Use of polyamide 6

Abstract

To provide the use of polyamide 6.SOLUTION: The invention relates to the use of polyamide 6 for reduction of the melt viscosity, measured at 260°C according to ISO 11443 and / or the fill pressure measured according to EN ISO 294-1 of compositions and molding compounds in which there are 10-115 pts.mass of glass fibers per 100 pts.mass of poly-C1 to C6 alkylene terephthalate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the use of polyamide 6 to reduce the melt viscosity and / or filling pressure, as measured at 260°C according to ISO 11443, of compositions and molding compounds containing 10 to 115 parts by mass of glass fibers per 100 parts by mass of poly-C1-C6-alkylene terephthalate. [Background technology]

[0002] Recent research has focused on the processability of polyalkylene terephthalate-based compositions for manufacturing articles for electric mobility, in addition to their mechanical properties, such as elongation at break, tensile strength, or tensile modulus. In particular, for processing by injection molding, the goals here are low shear viscosity of the molding compound to be processed and low filling pressure in filling the cavity in the injection molding die.

[0003] (Patent Document 1) discloses a method for reducing the melt viscosity of a composition comprising A) 99.9 to 10 parts by weight of at least one semicrystalline thermoplastic polyamide, B) 0.1 to 20 parts by weight of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol methacrylate or acrylic acid ester, 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, and F) 0% to 10% by weight of other commonly used additives, wherein copolymer B) has no further reactive functional groups, and the MFI of copolymer B) is not less than 100 g / 10 min.

[0004] (Patent Document 2) relates to a polyester-based molding compound, and solves the problem of viscosity reduction in the polyester composition, thereby reducing the filling pressure of the molding compound.

[0005] Those skilled in the art know from (Patent Document 3) that a mixture of thermoplastic polyester and a copolymer of α-olefin and aliphatic alcohol (meth)acrylic acid ester having an MFI of no less than 100 g / 10 min results in a reduction in the melt viscosity of the molding compound produced therefrom, without loss of properties such as impact resistance, elongation at break, and hydrolysis stability compared to the molding compound without the copolymer, and in some cases even improvement. The examples in (Patent Document 3) further demonstrate that the copolymer reduces the filling pressure in injection molding, as measured according to both ISO 527 and ISO 178. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] German Patent Application Publication No. 10 2004 027 872A1 Specification [Patent Document 2] European Patent Application Publication No. 1 790 692A2 Specification [Patent Document 3] International Publication No. 2005 / 121245A1 Pamphlet [Overview of the project] [Problems that the invention aims to solve]

[0007] Building upon this prior art, the problems addressed by the present invention are to reduce the shear viscosity of glass fiber reinforced poly-C1~C6-alkylene terephthalate compositions and to reduce the filling pressure in injection molding of glass fiber reinforced poly-C1~C6-alkylene terephthalate compositions or molding compounds based thereon without impairing heat strain resistance and without causing defects in mechanical indicators, particularly tensile modulus, tensile strength, and elongation at break, compared to the values ​​in International Publication No. 2005 / 121245A1. What could be disadvantageous to the objectives of the present invention is a decrease in the heat strain resistance of the processed molding compound below 180°C, or a difference of more than 10% in all three mechanical properties of tensile modulus, tensile strength, and elongation at break compared to the polyamide 6-free composition used in the present invention. [Means for solving the problem]

[0008] Surprisingly, it was found that simply adding polyamide 6 could reduce both the melt viscosity of glass fiber reinforced poly-C1~C6-alkylene terephthalate molding compounds, particularly polybutylene terephthalate-based molding compounds, and the filling pressure when using glass fiber reinforced poly-C1~C6-alkylene terephthalate molding compounds in injection molding. By simply adding polyamide 6, the filling pressure when using glass fiber reinforced poly-C1~C6-alkylene terephthalate molding compounds in injection molding could be reduced by more than 10% compared to the results of International Publication No. 2005 / 121245A1, compared to the same glass fiber reinforced composition in which ethylene-butyl acrylate copolymer is present but polyamide 6 is not.

[0009] The melt volumetric flow rate (MVR) is measured by means of a capillary viscometer in accordance with ISO 1133, as described in International Publication No. 2005 / 121245A1. The subject of study in relation to the present invention is melt viscosity, which is measured in relation to the present invention in accordance with ISO 11443 at 260°C at predetermined shear rates. See 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 measure the filling pressure in accordance with EN ISO 294-1 for a molded compound based on the composition of the present invention, which is processed by injection molding, a dumbbell-shaped test specimen having dimensions in accordance with ISO 527-2 / Type 1A is injection molded in connection with the present invention, and the pressure required by the injection molding machine is recorded. The melting temperature is set to 260°C, and the mold temperature is set to 80°C.

