACN) or Polyvinyl alcohols (PVA). These polymers can be incorporated into the polymer composition according to the invention be incorporated. This incorporation is preferably carried out in the following manner: Certain polymer solvents, such as DMAc, DMSO or DMF also solve synthetic polymers, such as those mentioned above. Such solutions can again in combination with known cellulose solvents, such as LiCl / DMAc, DMSO / PF, tertiary Amine oxides / water are combined to form a polymer composition.

Examples for modified Cellulose include carboxyethyl cellulose, methyl cellulose, nitrate cellulose, copper cellulose, Viscanthogenate, cellulose carbamate and cellulose acetate. Examples for polycondensation and polymerization polymers are polyamides, e.g. with methyl, Hydroxy or benzyl groups are substituted. Examples of polyurethanes are those which are based on polyester polyols.

The at least one alkaloid contained in the polymer composition of the present invention may be any alkaloid. Preferably, the alkaloid is selected from the group of capsaicides, more preferably capsaicin and / or dihydrocapsaicin, more preferably capsaicin. The at least one alkaloid-containing material which can be incorporated in the polymer composition of the present invention may be any alkaloid-containing naturally occurring material. Preferably, this material is a capsaicid-containing material, particularly preferably chilli powder, cayenne pepper or rose paprika, and mixtures thereof. Other pepper varieties that can be used include Habanero, Scotch Bonnet, Jamaican Hot, Thai, Cayenne, Tabasco, Serrano, Wax, Jalapeno, Rocotilo, Poblano and New Mexico powders. The sharpness of the varieties can be expressed by a subjective classification in severity levels or in Scoville units. For example, pure capsaicin has a Scoville sharpness of 16,000,000, Habanero 200,000 to 300,000. Ingredients of typical chillies include: protein 1.8% fat 0.6% Carbohydrates table 1.5% Alkali and alkaline earth ions 0.3% vitamins 0.2% capsaicin 0.05 to 3.5% carotenoids 0.12 to 0.35%

The used according to the invention At least one alkaloid-containing material is usually selected from commercially available Materials. For the purposes of the invention Is it possible, Particles of the material in the particle size range from 200 to 400 μm, preferably 150 to 300 microns use. Preferably also particles with small grain sizes are used, like 1 to 100 μm, stronger preferably 1 to 5 microns. It can also Komgrößengemische be used.

The at least one alkaloid or at least one alkaloid containing Material is preferably added to the polymer composition in an amount from 0.01 to 2% by weight, stronger preferably from 0.05 to 1.5 wt .-% and particularly preferably from 0.1 to 1% by weight, based on the weight of the biodegradable Polymers, added.

there the content of the content refers to the amount of alkaloid, i.e. the amount of the at least one alkaloid-containing material can be higher be, since in the quantity used here only the Alkaloidgehalt considered becomes.

The Moldings according to the invention can be used with usual Process of the polymer composition according to the invention are prepared, wherein the components for the preparation of the polymer composition first mixed and then the molding will be produced. The mixing of the components can be continuous or discontinuously, for example with apparatuses and A method described in WO96 / 33221, US-A-5,626,810 and WO96 / 33934.

Especially Preferably, the shaped body according to the invention is in the form of fibers, on strongest preferred in the form of cellulose fibers.

method for the production of cellulose fibers according to the invention are known such as the lyocell or NMMNO, rayon or viscose or carbamate method.

The Lyocell method can be carried out as described below. For producing a deformable mass and then from it the cellulose fiber of the invention, will be a solution Cellulose, NMMNO and water produced by first a Suspension of cellulose, NMMNO and water is formed. These Suspension is under reduced pressure in a 1 to 20 mm thick layer continuously over a heat exchange surface transported rotating elements. During this process will while water was evaporated until a homogeneous cellulose solution was formed is. The cellulose solution thus obtained For example, an amount of cellulose of from 2 to 30 weight percent, of NMMNO of 68 to 82% by weight and of water from 2 to 17% by weight. If he wishes, can this solution Additives, such as inorganic salts, inorganic oxides, finely divided organic substances or stabilizers.

