MASTERBATCH AND USE OF THE MASTERBATCH, POLYMER MATERIALS CONTAINING THE MASTERBATCH, AND MOLDED BODIES OBTAINED FROM THE POLYMER MATERIAL

Description

[0001] The present invention relates to a masterbatch, particularly in granulate form. Furthermore, the invention relates to the use of the masterbatch according to the invention for coloring polymer materials and molded articles. The invention also relates to a polymer material containing the masterbatch according to the invention in a minor amount. Finally, the invention relates to molded articles obtained or obtainable from the polymer material according to the invention.

[0002] Masterbatches are regularly used for application-specific modification of plastics. Masterbatches are polymer-bound additive concentrates. The advantage of masterbatches is that they only need to be added to a polymer material in relatively small quantities to achieve the desired coloring or modification.

[0003] Basically, two classification systems can be used to classify masterbatches. Firstly, masterbatches can be divided into color, additive, and combination masterbatches. This classification is function-oriented. Secondly, masterbatches can be divided into universal and polymer-specific masterbatches based on the polymer matrix material into which they are blended. Due to compatibility issues resulting from the partial incompatibility of the polymers used for the masterbatch on the one hand and the polymer matrix material on the other, and resulting in demixing phenomena and dispersion errors, universal masterbatches are still problematic for many applications, even though universal masterbatches offer considerable potential for streamlining storage and logistics.Currently, there are numerous specialized masterbatch types for each plastic class. The successful use of masterbatches is also due to the fact that solid-based additives can be completely or almost completely dispersed in masterbatch preparations. This means that dispersive mixing to break up and divide agglomerates and aggregates is hardly necessary during the production of plastic materials. Accordingly, no additional dispersing agents are generally required when mixing masterbatches into polymer matrix materials. While the goal is often to obtain masterbatches in the form of granules that are free-flowing and dust-free, it is not uncommon to obtain masterbatch particles with a sticky consistency.

[0004] Masterbatches are generally produced using a single-stage or two-stage process. In single-stage production, all raw materials are initially prepared and extruded. In the two-stage process, so-called monoconcentrates are first produced, which are then mixed again, optionally with additives, and extruded. The homogeneity of the color in the plastic depends on the flow behavior achieved in the melt and how well the masterbatch is distributed in the matrix. In many cases, it is not possible, or only to an insufficient extent, to incorporate pigments into a masterbatch while maintaining a homogeneous color. For example, pigments produced by dry calcination can usually only be distributed in a masterbatch with a high energy input and, moreover, usually only incompletely. These are also referred to as dispersible pigments.Common masterbatches, especially silicone-based masterbatches, still pose problems and leave something to be desired. For example, masterbatches in granular form often tend to stick together or block, even at high filler levels.

[0005] EP 2 113 522 A1 relates to a process for producing a color masterbatch comprising the steps: a) Mixing a siloxane structure terminated with an amino, hydroxy or carboxy group of the general formula I (component A): where R1 is independently a monovalent hydrocarbon radical having 1 to 20 carbon atoms, R2 is independently an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- groups, or an arylene radical having 6 to 22 carbon atoms, X and Y are independently a hydroxy, carboxy or amino group -NR'- with R' = hydrogen, alkyl radical having 1 to 10 carbon atoms or aryl radical having 6 to 22 carbon atoms and n is a number from 1 to 10,000, with at least one bifunctional compound (component B) which has two groups which can be linked to X and Y by polyaddition or polycondensation, b) polymer formation of the mixture of components A and B and c) melting the polymer in an extruder or discontinuous internal mixer with subsequent granulation, At least one colorant is added before polymer formation is complete. This process is said to be highly efficient and to produce color masterbatches characterized by high compatibility with added colorants and their amounts.

[0006] EP 3 118 245 A1 relates to a process for producing a masterbatch, comprising the steps: a1) Providing a siloxane compound terminated with at least one amino, hydroxy, carboxy, carboxylate, carboxylic acid ester or carboxylic acid anhydride group of the general formula (component A1): where R1 is, independently of one another, a monovalent hydrocarbon radical having 1 to 20 carbon atoms, R2 is, independently of one another, an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- groups, or an arylene radical having 6 to 22 carbon atoms, X, Y is, independently of one another, a hydroxy, carboxy, carboxylate, carboxylic acid ester, carboxylic acid anhydride or amino group NHR' where R' = hydrogen, alkyl radical having 1 to 10 carbon atoms or aryl radical having 6 to 22 carbon atoms, and n is a number from 75 to 215; a2) providing an at least bifunctional compound (component A2) which has two or more groups which can be linked to X and Y, in particular by polyaddition or polycondensation; a3) provision of a colorant (component A3) and / or a4) provision of a functional additive (component A4);b) mixing the components according to a1), a2) and a3) or according to a1), a2) and a4) or according to a1), a2), a3) and a4); c) polymer formation of the mixture according to b) and d) melting and / or keeping the melt liquid of the polymer formed in step c) and e) converting the polymer according to step d) into a solid state. ;

[0007] This process is intended to provide economical and reliable access to so-called universal masterbatches that do not lead to significant deposits during processing in the extruder, during incorporation into polymer matrix materials, or during further processing of the molten polymer materials in, for example, injection molding machines.

