WO2005078015A1

WO2005078015A1 - Granular stabiliser compositions for polymers containing halogen and their production

Info

Publication number: WO2005078015A1
Application number: PCT/EP2005/001091
Authority: WO
Inventors: Ansgar Luttermann; Valentin Ausserbauer
Original assignee: Baerlocher Gmbh
Priority date: 2004-02-16
Filing date: 2005-02-03
Publication date: 2005-08-25
Also published as: DE102004007429B4; DE102004007429A1

Abstract

The invention relates to granular stabiliser compositions for polymers containing halogen, in particular polyvinyl chloride (PVC), in addition to a method for producing said compositions. According to said method, non-fusible stabiliser constituents are heated, a fusible granulation component is then added and the mixture is subsequently granulated.

Description

Granular stabilizer compositions for halogen-containing polymers and their production

The present invention relates to granular stabilizer compositions for halogen-containing polymers, in particular polyvinyl chloride (PVC), and to a process for their production in which non-meltable stabilizer components are heated and then mixed with a lower-melting granulation component and granulated. As is known, halogen-containing plastics tend to undergo undesired decomposition and degradation reactions when subjected to thermal stress during processing or in long-term use. When halogenated polymers are broken down, in particular when PVC is broken down, hydrochloric acid is formed, which is eliminated from the polymer strand, which results in a discolored, unsaturated plastic with coloring polyene sequences.

It is particularly problematic that halogen-containing polymers only have the theological framework necessary for processing at a relatively high processing temperature. At such temperatures, however, a noticeable decomposition of the polymer already begins in the case of unstabilized polymers, which leads both to the undesired color change described above and to a change in the material properties. In addition, the hydrochloric acid released from unstabilized, halogen-containing polymers at such a processing temperature can lead to noticeable corrosion of the processing plants. This process plays a role in particular if, during the processing of such halogenated polymers to give shaped articles, for example by extrusion, production is interrupted and the polymer mass remains in the extruder for a longer period of time. During this time, the above called decomposition reactions occur, which makes the batch in the extruder unusable and the extruder may be damaged.

Furthermore, polymers which are subject to such decomposition tend to form attachments to the processing plants which are difficult to remove.

In order to avoid this, halogen-containing polymers for processing are usually added as so-called stabilizers, which are intended to prevent the above-mentioned decomposition reactions as far as possible. As a rule, such stabilizers are solids which are added to the polymer to be processed before it is processed.

Corresponding stabilizer-containing compositions are usually mixed into the plastics in powder form, which, for example, are likewise in powder form or as very fine-grained granules.

However, powdered stabilizer compositions have a number of serious disadvantages. Stabilizer compositions sometimes contain harmful components that should not be inhaled. For this reason, special health and safety measures must be taken when processing such powdered stabilizer compositions in many countries. For this reason, fully encapsulated systems are often used in the processing of powdered stabilizer compositions, which enables largely dust-free processing of the powdered stabilizer composition from delivery to the finished mixture of plastic and stabilizer composition and beyond. However, the investments are both in terms of acquisition costs also very complex with regard to ongoing maintenance, which has a disadvantageous effect on the economy of plastics equipped with appropriate stabilizers. For these reasons, various proposals are made in the prior art to assemble stabilizer compositions by granulation in order to avoid the disadvantages mentioned above.

WO87 / 00543 AI describes a process for the preparation of additives for plastics and a resultant additive in granular form. According to the document, a wax in the molten state is added to the remaining constituents of the stabilizer composition in a high-speed mixer in several stages. When the first fraction of the wax is added, the individual powder particles are given a thin coating with the wax. When the further fractions of the wax are added, the particles coated with wax are aggregated. The granules obtained therefore consist entirely of the wax mentioned, for. B. glycerin monostearate, in which the other particles are embedded as in a matrix. It is therefore necessary in the production of these granules that the binder is added in the molten state, that is to say at a temperature above the melting temperature.

DE OS 2031445 describes a process for the granulation of auxiliaries for the stabilization of halogen-containing vinyl polymers. Molten binder is added to the other components to produce the granules.

WO 00/63284 relates to dust-free stabilizer compositions for plastics and processes for their production. The stabilization described The gate composition consists of granules, each granule consisting of several particles of the stabilizer composition and encased in a binder which contains the lowest melting component of the stabilizer composition. To produce the stabilizer compositions described, a mixture of all the compounds provided in the stabilizer composition is heated in a suitable mixer until the mixture is agglomerated. However, according to the publication, the agglomerates obtained are often sticky due to their high energy content and the associated static charge.

DE 100 51 739 A1 relates to granular stabilizer compositions whose agglomerate grains consist of several particles of the stabilizer composition and are completely covered by a layer of a binder. The binder contains the lowest melting component of the stabilizer composition. However, the inside of the agglomerate grain is free of this binder and contains the above-mentioned particles in a flowable form.

The fact that the energy consumption for the described processes is often greater than is necessary to achieve the actual purpose, namely the production of the granules, often has problems with the above-mentioned processes. In addition, the methods known from the prior art often have problems with the granulate yield. Due to the high energy input, the granulate size can only be regulated unsatisfactorily, which can lead to a large number of oversized granules. These granules, which can reach a diameter of up to several cm, must then be comminuted again by suitable devices, ie after the actual granulation. Thereby there are usually fine parts that have to be separated and fed back into the granulation process. In addition, due to the high energy content, the granules tend to cake long after the granulation process.

In particular, however, the processes known from the prior art often lead to granules which have an uneven distribution of the ingredients. However, when used to stabilize halogen-containing plastics, such granules can lead to local problems due to uneven distribution of the stabilizer. Particularly noteworthy here are locally occurring discolorations which, for example, occur immediately after processing due to the different distribution of the constituents of the stabilizer, but possibly only after prolonged thermal stress or weathering of a molded article made from such a plastic. Not only is the homogeneous distribution of those substances important, which contributes to a direct stabilization against the effects of heat or high-energy radiation. Also of importance is the distribution of ingredients that, for example, influence certain properties (such as rheology) during processing. If these properties fluctuate, for example, when processing halogen-containing plastics in an extruder, discolouration can occur despite a sufficient amount of compounds stabilizing against the action of heat or high-energy radiation, which discolouration occurs, for example, due to fluctuations in the rheology of the plastic to be processed.

The present invention is based on the object of providing a granular stabilizer composition for halogen-containing plastics, in particular for PVC, which does not have the disadvantages of the stabilizer compositions known from the prior art. Beispiels- wise, a granular stabilizer composition for plastics, in particular for halogen-containing plastics such as PVC, is to be made available, which has an even distribution of the ingredients as possible. Furthermore, a granular stabilizer composition is to be made available which, in particular, enables a particle size distribution that is as uniform as possible without or largely without regrinding of the granules. In addition, a process for the production of granules is to be made available which enables rapid granulation and preferably has a lower proportion of clumped material.

The above-mentioned objects are achieved by stabilizer compositions and processes for their production, as are described in more detail in the context of the text below.

The term agglomerate is used synonymously with the term granules in the context of the present text. Accordingly, the terms agglomeration and granulation are synonymous, as are the terms agglomerator and granulator.

