WO2002012381A1

WO2002012381A1 - Polymer composition and a moulded body produced therefrom containing alkaloids

Info

Publication number: WO2002012381A1
Application number: PCT/EP2001/007714
Authority: WO
Inventors: Stefan Zikeli
Original assignee: Zimmer Ag; Stefan Zikeli
Priority date: 2000-08-03
Filing date: 2001-07-05
Publication date: 2002-02-14
Also published as: DE10037983B4; GB2389853A; GB2389853A9; AU2001281956A1; GB0302452D0; DE10037983A1; GB2389853B; AT7008U1

Abstract

The invention relates to a polymer composition comprising a biodegradable polymer and at least one alkaloid or at least one substance containing at least one alkaloid.

Description

Polymer composition and molded body made therefrom containing alkaloid

The invention relates to a polymer composition which comprises a biodegradable polymer, the use thereof for the production of a shaped body, the shaped body produced from the polymer composition, a process for its production and use and a garment which comprises the shaped body in the form of fibers.

Polymer compositions with various additives for the production of moldings are known.

For example, US Pat. No. 5,766,746 describes a nonwoven made of cellulose fibers which contain a flame-retardant, phosphorus-containing component.

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

Furthermore, US-A-4,055,702 describes melt-spun, cold-drawn fibers made of a synthetic, organic polymer with additives. These additives can be receptors, flame retardants, antistatic agents, stabilizers, powdery mildew inhibitors or antioxidants.

A "Lyocell fiber" is also known from "Lenzinger reports", 76/97, page 126, which was spun from a cellulose solution in N-methylmorpholine-N-oxide (hereinafter "NMMNO") which contains 0.5 to 5% by weight. , based on the weight of the cellulose, can be incorporated in crosslinking agents to improve the wet abrasion value. It also describes lyocell fiber carboxymethylchitin, carboxymethylchitosan or polyethyleneimine to improve the fungicidal properties, polyethyleneimine for metal ion adsorption and dye absorption, hyaluronic acid to improve the bactericidal properties, xanthan, guarane, carubin, bassorin or starch for processing. Improve hydrophilicity, water absorption and water vapor permeability or starch for accelerated enzymatic hydrolysis.

WO 98/58015 further describes a composition which contains fine solid particles for admixing 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 additional substance can be a stabilizer or a dispersant. The solid particles can be pigments.

But it is also known that high concentrations of iron and transition metals affect the stability of a spinning mass made of cellulose, NMMNO and water. High concentrations of iron reduce the decomposition temperature of the solution so much that explosive decomposition reactions of the solution can occur. The decomposition and stabilization of cellulose, dissolved in NMMNO, is described in "Das Papier", FA Buitenhuijs, 40 ahrgang, issue 12, 1986. The influence of iron (III) on these cellulose solutions is also shown. An addition of 500 ppm iron (III) over 40% of the NMMNO was converted into the decomposition product N-methylmorpholine (hereinafter "NMM"). It was also reported that the addition of copper (II) cations also reduces the stability of the solution. The decomposition temperature (T onset ° C) was reduced from 175 ° C to 114 ° C in the presence of 900 mg copper / kg mass when copper was added to an NMMNO cellulose solution without copper. The positive effect of stabilizers such as propyl gallates and ellagic acid is also described.

When additives are added to fibers, however, difficulties arise in obtaining the properties of the fibers that are necessary in practice, such as mechanical strengths, fiber stretching, loop strengths, abrasion properties and dyeability.

However, due to the strong development of so-called functional fibers or clothing items, fibers with specific additives are in particularly high demand. It is important that the difficulties described above are overcome so that not only functionalized fibers are obtained, but these fibers also meet the requirements that are usually placed on them, particularly in mechanical terms Respects. The additives that are of particular interest are additives that can have an effect on the organism.

It is therefore the object of the present invention to provide a polymer composition which contains an additive with good stability and processability, as well as a molded article produced therefrom and a process for its production.

The solution to this problem is a polymer composition which comprises a biodegradable polymer and at least one alkaloid or at least one material containing an alkaloid, a molded body produced therefrom and a method for its production.

Preferred embodiments result from the subclaims.

The at least one alkaloid or the material containing at least one alkaloid are also referred to below as “additive according to the invention”.

The biodegradable polymer is preferably selected from the group consisting of cellulose, modified cellulose, latex, protein of vegetable and animal origin, in particular cellulose, and mixtures thereof. Polycondensation and polymerization polymers, polyurethanes, polyesters and mixtures of these materials can also be used insofar as they are biodegradable. The polymer composition according to the invention or the molded body produced therefrom preferably contains no non-biodegradable polymers or mixtures of such polymers.

