DE2219656A1 - Microcapsule-shaped bodies with a thread-like structure - Google Patents

Description

Microcapsule-shaped bodies with a thread-like structure

So-called "microcapsules ¹ " are known which are made from spheres with a diameter of generally between 20 and 400 μ, but also with a smaller diameter and which have a wall or spherical shell and a core. The spherical shell has a mechanical resistance and protects the core so that the microcapsules can be conveniently handled, whatever the properties of the core, and the shell has chemical and physical properties that allow it to be broken or loosened or opened at the right moment, thereby exposing the core enable material contained in the core under predetermined conditions, for example at a certain pressure, a certain temperature or in the presence of a certain physical or chemical

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ORIGINAL WSfECTBD

misclien solvent.

The core consists of an active substance that is very different May have properties, and can be solid or even gaseous. The possible uses of these microcapsules are numerous and range from, for example, the inclusion of adhesives that can be handled as a powder to the Incorporation of reagents which, if mixed in a suitable manner when opening the capsules, will react with one another and provide any kind of reaction, for example a polymerization in biologically active materials and even for pharmaceutical purposes, etc.

There is extensive literature on this coinage in the Technique is well known, so that detailed discussions are not necessary.

The material from which the shell is made is often, but not necessarily, polymeric and can be made with the help of a number of also methods known and described in the literature are produced.

The microcapsules have been used for numerous applications and have achieved a high degree of effectiveness but not without IT disadvantages and errors, especially with regard to * on the difficulty and cost of their manufacture, and especially when the microcapsules are made in very small sizes should be, as well as in many cases with regard to the difficulty of handling.

The bodies of thread-like structure that are the subject of the present Forming the invention, generally have an indefinite length and have a protective shell and an active core. They have properties which are in many respects similar to those of the known capsules, and many common uses with these, but from the point of view of the manufacturing process.

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Procedure, costs, percentage of active material, that can be included, handling, etc. numerous advantages.

The shell of the body is tubular and has adequate mechanical Properties in addition to the physical and chemical properties required with regard to the core, which are determined by the The need to protect the core itself and this, release if necessary.

In the vial the entire mechanical depends on the shell Solidity of the whole. The core consists of or contains an active substance that fills the tubular shell.

The arrangement of the core in the shell can be concentric, but also eccentric or completely different, and the following the properties and advantages mentioned.

All in all, all materials are used to make the bowl into consideration, which are used for the known microcapsular shells, but in particular artificial or synthetic linear polymers. The core can consist entirely of an active substance or of a homogeneous phase in which an active Contains substance in dissolved form or otherwise absorbed is, or may have a composite structure that may or may not be remarkably similar to the mechanical Contributes to the strength of the overall arrangement.

Practically all substances can be considered as active substances, which are used for microcapsules, especially liquids and - occasionally - solids, but in this case the can make up the entire core, at least if they are not liquid when the body is made.

The thread-like body upon which the present invention is based usually have an indefinite length and a

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quite small cross-sectional size (generally linear and preferably between 15 and 40 μ), although larger dimensions can be made for certain applications, such as for example 100 μ and even above.

The bodies preferably have a circular cross-section, and the size is determined by the diameter, which is preferably within the above size limits.

The bodies can be cut very long if desired, namely to about 10 times, 100 times or 1000 times the diameter, or even more. However, if necessary, they can can be made relatively short and in pieces, but always very long in relation to the diameter, i.e. at least 100 times as long as the diameter is.

The invention also relates to the method of manufacture the fa & egg-shaped body, which is characterized in that at the same time the Sohale and the core are extruded concentrically, preferably using substances that are in the liquid State and have a similar viscosity under extrusion conditions.

If the viscosity differs significantly, it is necessary to to use special solutions, which are described below in the are to be described individually, and the production of the arrangement in an eccentric form is more difficult.

The extruded materials are subjected immediately after extrusion on the outer cylindrical surface of a treatment that solidifies at least the shell material without the ^continuity: to interrupt, so that the material of the core is held and protected and a thread-like arrangement of indefinite length is produced.

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These treatments meet the in the production of art ^{fabric or synthetic fibers known methods and are therefore to be mentioned only briefly. In the process of extrusion and the subsequent solidification, the threads of the extruded material can be subjected to a strong reduction in cross-section, which can be distributed and localized in various ways and, above all, takes place in the solid state, as will be explained later.

