DE102010034453A1 - Process for the preparation of a masterbatch comprising TPE compound and masterbatch - Google Patents

Abstract

The present invention relates to a method for producing a masterbatch containing TPE compound, a masterbatch, a method for producing a molded part containing at least one active ingredient, and a molded part.

Description

The present invention relates to a process for the preparation of a masterbatch comprising TPE compound, to a masterbatch, to a process for the preparation of a molding containing at least one active substance and to a molding.

Isolated on the market Duftbatche with low concentrations (less than 40% loading) are known. Current products are based on strandgranulierten Batch, in which the active ingredient is incorporated on extruders in a plastic melt. For this purpose, the carrier plastics usually have to be melted at high temperatures which are significantly above their melting temperatures.

The direct incorporation of liquid ingredients such. As fragrance, flavor, care or drugs, in plastics prepares due to their liquid state of matter in the manufacture of precast problems. Nevertheless, in order to be able to introduce these liquids during production, they must be brought into a meterable solid form. This is usually ensured by the provision of a batch.

The current production process of Wirkstoffbatchen run over hot melts to liquefy the Trägerkunststoffes. Due to this thermal stress, the active ingredient can be damaged and / or it can, if it is volatile, evaporate. Due to the high Extrudertemperatuen agents can be degraded or decomposed. If the active ingredient is a composition of several constituents, there is a risk that some constituents are more susceptible to degradation or more volatile than others. As a result, the effect of the active ingredient, for. B. fragrance, taste, nourishing or healing effect, altered and, where appropriate, impaired. Due to loss of significant amounts of the active substance due to evaporation or thermal damage, in addition to the risks mentioned above, the costs and thus the price rise.

The loading (%) with the active ingredient are limited in the hot process limits. In the case of highly volatile active substances, the risk of spontaneous combustion or of inflammation on hot machine parts is also to be expected in hot production. Furthermore, there is a significant burden on production by the evaporation of volatile components, which may be harmful in some cases to the human organism.

In the incorporation of fragrances such. As essential oils, however, it is problematic at high temperatures in the extruder to incorporate the fragrances in thermoplastic elastomers, since the fragrances on the one hand quickly volatilize again, on the other hand, to some extent subject to thermoplastic degradation. On the other hand, the volatilization of essential oils is also problematic insofar as explosive mixtures can arise. The known from the prior art production methods for masterbatches or processing methods are therefore only of limited use for fragrances and / or active ingredients and are for the reasons mentioned above with disadvantages.

It was therefore an object of the present invention to provide a process for the preparation of a masterbatch based on thermoplastic elastomers, which circumvents the aforementioned problems. It was likewise an object of the present invention to provide a correspondingly prepared masterbatch, a process for the further processing of the masterbatch, d. H. for the production of a molded part, as well as a correspondingly produced molded part.

These objects are in terms of the process for preparing the masterbatch based on thermoplastic elastomers with the features of claim 1, with respect to the masterbatch with the features of claim 13, with respect to the method for producing a molded part having the features of claim 14 and in terms of the molding with the Characteristics of claim 17 solved. Claim 18 specifies the uses of a masterbatch according to the invention. The respective dependent claims are advantageous developments.

According to the invention, a method is thus provided for producing a TPE compound-containing masterbatch. The term "TPE compound" is to be used interchangeably with thermoplastic elastomers in general. In the method according to the invention, at least one active substance is mixed during an extrusion process with at least one raw material containing at least one thermoplastic elastomer. Alternatively or additionally, however, it is also possible to mix the active substance before the extrusion process with the thermoplastic elastomer-containing raw material. In the case of liquid under normal conditions, this is done by pre-swelling the thermoplastic elastomer-containing raw material with the liquid active ingredient. In the case of solid substances which are solid under normal conditions, the raw material is premixed with the at least one active substance, for example by mechanical mixing methods. In any case, then followed by an extrusion of the raw material with or without further addition of an active ingredient to the raw material. Decisive and essential to the invention here is that the Processing temperature during the extrusion process is below the softening point of the raw material used.

