Methods for manufacturing patient-specific comfort ear molds for the hearing aid, audio and hearing protection industries, molded bodies produced therewith and their use

Abstract

A method for producing a shaped body using a radiation-induced printing process, characterized in that: - the shaped body is produced by solidifying a liquid or viscous material which contains a starting component with cycloolefinic groups, a thiol with at least two thiol groups per molecule, and an initiator and / or catalyst for the radiation-induced thiol-ene addition reaction between the thiol groups and a double bond of the cycloolefinic groups; and - the solidification is carried out by directing light from a radiation source onto an area of ​​a substrate surface, wherein a layer of the liquid or viscous material located therein is subjected to organic polymerization by the action of radiation and thereby solidified, whereupon further layers of the liquid or viscous material, each located on top of the layer of the last solidified material, are successively applied.solidify using this radiation source, whereby the molded body, within a temperature range of -25 °C to 110 °C, experiences a drop in its storage modulus of at least 800 MPa for a temperature increase of no more than 20 K, as determined by a DMA test on the molded body using a NETZSCH DMA242C with the following settings: support distance = 20 mm; frequency = 1 Hz; heating rate = 2.0 °C / min; max. dynamic force = 4.00 N; atmosphere = air.

Description

The present invention relates to a process for producing a shaped article by means of a 3D printing technique, in which a liquid or viscous material which contains cycloolefinic groups and thiol groups is subjected to organic crosslinking and hence to solidification by the action of light. The invention further relates to a shaped body having special thermomechanical properties, which is obtainable by this process and can be used in particular as an otoplastic.Currently, in federal republic, approximately 5.3 million hearing systems are used, with the tendency of the heel increasing. This was 2014 already over 1 million in Germany alone. The individual ear tips seated in the ear cup and in the ear canal for behind-the-ear hearing aids (BTE hearing aids) or in-the-ear hearing aids (ITE hearing aids) which connect the hearing aid to the ear are referred to as otoplasties. Different materials are used for the production of hearing systems, wherein these can be divided into hard and soft otoplastics depending on the material. As standard, otoplastics are produced on the basis of acrylates, in particular methyl methacrylate. These are usually two-component-curing materials for hard otoplastics. A disadvantage here is the residual monomer content in the cured material, which can lead to severe allergic reactions. In addition, hard otoplastics tend to interfere with the whistle sounds, especially in the case of large hearing losses, which arise as a result of the sound being fed back if the earpiece is not seated stably in the ear and does not lie all the way round on the skin. However, soft otoplastics seal better, whereby the risk of feedback is reduced. Silicone is used as permanently elastic material for this purpose. However, the insertion of soft otoplastics is made more difficult due to the blunt surface.Furthermore, there are first thermoformable materials which are hard at room temperature and soft / flexible at body temperature and therefore adapt well to the individual ear shape. The dimensionally stable otoplastic which is solid at room temperature can thus be easily used and adapts to the individual ear shape at body temperature, which ensures high wear comfort. However, the toxic vapors during processing of the material and the purely organic, monomer-based crosslinking are disadvantageous here.A great disadvantage of all the previously mentioned material systems is, moreover, the complicated, conventional manner of producing the otoplastics. This can be effected by a so-called positive-negative-positive method. The ear is first molded with silicone rubber, then a negative mold is made with silicone, agar-agar or gypsum, which is then poured out with the corresponding material. In a complicated post-processing step, the blanks must be manually shaped and painted using hand-guided milling and grinding tools. Disadvantageous in this case is the high material loss due to subtractive manufacturing and the necessary negative shape. It is also disadvantageous that special tools must be used, which is associated with further costs due to tool wear, as well as the complicated / time-consuming manual work. Another method employs an automated CAD / CAM milling process. In this case, the impression of the ear is scanned and its 3D data is processed and modeled with software before the milling of the otoplastic takes place out of a prefabricated milling disk (a so-called blank). Subsequently, a polishing and painting step is carried out again. Here too, a high loss of material and tool wear occur.These disadvantages of the currently used production process of otoplastics can be avoided by the production by means of 3D printing processes. The positive impression of the ear mold is digitally recorded by means of 3D scanners. Subsequently, the virtual data of the ear imprint edited with specific CAD programs can be directly converted into the real end product by means of 3D printers. The automated manufacturing process eliminates many manual steps, thereby reducing the amount of work. Complicated geometries can also be formed in this way. In 3D printing processes, the material loss is also low.The commercial materials already described are, however, not suitable for use in the printing process. For 3D printing of otoplastics, one-component (meth)acrylate-based resin systems or silicones are used. However, the purely organic polymers have the disadvantage that they are not monomer-free and thus are not antiallergic. Moreover, these materials have hitherto been able to produce only hard otoplastics which are only slightly flexible and poorly adapt to the ear. Hitherto, it has been the case to coat the otoplastic in the case of allergic persons (for example using a glazing or glazing) in order to avoid direct contact of the plastic with the ear canal.As already mentioned, otoplastics made of silicones can only be inserted into the ear with difficulty because of the soft surface.DE 102014116402 A1 discloses the production of shaped bodies by means of stereolithography methods, in which a vertically movable substrate platform situated at a distance of a layer thickness from the base is immersed in a bath of the material to be cured and, after crosslinking by a laser, is moved upward in each case by a layer thickness.WO 2013 / 053 693 A1 discloses stereolithography methods and mentions silica polycondensates as suitable materials, which are reacted via a thiol-ene reaction with di- and polythiols in the presence of initiators and activators and particulate additives.The object of the invention is to provide shaped bodies, including in particular otoplastics, which exhibit slight softening and thus moldability at elevated temperatures, so that they can be used, for example, for patient-specific end components with an adapted, high-quality profile of properties for hearing acoustics / audio and hearing protection and further purposes. These shaped bodies should consist of a material which can be brought into the desired shapes by means of 3D printing as mentioned above. In particular, it would be desirable to be able to produce an otoplastic whose materials-unlike those known up to now-are both biocompatible (and in particular antiallergic), and also have a thermo effect for optimum adaptation to the ear at body temperature and thus have a high wear comfort.In addition, for an appealing aesthetic, colorless / transparent versions and also various color variants should be available for them as far as possible. It should thus be possible to produce transparent-colorless, transparent-colored, opaque-colorless and opaque-colored shaped bodies, it being possible for the colors to be different. An important color variant is skin color.The object is achieved by providing a method for producing a shaped body with the aid of a radiation-induced printing method, characterized in thatthe shaped body is produced by solidification of a liquid or viscous material which comprises a starting component having cycloolefinic groups, preferably a silica (hetero)polycondensate modified with such groups, a thiol having at least two thiol groups per molecule and an initiator and / or catalyst for the light-induced thiol-ene addition reaction between the thiol groups and a double bond of the cycloolefinic groups, andthe solidification is effected by directing light from a radiation source onto a region of a surface of a substrate, wherein a layer of the liquid or viscous material located there is subjected to an organic polymerization by the action of radiation and is thereby solidified, whereupon further layers of the liquid or viscous material located in each case on the layer of the last solidified material are solidified successively with the aid of this radiation source, wherein the molded body suffers a decrease in its storage modulus of at least 800 MPa within a temperature window of -25° C. to 110° C. with a temperature increase of at most 20 K, determined by a DMA examination on the molded body by means of NETZSCH DMA242C with the following settings: deposition distance=20 mm; frequency=1 Hz; heating rate=2.0° C. / min; max. dynes. Force = 4.00 N; Atmosphere = air.The object is also achieved by providing a shaped body made of a material which has been formed by photoinduced thiol-ene addition of a thiol compound having at least two thiol groups per molecule to a starting component having cycloolefinic groups, obtainable by the process of the invention, where the shaped body suffers a decrease in its storage modulus E' of at least 800 MPa, preferably of 1200 MPa, within a temperature window of from -25° C. to 110° C., preferably of from -15° C. to 70° C., more preferably of from -15° C. to 60° C. with a temperature increase of at most 20 K. It preferably has a storage modulus E' RT( at 22° C.) between 20 and 4000 MPa, more preferably between 500 and 2600 MPa, a minimum storage modulus E' min between 5 and 300 MPa, preferably between 15 and 60 MPa, and a temperature T W( at 2·E' min) between 0° C. and 110° C., more preferably between 10° C. and 60° C. All these values are in each case determined by a DMA investigation on the molded body by means of NETZSCH DMA242C with the following settings: deposition distance=20 mm; frequency=1 Hz; heating rate=2.0° C. / min; max. dynes. Force = 4.00 N; Atmosphere = air.If the shaped body has been produced by the process according to the invention, it is generally composed of layers having a thickness of from 10 to 150 μm.In the accompanying figures, FIG. 1 is a graph showing DMA curves of some selected molded articles of different compositions and production / post-curing processes, FIG. 2 shows sample bodies produced by the method according to the invention, which are suitable for determining the faulty throughpolymerization, FIG. 3 