[0011] The tensile modulus, tensile strength, and elongation at fracture are measured in accordance with ISO 527 in relation to this invention. The modulus (also called the E modulus, tensile modulus, elastic modulus, extrinsic modulus, or Young's modulus) is a material index from materials science that describes the proportional correlation between stress and strain in the deformation of a solid material, assuming linear elastic behavior. See https: / / www.krv.de / artikel / elastizitaetsmodul-e-modul.

[0012] For information on tensile strength, please refer to https: / / wiki.polymerservice-merseburg.de / index.php / Zugfestigkeit.

[0013] The elongation at break is a specific material index that represents the deformation ability (also called ductility) of the material in the plastic region just before breakage. See https: / / www.maschinenbau-wissen.de / skript3 / werkstofftechnik / metall / 23-bruchdehnung.

[0014] The present invention provides the use of polyamide 6 for reducing the melt viscosity measured at 260 °C in accordance with ISO 11443 and / or the filling pressure measured in accordance with EN ISO 294-1 of compositions and molding compounds in which there are 10 to 115 parts by mass of glass fibers per 100 parts by mass of poly-C1-C6-alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly polybutylene terephthalate.

[0015] To avoid doubt, it should be noted that the scope of the present invention encompasses all definitions and parameters described below in any desired combination as general items or preferred ranges. This applies both to the claimed compositions, molding compounds and articles of manufacture and to the methods and uses in the present invention. The cited standards refer to the valid editions at the filing date of the present invention.

[0016] The term "alkyl" refers, in the context of the present invention, to linear or branched saturated hydrocarbon groups. The corresponding definition applies to alkylene. In the present invention, C1-C6-polyalkylene terephthalates are discussed. Preferred alkylene groups are the following: methylene (Me), ethylene (Et), propylene, particularly n-propylene and isopropylene, butylene, particularly n-butylene, isobutylene, sec-butylene, tert-butylene, pentylene groups, particularly n-pentylene, isopentylene, neopentylene and isomers of hexylene known to the person skilled in the art.

[0017] The present invention further relates to a method for reducing the melt viscosity measured at 260 °C in accordance with ISO 11443 and / or the filling pressure measured in accordance with EN ISO 294-1 of a composition and a molding compound of poly-C1-C6-alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly polybutylene terephthalate, by adding polyamide 6, preferably in an amount in the range of 0.5 to 15 parts by mass.

[0018] Finally, the present invention relates to compositions, molding compounds and articles of manufacture comprising: A) per 100 parts by mass of poly-C1-C6-alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly polybutylene terephthalate, B) 10 to 115 parts by mass of glass fibers, C) 0.5 to 15 parts by mass of polyamide 6, and D) 0.5 to 30 parts by mass of at least one copolymer of at least one α-olefin and at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol The present invention also provides compositions, molding compounds and articles of manufacture containing the same.

Mode for Carrying Out the Invention

[0019] The present invention relates to the use of polyamide 6 to reduce the melt viscosity, measured at 260°C according to ISO 11443, and / or the filling pressure, measured according to EN ISO 294-1, of compositions and molding compounds, preferably poly-C1-C6-alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly polybutylene terephthalate, containing 10 to 115 parts by mass of glass fibers and 0.5 to 30 parts by mass of at least one copolymer of at least one α-olefin and at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol, per 100 parts by mass of polybutylene terephthalate.

[0020] The present invention relates to the use of polyamide 6 to reduce the melt viscosity, measured at 260°C according to ISO 11443 and / or the filling pressure, measured according to EN ISO 294-1, of compositions and molding compounds, more preferably poly-C1~C6-alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly 10 to 115 parts by mass of glass fiber per 100 parts by mass of polybutylene terephthalate, and at least one copolymer of at least one α-olefin and at least one aliphatic alcohol methacrylic acid ester or acrylic acid ester, as measured according to ISO 11443 and / or as measured according to EN ISO 294-1, wherein the amount of polyamide 6 used is 0.5 to 15 parts by mass.