According to the invention, therefore, a TPE compound-containing masterbatch can be prepared which contains at least one raw material containing at least one thermoplastic elastomer and at least one active substance contained therein.

It has been shown that a brief warming up to 100 ° C does not change the impression of a fragrance. The preparation at low temperatures below 100 ° C is achieved by using swellable with the active ingredient carrier materials. It is advantageous if the carrier and active substance have similar polarities.

To obtain the best result, it is best to note that the carrier is pre-swelled with the active ingredient. When swelling the entire added active ingredient can be used, then no further addition of an active ingredient in the subsequent extrusion process. However, it is also possible to mix in the pre-swelling part of the active ingredient, the remaining active ingredient is then abandoned during the extrusion process. This can be done in a pre-mixer in which the carrier is presented and then the active ingredient with continuous mixing z. B. is sprayed. Subsequently, the pre-swollen preliminary batch is mixed via a cold extruder (less than 100 ° C in one of the last heating zone) to a homogeneous mass, then a strand granulation can be carried out under water.

This process can alternatively be carried out via a cold (less than 100 ° C.) internal mixer followed by extrusion and optionally granulation.

• – keine Explosion oder Brandgefahr, Schonung der Rohstoffressourcen,
• – höhere Beladung des Trägers mit Wirkstoffen als bei herkömmlichen Verfahren (Beladungen lediglich bis 70% waren möglich),
• – keine thermische Schädigung des Wirkstoffes,
• – keine Umweltbelastung durch übermäßiges Abdampfen,
• – einfache Zugabe eines Wirkstoffes ähnlich eines Farbbatches beim Verarbeiter,
• – Verwendung von „state of the art”-Technologie beim Verarbeiter,
• – Ausweitung auf weitere Thermoplasten ist möglich,
• – leichte Bedienung von Marketing-Aktionen beim Kunden, sowie
• – Anpassung des Trägers auf die im Fertigprodukt verwendeten Materialien.

In particular, the invention provides the following advantages:

• - no explosion or fire hazard, protection of raw material resources,
• Higher loading of the carrier with active substances than with conventional methods (loadings only up to 70% were possible),
• No thermal damage to the active substance,
• - no environmental pollution due to excessive evaporation,
• Simple addition of an active substance similar to a color batch at the processor,
• - use of "state of the art" technology by the processor,
• - extension to other thermoplastics is possible
• - easy handling of marketing actions at the customer, as well
• - Adaptation of the carrier to the materials used in the finished product.

In a preferred embodiment, the at least one admixed active ingredient has a flash point of <200 ° 0, preferably <80 ° 0, particularly preferably <70 ° C, wherein the processing temperature is kept within ± 15 ° C of the flash point.

In particular, the processing temperature is between 0 and 95 ° C, preferably between 60 and 85 ° C, more preferably between 65 and 80 ° C. According to this preferred embodiment of the method, in particular cold extrusion processes are used to prepare the masterbatch.

Preferably, the at least one active ingredient can be incorporated into the thermoplastic elastomer in virtually any amount. It is possible, for example, that, based on a certain proportion of the underlying thermoplastic elastomer-containing raw material, a lower compared to this amount of the active ingredient is incorporated, however, it is also possible that, based on the absolute amount of the raw material, added more active ingredient becomes. Preferred amounts of the active ingredient, based on the raw material, are between 20 and 300 wt .-%, d. H. it is possible to incorporate up to 3 parts of active ingredient, based on one part of raw material, in the masterbatch. However, it is preferred if the amounts of the raw material are between 30 to 80 wt .-%, more preferably 35 to 75 wt .-%, more preferably 40 to 70 wt .-%, particularly preferably between 40 and 60 wt .-% , so that, based on the thermoplastic elastomer compound (something), less active ingredient (based on the TPE matrix) is contained in the masterbatch.

It is also advantageous if the residence time of the raw material and of the at least one active substance in the extruder is between 1 and 5 minutes, preferably between 1 and 4 minutes, particularly preferably between 1 and 3 minutes.