illustrates the pressure of such a sample body and thus a possible principle of the method according to the invention FIG. 4 shows the model for an otoplastic (exterior view / interior view), and Figure 5 shows the model of an infusion needle (with a continuous internal opening).The present invention uses a method in which the body is produced by solidification of a liquid or viscous material, the solidification being effected by directing light from a radiation source onto a region of a surface of a substrate on which is located a layer of the liquid or viscous material, which is subjected to an organic polymerization by the action of radiation from this radiation source and is thereby solidified, whereupon further layers of the liquid or viscous material, which are each located on the layer of the last solidified material, are solidified successively by means of this radiation source.The "light of a radiation source" as defined herein does not necessarily have to lie in the visible range. For example, UV light is intended to be included in this term.Layers that are "on top of the layer of the last solidified material" are located thereon as viewed in the direction of the radiation source. If, for example, the substrate is arranged in a bath and the substrate surface is irradiated by a base of the bath container which is transparent to the light of the radiation source, the layers of the liquid or viscous material to be solidified in each case are located below the substrate together with the layers already solidified thereon.According to the invention, all techniques can be used which start from a liquid or viscous ("pasty"), i.e. flowable material which can solidify in a location-selective manner by exposure to light. Each layer is exposed in a planar manner, i.e. generally with a fixed amount in the z direction and with any desired contour of the respective layer in the x-y direction. The respective area / areas of each layer can be exposed simultaneously (then this is a flat exposure), or it is / are scanned with a beam (the entire area is then not exposed simultaneously but rather in narrow strips to the exposure). These techniques are referred to as "printing techniques"; they belong to the group of 3D printing methods.In particular, the so-called DLP (Digital Light Processing) is suitable for the production of the shaped bodies according to the invention. This is a material-saving, automated and thus rapid and cost-effective method, in which the material is located inside a bath, i.e. in a bath container. In this case, a substrate movable in the z-direction is mounted in the bath in the form of a platform in such a way that a thin layer of the bath material is located in each case between the base of the bath container and the downwardly directed surface of the platform or of the already solidified layers, which thin layer can be exposed and solidified, whereupon the platform is moved and in the process is ultimately pulled upward by a layer thickness in the z-direction, so that bath material flows into the gap formed. Each solidified layer has a generally constant thickness in the z direction, which however may be non-substantially small, as explained in more detail below. In the x-y direction, however, it can have any desired shape (even multiple parts) or any desired contour, as a result of which the molded body produced can also have, for example, undercuts or individual columns. It is also possible to form a plurality of individual molded bodies simultaneously. Solidification at the bath base is achieved by irradiating the bath material through the transparent base (or a transparent part thereof) or a transparent wall of the bath container. In this case, either a writing beam (for example in stereolithography) can be used, so that individual parts of the area are "scanned", i.e. are exposed one after the other in narrow strips, or the exposure can take place at once (simultaneously) over the entire area, which is therefore exposed simultaneously. The latter is preferred because the area exposure is substantially faster. The exposure wavelengths used are preferably those with which a one-photon polymerization reaction can be brought about. Exemplary sketches for explaining the exposure path can be found in FIG. 3.A further development of the DLP method is the so-called CLIP method (continuous liquid interface production). In this case, the bath base through which the radiation from the exposure source falls is preferably permeable to oxygen. This prevents the polymerization in the immediate vicinity of the bath bottom (as a rule, the oxygen-inhibiting layer adjoining the bottom has a thickness of about 20-30 μm), and the separate and relatively time-consuming step of controlled subsequent flow of liquid / viscous material into the narrow gap, which is provided in each case for the polymerization of the next layer, which is otherwise necessary in the case of DLP, is dispensed with. The exposure can therefore be continuous while the stage is continuously pulled upward (in the z direction). This naturally has the consequence that no individual layers with a strength that can be measured in the z direction are formed. Nevertheless, the method is a variant of printing in layers, since the solidification in each x-y plane takes place simultaneously. The term "layer" is therefore intended in this sense according to the invention to also encompass layers with an infinitely low thickness.Very generally, printing methods are preferably used according to the invention in which the printing takes place within a bath of the material to be consolidated. Among these, the aforementioned DLP method including the CLIP variant is particularly preferably used. Both the DLP method and the CLIP variant can be combined with all the embodiments of the invention listed below and relating to other aspects.Another example of 3D printing is stereolithography (SLA) in the narrow sense, where the formation of the shaped body is done by placing a support just below the surface of a bath or, alternatively, in the vicinity of a transparent bath bottom, such that only a thin layer of material is above / below. This is solidified (scanned) with the aid of a laser in accordance with a previously prepared digital form, whereupon the carrier is lowered / raised to such an extent that the solidified layer is coated by a further liquid layer or that a further liquid layer reaches between the solidified layer and the bath base. This layer is then likewise solidified with the laser beam. Each layer has a fixed thickness (thickness) in the z-direction, but can have any desired shape in the x-y-direction, as a result of which a shaped body can also be produced, for example, with undercuts. Further processes which can be used according to the invention are μ-stereolithography (μ-SLA), multi-jet modelling (MJM) and poly-jet printing (PJP) and variations of some of these processes, in which, for example, processing is carried out using doctor blade systems, for example lithography-based ceramic manufacturing (LCM), or in which, for example, processing is carried out using film systems, for example film transfer imaging (FTI) (for example Admaflex Technology), or further process variations, such as, for example, the TwoCur process or mask stereolithography (MSLA). For the MJM and PJP, a liquid, light-sensitive material is applied layer by layer to a platform via a print head, and each deposited strand (which is to be regarded as a constituent of a layer in the sense of the invention) is cured immediately by a light source integrated, for example, in the print head (this is an example of a technique in which the respective layer is exposed to the exposure not simultaneously but in narrow strips, which corresponds to the "scanning" mentioned above). To produce overhanging structures, support structures are produced by means of a plurality of print heads, which support structures have to be removed or washed out mechanically after printing. In the film transfer imaging method, the light-sensitive material is applied to a platform via a transport film and cured, for example, in layers by means of a projector. This method is particularly suitable for high viscosity materials. The same applies to film transfer imaging according to Admaflex technology, in which the material to be consolidated is likewise supplied via a film. The LCM, on the other hand, operates with a doctor blade. In this case, the material trough rotates in a circle after each layer solidification, so that new material is applied to the bottom of the trough by means of the doctor blade. Otherwise, there is great similarity to the DLP principle. Materials of higher viscosity are also favorable for this process. The TwoCur method uses solidification with cold in addition to photochemical crosslinking. Cold, wax-like but not chemically solidified material which serves as support can subsequently be liquefied after the pressure at room temperature. Finally, mention may also be made of mask stereolithography, in which, as in the case of DLP, a construction platform projects into a material bath and the irradiation takes place from below through the radiation-transmissive bath base. In contrast to DLP, however, the exposure field is not generated using a DLP chip, but rather using a liquid crystal exposure mask.Processes using single-photon polymerization are preferred, since only with this process can whole layers be exposed simultaneously in the x-y direction and thus exposed to the polymerization much more quickly.If the DLP technique is used for the method according to the invention, the material in the interior of the bath is solidified, so that surface effects that could possibly occur can be avoided. Also, a smaller material supply is required compared to systems in which the construction platform moves into the material bath and is exposed from above. In the latter technique, moreover, a wiper or squeegee is often required to produce a smooth surface.The expression "multiplicity of layers" is to be understood as meaning that the shaped body is constructed according to the invention from very many layers (theoretically even an infinite number, if the CLIP method is used). The actual number depends on the structure and size of the shaped body and the selected layer thickness; the layer thickness generally varies between 10 and 150 μm, but may optionally also be selected to be even smaller. The size of the shaped bodies will generally be in the mm range or cm range, with deviations downwards or upwards being possible.The terms "shaped body" and "component" are used interchangeably herein.The terms "layer thickness" and "layer thickness" are used interchangeably herein.By "liquid or viscous material" is meant the invention a material which is in any case still flowable. However, the flowability may optionally also be relatively low.The term "silicic acid (hetero)polycondensate" is intended in the present invention always to include both silicic acid polycondensates (with or without foreign hetero elements as well as silicic acid heteropolycondensates containing foreign hetero elements as mentioned.The starting component having cycloolefinic groups to be used according to the invention may preferably be one