[0021] The present invention relates to a method for reducing the melt viscosity, as measured at 260°C according to ISO 11443, and / or the filling pressure, as measured according to EN ISO 294-1, of compositions and molding compounds containing poly-C1-C6-alkylene terephthalate, preferably in an amount in the range of 0.5 to 15 parts by mass, polyamide 6, preferably in an amount in the range of 0.5 to 15 parts by mass, 10 to 115 parts by mass of glass fiber per 100 parts by mass of polybutylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), particularly polybutylene terephthalate, and 0.5 to 30 parts by mass of at least one copolymer of at least one α-olefin and at least one aliphatic alcohol methacrylic acid ester or acrylic acid ester.

[0022] In a more preferred embodiment, the composition, molding compound and manufactured article of the present invention contain, in addition to components A) to D), at least one further additive E) different from components B), C), and D), preferably in an amount ranging from 0.01 to 80 parts by mass based on 100 parts by mass of component A).

[0023] The compositions of the present invention, also commonly referred to as molding compounds in the plastics industry, are obtained by processing the individual components, preferably as pelletized raw materials or powders in the form of extruded materials. The molding compounds of the present invention are obtained by mixing the compositions of the present invention in at least one mixing device, preferably a compounder, more preferably a co-rotating twin-screw extruder. The operation of mixing the individual components to produce the compositions of the present invention in the form of powder, pellets, or extruded materials is also called compounding in the plastics industry. This yields molding compounds based on the compositions of the present invention as intermediates. These molding compounds (also called thermoplastic molding compounds) may consist only of components A), B), C), and D), or may include at least one further component E) in addition to those components. In a further step, the molding compounds of the present invention are then subjected to injection molding or extrusion molding, preferably injection molding, as a matrix material to produce manufactured articles according to the present invention.

[0024] Poly-C1~C6-alkylene terephthalate (component A) Poly-C1~C6-alkylene terephthalates can be prepared by various methods and synthesized from a variety of starting materials. In specific use scenarios, they can be modified alone or in combination with processing aids, stabilizers, polymer alloying components (e.g., elastomers) or other reinforcing agents (e.g., mineral fillers or glass fibers) and optionally further additives to obtain materials with multiple properties as needed. Blends containing other polymers in certain proportions are also preferable, in which case one or more compatibilizers may be used. The properties of the polymer can also be improved by adding elastomers as needed.

[0025] Preferred poly-C1~C6-alkylene terephthalates can be prepared by known methods from terephthalic acid or its reactive derivatives and aliphatic or alicyclic diols having 2 to 10 carbon atoms (Kunststoff-Handbuch [Plastics Handbook], vol. VIII, p. 695ff, Karl Hanser Verlag, Munich, 1973).

[0026] Preferred poly-C1~C6-alkylene terephthalate contains at least 80 mol%, preferably at least 90 mol%, of terephthalic acid groups based on the dicarboxylic acid, and at least 80 mol%, preferably at least 90 mol%, of cyclohexane-1,4-dimethanol and / or ethylene glycol and / or propane-1,3-diol (in the case of polypropylene terephthalate) and / or butane-1,4-diol groups based on the diol component.

[0027] Preferred poly-C1~C6-alkylene terephthalates may contain, in addition to the terephthalic acid group, 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, more particularly phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, and cyclohexanedicarboxylic acid groups.

[0028] Preferred poly-C1~C6-alkylene terephthalates may contain, in addition to cyclohexane-1,4-dimethanol 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, which are preferably: propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane- It is the base for 2,4-diol, 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-di(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.

[0029] Particularly preferred poly-C1~C6-alkylene terephthalates are prepared solely from terephthalic acid and its reactive derivatives, particularly dialkyl esters of terephthalic acid, and cyclohexane-1,4-dimethanol and / or ethylene glycol and / or propane-1,3-diol and / or butane-1,4-diol, but especially preferred are polycyclohexane-1,4-dimethanol terephthalate, polyethylene terephthalate and polybutylene terephthalate and mixtures thereof.

[0030] Poly-C1~C6-alkylene terephthalate may be a recycled product. Recycled products are generally understood to mean the following: 1) Recycled products after the manufacturing process (recycled products before sale): These include product waste from polycondensation, compounding (e.g., substandard materials) or processing, such as sprues in injection molding, start-up materials in injection molding or extrusion molding, or edge trimmings from extruded sheets or films. 2) Used recycled items: This includes plastic items that have been collected and processed after being used by end users. The overwhelming majority of these items are blow-molded PET bottles for mineral water, soft drinks, and juices.

[0031] PET recycled products from recycled PET bottles for use in the present invention can preferably be obtained by methods in accordance with German Patent Application Publication No. 103 24 098A1, International Publication No. 2004 / 009315A1, or International Publication No. 2007 / 116022A2.

