Uses of Polyamide 6

Abstract

This invention relates to the use of polyamide 6 for reducing the melt viscosity of compositions and molding compounds in which 10 to 115 parts by weight of glass fiber are present per 100 parts by weight of poly(C1-C6-alkylene terephthalate) at 260°C, as determined according to ISO 11443, and / or the filling pressure as determined according to EN ISO 294-1.

Description

Technical Field

[0001] This invention relates to the use of polyamide 6 for reducing the melt viscosity and / or filling pressure of compositions and molding compounds in which 10 to 115 parts by weight of glass fiber are present per 100 parts by weight of poly(C1-C6-alkylene terephthalate) as determined according to ISO 11443 at 260°C. Background Technology

[0002] In addition to mechanical properties such as elongation at break, tensile strength, or tensile modulus, recent research has focused particularly on the processability of polyalkylene terephthalate-based compositions for the production of articles for electric vehicles. Specifically, for processing via injection molding, the aim is to achieve low shear viscosity of the molded compound to be processed and low filling pressure during the filling of cavities in the injection mold.

[0003] DE 10 2004 027 872 A1 discloses a method for reducing the melt viscosity of a composition comprising A) 99.9 to 10 parts by weight of at least one semi-crystalline thermoplastic polyamide, B) 0.1 to 20 parts by weight of at least one copolymer of at least one α-olefin with at least one aliphatic alcohol in the form of methacrylate or acrylate, C) 0 to 70 parts by weight of at least one filler or reinforcing agent, D) 0 to 30 parts by weight of at least one flame retardant additive, and E) 0 to 60 parts by weight of at least one elastomer modifier, F) 0% to 10% by weight of other conventional additives, wherein copolymer B) does not contain any additional reactive functional groups and the MFI of copolymer B) is not less than 100 g / 10 min.

[0004] EP 1 790 692 A2 relates to polyester-based molding compound and addresses reducing the viscosity of polyester compositions while simultaneously reducing the filling pressure of the molding compound based thereon.

[0005] Those skilled in the art will know from WO 2005 / 121245 A1 that mixtures of thermoplastic polyesters with copolymers of α-olefins and aliphatic alcohols (meth)acrylates (having an MFI of not less than 100 g / 10 min) result in a reduction in the melt viscosity of the molded compounds produced therefrom, without any loss compared to molded compounds without the copolymer, but in some cases even with improvements in properties such as impact resistance, elongation at break, and hydrolytic stability. Examples in WO 2005 / 121245 A1 further demonstrate that the copolymer reduces the filling pressure in injection molding as determined according to both ISO 527 and ISO 178. Summary of the Invention

[0006] Starting from the prior art, the problem solved by the present invention is to reduce the shear viscosity of glass fiber reinforced poly(C1-C6-alkylene terephthalate) compositions and the filling pressure of glass fiber reinforced poly(C1-C6-alkylene terephthalate) compositions or molding compounds based thereon in injection molding, compared to the value in WO 2005 / 121245 A1, without gaining a loss of heat deformability and without gaining disadvantages in mechanical properties, especially tensile modulus, tensile strength and elongation at break. For the purposes of the present invention, it would be disadvantageous that, compared to the polyamide 6-free compositions used according to the present invention, the heat deformability of molding compounds processed below 180°C is reduced, or the difference in all three mechanical properties—tensile modulus, tensile strength and elongation at break—is greater than 10%.

[0007] This is because it has been unexpectedly found that adding polyamide 6 alone can reduce both the melt viscosity of glass fiber reinforced C1-C6-alkylene terephthalate molding compounds, especially those based on polybutylene terephthalate, and the filling pressure of glass fiber reinforced C1-C6-alkylene terephthalate molding compositions in injection molding. Compared to the same glass fiber reinforced composition in the presence of ethylene-butyl acrylate copolymer but without polyamide 6, and compared to the results of WO 2005 / 121245 A1, adding polyamide 6 alone can further reduce the filling pressure of glass fiber reinforced C1-C6-alkylene terephthalate molding compounds in injection molding by more than 10%.

[0008] Melt volumetric flow rate (MVR) is determined by capillary rheometer according to ISO 1133 in WO 2005 / 121245 A1. The subject of this study is melt viscosity, which, in the context of this invention, is determined at 260°C and a correspondingly specified shear rate according to ISO 11443. See also:

[0009] https: / / de.wikipedia.org / wiki / Viskosit%C3%A4t#:~:text=Ohne%20weitere%20Angaben%20ist%20der%20Widerstand%20des%20Fluids,der%20dynamischen%20Viskosit%C3%A4t%20und%20der%20kinematischen%20Viskosit%C3%A4t%20unterschieden

[0010] To determine the filling pressure of a molding compound based on the composition according to the invention, processed by injection molding according to EN ISO 294-1, in the context of this invention, a dumbbell-shaped sample having a geometry according to ISO 527-2 / 1A type was injection molded, and the required pressure in the injection molding machine was recorded. The melt temperature was set to 260°C and the mold temperature was set to 80°C.

[0011] Tensile modulus, tensile strength, and elongation at break are measured according to ISO 527 in the context of this invention. Elastic modulus (also known as E modulus), tensile modulus, elastic modulus, elongation modulus, or Young's modulus are material indices from materials engineering that describe the proportional relationship between stress and strain during deformation of a solid under given linear elastic behavior. See also:

[0012] https: / / www.krv.de / artikel / elastizitaetsmodul-e-modul

[0013] For information on tensile strength, see:

[0014] https: / / wiki.polymerservice-merseburg.de / index.php / Zugfestigkeit

[0015] Elongation at break is a specific material index that indicates a material's ability to deform in the plastic region before fracture (also known as ductility). See also:

[0016] https: / / www.maschinenbau-wissen.de / skript3 / werkstofftechnik / metall / 23-bruchdehnung

[0017] The present invention provides the use of polyamide 6 for reducing the melt viscosity (determined according to ISO 11443 at 260°C) and / or filling pressure (determined according to EN ISO 294-1) of compositions and molded mixtures in which 10 to 115 parts by weight of glass fiber are present per 100 parts by weight of poly(C1-C6-alkylene terephthalate), preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), especially polybutylene terephthalate.

[0018] For the avoidance of doubt, it should be noted that the scope of this invention includes all the definitions and parameters referred to below in any desired combination, either in a general sense or within the preferred scope. This applies to compositions, molded mixtures, and articles claimed according to the invention, as well as methods and uses. Standard references refer to the versions effective as of the date of filing of this invention.

[0019] In the context of this invention, "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. The corresponding definition applies to alkylene groups. This invention discusses C1-C6-alkylene terephthalates. Preferred alkylene groups are methylene (Me), ethylene (Et), propylene, especially n-propylene and isopropylene, butylene, especially n-butylene, isobutylene, secondary butylene, tert-butylene, pentylene, especially n-pentylene, isopentylene, neopentylene, and isomers of hexylene known to those skilled in the art.

[0020] The present invention further relates to a method for reducing the melt viscosity (determined according to ISO 11443 at 260°C) and / or filling pressure (determined according to EN ISO 294-1) of compositions and molding compounds wherein 10 to 115 parts by weight of glass fiber are present per 100 parts by weight of polyamide 6, preferably by adding polyamide 6 in an amount ranging from 0.5 to 15 parts by weight of polyamide 6.

[0021] Finally, the present invention also provides compositions, molded mixtures, and articles, each comprising...

[0022] A) 100 parts by weight of poly(C1-C6-alkylene terephthalate), preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), especially polybutylene terephthalate.

[0023] B) 10 to 115 parts by weight of glass fiber,

[0024] C) 0.5 to 15 parts by weight of polyamide 6, and

[0025] D) 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in the form of a methacrylate or acrylate. Detailed Implementation

[0026] The present invention preferably relates to the use of polyamide 6 for reducing the melt viscosity (determined at 260°C according to ISO 11443) and / or filling pressure (determined according to EN ISO 294-1) of compositions and molding compounds in which per 100 parts by weight of poly(C1-C6-alkylene terephthalate), preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), especially polybutylene terephthalate, contains 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in methacrylate or acrylate.