having monocycloolefinic and / or bicycloolefinic groups.As bicycloolefinic groups, the following can be preferably used: wherein R**=H, or an organic group, e.g., an alkyl group having 1 to 12 carbon atoms, which may be unsubstituted or substituted with a functional group, R**=H, or an organic group, e.g., an alkyl group having 1 to 12 carbon atoms, which may be unsubstituted or substituted with a functional group, or wherein R**is an organic group containing C=C groups, and Z is -O- (i.e., an oxygen bridge), or -(CHR***) n- with n=1, 2, or 3 or greater than 3 (e.g., to 20), R**=H, alkyl. Suitable examples are In general, the norbornenyl group is the preferred variant with respect to the bicycloolefinic group.As monocycloolefinic groups, those of the above formula can be used with the definitions of the radicals R* and R** specified for this purpose, in which Z is not present (the bonds to Z specified in the formula then represent bonds to hydrogen atoms).Bicycloolefinic groups are preferred over monocycloolefinic groups.As starting component having cycloolefinic groups, it is possible to use purely organic substances (compounds having at least two such groups). However, it is preferred to use a silica polycondensate modified with cycloolefinic groups, which has been produced from or with silanes which have at least one radical bonded to the silicon via carbon, which radical is substituted by at least one cycloolefinic group. The above discussion applies in both cases to the preference of specific cycloolefinic radicals. The cycloolefinic groups mentioned above as preferred are also to be regarded as preferred in all individual cases below.The cycloolefinic group may be bonded directly or via a coupling group to the carbon skeleton of a hydrocarbon-containing radical of a silicon atom. Examples of groups and radicals via which this radical can be bonded to the silicon can be found, inter alia, in DE 196 27 198 A1; mention is made therein of: -(CHR 6- CHR 6)n- where n=0 or 1, -CHR 6- CHR 6- S-R 5-, - C(O)-S-R 5-, - CHR 6- CHR 6- NR 6- R 5, - Y-C(S)-NH-R5, -S-R5-, -Y-C(O)-NH-R 5-, - C(O)-O-R 5-, - Y-CO-C 2 H 3( COOH)-R 5-, - Y-CO-C 2 H 3( OH)-R 5- and -C(O)-NR 6- R 5-, where R_NER31 in this context is an alkylene, arylene, arylenealkylene or arylenealkylene and R6hydrogen, The alkyl or aryl may preferably be of 1 to 10 carbon atoms.It is preferred that the silica polycondensate has at least one bicycloolefinic group per -Si-O- unit. However, it is also possible to build up from or integrate silanes with or without cycloolefinic groups which carry further functional, for example polymerizable, C=C-containing groups. These can be, for example, (meth)acrylate groups which lead to a later additive polymer structure (in the sense of a homopolymerization or thiol-ene polyadenylation) and thus to a corresponding stiffening of the structure of the later molded body. Alternatively, silanes having groups bonded to the silicon via carbon and bearing at least one hydroxy group or one carboxylic acid group in addition to one or two (bi)cycloolefinic groups can be used as starting materials for the silica polycondensate.The terms "(meth)acryl" and "(meth)acrylate" are intended to encompass acryl, acrylate, methacrylic and methacrylate, respectively.In particular, the silica (hetero)polycondensates used may be structures of the following formula (1) in which the radicals and indices have the following meaning:R 1 denotes a mono- or bicycloolefinic group. This is accessible to a thiol-ene polyaddition on addition of a thiol and, if it is a bicycloolefinic group, can additionally be polymerized by a ROMP (ring opening metathesis polymerization).R 2 is selected from (a) organically polymerizable groups which, upon addition of a thiol, are susceptible to thiol-ene polyaddition but are not susceptible to ROMP, and (b) -OH, -COOH, carboxylic acid and other esters and salts thereof.Specific variants of the compounds of the formula (1) are known, for example, from DE 102011054440A 1.The radical R 3 is a hydrocarbonaceous radical bonded to the silicon via carbon.If two groups (R 1) accessible to a ROMP or one such group (R 1) and one organically polymerizable group (R 2) are present, groups are available which can be cured in a graded manner, optionally by different curing mechanisms and thus also at different speeds. This can be used for the production of molded bodies with graded (gradual) mechanical and thermomechanical properties. If thiol is added in deficiency to such a silica (hetero)polycondensate, it is possible to add a ROMP catalyst (with sensitivity at a different wavelength than that of the initiator used for thiol-ene addition) to the bath material. The molded body produced according to the invention can then subsequently be postcrosslinked either completely or spatially selectively by ROMP. This selective crosslinking again gives rise to a body having different mechanical properties.In the silicic acid (hetero)polycondensates of formula (1) different R 3 radicals may be present. Such a system can be adjusted in a targeted and simple manner by the ratio of the starting materials to one another. As a result, a plurality of condensates similar to each other can be produced based on a single starting material, which condensates differ in their physical properties. Condensates having at least two groups on a radical R 3, each of which is accessible to thiol-ene addition, can be cured to form an organic polymer having very dense organic crosslinking. Other curing reactions, such as ROMP or polymerization by polyaddition of radicals R 2 having the meaning (a) (and here in particular of (meth)acrylic groups present as double bonds), can also be finely graded, as explained in detail in the cited DE 10 2011054440 A1.The silica (hetero)polycondensate modified with cycloolefinic groups can be prepared, for example, from silanes which have radicals bonded to the silicon via carbon atoms and each have one or more of the cycloolefinic groups mentioned. Hydrolysis of such silanes produces a ≡Si-O-Si≡-based polymer structure. In addition to silicon, the silica polycondensate can further comprise hetero elements such as B, Al, Zr, Sn, Zn, Ti and the like to a lesser extent, as known from the prior art, including the cited DE 102011054440 A. These can be incorporated into the polycondensate by addition of, for example, the corresponding alkoxides.In the case of purely organic systems, at least two cycloolefinic groups per base unit (i.e. in the molecule) are required. Although this embodiment of the invention is less preferred, in cases where a purely organic matrix system (the material without any inorganic fillers which may then be added is desired with matrix), it has the advantage over known purely organic systems that the shaped body produced therewith exhibits an antiallergic behavior since it does not contain any (meth)acrylate-based monomers.Furthermore, the liquid or viscous material to be used for the method according to the invention contains a thiol having at least two thiol groups per molecule. The term "molecule" in this context is intended to refer not only to monomeric compounds, but also to oligo- or polymeric compounds such as (hetero)polycondensates of silicic acid (produced hydrolytically from silanes). In any case, the molecule must contain at least two thiol groups, wherein in the case of condensates or the like the number is naturally generally substantially higher, e.g. about one thiol group per silicon atom. Thiol-containing systems based on silica polycondensate are described by way of example in WO 97 / 02272 A1 and DE 19627220 A1 on pages 30-33 of the published patent application. These may be used without limitation as long as they contain at least one thiol group per silane unit. Instead, purely organic systems (monomeric compounds, oligomers) can be used which must contain at least two thiol groups per molecule. Examples which may be mentioned are the following thiols: trimethylolpropane tri(3-mercaptopropionate) (TMPMP), trimethylolpropane tri(mercaptoacetate) (TMPMA), pentaerythritol tetra(3-mercaptopropionate) (PETMP), Pentaerytritoltetra(mercaptoacetat) (PETMA), glycol dimercaptoacetate; glycol di(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), biphenyl-4-4'-dithiol, P-terphenyl-4,4"-dithiol; 4,4'-thiobisbezenethiol; 4,4'-dimercaptostilbene, benzene-1,3-dithiol; benzene-1,2-dithiol; benzene-1,4-dithiol, 1,2-benzenedimethanethiol; 1,3-benzenedimethanethiol; 1,4-Benzenedimethanethiol, 2,2'-(ethylenedioxy)diethanethiol; mercaptoethyl ether and 1,6-hexanedithiol; 1,8-octanedithiol; 1,9-nonanedithiol, which can be used alone or in admixture. It can be seen from these examples that the large number of the most varied thiols (e.g. with different lengths, different hydrophilicity / hydrophobicity and different number of thiol groups) enables a wide range of material properties.Generally, the thiol is used in a small deficit (e.g. 70-90 mol %) to the cycloolefinic groups; however, in some cases it is advantageous to increase the proportion to 100% or even above. Any SH groups which remain free can then be used for further reactions.In order that the cycloolefinic groups of the starting component present in the liquid or viscous material and the thiol groups of the thiol can undergo a light-induced (radical) addition reaction, a photoinitiator is furthermore required. For this purpose, it is possible to use, for example, phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (LTPO). If thermal post-curing is also provided, an additive for initiating thermal polymerization should also be added to the liquid or viscous material which is subjected to the printing process. Mixtures of the various initiators can also advantageously be used. Examples of initiators which can be used are also described in EP 3 090 722 A1 (see S 9).When exposing (irradiating) the liquid or viscous material to be used for the method according to the invention, the cycloolefinic groups react with the thiols as crosslinking agents in the context of a thiol-ene polyaddition. In order to stabilize the liquid or viscous material, it may be necessary in certain cases to add a stabilizer (also referred to as a "thiol-ene stabilizer"). This is because a premature thiol-ene (addition) reaction of the components should naturally be avoided. Such stabilization is necessary or at least favorable in particular when the system contains strained rings, i.e. for example bicycloolefinic groups such as norbornenyl groups. Stabilizers for thiol-ene systems are known from the literature. Examples are pyrogallol, gallic acid, propyl, octyl, lauryl gallate, 4-methoxyphenol, butylhydroxytoluene, (iso)eugenol, tocopherol, 4-tert-butylpyrocatechin, phenothiazine, hydroquinone, 4-tert-butylphenol and others, as described, for example, in Edler M. et al.: Enhancing the stability of UV-curable thiol / vinyl carbonate resins; Journal of Applied Polymer Science, 2017, Esfandi P. et al.: Efficient Stabilization of Thiol-ene Formulations in Radical Photopolymerization; Journal of Polymer Science: Part A, 2013, 51 and Hoyle, C. E. et al.: Thiol-Enes: Chemistry of the Past with Promise for the future; Journal of Polymer Science: Part A, 2004, 42.Although the starting materials and the