Of the thus obtained cellulose solution is then the at least one additive according to the invention in the form of powder, Powder suspension or in liquid Form, added as an extract or suspension. The admitting can be continuous or discontinuously.

Due process the at least one additive according to the invention may also be present after or during the continuous Comminution of the dry cellulose, described in the above Form, to be added. If a powder suspension is added, then can the powder suspension in water or any solvent in the desired and for needed the procedure Concentration are produced.

Of further there is also the possibility the at least one additive according to the invention a Pulpprozeß with simultaneous Feed crushing. The pulp can either be in water, in alkalis or in the later to resolution the necessary solvent for the cellulose carried out become. Again, the at least one alkaloid or at least an alkaloid-containing material in the above-described form be added.

The with the at least one alkaloid or the at least one alkaloid containing material enriched polymer composition can in the presence of a derivatizing agent and / or one known for the dissolution process solvent be converted into a deformable extrusion mass.

A another possibility the addition of the at least one additive according to the invention is the addition while a continuously run Solution process, described in EP-A-356419, US-A-5,049,690 and US-A-5,330,567.

alternative The addition may be discontinuous to give a master batch the cellulose solution. Preferably, the at least one alkaloid or at least an alkaloid-containing material is added continuously.

However, the at least one additive according to the invention can also be used in any other stage of the manufacture lungsverfahrens be added to the molding. For example, it can be fed into a piping system with appropriate mixing by static mixer elements or stirrers mounted therein, such as known inline refiners or homogenizers, eg Ultra Turrax units. If the process is carried out in continuous batch operation, for example via a stirred tank cascade, the at least one alkaloid or the material containing at least one alkaloid can be introduced in solid, powdered, suspension-like or liquid form at the most optimal location for the process. The fine distribution can be achieved with known mixing elements adapted to the process.

He follows the addition in the form of solid particles, the extruded or dope subsequently be filtered. Dependent on on the fineness of the solid material used can in spinning process with big Nozzle diameters However, to be dispensed with a filtration.

These it can be very sensitive extrusion or spinning masses, so can the at least one alkaloid or at least one alkaloid containing Material in suitable form directly in front of the spinneret or the Supplied to the extrusion tool so that the added material does not last long in the composition is present, so that adverse reactions are prevented. Prefers in this case the addition takes place in liquid Form, wherein preferably adapted in the spinning or extrusion mass viscosity is adjusted to simplify the mixing.

A another possibility is it, in liquid Form present additives while of the spinning process to the continuously spun yarn.

The Spinning can be done with conventional Processes such as the dry-jet-wet; the wet-spinning; the melt blown process, centrifuge spinning, funnel spinning or the dry-spinning process. Examples of the production of cellulose fibers after The NMMNO method is described in US-A-5,589,125, US-A-5,939,000, EP-A-0 574 870 and WO98 / 07911 called. Optionally, the shaped body formed the usual Chemical fiber aftertreatment process for filaments or staple fibers be subjected.

Next The spinning process also offer extrusion processes for Production of flat films, round films, skins (sausage skins) as well as On membranes.

The also usable viscose process can be carried out as follows. Pulp with about 90 to 92 wt .-% α-cellulose with aqueous NaOH treated. Thereafter, the cellulose is converted by reaction with carbon disulfide converted into cellulose xanthogenate and a viscose solution by Addition of aqueous NaOH under constant stir receive. This viscose solution contains about 6% by weight of cellulose, 6% by weight of NaOH and 32% by weight of carbon disulfide, based on the cellulose content. After the suspension has been stirred, becomes the additive according to the invention either as a powder or as a liquid Extract, added. If desired is conventional additives, as surfactants, dispersants or stabilizers are added.

The Inventive additive Alternatively, it may be added at any stage of the process.

thereupon becomes the solution thus obtained spun into fibers as described in US-A-4,144,097.

The Carbamate process can be carried out as described below. For this purpose, from cellulose with about 92 to 95 wt .-% α-cellulose Cellulose carbamate prepared as in, for example, U.S. Patent 5,906,926 or DE-PS 196 35 707 described. This is Alkalicellulose from the pulp used by treatment with aqueous NaOH produced. After defibering, the alkali cellulose becomes ripe subjected to, and then the sodium hydroxide is washed out. The way activated cellulose is mixed with urea and water and in a reactor in a solvent brought in. The resulting mixture is heated. The resulting carbamate is separated and made from a carbamate spinning solution, as in the DE-PS-197 57 958 described. This spinning solution becomes the additive according to the invention added.