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

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

The at least one alkaloid contained in the polymer composition according to the invention can be any alkaloid. The alkaloid is preferably selected from the group of capsaicides, more preferably capsaicin and / or dihydrocapsaicin, particularly preferably capsaicin. The at least one alkaloid-containing material that can be incorporated into the polymer composition according to the invention can be any naturally occurring material containing alkaloid. This material is preferably a material containing a capsaicid, particularly preferably chili powder, cayenne pepper or rose paprika, and mixtures thereof. Other types of pepper 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 degrees of severity or in Scoville units. Pure capsaicin has e.g. a sharpness unit according to Scoville of 16,000,000, Habanero 200,000 to 300,000.

Typical chilli ingredients 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 material containing at least one alkaloid used according to the invention is usually selected from commercially available materials. For the purposes of the invention it is possible to use particles of the material in the grain size range of 200 to 400 μm, preferably 150 to 300 μm. Particles with small grain sizes are preferably also used, such as 1 to 100 μm, more preferably 1 to 5 μm. Grain size mixtures can also be used.

The polymer composition preferably contains the at least one alkaloid or the material containing at least one alkaloid in an amount of from 0.01 to 2% by weight, more preferably from 0.05 to 1.5% by weight and particularly preferably from 0.1 up to 1 wt .-%, based on the weight of the biodegradable polymer, added. The content indicated relates to the amount of alkaloid, i.e. the amount of the material containing at least one alkaloid can be higher, since only the alkaloid content is taken into account in the amount used here.

The molded articles according to the invention can be produced from the polymer composition according to the invention by conventional methods, the components for producing the polymer composition being mixed first and then the molded article being produced. The components can be mixed continuously or batchwise, for example using apparatuses and processes described in WO96 / 33221, US Pat. No. 5,626,810 and WO96 / 33934.

The shaped body according to the invention is particularly preferably in the form of fibers, most preferably in the form of cellulose fibers.

Processes for producing the cellulose fibers according to the invention are known, such as the Lyocell or NMMNO, rayon or viscose or carbamate process.

The Lyocell process can be carried out as described below. To produce a deformable mass and subsequently the cellulose fiber according to the invention, a solution of cellulose, NMMNO and water is produced by first forming a suspension of cellulose, NMMNO and water. This suspension is continuously under reduced pressure in a 1 to 20 mm thick layer over a heat exchange surface by rotating elements transported. During this process, water is evaporated until a homogeneous cellulose solution has formed. The cellulose solution thus obtained can contain an amount of cellulose from 2 to 30% by weight, of NMMNO from 68 to 82% by weight and of water from 2 to 17% by weight. If desired, additives such as inorganic salts, inorganic oxides, finely divided organic substances or stabilizers can be added to this solution.

The at least one additive according to the invention is then added to the cellulose solution thus obtained in the form of powder, powder suspension or in liquid form, as an extract or suspension. The addition can take place continuously or discontinuously.

Depending on the process, the at least one additive according to the invention can also be added after or during the continuous comminution of the dry cellulose, in the form described above. If a powder suspension is added, the powder suspension can be prepared in water or any solvent in the concentration desired and required for the process.

Furthermore, there is also the possibility of feeding the at least one additive according to the invention to a pulping process with simultaneous comminution. The pulping can be carried out either in water, in alkalis or in the solvent which is later required to dissolve the cellulose. Here, too, the at least one alkaloid or the material containing at least one alkaloid can be added in the form described above.

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

A further possibility of adding the at least one additive according to the invention is the addition during a continuously conducted dissolution process, described in EP-A-356419, US-A-5,049,690 and US-A-5,330,567. Alternatively, the addition can be carried out batchwise to obtain a master batch of the cellulose solution. The at least one alkaloid or the material containing at least one alkaloid is preferably added continuously.

However, the at least one additive according to the invention can also be added in any other stage of the production process for the shaped body. For example, it can be mixed into a pipeline system by means of static mixer elements or stirring elements, such as known inline refiners or homogenizers, e.g. Ultra Turrax devices can be fed in. If the process is in continuous batch operation, e.g. Carried out via a cascade of stirred tanks, the material which contains the at least one alkaloid or the at least one alkaloid at the most optimal point for the process can be introduced in solid, powdered, suspension or liquid form. The fine distribution can be achieved with known stirring elements matched to the method.