[0032] A preferred poly-C1~C6-alkylene terephthalate is also a copolyester prepared from at least two of the acid components described above and / or at least two of the alcohol components described above. A particularly preferred copolyester is poly(ethylene glycol / butane-1,4-diol) terephthalate.

[0033] Preferred poly-C1~C6-alkylene terephthalates, in each case, measured at 25°C in phenol / o-dichlorobenzene (1:1 parts by weight), yielded 30~150 cm³. 3 The range is / g, more preferably 40-130cm 3 The range is / g, most preferably 50-100cm 3It has an intrinsic viscosity in the range of / g. The intrinsic viscosity iV, also called the Staudinger index or intrinsic viscosity, is proportional to the average molecular mass according to the Mark-Hoink formula and is the value obtained by extrapolating the viscosity number VN to zero polymer concentration. It can be predicted from a series of measurements or 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 an indicator of the average molecular weight of the plastic. Its measurement is carried out for polymers dissolved in various solvents, preferably formic acid, m-cresol, tetrachloroethane, phenol, and 1,2-dichlorobenzene at various concentrations. The viscosity number VN makes it possible to monitor the processing and performance characteristics of the plastic. Thermal load, aging or exposure to chemicals, weather resistance and light resistance of the polymer can be investigated by means of appropriate measurement methods. The methods are standardized for common polymers and, in relation to the present invention, follow DIN ISO 1628-5 for polyesters. For further information on this point, please refer to http: / / de.wikipedia.org / wiki / Viskosimetrie and http: / / de.wikipedia.org / wiki / Mark-Howink-Gleichung.

[0034] The poly-C1-C6 alkylene terephthalate used in the present invention may be in the form of a mixture with other polyesters and / or further polymers.

[0035] During compounding, the poly-C1~C6-alkylene terephthalate for use in the present invention may be mixed in a molten state with commonly used additives, particularly release agents. Those skilled in the art will understand that compounding, as a term from plastics technology, is synonymous with processing plastics and refers to the process of improving the performance of plastics by mixing in auxiliary agents (fillers, additives, etc.) to bring the performance profile to a target optimal value. Compounding is preferably carried out in an extruder, particularly preferably a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, a planetary gear extruder, or a conninder, and includes process operations of conveying, melting, dispersion, mixing, degassing, and pressurizing.

[0036] It is preferable to use 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], available from Lanxess Deutschland GmbH (Cologne) under the brand name Pocan®, is particularly preferred.

[0037] Glass fiber (component B) According to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund", the glass fibers used in this invention are classified into chopped fibers (also known as short fibers) having a length in the range of 0.1 to 1 mm, long fibers having a length of 1 to 50 mm, and continuous fibers having a length of L > 50 mm. Short fibers are used in injection molding and can be processed directly in an extruder. Long fibers can also be processed in an extruder. The aforementioned fibers are widely used in the fiber spray method. Long fibers are often added as fillers to thermosetting resins. Continuous fibers are used in fiber-reinforced plastics in the form of roving or woven fabric. The highest stiffness and strength values ​​are achieved in manufactured articles containing continuous fibers. Further available are ground glass fibers, whose length after grinding is typically in the range of 70 to 200 μm. Ground glass fibers can also be used in this invention.

[0038] In the present invention, it is preferable to use chopped glass fibers having an initial length in the range of 1 to 50 mm, more preferably in the range of 1 to 10 mm, and most preferably in the range of 2 to 7 mm. The initial length represents the average length of the glass fibers before compounding the composition of the present invention to obtain the molding compound in the present invention. As a result of processing, particularly compounding, to obtain the molding compound or the manufactured article, the glass fibers used as component B) may have a smaller d97 or d50 value in the molding compound or the manufactured article than the glass fibers originally used. Therefore, the arithmetic mean of the lengths of the glass fibers after processing is often in the range of only 150 μm to 300 μm.

[0039] In connection with the present invention, the length and length distribution of processed glass fibers are measured according to ISO 22314, which specifies that the sample is first ashed at 625°C. The ash is then placed on a microscope slide coated with deionized water in a suitable crystallization dish, and the ash is dispersed using an ultrasonic bath without mechanical action. The next step involves drying in an oven at 130°C, followed by measuring the length of the glass fibers using optical microscope images. For this purpose, at least 100 glass fibers are measured from three images, and a total of 300 glass fibers are used to determine the length. The length of the glass fibers is given by the following formula

number

number

[0040] In this formula, l c And σ are parameters specific to the normal distribution, and l c σ is the mean value, and σ is the standard deviation (see M. Schossig, Shaedigungsmechanismen in faserverstaerkten 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 incorporated into the polymer matrix are analyzed in terms of their length according to the method described above, except that ashing and separation from ash are not performed.