The thus obtained spinning solution is spun into fibers by known methods, and it is cellulose fibers according to the invention receive.

It has surprisingly been found that the cellulose fibers according to the invention, despite the addition of the additive according to the invention show the same excellent properties, such as pure cellulose with regard to their fineness, breaking strength, breaking force variation, elongation, wet elongation, fineness-related breaking strength, fineness-related wet breaking strength, fineness-related loop breaking strength, wet burn at break, wet abrasion variation and wet modulus. At the same time, the fibers show the positive properties conferred by the material. This is particularly surprising because the addition of additives to cellulose pulp, NMMNO and water otherwise has the disadvantage that they discolor at the temperature of use, are not stable in storage and introduce impurities in the cellulosic end products.

In spite of the incorporation of an additive according to the invention, in particular Chili powder, surprisingly no decomposition of a spinning solution from cellulose, NMMNO and water.

One further, the moldings of the invention by the addition of additives according to the invention The advantage conferred is the even incorporation of the active ingredients in the fiber matrix in different manufacturable fiber cross-sections. Furthermore, the processing is as monofilament or continuous filament yarn possible. This results in a particularly good use of technical Articles.

Especially, when the molding according to the invention from a polymer composition which is exclusively biological contains degradable material, is its complete biodegradability advantageous.

The Moldings according to the invention can be used as Packaging material, fibrous material, nonwovens, nonwoven fabrics, Fiber composites, nonwovens, needlefelt, upholstery, fabrics, Knitted fabrics, as home textiles, such as bed linen, as a filler, flocking fabric, Hospital textiles, such as documents, diapers or mattresses, as Fabric for Thermal blankets, Shoe inserts, as well as wound dressings be used. Further uses are in the lexicon textile interior design, Buch und Medien Verlag Buurmann KG, ISBN 3-98047-440-2 is described.

If from the molding according to the invention in Form of fibers a fabric is made, then this can either exclusively consist of this fiber or contain an additional component. This additional Component may be selected from the group consisting of cotton, lyocell, Rayon, Carbacell, Polyester, Polyamide, Cellulose acetate, Acrylate, Polypropylene or mixtures thereof may be selected. The fibers of the invention with an additive according to the invention are preferably in the tissue in an amount of up to about 70 Wt .-% present. The additive according to the invention is preferably in the tissue in an amount of 0.05 to 1.5 wt .-% present, based on the Content of alkaloid in the fiber.

The fiber according to the invention can due to the incorporated elements, possibly via a fat layer to be applied, like a cream layer, the active ingredients to the body pass. Because the alkaloid Capsaicin not water soluble but dissolves in both fat and alcohol the fabric made from this cellulosic material, too with alcoholic solutions or fatty alcohol solutions be impregnated, to the active substances to the body to pass on. One more way the drug delivery is in conjunction with the therapeutic Application of iontophoresis. Because of the cellulosic material can also breathable fabrics are made. Thus, the active ingredients of the skin targeted fed become. Through incorporation, the active ingredients are long in the Fiber or tissue, even after frequent washing.

Especially the use of capsaicides, preferably capsaicin and / or dihydrocapsaicin allows the Production of polymer compounds or of fibers, fabrics or fleeces, the valuable health-promoting Have properties.

Therefore can the materials of the invention to therapeutic articles, such as patches, dressings or bandages become.

The capsaicides are known as traditional drugs for analgesic or antiflamatory treatment, usually in cutaneous form. The fibers according to the invention can therefore provide this active ingredient on a long-term basis on account of their content of capsaicides. Since capsaicin and its derivatives are very difficult to dissolve in water, a layer of fat should be used to increase the transmission of the active substance. This can preferably be applied directly to the nonwoven fabric according to the invention or the fabric according to the invention, so that subsequently the combination of fabric / nonwoven with a fatty layer is applied to the skin. Such structures can be used, for example, for the treatment of arthritis, shingles, nerve pain, itching by infections, tumors, parasites, etc. Also conceivable is the treatment of rheumatic pain, with the grease-coated fleece or the grease-coated Tissue is applied to the skin area to be treated. The transfer of the alkaloid allows a heat-stimulating treatment.