The present invention therefore relates to a granular stabilizer composition for halogen-containing plastics, obtainable by heating at least one first stabilizer component in a reactor to a first process temperature below the melting point of the at least one first stabilizer component and then adding at least one granulating component, the granulating component being a softening agent. or melting point below the first process temperature, and then the mixture is granulated with constant agitation to obtain granules. In the context of the present invention, a “stabilizer composition” is understood to mean a composition which can be used to stabilize halogen-containing polymers. To achieve this stabilization effect, a stabilizer composition according to the invention is generally mixed with a halogen-containing polymer provided for stabilization and then processed. However, it is also possible to add a stabilizer composition according to the invention to the halogen-containing polymer to be stabilized during processing.

A stabilizer composition according to the invention can be obtained within the scope of the present invention by the targeted mixing of at least two different compounds under suitable conditions. In the context of the present text, at least one component is referred to as a “stabilizer component”, while at least a second component is referred to as a “granulating component”. However, it should be emphasized that this does not necessarily mean that the “stabilizer component” has an exclusively or partially stabilizing effect or that the “granulating component” has no stabilizing effect. Rather, the term "stabilizer component" is used in the context of the present text to designate those constituents of the stabilizer composition which do not melt at the temperature selected in the course of adding the "granulating component". Accordingly, the term "granulating component" is used to denote those constituents of the stabilizer compositions which melt at the temperature selected in the course of adding the "granulating component". Both the "stabilizer component" and the "granulating component" can therefore contain constituents which serve to stabilize a corresponding plastic, in particular a halogen-containing plastic. However, it is also possible that the "stabilizer component" or the "granulating component" according to the present text do not contain such components. Overall, in order to achieve a stabilizing effect, the stabilizer composition naturally contains at least one component which serves to stabilize plastics, in particular halogen-containing plastics.

In the context of the present invention, a granular stabilizer composition according to the invention for halogen-containing plastics is by heating at least one first stabilizer component in a reactor to a first process temperature below the melting point of the at least one stabilizer component and then adding at least one granulating component, the granulating component having a softening or melting point has below the first process temperature, and then the mixture is granulated with constant agitation to obtain granules.

In the context of the present invention, a “softening point” is understood to mean a temperature at which the granulation component is in a state which allows the production of a granulate according to the invention in the process according to the invention.

The first stabilizer component used in the context of the present invention is at least one compound whose melting point is above about 60 ° C., but preferably above at least about 70, 80, 90 or 100 ° C. It can also be provided according to the invention to use as the first stabilizer component a compound whose melting point is above about 110, 120 or, for example, above about 130 or 140 ° C. or above. If, for example, a basically fusible organic compound is used as the first stabilizer component, the melting point of this compound will generally be above about 80 ° C. If an inorganic compound is used as the first stabilizer component, its melting point will generally be significantly above the melting point specified for the organic component.

In principle, it is possible according to the invention that only one connection is used as the stabilizer component. However, it is also provided according to the invention that a mixture of two or more compounds is used as the stabilizer component. It can be a mixture of exclusively inorganic compounds or a mixture of exclusively organic compounds. However, it is also possible within the scope of the present invention and possibly even advantageous with regard to stabilizing effects if a mixture of organic compounds and inorganic compounds is used as the stabilizer component. The number of individual compounds in such a mixture can be between two and an essentially arbitrary high number, for example about 100. Often the number of compounds present in the stabilizer component ranges from about 3 to about 15, for example about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

The stabilizer component can in principle be used in any form within the scope of the present invention. However, in order to achieve a granulate that is as homogeneous as possible, it is advantageous if the stabilizer component is used in powder form. In principle, powders with an essentially arbitrary particle size and an essentially arbitrary particle size distribution can be used. In the context of the present invention, however, it has proven to be advantageous if compounds are used as a constituent of the stabilizer component whose average particle size d50 is in a range from about 0.1 to about 1000 μm, in particular approximately 0.5 to approximately 800 μm or approximately 1 to approximately 50 μm, can be used.

The determination of the particle size and the distribution of the particle sizes can be carried out by all methods known to the person skilled in the art. For example, screening processes, light microscopy, electron microscopy, scanning electron microscopy, light scattering, laser diffraction, X-ray diffractometry and the like are suitable. Particle sizes, as specified in the context of the present text, are preferably determined by sieving methods or by laser diffraction methods.

In the context of the present invention, at least one compound is used as the granulation component, the melting point of which is below the melting point of the stabilizer component. At least one compound is preferably used, the melting point of which is below approximately 130 ° C., in particular below approximately 120 ° C. or below approximately 110 ° C. Particularly suitable granulation components have, for example, a melting point of at least about 40 to at least about 120 ° C., for example about 50 to about 110 ° C.

In principle, it is possible according to the invention that only one compound is used as the granulation component. However, it is also provided in the context of the present invention that a mixture of two or more compounds is used as the granulation component. The number of individual compounds in such a mixture can be between 1 and an essentially arbitrarily high number, for example about 100. The number of compounds present in the granulation component often ranges from 1 to about 10, for example about 2, 3, 4, 5, 6, 7, 8 or 9. If a mixture of two or more compounds is used as the granulation component, one or more of these compounds can have, for example, a melting point which is above the temperatures mentioned above for the constituents of the granulation component. In such cases, it is advantageous if such a component, in particular a component whose melting point is above the temperature at which the granulation component is added to the stabilizer component, together with the other components present in the granulation component, has a melting point which is below the melting point the corresponding pure connection. In exceptional cases it may be possible for a granulation component to contain a compound which does not melt at the temperature prevailing when the granulation component is added to the stabilizer component. In such cases, however, it is advantageous if this compound has a particularly fine and uniform distribution within the granulation component.

The mixing of the stabilizer component and the granulation component can in principle be carried out in any manner. To achieve the advantage according to the invention, however, it is expedient if the mixing is carried out in an apparatus which ensures thorough mixing of the stabilizer component and the granulation component.

Mixers known to those skilled in the art, such as vertical heating / cooling mixers, are suitable. A “heating-cooling mixer” is understood to mean a mixer in which one part can be heated and another part can be cooled. Mixers with wall-mounted scrapers or mixers with floor scrapers or mixers with a combination of both tools can be advantageous. So-called drain mixers, for example, are particularly suitable in the present case. It is a ploughshare mixer that has a hydraulically operated, horizontally installed shaft. The mixer can preferably be heated and cooled via a jacket.

While the stabilizer compositions according to the invention can in principle be obtained with the aid of such a mixing apparatus, it has proven to be advantageous in the context of the present invention if the granules can be subjected to a first grinding 2 during or immediately after the granulation, if appropriate still in a warm state. For this purpose, for example, the integration of comminution elements, for example grinding elements, in particular knife mills, into the mixing apparatus has proven to be advantageous. In the context of a preferred embodiment of the present invention, a mixing apparatus used to produce the stabilizer compositions according to the invention therefore has one or more comminution devices, for example knife mills. These comminution devices are preferably located in the area of the removal of the granulate.

It has furthermore proven to be advantageous if the still warm, granulated and optionally additionally comminuted material is cooled in a separate reactor, preferably with movement of the granulate. Vertical or preferably horizontal cooling mixers, for example ploughshare mixers, are particularly suitable for this purpose, and if appropriate with the aid of cooling water they dissipate heat from the granulate in a suitable manner.