If the addition is in the form of solid particles, the extrusion or spinning mass formed can then be filtered. Depending on the fineness of the solid material used, filtration can also be dispensed with in spinning processes with large nozzle diameters.

If it is a matter of very sensitive extrusion or spinning masses, the at least one alkaloid or the at least one alkaloid-containing material can be supplied in a suitable form directly in front of the spinneret or the extrusion tool, so that the added material is not present in the composition for a long time that adverse reactions are prevented. The addition is preferably carried out in liquid form, with the viscosity preferably being adjusted in the spinning or extrusion composition in order to simplify the mixing.

Another possibility is to add additives present in liquid form to the continuously spun thread during the spinning process.

Spinning can be carried out using conventional methods, such as dry-jet-wet-; the wet spinning; the melt blown process, centrifugal spinning, funnel spinning or dry spinning. Examples of the production of cellulose fibers according to the NMMNO process are mentioned in US-A-5,589,125, US-A-5,939,000, EP-A-0 574 870 and WO98 / 07911. If necessary, the shaped bodies formed can be subjected to the conventional chemical fiber aftertreatment processes for filaments or staple fibers.

In addition to the spinning process, there are also extrusion processes for the production of flat films, round films, skins (sausage skins) and membranes.

The viscose process, which can also be used, can be carried out as follows. Cellulose with about 90 to 92% by weight of α-cellulose is treated with aqueous NaOH. The cellulose is then converted into cellulose xanthate by reaction with carbon disulphide and a viscose solution is obtained by adding aqueous NaOH with constant stirring. This viscose solution contains approximately 6% by weight of cellulose, 6% by weight of NaOH and 32% by weight of carbon disulphide, based on the cellulose content. After the suspension has been stirred, the additive according to the invention is added either as a powder or a liquid extract. If desired, conventional additives such as surfactants, dispersants or stabilizers can be added.

The additive according to the invention can in turn alternatively be added in each stage of the process.

The solution so obtained is then spun into fibers as described in US-A-4, 144,097.

The carbamate process can be carried out as described below. For this purpose, cellulose carbamate is produced from cellulose with about 92 to 95% by weight of α-cellulose, as described, for example, in US Pat. No. 5,906,926 or DE-PS-196 35707. Alkali cellulose is produced from the pulp used by treatment with aqueous NaOH. After defibrating, the alkali cellulose is ripened and then the sodium hydroxide solution is washed out. The cellulose activated in this way is mixed with urea and water and introduced into a solvent in a reactor. The mixture thus obtained is heated. The carbamate formed is separated off and a carbamate spinning solution is prepared therefrom, as described in DE-PS-197 57 958. The additive according to the invention is added to this spinning solution. The spinning solution thus obtained is spun into fibers by known processes, and cellulose fibers according to the invention are obtained.

It has surprisingly been found that the cellulose fibers according to the invention, despite the addition of the additive according to the invention, have the same outstanding properties as pure cellulose fibers, in terms of their fineness, tensile strength, tensile strength variation, elongation, wet elongation, fineness-related tensile strength, fineness-related wet tensile strength, fineness-related loop tensile strength, wet abrasion Fracture, wet abrasion variation and wet modulus. At the same time, the fibers show the positive properties imparted by the material. This is particularly surprising since the addition of additives to spinning masses made of cellulose, NMMNO and water has the disadvantage that they change color at the temperature of use, are not stable in storage and introduce contaminants into the cellulosic end products.

Despite the incorporation of an additive according to the invention, in particular chili powder, surprisingly no decomposition of a spinning solution made of cellulose, NMMNO and water is observed.

Another advantage conferred on the shaped bodies according to the invention by the addition of additives according to the invention is the uniform incorporation of the active ingredients into the fiber matrix with fiber cross sections that can be produced in different ways. Processing as monofilament or continuous filament yarn is also possible. This results in a particularly good use of technical articles.

In particular, if the molded body according to the invention is made from a polymer composition that contains exclusively biodegradable material, its complete biodegradability is advantageous.

The moldings according to the invention can be used as packaging material, fiber material, non-wovens, textile composites, fiber composites, non-woven fabrics, needle felts, upholstery wadding, fabrics, knitted fabrics, as home textiles, such as bed linen, as a filler, flocking material, hospital textiles, such as underlays, diapers or mattresses, as a material can be used for thermal blankets, shoe inserts and wound dressings. Other uses Possible uses are described in the encyclopedia of textile furnishings, book and media Verlag Buurmann KG, ISBN 3-98047-440-2.