In a particularly advantageous embodiment, it is provided that prior to the extrusion process, the raw material is swollen with the at least one active ingredient in the case of a liquid under normal conditions or premixed in the case of a solid under normal conditions with this active substance and the resulting swollen raw material is fed to the extrusion process. According to this particularly preferred embodiment, a two-stage incorporation of the at least one active substance into the thermoplastic elastomer matrix takes place. It is, in the event that it is a liquid raw material, first the TPE matrix or the TPE raw material with the active ingredient preswollen, then the extrusion according to the invention is carried out for the preparation of the finished masterbatch. Likewise, however, it is possible that - in the case of solid active substances - premixing of the TPE raw material with the active ingredient takes place, followed by the extrusion process according to the invention at low temperatures.

According to this embodiment, it is possible, the entire amount of the active ingredient to be added already in this preliminary stage, d. H. through the swelling process or premixing, to incorporate into the thermoplastic raw material; the extrusion process according to the invention ensures particularly good homogenization of the active ingredient in the TPE compound, and achieves good retention of the active ingredient in the TPE compound.

Alternatively, however, it is also possible in the premix stage, i. H. the swelling process or the premixing process, to give up a certain proportion of the at least one active substance, and to add the remainder of the active ingredient in the extrusion stage to the TPE raw material. This stepwise addition is particularly advantageous in the achievement of high drug concentrations in the masterbatch, as a result, a higher degree of loading of the masterbatch can be achieved. For example, it is possible to add, based on the total amount of the at least one active substance to be added in the abovementioned premixing stage, 20, 30, 40, 50, 60, 70, 80, 90% by weight of the active ingredient to be applied.

Particularly preferred in the above premixing stages, i. H. swelling or mechanical pre-mixing, 100% by weight of the raw material between 10 and 300% by weight, preferably between 10 and 100% by weight, more preferably between 20 and 70% by weight, particularly preferably between 35 and 65 wt .-% of the at least one active ingredient added, wherein optionally during the subsequent extrusion process, the remaining amount of the at least one active ingredient is admixed, so that the added during the swelling or Vormischvorgangs and the extrusion process amount to the total amount of the added active ingredient ,

Furthermore, one or more further processing steps can follow directly on the extrusion process according to the invention, for example a strand granulation, preferably an underwater strand granulation.

Preferably usable active ingredients are selected from the group consisting of fragrances, flavors, care agents and / or essential oils in the form of pure substances, mixtures, solutions and / or suspensions.

• a) Styrol-Blockcopolymere (TPE-S), insbesondere SBS, SEBS, SEPS, SEEPS und/oder Kombinationen hieraus,
• b) thermoplastische Elastomere auf Olefinbasis (TPE-O), bevorzugt OBC (olefinische Block Copolymere),
• c) vernetzte und/oder vulkanisierte thermoplastische Elastomere auf Olefinbasis (TPE-V), bevorzugt vulkanisiertes PP/EPDM,
• d) thermoplastische Elastomere auf Polyurethanbasis (TPE-U),
• e) thermoplastische Copolyester (TPE-E),
• f) thermoplastische Polyetherblock(co)polyamide (TPE-A), sowie
• g) Kombinationen oder Mischungen aus den zuvor genannten thermoplastischen Elastomeren.

As a thermoplastic elastomer of the raw material, ie matrix of the masterbatch, in particular the following thermoplastic elastomers can be used:

• a) styrene block copolymers (TPE-S), in particular SBS, SEBS, SEPS, SEEPS and / or combinations thereof,
• b) olefin-based thermoplastic elastomers (TPE-O), preferably OBC (olefinic block copolymers),
• c) crosslinked and / or vulcanized olefin-based thermoplastic elastomers (TPE-V), preferably vulcanized PP / EPDM,
• d) polyurethane-based thermoplastic elastomers (TPE-U),
• e) thermoplastic copolyesters (TPE-E),
• f) thermoplastic polyether block (co) polyamides (TPE-A), and
• g) combinations or mixtures of the aforementioned thermoplastic elastomers.