underlying crosslinking reaction are not novel, it has been found completely surprisingly that the products formed have previously unknown thermomechanical properties, for which reason they appear particularly suitable-above all in combination with good biocompatibility (e.g. skin-compatible, antiallergic)-for use in the medical sector, i.e. on the human body, and here in particular for use as inserts which can be adapted to the ear, such as otoplastics. Further possible applications result from the fact that many of the molded bodies produced exhibit, in a narrow temperature range difference, for example of 15 K, a drop in their storage modulus E' from above 2000 MPa to only a few hundred MPa or even below. If, as is often the case, this elastic modulus drop occurs in a temperature window between below room temperature (up to about 15° C.) and about the temperature of the human body (37° C.), the moldings according to the invention are suitable for medical purposes. Thus, puncture or infusion needles in the body become soft, and the otoplastics already mentioned above adapt their shape to the auditory canal in which they have been inserted, which greatly increases the wearing comfort.Polyaddition, i.e. curing, is effected by irradiation in the course of the 3D printing process used, preferably by reaction of a DLP process. It is therefore possible, using a material-saving, automated and thus rapid / cost-effective method, to make available, for example, high-quality, patient-specific components for the auditory acoustics / audio and hearing protection sector, especially also for long-term use, but not only for this sector.In the production of bodies / components with overhangs or undercuts, a defect known from the literature can occur in some cases. In the case of materials with a high transparency in the uncured and cured state, the light is in fact under certain circumstances not completely absorbed by the layer to be exposed, but rather is passed on and through the already printed layers, in particular in the z direction (so-called overcuing). This is not a problem for rectangular and similar shaped bodies, since the light is only transmitted into already cured layers. This becomes problematic for complicated shapes such as otoplastics. Here, the light is partly directed back into the material bath during the printing of layers which have a larger outline than previous ones, whereby a polymerization of the material is initiated there. Thus, at these points, undesired hardening of material takes place and thus an accumulation of material. This effect is called "faulty throughpolymerization" (FD) or "overcurring" (see FIG. 3 ).The defective throughpolymerization (FD) in the DLP technique, including further developments thereof such as CLIP, is preferably determined according to the invention on the basis of special test specimens which have an overhang which is as large and readily measurable as possible and are capable of being printed quickly. The test specimens used are those having at least two different sections delimited from one another parallel to the z direction, wherein a section A has at least one, preferably a plurality of, solidified layers which are formed starting from the surface of the platform, and a section B has solidified layers which do not extend as far as the construction platform in the z direction. The layers of section B may, but need not, be or comprise the layer last solidified in the method or a plurality of such layers. They may have the form of a single, thick layer or may have a plurality of, thinner layers or lamellae (e.g. webs). At least a portion of the specimens must have the last-formed layers. This may be one of the sections A or B or a combination of both; however, there may just as well be a third section C which additionally or exclusively has the last printed layers.The components are therefore designed such that, after the printing has been completed, a section B of the component, as viewed in the z direction, does not extend as far as the construction platform, such that between the cured side of the section B located "at the top" during the method and the construction platform there remains a space with uncured material (or with air if the molded body is no longer located in the bath), or that, as viewed in the z direction, spaces with uncured material or air remain between cured parts in this section B of the component.In a preferred embodiment, the test specimens have the shape of bridges or have the shape of an "H". In both cases, these are test specimens with two beams which bear against the construction platform (sections A), a crossbar being located between the two beams, which crossbar does not bear against the construction platform (section B), but leaves a free space between its side located "at the top" during the method and the movable platform. When this cross bar rests against the bath floor at the end of the process, the test specimen is in the form of a bridge, as shown, for example, in FIG. 1. If the cross beam does not extend to the bath floor, but the beams of the sections A are very well, the test specimen has the shape of an "H".The dimensions of a virtual model for each sample body in the z-direction, which are used as the basis for the method, including the total component height, must be known, and the actual dimensions of the sample body in the z-direction, which is produced with the method, are determined after the end of the method.After inclusion of the shrinkage of the components by post-curing, the FD can be calculated by the following formula: wherein h mod denotes the height of the virtual model of the specimen in the z-direction, h tat denotes the specific structural height of the produced specimen in the z-direction, d mod denotes the dimensions of the or a layer in section B of the virtual model of the specimen and d tat denotes the specific height of this layer in section B of the produced specimen.Using bridges as shown in FIG. 2, it has been determined in concrete terms how strongly the FD has an effect depending on the material or variable process parameters by correlating the actual thickness of the crossbar (d tat) with that of the digital model (d mod).In order to be able to nevertheless realize complex component geometries, for example with overhanging structures, suitable stabilizers are used as additives which absorb these in the region of the radiation used for the polymerization reaction. Such stabilizers must not be confused with the stabilizers which are intended to avoid premature thiol-ene addition. The radiation-absorbing additives are referred to herein as photoabsorbers / photostabilizers or lightabsorbers / lightstabilizers, optical brighteners, but also as UV absorbers / UV stabilizers, since a preferred method of the invention is a 3D printing process which uses radiation having wavelengths in the range of the transition from UV to visible (preferably in the range at about 360 to 490 nm). Of course, the photostabilizer is, with respect to its absorption spectrum, optionally to be adapted to the radiation wavelength used for the method used in each case.With the aid of light stabilizers, the problems which arise in connection with so-called "overcuing" can be counteracted and overhanging structures can be printed dimensionally accurately. In this case, unfilled to highly filled materials can be used with and without light absorbers and the respective effects of the light absorbers and / or fillers can be determined. Accordingly, light absorbers, particularly preferably inorganic and organic light absorbers and also optical brighteners can be added to the compositions used according to the invention, as required, the latter having comparable properties to the light absorbers, i.e. likewise being able to reduce the FD. Organic light absorbers act, for example, via the mechanism of energy dissipation. In this regard, reference may be made to G. Wypych, Handbook of UV Degradation and Stabilization, ChemTec Publishing, Toronto 2015, pp. 34, 43-46.Examples of inorganic light absorbers are titanium oxide, zirconium oxide or zinc oxide. Examples of organic light absorbers are benzophenones such as DHDMBP=2,2'-dihydroxy-4,4'-dimethoxybenzophenone, Cyasorb UV-416=2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, Cyasorb UV-531=2-hydroxy-4-n-octoxybenzophenone, Cyasorb UV-9=2-hydroxy-4-methoxybenzophenone, Chiguard BP-1=2,4-dihydroxybenzophenone, Chiguard BP-4=2-hydrox-4-methoxybenzophenone-5-sulfonic acid, Chiguard BP-2=2,2',4,4'-tetrahydroxybenzophenone and benzotriazoles such as Tinuvin 327=2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, Chiguard 323=2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate, Chiguard R-445 (benzotriazole), Chiguard 5431=2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3,tetramethylbutyl)phenol, Tinuvin P=2-(2'-hydroxy-5'-methylphenyl)benzotriazole, Tinuvin 326=2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol, Tinuvin 328=2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, Chiguard 5411=2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, Chiguard 234 = 2-[2-hydroxy-3,5-di-(1,1-dimethylbenzyl)]-2H-benzotriazole. Examples of optical brighteners are TBT = 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), Uvitex OB-ONE = 2,2'-(1,2-ethylenediyldi-4,1-phenylene)bisbenzoxazole, Eutex 127 = 1,1'-biphenyl-4,4'-bis[2-(methoxyphenyl)ethenyl], Eutex KCB = 2,2'-(1,4-naphthaleneeddiyl)bisbenzoxazole, Eutex CBS = 1,1'-biphenyl-4,4'-bis[2-(sulphophenyl)ethenyl]disodium salt, Eutex KSN = 4,4-bis(5-methyl-2-benzoxazole)ethylenes or tris(dibenzoylmethanes)mono(1,10-phenanthroline) europium(III).Organic light absorbers which have reactive groups which can co-polymerize with reactive groups of the starting compounds used, for example (meth)acrylate groups, are particularly preferred. Examples of these are Chiguard 323 and Cyabsorb UV-416.Inorganic, organic as well as hybrid polymer-based fillers can also be contained. Mixtures which comprise at least inorganic-organic hybrid polymers and fillers are also referred to as composites. The starting component having cycloolefinic groups and the thiol having at least two thiol groups per molecule and any additives dissolved therein act here as a matrix in which the fillers are present in dispersed form.The fillers can be primary particles in the nanometer range, which, as explained further below by the invention, can be present as required agglomerated to form larger particles or (completely) dispersed and exhibit surprising effects, such as, for example, the modification of the refractive index of the matrix system. Instead or additionally, larger particles may be added to modify, for example, the mechanical or tribological properties. Inorganic, particulate or spherical fillers are preferred, but fibrous fillers can also be used. Particularly preferred chip-shaped fillers are dental glass powders having particle sizes between 0.18 μm and 5 μm. Particularly preferred spherical fillers are SiO 2-, TiO 2-, ZnO, ZnS and ZrO 2- nanoparticles having particle sizes between 5 nm and 100 nm. Examples of fillers which can be used are also described in EP 3 090 722 A1 (see pages 9 and 10) and in DE 1964378, DE 10018405, DE 102011053865 A1 and DE 