[0041] The glass fiber [CAS No. 65997-17-3] used in the present invention preferably has a fiber diameter in the range of 7 to 18 μm, more preferably in the range of 9 to 15 μm, which can be determined by at least one means available to those skilled in the art, particularly computerized X-ray microtomography following the following documents: "Quantitative Messung von Faserlaengen und -verteilung in faserverstaerkten Kunststoffteilen mitteels μ-Roentgen-Computertomographie" [Quantitative measurement of fibre lengths and fibre distribution in fibre-reinfrced plastic components by computed x-ray microtomography], J. KASTNER, et al, DGZfP annual meeting, 2007, paper 47. The glass fiber for use as component B) is preferably added as continuous fiber or chopped or milled glass fiber.

[0042] In one preferred embodiment, the glass fiber used is modified with a suitable sizing system or adhesion promoter or adhesion promoting system, more preferably one based on silane.

[0043] The preferred silane-based adhesion promoter for pretreating glass fiber has the general formula (I) (X-(CH2) q ) k -Si-(O-C r H 2r+1 ) 4-k (I) (wherein the substituents are defined as follows: X: NH2-, HO-

Chemical formula

[0044] Particularly preferred adhesion promoters are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and the corresponding silanes containing a glycidyl group as substituent X.

[0045] To modify the glass fibers, it is preferable to use a silane compound as a filler and / or reinforcing agent, particularly in an amount ranging from 0.05% to 2% by weight, more preferably from 0.25% to 1.5% by weight, and especially from 0.5% to 1% by weight, based on 100% by weight of the glass fibers, for surface coating.

[0046] Polyamide 6 (component C) The polyamide 6 used in the present invention is preferably a semicrystalline polyamide whose enthalpy of melting, as specified in German Patent Application Publication No. 10 2011 084 519A1, is in the range of 4 to 25 J / g, determined by integrating its melting peak during the second heating operation using the DSC method in accordance with ISO 11357.

[0047] The identification designations for polyamides used in connection with this application correspond to the international standard, namely DIN 7728. For example, when only a single number is indicated, as in the case of PA6, this means that the starting material is an α,ω-aminocarboxylic acid or a lactam derived therefrom, i.e., ε-caprolactam in the case of PA6. For further information, please refer to the following document: H. Domininghaus, Die Kunststoffe und ihre Eigenschaften [Plastics and their properties], p.272 ff, VDI-Verlag, 1976.

[0048] It is preferable to use a low viscosity polyamide 6 having a viscosity number in the range of 80 to 135 mL / g, more preferably in the range of 90 to 130 mL / g, even more preferably in the range of 90 to 125 mL / g, and especially preferably in the range of 95 to 115 mL / g, measured at 25°C in a 0.5 wt% solution in 96 wt% sulfuric acid, according to ISO 307.

[0049] In a particularly preferred embodiment, polyamide 6 having a viscosity number in the range of 95 to 115 mL / g is used, measured at 25°C in a 0.5 wt% solution in 96 wt% sulfuric acid according to ISO 307.

[0050] It is particularly preferable to use polyamide 6 prepared by hydrolysis polymerization of ε-caprolactam. The polyamide 6 used in the present invention can be supplied by Lanxess Deutschland GmbH (Cologne) as Durethan® B26.

[0051] Copolymer (Component D) Preferably, the copolymer is a copolymer of at least one α-olefin and at least one aliphatic alcohol methacrylate or acrylic acid ester.

[0052] Particularly preferred is a copolymer of one α-olefin and one aliphatic alcohol methacrylate or acrylic acid ester.

[0053] Particularly preferred is a copolymer of one α-olefin and an acrylic acid ester of one aliphatic alcohol.

[0054] Particularly preferred here is a copolymer in which the α-olefin is formed from ethene, and the methacrylic acid ester or acrylic acid ester contains a linear or branched alkyl group having 6 to 20 carbon atoms as an alcohol component.

[0055] In this case, it is particularly preferable that the α-olefin is ethene, and the acrylic acid ester thereof is a copolymer containing a linear or branched alkyl group having 6 to 20 carbon atoms as an alcohol component.

[0056] The copolymer used, consisting of at least one α-olefin and at least one acrylic acid ester, is most preferably a copolymer of ethene and 2-ethylhexyl acrylate or a copolymer of ethene and butyl acrylate.