Furthermore, it can be provided according to the invention that the raw material used contains at least one further thermoplastic polymer which is admixed to the at least one thermoplastic elastomer, wherein the at least one further thermoplastic polymer is preferably selected from the group consisting of polyolefins, in particular, polyethylene and / or polypropylene , and / or preferably the mixing ratio between the at least one thermoplastic elastomer and the at least one further thermoplastic polymer is between 50:50 and 95: 5, preferably between 70:30 and 80:20, in each case based on the weight ratios.

Likewise, the possibility is included that the raw material contains at least one additive selected from the group consisting of paraffin oils, medicinal white oils and / or combinations thereof, preferably in a weight ratio between the at least one thermoplastic elastomer and the at least one additive between 50:50 and 95: 5, more preferably between 65:35 and 75:25.

The invention likewise provides a masterbatch comprising a TPE compound which contains at least one thermoplastic elastomer, wherein at least one active ingredient is present mixed in the TPE compound. Preferably, the masterbatch is in the form of granules. Here are the above statements made with regard to the process for the preparation of the masterbatch, z. B. the preferred loading levels, of course, also for the final product, d. H. the masterbatch, too. If the method z. B. 80 wt .-% active ingredient incorporated with respect to the TPE compounds, the masterbatch also contains 80 wt .-% active ingredient, based on the TPE compound.

The invention also provides a process for producing a molded part containing at least one active substance, in which a previously described masterbatch is mixed with at least one second thermoplastic elastomer compound containing at least one thermoplastic elastomer in an extruder, extruded and subjected to a shaping process. The second TPE compound can be the same or different from the TPE compound on which the masterbatch is based.

In a preferred embodiment, the masterbatch is used with respect to the second TPE compound in a weight ratio between 0.1% and 20%, preferably between 0.5% and 10%, particularly preferably between 1% and 6%.

The molding process used in the production process for the production of the molding is in particular selected from the group consisting of injection molding, film extrusion, profile extrusion, and / or extrusion processes, so that corresponding moldings, d. H. z. As handles, films and / or hollow body can be produced.

Furthermore, according to the invention, a correspondingly produced molded part is specified, which preferably has a content of the at least one active substance between 0.5% and 10% by weight, more preferably between 0.5% and 5% by weight, particularly preferably between 0, 5% and 3% wt .-% has.

Uses of the above-described masterbatch according to the invention are in particular the scenting of hygiene articles, in particular toothbrushes, razor cartridges, diapers, aroma batch for dental care articles or toothbrushes with flavorings, as a care batch for razor cartridges and / or as a lubricant batch for razor cartridges.

Claims (18)