After the granulate has been cooled to a suitable temperature, a further comminution step can follow if necessary. For the appropriate size reduction of the granulate suitable crushers and mills can be used. It is also possible within the scope of the present invention to recycle fine particles formed during comminution, provided that such fine particles arise at all. For this purpose, for example, a processing step can be carried out in the process in which the fine fractions are separated off by suitable processes, for example by a sieve treatment. The fine particles can be returned to the process either as part of the stabilizer component or as part of the granulating component. It must be ensured that the fine fractions in the stabilizer component do not lead to an adverse change in the granulation behavior, in particular not to premature caking of the powdery stabilizer component.

To carry out the method described according to the invention, the stabilizer component composed of one or more compounds is first transferred in powder form to a suitable heatable mixer. The mixer can already be preheated in the context of the present invention. However, it is also possible for the mixer to be heated only during or after the addition of the stabilizer component. The stabilizer component is then heated to a suitable temperature. In principle, any temperature is suitable as “suitable temperature” in the context of the present invention, provided that the granulation component changes its aggregate state at this temperature after addition in such a way that granules with the properties improved according to the invention are produced. However, it has proven to be particularly practical if the stabilizer component is heated to a temperature of at least about 50, but preferably at least about 60 ° C. In the context of a preferred embodiment of the present invention, the stabilizer component is heated to a temperature which corresponds approximately to the softening or melting temperature of the granulating component. It is possible according to the invention to heat the stabilizer component in such a way that the temperature of the stabilizer component before the addition of the granulating component lies within a temperature range which is from approximately 30 ° C. below or the melting temperature of the lowest melting component of the granulating component to approximately 20 ° C. extends above the melting temperature of the lowest melting component of the granulating component. If the constituents of the granulating component form a eutectic which has a lower melting point than the respective melting points of the constituents of the granulating component, it is preferred that the stabilizer component is heated in such a way that the temperature of the stabilizer component before the addition of the granulating component lies within a temperature corridor which extends from about 30 ° C below the melting temperature of the eutectic to about 20 ° C above the melting temperature of the eutectic.

It is not absolutely necessary in the context of the present invention that the granulation component is exposed to a temperature at which it is in the molten state. It may also be sufficient for the granulating component to be in a plastically softened state sufficient to granulate the stabilizer component in accordance with the object of the invention. This form of granulation according to the invention can be particularly successful if a composition without a sharply defined melting point is used as the granulation component. Such compositions arise, for example, when waxes are used as a component of the granulating component, which consist of several different compounds with different molecular weights. such Waxes often do not have a sharply defined melting point. The behavior of such waxes when heated frequently runs through a softening phase into a melting phase, with viscosities which are sufficient for granulation according to the present invention being able to be established during the softening phase.

In the course of a granulation process according to the invention which leads to the stabilizer compositions according to the invention, at least one stabilizer component is placed in a correspondingly suitable mixer and, preferably with agitation, heated to a suitable temperature, as stated above. If a stabilizer component according to the invention consists of two or more compounds, the individual compounds can be added simultaneously or in succession. If appropriate, it can be advantageous to assemble certain constituents of a mixture forming the stabilizer component accordingly by mixing before addition to the mixer. In most cases, however, it is sufficient to feed the constituents of the stabilizer component to the mixer at the same time or in succession.

In principle, the stabilizer component in the mixer can be heated in any manner. However, heat is advantageously transferred from the wall of the mixer to the stabilizer component. Mixers are accordingly suitable for carrying out the method described according to the invention, which ensure a sufficiently good mixing of the material to be mixed even at relatively low speeds, for example at a speed of about 30 to about 150, in particular at about 50 to about 100 rpm. In the context of the present invention, the granulation component can be added essentially in any manner. However, it has proven to be advantageous if the pelletizing component is fed to the stabilizer component in the mixer in a comminuted, in particular powdered, state. The particle size can vary within wide limits. For example, particles with a size of approximately 10 to approximately 10,000 μm are suitable, in particular with an average particle size d50 of approximately 20 to approximately 5000 or approximately 30 to approximately 3000 μm.

It has also proven to be advantageous if, after the addition of the granulating component, the external heat supply to the mixer is switched off. In the context of a preferred embodiment of the present invention, the heating of the mixing apparatus is therefore switched off before the granulation component is added or during the addition of the granulation component. It is also possible to cool the mixing unit slightly before or during the addition of the granulation component, so that no more heat transfer takes place from the wall of the mixer to the mixture of stabilizer component and granulation component, which results in the mixture being heated above the temperature already reached leads out.

As a rule, the granulation of the mixture begins within a short time after the addition of the granulation component, for example within a period of about 1 to about 60 minutes. Granulation is often associated with a reduction in the volume of the mixture.

The granulation is then continued until a granulate of the desired appearance and size is obtained. If necessary, for example if the granulate has an average that is outside the desired range due to the unfavorable properties of the granulation component If the particle size is large, the granules can be comminuted during the granulation by knife mills present in the mixer. A corresponding comminution can, however, also take place, for example, only during or after the granulate has been removed from the mixer.

The granulate can be cooled to a desired temperature in the mixer even after the external heat supply has been switched off. However, it is also provided within the scope of the present invention and has proven to be advantageous if the granules are removed from the mixer while still warm and transferred to a cooling mixer, that is to say the granules are cooled while moving outside the reactor after the granulation. As part of this transfer, shredding can take place, if desired. The granulate is then cooled to a desired temperature in an appropriate cooling mixer.

After the granulate has cooled, it can be filled, for example, directly or after an appropriate intermediate storage in conventional containers, in particular in so-called big bags. If necessary, the material can be further sized before such a backfilling, if the material makes this necessary, the granules being comminuted to the desired size.

The proportion of stabilizer component and of granulating component in a stabilizer composition according to the invention can vary within wide limits and depends on the desired properties of the stabilizer compositions. The granulation component preferably has a proportion of 0.1 to 70% by weight, for example from 0.5 to about 60 or from 1 up to about 50 or from about 2 to about 40% by weight of the stabilizer composition.

In the context of the present invention, the granulation component is added at a temperature which permits the formation of granules with the desired properties. According to the invention, the temperature should be at least 60 ° C and not exceed about 140 ° C. Temperatures of approximately 65 to approximately 130 or approximately 70 to approximately 125 or approximately 75 to approximately 120 or approximately 80 to approximately 115 or approximately 85 to approximately 110 or approximately 90 to approximately 105 or approximately 95 to approximately 100 ° C. are particularly suitable , The temperature data relate to the temperature of the stabilizer compositions. The temperature of the reactor wall can optionally have a value which deviates from the temperature of the stabilizer component.

The length of time during which the mixture of stabilizer component and granulating component is moved in the mixer depends to a large extent on the properties of the compounds involved in the individual components. Basically, it can be said that the person skilled in the art can recognize a suitable point in time for stopping the granulation process from the appearance of the granulate in the mixer. Usually after the addition of the granulating component, granulation takes place for a period of about 5 minutes to about 2 hours, in particular for a period of about 10 minutes to about 1 hour.