[0008] The present invention was therefore based on the object of providing masterbatches that no longer suffer from the disadvantages of the prior art and that, in particular, enable moldings characterized by reduced water absorption and / or that provide polymer materials that produce no or only a reduced amount of rejects during the production of moldings. In particular, the invention was also based on the object of providing masterbatches that, even when they contain natural fibers or fillers of organic origin such as wood flour or wood fibers, enable moldings characterized by reduced water absorption.

[0009] Accordingly, a masterbatch was found, in particular in granulate form, consisting of or containing, in particular containing, a) at least one silicon-containing block copolymer A), b) at least one inorganic pigment and / or one inorganic filler B), in particular at least one inorganic pigment, and c) at least one polymer C) selected from the group consisting of thermoplastic polymers, selected from the group consisting of polyolefin homo- and copolymers, polyesters, polyvinyl chloride and any mixtures thereof, thermoplastic elastomers, comprising or constituting thermoplastic polyurethane elastomers, or mixtures thereof, in particular at least one thermoplastic polymer.

[0010] In particularly expedient embodiments, the weight ratio of the at least one silicon-containing block copolymer A) to the at least one polymer C), in particular the at least one thermoplastic polymer, is in the range from 1:9 to 9:1, preferably in the range from 1:7 to 1:2 and particularly preferably in the range from 1:6 to 1:3. A particular advantage associated with the masterbatches according to the invention is that it is not absolutely necessary for the polymer C) to be identical to the matrix polymer of the polymer material containing this masterbatch. The simultaneous presence of the at least one silicon-containing block copolymer A) and the at least one inorganic pigment and / or the at least one inorganic filler makes it possible to obtain a mixture of different polymers that does not tend to demix, even though these polymers are not homogeneously miscible as a binary mixture.

[0011] In particularly preferred embodiments, the masterbatches according to the invention a) the at least one silicon-containing block copolymer A) in an amount of less than 10 wt.%, based on the total weight of the masterbatch, b) the at least one inorganic pigment and / or the one inorganic filler B), in particular at least the one inorganic pigment, in an amount of less than or equal to 80 wt.%, preferably in the range from 55 to 78 wt.%, in each case based on the total weight of the masterbatch, and / or, in particular and, c) the at least one polymer C), in particular the at least one thermoplastic polymer, in an amount of less than or equal to 35 wt.%, preferably in the range from 5 to 28 wt.%, in each case based on the total weight of the masterbatch, wherein the components forming the masterbatch each add up to 100.0 wt.%.

[0012] In particular, those masterbatches according to the invention are also preferred in which a) the at least one silicon-containing block copolymer A) is present in an amount of less than 10% by weight, based on the total weight of the masterbatch, b) the at least one inorganic pigment is present in an amount in the range from 55 to 78% by weight, based on the total weight of the masterbatch, and c) the at least one thermoplastic polymer C) is present in an amount in the range from 5 to 28% by weight, based on the total weight of the masterbatch, where the components forming the masterbatch each add up to 100.0 wt.%.

[0013] The masterbatches according to the invention can further be provided with d) at least one functional additive and / or with e) at least one paraffinic oil, in particular white oil.

[0014] In particularly preferred masterbatches, it is provided that the at least one silicon-containing block copolymer A) is selected from the group consisting of i) a first block copolymer A1) having the general formula (I) B-[R 2 -(O-Si(R 1 ) 2 ) n -O-Si(R 1 ) 2 -R 2 -NH-CO-NH-R 3 -NH-CO-NH] a -B' with R1 independently of one another a monovalent hydrocarbon radical having 1 to 20 carbon atoms, optionally substituted by fluorine or chlorine, R2 - independently of one another - an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- groups or an arylene radical having 6 to 22 carbon atoms, R3 an optionally fluorine- or chlorine-substituted alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- groups or an arylene radical having 6 to 22 carbon atoms, B, B' a reactive or non-reactive end group, which is covalently bonded to the polymer, n: a number from 1 to 10,000, preferably in the range from 75 to 215,particularly preferably in the range from 80 to 200 and in particular in the range from 100 to 180 or 110 to 160, and a: a number of at least 1, preferably in the range of or between 1 to 140, particularly preferably in the range from 5 to 100 and further preferably in the range from 10 to 50; ii) a second block copolymer A2) having the general formula (II) B-[R 2< -(O-Si(R 1< ) 2 ) n -O-Si(R 1< ) 2 -R 2< -NH-CO-NH-R 3< -NH-CO-VR 4< -W-CO-NH-R 3< -NH-CO-NH] a -B' with R1 independently of one another a monovalent hydrocarbon radical having 1 to 20 carbon atoms, optionally substituted by fluorine or chlorine, R2 - independently of one another - an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- groups or an arylene radical having 6 to 22 carbon atoms, R3 an alkylene radical having 1 to 20 carbon atoms, optionally substituted by fluorine or chlorine,in which non-adjacent methylene units can be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms, R4 is an alkylene radical having 1 to 700 C atoms, optionally substituted by fluorine, chlorine, C1-C6-alkyl or C1-C6-alkyl esters, in which non-adjacent methylene units can be replaced by groups -O-, -COO-, -OCO- or -OCOO-, V, W independently of one another are -O- or -NR5-, where R5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 C atoms, B, B': a reactive or non-reactive end group which is covalently bonded to the polymer, n: a number from 1 to 10,000, preferably in the range from 75 to 215, particularly preferably in the range from 80 to 200 and in particular from 100 to 180 or 110 to 160, a: a number of at least 1, preferably in the range of or between 1 to 140, particularly preferably in the range of 5 to 100 and further preferably in the range of 10 to 50,and iii) any mixtures of the block copolymers A1) and A2).