The open ends of the thread-like bodies, which according to the Er-. Finding cut and finished are generally conditional no disadvantages, since the material of the core is sufficiently strong and the capillary action of this in the shell or sleeve holds. If losses nevertheless occur, these are irrelevant.

However, if necessary in some cases, even in general To avoid significant losses, the thread-like ones Body made from a thermoplastic shell and cut off under heat so that the ends close, or other methods suitable for sealing the ends are used.

This method can be particularly desirable when it is necessary to cut the thread-like body into relatively short pieces cut.

For certain applications, however, open ends such as to be explained later to be beneficial, and the presence of these open ends can enhance the properties of the thread-like Determine body.

To achieve similar viscosity properties of shell and core material, different solutions are required, depending on the individual

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if possible, as will now be explained.

In general, the shell material is melted or in a highly viscous state in an organic or inorganic liquid extruded. It is obvious that in the first case the Hardening of the shell takes place simply by cooling and in the second case by elimination of the solvent by evaporation at a suitable temperature or by extraction in a coagulation bath.

The most common trays have during the extrusion conditions im molten or liquid state, has a viscosity generally between about 10,000 and 40,000 micropoise.

At higher viscosity, plasticized masses can be used rather than correct polymer solutions can be achieved. To achieve a viscosity similar to that of the active material in the core Different solutions can be used depending on the nature of the material itself.

In the first case the material can be an aqueous solution of a salt or another chemical agent soluble in water.

In this case, the solution can be made highly viscous with the help of a suitable Thickeners are made, for example with polyvinyl alcohol, or one of the various rubbers or cellulose derivatives, which are well known.

When using polyvinyl alcohol in a suitable molecular weight for example, it is easy to achieve a viscosity of 30,000 to 40,000 micropoise at room temperature.

Similar arrangements can also be used for organic solvents be used.

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In a second case, the adhesive can be a sticky or rubber-like material, or a material that has Does not become liquid at room temperature. In this case "it is possible that the material already has the desired fluidity and viscosity under hot extrusion conditions, or it can be possible to achieve this by being melted or having Plasticized using a suitable organic solvent will.

When making the thread-like body at room temperature or takes place in their vicinity, the theological properties, that the core has at the time of extrusion is generally retained in the finished body. However, it is it is also possible that they change during the hardening process of the shell, if this has an influence on the core, such as For example, when hardening by coagulation in a coagulation bath, one part of the solvent can be the case withdraws from the core, or when this solvent enters the shell and optionally withdrawn from it or evaporates or remains trapped in the shell.

On the other hand, when the extrusion is carried out at a high temperature, the rheological properties of the material constituting the core become changed at room temperature, and this material is generally thickened until all fluidity is lost, or in some Cases solidified. The core can be made of a material having a melting temperature with respect to the extrusion temperature at which the desired rheological properties are present at the moment of extrusion and then at room temperature solidify. In any case, it is necessary that the core material has rheological properties that permit reduction allow the cross-section of the thread-like body during the manufacturing phase. This cross-section reduction takes place inevitable after the exit of the extruded thread through the spinnerets through which the shell and core material are extruded.

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In general, the liquid threads expand at the exit the spinneret, but the cross-section is then reduced by the pull of the mechanical organs that pull off the thread-like bodies. This cross section can then be as a result a subsequent cold expansion in the air or in a solvent or at a temperature above room temperature, but below the melting point temperature, further decrease.

This stretching can be desirable to the shell material with to provide the desired mechanical properties. If it is in particular a linearly oriented polymer, this expansion serves to increase the strength of the thread-like body in the longitudinal direction and at the same time contributes to a reduction the strength of the shell in the radial direction. This is a muchfaoh useful effect in enabling the sharing of the core material at the right moment.

With regard to the various solutions that can be used for the material forming the core, it is possible that the active substance is also solid, and in this case the core material can be used to manufacture the core within a support material be accommodated, which in turn, the special rheological properties, and in particular the appropriate Has viscosity under extrusion conditions. The support material can in turn be water or an aqueous solution based on suitable type is thickened with the help of a thickener, or a plasticized polymer or one in an organic one Solvent-dissolved polymer or even a liquid substance with the appropriate viscosity under extrusion conditions and be solid at room temperature.

Another achievable solution is to make the core out of two produce different substances, namely an outer layer of an active substance and an inner layer for

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Supports that have any desired chemical property, can and for example in the processing phases »that follow the extrusion, solidify or other desired Properties can get. ··,

In this case, the thread-like body has a double-concentric structure, so to speak. .