In the context of the present invention, all compounds which can be used in stabilizer compositions for stabilizing plastics, in particular for stabilizing halogen-containing plastics, and are successfully used as constituents of the process according to the invention are basically suitable as stabilizer components Stabilizer components can be used. These include, in particular, compounds which, at a temperature at which the granulation component is added, do not show any change in properties, which negatively or more than avoidably negatively affects the success of a particularly uniform distribution of the ingredients and the maintenance of granules with excellent stabilizing properties ,

The method described according to the invention shows the person skilled in the art a generally and fundamentally applicable way of obtaining granules which have a particularly uniform distribution of the ingredients. It is in the nature of the matter that the description of such a method can in principle only actually and in detail describe a limited number of method variants. The following list of substances is therefore only intended to provide a general overview of the large number of constituents that can be used as ingredients in the stabilizer component or granulating component.

In principle, the stabilizer compositions according to the invention are suitable for stabilizing any plastics, but they are preferably used for stabilizing plastics which contain at least some halogen-containing plastics. Particularly suitable and preferred within the scope of the present invention is the use of the granules according to the invention for stabilizing plastics which contain a proportion of polyvinyl chloride (PVC). The corresponding granules can be used, for example, to stabilize hard PVC or soft PVC, in particular for stabilizing wire sheaths, automotive components, for example automotive components such as are used in the interior of the automobile, in the engine compartment or on the exterior surfaces, cable insulation, decorative foils, agricultural foils , Hoses, sealing profiles, office foils, hollow bodies (bottles), packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (window frames), light wall profi les, building profiles, sidings, fittings, plates, foam plates, gutters, co-extrudates with recycled core or housings for electrical equipment or machines, e.g. computers or Domestic appliances.

Already from this list, which is only given by way of example, it follows that a granulate according to the invention which can be used for stabilizing halogen-containing plastics can contain a large number of ingredients which can vary depending on the use of the stabilizer composition. In principle, within the scope of the method described according to the invention, the stabilizer component can contain any ingredient required for the production of such a stabilizer composition, provided that the method according to the invention for its production is no longer adversely affected as tolerably, that is, provided the advantages according to the invention, in particular the advantage of a particular one Even distribution of the ingredients is guaranteed.

A stabilizer composition according to the invention can contain, for example, at least one lead compound.

In the context of the present invention, all organic or inorganic substances which contain lead in ionic or coordinated or metallic form are suitable as lead compounds. For example, basic lead salts of inorganic acids such as three-base lead sulfate, four-base lead sulfate, two-base lead phosphite or two-base lead phosphite sulfite or lead carbonate (lead white), lead salts of linear or branched, saturated or unsaturated, aliphatic or cycloaliphatic or aromatic mono-organic or aromatic are particularly suitable. or polycarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9 , 10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid , Ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, sorbic acid, divergent carboxylic acids or their monoesters such as oxalic acid, malonic acid, maleic acid, fumaric acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salic acid, salic acid Polyglycol dicarboxylic acids with a degree of polymerization of about 10 to about 12, phthalic acid, isophthalic acid, Terephthalic acid or hydroxyphthalic acid, tri- or tetravalent carboxylic acids or their mono-, di- or triesters such as hemimellitic acid, trimellitic acid, pyromellitic acid or citric acid, or dimerized or trimerized linoleic acid, acrylic acid, methacrylic acid and the mono mentioned in the further course of this text - or polycarboxylic acids. Also suitable are cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid or 4-methylhexahydrophthalic acid. Neutral or basic lead stearate, lead white, 3 or 4-base lead sulfate, 2-base lead phosphite, 2-base lead phthalate or 4-base lead foamate are particularly suitable.

Also suitable as lead compounds are lead compounds as can be obtained by reacting lead oxide with organic hydroxycarboxylic acids such as dimethyl propionic acid. Such compounds and their preparation are described for example in EP 0 313 113, the disclosures ranked this document with regard to lead compounds, as can be obtained by reacting lead oxide with organic hydroxycarboxylic acids, as part of the disclosure of the present text. A stabilizer composition according to the invention can contain, for example, only a lead compound. However, it is also possible and provided according to the invention that a stabilizer composition according to the invention contains a mixture of two or more lead compounds. However, it is possible, for example, for one or more lead compounds to be inorganic and one or more lead compounds to be organic. However, it is also possible that only a mixture of inorganic lead compounds or a mixture of organic lead compounds is used. In the context of a preferred embodiment of the present invention, a stabilizer composition according to the invention contains a mixture of two or more, for example a mixture of 2, 3, 4 or 5 different lead compounds. In the context of a further embodiment of the present invention, a stabilizer composition according to the invention contains a mixture of one, two or three inorganic lead compounds and one, two or three organic lead compounds. In the context of a further embodiment of the present invention, a stabilizer composition according to the invention contains a mixture of lead phosphite or sulfate or a mixture thereof and at least one organic lead compound, in particular a lead salt of an organic carboxylic acid.

The content of lead compounds in a stabilizer composition according to the invention, always based on the total stabilizer composition, can be, for example, at least about 5% by weight. In the context of a preferred embodiment of the present invention, the content of a stabilizer composition according to the invention is one or more Lead compounds, for example, about 10 to about 95% by weight. A composition according to the invention can, for example, also have lead compound contents within these limits, for example about 20 to about 90% by weight or about 30 to about 75% by weight or essentially any values in between, provided that the corresponding lead contents are one effect sufficient stabilization.

If a stabilizer composition according to the invention contains inorganic and organic lead compounds, the weight ratio of inorganic to organic lead compounds is preferably about 100: 1 to about 1: 100.

In addition to a lead compound or a mixture of two or more lead compounds, as described, for example, above, a stabilizer composition according to the invention can also contain at least one salt of a halogen-containing oxy acid or a mixture of two or more salts of a halogen-containing oxy acid or a mixture of two or more salts contain various halogen-containing oxyacids.

Salts of halogen-containing oxyacids, in particular the perchlorates, are suitable as at least one further compound. Examples of suitable perchlorates are those of the general formula M (ClO ₄ ) _n , where M represents Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. The index n stands for the number 1, 2 or 3 depending on the valency of M. The perchlorate salts mentioned can be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The polyol partial esters are also to be counted among the ester alcohols. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and also di-, tri- and Tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization and saponification. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial esters. Sugar alcohols are also suitable. The perchlorate salts can be used in various common forms of administration, for example as a salt or aqueous solution applied to a suitable carrier material such as PVC, calcium silicate, zeolites or hydrotalcites or incorporated into a hydrotalcite by chemical reaction. A combination of Na perchlorate and calcium silicate which is suitable as a constituent of the stabilizer composition according to the invention can be carried out, for example, by combining an aqueous solution of Na perchlorate (content of Na perchlorate about 60% or more) with calcium silicate, for example a synthetic, amorphous calcium silicate , Suitable particle sizes for the calcium silicate that can be used are, for example, about 0.1 to about 50, for example about 1 to about 20 μm. Suitable perchlorate-containing dosage forms are described, for example, in US Pat. No. 5,034,443, the disclosure of which perchlorate-containing dosage forms is expressly referred to and which disclosure is regarded as part of the disclosure of the present text.

Further suitable dosage forms are mentioned, for example, in EP-A 394,547, EP-A 457,471 and WO 94/24200, to the disclosure of which suitable dosage forms are expressly referred, and which disclosure is regarded as part of the disclosure of the present text ,

In addition to the inorganic salts of halogen-containing oxyacids described above, a stabilizer composition according to the invention can also be contain ganic onium salts of halogen-containing oxyacids. Onium salts of halogen-containing oxyacids, as described in WO 03/082974 AI, are particularly suitable. Reference is expressly made to the latter publication. The disclosure of the latter publication is considered part of the disclosure of the present application.