[0015] The end groups B and B' can be reactive or non-reactive end groups. It is possible for both end groups B and B' to be non-reactive end groups or for both end groups B and B' to be reactive end groups. Furthermore, one end group B can be a reactive end group and the other end group B' can be a non-reactive end group. Accordingly, it is possible for the end groups B and B' to be the same or different. In a preferred embodiment, in the compound (I) or in the compound (II), the end group B can be a hydroxyl, carboxy, carboxylate, carboxylic acid ester, carboxylic acid anhydride group or an amino group NHR' with R' = hydrogen, an alkyl radical having 1 to 10 carbon atoms, in particular methyl, ethyl or i- or n-propyl, preferably n-propyl, or an aryl radical having 6 to 22 carbon atoms, with an NH2 group being particularly preferred.In a further preferred embodiment, in the compound (I) or the compound (II), the end group B' may represent an NCO group or a -CO-NH-R 3 -NH2 radical.

[0016] In a further preferred embodiment, the masterbatches according to the invention for the silicon-containing block copolymers A) accordingly contain those with end groups B, B' which are aminoalkylsiloxane end groups, in particular aminopropylsiloxane end groups.

[0017] The silicon-containing block copolymers A) can be obtained by reacting at least one siloxane compound terminated with at least one, in particular with at least or exactly two, amino, hydroxy, carboxy, carboxylate, carboxylic acid ester or carboxylic acid anhydride groups with at least one at least bifunctional, in particular bifunctional, compound which has two or more, in particular two, groups which can be linked, in particular by polyaddition or polycondensation.

[0018] Among the particularly suitable bifunctional monomers, those selected from the group consisting of diisocyanates, diamines, diols, dicarboxylic acids, diformaldehyde-terminated compounds and mixtures thereof are particularly suitable, with diisocyanates being particularly preferred. Suitable diisocyanates can be selected from the group consisting of aliphatic diisocyanates, in particular 1,6-diisocyanate-hexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and / or 1-isocyanato-4-[(4-isocyanatocyclohexyl)-methyl]cyclohexane, and aromatic diisocyanates, in particular 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-2,2'-diphenylmethane diisocyanate, 2,4'-2,2'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4-methyl-m-phenylene diisocyanate, 1,3-bis-(1-isocyanato-1-methylethyl)-benzene, polyphenyl polymethylene polyisocyanates and / or urethane-modified 4,4'-diphenylmethane diisocyanates, and mixtures thereof.Among these, aliphatic diisocyanates are preferred.

[0019] In the masterbatches according to the invention, the proportion of component A) is very particularly preferably less than or equal to 12.0% by weight, preferably less than or equal to 10.0% by weight, and preferably less than or equal to 8.0% by weight, in each case based on the total weight of the masterbatch. Alternatively, and in particular additionally, it can be provided that the proportion of the at least one inorganic pigment and / or the inorganic filler B), in particular the at least one inorganic pigment, is in the range from 60 to 80% by weight, based on the total weight of the masterbatch. Furthermore, alternatively, and in particular additionally to one or in particular to both of the aforementioned embodiments, it can be provided that the proportion of the at least one polymer C) is in the range from 15 to 25% by weight, based on the total weight of the masterbatch, the components forming the masterbatch always adding up to 100.0% by weight.

[0020] In this case, those masterbatches according to the invention are also particularly preferred in which the proportion of component A) is less than or equal to 8.0% by weight, based on the total weight of the masterbatch, the proportion of the at least one inorganic pigment B) is in the range from 60 to 80% by weight, based on the total weight of the masterbatch, the proportion of the at least one polymer C) is in the range from 15 to 25% by weight, based on the total weight of the masterbatch, the components forming the masterbatch always amounting to 100.0% by weight.