[0027] More preferably, the present invention relates to the use of polyamide 6 for reducing the melt viscosity (determined according to ISO 11443 at 260°C) and / or filling pressure (determined according to EN ISO 294-1) of compositions and molding compounds in which per 100 parts by weight of poly(C1-C6-alkylene terephthalate), preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), especially polybutylene terephthalate, contains 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in methacrylate or acrylate, wherein the amount of polyamide 6 used is 0.5 to 15 parts by weight.

[0028] The present invention preferably relates to a method for reducing the melt viscosity (determined at 260°C according to ISO 11443) and / or filling pressure (determined according to EN ISO 294-1) of a composition and molding compound wherein per 100 parts by weight of polyamide 6, preferably by adding polyamide 6 in an amount ranging from 0.5 to 15 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol, of glass fiber and glass fiber, and 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of at least one copolymer of methacrylate or acrylate of at least one α-olefin and at least one aliphatic alcohol, by adding polyamide 6, preferably by adding polyamide 6 in an amount ranging from 0.5 to 15 parts by weight of polyamide 6.

[0029] In a further preferred embodiment, the compositions, molded mixtures and articles according to the invention contain, in addition to components A) to D), at least one additional additive E) different from components B), C) and D), preferably in an amount ranging from 0.01 to 80 parts by weight based on 100 parts by weight of component A).

[0030] The compositions according to the invention (also commonly referred to as molding compounds in the plastics industry) are preferably obtained as granulated materials, in the form of extrusions, or as powders when processing individual components. Molding compounds according to the invention are prepared by mixing the compositions according to the invention in at least one mixing device, preferably in a compounding machine, more preferably in a co-rotating twin-screw extruder. The operation of mixing these individual components to produce compositions according to the invention in the form of powders, granules, or extrusions is also referred to as compounding in the plastics industry. This provides molding compounds based on the compositions according to the invention as intermediates. These molding compounds—also called thermoplastic molding compounds—may consist only of components A), B), C), and D), or may contain at least an additional component E in addition to these components. In a further step, the molding compounds of the invention are then subjected to injection molding or extrusion operations as a matrix material, preferably injection molding, to produce articles according to the invention.

[0031] Poly(C1-C6-alkylene terephthalate) (Component A)

[0032] Poly(C1-C6-alkylene terephthalate) can be prepared by various methods, synthesized from different starting materials and in specific application scenarios, and modified alone or in combination with processing aids, stabilizers, polymer alloying components (e.g., elastomers) or additional reinforcing materials (such as mineral fillers or glass fibers), and optionally additional additives, to obtain materials with a customized combination of properties. Blends containing a certain proportion of other polymers are also suitable, in which case one or more compatibilizers may be used. If desired, the properties of these polymers can be improved by adding elastomers.

[0033] Preferred poly(C1-C6-alkylene terephthalate) can be prepared from terephthalic acid or its reactive derivatives and aliphatic or alicyclic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch [Plastics Handbook], Vol. VIII, p. 695 and thereafter, Karl Hanser Verlag, Munich 1973).

[0034] Preferred poly(C1-C6-alkylene terephthalate) contains at least 80 mol% and preferably at least 90 mol% of terephthalic acid groups based on dicarboxylic acid, and at least 80 mol% and preferably at least 90 mol% of cyclohexane-1,4-diethanol and / or ethylene glycol and / or propane-1,3-diol (in the case of poly(propylene terephthalate)) and / or butane-1,4-diol groups based on diol components.

[0035] Preferred poly(C1-C6-alkylene terephthalate) may contain, in addition to terephthalic acid groups, up to 20 mol% of other aromatic dicarboxylic acid groups having 8 to 14 carbon atoms or aliphatic dicarboxylic acid groups having 4 to 12 carbon atoms, and more particularly phthalic acid groups, isophthalic acid groups, naphthalene-2,6-dicarboxylic acid groups, 4,4'-biphenyl dicarboxylic acid groups, succinic acid groups, adipic acid groups, sebacic acid groups, azelaic acid groups, cyclohexanediacetic acid groups, and cyclohexanedicarboxylic acid groups.

[0036] Preferred poly(C1-C6-alkylene terephthalate) may contain, in addition to cyclohexane-1,4-diethanol and / or ethylene glycol and / or propane-1,3-diol and / or butane-1,4-diol, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or up to 20 mol% of alicyclic diols having 6 to 21 carbon atoms, preferably propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, or 3-methylpentane-2,4-diol. The groups of 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2,4-trimethylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-bis(β-hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(3-β-hydroxyethoxyphenyl)propane, and 2,2-bis(4-hydroxypropoxyphenyl)propane.

[0037] Particularly preferred poly(C1-C6-alkylene terephthalate) is prepared solely from terephthalic acid and its reactive derivatives, especially its dialkyl esters, as well as cyclohexane-1,4-diethanol and / or ethylene glycol and / or propane-1,3-diol and / or butane-1,4-diol; particularly preferred are poly(cyclohexane-1,4-diethanol terephthalate), polyethylene terephthalate, and polybutylene terephthalate, and mixtures thereof.

[0038] Poly(C1-C6-alkylene terephthalate) can also be recycled. Recyclables should generally be understood to mean:

[0039] 1) So-called post-industrial recyclables (also known as pre-consumer recyclables): This includes production waste from polycondensation, from blending (e.g., substandard materials), or from processing, such as gate material in injection molding, starting material in injection molding or extrusion, or edge material cut from extruded sheets or films.

[0040] 2) Post-consumer recyclables: This includes plastic products that are collected and processed after use by end consumers. To date, the bulk-dominant products are blow-molded PET bottles used for mineral water, soft drinks, and juices.

[0041] PET recyclables from recycled PET bottles for use according to the invention are preferably obtained by methods according to DE 10324 098 A1, WO 2004 / 009315 A1 or WO 2007 / 116022 A2.

[0042] Preferred poly(C1-C6-alkylene terephthalate) is a copolyester prepared from at least two of the above-mentioned acid components and / or from at least two of the above-mentioned alcohol components. Particularly preferred copolyester is poly(ethylene glycol / butane-1,4-diol) terephthalate.

[0043] Preferred poly(C1-C6-alkylene terephthalate) has a range from 30 cm 3 / g to 150cm 3 Within the range of / g, more preferably from 40cm 3 / g to 130cm 3 Within the range of / g, most preferably from 50cm 3 / g to 100cm 3The intrinsic viscosity is measured in the range of 1 ml / g in phenol / o-dichlorobenzene (1:1 by weight) at 25°C in each case. Intrinsic viscosity iV, also known as the Staudinger Index or limiting viscosity, is proportional to the average molecular weight according to the Mark-Howwink equation and is an extrapolation of the viscosity value VN when the polymer concentration becomes zero. Intrinsic viscosity can be estimated by a series of measurements or by using a suitable approximation method (e.g., Billmeyer). VN [ml / g] is obtained by measuring the solution viscosity in a capillary viscometer, preferably an Ubbelohde viscometer. Solution viscosity is a measure of the average molecular weight of the plastic. It is determined using various solvents (preferably formic acid, m-cresol, tetrachloroethane, phenol, 1,2-dichlorobenzene) and concentrations on a dissolved polymer. The viscosity value VN allows for monitoring the processing and performance characteristics of the plastic. Thermal stress, aging processes, or exposure to chemicals, weathering, and light on the polymer can be studied by comparing measurements. For common polymers, the method is standardized: in the context of this invention, according to DIN ISO 1628-5 for polyesters. See also: http: / / de.wikipedia.org / wiki / Viskosimetrie and http: / / de.wikipedia.org / wiki / Mark-Houwink-Gleichung.