[0057] The copolymers preferred for use in the present invention are noteworthy not only for their composition but also for their low molecular weight. Therefore, particularly preferred are 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, measured at 190°C and under a load of 2.16 kg. MFI, or melt flow index, characterizes the flow properties of the molten thermoplastic, and is defined in standard ISO 1133 or ASTM D 1238. In connection with the present invention, all MFI and related values ​​are related to the standard method described in ISO 1133, or measured or specified therein at 190°C and a test load of 2.16 kg. In the present invention, it is particularly preferred to use the ethylene-butyl acrylate copolymer available from SK Functional Polymer as Lotryl® 28BA700T.

[0058] Additive (Component E) In some cases or in one preferred embodiment, the compositions, molded compounds and manufactured articles of the present invention contain, as component E), at least one additive different from components A), B), C), and D). Preferred additives of component E) are: lubricants and release agents, fillers and / or reinforcing agents in addition to component B), UV stabilizers, colorants, chain extension additives, plasticizers, flow promoters other than component D), heat stabilizers, antioxidants, gamma-ray stabilizers, hydrolysis stabilizers, elastomer modifiers, antistatic agents, emulsifiers, nucleating agents, processing aids, anti-sagging agents, and flame retardants. Additives of component E) may be used alone or in the form of a mixture / masterbatch. In addition to component B), it is preferable to use at least one from the following group as a filler and / or reinforcing agent: mica, silicate, quartz, especially quartz powder, titanium dioxide, wollastonite, nepheline cyanite, kaolin, amorphous silica, magnesium carbonate, chalk, feldspar, metal sulfates, glass fibers other than component B), glass beads, glass powder and / or fibrous fillers and / or carbon fiber-based reinforcing agents.

[0059] It is preferable to use particulate mineral fillers and / or reinforcing agents based on mica, silicate, quartz, wollastonite, kaolin, amorphous silica, magnesium carbonate, chalk, or feldspar. Furthermore, it is particularly preferable to use needle-shaped mineral fillers. In this invention, "needle-shaped mineral fillers and / or reinforcing agents" is understood to mean mineral fillers having extremely pronounced needle-like characteristics. The needle-shaped mineral fillers and / or reinforcing agents preferably have a length: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 particle size d50 of the needle-shaped mineral for use in this invention is preferably less than 20 μm, more preferably less than 15 μm, and particularly preferably less than 10 μm, as measured by laser diffraction using a CILAS GRANULOLMETER in accordance with ISO 13320:2009.

[0060] Fillers and / or reinforcing agents other than component B), which are used as part of the process to obtain a molded compound or a manufactured article, or as part of component E in one preferred embodiment, may have a d97 or d50 value lower than that of the fillers and / or reinforcing agents and / or glass fibers originally used in the molded compound or manufactured article. They may be used individually or as a mixture of two or more fillers and / or reinforcing agents.

[0061] The fillers and / or reinforcing agents used as component E), other than component B), may in one preferred embodiment be surface-modified, more preferably using an adhesion promoter or adhesion promoter system, particularly preferably an epoxide-based one. However, pretreatment is not mandatory.

[0062] Preferably, the filler and / or reinforcing agent used as component E) may be modified using a suitable sizing system or adhesion promoter or adhesion promoter, more preferably a silane-based one. A preferred silane-based adhesion promoter for pretreatment is general formula (I) (X-(CH2) q ) k -Si-(OC r H 2r+1 ) 4-k (I) (In the formula, substituents are defined as follows: X:NH2-, HO-, [ka] q: an integer between 2 and 10, preferably between 3 and 4. r: an integer between 1 and 2, preferably between 1 and 5. k: an integer between 1 and 3, preferably 1) It is a silane compound.

[0063] Particularly preferred adhesion promoters are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and the corresponding silanes containing a glycidyl group as substituent X.

[0064] The lubricant and release agent for use as component E) is selected from at least one of the following groups: long-chain fatty acids, salts of long-chain fatty acids, ester derivatives of long-chain fatty acids, and montan wax.

[0065] Preferred long-chain fatty acids are stearic acid or behenic acid. Preferred salts of long-chain fatty acids are calcium stearate or zinc stearate. Preferred ester derivatives of long-chain fatty acids are pentaerythritol-based, and more particularly pentaerythritol-based C 16 ~C 18 It is a fatty acid ester [CAS No. 68604-44-4] or [CAS No. 85116-93-4].