The for improved drug delivery Applied fat can be a common one Fat or a usual cream be used in medical or cosmetic fields place.

If the fiber of the invention is in the form of staple fibers or crushed filaments, can with these surfaces of carriers, like fabrics or foils, are flocked. This will be the surface of the to flocking carrier treated with an adhesive and then the staple fibers or shredded filaments applied thereto. Then you can also a fat layer described above are applied.

below the invention will be explained by way of examples.

example 1

3039 g NMMNO (62.1%), 315 g MoDo pulp, DP 500, dry content 94%, 1.9 g propyl gallate (0.63% based on the cellulose content) and 444 mg capsaicin (solid, O, 15 wt .-% based on the cellulose content) type M 2028 from Sigma, were mixed and the resulting mixture heated to 94 ° C. There was obtained a discontinuous spinning solution having a cellulose content of 12.1% and a viscosity of 7,495 Pa · s. The spinning solution thus obtained was spun into fibers while maintaining the following spinning conditions: Temperature of the reservoir = 90 ° C Temperature spinning block, nozzle = 80 ° C spinning bath = 5 ° C Spinning bath concentration (beginning) = 0% (distilled water) Spinning bath concentration (end) = 6% NMMNO spinning pump = 20.0 cm ³ / min nozzle filters = 19200 M / cm ² Spinning nozzle = 165 holes 70 μm; Au / Pt final image = 30 m / min.

The Fibers became manual on 40 mm staple length cut, solvent-free washed and with a 10 g / l Avivage (50% Leomin OR - 50% Leomin WG (nitrogen-containing fatty acid polyglycol ester Fa. Clariant GmbH)) at 45 ° C equipped or the fat layer applied for better fiber processing and at 105 ° C dried. In connection to the drying was set to a fiber moisture of 11%. An additional one Bleaching before drying was not performed in this case Spinning behavior according to this Example obtained spinning solution was good.

The following tables show the physical properties of the cellulose fibers thus obtained. Table 1

Of the Capsaicin content was determined by HPLC according to the Sigma-Aldrich product information for capsaicin determined (product number M2028).

Example 2

2932 g NMMNO (62.1%), 305 g MoDo pulp, DP 500, dry content 94%, 1.8 g of propyl gallate (0.63% based on the cellulose content) and 573 mg of capsaicin (solid, 0.15% based on the cellulose content) mixed and at 94 ° C heated. It became a spinning solution with a cellulose content of 12.1% and a viscosity of 6.892 Pa.s receive. The spinning solution thus prepared was as in Example 1 spun into fibers. The spinning behavior was good.

The physical properties of the cellulose fibers thus obtained are shown in Table 2 below. Table 2

Example 3

deviant from Examples 1 and 2, Habanero cayenne pepper was used. The pepper had a size of 200 μm (J. Kotanyi, A-2120, Wolkersdorf). On a counter jet mill from Fluidized bed type (Hosokawa Alpine AFG100) was further crushed. After crushing the capsaicin content (see Example 1) was determined to be 1.2%. 27.7 g of ground pepper, 3.425 g NMMNO (60.8%), 354 g MoDo pulp, DP 500, Dry content 94%, 2.1 g of propyl gallate (0.63% based on the cellulose content) were mixed and heated to 94 ° C heated. It was a discontinuous dope produced with a solids content of 13.2% and a viscosity of 7,843 Pa.s receive. The spinning was carried out as in Example 1.

The physical properties of the lyocell fibers thus obtained are shown in Table 3 below. Table 3

Example 4

It Three experiments were carried out to produce lyocell filaments. When Standard experiment, a standard spinning solution (A) was prepared containing 12% cellulose, 0.63% GPE (gallic acid propyl ester). The spinning took place one day after production.

Farther two corresponding spinning solutions were prepared, the an additional 0.15% capsaicin contained (B) and the third dope solution 0.15% Capsaicin but no GPE contained (C).