[0044] The poly(C1-C6-alkylene terephthalate) used for purposes according to the invention can also be used in mixtures with other polyesters and / or additional polymers.

[0045] During compounding, the poly(C1-C6-alkylene terephthalate) used according to the invention can be blended in the melt with conventional additives, especially mold release agents. Those skilled in the art will understand compounding as a term from plastics technology, which can be equivalent to plastics processing and describes a process for the directional optimization of characteristic profiles of modified plastics by incorporating additives (fillers, additives, etc.). Compounding is preferably carried out in an extruder, particularly preferably in a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, a planetary gear extruder, or a co-kneader, and includes process operations of conveying, melting, dispersing, mixing, venting, and pressure buildup.

[0046] Preferred materials include at least one poly(C1-C6-alkylene terephthalate) selected from polyethylene terephthalate [CAS No. 25038-59-9] and polybutylene terephthalate [CAS No. 24968-12-5], particularly polybutylene terephthalate (PBT). Polybutylene terephthalate (PBT) [CAS No. 24968-12-5] is especially preferred, sourced from Lanxess Deutschland GmbH, Cologne. Trademarks are available.

[0047] Glass fiber (component B)

[0048] According to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund", glass fibers used in the applications according to the invention are classified into chopped fibers (also called short fibers) having a length ranging from 0.1 mm to 1 mm, long fibers having a length ranging from 1 mm to 50 mm, and continuous fibers having a length L>50 mm. Short fibers are used in injection molding and are directly processable by an extruder. Long fibers can also be processed in an extruder. These fibers are widely used in fiber spraying. Long fibers are often added to thermosetting materials as fillers. Continuous fibers are used in fiber-reinforced plastics in the form of rovings or fabrics. Articles containing continuous fibers achieve the highest stiffness and strength values. Ground glass fibers are also available, typically ranging in length from 70 μm to 200 μm after grinding. Ground glass fibers can also be used according to the invention.

[0049] According to the invention, it is preferred to use short-cut glass fibers having an initial length in the range of 1 mm to 50 mm, more preferably in the range of 1 mm to 10 mm, and most preferably in the range of 2 mm to 7 mm. The initial length describes the average length of the glass fibers before blending one or more compositions according to the invention to provide a molded compound according to the invention. As a result of processing, especially blending, to obtain a molded compound or article, the glass fibers used as component B) may have a smaller d97 or d50 value in the molded compound or article than the glass fibers originally used. Therefore, the arithmetic mean length of the glass fibers after processing is often still only in the range of 150 μm to 300 μm.

[0050] In the context of this invention, in the case of processed glass fibers, the glass fiber length and length distribution are determined according to ISO 22314, which first specifies that the sample is ashed at 625°C. Subsequently, in a suitable crystallizing dish, the ash is placed on a microscope slide covered with softened water and distributed in an ultrasonic bath without mechanical force. The next step involves drying in an oven at 130°C, followed by determination of the glass fiber length using optical microscopic images. For this purpose, at least 100 glass fibers are measured from three images, and thus a total of 300 glass fibers are used to determine their length. The glass fiber length can be calculated as an arithmetic mean using the following equation: n

[0051]

[0052] Among them l i = the length of the i-th fiber and n = the number of fibers measured, and appropriately represented by a histogram, or assuming a normal distribution of the measured glass fiber lengths l, determined using a Gaussian function according to the following equation.

[0053]

[0054] In this equation, l c And σ are specific parameters of the normal distribution: l c It is the mean, and σ is the standard deviation (see: M. Schoβig, in Kunststoffen, *Mechanisms of Damage in Fiber-Reinforced Plastics*, 1, 2011, Vieweg und Teubner Verlag, p. 35, ISBN 978-3-8348-1483-8). Glass fibers not bound to the polymer matrix were analyzed regarding their length using the methods described above, but not through ashing or separation from the ash.

[0055] The glass fibers used in this invention [CAS No. 65997-17-3] preferably have a fiber diameter in the range of 7 μm to 18 μm, more preferably in the range of 9 μm to 15 μm, which can be determined by at least one means available to those skilled in the art, in particular by computed tomography similar to the following document: “Quantitative Messung von und-verteilung in Kunststoffteilen mittelsμ- "Computer tomographie" [Quantitative measurement of fiber lengths and fiber distribution in fiber-reinforced plastic components by computed x-ray microtomography], J. Kastener et al., DGZfP Annual Meeting 2007 - Paper 47. The glass fibers used as component B are preferably added as continuous fibers or as chopped or ground glass fibers.

[0056] In a preferred embodiment, the glass fiber to be used is modified with a suitable adhesive system or adhesion promoter or adhesion promoter system (more preferably based on silane).

[0057] Preferred silane-based adhesion promoters for the pretreatment of glass fibers are silane compounds of general formula (I).

[0058] (X-(CH2) q ) k -Si-(O-CrH 2r+1 ) 4-k (I)

[0059] The substituents are defined as follows:

[0060] X: NH2-, HO-,

[0061] q: an integer from 2 to 10, preferably from 3 to 4.

[0062] r: an integer from 1 to 5, preferably from 1 to 2.

[0063] k: an integer from 1 to 3, preferably 1.

[0064] Particularly preferred adhesion promoters are silane compounds from the group consisting of: aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and corresponding silanes containing a glycidyl group as a substituent X.

[0065] For the modification of glass fibers, these silane compounds are preferably used for surface coating in an amount based on 100% by weight of filler and / or reinforcing agent (especially glass fiber) in the range of 0.05% by weight to 2% by weight, more preferably in the range of 0.25% by weight to 1.5% by weight, and especially in the range of 0.5% by weight to 1% by weight.

[0066] Polyamide 6 (component C)

[0067] The polyamide 6 used according to the invention is preferably a semi-crystalline polyamide, whose enthalpy of melting according to DE 10 2011 084 519A1 is in the range of 4 J / g to 25 J / g, and is measured and integrated over the melting peak during the second heating run by DSC method according to ISO 11357.

[0068] In the context of this application, the designation of polyamide corresponds to the International Standard or DIN 7728. If only a number is stated, such as in the case of PA 6, this means that the starting material is α,ω-aminocarboxylic acid or a lactam derived therefrom, i.e., ε-caprolactam in the case of PA 6; for further information, see H. Domininghaus, Die Kunststoffe und ihre Eigenschaften [Plastics and their properties], p. 272 ​​and thereafter, VDI Publishers (VDI-Verlag), 1976.

[0069] It is preferred to use low-viscosity polyamide 6, which has a viscosity value in the range of 80 ml / g to 135 ml / g, more preferably from 90 ml / g to 130 ml / g, even more preferably from 90 ml / g to 125 ml / g, and particularly preferably from 95 ml / g to 115 ml / g, as determined according to ISO 307 in a 0.5 wt% solution of 96 wt% sulfuric acid at 25°C.

[0070] In a particularly preferred embodiment, polyamide 6 is used, having a viscosity value in the range of 95 ml / g to 115 ml / g as determined according to ISO 307 in a solution of 0.5 wt% sulfuric acid at 25°C in a solution of 96 wt%.

[0071] Particularly preferred is the use of polyamide 6, which has already been prepared by the hydrolytic polymerization of ε-caprolactam. The polyamide 6 used according to the present invention can be used as… B26 originates from Lanxess Deutschland GmbH, Cologne.

[0072] Copolymer (Component D)

[0073] The preferred embodiment is a copolymer of at least one α-olefin and at least one aliphatic alcohol in the form of a methacrylate or acrylate.

[0074] A copolymer of an α-olefin and an aliphatic alcohol in the form of a methacrylate or acrylate is particularly preferred.

[0075] A copolymer of an acrylate of an α-olefin and an aliphatic alcohol is given a very particular preference.