102005061965.7. To improve the bond between the filler particles and the crosslinked matrix, the fillers can be surface-modified. Preferably, the surface modification carries groups which can be polymerized into the organic network of the silica polycondensate. An example is the surface modification with norbornenyl groups or methacrylic groups, for example in the form of methacryloxypropyltrimethoxysilane, see EP 3 090 722 A1 (page 10), if the polysiloxane component of the liquid or viscous material on which the process according to the invention is based has norbornenyl groups, methacrylic groups or other groups copolymerizable with the groups mentioned as organically polymerizable radicals. The surface modification brings about improved dispersion of the particles. If nanoparticles are concerned (below a certain particle size), they therefore no longer have a light-scattering effect, but modify the refractive index of the matrix, the constituent of which has become them. The mechanical values of the material are generally only slightly influenced by this measure, as can be seen from the examples below. The increased refractive index matrix system can then be combined with suitable fillers of similar refractive index to provide improved mechanical properties while maintaining translucence. Certain particles, such as ZrO 2 and TiO 2 additionally have the ability to absorb energy in the form of light, for example by raising an electron from the valence to conduction band (formation of an electron-hole pair). Subsequently, for example, recombination again takes place. As a result, they also function as light absorbers. In this regard, reference may be made to G. Wypych, Handbook of UV Degradation and Stabilization, ChemTec Publishing, Toronto 2015, page 45. There, the effect is shown on the basis of TiO 2- and ZnO nanoparticles.The surprising thermo-mechanical effect observed after curing is found in the fact that, in the event of a temperature rise to which the shaped body or the workpiece is exposed, its modulus of elasticity drops sharply. This effect is dependent on the particular material used and frequently occurs in a narrow temperature range (about 10 to 40° C., sometimes already about 5 to 15 or 20° C., but also significantly higher depending on the starting materials used). Below and above this range, relatively stable, i.e. constant, modulus values are observed. In other words, the photochemically polymerized material changes its consistency from rigid to soft / flexible. The temperature at which the flexibility takes place can be adjusted in a broad temperature field by the selection of the starting substances and can thus be adapted to different applications such as, for example, the described otoplastics (in the region around the body temperature). The variables used can be the C=C and the SH fraction per structural basic unit, the distance between the C=C and the SH groups and the core structure and the respective distance from one another, the possible fraction of the ≡Si-O-Si≡-based polymer structure and hence the organic, inorganic and overall crosslinking density. An important influencing factor is, moreover, the degree of conversion in the thiol-ene polyaddition. It should be noted here that non-converted norbornenyl groups are unproblematic from an application-specific point of view, since they are not reactive under "normal" conditions and are therefore stable. Specifically, the following data on the stiffening / flexibility temperature ("T w") were determined on exemplary molded bodies produced according to the invention:System E-> Of additives / post-treatment in the range of ≈36-49°CSystem A-> Additives / post-treatment in the range of ≈15-18.5°CSystem B-> Of additives / post-treatment in the range of ≈35-50°CThe dependence on additives can be explained inter alia as follows: when the amount of initiator is increased, the degree of crosslinking generally increases, leading to a higher storage modulus E'; if, on the other hand, light absorbers are added, the storage modulus E' falls slightly.Further thermal effects to be observed on the materials of the invention are a reduction in refractive index and an increase in the coefficient of thermal expansion with increasing temperature.Preferred post-treatments after the actual printing process comprise a post-curing in order to increase the conversion of the polymerizable groups of the shaped bodies. The postcure can advantageously be effected photoinitiated with a flash apparatus. In the thiol-ene polyaddition used according to the invention, a protective gas atmosphere is not required to avoid an oxygen inhibiting layer. Alternatively or additionally, the post-light curing can be carried out, for example, with a Spectramat device (a dental light oven, Ivolcar, Schaan, (Lichtenstein)) and / or a conventional dental emitter. Additionally or alternatively, the post-curing can be effected thermally initiated in an oven at elevated temperature (e.g. 100° C.) and / or by means of IR emitters and / or microwave.In particular in the case of planned thermal post-curing, a photoinitiator can be combined with a thermal initiator, for example, wherein the photoinitiator is used during the pre-crosslinking during the 3D pressure and the thermal initiator is subsequently used in the oven during the post-curing. If required, a combination of different photoinitiators can also be used which have their absorption maximum at different wavelengths, the one photoinitiator splitting during 3D printing and the second one splitting during post-curing with light of a specific wavelength which deviates from the emission wavelength of the LED of the printer. An example of such a combination is the use of LTPO as initiator for 3D printing (effective from about 420 / 410 nm and below) and camphorquinone, which is effective in a wavelength range of about 400-500 nm, for post-curing. Alternatively, a UV initiator can be used as the second initiator for the post-curing. The post-curing with light can be effected photoinitiated, for example, with a flash apparatus (optionally under protective gas) and / or spectramat and / or dental emitter and / or high-intensity LED spotlight (Bluepoint LED eco from Honele, Gradefing / Munich).After addition of various types of additives, if necessary, for example, for thiol-ene stabilization, initiation, etc., the photosensitive flowable resin systems or composites can be converted ("printed") according to the invention with the aid of a 3D printing process and particularly preferably by means of digital light processing (DLP) to give moldings, in particular to give patient-specific components, in which the above-mentioned thermomechanical property profile is combined with high dimensional accuracy / dimensional accuracy / dimensional accuracy / dimensional accuracy.Despite high elasticity / elongation, the systems are easily printable (i.e. without printing defects, such as, for example, step formation) (even without support structures / supports). The following problem exists in the pressing of elastic materials by means of DLP methods: the pull-off forces of the cured layer from the bath base are often very high in the case of flexible materials. As a result, the layer may remain adhering to the bath floor and the already printed component may deform / expand during the raising of the construction platform, since it does not tear off from the floor. Pressure errors can occur, among other things, as a result, such as undesirable steps in the component. In order to avoid these problems of printing, support structures for supporting the flexible material must frequently be used. The present inventors have found that this problem does not exist.To realize an attractive optical system, the molded bodies / components can be embodied as transparent. Alternatively, fillers or pigments can be added to the material to be polymerized in order to produce molded bodies / components having different color variants (e.g. skin colors).If the process according to the invention is to be used for the production of otoplastics, the skin compatibility (antiallergic behavior) required for this purpose is likewise given, since the material usable according to the invention makes do without the addition of otherwise customary (meth)acrylate-based monomers.In summary, it can be stated:An important advantage of the method according to the invention can be seen in the fact that a widely studied and known material base can be used for, for example, an otoplastic which, in comparison with previous materials, is both biocompatible (specific antiallergic) and-surprisingly-has the necessary thermo effect for optimum adaptation to the ear at body temperature and thus a high wear comfort and, in contrast to previous thermoformable materials, can be pressed. Thus, a great variability with regard to the additional functionalization and thus the resulting properties (e.g. for realizing an antibacterial design) can be used.A location-dependent stiffening (e.g. in the "cover region") is likewise possible as described above. This ensures a material-saving, automatable and thus rapid and cost-effective method for producing medical components such as otoplastics. In addition, transparent and different color variants are possible with regard to an appealing aesthetic. These can be obtained, for example, by the addition of coloured inorganic particles such as those containing iron oxide or of (usually organic) dyes which are soluble in the liquid or viscous material. Furthermore, the curing described is generally a very rapid reaction, which enables a reduction in the compression and post-curing time even in the case of very complex components. It is also possible to ensure the time required for the printing process and more the required (storage) stability of the starting materials. The addition of a thiol-ene stabilizer such as pyrogallol furthermore has no adverse effects on print qualities.The thermomechanical effect found for the first time by the inventors and its adjustable extent / adjustable extent depending on the starting materials used in each case (see also the examples below) enables the cost-effective production (by means of 3D printing process) of patient-specific components such as, for example, an otoplastic, which is not perceived as an interfering foreign body in the ear, even in the case of several hours a day in the auditory canal. Depending on the nature and sensitivity of the ear canal, it is thus possible to use adapted, i.e. patient-specific harder or softer systems. Furthermore, the material can be chosen to conform to the ear, i.e., is hard at room temperature and flexible at body temperature. A material which is solid and handle at room temperature for good handling can thus be used easily and becomes pleasantly soft at body temperature, whereby it seals and prevents pressure pain. At the same time, there is good basic stability for a long durability of the otoplastic. A high wear and handling comfort as one of the most important properties of otoplastics can thus be realized.Particular preference is given to use in the field of the auditory acoustics / audio and hearing protection industry, such as, for example, for• Ear Fittings for Behind-the-Ear Hearing Devices (Otoplastics)• Ear Fittings / Shells / Housings for In-the-Ear Hearing Devices• Receiver-in-the-ear hearing aids (RITE)• Receiver-in-the-ear canal hearing aids (RIC)• Monitoring (for e.g. musicians, racers, reporters, security workers)• In-ear loudspeaker• Passenger, military, pilots, etc. (on the one hand very sensitive listening and on the other hand returning sensitivity to shot sounds)• Hearing protection (prescribed for e.g. disco, work with noise (from 85 dB, e.g. road construction, airport))• Snarking• As a protection against water, dirt, etc. Ear drum membrane perforation (tear, hole), carrier of "Paukentubes" (dragenage)• Ornamental otoplastics (colour + strasse, exceptional shape).Furthermore, use is generally possible in the medical sector, such as for the following applications• Implants → Thus, thin films can be handled much better at ambient temperature, i.e. in the stiffened form within the scope of further application-related modifications (e.g. application of conductor tracks, etc.) (even during film production and post-hardening), while during / after implantation, e.g. in brain regions, other soft tissue regions, etc., become very flexible and tissue damage can thus be avoided.