[0021] The at least one inorganic pigment is preferably selected from the group consisting of oxides, in particular iron oxide, chromium oxide and / or titanium dioxide; carbon black; chromates, in particular lead chromate yellow; molybdate orange; complexes of inorganic colored pigments, in particular chromium titanium yellow, chromium iron brown, cobalt blue, nickel titanium yellow, zinc iron brown and / or bismuth vanadate yellow; sulfides, in particular cadmium sulfide, cerium sulfide, ultramarine or zinc sulfide, and any mixtures thereof. In addition to the inorganic pigments and / or fillers, organic pigments and / or dyes can also be used or co-used for color adjustment. Suitable organic pigments can be selected from the group consisting of azo pigments, e.g.laked azo pigments (yellow, red), disazo pigments (yellow, orange, red), diazo condensation pigments (yellow, red), benzimidazole pigments (yellow, orange), metal complex pigments (yellow), isoindoline pigments (yellow), isoindolinone pigments (yellow), and polycyclic pigments, e.g. quinacridone (violet, blue), quinophthalone (yellow), diketo-pyrrolo-pyrrole (orange, red, violet), disoxazine pigments (violet), indanthrone (blue), perylene (red, violet) or phthalocyanine (blue, green) and any mixtures thereof. Suitable dyes can, for example, be selected from the group consisting of anthraquinone, quinophthalone, pyrazolone, perinone, monoazo dyes and fluorescent dyes, e.g. perylene, naphthalimide, cumin derivatives, thioindigo or thioxanthene-benzanthrone, and any mixtures thereof. In contrast to pigments, dyes are colorants that are soluble in the polymer material to be colored.In the masterbatches according to the invention, inorganic pigments are preferably used for coloring.

[0022] The thermoplastic polymers in the form of polyolefin homopolymers represent or comprise in particular polypropylene and / or polyethylene and preferably represent polypropylene and / or polyethylene. The thermoplastic elastomers in the form of thermoplastic polyurethane elastomers represent or comprise in particular thermoplastic polyurethane elastomers based on polyester polyols or polyether polyols and preferably represent thermoplastic polyurethane elastomers based on polyester polyols or polyether polyols.

[0023] Particularly suitable thermoplastic polymers can be selected from the group consisting of polypropylene and polyethylene, preferably LD polyethylene and particularly preferably HD polyethylene and any mixtures thereof.

[0024] Suitable functional additives are selected in particularly suitable embodiments from the group consisting of nucleating agents, nanofillers, layered silicates, in particular delaminated layered silicates, stabilizers, in particular thermal stabilizers and / or light stabilizers, antistatic agents, flame retardants, adhesion promoters, antiblocking agents, processing aids, blowing agents, antimicrobial agents, in particular antibacterial agents, and any mixtures of the aforementioned components.

[0025] In the block copolymers according to formula (I) and / or (II), the parameter "n" is preferably in the range from 80 to 200, more preferably in the range from 100 to 180, and particularly preferably in the range from 110 to 160. Furthermore, in the block copolymers according to formula (I) and / or (II), alternatively and in particular additionally, the parameter "a" is in the range from 5 to 100 and preferably in the range from 10 to 50.

[0026] In particular, it can be provided that in the block copolymers according to formula (I) and / or (II), "n" is in the range from 80 to 200 and "a" is in the range from 5 to 100 or in the range from 10 to 50, or that "n" is in the range from 100 to 180 and "a" is in the range from 5 to 100 or in the range from 10 to 50, or that "n" is in the range from 110 to 160 and "a" is in the range from 5 to 100 or in the range from 10 to 50. In particular, it can be provided that in the block copolymers according to formula (I) and / or (II), "n" is in the range from 100 to 180 and "a" is in the range from 5 to 100 or in the range from 10 to 50, preferably in the range from 10 to 50, wherein preferably "n" is in the range from 110 to 160 and "a" is in the range from 5 to 100 or in the range from 10 to 50, and wherein particularly preferably "n" is in the range from 110 to 160 and "a" is in the range from 10 to 50.

[0027] In a suitable embodiment, the number of repeating units "a" refers to the average number of repeating units in the block copolymer or copolymer according to compounds (I) and (II) as obtained in the preparation of the masterbatches according to the invention. The number of repeating units "a" is preferably an absolute value.

[0028] The masterbatches according to the invention make it possible to reliably and economically achieve systems in which pigments, whose primary particles can range in size from a few nanometers to a few micrometers, are homogeneously distributed, excluding pigment aggregates and agglomerates. It is not even necessary to remelt and regranulate a polymer material that has already been melted and granulated, thereby preventing or reducing thermal stress and thus degradation of the polymer material. A higher-quality polymer material compounded with a masterbatch is obtained. Furthermore, the masterbatches according to the invention can be very easily incorporated into polymer matrix materials, regardless of the selected concentration, without the pigments or active ingredient additives clumping or inhomogeneities occurring in the compounded polymer materials.

[0029] The object underlying the invention is accordingly further achieved by a polymer material consisting of or containing i) the masterbatch according to any one of the preceding claims in a minor amount and ii) a matrix polymer in a major amount.

[0030] A major amount within the meaning of the invention is understood to mean a proportion by weight, based on the total weight of the polymer material, which is above 50% by weight, and a minor amount within the meaning of the invention is understood to mean a proportion by weight, based on the total weight of the polymer material, which is below 50% by weight, preferably below 20% by weight.