[0076] Of particular preference are copolymers in which the α-olefin is formed from ethylene and the methacrylate or acrylate contains a straight-chain or branched alkyl group having 6 to 20 carbon atoms as an alcohol component.

[0077] A copolymer is particularly preferred here, wherein the α-olefin is ethylene and the acrylate contains a straight-chain or branched alkyl group having 6 to 20 carbon atoms as an alcohol component.

[0078] Most particularly preferably, the copolymer of at least one α-olefin and at least one acrylate used is a copolymer of ethylene and 2-ethylhexyl acrylate or a copolymer of ethylene and butyl acrylate.

[0079] The copolymers used according to the invention are noteworthy not only for their composition but also for their low molecular weight. Therefore, copolymers having an MFI of at least 100 g / 10 min, preferably at least 150 g / 10 min, and more preferably at least 300 g / 10 min, as measured at 190°C and a load of 2.16 kg, are particularly preferred. The MFI (Mel Flow Index) is characterized by the flow of the melt in the thermoplastic and is constrained by standards ISO 1133 or ASTM D 1238. In the context of this invention, MFI and all figures related to MFI refer to the following standard methods or are measured or determined according to ISO 1133 at 190°C with a test weight of 2.16 kg. According to the invention, copolymers with a MFI of at least 100 g / 10 min, preferably at least 150 g / 10 min, and more preferably at least 300 g / 10 min, as measured at a load of 2.16 kg, are particularly preferred. 28BA700T is an ethylene-butyl acrylate copolymer available from SK Functional Polymer.

[0080] Additive (Component E)

[0081] Optionally, or in a preferred embodiment, the compositions, molded compounds, and articles according to the invention contain at least one additive as component E, different from components A), B), C), and D). Preferred additives for component E) are lubricants and release agents, fillers and / or reinforcing agents other than component B), UV stabilizers, colorants, chain extenders, plasticizers, flow promoters different from component D), heat stabilizers, antioxidants, gamma-ray stabilizers, hydrolytic stabilizers, elastomer modifiers, antistatic agents, emulsifiers, nucleating agents, processing aids, anti-dripping agents, and flame retardants. The additives for component E) can be used alone or in the form of mixtures / masterbatches. It is preferred to use at least one of the following groups, other than component B), as fillers and / or reinforcing agents: mica, silicates, quartz (especially quartz powder), titanium dioxide, wollastonite, nepheline syenite, kaolinite, amorphous silica, magnesium carbonate, chalk, feldspar, metal sulfates, glass fibers, glass beads, glass powder, and / or fiber-based fillers and / or reinforcing agents different from component B).

[0082] Preferred materials include microparticle mineral fillers and / or reinforcing agents based on mica, silicates, quartz, wollastonite, kaolin, amorphous silica, magnesium carbonate, chalk, or feldspar. Needle-shaped mineral fillers are also particularly preferred. According to the invention, needle-shaped mineral fillers and / or reinforcing agents should be understood as mineral fillers having very pronounced needle-like characteristics. The needle-shaped mineral fillers and / or reinforcing agents preferably have a length-to-diameter ratio in the range of 2:1 to 35:1, more preferably in the range of 3:1 to 19:1, and most preferably in the range of 4:1 to 12:1. The median grain size d50 of the needle-shaped minerals used according to the invention, determined by laser diffraction according to ISO 13320:2009 using a CILAS GRANULOMETER, is preferably less than 20 μm, more preferably less than 15 μm, and particularly preferably less than 10 μm.

[0083] As a result of processing to provide a molded compound or article, optionally or in a preferred embodiment, fillers and / or reinforcing agents different from component B) to be used as component E) in the molded compound or article may have smaller d97 or d50 values ​​than the originally used fillers and / or reinforcing agents and / or glass fibers. They may be used alone or as a mixture of two or more different fillers and / or reinforcing agents.

[0084] In a preferred embodiment, the filler and / or reinforcing agent to be used as component E, different from component B), may be surface-modified, more preferably surface-modified with an adhesion promoter or adhesion promoter system, particularly preferably an epoxide-based adhesion promoter or adhesion promoter system. However, pretreatment is not absolutely necessary.

[0085] Preferably, the fillers and / or reinforcing agents to be used as component E) are also modified with a suitable adhesive system or adhesion promoter or adhesion promoter system (more preferably silane-based). Preferred silane-based adhesion promoters for pretreatment are silane compounds of general formula (I).

[0086] (X-(CH2) q ) k -Si-(O-CrH 2r+1 ) 4-k (I)

[0087] The substituents are defined as follows:

[0088] X: NH2-, HO-,

[0089] q: an integer from 2 to 10, preferably from 3 to 4.

[0090] r: an integer from 1 to 5, preferably from 1 to 2.

[0091] k: an integer from 1 to 3, preferably 1.

[0092] Particularly preferred adhesion promoters are silane compounds from the group consisting of: aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and corresponding silanes containing a glycidyl group as a substituent X.

[0093] The lubricant and release agent used as component E) are selected from at least one of the group consisting of long-chain fatty acids, salts of long-chain fatty acids, ester derivatives of long-chain fatty acids and lignite waxes.

[0094] Preferred long-chain fatty acids are stearic acid or behenic acid. Preferred long-chain fatty acid salts are calcium stearate or zinc stearate. Preferred long-chain fatty acid ester derivatives are those based on pentaerythritol, and more particularly on the C16 of pentaerythritol. 16 -C 18 Fatty acid esters [CAS No. 68604-44-4] or [CAS No. 85116-93-4].

[0095] In the context of this invention, lignite wax is a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms. According to the invention, lubricants and / or release agents comprising esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms and aliphatic saturated alcohols having 2 to 40 carbon atoms, and metal salts comprising saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms, with pentaerythritol tetrastearate, calcium stearate [CAS No. 1592-23-0] and / or ethylene glycol dilignite ester, particularly from Clariant, Muttenz, Basel, are given special preference. E [CAS No. 74388-22-0], and particularly, very particularly preferred, pentaerythritol tetrastearate [CAS No. 115-83-3] (e.g., as...). P861 is available from Emery Oleochemicals GmbH, Düsseldorf, Germany.

[0096] The UV stabilizer to be used as component E) is preferably a substituted resorcinol, salicylate, benzotriazole, triazine derivative or benzophenone.

[0097] The colorant to be used as component E) is preferably an organic pigment, preferably phthalocyanine, quinacridone, dinaphthalene, and dyes, preferably aniline black or anthraquinone, and also inorganic pigments, especially titanium dioxide (if not already used as a filler), metal sulfates (if not already used as fillers), ultramarine, iron oxide, zinc sulfide or carbon black.

[0098] Useful titanium dioxide pigments, preferably preferred as pigments according to the invention, include titanium dioxide pigments whose parent oxides can be produced by sulfate (SP) or chloride (CP) methods and have anatase and / or rutile structures, preferably rutile. The parent oxide does not necessarily need to be stable, but specific stabilization is preferred: in CP parent oxides, by doping with 0.3 wt% to 3.0 wt% Al (calculated as Al₂O₃) and at least 2% excess oxygen in the gas phase during the oxidation of titanium tetrachloride to form titanium dioxide; in the case of SP parent oxides, by doping with, for example, Al, Sb, Nb, or Zn. "Light" stabilization with Al, or, at higher Al doping levels, compensation with antimony, is particularly preferred. It is known that when titanium dioxide is used as a white pigment in paints and coatings, plastic materials, etc., unwanted photocatalytic reactions caused by UV absorption lead to the decomposition of the colored material. This involves the absorption of light in the near-ultraviolet range by titanium dioxide pigments, thus forming electron-hole pairs that generate highly reactive free radicals on the titanium dioxide surface. The resulting free radicals lead to binder decomposition in organic media. According to the invention, it is preferable to reduce the photoactivity of titanium dioxide by performing an inorganic post-treatment (particularly preferably with oxides of Si and / or Al and / or Zr and / or by using Sn compounds).

