WO2012022464A1

WO2012022464A1 - Process for producing a masterbatch comprising tpe compound and masterbatch

Info

Publication number: WO2012022464A1
Application number: PCT/EP2011/004115
Authority: WO
Inventors: Frieder Vielsack
Original assignee: Kraiburg Tpe Gmbh & Co. Kg
Priority date: 2010-08-16
Filing date: 2011-08-16
Publication date: 2012-02-23
Also published as: DE102010034453A1

Abstract

The present invention relates to a process for producing a masterbatch comprising TPE compound, to a masterbatch, to a process for producing a molding comprising at least one active ingredient, and to a molding.

Description

Process for the preparation of a masterbatch comprising TPE compound and masterbatch

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 active substances, such as fragrances, flavorings, conditioners or medications In plastics, due to its liquid state of aggregate, it is causing problems in the production of finished parts. 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 processes for active substance batches run via hot melts to liquefy the carrier plastic. 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. This will reduce the effect of the active agent, e.g. Fragrance, taste, nourishing or healing properties, altered and possibly 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. On incorporation of fragrances such as essential oils, however, it is problematic at high temperatures in the extruder to incorporate the fragrances in thermoplastic elastomers, as the perfumes on the one hand evaporate quickly, ande ^¬ hand, are subject to some degree of 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 substances and are disadvantageous for the reasons mentioned above.

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, i. 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 12, with respect to the method for producing a molded part having the features of claim 13 and in terms of the molding with the Characteristics of claim 16 solved. Claim 17 indicates the uses of a masterbatch according to the invention. The respective dependent claims present Partial developments.

According to the invention a method for the manufacture of a lung ^¬ TPE containing masterbatch is thus provided. The term "TPE compound" is to be used synonymously with thermoplastic elastomers in general In the process 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, but it is alternatively or in addition thereto In the case of active ingredients which are liquid under normal conditions, this is done by pre-swelling the thermoplastic elastomer-containing raw material with the liquid active substance Raw material is premixed with the at least one active substance, for example by mechanical mixing methods .Always, an extrusion of the raw material with or without further addition of an active substance to the raw material takes place In this case, the processing temperature during the extrusion process is below the softening point of the raw material used. The active ingredients used according to the invention are selected from the group consisting of fragrances, flavors and / or essential oils in the form of pure substances, mixtures, solutions and / or suspensions.

The active ingredients added according to the invention are thus all olfactorily active and therefore all selected from the group of substances which stimulate the sense of smell. Between the inventively used Fragrances, flavors and / or essential oils may also be given partial material identity. According to the invention is under a perfume a

Smell-stimulating chemical substance understood that may be, for example, a vegetable or a synthetic fragrance. A synonymous term for fragrances is an odorant or an odoriferous substance; this includes all natural and synthetic substances that have a smell.

Flavorings are all substances that can be divided into the following classes: natural flavors, nature-identical flavors, artificial

Aromas, reaction aromas, aroma extracts and smoke flavors.

According to the invention, extracts which are soluble in organic solvents in the case of ethereal oils or of the organic phase from extracts of plants or parts of plants contained by steam distillation have a strong odor which is characteristic of the plant of origin. Essential oils may include, for example, onoterpenes, sesquiterpenes or aromatic moieties. The monosurfers or sesquiterpenes can be selected from the substance classes of hydrocarbons, alcohols, aldehydes, ketones, ethers or esters. Specific examples of this are, inter alia. Ocimen, myrcene, limonene, a-

Terpinene, phellandrene, pinene, camphene; Linalool, geraniol, sabinol, borneol; Neral, citronellal;

Carvon, Menthon, Menthol, Camphor, Fenchon;

Menthofuran, cineole, anethofuran; Geranyl acetate, linalyl acetate; Farnesol, farnesene, α-bisabolol, a-

Caryophyllene, chamazulene, β-caryophyllene, etc. The aromatic substance group includes, for example, compounds from the class of phenols, phenylpropanoids or furanocoumarins. Examples include carveol, carvacrol, thymol; Apiol, cinnamic aldehyde, anethole, dillapiol, estragol; Coriandrin.

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. In the case of pre-swelling, the entire added active substance can be used; in the subsequent extrusion process, no further addition of an active substance takes place. However, it is also possible to premix a part of the active ingredient, the remaining active ingredient is then added during the extrusion process. This can be done in a premixer, in which the carrier is presented and then the active ingredient is sprayed with constant mixing, for example. Subsequently, the pre-swollen or pre-mixed Vorbatch via a cold extruder (less than 100 ° C in a last heating zone) is mixed to a homogeneous mass, then a Underwater granulation take place.