A process for preparing a masterbatch comprising TPE compound, comprising at least one raw material containing at least one thermoplastic elastomer and at least one active substance contained therein, wherein the at least one active ingredient is mixed during an extrusion process with the at least one raw material containing at least one thermoplastic elastomer and / or before the extrusion process, the raw material is swollen with the at least one active ingredient in the case of a liquid under normal conditions or premixed in the case of a solid under normal conditions with this, characterized in that the processing temperature is below the softening point of the raw material used during the extrusion process , A method according to claim 1, characterized in that the at least one admixed active ingredient has a flash point of <200 ° C, preferably <80 ° C, more preferably <70 ° C, wherein the processing temperature is maintained within ± 15 ° C of the flash point. A method according to claim 1 or 2, characterized in that the processing temperature between 0 and 95 ° C, preferably between 60 and 85 ° C, more preferably between 65 and 80 ° C. Method according to one of the preceding claims, characterized in that with respect to 100 wt .-% of the raw material 20 to 300 wt .-%, preferably 30 to 80 wt .-%, more preferably 35 to 75 wt .-%, more preferably 40 to 70 wt .-%, more preferably between 40 and 60 wt .-% of the at least one active ingredient are mixed. Method according to one of the preceding claims, characterized in that the residence time of the raw material and the at least one active ingredient in the extruder between 1 and 5 minutes, preferably between 1 and 4 minutes, more preferably between 1 and 3 minutes. Method according to one of the preceding claims, characterized in that swelled before the extrusion process, the raw material with the at least one active ingredient in the case of a liquid under normal conditions active ingredient or premixed in the case of a normal solid ingredients with this and the resulting swollen raw material supplied to the extrusion process becomes. Method according to the preceding claim, characterized in that, when swelling or premixing, with respect to 100% by weight of the raw material, between 10 and 300% by weight, preferably between 10 and 100% by weight, more preferably between 20 and 70% by weight , more preferably between 35 and 65 wt .-% of the at least one active ingredient are added, wherein during the subsequent extrusion process, the remaining amount of the at least one active ingredient is admixed, so that added during the swelling or Vormischvorgangs and the extrusion process amount add to the total amount of added active ingredient. Method according to one of the preceding claims, characterized in that the extrusion process is followed by a strand granulation, preferably an underwater strand granulation. Method according to one of the preceding claims, characterized in that the at least one active ingredient is selected from the group consisting of fragrances, flavors, care agents and / or essential oils in the form of pure substances, mixtures, solutions and / or suspensions. Method according to one of the preceding claims, characterized in that the at least one thermoplastic elastomer of the raw material is selected from the group consisting of a) styrene block copolymers (TPE-S), in particular SBS, SEBS, SEPS, SEEPS and / or combinations thereof, b) olefin-based thermoplastic elastomers (TPE-O), preferably OBC (olefinic block copolymers), c) crosslinked and / or vulcanized olefin-based thermoplastic elastomers (TPE-V), preferably vulcanized PP / EPDM, d) polyurethane-based thermoplastic elastomers (TPE-U), e) thermoplastic copolyesters (TPE-E), f) thermoplastic polyether block (co) polyamides (TPE-A), and g) combinations or mixtures of the aforementioned thermoplastic elastomers. Method according to one of the preceding claims, characterized in that the raw material contains at least one further thermoplastic polymer which is admixed to the at least one thermoplastic elastomer, wherein the at least one further thermoplastic polymer is preferably selected from the group consisting of polyolefins, in particular polyethylene and / or polypropylene, and / or preferably the mixing ratio between the at least one thermoplastic elastomer and the at least one further thermoplastic polymer is between 50:50 and 95: 5, preferably between 70:30 and 80:20, in each case based on the weight ratios. Method according to one of the preceding claims, characterized in that the raw material contains at least one additive selected from the group consisting of paraffin oils, medicinal white oils and / or combinations thereof, preferably in a weight ratio between the at least one thermoplastic elastomer and the at least one additive between 50:50 and 95: 5, more preferably between 65:35 and 75:25. Masterbatch, preferably in the form of granules, containing a TPE compound containing at least one thermoplastic elastomer, wherein at least one active ingredient is present mixed in the TPE compound. Process for the preparation of a molded part containing at least one active substance, in which a masterbatch according to the preceding claim is mixed with at least one second thermoplastic elastomer compound containing at least one thermoplastic elastomer in an extruder, extruded and subjected to a shaping process. Method according to the preceding claim, characterized in that the masterbatch is used with respect to the second TPE compound in a weight ratio between 0.1% and 20%, preferably between 0.5% and 10%, particularly preferably between 1% and 6%. Method according to one of the two preceding claims, characterized in that the forming process is selected from the group consisting of injection molding, film extrusion, profile extrusion, and / or extrusion processes. Molding obtainable by a process according to one of claims 14 to 16, preferably with a content of the at least one active substance between 0.5% and 10% by weight, more preferably between 0.5% and 5% by weight, more preferably between 0.5% and 3% by weight. Use of the masterbatch according to Claim 13 for perfuming hygiene articles, in particular toothbrushes, cartridges for razors, diapers, as a flavoring patch for dental care articles or toothbrushes with flavorings, as a care batch for cartridges for razors and / or as a lubricant batch for cartridges for razors.