A stabilizer composition according to the invention can also contain inorganic bases. The inorganic bases are solid compounds such as the hydroxides of the elements of the first and second main groups of the periodic table and the hydroxides of the elements of the first subgroup of the periodic table. Magnesium hydroxide, calcium hydroxide, barium hydroxide or strontium hydroxide are particularly suitable.

The content of corresponding compounds in a composition according to the invention, provided such compounds are present in a stabilizer composition according to the invention, is, for example, about 0.1 to about 40% by weight.

Epoxy compounds are also suitable as constituents of a granular stabilizer composition according to the invention. Examples of such epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized cottonseed oil and glycidyl compounds.

Glycidyl compounds contain a glycidyl group attached directly to a carbon, oxygen, nitrogen or sulfur atom. Glycidyl or methyl glycidyl esters can be obtained by reacting a compound with at least one carboxyl group in the molecule and epichlorohydrin or glycerol chlorohydrin or methyl-epichlorohydrin available. The reaction is conveniently carried out in the presence of bases.

Particularly suitable epoxy compounds are described, for example, in EP-A 1 046 668 on pages 3 to 5, reference being expressly made to the disclosure contained therein, which is considered to be part of the disclosure of the present text.

Also suitable as constituents of a composition according to the invention are 1,3-dicarbonyl compounds, in particular the β-diketones and β-keto esters. Suitable for the purposes of the present invention are dicarbonyl compounds of the general formula RC (0) CHR -C (O) R, as described, for example, on page 5 of EP-1 046 668, to which, in particular with regard to the radicals R ', R "and R'" is expressly referred to and the disclosure of which is considered to be part of the disclosure of the present text.

Polyols are also suitable as constituents in the context of a stabilizer composition according to the invention. Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose, leucrose, methylamine, trichlorohexylurol (trichloroethyl) isocyanate, trichloro-cyclo-methylamine , Tetramethylolcyclopentanol, tetramethylolcycloheptanol, glycerin, diglycerin, polyglycerol, thiodiglycerol or α-D-glycopyranosyl-D-mannitol dihydrate.

The polyols suitable as additives can be contained in an inventive stabilizer composition in an amount of up to about 30% by weight, for example up to about 10% by weight. Also suitable as constituents are, for example, sterically hindered amines as mentioned on pages 7 to 27 in EP-A 1 046 668. Reference is expressly made to the sterically hindered amines disclosed therein, the compounds mentioned there are considered to be part of the disclosure of the present text.

The sterically hindered amines suitable as additives can be present in an inventive stabilizer composition in an amount of up to about 30% by weight, for example up to about 10% by weight.

For example, heterocyclic amino alcohols can be used which have at least 2, preferably at least 3 amino groups in the ring. The trimerization products of isocyanates are particularly suitable as the central ring component of the amino alcohols which can be used according to the invention.

Hydroxyl group-containing isocyanurates of the general formula I are particularly suitable

CHYOH (CH ₂ ) _m

wherein the groups Y and the indices m are each the same or different and m is an integer from 0 to 20 and Y is a hydrogen atom or a linear or branched, saturated or unsaturated alkyl group having 1 to about 10 carbon atoms. Is particularly preferred in the context of the present Invention the use of tris (hydroxymethyl) isocyanurate (THEIC) as part of the stabilizer compositions according to the invention.

Also suitable as constituents in the stabilizer compositions according to the invention are hydrotalcites, zeolites and alkali alumocarbonates. Suitable hydrotalcites, zeolites and alkali alumocarbonates are, for example, in EP-A 1 046 668 on pages 27 to 29, EP-A 256 872 on pages 3, 5 and 7, and DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 on page 2 and 3. Reference is expressly made to these publications and their disclosure at the specified points is regarded as part of the disclosure of the present text.

The hydrotalcites, zeolites and alkali alumocarbonates suitable as additives can be contained in an inventive stabilizer composition in an amount of up to about 50% by weight, for example up to about 30% by weight.

Also suitable as constituents in the context of the stabilizer compositions according to the invention are, for example, hydrocalumites of the general formula II

wherein M stands for calcium, magnesium or zinc or mixtures of two or more thereof, A for a k-valued inorganic or organic acid anion, k for 1, 2 or 3, B for a different inorganic or organic acid anion, n for one is an integer> 1 and, if n is> 1, indicates the degree of polymerization of the acid anion and 1 represents 1, 2, 3 or 4 and indicates the valency of the acid anion, where n = 1 1 represents 2, 3 or 4 and for n> 1 1 indicates the valency of the individual monomer units of the polyanion and stands for 1, 2, 3 or 4 and nl indicates the valency of the polyanion and the following rules for the parameters x, y, a, b, n, z, and k apply: 0 <x <0.6, 0 <y <0.4, where either x = 0 or y = 0, 0 <a <0.8 / n and z = l + 2x + 3y-ka-n / b.

In a preferred embodiment of the present invention, compounds of the general formula II are used as additives, in which M stands for calcium, which may optionally be present in a mixture with magnesium or zinc or magnesium and zinc.

In the general formula II, A stands for a k-value inorganic or organic acid anion, where k stands for 1, 2 or 3. Examples of acid anions present in the context of hydrocalumites which can be used according to the invention are halide ions, SO ₃ ² \ SO ₄ ² \ S ₂ O ₃ ^{2 "} , S ₂ O ₄ ^2" , HPO ₃ ^2_ , P0 ₄ ^{3 "} , CO ₃ ^2" , alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates, in which the alkyl groups can be the same or different, straight-chain, branched or cyclic and preferably have 1 to about 20 C atoms. Also as

Acid anions A are suitable, if appropriate the functionalized anions

Di-, tri- or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate,

Pyromellitate, maleate, tartrate, citrate and anions of the isomeric forms of

Hydroxyphthalic acid or hydroxymesic acid. In the context of a preferred embodiment of the present invention, A stands for an inorganic

Acid anions, in particular a halide ion, for example F ^" , Cl ^" or Br ^" , preferably for Cl ^" . In general formula II, B represents an acid anion that is different from A. In the event that in the general formula II n stands for the number 1, letter B stands for a 1-valent, inorganic or organic acid anion, where 1 stands for the number 2, 3 or 4. Examples of compounds of the general formula II which can be used according to the invention are, for example, O ^" , SO ₃ ^" , SO ₄ ^" , S ₂ O ₃ ^" , S ₂ θ ^" , HPO ₃ ^" , PO ^3" , CO ₃ ^{2 "} , alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates, in which the alkyl groups, the same or different, can be straight-chain or branched or cyclic and preferably have 1 to about 20 C atoms. Also suitable as acid anions A are the anions of optionally functionalized di-, tri- or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate, pyromellitate, maleate, tartrate, citrate and anions of the isomeric forms of hydroxyphthalic acid or hydroxymesic acid. In the context of the present invention, formula VII preferably denotes a borate or an anion of an optionally functionalized di-, tri or tetracarboxylic acid. Carboxylic acid anions and anions of hydroxycarboxylic acids with at least two carboxyl groups are particularly preferred, citrates being very particularly preferred.