• Artificial blood vessels or stents → Very delicate "hollow fibers" or stents can be produced which can be handled and also inserted much better at ambient temperature, i.e. in the stiffened form (even during their production and post-hardening), while after implantation they become very flexible and adapt to the ambient conditions (e.g. during body movements).• Catheters, needles and the like for infusion systems → Systems (highly) filled with nanoparticles are preferably used for such applications. The combination with nanoparticles has the effect on the one hand that the molded bodies produced remain transparent, while on the other hand they have good hardness or sharpness, so that at ambient temperature, i.e. in the stiffened shape, they are suitable for "puncturing" (without a separate enveloping needle system) into the skin, e.g. of the human body, e.g. in the form of infusion needles, but become very flexible after contact with the body and the corresponding temperature adjustment and adapt themselves as an "infusion cannula" to the ambient conditions (e.g. during body movements).• (Hard) dimensionally stable (special) wafers, for example in the case of individual visual defects and eye diseases (generally individual production with regard to individual corneal geometry), are easier to handle in stiffened form before insertion (for example during care, during cleaning, during insertion) and adapt to the bulb shape after heating to the temperature of the cornea. This brings about a high level of wearing comfort (no / less feeling of foreign bodies)The shaped bodies according to the invention can also be used for biological purposes, namely for scaffolds and other supports or substrates for biological material, in particular cells. Cells require mechanical properties (e.g. modulus of elasticity) that are very closely matched to the respective cell type in order to feel comfortable and grow on a substrate. These properties can be readily adjusted with the materials of the invention.Moreover, with scaffolds and similar supports made of the materials usable according to the invention, novel effects can be used: because of their thermomechanical flexibility, it is possible to bring about a substantial softening / flexibility of the scaffolds / supports by only a small temperature increase beyond the other, customary ambient temperature of the cells and of the (growth) medium in which they are located. By reducing the modulus of elasticity required for "well-being" of the cells, the cells lose the feel of being in a "habitual" environment, reduce their adhesion to the substrate, and are easier to peel off. Conversely, this effect can also be achieved by lowering the temperature, the material according to the invention then achieving an elastic modulus or hardness which is unfavourable for cell growth and for adhesion of the cells.Instead, it can also proceed by another method to remove cells growing on a scaffold or other substrate and adhering well there. In this case, the material usable according to the invention used is one which, in addition to the cycloolefinic groups, also has groups which are accessible to a ROMP, as explained above. For the scaffold on which the cells are to grow, the material is chosen to have the required mechanical properties without additional cross-linking by ROMP having taken place. However, it contains the above-mentioned ROMP catalyst. If it is now desired to remove the cells, the scaffold / substrate is exposed to the appropriate wavelength at which a ROMP is triggered. The additional cross-linking which occurs in this process stiffens the material and the cells are easier to separate.Furthermore, use in the following fields is possible• (Micro)optical and (Micro)electronics → Principle, see above for implants• Optical, electronic and mechanical switchesThe curing by the thiol-ene reaction can take place via two different mechanisms: a radical thiol-ene reaction with all C=C double bonds, for example with C=C double bonds of the norbornenyl group, is possible here, while a thiol-Michael addition takes place only with activatable C=C double bonds, as can be present, for example, in the form of methacrylic groups, in particular methacrylate. The radical mechanism is initiated by a radical initiator (thermally and / or photoinduced and / or redoxinduced). In particular, nonactivated C=C double bonds such as the double bond of the norbornenyl group are suitable for this type of initiation. In order to be able to initiate a thiol-Michael addition in a localized and / or temporary manner, photobases can be used, since the thiol-Michael addition proceeds with base catalysis. Photobases release a base upon exposure and thus can initiate thiol-Michael addition. The preparation and use of photobases is described in the literature.If photochemical work is carried out, the irradiation can be carried out with visible and / or UV light. Combinations of different reactions, for example photochemical and thermal or a combination of redox-induced curing with, for example, photoinduced or thermal curing, are likewise possible.The invention will be explained in more detail below with reference to specific exemplary embodiments.A. SynthesesI. Synthesis of Resin System-1 (Silane-Based System)1. Synthesis step (from DE 4416857) (Preparation of a methacrylate-based silane resin having free OH groupsBase resin (a):Triphenylphosphine as cat., BHT as stabilizer and then 47.35 g (0.550 mol) of methacrylic acid are added dropwise under a dry atmosphere to the initial charge of 125.0 g (0.503 mol) of 3-glycidyloxypropymethyldiethoxysilane and the mixture is stirred at 80° C. (about 24 h). After addition of ethyl acetate (1000 ml / mol silane) and H 2 O for hydrolysis with HCl as cat., the mixture is stirred at 30° C. After stirring for about several days, the mixture is worked up by shaking repeatedly with aqueous NaOH and with water and filtration over hydrophobicized filters. It is first of all rotated off and then drawn off with oil pump vacuum. This results in a liquid resin without the use of reactive diluents (monomers) having a viscosity of about 3-5 Pa·s at 25° C.2. Synthesis step (from DE 102011054440A1) (reaction of the methacrylate groups with dicyclopentadiene to form norbornenyl groups, resin system-1)To obtain 80.0 g (0.30 mol) of base resin (a), about 45.5 g (0.69 mol) of cyclopentadiene (CP) (freshly prepared by splitting dicyclopentadiene) are added by distillation while stirring at about 90° C., and the mixture is then stirred at 90° C. for a further about 1-2 hours. The reaction can be monitored by NMR. The volatile constituents, such as unreacted cyclopentadiene, are removed in an oil pump vacuum at temperatures up to 90° C. This results in a liquid resin having a viscosity of about 53-110 Pa·s at 25° C. No further workup is generally required.Synthesis of Resin System-2a / b / c (Silane-Based System)1. Synthesis step (from DE 103.49766.8) (Production of a silane resin which has partly one methacrylic group per silicon atom, partly one methacrylic group and one acrylic group per silicon atom, wherein the methacrylic group and acrylic group are each present on the same residue bonded to the silicon via carbon, by reaction of the free OH group with acyl acid chloride.Base resin (b1) (ratio of methacrylic groups to acrylic groups 1: 0.74)36.66 g (0.405 mol) of acryloyl chloride are added dropwise to the initial charge of 120.7 g (0.45 mol) of base resin (a) (from I.) and 45.1 g of triethylamine (0.446 mol) in 450 ml of THF as solvent under a dry atmosphere and cooling by means of an ice bath with stirring, and stirring is continued at RT. Conventional work-up for separating off the amine hydrochloride formed in the addition and acidic by-products and withdrawing the volatile constituents with an oil pump vacuum results in a liquid resin having a viscosity of about 2.7 Pa·s at 25° C.Base resin (b 2) ( ratio of methacrylic to acrylic groups 1:0.30):The initial charge of 78.15 g (0.30 mol) of base resin (a) (from I.) and 11.69 g of triethylamine (0.385 mol) in 300 ml of THF is reacted with acryloyl chloride (9.50 g (0.105 mol)) according to the procedure of base resin (b 1) and the resulting reaction mixture is further processed and worked up. A liquid resin having a viscosity of about 2.7 Pa·s at 25° C. results.Base resin (b 3) ( ratio of methacrylic to acrylic groups 1:0.45):The initial charge of 78.15 g (0.30 mol) of base resin (a) (from I.) and 16.70 g of triethylamine (0.55 mol) in 300 ml of THF is reacted with acryloyl chloride (13.52 g (0.15 mol)) in accordance with the instructions of base resin (b 1) and the resulting reaction mixture is further processed and worked up. A liquid resin having a viscosity of about 2.5 Pa·s at 25° C. results.2. Synthesis step (from DE 102011054440A1) (reaction of the methacrylate and acrylate groups with dicyclopentadiene to form norbornenyl groups)Resin system-2a (ratio 1.74 norbornenyl groups per silicon atom):To initially charge 92.4 g of base resin (b 1) about 22.0 g of CP are added dropwise with stirring at about 50° C. After heating the reaction mixture to about 90° C., 39.2 g of CP are added by distillation while stirring and then stirring is continued for about 1.5 h at 90° C. The volatile constituents, such as unreacted cyclopentadiene, are removed in an oil pump vacuum at temperatures up to 90° C. This results in a liquid resin having a viscosity of about 380 Pa·s at 25° C. No further workup is generally required.Resin system-2b (ratio of 1.30 norbornenyl groups per silicon atom):To initially charge 63.7 g of base resin (b 2) CP is added according to the procedure of resin system 2a (total of about 38.1 g, reacted therewith and the resulting reaction mixture worked up. This results in a liquid resin having a viscosity of about 177 Pa·s at 25° C. No further workup is generally required.Resin system-2c (ratio of 1.45 norbornenyl groups per silicon atom):To initially charge 63.7 g of base resin (b 3) CP is added according to the procedure of resin system 2a (total of about 77.7 