[0099] Preferably, the surface of the pigment titanium dioxide is covered with an amorphous precipitated oxide hydrate of compounds SiO2 and / or Al2O3 and / or zirconium oxide. The Al2O3 shell promotes pigment dispersion into the polymer matrix; the SiO2 shell makes charge exchange on the pigment surface more difficult, thus preventing polymer degradation.

[0100] According to the present invention, titanium dioxide preferably has a hydrophilic and / or hydrophobic organic coating, particularly a siloxane or polyol.

[0101] Titanium dioxide [CAS No. 13463-67-7] used as a colorant in component E) according to a preferred application of the invention has a median particle size d50 in the range of 90 nm to 2000 nm, more preferably in the range of 200 nm to 800 nm. The median particle size d50 is a value determined by a particle size distribution in which 50% by weight of the particles have an equivalent sphere diameter smaller than this d50 value. The relevant standard is ISO 13317-3.

[0102] The particle size distribution and reported median particle size of titanium dioxide are based on so-called surface-based particle size, in each case prior to incorporation into thermoplastic molding compounds. Particle size is determined according to the invention by laser diffraction; see CMKeck, Modern Pharmaceutical Technology, 2009, Free University of Berlin, Chapter 3.1, or QUANTACHROME PARTIKELWELT NO 6, June 2007, pp. 1-16.

[0103] Commercially available titanium dioxide includes, for example, products from Kronos Corporation (Dallas, USA). 2230 2233、 2225 and vlp7000.

[0104] It is preferred to use titanium dioxide as a pigment, in each case based on 100 parts by mass of component A), the amount of which is in the range of 0.1 to 60 parts by mass, more preferably in the range of 1 to 35 parts by mass, and most preferably in the range of 2 to 20 parts by mass.

[0105] The nucleating agent used as component E) is preferably sodium or calcium phenylphosphine, alumina, silica, or talc. Talc [CAS No. 14807-96-6] is particularly preferred as the nucleating agent, especially microcrystalline talc. Talc has the chemical composition Mg3[Si4O3]. 10 The lepidocrocite of [OH]₂, depending on the modification, crystallizes as talc-1A in the triclinic system or talc-2M in the monoclinic system (http: / / de.wikipedia.org / wiki / Talkum). The talc used according to the invention is, for example, named... R10 is commercially available from Imerys Talc Group, Toulouse, France (Rio Tinto Group).

[0106] Alternatively, as component E), it is possible to preferably use difunctional or polyfunctional branching or chain-extending additives containing at least two and no more than 15 branching or chain-extending functional groups per molecule. Suitable branching or chain-extending additives include low molecular weight or oligomer compounds having at least two and no more than 15 branching or chain-extending functional groups per molecule, and they are capable of reacting with primary and / or secondary amines, and / or amides and / or carboxylic acids. The chain-extending functional groups are preferably isocyanates, alcohols, terminal isocyanates, epoxides, maleic anhydrides, oxazolines, oxazines, oxazolones, with epoxides being preferred.

[0107] Particularly preferred di- or multi-functional branched or chain-extending additives are diglycidyl ethers (bisphenol and epichlorohydrin), amine epoxy resins (aniline and epichlorohydrin), diglycidyl esters (alicyclic dicarboxylic acids and epichlorohydrin), alone or in mixtures, and also 2,2-bis[p-hydroxyphenyl]propane diglycidyl ether, bis[p-(N-methyl-N-2,3-epoxypropylamino)phenyl]methane, and epoxidized fatty acid glycerides comprising at least two and no more than 15 epoxy groups per molecule.

[0108] Particularly preferred di- or polyfunctional branching or chain-extending additives are glycidyl ethers, very particularly preferred are bisphenol A diglycidyl ether [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, and even more particularly preferred are epoxidized soybean oil [CAS No. 8013-07-8].

[0109] Furthermore, the following are particularly preferred for branching / chain extension:

[0110] 1. Polymeric or oligomeric glycidyl ethers or poly(β-methylglycidyl) ethers, obtained by reacting a compound containing at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups with a suitably substituted epichlorohydrin under alkaline conditions, or by reacting it in the presence of an acidic catalyst and subsequently by alkaline treatment.

[0111] Polymeric or oligomeric glycidyl ethers or poly(β-methylglycidyl) ethers, preferably derived from noncyclic alcohols, particularly ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycol, propane-1,2-diol, poly(oxypropylene) glycol, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycol, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylpropane, bis(trimethylolpropane), pentaerythritol, sorbitol, or derived from polyepoxychloropropane.

[0112] However, the ethers are also preferably derived from alicyclic alcohols, particularly 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3-ene, or they include an aromatic nucleus, particularly N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.

[0113] These epoxy compounds can also preferably be derived from monocyclic phenols, particularly from resorcinol or hydroquinone; or based on polycyclic phenols, particularly bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, or based on condensation products of phenol and formaldehyde under acidic conditions, particularly phenolic varnishes.

[0114] 2. Polymer or oligomer (N-glycidyl) compounds, further obtained by dehydrochlorination of the reaction product of epichlorohydrin and an amine containing at least two amino hydrogen atoms. These amines are preferably aniline, toluene, n-butylamine, bis(4-aminophenyl)methane, m-phenylenediamine, or bis(4-methylaminophenyl)methane, and also contain N,N,O-triglycidyl-m-aminophenyl or N,N,O-triglycidyl-p-aminophenol.

[0115] However, poly(N-glycidyl) compounds also preferably include N,N'-diglycidyl derivatives of cycloalkyl ureas (particularly ethylidene urea or 1,3-propylidene urea) and N,N'-diglycidyl derivatives of hydantoin (especially 5,5-dimethylhydantoin).

[0116] 3. Polymer or oligomer (S-glycidyl) compounds, particularly di-S-glycidyl derivatives derived from dithiols, preferably ethane-1,2-dithiol or bis(4-mercaptomethylphenyl) ethers.

[0117] 4. Epoxidized fatty acid glycerides, particularly epoxidized vegetable oils. The esters are obtained by the epoxidation of the reactive olefinic groups of triglycerides of unsaturated fatty acids. Epoxidized fatty acid glycerides can be produced from unsaturated fatty acid glycerides, preferably vegetable oils, and organic percarbonate (Prilezhaev reaction). Methods for producing epoxidized vegetable oils are described, for example, in *Advanced Organic Chemistry, Smith, March, March* (5th edition, Wiley-Interscience, New York, 2001). Preferred epoxidized fatty acid glycerides are vegetable oils. A particularly preferred epoxidized fatty acid glyceride according to the invention is epoxidized soybean oil [CAS No. 8013-07-8].

[0118] 5. A styrene-acrylate polymer modified with glycidyl methacrylate, which can be obtained by polymerization of styrene, glycidyl methacrylate and acrylic acid and / or methacrylic acid.

[0119] Preferred plasticizers used as component E) are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oil, or N-(n-butyl)benzenesulfonamide.

[0120] Preferred elastomeric modifiers used as component E) include one or more grafted polymers of the following:

[0121] E.1 5% to 95% by weight, preferably 30% to 90% by weight, of at least one vinyl monomer

[0122] E.2 95 wt% to 5 wt%, preferably 70 wt% to 10 wt%, of one or more grafted matrices having a glass transition temperature of <10°C, preferably <0°C, more preferably <-20°C. In this case, the weight percentage is based on 100 wt% of component E).

[0123] The graft matrix E.2 typically has a median particle size (d50) in the range of 0.05 μm to 10 μm, preferably in the range of 0.1 μm to 5 μm, and more preferably in the range of 0.2 μm to 1 μm.