Also suitable as constituents of the stabilizer compositions according to the invention are, in addition to the compounds already described above in the context of the inorganic bases, further metal oxides, metal hydroxides and metal soaps of saturated, unsaturated, straight-chain or branched, aromatic, cycloaliphatic or aliphatic carboxylic acids or hydroxycarboxylic acids, preferably with about 2 to about 22 carbon atoms.

As metal cations, the metal oxides, metal hydroxides or metal soaps suitable as additives preferably have a divalent cation, the cations of calcium or zinc or mixtures thereof are particularly suitable.

Examples of suitable carboxylic acid anions include anions of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, lauryl acid, palritic acid, Isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di- tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, sorbic acid, anions of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid , Malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol dicarboxylic acids with a Degree of polymerization from about 10 to about 12, phthalic acid, isophthalic acid, terephthalic acid or hydroxyphthalic acid, anions of tri- or tetravalent carboxylic acids or their mono-, di- or triesters such as those in hemimelithic acid, trimellitic acid, pyromellitic acid or citric acid and also so-called overbased carboxylates as described, for example, in DE-A 41 06 404 or DE-A 40 02 988, the disclosure of the latter documents being regarded as part of the disclosure of the present text.

A stabilizer composition according to the invention can furthermore contain an organotin compound or a mixture of two or more organotin compounds as a thermostabilizer component. In addition, the organotin compounds mentioned in EP-A 0 742 259 on pages 18 to 29 and described in their preparation can be used in the context of the stabilizer compositions according to the invention. Reference is expressly made to the above-mentioned disclosure, the compounds mentioned there and their preparation being understood as part of the disclosure of the present text.

A stabilizer composition according to the invention can contain the organotin compounds described in an amount of up to about 20% by weight, in particular up to about 10% by weight.

In the context of a further embodiment of the present invention, a stabilizer composition according to the invention can contain organic phosphite esters with 1 to 3 identical, pair-wise identical or different organic residues.

A stabilizer composition according to the invention can also contain fillers as described in the "Handbook of PVC Formulating", EJ Wickson, John Wiley & Sons, Inc., 1993, pages 393-449 or reinforcing agents as described in the "Taschenbuch der Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 1990, pages 549-615. Particularly suitable fillers or reinforcing agents are, for example, calcium carbonate (chalk), dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, carbon black or graphite, wood flour or other renewable raw materials. In the context of a preferred embodiment of the present invention, a stabilizer composition according to the invention contains chalk. A stabilizer composition according to the invention can also contain impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, flame retardants and antifogging compounds. Suitable compounds of these classes of compounds are described, for example, in "Kunststoff Additive", R. Kessler / H. Müller, Carl Hanser Verlag, 3rd edition, 1989 and in the "Handbook of PVC Formulating", EJ. Wilson, J. Wiley & Sons, 1993.

A stabilizer composition according to the invention can have a complex composition in the context of preferred embodiments of the present invention. Basically, the compounds already mentioned in the context of this text can essentially be used as part of the compositions according to the invention. A stabilizer composition according to the invention can therefore, for example, only contain compounds which are effective with regard to the initial color or the color stability. However, a stabilizer composition according to the invention can also contain further of the above-mentioned compounds, in particular additives, which influence the processability of halogen-containing plastics or the properties of moldings produced from such plastics.

A stabilizer composition according to the invention can contain, in particular, lubricants such as montan wax, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, oxidized polyethylene waxes, amide waxes, chlorinated paraffms, glycerol esters or alkaline earth metal soaps as a granulating component. Lubricants that can also be used are also described in "Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pp. 478-488. Also suitable as lubricants in the granulation component are, for example Fat ketones as described in DE 42 04 887 as well as silicone-based lubricants, as described for example in EP-A 0 259 783, or combinations thereof, as mentioned in EP-A 0 259 783. Reference is hereby expressly made to the documents mentioned, the disclosure of which relates to lubricants is considered to be part of the disclosure of the present text.

Also suitable are granulating components made from fatty acids with 8 to 24 carbon atoms, fatty alcohols with 12 to 24 carbon atoms, esters from fatty acids with 8 to 24 carbon atoms and fatty alcohols with 6 to 24 carbon atoms, esters from fatty acids with 8 contains up to 24 carbon atoms and polyhydric alcohols with 4 to 6 hydroxyl groups and hydroxystearic acid esters. The compounds mentioned can be used both individually and in a mixture with one another.

Both fatty and synthetic straight-chain saturated compounds of this class of substances can be considered as fatty acids with 8 to 24 carbon atoms. If fatty acid mixtures are used, they can contain minor amounts of unsaturated fatty acids, provided that the melting point of such mixtures is in any case above 25 ° C. Examples of fatty acids which can be used as softenable or meltable components are caprylic, capric, lauric, tridecane, myristic, pentadecanoic, palmitic, margaric, stearic, behenic and lignoceric acids. Fatty acids containing hydroxyl groups, such as 12-hydroxystearic acid, are also suitable here.

Such fatty acids can be obtained from naturally occurring fats and oils, for example via fat splitting at elevated temperature and pressure and subsequent separation of the fatty acid mixtures obtained. if necessary, hydrogenation of the double bonds present can be obtained. Technical fatty acids are preferably used here, which as a rule represent mixtures of different fatty acids of a certain chain length range with a fatty acid as the main constituent. Fatty acids with 12 to 18 carbon atoms, in particular stearic acid, are preferably used here.

Also suitable as constituents of the granulating components are the metal salts, for example the alkali metal or alkaline earth metal salts of the above-mentioned fatty acids and mixtures of two or more thereof. The Ca, Mg or zinc salts are particularly suitable.

The fatty alcohols with 12 to 24 carbon atoms which are suitable as granulating components are straight-chain saturated representatives of this class of substances which, without exception, have a melting point above 25 ° C. Corresponding fatty alcohols can u. a. can be obtained from naturally occurring fats and oils by transesterification with methanol, subsequent catalytic hydrogenation of the methyl esters obtained and fractional distillation. In addition, synthetic fatty alcohols, such as those obtained via oxo and Ziegler synthesis, can also be used. Examples of such fatty alcohols are lauryl, myristyl, cetyl, stearyl and behenyl alcohol. These compounds can be used individually and in a mixture with one another. Technical fatty alcohols are preferably used, which are normally mixtures of different fatty alcohols of a limited chain length range, in each of which a fatty alcohol is present as the main constituent. Fatty alcohols with 12 to 18 carbon atoms are preferably used here.

The above-mentioned esters from fatty acids with 8 to 24 C atoms and fatty alcohols with 6 to 24 C atoms should in turn meet the condition that their melting point is above 25 ° C. Suitable starting materials for the production of such fatty alcohol fatty acid esters are the fatty acids and fatty alcohols already described in detail above, and in such esters also fatty alcohols having 6 to 11 carbon atoms, for example n-hexanol, n-octanol and n-decanol , may be present as an alcohol component. Examples of esters which can be used according to the invention are stearyl caprylate, stearyl caprinate, cetyl laurate, cetyl myristrate, cetyl palmitate, n-hexanol stearate, n-octyl stearate, lauryl stearate, stearyl stearate, stearyl behenate, beh.enyl laurate and behenyl behenate. In addition, esters of fatty alcohols and aromatic mono- or dicarboxylic acids are suitable, for example distearyl phthalate.