g, reacted therewith and the resulting reaction mixture worked up. This results in a liquid resin having a viscosity of about 194 Pa·s at 25° C. No further workup is generally required.Note: the viscosities of the resins (b 1) to (b 3) and of the resin systems-2a, 2b and 2c are greatly dependent on the exact synthesis and workup conditions chosen in each case, especially also of the precursors. The values can therefore deviate during a revision.Synthesis of Resin System-3 (Purely Organic System, Reaction of Glycerol Dimethacrylate to The Corresponding Norbornenyl Derivative)Resin System-3To initially charge 30.00 g (0.131 mol) of glycerol dimethacrylate (isomer mixture) with dissolved 0.04% by weight of butylhydroxytoluene (BHT), about 39.7 g of CP are added dropwise with stirring at about 80° C. and the mixture is stirred further. The conversion of the methacrylate group is monitored by means of 1 H-NMR. The volatiles such as unreacted cyclopentadiene are stripped under vacuum at temperatures up to 90°C. This results in a liquid resin having a viscosity of about 6.3 Pa·s at 25° C. No further workup is generally required.B. Preparation of Resin Blends for 3D Printing and Compared to Classical ProcessingGeneral procedure: A light stabilizer is optionally dissolved beforehand in the respective resin system, for which purpose a solvent is optionally added, which is then drawn off again. Subsequently, the thiol in which a photoinitiator and, if a strained ring system is used as cycloolefinic group, a thiol-ene stabilizer have been dissolved beforehand is added with stirring at elevated temperature (usually about 40° C.). The resulting resin mixtures are used for 3D printing and for conventional test specimen production in the context of a preferably photoinduced thiol-ene polyaddition.As the resin systems, the above-mentioned Systems 1, 2a, 2b, 2c and 3 were used.The optical brightener 2,5-bis(5-tert-butylbenzoxazol-2-yl)thiophene (TBT) was used as an example of a light stabilizer, which was used here with 0.0003-0.0005 mmol / g resin mixture (based on resin system+thiol).Unless stated otherwise, the thiol used was trimethylolpropane tri(3-mercaptopropionate) (TMPMP) (generally in the molar ratio of SH:C=C=0.9:1), in which the stabilizer pyrogallol (0.05-0.2% by weight, based on resin system+thiol) and the photoinitiator LTPO (1.0 and 2.0% by weight, based on resin system+thiol) had been dissolved with stirring at 40° C. In another case, the thiol used was a mixture consisting of TMPMP and 2,3-di((2-mercaptoethyl)thiol-1-propanethiol (DMPT; it contains no ester groups but additional thioether groups, whereby the refractive index is increased) in a molar ratio of 0.3:0.9. the molar ratio of SH:C=C is 0.9:1. otherwise everything remained the same.Pyrogallol served in the specific case as thiol-ene stabilizer.C. Preparation of the composites for 3D printing and compared with classical processingC1. General Specification for Composite Production with TiO 2 as Filler:In the respective resin mixture (made of B., with a molar ratio of SH:C=C=0.9:1), 0.5% by weight of TiO 2- filler (in agglomerated form; rutile; primary particle φ=10-30 nm; 99.5% strength; van io-li-tec nanomaterials) are incorporated in the speedmixer (2×60 sec). The materials are then evacuated at 37°C until bubble free. The resulting composites are used for 3D printing and for conventional test specimen production in the context of a preferably photoinduced thiol-ene polyaddition.C2. General Specification for Composite Production with ZrO 2- NP as Filler:A dispersion of ZrO 2- NP from Pixelligent (PixClea PCPB-2-50-ETA, Ø=7-10 nm, dispersed to 50% by weight in ethyl acetate, methacrylate-functionalized) is added to the respective resin mixture (from B.), and the material is stirred at RT. The next day, the solvent is removed by vacuum at 40° C. The resulting composites having a ZrO 2- content of 30% by weight are used for 3D printing and for conventional test specimen production in the context of a preferably photoinduced thiol-ene polyaddition.D. Determination of Refractive Index Change and Mechanical DataD1. Test Piece Production for Determining the Refractive Index Change in the Region of the T W:The resin mixture consisting of resin system-2b and 1% LTPO (based on resin system-2b+thiol) and thiol TMPMP (in the molar ratio of SH:C=C=0.9:1) and stabilizer pyrogallol (0.2% by weight based on resin system 2b+thiol) is placed in a mold (20×8×4 mm 3). By means of dental emitters (Polofil Lux der Fa. Voco GmbH, Cuxhaven); (100 sec VS / RS each) and flash apparatus G171 Otoflase (NK Optik, Baierbrunn, D) (3000 flashes), the C=C double bonds of the norbornenyl groups are reacted in the course of a photoinduced polyaddition and the resin mixture is cured. The refractive index before or after heating is determined by means of an Abbe refractometer (immersion liquid is 1-bromonaphthalene) and thus the change in refractive index in the region of the T w is determined. Since the heating was carried out with a hair, since a tempering of the sample during the measurement was not possible, the values are not very accurate.• Refractive index before heating (at 20° C.)≈1,548• Refractive index after heating (about 40-60° C.)≈1,533Result: Δn≈0.015 ⇒ The refractive index decreases since the samples become more flexible and thus the structure density decreases.D2. Conventional test specimen production for determining the mechanical data (abbreviated to "classic" in the table):The respective resin mixture (made of B.) or the composite (C1or C2.) is added to a rod shape (40×2<5 mm 3). The C=C double bonds of the norbornene groups are preferably reacted by means of dental emitters (Polofil Lux; 100 sec VS / RS each), in the course of photoinduced polyaddition, and the resin mixtures or the composites are cured.D3. Test Piece Production for Determining the Mechanical Data by means of 3D Pressure (abbreviated to "3D Pressure" in the Table):The rod-shaped test specimens (40×2×2×2 mm 3) are printed by means of 3D printer S 60 LED from Rapidshape (DLP principle) with a layer thickness of 100 μm and an exposure time of 31 s per layer at a light intensity of approximately 6.15 W / m 2 with a perpendicular orientation to the construction platform (corresponding to 40 mm in the z direction), subsequently washed in isopropanol for 90 s in the ultrasonic bath, blown off with compressed air, dried for 5 min at RT and subsequently by means of a UV lamp Bluepoint LED eco (insg. 200 sec.), flash device G171Otoflase (3000 flashes) or spectamat (3 min).DMA studies (dynamic mechanical analyses) on the above specimens were carried out by means of NETZSCH DMA242C with the following settings: Contact distance=20 mm; Frequency=1 Hz; T range=-10° C. to 70° C.; Heating rate=2.0° C. / min; max. dynes. Force = 4.00 N; Atmosphere = air. The storage modulus E' RT( at 22° C.), the minimum storage modulus E' min and the temperature T W( at 2 E' min), i.e. the temperature at which the material has virtually the most flexible consistency ("virtually" because E' converges towards E' min as the temperature rises, were determined. High temperature increases which are of no importance for use therefore lower the E' above 2 E' min only insignificantly). The data are given in the following table; the DMA curves are shown in Figure 1.Resin Blends (Unfilled)A KResin system 1 + thiol0,02 % pyrogallol / 1 % LTPOClassicn.b.n.b.18,5A DResin system 1 + thiol0,2 % pyrogallol / 1 % LTPO / 0.0005 mmol / g TBTPrinted + Flash Device1119915,0B K1Resin system 2a + thiol1 % LTPOClassic25503050B K2Resin system 2a + thiol0,02 % pyrogallol / 1 % LTPOClassic15503435Viscosity at 25° C. / 40° C.->B K1 ≈16 / 4.5 Pa·sB K2 ≈8.2 / 2.3 Pa·sC KResin system 2b + thiol1 % LTPOClassic13701941C DResin system 2b + thiol0,2 % pyrogallol / 1 % LTPO / 0.0005 mmol / g TBTPrinted + Flash Device6785332E K1Resin system 2c + thiol1 % LTPOClassic18802745E K2Resin system 2c + +0,05 % pyrogallol / %Classic19202449thiol2 % LTPOE D1Resin system 2c + thiol0,05 % pyrogallol / 1.5 % LTPOPrinted + Spectramat16303341E D2Resin system 2c + thiol0,2 % pyrogallol / 1 % LTPO / 0.0005 mmol / g TBTPrinted + Flash Device10005136E D3Resin system 2c + thiols TMP / DMPT0,2 % pyrogallol / 1 % LTPOPrinted + Flash Device14371547D KResin system 3 + thiol1 % LTPOClassic16401045CompositesF DResin system 1 + thiol + 30% ZrO 2- NP0,2 % pyrogallol / 1 % LTPOPrinted + Flash Device1302627The results show that, depending on the resin structure (e.g. C=C number per structural unit, i.e. the organic crosslinking density), the additives used or their concentration (which may be different in order to meet the respective requirements with respect to the desired printing result, the resolution, the complexity of the structures and the like), the storage modulus E' RT, the storage modulus E' min and the temperature T W( at 2·E' min) and in particular also the change / the extent of the rigidity / flexibility in the range around the temperature at E' min( ↔ thermal effect) can be set within wide limits for different application cases.For example, the following can be seen from the above table:Comparison A K and A D shows that TBT (and therefore probably also other light stabilizers) has little effect on the temperature T W. In some cases, this falls slightly, as already mentioned above.As the number of norbornenyl groups per silicon atom increases and thus as the crosslinking increases (since the ratio SH to C=C double bond remains the same), the temperature T increases W: For A D with a norbornenyl group per silicon, it is 15.0° C., for C D(1,30 norbornenyl groups per silicon atom), it is 32° C., and for E D2(1,45 norbornenyl groups per silicon atom), it is 36° C. This shows that the temperature T W can be adjusted within wide limits and even higher values than those shown in the examples can be achieved. The value can also be further increased by the addition of suitable amounts of suitable fillers. Attainable in this way should be values for T W of above 50°C, e.g. up to 60°C, up to 70°C, up to 80°C, up to 90°C or even up to 110°C.The addition of the nanoparticles of ZrO 2 results in a transparent composite (see F D in the above table) and the storage modulus and surprisingly also the temperature at E' min are expected to increase compared with the unfilled resin mixture A K. The use of fillers thus also allows the flexibility temperature (↔ thermo-effect) to be raised and thus the area of use to be shifted into higher T-ranges.The inventors were furthermore able to show that, when dispersed (isolated!) inorganic, preferably oxidic, nanoparticles (in particular in the primary particle size range of about 5-100 nm) are added (in the present case in an amount of 30% by weight, see F D) for the production of moldings having overhangs or holes, it is possible to dispense with the addition of a light absorber such as TBT, since they themselves can function as photoabsorbers. In addition, the addition of these particles increases the refractive index of the matrix, the constituent of which has become it, as already explained above.As the number of norbornenyl groups per silicon atom increases and thus as the crosslinking increases (since the ratio SH to C=C double bond remains the same), E' RT: For C K with 1.30 