[0031] In a preferred embodiment, it can be provided that the matrix polymer according to ii) and the polymer C) of the masterbatch are identical. In an alternative embodiment, it can be provided that the matrix polymer according to ii) and the polymer C) of the masterbatch are not identical. Suitable matrix polymers according to ii) and polymers C) of the masterbatch that do not correspond are expediently selected such that they are miscible with one another, in particular homogeneously, at least within certain range limits, or are essentially not prone to demixing phenomena in the shaped body produced from the mixture.

[0032] For the matrix polymer as well as the polymer C) of the masterbatch, polymeric materials can be used, selected from the group consisting of thermoplastics, thermoplastic elastomers and mixtures thereof, with preference being given to polymers selected from the group consisting of polyolefins, in particular polyethylene, e.g. HD-PE, and / or polypropylene or propylene copolymers, polyamides, polyesters such as polyethylene terephthalate and / or polybutylene terephthalate, polymethyl methacrylate, polyaryletherketones, polyacrylonitrile, polyethylene naphthalates, polyethersulfones, polyimides, polyketones, polyphenylene sulfides, polyphenylene sulfones, polysulfones, styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, natural rubbers, thermoplastic elastomers based on crosslinked rubber, ethylene-vinyl acetate copolymers, polyhydroxybutyrate, polylactides, Polyetherimides, polyoxyethylene, polycarbonates, polystyrene,impact-modified polystyrene, styrene-based (co)polymers such as ABS, SAN, PS, HIPS and / or ASA, styrene-based thermoplastic elastomers such as SEBS, olefinic-based thermoplastic elastomers such as LLDPE, EOC, TPV and / or EVA, PE / polyester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyether block amides (PE-BA), PVC, polyurethanes, e.g. thermoplastic polyurethanes, and thermoplastic starch or any mixtures thereof, in particular polyethylene, polypropylene, polyamides, polyethylene terephthalate and / or polybutylene terephthalate.

[0033] The matrix material of the polymer materials according to the invention is preferably selected from the group consisting of polyolefin homo- and copolymers, in particular polypropylene and / or polyethylene, polyesters, polyoxymethylene, polyvinyl chloride, thermoplastic polyurethane elastomers, in particular based on polyester polyols or polyether polyols, and any mixtures thereof.

[0034] In the polymer materials according to the invention, the proportion of the masterbatch is preferably less than or equal to 7.0 wt.%, preferably less than or equal to 5.0 wt.%, and particularly preferably in the range from 0.5 to 3 wt.%, in each case based on the total weight of the polymer material.

[0035] Alternatively and in particular additionally, it can be provided that in the polymer materials according to the invention the proportion of component A) in the polymer material is preferably less than or equal to 0.8 wt.%, preferably less than or equal to 0.6 wt.% and particularly preferably less than or equal to 0.4 wt.%, based on the total weight of the polymer material.

[0036] Furthermore, alternatively and in particular in addition to one and in particular both of the above-mentioned embodiments, it can be provided that the proportion of the at least one inorganic pigment and / or the inorganic filler B), in particular the at least one inorganic pigment, is in the range from 0.5 to 6.0 wt.%, in particular in the range from 1.0 to 4.0 wt.%, based on the total weight of the polymer material.

[0037] In particular, those polymer materials according to the invention are also preferred in which the proportion of component A) of the masterbatch in the polymer material is less than or equal to 0.4 wt.%, based on the total weight of the polymer material, and the proportion of the at least one inorganic pigment B) of the masterbatch in the polymer material is in the range from 1.0 to 4.0 wt.%, based on the total weight of the polymer material.

[0038] For the polymer material according to the invention, polypropylene or polyethylene, preferably LD polyethylene and particularly preferably HD polyethylene, are considered as a particularly suitable matrix polymer, and at the same time polypropylene or polyethylene, preferably LD polyethylene and particularly preferably HD polyethylene, are considered as a particularly suitable polymer C) of the masterbatch.

[0039] Very particularly preferred polymer materials according to the invention are characterized by an amount in the range from 96.0 to 99.9% by weight, preferably in the range from 98.0 to 99.5% by weight, of the matrix polymer polypropylene or polyethylene, preferably LD polyethylene and particularly preferably HD polyethylene, based on the total weight of matrix polymer and polymer C), and / or, in particular and, an amount in the range from 0.1 to 4.0% by weight, preferably in the range from 0.5 to 2.0% by weight, of polypropylene or polyethylene, preferably LD polyethylene and particularly preferably HD polyethylene, as polymer C) of the masterbatch.

[0040] Also particularly preferred are those polymer materials according to the invention in which the amount of the matrix polymer polypropylene or polyethylene, in particular HD polyethylene, based on the total weight of matrix polymer and polymer C), is in the range from 98.0 to 99.5 wt.%, and the amount of the polymer C) of the masterbatch in the polymer material, namely HD polyethylene, is in the range from 0.5 to 2.0 wt.%, based on the total weight of matrix polymer and polymer C).