The fatty acids already described above are again suitable as starting materials for the production of the above-mentioned esters from fatty acids with 8 to 24 carbon atoms and alcohols with 4 to 6 hydroxyl groups. Aliphatic polyols having 4 to 12 carbon atoms, for example erythritol, pentaerythritol, dipentaerythritol, ditrimethylolpropane, diglycerol, triglycerol, tetraglycerol, mannitol and sorbitol, are particularly suitable as alcohol components. These polyol esters can be full esters in which all the hydroxyl groups of the polyol are esterified with fatty acid. However, partial polyol esters which have one or more free hydroxyl groups in the molecule are also suitable. These fatty acid polyol esters can also be prepared by known methods of organic synthesis. Esterification of the polyols with stoichiometric or substoichiometric Ϊ narrow free fatty acids can be obtained. Examples of such polyol fatty acid esters are the full stearic acid and full stearic acid / palmitic acid esters of erythritol, pentaerythritol and diglycerol, the dilaurates of dipentaerythritol, ditrirnethylolpropane, triglycerol, mannitol and sorbitol, the distearates of erythritol, dipeteretrithritol, pentatrithritol, and pentatrithritol, and tereitrite so-called sesquiests of pentaerythritol, dipentaerythritol, mannitol and sorbitol, to theirs Production is used on 1 mol of polyol, 1.5 mol of fatty acid, especially palmitic and / or stearic acid. The polyol fatty acid esters mentioned are generally mixtures of substances, based on the starting materials used in each case.

A particular category of possible constituents of the granulating component in the context of the invention are the esters of hydroxystearic acid, since here compounds are considered in which the hydroxystearic acids are esterified via their carboxyl group with a mono- or polyhydric alcohol, as well as those in which they are esterified with their hydroxyl group with fatty acids. These are preferably derivatives of 12-hydroxystearic acid, which can be obtained, for example, from the fatty acid component of hydrogenated castor oil. The derivatives of the first-mentioned type include 12-hydroxystearic acid esters of the fatty alcohols described in detail above, as well as full and partial 12-hydroxystearic acid esters with polyols with 2 to 6 hydroxyl groups and 2 to 12 C atoms, in particular those which differ from ethylene glycol, 1,2- and 1,3-propylene glycol, the isomeric butylene glycols, 1,12-dodecanediol, glycerol, trimethylolpropane, erythritol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, diglycerol, triglycerol, tetraglycerol, mannitol and sorbitol. Examples of such esters are the 12-hydroxystearic acid full esters of ethylene glycol, 1,3-propylene glycol, erythritol and pentaerythritol, the di-12-hydroxystearates of pentaerythritol, dipentaerythritol, diglycerol, tetraglycerol and sorbitol as well as the 12-hydroxystearic acid estershritol, pentene erythritol Mannits. Hardened castor oil, which is known to be a triglyceride mixture with a fatty acid component consisting mainly of 12-hydroxystearic acid, is also regarded as a member of this group. The 12-hydroxystearic acid esters of the second type are esterification products of 12-hydroxystearic acid and fatty acids with 8 to 24 C- Atoms, the latter of which have already been described in more detail above. From this group of 12-hydroxystearic acid derivatives, the esterification product of 12-hydroxystearic acid and behenic acid is of particular importance because it has the characteristic property of dispersing the stabilizer composition in plastic melts so well that, when used, the usual amounts used for the other components of the stabilizer composition are considerably reduced can be. In addition, this esterification product at 60 ° C. has such a favorable melting point that the agglomerates according to the invention can be produced at correspondingly low temperatures. On the other hand, the melting point is high enough to enable the agglomerates to be stored without caking or exudation, even at summer temperatures.

The stabilizer compositions according to the invention are suitable for stabilizing halogen-containing polymers.

Examples of such halogen-containing polymers are polymers of vinyl chloride, vinyl resins which contain vinyl chloride units in the polymer backbone, copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid or acrylonitrile or mixtures of two or more thereof, copolymers of vinyl chloride with diene compounds or unsaturated dicarboxylic acids or their anhydrides, for example copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, such as ketones and other compounds Acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like, polymers and copolymers of the vinyl nylidene chloride with vinyl chloride and other polymerizable compounds, as already mentioned above, polymers of vinyl chloroacetate and dichlorodivinyl ether, chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and of α-substituted acrylic acids, chlorinated polystyrenes, for example polydichlorostyrene, chlorinated polymers of ethylene, polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride as well as mixtures of two or more of the said polymers or polymer mixtures which contain one or more of the above-mentioned polymers.

The graft polymers of PVC with EVA, ABS or MBS are also suitable for stabilization with the stabilizer compositions according to the invention. Preferred substrates for such graft copolymers are also the abovementioned homopolymers and copolymers, in particular mixtures of vinyl chloride homopolymers with other thermoplastic or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE; MBAS, PAA (polyalkyl), PAMA _(polyalkyl). EPDM, polyamides or polylactones.

Mixtures of halogenated and non-halogenated polymers, for example mixtures of the above-mentioned non-halogenated polymers with PVC, in particular mixtures of polyurethanes and PVC, are also suitable for stabilization with the stabilizer compositions according to the invention.

Furthermore, the stabilizer compositions according to the invention can also be used to stabilize recyclates of chlorine-containing polymers, in principle all recyclates of the above-mentioned halogenated polymers being suitable for this are. PVC recyclate, for example, is suitable in the context of the present invention.

The invention also relates to a method for producing a stabilizer composition for plastics, in particular for PVC, wherein at least one first stabilizer component in a reactor is heated to a first process temperature below the melting point of the at least one stabilizer component and then at least one granulating component is added, the granulating component has a melting point below the first process temperature, and then the mixture is granulated with constant agitation to obtain granules. Details of the granulation process according to the invention have already been explained above in the context of the present text.

The present invention also relates to a method for stabilizing halogen-containing polymers, in which a halogen-containing polymer or a mixture of two or more halogen-containing polymers or a mixture of one or more halogen-containing polymers and one or more halogen-free polymers is mixed with a stabilizer composition according to the invention becomes.

The mixing of polymers or polymers and the stabilizer composition according to the invention can in principle take place at any time before or during the processing of the polymer. For example, the stabilizer composition can be mixed with the polymer in powder or granule form before processing.

A polymer composition according to the invention can be brought into a desired shape in a known manner. Suitable methods are wise calendering, extrusion, injection molding, sintering, extrusion bubbles or the plastisol process. A polymer composition according to the invention can also be used, for example, for the production of foams. Basically, the polymer compositions according to the invention are suitable for the production of hard or soft PVC, as already mentioned above.

A polymer composition according to the invention can be processed into moldings. In the context of the present invention, the term “molded body” basically includes all three-dimensional structures that can be produced from a polymer composition according to the invention. In the context of the present invention, the term “shaped body” encompasses, for example, wire sheaths, automotive components, for example automotive components such as are used in the interior of the automobile, in the engine compartment or on the outer surfaces, cable insulation, decorative foils, agricultural foils, hoses, sealing profiles, office foils, hollow bodies (bottles) , Packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (window frames), light wall profiles, building profiles, sidings, fittings, plates, foam plates., Coextrudates with recycled core or housing for electrical equipment or machines, for example computers or household appliances. Further examples of moldings which can be produced from a polymer composition according to the invention are synthetic leather, floor coverings, textile coatings, wallpapers, coil coatings or underbody protection for motor vehicles.