[0124] Monomer E.1 is preferably a mixture of the following:

[0125] E.1.1 50% to 99% by weight of vinyl aromatic compounds and / or cyclic-substituted vinyl aromatic compounds (especially styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C1-C8)-alkyl methacrylates (especially methyl methacrylate, ethyl methacrylate), and

[0126] E.1.2 1% to 50% by weight of vinyl cyanides (especially unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and / or (C1-C8)-alkyl (meth)acrylates (especially methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and / or derivatives of unsaturated carboxylic acids (especially acid anhydrides and imides, especially maleic anhydride or N-phenylmaleimide). In this case, the weight percentage is based on 100% by weight of component E).

[0127] Preferred monomer E.1.1 is selected from at least one of styrene, α-methylstyrene and methyl methacrylate; preferred monomer E.1.2 is selected from at least one of these monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.

[0128] The particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.

[0129] Grafting matrices E.2 suitable for use with these elastomeric modifiers include, for example, diene rubbers, EPDM rubbers (i.e., those based on ethylene / propylene and optionally diene), as well as acrylates, polyurethanes, silicones, chloroprene, and ethylene / vinyl acetate rubbers. EPDM stands for ethylene-propylene-diene rubber.

[0130] The preferred graft matrix E.2 is a diene rubber (especially based on butadiene, isoprene, etc.) or a mixture of diene rubbers, or a copolymer of diene rubber or a mixture thereof with other copolymerizable monomers (especially E.1.1 and E.1.2), provided that the glass transition temperature of component E.2 is <10°C, preferably <0°C, more preferably <-10°C.

[0131] The particularly preferred graft matrix E.2 is an ABS polymer (emulsion, bulk, and suspension ABS), where ABS represents acrylonitrile-butadiene-styrene, as described, for example, in DE-A 2 035 390 or DE-A 2 248 242 or Ullmann, der Technischen Chemie [Encyclopaedia of Industrial Chemistry], Volume 19 (1980), page 280 and thereafter.

[0132] These elastomer modifiers / graft polymers are produced by free radical polymerization, preferably by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, especially by emulsion polymerization or bulk polymerization.

[0133] Particularly suitable grafted rubbers also include ABS polymers, which are produced by redox initiation using an initiator system consisting of organic hydroperoxides and ascorbic acid, according to US-A 4 937 285.

[0134] As is well known, in a grafting reaction, the grafting monomer may not be completely grafted onto the grafting matrix. According to the present invention, the grafted polymer is also understood to mean the product generated by the (co)polymerization of the grafting monomer in the presence of the grafting matrix and the product obtained in the workup.

[0135] Equally suitable acrylate rubbers are based on grafted matrices E.2, which are preferably alkyl acrylates, optionally polymers having up to 40% by weight of other polymerizable olefinically unsaturated monomers based on E.2. Preferred polymerizable acrylates include C1-C8 alkyl esters, preferably methyl, ethyl, butyl, n-octyl, and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-C8 alkyl esters, preferably ethyl chloride acrylate, glycidyl acrylate, and mixtures of these monomers. In this context, grafted polymers having butyl acrylate as a core and methyl methacrylate as a shell are particularly preferred, especially those from Dow Corning Corporation, Midland Michigan, USA. EXL2300.

[0136] According to E.2, another preferred suitable grafting matrix is ​​silicone rubber with active grafting sites, as described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.

[0137] Preferred graft polymers containing a silicone portion are those comprising methyl methacrylate or styrene-acrylonitrile as a shell and silicone / acrylate grafted as a core. Available graft polymers having styrene-acrylonitrile as a shell include, for example... SRK200. Available graft polymers having methyl methacrylate as a shell include, for example... S2001 S2030 and / or SX-005. It is particularly preferred to use... S2001. Has a trade name. The products are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.

[0138] Crosslinking can be achieved by copolymerizing monomers having more than one polymerizable double bond. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate and allyl methacrylate; polyunsaturated heterocyclic compounds, preferably triethylene cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, preferably divinylbenzene and trivinylbenzene; and also triallyl phosphate and diallyl phthalate.

[0139] Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds having at least three olefinically unsaturated groups.

[0140] Particularly preferred crosslinking monomers are cyclic monomers: triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-S-triazine, and triallylbenzene. The amount of these crosslinking monomers is preferably 0.02% to 5% by weight, particularly 0.05% to 2% by weight, based on 100% by weight of the graft matrix E.2.

[0141] In the case of a cyclic crosslinking monomer having at least three olefinic unsaturated groups, it is advantageous to limit the amount to less than 1 wt% based on 100 wt% of the grafted matrix E.2.

[0142] Preferred "other" polymerizable, olefinically unsaturated monomers (optionally used in the production of graft matrix E.2, in addition to acrylates) are acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C1-C6-alkyl ethers, methyl methacrylate, glycidyl methacrylate, and butadiene. Preferred acrylate rubbers as graft matrix E.2 are emulsion polymers having a gel content of at least 60% by weight.

[0143] In addition to graft polymer-based elastomer modifiers, elastomer modifiers that are not based on graft polymers and have a glass transition temperature of <10°C, preferably <0°C, more preferably <-20°C may also be used. These preferably include elastomers with block copolymer structures and additionally thermoplastic fusible elastomers, especially EPM, EPDM and / or SEBS rubbers (EPM = ethylene-propylene copolymer, EPDM = ethylene-propylene-diene rubber and SEBS = styrene-ethylene-butene-styrene copolymer).

[0144] The preferred flame retardant to be used as component E) is halogen-free.

[0145] Preferred phosphorus-containing flame retardants used as component E) include, for example, phosphorus-containing compounds from the group consisting of: organometallic phosphinates, especially diethyl phosphinates; inorganic metal phosphinates, especially aluminum and zinc phosphinates; mono- and oligomeric polyphosphates and phosphonates, especially triphenyl phosphate (TPP); resorcinol bis(diphenyl phosphate) (RDP); bisphenol A bis(diphenyl phosphate) (BDP), including oligomers; polyphosphonates, especially bisphenol A-diphenylmethyl phosphonate copolymers, such as Nofia from FRX Polymers, Chelmsford, USA. TMHM1100 [CAS No. 68664-06-2]), and derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO derivatives), phosphonate amines, metal phosphonates, especially aluminum phosphonates and aluminum alkyl phosphonates, as well as zinc phosphonates and zinc alkyl phosphonates, and phosphine oxides and phosphazenes. Particularly preferred phosphazenes are phenoxyphosphazene oligomers. Other phosphorus-containing flame retardants preferably used as component E) are melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminum phosphate), melamine poly(zinc phosphate), and the reaction products of melamine, melamine, cyanuramide and condensed phosphoric acid.

[0146] Phosphorus-free nitrogen-containing flame retardants can also be used alone or in mixtures as additional flame retardants to component E). Preferred nitrogen-containing flame retardants are reaction products of trichlorotriazine, piperazine, and morpholine (CAS No. 1078142-02-5), especially MCA PPM triazine HF from MCA Technologies GmbH, Biel-Benken, Switzerland, and also melamine cyanurate and condensation products of melamine (especially melamine, melamine, cyanuramide, or higher condensation compounds of this type). Preferred inorganic nitrogen-containing compounds are ammonium salts.

[0147] Other flame retardants or flame retardant synergists not specifically mentioned herein may also be used as component E. These include pure inorganic phosphorus compounds, particularly red phosphorus or boron phosphate hydrate. Mineral flame retardant additives, such as magnesium hydroxide, or salts of aliphatic and aromatic sulfonic acids, particularly metal salts of 1-perfluorobutane sulfonic acid, may also be used. Also suitable are flame retardant synergists from the group consisting of oxygen-, nitrogen-, or sulfur-containing metal compounds, wherein the metal is antimony, zinc, molybdenum, calcium, titanium, magnesium, or boron, preferably antimony trioxide, antimony pentoxide, sodium antimonate, zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide, molybdenum oxide, and (if not already used as a colorant) titanium dioxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, boron nitride, magnesium nitride, zinc nitride, calcium borate, magnesium borate, or mixtures thereof.