[0041] The polymer materials according to the invention also allow for satisfactory incorporation of fibers. Surprisingly, the molded articles containing these fibers can be colorized satisfactorily and uniformly even with relatively small amounts of pigments contained in the masterbatches according to the invention.

[0042] Suitable fiber materials can be selected from the group consisting of mineral fibers, plastic fibers, cotton, cellulose fibers, viscose fibers, natural fibers and any mixtures thereof, and / or particulate additives from renewable raw materials.

[0043] Furthermore, particularly preferred natural fibers can be selected from the group consisting of wood fibers, hemp fibers, flax fibers, jute fibers, hemp fibers, bamboo fibers, kenaf fibers, nettle fibers, seagrass, elephant grass, mescanthum, reed, coconut fibers, straw, and any mixtures thereof, and / or the mineral fibers are selected from the group consisting of basalt, ceramic, and / or glass fibers, and / or the plastic fibers are selected from the group consisting of polyethylene, polypropylene, polyester, and polyamide fibers and any mixtures thereof. Suitable natural fibers, in particular wood fibers, generally have an aspect ratio (ratio of length to width) greater than 10:1, preferably greater than 20:1.

[0044] Particulate additives are preferably made from renewable raw materials, selected from the group consisting of rice hulls, sunflower seed hulls, wood particles, especially hardwood particles, and any mixtures thereof. Suitable wood particles also include, for example, wood flour. Suitable wood particles generally have an aspect ratio (ratio of length to width) of less than or equal to 10:1, preferably less than 5:1.

[0045] Particularly suitable fiber materials have an average fiber length in the range of 100 to 4500 µm, e.g. in the range of 100 to 2000 µm, in particular in the range of 300 to 3000 µm, e.g. in the range of 500 to 3000 µm, and / or that the particulate additives from renewable raw materials have an average particle size in the range of 100 to 500 µm, in particular in the range of 200 to 400 µm.

[0046] Particularly preferred polymer materials according to the invention contain a proportion of the masterbatch in the range from 0.5 to 3.0 wt.%, in particular in the range from 0.5 to 2.0 wt.%, and a proportion of matrix polymer in the range from 98.0 to 99.5 wt.%, the components forming the polymer material always amounting to 100.0 wt.%.

[0047] Furthermore, particularly preferred polymer materials according to the invention contain a proportion of component A) in the polymer material of less than or equal to 0.4% by weight and a proportion of the at least one inorganic pigment in the range from 1.0 to 4.0% by weight, in each case based on the total weight of the polymer material, wherein the matrix polymer is polyethylene, in particular HD polyethylene, and the polymer C) of the masterbatch is polyethylene, preferably HD polyethylene.

[0048] In a further preferred embodiment, particularly preferred polymer materials according to the invention contain a proportion of component A) in the polymer material of less than or equal to 0.4% by weight and a proportion of the at least one inorganic pigment B) in the range from 1.0 to 4.0% by weight, in each case based on the total weight of the polymer material, as well as natural fibers, in particular wood fibers, and / or particulate additives from renewable raw materials, in particular wood particles, wherein the matrix polymer is polyethylene, in particular HD polyethylene, and the polymer C) of the masterbatch is polyethylene, preferably HD polyethylene, and wherein the components forming the polymer material always add up to 100.0% by weight.

[0049] The molded bodies according to the invention are preferably accessible by injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, fused deposition modeling (FDM), granulation and / or casting of the polymer material according to the invention.

[0050] With the masterbatches according to the invention, polymer materials and thus also molded articles can be colored particularly satisfactorily and reliably and, if necessary, additionally or alternatively, even provided with functional additives.

[0051] The present invention is based on the surprising discovery that when special silicon-containing block copolymers are used and when the specified quantities of the components to be used are observed, masterbatches in granular form are obtained which are easy to produce, have good flow properties, i.e. do not tend to stick together, and show reduced blocking behavior. Furthermore, it has been surprisingly found that the molding compositions and moldings obtained from the masterbatches according to the invention show no or only reduced water absorption. Without being bound to any theory, it is suspected that this could be related to the fact that the molding compositions and moldings according to the invention are characterized by reduced porosity. It has also been found to be advantageous that the molding compositions according to the invention have better or even better water absorption when moldings are produced in the molten state.exhibit more controlled lubricity in the mold, particularly in the extruder. The molded articles according to the invention can advantageously be demolded reliably and without problems from the mold, for example, an injection mold. The molded articles according to the invention also exhibit pronounced abrasion resistance. Surprisingly, the masterbatches according to the invention allow a very high pigment loading, and the pigments in the masterbatch also exhibit a high dispersity.

[0052] The features of the invention disclosed in the above description and in the claims may be essential, either individually or in any combination, for the realization of the invention in its various embodiments. The scope of protection is determined by the patent claims.