norbornenyl groups per silicon atom, it is 1370 MPa, for E K1(1,45 norbornenyl groups per silicon atom), it is 1880 MPa, and for B K1(1,74 norbornenyl groups per silicon atom), it is 2550 MPa. This shows that the storage modulus E' RT can be set within wide limits at room temperature.The same applies to E' RT in the following systems: For A D with a norbornenyl group per silicon, E' RT is 111 MPa, for C D(1,30 norbornenyl groups per silicon atom), it is 678 MPa, and for E D2(1,45 norbornenyl groups per silicon atom), it is 1000 MPa. This also shows that the storage modulus E' RT can be adjusted within wide limits at room temperature.As the number of norbornenyl groups per silicon atom increases and thus as the crosslinking increases (since the ratio SH to C=C double bond remains the same), E' min: For C K with 1.30 norbornenyl groups per silicon, it is 19 MPa, for E K1(1,45 norbornenyl groups per silicon atom), it is 27 MPa, and for B K1(1,74 norbornenyl groups per silicon atom), it is 30 MPa. This shows that the storage modulus E' min can be set within wide limits.By the simultaneous addition of pyrogallol and TBT, E' RT decreases and E' min increases. This can be seen in the systems C K( no pyrogallol / TBT) with an E' RT of 1370 MPa and E' min of 19 MPa compared to C D(0,2 wt % pyrogallol and 0.0005 mmol / g TBT) with an E' RT of 678 MPa and E' min of 53 MPa. The same applies to the systems E K1( no pyrogallol / TBT) with an E' RT of 1880 MPa and E' min of 27 MPa and E D2(0,2 wt % pyrogallol and 0.0005 mmol / g TBT) with an E' RT of 1000 MPa and E' min of 51 MPa.The use of the trithiol DMPT in a proportion, which has no ester groups but thioether groups and also has a shorter connecting structure between the thiol groups than the trithiol TMPMP, achieves a higher E' RT at lower E' min(15 MPa) in conjunction with a higher temperature T w(47 ° C.) in comparison with system E D2 at 1437 MPa. Thus, the material characteristics can also be clearly modified by using a thiol with an altered connecting structure between the thiol groups.The thermal expansion coefficient of the moldings produced according to the invention and conventionally should increase very greatly in the T W- range, since it generally correlates with the flexibility of the moldings. In addition, the refractive index decreases as the temperature rises, as explained above. The shaped bodies should therefore also be suitable inter alia as optical or mechanical switches.E. 3D Printing Fabrication of Model Otoplastics (Ear Fittings)The ear tips according to the model shown in FIG. 4 were printed with the unfilled material systems C D and E D2 by means of 3D printer S 60 LED from Rapidshape (DLP principle) with a layer thickness of 100 μm and an exposure time of 31 s per layer at a light intensity of 6.15 W / m 2 with the alignment with the construction platform as shown in the figure, subsequently washed in isopropanol for 3 min in an ultrasonic bath, blown through / off with compressed air, dried for 5 min at RT and by means of a UV lamp (insg. 200 sec.), flash device (3000 flashes) or spectamat (3 min).The printed ear tips are transparent, have good surface quality and include well-resolved through holes. At room temperature they are solid / sparingly flexible and at body temperature they exhibit a soft / flexible behaviour, the E D2 based eartips exhibiting a higher stiffness at RT and at body temperature than those based on C D.It is thus possible to produce ear fittings of high quality in conjunction with different thermal / elastic modulus behavior and thus patient-specific requirements by means of 3D printing.F. 3D Printing Production of "Tube-like" MoldingsUsing the unfilled material system E D2 tube-like moldings as model for infusion needles, as shown in FIG. 5, artificial blood vessels, catheters were printed using 3D printer S 60 LED from Rapidshape (DLP principle) with a thickness of 100 μm and an exposure time of 31 s per layer at a light intensity of 6.15 W / m 2 with a perpendicular orientation to the construction platform, then washed in isopropanol for 3-4 min in an ultrasonic bath, blown through / off with compressed air, dried for 5 min at RT and printed using a UV lamp (insg. 200 sec.) or flash device (3000 flashes).They are transparent, have a good surface quality (inside / outside) with a well-formed "tip" (example infusion needle) with an outside diameter of 2.0 or 3.0 mm and have a wall thickness of 0.5 or 0.75 mm. At room temperature they are less flexible and at body temperature they show a soft / flexible behaviour.It is thus possible to produce tube-like medical molded parts of high quality in conjunction with different diameters / wall thicknesses and thus individual requirements by means of 3D printing.

Claims

A process for producing a shaped body by means of a radiation-induced printing process, characterized in that - the shaped body is produced by consolidation of a liquid or viscous material which comprises a starting component having cycloolefinic groups, a thiol having at least two thiol groups per molecule and an initiator and / or catalyst for the radiation-induced thiol-ene addition reaction between the thiol groups and a double bond of the cycloolefinic groups, and - the consolidation is effected by directing light from a radiation source onto a region of a surface of a substrate, a layer of the liquid or viscous material located there being subjected to an organic polymerization by the action of radiation and is thus consolidated, whereupon further layers of the liquid or viscous material located in each case on the layer of the last consolidated material are consolidated successively by means of this radiation source, wherein the molded body suffers a decrease in its storage modulus of at least 800 MPa within a temperature window of -25° C. to 110° C. with a temperature increase of at most 20 K, determined by a DMA investigation on the molded body by means of NETZSCH DMA242C with the following settings: contact distance=20 mm; frequency=1 Hz; heating rate=2.0° C. / min; max. dyn. Force = 4.00 N; Atmosphere = air.The method of claim 1, wherein the liquid or viscous material is in a bath container having a bottom that is at least partially translucent, and the substrate is a platform immersed in the liquid or viscous material and movable away from the bottom of the bath container.Method according to claim 1 or 2, wherein the irradiation takes place with a wavelength in the range of below 500 nm and / or wherein the layer thickness of the individual layers is selected in the range of 3 to 150 μm and / or wherein irradiation takes 0.2 to 100 s and / or wherein the bath material is exposed with an intensity of 4 to 50 W / m 2.A process according to any preceding claim wherein the starting component having cycloolefinic groups is a silica (hetero)polycondensate modified with mono- or bicycloolefinic groups.Process according to any of the preceding claims, wherein the starting component with cycloolefinic groups is a silica (hetero)polycondensate of or with silanes in which radicals bonded to the silicon via carbon have a norbornenyl group, a norbornenyl group and a hydroxyl group or two norbornenyl groups, or wherein the starting component with cycloolefinic groups is a purely organic compound having two terminal norbornenyl groups.A method according to any preceding claim wherein the thiol having at least two thiol groups per molecule is a trithiol or a mixture of two trithiols.A process according to any preceding claim wherein the ratio of thiol groups to cycloolefinic or bicycloolefinic groups is 0.5-1.2 to 1.0.A process according to any preceding claim, wherein a phosphine oxide is added to the liquid or viscous material as initiator and / or catalyst for the photoinduced thiol-ene addition reaction.A process according to any preceding claim, wherein the shaped article is prepared from the liquid or viscous material in a bath and, after its formation, is taken out of the bath, washed with a solvent, dried and subsequently postcured.A method according to any preceding claim, wherein the liquid or viscous material further comprises a thiol-ene stabiliser.Process according to any of the preceding claims, wherein the liquid or viscous material is a composite which comprises, in addition to the starting component having cycloolefinic groups, the thiol and the initiator and / or catalyst, a particulate and / or fibrous additive.The method of claim 11, wherein the particulate additive is inorganic particles.A process according to any one of claims 11 and 12, wherein the inorganic particles have an average primary particle diameter of from 1 to 100 nm and are in agglomerated or dispersed form.A process according to claim 12 or 13, wherein the inorganic particles are provided with a coating modified with an organically polymerisable radical such that this organically polymerisable radical is subjected to a thiol-ene addition reaction upon irradiation of the liquid or viscous material.A method according to any preceding claim, wherein the liquid or viscous material further comprises a dissolved or particulate material capable of absorbing light of the exposure wavelength.The method of claim 15, wherein said material is a dissolved fluorescent material.A molded article made of a material which has been formed by photoinduced thiol-ene addition reaction of a thiol compound having at least two thiol groups per molecule to a starting component having cycloolefinic groups, obtainable by the process according to any of the preceding claims, characterized in that the molded article suffers a decrease in its storage modulus of at least 800 MPa within a temperature window of -25°C to 110°C with a temperature rise of at most 20 K, determined by a DMA investigation on the molded article by means of NETZSCH DMA242C with the following settings: deposition distance = 20 mm; frequency = 1 Hz; heating rate = 2.0°C / min; max. dyn. Force = 4.00 N; Atmosphere = air.Shaped body according to claim 17, which is formed in a spatial direction from individual layers having a thickness in the range from 3 to 150 μm or in which the layers have been formed by continuous exposure.Shaped body according to claim 17 or 18 having a storage modulus E' RT( at 22°C) between 20 and 4000 MPa, a minimum storage modulus E' min between 5 and 300 MPa and a temperature T W( at 2·E' min) between 0°C and 110°C, in each case determined by a DMA investigation according to the method specified in claim 17.A shaped article according to any one of claims 17 to 19, further comprising a filler.Shaped body according to Claim 20, in which the filler consists of dispersed zirconium dioxide particles having a primary particle diameter of about 5 - 50 nm or contains these.Shaped body according to one of Claims 17 to 21 having a translucence of at least 75%.Use of a shaped body according to any of claims 17 to 22 in the medical sector, selected from the use as otoplastic and / or for hearing acoustic / audio and / or hearing protection purposes or as a puncture or infusion needle or as a carrier for the cultivation of biological organisms or cells.Use of a shaped body according to one of Claims 17 to 22 as an optical or mechanical switch.

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