The shell material must enable the core material to be released under the "desired" conditions.

This can be done in the same way as with the known Microcapsules is the case. .

The release can be done under pressure or by melting the shell or by dissolving them in a given physical or chemical solvent or by chemical means.

In some cases the release can be accomplished by abrading or breaking the end of the filamentary material. This The procedure is suitable for some special purposes.

The shell material can also pass through after extrusion chemical reaction with an external agent can be cured, and if the reaction is reversible, a way can be found in it Release of the core lie.

To enable the core material to be released by simple pressure or by abrasion, it is useful in many cases to use a to choose an eccentric arrangement, i.e. to give the shell a non-uniform thickness and to arrange the core eccentrically so the shell cross-section required for the desired mechanical properties of the thread body is achieved, but for At the same time, a longitudinal line of lesser thickness is created, in which the breaking of the shell is more easily carried out by mechanical action can be, taking into account that with thread-

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narrow bodies of small diameter, which are considered here come, breaking when cold is not always easy.

In such a case, the cross-section must be particularly precise, otherwise it can happen that in some points the Shell's thickness is reduced to zero, and the body therefore does not meet the required conditions.

The facilities for producing the cross-sections with the desired geometric shapes are known in the art. However, they should be used in the following as part of a description of exemplary preferred embodiments of the invention explained in more detail with reference to the accompanying drawing will.

Fig. 1 shows a schematically illustrated spinneret for Manufacture of concentric bodies;

Fig. 2 shows a similar spinneret for an eccentric one Arrangement;

Fig. 3 illustrates a spinneret, in particular for materials with very different viscosity and - in the trap illustrated - is suitable with an eccentric arrangement;

Fig. 4 shows an apparatus for hardening the shell in a coagulation bath; _{,, v}

FIGS. 5 and 6 show two cross sections of thread-like bodies with concentric and eccentric arrangement.

To produce a concentrically arranged thread-like Body with the core 6 and the shell 7 according to FIG. 5 with the desired properties can be an extrusion spinneret, such as it is shown in Fig. 1 can be used. In this case, the core material with a fixed output of one first, volumetric pump through a bore 10 in one

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Body 11 delivered while the shell material with a set Output from a second, volumetric pump the bore 12 in the body 11 via a gap 13 between this and a body 14 und.sodann is released through a bore 15.

The bores 10 and 15 end in spinnerets 16 and 17. The material, that .ausfalls from the nozzle 16, forms a liquid ■ Thread emerging into bore 15 where it is surrounded by shell material. The composite arrangement then occurs from the nozzle 17.-.

It is obvious that Bich will consider the rheological properties of the materials in question in the case of heat extrusion must relate to the extrusion temperature. The solidification then takes place by simple cooling at the outlet of the above-described Spinneret.

When the shell is hardened by evaporation of volatile solvents, the extruded filaments are heated again and again Case of hardening of the solvent by coagulation by extraction in a liquid or by chemical reaction the threads are extruded into a bath with a liquid. Details of these devices are not explained as they are well known.

In the case of eccentric cross-sections with a core 8 and a shell 9 according to FIG. 6, the device of FIG. 2 is used, in which different ropes have the same reference numerals as in FIG. 1, but which are provided with a prime. In this case, only the axis of the bore 10 'and the nozzle 16 ^{1 is} offset with respect to the bore 15 * and the nozzle 17'.

Conversely, if the cross section to be controlled better, ^s in particular in the case of very liquid core materials is

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expedient, according to Pig. 3 to extend the opening through a thin tube 26 that extends into the nozzle 27 for the shell material or beyond it, if an eccentric core is provided is like in Pig. 3 is shown, right down to the strand of fluid material that forms the shell, preferably up to its threshold point.

When using a spinneret of this type, the importance of the Viscosity ratio of core and shell material largely reduced. Practically * can thread-like according to the invention Body can also be obtained with a very fluid core, especially if the arrangement is concentric and hence the small tube 26 lies coaxially in the nozzle 27.

This arrangement is particularly easy to manufacture and is desirable for bodies with a relatively large diameter, i.e. with a diameter of 100μ or even more.

The diameter of the nozzle 17 (or 17 *, 27 *) stands for the bowl in relation to your desired diameter of the finished thread-like Body, however, it is generally possible, with the aforementioned opening diameters between 60 and 35Op ,, each according to material, with the help of various cross-section reductions thread-like ^; Bodies with very different final diameters, for example between 10 and 40μ, while for large diameters it is advantageous to adjust the dimensions of the nozzle for the shell to enlarge.