Claims

1. Masterbatch, in particular in granulate form, consisting of or containing a) at least one silicon-containing block copolymer A), b) at least one inorganic pigment and / or an inorganic filler B), in particular at least one inorganic pigment, and c) at least one polymer C) selected from the group consisting of thermoplastic polymers, selected from the group consisting of polyolefin homo- and copolymers, polyesters, polyvinyl chloride and any desired mixtures thereof, thermoplastic elastomers, comprising or representing thermoplastic polyurethane elastomers, or mixtures thereof.

2. Masterbatch according to Claim 1, characterized in that the weight ratio of the at least one silicon-containing block copolymer A) to the at least one polymer C), in particular the at least one thermoplastic polymer, is in the range from 1:9 to 9:1, in particular in the range from 1:7 to 1:2.

3. Masterbatch according to Claim 1 or 2, containing a) the at least one silicon-containing block copolymer A) in an amount of less than 10% by weight, based on the total weight of the masterbatch, b) the at least one inorganic pigment and / or the one inorganic filler B), in particular at least the one inorganic pigment, in an amount of less than or equal to 80% by weight, preferably in the range from 55 to 78% by weight, in each case based on the total weight of the masterbatch, and / or, in particular and, c) the at least one polymer C), in particular the at least one thermoplastic polymer, in an amount of less than or equal to 35% by weight, preferably in the range from 5 to 28% by weight, in each case based on the total weight of the masterbatch, wherein the components forming the masterbatch in each case add up to 100.0% by weight.

4. Masterbatch according to any of the preceding claims, characterized in that the at least one silicon-containing block copolymer A) is selected from the group consisting of - a first block copolymer A1) having the general formula (I)         B-[R2-(O-Si(R1)2)n-O-Si(R1)2-R2-NH-CO-NH-R3-NH-CO-NH]a-B' where R1 independently of one another a monovalent hydrocarbon residue which has 1 to 20 carbon atoms and is optionally substituted by fluorine or chlorine, R2 - independently of one another - an alkylene residue having 1 to 20 carbon atoms, in which methylene units which are not adjacent to one another may be replaced by -O- groups, or an arylene residue having 6 to 22 carbon atoms, R3 an alkylene residue which has 1 to 20 carbon atoms and is optionally substituted by fluorine or chlorine, in which methylene units which are not adjacent to one another may be replaced by -O- groups, or an arylene residue having 6 to 22 carbon atoms, B, B' a reactive or nonreactive end group which is covalently bonded to the polymer, n: a number from 1 to 10000, preferably in the range from 75 to 215, particularly preferably in the range from 80 to 200 and in particular in the range from 100 to 180 or 110 to 160, and a: a number of at least 1, preferably in the range from or between 1 and 140, particularly preferably in the range from 5 to 100 and further preferably in the range from 10 to 50; a second block copolymer A2) having the general formula (II)         B-[R2-(O-Si(R1)2)n-O-Si(R1)2-R2-NH-CO-NH-R3-NH-CO-V-R4-W-CO-NH-R3-NH-CO-NH]a-B' where R1 independently of one another a monovalent hydrocarbon residue which has 1 to 20 carbon atoms and is optionally substituted by fluorine or chlorine, R2 - independently of one another - an alkylene residue having 1 to 20 carbon atoms, in which methylene units which are not adjacent to one another may be replaced by -O- groups, or an arylene residue having 6 to 22 carbon atoms, R3 an alkylene residue which has 1 to 20 carbon atoms and is optionally substituted by fluorine or chlorine, in which methylene units which are not adjacent to one another may be replaced by -O- groups, or an arylene residue having 6 to 22 carbon atoms, R4 an alkylene residue which has 1 to 700 carbon atoms optionally substituted by fluorine, chlorine, C1 -C6 -alkyl or C1 -C6 -alkyl ester, in which methylene units which are not adjacent to one another may be replaced by -O-, - COO-, -OCO- or -OCOO- groups, V, W independently of one another -O- or -NR5-, wherein R5 is hydrogen, an alkyl residue with 1 to 10 carbon atoms or an aryl residue having 6 to 22 carbon atoms, B, B': a reactive or nonreactive end group which is covalently bonded to the polymer, n: a number from 1 to 10000, preferably in the range from 75 to 215, particularly preferably in the range from 80 to 200 and in particular from 100 to 180 or 110 to 160, a: a number of at least 1, preferably in the range from or between 1 and 140, particularly preferably in the range from 5 to 100 and further preferably in the range from 10 to 50, and - any desired mixtures of the block copolymers A1) and A2).

5. Masterbatch according to any of the preceding claims, characterized in that the proportion of component A) is less than or equal to 12.0% by weight, preferably less than or equal to 10.0% by weight and particularly preferably less than or equal to 8.0% by weight, in each case based on the total weight of the masterbatch, and / or, in particular and, in that the proportion of the at least one inorganic pigment and / or the inorganic filler B), in particular the at least one inorganic pigment, is in the range from 60 to 80% by weight, based on the total weight of the masterbatch, and / or in that the proportion of the at least one polymer C) is in the range from 15 to 25% by weight, based on the total weight of the masterbatch, wherein the components forming the masterbatch always give 100.0% by weight.