Exemplary embodiments according to the invention and comparative examples are described in detail below. EXAMPLES l. Objective To prepare a recipe according to the prior art (WO 00/63284), example 1, “soft PVC cube formulation” as build-up granules and to produce a recipe according to the prior art (WO 00/63284), example 3, hard PVC sewer pipe recipe in accordance with the method described therein. Furthermore, the recipes are granulated with the aid of the method according to the invention. The products obtained are analyzed.

2. Execution of the experiment

The tests were carried out on a heatable and coolable 150-1 ploughshare mixer with a horizontally installed mixing tool and a knife mill for crushing large lumps. Unless otherwise stated, 75 kg was selected as the batch size.

2.1 Procedure

2.1.1 Method according to the invention

The speed of the stirring tool was set to 96min ^"1. The individual components were added to the mixer one after the other. Similar individual components were combined into grapples (premixes). The non-melting or high-melting components were added to the mixing room and heated up. The temperature The steam (heating) was switched off when the temperature was reached, and the jacket was briefly cooled with cooling water and no more To enter heat. The meltable components were then added.

This cooled the mixture. The components were cooled further by melting. Granulation took place during this process. If necessary, the knife mills were switched on in order to destroy agglomerates that were too large.

2.1.2 State of the art methods

The speed of the stirring tool was set to 150min ^"1. All components were added to the mixer together. The heating was set to a wall temperature of approximately 85 ° C. The heating was carried out continuously until the end of the granulation. The formulation was granulated and emptied according to the termination criterion - as mentioned in the prior art.

3. Tests carried out

3.1 Recipes

3.1.1 Recipe 1

3.1.1.1 Results

a) Procedure

Experiment VI, comparative experiment The total batch amount was 60kg. In the first attempt to produce the recipe according to the prior art, a temperature of 75 ° C. was set after the non-meltable and refusible components had been abandoned. When the temperature was reached, the paraffin (5.5%) was added as the melting component. At this temperature there was no pelletizing.

The mixture was gradually heated until the reactor temperature (thermocouple) was 95 ° C and the powder temperature was approximately 90 ° C (Raytec laser thermometer). Despite a total granulation time of approximately 1.5 hours, only a slight granulation took place. Trial V2

In experiment V2, the reactor temperature was set to 95 ° C and the wall temperature to about 85 ° C. All individual components were abandoned and the agitator started. When the powder temperature reached 63 ° C, the volume of the mixture was reduced. No granulation took place yet. Over the next 50 minutes the powder temperature rose continuously to about 90 ° C. When this temperature was reached, the current strength began to rise and the mixture no longer dusted. With a current consumption of 14A, the batch was emptied. The time from the start of the increase in power consumption to emptying was about 9 minutes (= pure granulation time). Caking is on the reactor wall.

Method according to the invention

Trial V3

In experiment 3, a powder temperature of 95 ° C. and a reactor temperature of 105 ° C. were set after the non-meltable and high-melting components had been given up. When the temperature was reached, pencil stearate (5.6%) and paraffin wax (5.5%) were added as melting components. After adding the lead stearate, the reactor was 100% full. After adding the paraffin wax, the volume was reduced by approx. 50%. Then the current began to rise slowly. The mixture was granulated about 50 minutes after the meltable components had been added. The reactor was emptied at a current of 12A.

There were no appreciable aria baking on the reactor walls. Products:

In order to check the even distribution of the ingredients according to the individual processes, the ash values of individual com fractions were determined according to DIN 53568, sheet 1 (determination of the residue on ignition):

3.1.2: Test formulation 2

3.1.2.1 Results of experiment 1

In the course of experiment V4, the reactor temperature was set to 95 ° C. and the wall temperature to about 85 ° C. All individual components were abandoned and the agitator started. The reactor was about 90% full. After 20 minutes the current began to rise and the mixture stopped dusting. The product had a temperature of 58 ° C. The current rose to 23A within 3 minutes. The approach has been emptied.

There were strong, solid deposits on the reactor wall.

Trial V5

In experiment V5, a powder temperature of 80 ° C. and a reactor temperature of 95 ° C. were set after the non-meltable and meltable components had been fed in. When the temperature was reached, calcium stearate (17.5%) and paraffin wax (10%) were added as melting components. After adding the paraffin wax, the reactor was 90% full.

The material was granulated 8 minutes after the addition of the paraffin wax. This was evident from an increase in current. The reactor was emptied further to avoid doughing the batch. There were no caking on the reactor walls.

The share of 27% of fusible compounds is relatively high.

4. Comparison / discussion of the results

4.1 Product:

1.) The laboratory results show that the granules produced by the process according to the invention show narrower error limits and narrower distributions:

2.) Ash: The test of various fractions screened in the laboratory shows that the distribution of the ash values during production using the method according to the invention is considerably narrower and that as a result significantly lower standard deviations and thus relative errors occur. The method according to the invention is advantageous here.

4.3 Procedure

1.) The process according to the prior art shows caking in the reactor in both test products.

2.) In the method according to the prior art, due to the arcing, high mechanical loads on the mixing tool and thus high current consumption occur, which could lead to considerable problems, especially during scale-up.

3.) In general, there are hardly any aribackings in the method according to the invention.

Claims

claims

1. Granular stabilizer composition for halogen-containing plastics, obtainable by heating at least one first stabilizer component in a reactor to a first process temperature below the melting point of the at least one stabilizer component and then adding at least one granulating component in the solid state, the granulating component having a softening or melting point below the first Process temperature has, and then the mixture is granulated with constant agitation to obtain granules.

2. Stabilizer composition according spoke 1, characterized in that the pelletizing takes place after addition of the pelletizing component without external heat.

3. Stabilizer composition for halogen-containing plastics according to spoke 1 or 2, characterized in that the granulate is cooled while moving outside of the reactor after the granulation.

4. stabilizer composition for halogen-containing plastics according to one of claims 1 to 3, characterized in that the granules are comminuted to the desired size.

5. stabilizer composition for halogen-containing plastics according to one of claims 1 to 4, characterized in that the granulating component has a proportion of 0.1 to 60 wt .-% in the stabilizer composition.

6. Stabilizer composition for halogen-containing plastics according to one of claims 1 to 5, characterized in that the granulating component has a melting point of less than 120 ° C.

7. A process for producing a granular stabilizer composition for plastics, in which at least one first stabilizer component in a reactor is heated to a first process temperature below the melting point of the at least one stabilizer component and then at least one granulating component is added in the solid state, the granulating component having a melting point below the has first process temperature, and then the mixture is granulated with constant agitation to obtain granules.

8. The method according spoke 7, characterized in that the pelletizing is carried out without external heat supply.

9. The method according spoke 7 or 8, characterized in that the granulation is carried out at slow speed.

10. The method according to any one of claims 7 to 9, characterized in that the granules are crushed with a knife mill before cooling.

11. The method according spoke 7, characterized in that the granulating is continued until the granules have a bulk density of 100 to 800 g / 1.

12. Polymer 2 composition prepared using a granulate according to one of claims 1 to 6 or using a granulate obtainable according to one of claims 7 to 11.

13. Use of a granulate according to one of claims 1 to 6 or of a granulate obtainable according to one of claims 7 to 11 for stabilizing halogen-containing polymers.