The dope with 0.15% capsaicin and 0.63% GPE was also given one day after the production spun. The spinning solution without GPE became direct spun after manufacture. The spinning is done by a Nozzle with 2 × 165 holes with 70 μm Bore diameters at a nominal titer of 650 dtex F330.

The resulting filaments were tested in the usual manner, the results are summarized in Table 4. Table 4

The comparison of experiments (A) and (B) shows that the addition of capsaicin does not cause any deterioration of the mechanical properties. Some of these are even compared to the standard cellulose Ly improved ocellfaser.

Of the Experiment without GPE (C) shows that capsaicin obviously has one exerts a comparable stabilizing effect on the cellulose spinning solution, the otherwise by the usual Stabilization additive GPE is exercised.

This demonstrates that the addition of capsaicin, surprisingly, the mechanical Properties of cellulose lyocell filaments can even improve at the same time valuable functionalized fibers are obtained.

Claims (22)

Polymer compositions comprising a biological degradable polymer selected from the group consisting of cellulose, carboxyethylcellulose, Nitrate cellulose, copper cellulose, viscanthogenate and cellulose carbamate, and at least one alkaloid or at least one at least one alkaloid containing material. A polymer composition according to claim 1, wherein the biodegradable polymer is cellulose. Polymer compositions according to one of the preceding Claims, wherein the at least one alkaloid-containing material is selected from the group consisting of chilli powder, cayenne pepper, rose paprika and mixtures thereof. Polymer compositions according to claim 1 or 2, wherein the at least one alkaloid is selected from the group of Capsaiciden. Polymer composition according to one of the preceding Claims, wherein the polymer composition has an alkaloid content of 0.01 to 2%, based on the weight of the biodegradable polymer having. Polymer composition according to one of the preceding Claims, wherein the biodegradable polymer is cellulose and the at least an alkaloid-containing material is chilli powder, habanero, scotch Bonnet, Jamaica Hot, Thai, Cayenne, Tabasco, Seerrano, Wax, Jalapeno, Rocotilo, Poblano and New Mexico powder is. Polymer composition according to one of the preceding Claims, wherein the biodegradable polymer is cellulose and the at least an alkaloid is a capsaicid. Moldings, comprising a polymer composition according to any of the preceding Claims. moldings according to claim 8, wherein the shaped body selected is from the group consisting of containers, foils, membranes, tissues and fibers. moldings according to claim 9, wherein the fibers are staple fibers, mono- or continuous filaments are. Use of a shaped article according to one of claims 8 to 10 as packaging material or fiber material. Use of a shaped article according to one of claims 8 to 10 in the form of fiber material as a mixture component for the production of yarns. Use of a shaped article according to one of claims 8 to 10 in the form of fiber material for the production of nonwovens or Tissues. Use of a shaped article according to one of claims 8 to 10 in the form of fibrous material for producing nonwovens or fabrics, wherein in the nonwoven fabric or fabric additionally a Component selected from the group consisting of cotton, lyocell, rayon, carbacell, Polyester, polyamide, cellulose acetate, acrylate, polypropylene or Mixtures of which is present. Use of a shaped article according to claim 14, wherein 0.1 to 30 wt .-% of the additional Kompo are included. A fabric comprising a molded article according to any one of claims 8 to 10th Nonwoven fabric comprising a molding after one of the claims 8 to 10. Fabric or nonwoven fabric according to claim 16 or 17 further comprising a fat layer. Clothing, comprising a shaped body according to one of the claims 8 to 10. A method for producing a shaped article according to one of the claims 8 to 10, comprising the steps: (A) continuous or discontinuous mixing of a biodegradable polymer and at least one alkaloid or at least one alkaloid-containing Material, (B) producing a deformable mass, (C) Processing the composition obtained in (B) into a shaped article, and (D) After treatment of the molded body produced. Material according to one of claims 9, 10, 16, 17, 18 and 19, further comprising an impregnation with alcohol or fat. Use of a material according to any one of claims 9, 10, 16, 17, 18, 19 and 21 for the manufacture of a patch, dressing or a bandage.