[0148] Suitable and preferred additional flame retardant additives for component E) are char formers, more preferably poly(2,6-diphenyl-1,4-phenyl) ethers, especially poly(2,6-dimethyl-1,4-phenylene) ether [CAS No. 25134-01-4], phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyetherketones, and anti-dripping agents (especially tetrafluoroethylene polymers). These tetrafluoroethylene polymers can be used in pure form or in combination with other resins (preferably styrene-acrylonitrile (SAN)) or acrylates (preferably methyl methacrylate / butyl acrylate).

[0149] Halogenated flame retardants may also be used if required by the application. These include commercially available organohalogen compounds with or without synergists. Halogenated, particularly brominated and chlorinated compounds preferably include ethylene-1,2-bistetrabromophthalimide, decabromodiphenyl ethane, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromobenzyl polyacrylate, brominated polystyrene, and brominated polyphenylene ether.

[0150] The additional flame retardant used as component E) can be in pure form and can also be added to polyalkylene terephthalate or polycycloalkylene terephthalate via masterbatch or compacted formulation.

[0151] The heat stabilizers preferably used as component E) are selected from the group consisting of sulfur-containing stabilizers, especially sulfides, dialkyl thiocarbamates or thiodipropionic acid, and those selected from the group consisting of iron salts and copper salts (especially copper iodide (I) in the latter case) (preferably used in combination with potassium iodide and / or sodium hypophosphite NaH2PO2), and sterically hindered amines (especially tetramethylpiperidine derivatives), aromatic secondary amines (especially diphenylamine), hydroquinone, substituted resorcinols, salicylates, benzotriazoles and benzophenones, and sterically hindered phenols and aliphatic or aromatic substituted phosphites, and representatives of different substitutions of these groups.

[0152] Among sterically hindered phenols, those having at least one 3-tert-butyl-4-hydroxy-5-methylphenyl unit and / or at least one 3,5-bis(tert-butyl-4-hydroxyphenyl) unit are preferred, and those having particularly preferred form are hexane-1,6-diol bis[3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate][CAS No. 35074-77-2]. 259, from BASF SE, Ludwigshafen, Germany), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][CAS No. 6683-19-8] 1010 (from BASF) and 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane [CAS No. 90498-90-1] (ADK) AO 80). ADK AO 80 is commercially available from Adeka-Palmerole SAS in Mulhouse, France.

[0153] Among aliphatic or aromatic substituted phosphites, pentaerythritol bis(2,4-dicumylphenyl) diphosphite [CAS No. 154862-43-8] is preferred, for example, from Dover Chemical Corp., Dover, USA, under the trade name... Available under S9228, and tetra(2,4-di-tert-butylphenyl)-1,1-diphenyl-4,4'-diyl bisphosphonate [CAS No. 38613-77-3], which may be, for example, from Clariant International Ltd., Muttenz, Switzerland as Available with P-EPQ.

[0154] Especially preferred applications

[0155] More preferably, the present invention relates to the use of polyamide 6 for reducing the melt viscosity of compositions and molding blends wherein 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of ethylene-butyl acrylate copolymer are present per 100 parts by weight of polybutylene terephthalate, as determined according to ISO 11443 at 260°C, and / or the filling pressure as determined according to EN ISO 294-1.

[0156] The present invention relates more particularly to the use of 0.5 to 15 parts by weight of polyamide 6 for reducing the melt viscosity of compositions and molding compounds wherein 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of ethylene-butyl acrylate copolymer are present per 100 parts by weight of polybutylene terephthalate, as determined according to ISO 11443 at 260°C, and / or the filling pressure as determined according to EN ISO 294-1.

[0157] Especially preferred method

[0158] More preferably, the present invention relates to a method for reducing the melt viscosity, as determined according to ISO 11443 at 260°C, and / or the filling pressure, as determined according to EN ISO 294-1, of a composition and molding compound comprising a polyamide 6, preferably in an amount ranging from 0.5 to 15 parts by weight, wherein each 100 parts by weight of polybutylene terephthalate contains 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of ethylene-butyl acrylate copolymer, by adding polyamide 6, preferably in an amount ranging from 0.5 to 15 parts by weight of polyamide 6.

[0159] Particularly preferred compositions, molded compounds and articles

[0160] In a preferred embodiment, the invention further relates to compositions, molded blends, and articles, each comprising A) 100 parts by weight of polybutylene terephthalate, B) 10 to 115 parts by weight of glass fiber, C) 0.5 to 15 parts by weight of polyamide 6, and D) 0.5 to 30 parts by weight of ethylene-butyl acrylate copolymer.

[0161] The preferred articles are those used in the electrical or electronic industries, and more preferably those used in electric vehicles.

[0162] The molded compound of the present invention is formulated for further use, particularly by injection molding or extrusion, by mixing the components to be used in at least one mixing device, preferably a mixing machine. This provides a molded compound of the composition based on the present invention as an intermediate. The molded compound is ultimately used to produce articles by suitable methods.

[0163] The present invention alternatively relates to a method for producing articles, preferably for use in the electrical industry, electric vehicle industry, or electronics industry, and more preferably for electronic or electrical components and parts, which involves mixing a composition according to the invention to obtain a molding compound, extruding it in the form of an extruder, cooling the extruder until it is granulatable and granulating it, and finally subjecting the granulated material in the form of a matrix material to an injection molding or extrusion operation, preferably an injection molding operation. In one embodiment, the molding compound can be fed directly to injection molding or extrusion without extruding it to form an extruder and granulating it.

[0164] The mixing is preferably carried out in the melt at a temperature ranging from 240°C to 310°C, more preferably from 260°C to 300°C, and particularly preferably from 270°C to 295°C. Especially preferably, for this purpose, a twin-screw extruder is used.

[0165] In one embodiment, before being subjected to an injection molding or extrusion process as a matrix material to produce an article according to the invention, the granular material comprising the composition according to the invention is dried in a vacuum drying oven or in a dry air dryer, preferably at a temperature in the range of about 120°C, for a duration in the range of 2 hours.

[0166] Injection molding and extrusion methods for thermoplastic molding compounds are known to those skilled in the art. The method according to the invention for producing polyester-based articles by extrusion or injection molding operates at a melt temperature in the range of 240°C to 330°C, preferably in the range of 260°C to 300°C, particularly preferably in the range of 270°C to 290°C, and optionally additionally at a pressure not exceeding 2500 bar, preferably not exceeding 2000 bar, particularly preferably not exceeding 1500 bar, and very particularly preferably not exceeding 750 bar.

[0167] Sequential co-extrusion involves extruding two different materials in an alternating sequence. This forms a preform with a material composition that differs segment by segment in the extrusion direction. It is possible to give precisely desired properties to specific sections of an article through appropriate material selection, such as providing soft ends and a hard central section or a single, soft, corrugated section (Thielen, Hartwig, Gust, "Blasformen von..."). "[Blow-Moulding of Hollow Plastics Bodies], Carl Hanser Verlag, Munich 2006, pp. 127-129."

[0168] In injection molding, a molding compound (preferably in granular form) comprising the composition according to the invention is melted (i.e., plasticized) in a heated cylindrical cavity and injected under pressure into the heated cavity as an injection material. After the material cools (solidifies), the injection-molded article is demolded.

[0169] Distinguish between the following items:

[0170] 1. Plasticizing / melting

[0171] 2. Injection stage (filling procedure)

[0172] 3. Maintain pressure during the crystallization process (due to thermal contraction).

[0173] 4. Demolding.

[0174] For this information, see http: / / de.wikipedia.org / wiki / Spritzgie%C3%9Fen. An injection molding machine comprises a closing unit, an injection unit, a driver, and a control system. The closing unit includes a fixed and movable platform for the mold, an end platen, multiple tie bars, and a driver (toggle joint or hydraulic closing unit) for the movable mold platform.