If a fabric is produced from the molded body according to the invention in the form of fibers, then this can either consist exclusively of this fiber or contain an additional component. This additional component can be selected from the group consisting of cotton, lyocell, rayon, carbacell, polyester, polyamide, cellulose acetate, acrylate, polypropylene or mixtures thereof. The fibers according to the invention with an additive according to the invention are preferably present in the fabric in an amount of up to about 70% by weight. The additive according to the invention is preferably present in the fabric in an amount of 0.05 to 1.5% by weight, based on the alkaloid content in the fiber.

The fiber according to the invention can pass on the active substances to the body due to the incorporated elements, possibly via a fat layer to be applied, such as a cream layer. Since the alkaloid capsaicin is not water-soluble, but dissolves both in fat and in alcohol, the tissue made from this cellulosic material can also be impregnated with alcoholic or fatty alcoholic solutions so that the active ingredients can be passed on to the body. Another possibility of active substance transport is in connection with the therapeutic application of ionophoresis. Because of the cellulosic material, breathable fabrics can also be made. The active ingredients can thus be supplied to the skin in a targeted manner. Through the incorporation, the active ingredients are present in the fiber or in the fabric for a long time, even after frequent washing.

In particular, the use of the capsaicides, preferably capsaicin and / or dihydro-capsaicin, enables the production of polymer compositions or of fibers, fabrics or nonwovens which have valuable health-promoting properties.

The materials according to the invention can therefore be processed further into therapeutic articles, such as plasters, bandages or bandages.

The capsaicides are known as traditional medications for analgesic or antiflamatory treatment, usually in cutaneous form. The invention Because of their capsaicide content, fibers can make this active ingredient available over the long term. As capsaicin and its derivatives are very difficult to dissolve in water, a layer of fat should be used to increase the transfer of the active ingredient. This can preferably be applied directly to the fleece according to the invention or the tissue according to the invention, so that the combination of tissue / fleece with a layer of fat is then applied to the skin. Such structures can be used, for example, for the treatment of arthritis, shingles, nerve pain, itching caused by infections, tumors, parasites, etc. The treatment of rheumatic pain is also conceivable, with the fat-coated fleece or the fat-coated tissue being placed on the area of the skin to be treated. A heat-stimulating treatment is made possible by the transfer of the alkaloids.

The fat applied to improve the transfer of active ingredient can be a conventional fat or a conventional cream that is used in medical or cosmetic fields.

If the fiber according to the invention is in the form of staple fibers or comminuted filaments, these surfaces can be used to flock carriers, such as fabrics or foils. For this purpose, the surface of the carrier to be flocked is treated with an adhesive and then the staple fibers or comminuted filaments are applied to it. Then a layer of fat described above can also be applied.

The invention is explained below using 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, 0, 15% by weight, based on the cellulose content) of Type M 2028 from Sigma, were mixed and the mixture thus obtained was heated to 94.degree. A discontinuously produced spinning solution with a cellulose content of 12.1% and a viscosity of 7,495 Pa • s was obtained. The spinning solution thus obtained was spun into fibers, the following spinning conditions being maintained: Storage tank temperature 90 ° C

Temperature spinning block, nozzle 80 ° C

Spin bath 5 ° C

Spin bath concentration (beginning) 0% (distilled water)

Spin pool concentration (end) 6% NMMNO

Spinning pump 20.0 cm ³ / min

Nozzle filter 19200 M / cm ²

Spinning nozzle 165 hole 70 μm; Au / Pt

Final take-off 30 m / min.

The fibers were cut by hand to a length of 40 mm, washed solvent-free and equipped with a 10 g / l softener (50% Leomin OR - 50% Leomin WG (nitrogen-containing fatty acid polyglycol ester from Clariant GmbH)) at 45 ° C or the fat layer for better Fiber processing applied and dried at 105 ° C. Following drying, a fiber moisture of 11% was set. An additional bleaching process before drying was not carried out in this case

The spinning behavior of the spinning solution obtained according to this example was good. The following table shows the physical properties of the cellulose fibers thus obtained.

Table 1

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

Example 2

2,932 g NMMNO (62.1%), 305 g MoDo pulp, DP 500, dry content 94%, 1.8 g propyl gallate (0.63% based on the cellulose content) and 573 mg capsaicin (solid, 0.15% based on the cellulose content) were mixed and heated to 94 ° C. A spinning solution with a cellulose content of 12.1% and a viscosity of 6,892 Pa • s was obtained. The spinning solution thus prepared was spun into fibers as in Example 1. The spinning behavior was good.