[0066] In relation to the present invention, montan wax is a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms. In the present invention, it is particularly preferable to use lubricants and / or release agents from the group of 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 of saturated or unsaturated aliphatic carboxylic acids containing 8 to 40 carbon atoms. Here, especially preferred are pentaerythritol tetrastearate, calcium stearate [CAS No. 1592-23-0] and / or ethylene glycol dimontanoate, in particular Licowax® E [CAS No. 74388-22-0] (manufactured by Clariant (Muttenz, Basle)), and especially preferred is pentaerythritol tetrastearate [CAS No. 115-83-3], for example, available as Loxiol® P861 from Emery Oleochemicals GmbH (Duesseldorf, Germany).

[0067] The UV stabilizer used as component E) is preferably a substituted resorcinol, salicylate, benzotriazole, triazine derivative, or benzophenone.

[0068] The colorants used as component E) are preferably organic pigments, preferably phthalocyanine, quinacridone, perylene and dyes, preferably nigrosine or anthraquinone, and also preferably inorganic pigments, particularly titanium dioxide (if not already used as a filler), metal sulfates (if not already used as a filler), ultramarine blue, iron oxide, zinc sulfide or carbon black.

[0069] Suitable and useful titanium dioxide pigments for use in the present invention include titanium dioxide pigments, whose oxides can be produced by a sulfate process (SP) or a chloride process (CP) and have anatase and / or rutile structures, preferably rutile structures. While stabilization of the oxides is not essential, it is preferable to perform certain stabilizations. For CP oxides, this is done by doping with 0.3 to 3.0 wt% Al (calculated as Al2O3), and in the gas phase when oxidizing titanium tetrachloride to form titanium dioxide, by providing at least 2% excess oxygen. For SP oxides, this is done by doping with, for example, Al, Sb, Nb, or Zn. For "mild" stabilization using Al or higher Al doping amounts, it is particularly preferable to compensate with antimony. When titanium dioxide is used as a white pigment in paints and coatings and plastic materials, it is known that undesirable photocatalytic reactions due to UV absorption can cause decomposition of the pigmented material. This involves the phenomenon in which titanium dioxide pigments absorb light in the near-ultraviolet region, thereby forming electron-hole pairs, which create highly reactive free radicals on the surface of the titanium dioxide. The formed free radicals lead to the decomposition of the binder in the organic medium. In this invention, it is preferable to reduce the photoactivity of titanium dioxide by inorganic post-treatment, particularly by using oxides of Si and / or Al and / or Zr, and / or Sn compounds.

[0070] It is preferable that the surface of the titanium dioxide pigment has a coating of amorphous precipitated oxide hydrate of the compound SiO2 and / or Al2O3 and / or zirconium oxide. The Al2O3 shell facilitates the dispersion of the pigment in the polymer matrix; the SiO2 shell makes charge exchange on the pigment surface more difficult, thereby preventing polymer degradation.

[0071] In the present invention, it is preferable that the titanium dioxide is provided with a hydrophilic and / or hydrophobic organic coating, particularly using a siloxane or polyalcohol.

[0072] Titanium dioxide [CAS No. 13463-67-7], which is suitably used as a coloring agent for component E) in the present 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 obtained from a particle size distribution in which 50% by weight of the particles have an equivalent spherical diameter smaller than this d50 value. The relevant standard is ISO 13317-3.

[0073] The reported particle size distribution and median particle size for titanium dioxide are, in each case, based on the so-called surface area-based particle size before incorporation into the thermoplastic molding compound. In this invention, particle size is determined 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.

[0074] Examples of titanium dioxide available on the market include Kronos® 2230, Kronos® 2233, Kronos® 2225, and Kronos® vlp7000 from Kronos (Dallas, USA).

[0075] Titanium dioxide used as a pigment is preferably used in an amount ranging from 0.1 to 60 parts by mass, more preferably from 1 to 35 parts by mass, and most preferably from 2 to 20 parts by mass, based on 100 parts by mass of component A) in each case.

[0076] The nucleating agent used as component E) is preferably sodium phenylphosphinate or calcium phenylphosphinate, aluminum oxide, silicon dioxide, or talc. It is particularly preferable to use talc [CAS No. 14807-96-6], especially microcrystalline talc, as the nucleating agent. Talc has the chemical composition Mg3[Si4O 10 It is a layered silicate containing [(OH)2], which crystallizes either as triclinic talc-1A or as monoclinic talc-2M depending on its modification (http: / / de.wikipedia.org / wiki / Talkum). The talc used in this invention is commercially available, for example, from Imerys Talc Group (Toulouse, France) (Rio Tinto Group) under the name Mistron® R10.