6. Masterbatch according to any of the preceding claims, characterized in that the polyolefin homopolymer comprises or represents polypropylene and / or polyethylene, or in that the thermoplastic polyurethane elastomers comprise or represent, in particular represent, thermoplastic polyurethane elastomers based on polyester polyols or polyether polyols.

7. Masterbatch according to any of the preceding claims, characterized in that the thermoplastic polymer is selected from the group consisting of polypropylene, polyethylene, preferably LD-polyethylene and particularly preferably HD-polyethylene, and any desired mixtures thereof.

8. Masterbatch according to any of Claims 4 to 7, characterized in that in the case of the block copolymers according to formula (I) and / or (II) "n" is in the range from 80 to 200, preferably in the range from 100 to 180 and particularly preferably in the range from 110 to 160, and / or, in particular and, in that in the case of the block copolymers according to formula (I) and / or (II) "a" is in the range from 5 to 100 and preferably in the range from 10 to 50.

9. Masterbatch according to any of Claims 4 to 8, characterized in that in the case of the block copolymers according to formula (I) and / or (II) "n" is in the range from 100 to 180 and "a" is in the range from 5 to 100 or in the range from 10 to 50, preferably in the range from 10 to 50, wherein preferably "n" is in the range from 110 to 160 and "a" is in the range from 5 to 100 or in the range from 10 to 50 and wherein particularly preferably "n" is in the range from 110 to 160 and "a" is in the range from 10 to 50.

10. Polymer material consisting of or containing i) the masterbatch according to any of the preceding claims in a minor amount and ii) a matrix polymer in a major amount.

11. Polymer material according to Claim 10, characterized in that the matrix polymer according to ii) and the polymer C) of the masterbatch correspond.

12. Polymer material according to Claim 10 or 11, characterized in that the matrix material is selected from the group consisting of polyolefin homo- and copolymers, in particular polypropylene and / or polyethylene, polyesters, polyoxymethylene, polyvinyl chloride, thermoplastic polyurethane elastomers, in particular based on polyester polyols or polyether polyols, and any desired mixtures thereof.

13. Polymer material according to any of Claims 10 to 12, characterized in that the proportion of the masterbatch is less than or equal to 7.0% by weight, preferably less than or equal to 5.0% by weight, and particularly preferably in the range from 0.5 to 3.0% by weight, based on the total weight of the polymer material.

14. Polymer material according to any of Claims 10 to 13, characterized in that the proportion of component A) in the polymer material is less than or equal to 0.8% by weight, preferably less than or equal to 0.6% by weight and particularly preferably less than or equal to 0.4% by weight, based on the total weight of the polymer material, and / or, in particular and, in that the proportion of the at least one inorganic pigment and / or the inorganic filler B), in particular the at least one inorganic pigment, is in the range from 0.5 to 6.0% by weight, in particular in the range from 1.0 to 4.0% by weight, based on the total weight of the polymer material, wherein the components forming the polymer material always give 100.0% by weight.

15. Polymer material according to any of Claims 10 to 14, characterized in that the matrix polymer comprises or represents, in particular represents, polypropylene or polyethylene, preferably LD-polyethylene and particularly preferably HD-polyethylene, and the polymer C) of the masterbatch comprises or represents, in particular represents, polypropylene or polyethylene, preferably LD-polyethylene and particularly preferably HD-polyethylene.

16. Polymer material according to Claim 15, characterized by an amount in the range from 96.0 to 99.9% by weight, preferably in the range from 98.0 to 99.5% by weight, of the matrix polymer polypropylene or polyethylene, preferably LD-polyethylene and particularly preferably HD-polyethylene, based on the total weight of matrix polymer and polymer C), and / or, in particular and, an amount in the range from 0.1 to 4.0% by weight, preferably in the range from 0.5 to 2.0% by weight, of polypropylene or polyethylene, preferably LD-polyethylene and particularly preferably HD-polyethylene, as polymer C) of the masterbatch.

17. Polymer material according to any of Claims 10 to 16, further comprising fibrous materials selected from the group consisting of mineral fibers, plastic fibers, cotton, cellulose fibers, viscose fibers, natural fibers, in particular wood fibers, and any desired mixtures thereof, in particular natural fibers such as wood fibers, and / or particulate additives from renewable raw materials, in particular selected from the group consisting of rice husks, sunflower husks, wood particles and any desired mixtures thereof, preferably wood particles.

18. Polymer material according to any of Claims 10 to 17, characterized in that the fibrous materials have an average fiber length in the range from 100 to 4500 µm, in particular in the range from 500 to 3000 µm, and / or in that the particulate additives from renewable raw materials have an average particle size in the range from 100 to 500 µm, in particular in the range from 200 to 400 µm.

19. Moulded body obtained or obtainable by injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, fused deposition modelling (FDM), granulation and / or casting of the polymer material according to any of Claims 10 to 18.

20. Use of the masterbatch according to any of Claims 1 to 9 for colouring polymer materials or moulded bodies.