The diameter of the nozzle 16 (16 ', 26') for the core material is generally, but not necessarily, a little smaller.

Reductions in cross-section (or enlargements) are caused by action on the return speeds of the extruded filamentary bodies, as in Pig. 4 schematically with reference on the pail of the shell hardening by coagulation

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is posed. It can be seen that in this case a group of 30 thread-like bodies - in general, for production-related reasons, spinnerets with several bore systems, such as those in Pig. 1 to 3 are shown within of a single body - enters the coagulation bath 31 around conveyor rollers 32 and 33 and one eventual Cross-section reduction in the bath is subjected and connected * on the system of reversing inclined rollers 34, from which s, ie another system of traction inclined rollers 35 is fed, which give the thread-like bodies a speed many times that of those who place them on the rollers 34 and thus bring about a further reduction in cross-section or pulling. This can be done in the cold or in the air take place as shown in the drawing, or under heat or in a liquid or in vapor. These process steps are known and do not need to be explained in detail.

The thread-like body runs from the rollers 35 to the collecting devices. In the coagulation of the .Fäden, by solvent removal, the volume of the trays decreases considerably, as for example, these shells from a polymer solution of 20 wt. ~ Io besteh s, and 80 wt -fo. Of the extruded viscous solution are removed in the coagulation bath, and stay there.

This leads to a reduction in the shell thickness, which coincides with the decrease or increase in thickness caused by the speed ratio between the speed of the thread on the roller system 34 and the speed at the outlet of the spinnerets due to the action of the volumetric pumps which pump the viscous solution through the spinnerets. Therefore, the coagulation must be precisely controlled in order to avoid small cracks in the shell of the core, which is not at all subjected to the action of coagulation in the bath, although it has already been said that this is not excluded and can be partially or directly if

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the core contains a liquid that can be removed by the coagulation bath, or indirectly if there is migration of a component of the core itself takes place from the core into the shell.

In some cases, this contraction of the shell material can be used to specifically weaken the shell and so on to facilitate the breaking of the shell under predetermined conditions and the release of the core material.

The cross-sectional reduction of the thread-like body takes place under the same conditions as in the solidification by heat evaporation a solvent contained in the shell. However, if the solidification occurs only by cooling, it is based the reduction is only based on the ratio of the reversal and extrusion speeds. The material forming the shell is, as mentioned, generally an artificial or synthetic one, linear polymer, for example regurgitated cellulose, an ester or another cellulose derivative, a polyamide, a polyester, an acrylic polymer, a chlorovinyl or acetovinyl, polyvinyl alcohol or a vegetable protein, a polyolefin, etc. It goes without saying that the material is selected with a view to its compatibility with the core, its. Theological properties, the extrusion conditions, the melting point and the mechanical properties, i.e. with regard to production and the inclusion of the core material.

As mentioned before, virtually any active substance or substance comes from it any combination of active and support substances is contemplated, especially those already in the field of microcapsule technology are known.

It is therefore possible to use monomers which lead to the formation of polymers react, or catalysts or accelerators; further

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Compounds that contribute to the formation of colors. have to react; Adhesives · or mixtures of adhesives; solid substances with catalytic or other puncture; Abrasive substances, pigments; Unites; Substances with biological punctures and many others Punctures that have already been used in microcapsule tea have been or which may be considered in the future.

The thread-like bodies produced can be in unchanged form Form in practically indefinite lengths or in very considerable lengths, for example up to 1 m or more, as well as in shorter lengths of the order of cm. or mm can be used.

The majority of uses of microcapsules are applied to bodies that are very small in size, but generally have at least two large dimensions, such as sheets, plates, etc.

In these cases the thread-like body of the present behaves Invention as a very large number of lined up and connected microcapsules with a very large number larger material content, and the thread-like body can be in two-dimensional shape arranged by any method will.

If, in particular, the thread-like body is curled, as can occur in particular with the eccentric arrangement, this generally offers no difficulty. - The invention, filamentary bodies can be joined, mixed, woven, and arranged and handled in any desired manner and in general they allow bulk and self-supporting arrangements. This makes a sizeable one Advantage over the known microcapsules.

A typical application of this body can be found in the.

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Adhesive technology when its core part is made of adhesive material consists.