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

Table 2

Example 3

In deviation from Examples 1 and 2, Cayenne pepper of the Habanero type was used. The pepper had a size of 200 μm (J. Kotanyi, A-2120, Wolkersdorf). On a counter-jet mill of the fluid bed type (Hosokawa Alpine AFG100) was further crushed. After comminution, the capsicine content (see Example 1) was determined to be 1.2%. 27.7 g of ground pepper, 3.425 g of NMMNO (60.8%), 354 g of MoDo Pulp, DP 500, dry content 94%, 2.1 g propyl gallate (0.63% based on the cellulose content) were mixed and heated to 94 ° C. A discontinuously prepared spinning solution with a solids content of 13.2% and a viscosity of 7,843 Pa • s was obtained. 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

Three attempts were made to produce Lyocell filaments. As a 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 the production.

Furthermore, two corresponding spinning solutions were prepared, one containing an additional 0.15% capsaicin (B) and the third spinning solution containing 0.15% capsaicin but no GPE (C).

The spinning solution with 0.15% capsaicin and 0.63% GPE was also spun one day after production. The spinning solution without GPE was immediately after the manufac lung spun. The spinning takes place through a nozzle with 2 x 165 holes with a bore diameter of 70 μm and a nominal titer of 650 dtex F330.

The filaments obtained were tested in the customary 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 in the mechanical properties. In some cases these are even improved compared to the standard cellulose Lyocell fiber.

The experiment without GPE (C) shows that capsaicin obviously has a comparable stabilizing effect on the cellulose spinning solution, which is otherwise exerted by the usual stabilizing additive GPE.

This demonstrates that the addition of capsaicin can surprisingly improve the mechanical properties of cellulose lyocell filaments, while at the same time obtaining valuable functionalized fibers.

Claims

claims

1. A polymer composition comprising a biodegradable polymer and at least one alkaloid or at least one material containing at least one alkaloid.

2. The polymer composition according to claim 1, wherein the biodegradable polymer is selected from the group consisting of cellulose, modified cellulose, latex, protein of vegetable and animal origin, and mixtures thereof.

3. 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 peppers and mixtures thereof.

4. The polymer composition according to claim 1 or 2, wherein the at least one alkaloid is selected from the group of capsaicides.

5. 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.

6. Polymer composition according to one of the preceding claims, wherein the biodegradable polymer cellulose and the at least one alkaloid-containing material chili powder, Habanero, Scotch Bonnet, Jamaican Hot, Thai, Cayenne, Tabasco, Serrano, Wax, Jalapeno, Rocotilo, Poblano and New Mexico powder is.

7. Polymer composition according to one of the preceding claims, wherein the biodegradable polymer is cellulose and the at least one alkaloid is a capsaicide.

8. Shaped body comprising a polymer composition according to any one of the preceding claims.

9. Shaped body according to claim 8, wherein the shaped body is selected from the group consisting of containers, foils, membranes, fabrics and fibers.

10. Shaped body according to claim 9, wherein the fibers are staple fibers, mono- or continuous filaments.

11. Use of a shaped body according to one of claims 8 to 10 as packaging material or fiber material.

12. Use of a shaped body according to one of claims 8 to 10 in the form of fiber material as a mixture component for the production of yarns.

13. Use of a shaped body according to one of claims 8 to 10 in the form of fiber material for the production of nonwovens or fabrics.

14. Use of a shaped body according to one of claims 8 to 10 in the form of fiber material for the production of 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 thereof is present.

15. Use of a shaped body according to claim 14, wherein 0.1 to 30 wt .-% of the additional component are contained.

16. Fabric comprising a shaped body according to one of claims 8 to 10.

17. Nonwoven fabric comprising a shaped body according to one of claims 8 to 10.

18. The fabric or nonwoven fabric of claim 16 or 17, further comprising a layer of fat.

19. Garment comprising a shaped body according to one of claims 8 to 10.

20. A method for producing a shaped body according to one of 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) making a deformable mass,

(C) processing the mass obtained in (B) into a shaped body, and

(D) aftertreatment of the molded article produced.

21. Material according to one of claims 9, 10, 16, 17, 18 and 19, further comprising an impregnation with alcohol or fat.

22. Recycling of a material according to any one of claims 9, 10, 16, 17, 18, 19 and 21 for the manufacture of a plaster, bandage or bandage.