This process can alternatively take place via a cold (less than 100 ° C.) internal mixer followed by an extrusion and, if appropriate, granulation

In particular, the invention provides the following advantages: no explosion or fire hazard,

Conservation of raw material resources,

higher loading of the carrier with active ingredients than with conventional methods (loadings only up to 30% 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 ° C., preferably <80 ° C., particularly preferably <70 ° C., the processing temperature being 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 the ^¬ ser preferred embodiment of the method are, in particular cold extrusion processes to produce 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 .-%, i. 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 with the at least one active ingredient is removed in the case of a liquid ingredient which is liquid under normal conditions. or in the case of a solid under normal conditions active substance is premixed with this and the resulting swollen raw material is supplied 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. In this case, in the event that it is a liquid raw material, first the TPE matrix or the TPE raw material with the active ingredient is pre-swollen, then the extrusion according to the invention is carried out to produce the finished masterbatch. However, it is also 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 to use the entire amount of the active substance to be added already in this preliminary stage, i. 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. the source 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. 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 during the Quellbzw. Premix process and the extrusion process added amount to the total amount of added active ingredient.

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

As a thermoplastic elastomer of the raw material, i. 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) cross-linked and / or cured thermoplasti ^¬ specific olefin-based 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), as well

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, medical 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. Counter ^¬ set on applied as active ingredients olfactory active substances have paraffin oils or white oils by no fragrance. The inherent odor of these substances is not considered to be olfactorily active according to the present invention; the paraffin oils or

White oils are therefore not among the active ingredients. 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, the above-mentioned statements regarding the method for the preparation of the master batch, e.g. the preferred loading levels, of course also for the final product obtained, i. the masterbatch, too. If, in the method, e.g. 80 wt .-% active ingredient with respect to

TPE compounds are incorporated, 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 master batch with respect to the second TPE compounds in a weight ratio between 0, 1% and 20%, preferably between 0.5% and 10%, more preferably between 1% and 6% used.

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, i. e.g. 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 invention described above masterbatches are in particular the

Scenting and / or incorporation of care substances in hygiene articles, in particular toothbrushes,

Cartridges for razors, diapers, as a flavoring match for

Tooth care articles or toothbrushes with flavorings, as a care batch for cartridges for razors and / or as a lubricant batch for cartridges for razors. Additionally or alternatively, the masterbatch may be used to incorporate conditioners into the appropriate articles. The masterbatch is used in particular in the production of the corresponding article.

Claims

claims

Process for the preparation of 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, selected from the group consisting of fragrances,

Flavorings and / or essential oils in the form of pure substances, mixtures, solutions and / or suspensions, in which the at least one active substance is mixed during an extrusion process with the at least one raw material containing at least one thermoplastic elastomer and / or the raw material prior to the extrusion process is swollen with the at least one active ingredient in the case of an active ingredient liquid under normal conditions or premixed in the case of a solid under normal conditions active substance,

The processing temperature during the extrusion process is below the softening point of the raw material used, ie, the processing temperature during the extrusion process is below the softening point of the raw material used.

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 ge ^¬ indicates 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% by weight, 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 before the

Extrusion process of the raw material with the at least one active ingredient is swollen in the case of a liquid under normal conditions active ingredient or premixed in the case of a solid under normal conditions with the active ingredient and the resulting swollen or premixed raw material is fed to the extrusion process. Method according to the preceding claim, characterized in that preferably contained in the sources or Vormi ^¬ rule with respect to 100 wt .-% of the raw material between 10 and 300 wt .-%, preferably between 10 and 100 wt .-%, more between 20 and 70. %, 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 during the swelling or Vormischvorgangs and the extrusion process add the amount added 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 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 selected from the group consisting of fragrances, flavors, care agents and / or essential oils in the form of pure substances, mixtures, solutions and / Suspensions in the TPE compound is present mixed.

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 shaping process is selected from the group consisting of injection molding, film extrusion, profile extrusion, and / or extrusion processions.

16. molding, producible by a process according to any one of claims 13 to 15, preferably with a content of at least one active ingredient between 0.5% and 10% wt .-%, more preferably between 0.5% and 5% by weight. %, more preferably between 0.5% and 3% by weight.

17. Use of the masterbatch according to claim 12 for the scenting and / or incorporation of care substances in hygiene articles, in particular toothbrushes, cartridges for razors, diapers, as an aroma batch for dental care articles or toothbrushes with flavorings, as a care substance batch for cartridges for razors and / or as lubricants. Stoffbatch for cartridges for razors.