In this case, a more or less thin layer can be made the thread-like bodies according to the invention, depending on If required, they can be woven, placed between two bodies to be bonded, and the whole can be a pressure or to the action of heat, or preferably both, for example in a calendering process, whereby the adhesive is exposed.

It is not excluded that in this or other cases the shell material and the core material with respect to one another are inert under the conditions of manufacture of the thread-like body, but react under conditions of use, i.e. release the core because, for example, under these conditions a higher temperature or a catalyst or a Accelerator etc. is present.

Another typical application is in resin production, which is derived from the reaction of the monomeric constituents in the presence of catalysts and accelerators, in this case, one or more of the monomer components, or the catalyst, or the accelerator, or all of them these substances are produced, preserved, and mixed in the core state of the thread-like body, as it is in a similar 'way the known microcapsules takes place.

Further purposes of use do not have to be described, since they emerge directly from the foregoing and in particular result from the known types of application of the microcapsules.

In the case of a special application, the thread-like Body used to deliver a fluid material

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den, in / which, for example, a bundle of thread-like bodies Is folded side by side, these are connected with an adhesive or in some other way, so that a thin rod arises that is sufficiently firm and then attached to the Tip is rubbed on a solid surface.

In this way, the liquid material contained in the thread-like bodies can be absorbed by the solid surface, if this is sufficiently porous. When the shell of the thread-like Body is sufficiently fragile, it is gradually worn away by friction and gives the core material free, even if this is not particularly fluid.

In this way writing implements can be made or devices the reactions with one in a sheet of paper or another treated by delivery of a suitable reactant Material absorbed materials cause the writing by color development in the thickness of the sheet material he follows. In a similar way, thread-like bodies can be produced which have a core, the abrasive Contains substances, so that a number of thread-like bodies can be used as abrasive bodies.

In this case, the fiber can consist of a material that sufficiently fragile, but not very hard, and an abrasive of very fine grain size can be used. so that special smoothing effects arise.

When the filamentary bodies of the present invention are shown in If short lengths are cut, many applications in paper technology come into consideration, and they can be used as cellulose fibers and manufacturing elements of paper , whereby the most diverse effects can be achieved, for example with the application of heat or in the presence of gases or liquids that attack the body shells can.

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The following examples serve to illustrate the invention, without limiting them.

example 1

In this example thread-like bodies are produced ', in which the active substance consists of some water-soluble salt. .

An aqueous salt solution is used in the desired concentration manufactured. 10 $ polyvinyl alcohol is added to this solution so that a viscosity of about 30,000 micropoise is obtained. stands. Separately, a normal solution of cellulose xanthate is used made as it is used in the manufacture of viscose rayon. A spinneret with 80 holes according to Pig. 1 is used. Through the hole 10 is a thick, aqueous solution, and through the bore 12 the viscous solution, which also has a viscosity of about 30,000 micropoise has, pumped. The flow rate of the volumetric The pump is dimensioned so that a ratio of 1 part by volume of core material to 0.7 parts by volume of shell material is calculated in! rock state, arises. The spinneret used has one Diameter of the nozzle 17 of 120μ, while the diameter of the nozzle 16 is 60μ. The thread-like bodies are in a Salt bath extruded, as it is commonly used in the production of viscose synthetic resin and is not described in detail must become.

The threads are collected on a rotating spool whose speed is dimensioned so that there is no reduction in cross-section. The usual treatment that follows for the production of rayon or rayon is used, whereby the bleaching can be omitted.

The result is threads that, when dry, have an outer diameter of 25μ.

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The diameter can of course be selected within certain limits by taking the speed of the thread pick-up and the flow rate of the volumetric pumps acted will.

Example 2

A polyisobutylene solution is used to produce threads with an adhesive core made in carbon disulfide, the one Has a viscosity of 10,000 micropoise.

A solution of 20 ^ polyacrylonitrile is made or a Solution of acrylonitrile copolymer in dimethylformamide.

The two yiscose solutions are extruded, the first as a core and the second as a shell. The spinneret according to. Fig. 1 has a diameter of 150μ in nozzle 17 and 80fi in the nozzle 16 on. The weight ratio of the two solutions is 1 part of the first to 2.5 parts of the second. It will be in an aqueous coagulation bath extruded, which consists of 75% V / water, The remainder is dimethylformamide.

The threads are subjected to the usual treatment for polyacrylonitrile threads, which need not be described, a total of "Lm ratio 1: 5, drawn, washed and dried.

The result is threads with an outside diameter of 20μ. This diameter can be changed by clicking on the extrusion capacity and the collection rate is acted upon.