[0175] The injection unit includes an electrically heated barrel, a screw actuator (motor, drive), and a hydraulic system for moving the screw and the injection unit. The injection unit melts, meteres, injects, and applies holding pressure (due to contraction) onto the powder / granulated material. The problem of melt backflow (leakage) within the screw is addressed by a check valve.

[0176] In an injection mold, the incoming melt is then separated and cooled, thus producing the article to be manufactured. For this purpose, two mold halves are typically required. In injection molding, the following functional systems are distinguished:

[0177] - Flow channel system

[0178] - Molded inserts

[0179] -exhaust

[0180] - Machine mounting and force absorption

[0181] - Demolding system and motion transmission

[0182] -Temperature control

[0183] Compared to injection molding, extrusion involves the continuous extrusion of plastics using the molding compound according to the invention in an extruder, a machine for producing molded thermoplastic articles. See http: / / de.wikipedia.org / wiki / Extrusionsblasformen for details. Distinctions are made between single-screw extruders and twin-screw extruders, as well as between corresponding subgroups of conventional single-screw extruders, conveyor single-screw extruders, counter-rotating twin-screw extruders, and co-rotating twin-screw extruders.

[0184] An extrusion system consists of the following components: extruder, die, downstream devices, and extrusion blow molding die. An extrusion system for producing profiles consists of the following components: extruder, profile die, calibration unit, cooling zone, crawler-type output device and roller-type output device, separation equipment, and chute.

[0185] Therefore, the present invention also relates to halogen-free articles, especially halogen-free articles resistant to leakage current, that can be obtained by extrusion (preferably profile extrusion) or injection molding of a molding compound obtainable from the composition according to the present invention.

[0186] Example

[0187] To demonstrate the improvements in melt viscosity and / or filling pressure described in this invention, the corresponding molding compound was first prepared by compounding. For this purpose, these individual components were mixed in a twin-screw extruder (ZSK 26Mega mixer, from Coperion Werner & Pfleiderer AG (Stuttgart, Germany)) at temperatures ranging from 260°C to 290°C, discharged as extrudate, cooled until granulatable, and granulated. After drying (approximately 2 hours in a vacuum drying oven at 120°C), these granules were processed to form test samples.

[0188] The test samples used for the study were injection molded on an Arburg 320-210-500 injection molding machine at a melt temperature of 260°C and a mold temperature of 80°C. Table 1 shows the test samples used for the study.

[0189] Reactants:

[0190] Component A): has 93cm 3 The intrinsic viscosity (measured at 25°C in a phenol:1,2-dichlorobenzene ratio of 1:1) of linear polybutylene terephthalate (PPT) is / g. B 1300, a commercial product from Lanxess Deutschland GmbH, Leverkusen, Germany.

[0191] Component B): Glass fiber (CS 7967(26 / 1493)D, a commercial product from Lanxess GmbH, Leverkusen, Germany)

[0192] Component C): Polyamide 6 ( B26, a commercial product from Lanxess Germany GmbH, Leverkusen, Germany.

[0193] Component D): Ethylene-butyl acrylate copolymer ( 28BA700T, SK Functional Polymer

[0194] One or more components (E):

[0195] E1) Nucleating agent: Talc

[0196] E2) Heat stabilizer: Additive DP0001 [CAS No. 649560-74-7], Lanxess GmbH, Germany

[0197] Table 1

[0198]

[0199]

[0200] To determine the filling pressure as defined in EN ISO 294-1, a dumbbell-shaped sample with geometry according to ISO 527-2 / 1A was injection molded, and the required pressure in the injection molding machine was recorded. The melt temperature was set to 260°C and the mold temperature was set to 80°C.

[0201] Determine the melt viscosity at a specified shear rate at 260°C according to ISO 11443.

[0202] Heat resistance to deformation (bending stress of 1.80 MPa) was determined on an 80 mm × 10 mm × 4 mm test specimen according to ISO 75-2 Method A.

[0203] Tensile modulus, tensile strength and elongation at break are measured according to ISO 527.

[0204] Resistance to tracking is described by the CTI (Comparative Tracking Index) and determined using the method described in standard ISO 60112:2003. A test sample (60 mm × 40 mm × 4 mm) is subjected to voltage using two electrodes while simultaneously being treated between the electrodes with droplets of an electrolyte solution simulating dust and moisture. The CTI is the highest voltage at which no failure (short circuit or ignition) occurs after 50 drops.

[0205] Table 1 shows that, especially in the comparison between Example 1 and Comparison 2 (according to WO 2005 / 121245 A1), the addition of polyamide 6 resulted in a further significant reduction in both melt viscosity and filling pressure.

Claims

1. Use of polyamide 6 for reducing the melt viscosity of compositions and molding compounds as determined according to ISO 11443 at 260°C, and / or the filling pressure as determined according to EN ISO 294-1, wherein the compositions and molding compounds contain 10 to 115 parts by weight of glass fiber and 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in methacrylate or acrylate per 100 parts by weight of poly(C1-C6-alkylene terephthalate), wherein the amount of polyamide 6 used is 0.5 to 15 parts by weight, said polyamide 6 having a viscosity value in the range of 80 ml / g to 135 ml / g as determined according to ISO 307 in a 0.5% by weight solution of 96% by weight sulfuric acid at 25°C.

2. The use according to claim 1, characterized in that, The poly(C1-C6-alkylene terephthalate) used is polyethylene terephthalate or polybutylene terephthalate.

3. The use according to claim 1 or 2, characterized in that, The poly(C1-C6-alkylene terephthalate) used is polybutylene terephthalate.

4. The use according to claim 1 or 2, characterized in that, The copolymer of at least one α-olefin and at least one acrylate used is a copolymer of ethylene and 2-ethylhexyl acrylate or a copolymer of ethylene and butyl acrylate.

5. A method for reducing the melt viscosity of a composition and molding compound at 260°C as determined according to ISO 11443 and / or the filling pressure as determined according to EN ISO 294-1, wherein the composition and molding compound contain 10 to 115 parts by weight of glass fiber per 100 parts by weight of poly(C1-C6-alkylene terephthalate), characterized in that, The composition or molding compound contains 0.5 to 15 parts by weight of polyamide 6, and the composition or molding compound further contains 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in methacrylate or acrylate, wherein the polyamide 6 has a viscosity value in the range of 80 ml / g to 135 ml / g as determined according to ISO 307 in a 0.5% by weight solution of 96% by weight sulfuric acid at 25°C.

6. The method according to claim 5, characterized in that, The poly(C1-C6-alkylene terephthalate) used is polyethylene terephthalate or polybutylene terephthalate.

7. The method according to claim 5 or 6, characterized in that, The poly(C1-C6-alkylene terephthalate) used is polybutylene terephthalate.

8. The method according to claim 5, characterized in that, The copolymer used is an ethylene-butyl acrylate copolymer.

9. Compositions, molded compounds and / or articles, each containing A) 100 parts by weight of poly(C1-C6-alkylene terephthalate), B) 10 to 115 parts by weight of glass fiber, C) 0.5 to 15 parts by weight of polyamide 6, and D) 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol in the form of a methacrylate or acrylate. The polyamide 6 described herein has a viscosity value in the range of 80 ml / g to 135 ml / g as determined according to ISO 307 in a 0.5 wt% solution of 96 wt% sulfuric acid at 25°C.

10. The composition, molded compound, and / or article according to claim 9, characterized in that, The component A used is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).

11. The composition, molded compound, and / or article according to claim 9, characterized in that, The component A used is polybutylene terephthalate.

12. The composition, molded compound, and / or article according to claim 9 or 10, characterized in that, The copolymer used is an ethylene-butyl acrylate copolymer.

13. The composition, molded compound, and / or article according to claim 9 or 10, characterized in that, They are used in the electrical or electronics industry.

14. The composition, molded compound, and / or article according to claim 9 or 10, characterized in that, They are used in electric vehicles.

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