Example 5 ^ -v ^: ■

A fatty acid with more than 4 carbon atoms turns into a Encapsulated capsule of, for example, stearic acid, in the molten state as a core from a nozzle according to FIG. 3

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extruded through a small tube 26 with an inner diameter of 100μ.

The shell material is a low-pressure polyethylene.

The diameter of the nozzle 27 is 500μ, the extrusion temperature 130 ⁰ G.

The volume amounts are in the ratio of 1 for the core material to 0.6 for the shell. A "cooling at 8O ⁰ C, the solidified shell, and the filaments can be drawn-cold. Cooling at room temperature also solidifies the core.

In the example, it is preferable to use the thread-like body with a relatively large diameter, for example 100μ.

BeisOJel 4

The procedure is as in Example 1, but now the core is a suspension of a water-insoluble material of medium size Grain size of 2μ and a maximum of 5μ in an aqueous solution of $ 10 polyvinyl alcohol or some other thickener, such as one Cellulose derivative, which provides a comparable viscosity. The extrusion can be carried out with a concentric or eccentric spinneret (Pig. 2).

When the grain size of the solid material in suspension much larger than mentioned, the diameter of the spinneret bores and the finished thread can be increased.

Example 5

Thread-like bodies are produced, the active substance of which consists of an "Inver'tase" enzyme that hydrolyses sucrose can catalyze glucose and fructose.

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A water-glycerol solution of the invertase is used (concentrated BDH invertase). There is also a 1Q solution made of cellulose triacetate in methylene chloride. The above solutions are extruded into a coagulation bath that consists of toluene, namely the first as the core and · the second as a bowl. A spinneret according to Pig. 1 with a Diameter of the nozzle 17 of 150μ and a diameter of the Nozzle 16 of 80μ used. The ratio of the above solutions is 1: 5 $

The threads are subjected to very little elongation and kept in a vacuum for a sufficient period of time so that the Toluene and methylene chloride are removed. "A section of the Strings equivalent to one gram of dry material are introduced into a flask which contains a 20% sucrose solution an acetate buffer of 4.5 pH.

The mixture is stirred and ^{kept at 25 °} C. by a thermostat, and the conversion is determined with the aid of a polarimeter.

900 mg sucrose are converted per minute.

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Claims (15)

P. atentansp'rüohe 1. Thread-like body, characterized by Microcapsule properties with a tubular protective shell and an active core therein. 2. Body according to claim 1, characterized in that the shell mainly the mechanical properties of the overall arrangement supplies. 3. Body according to claim 1 or 2, characterized in that the core and the shell are arranged concentrically. 4. Body according to claim 1 or 2, characterized in that the core and the shell are arranged eccentrically. 5. Body according to one or more of the preceding claims, characterized in that the shell is made of a polymer, in particular an artificial or synthetic linear polymer, which is preferably in the longitudinal axis of the thread-like Body oriented. 6. Body according to one or more of the preceding claims, characterized in that the core consists of an active substance or a homogeneous phase in which the active substance is included. 7. Body according to one or more of claims 1 to 5 »characterized in that the core is a composite Structure and in a remarkable way the overall * Order in terms of mechanical resistance supports. 209847/0725 8. Body according to one or more of the preceding claims, characterized in that it has an indefinite length on the order of 10,000 times the diameter and • has more. 9. Body according to one or more of claims 1 Ms 7, characterized characterized in that the length is on the order of cm or mm and the shell is closed at the ends. 10. Body according to claim 6, characterized in that the active substance is an enzyme. 11. A method for producing a thread-like body according to one of claims 1 to 40, characterized by an extrusion in a fluid state by a known method with simultaneous extrusion of an outer shell material and an inner core material in a concentric or eccentric arrangement and in that at least the shell material is solidified without breaking the continuity. 12. The method according to claim 1Ί, characterized in that the Shell material by cooling or by solvent evaporation or by solvent removal with the aid of a bath or by a chemical reaction with surrounding liquid equipment is solidified. 13. The method according to any one of claims 11 or 12, characterized in that the shell material and the core material have the same viscosity during the extrusion process. 14. The method according to one or more of claims 1Ί to 13, characterized in that the threads of the extruded material are greatly reduced in cross-section in one or more stages in the fluid and / or solid state. 209847/0 7 25 QRiOlNAL 15. The method according to claim 13, characterized in that the toughness of the core material and / or the shell material is increased by adding a thickener. 209847/0725