[0077] Alternatively, as component E), a bifunctional or polyfunctional branching or chain-extending additive containing at least two and no more than 15 branching or chain-extending functional groups per molecule is also suitably used. Suitable branching or chain-extending additives include low molecular weight or oligomeric compounds having at least two and no more than 15 branching or chain-extending functional groups per molecule and capable of reacting with primary and / or secondary amino groups, and / or amide groups, and / or carboxylic acid groups. The chain-extending functional groups are preferably isocyanates, alcohols, blocked isocyanates, epoxides, maleic anhydride, oxazolines, oxazines, and oxazolones, with epoxides being preferred.

[0078] Particularly preferred bifunctional or polyfunctional branching or chain-extending additives include: diglycidyl ether-based diepoxides (bisphenol and epichlorohydrin), amine epoxy resin-based diepoxides (aniline and epichlorohydrin), diglycidyl ester-based diepoxides (alicyclic dicarboxylic acid and epichlorohydrin) in individual or mixed forms, as well as 2,2-bis[p-hydroxyphenyl]propane diglycidyl ether, bis[p-(N-methyl-N-2,3-epoxypropylamino)phenyl]methane, and epoxidized fatty acid esters of glycerol containing at least 2 and no more than 15 epoxy groups per molecule.

[0079] Particularly preferred bifunctional or polyfunctional branching or chain-extending additives are glycidyl ethers, most preferably bisphenol A diglycidyl ether [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, and even more preferably epoxidized soybean oil [CAS No. 8013-07-8].

[0080] Furthermore, the following are particularly preferred as branching / chain extensions: 1. A poly- or oligoglycidyl or poly(β-methylglycidyl) ether obtainable by reacting a compound containing at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups with appropriately substituted epichlorohydrin under alkaline conditions, or by alkaline treatment following a reaction in the presence of an acidic catalyst.

[0081] Poly- or oligoglycidyl or poly(β-methylglycidyl) ethers are preferably derived from acyclic 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-trimethipropane, bistrimethylolpropane, pentaerythritol, sorbitol, or polyepichlorohydrin.

[0082] 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)cyclohexe-3-ene, or contain an aromatic nucleus, particularly N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.

[0083] The epoxy compounds may also preferably be derived from monocyclic phenols, particularly 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, or 4,4'-dihydroxydiphenylsulfone, or based on the condensation reaction products of phenol and formaldehyde under acidic conditions, particularly phenol novolacs.

[0084] 2. A poly- or oligo(N-glycidyl) compound that can be obtained by dehydrochlorinating the reaction product of epichlorohydrin and an amine having at least two aminohydrogen atoms.

[0085] These amines are preferably aniline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine, or bis(4-methylaminophenyl)methane, but more preferably N,N,O-triglycidyl-m-aminophenyl or N,N,O-triglycidyl-p-aminophenol.

[0086] However, these poly(N-glycidyl) compounds preferably include N,N'-diglycidyl derivatives of cycloalkylene urea, particularly preferably ethylene urea or 1,3-propylene urea, and hydantoin, particularly N,N'-diglycidyl derivatives of 5,5-dimethylhydantoin.

[0087] 3. Di-S-glycidyl derivatives derived from poly- or oligo(S-glycidyl) compounds, particularly dithiols, preferably ethane-1,2-dithiol or bis(4-mercaptomethylphenyl) ether.

[0088] 4. Fatty acid esters of epoxidized glycerol, especially epoxidized vegetable oils.

[0089] The esters are obtained by epoxidizing the reactive olefin groups of unsaturated fatty acid triglycerides. Epoxidized glycerol fatty acid esters can be produced from unsaturated fatty acid esters of glycerol, preferably vegetable oils and organic peroxycarboxylic acids (Pritzev reaction). Processes for producing epoxidized vegetable oils are described, for example, in Smith, March, March's Advanced Organic Chemistry (5th edition, Wiley-Interscience, New York, 2001). The epoxidized glycerol fatty acid esters are preferably vegetable oils. A particularly preferred epoxidized glycerol fatty acid ester in the present invention is epoxidized soybean oil [CAS No. 8013-07-8].

[0090] 5. A glycidyl methacrylate-modified styrene-acrylate polymer that can be obtained by polymerizing styrene, glycidyl methacrylate, and acrylic acid and / or methacrylic acid.

[0091] Suitable plasticizers for component E) are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oil, or N-(n-butyl)benzenesulfonamide.

[0092] Suitable elastomer modifiers for component E include one or more of the following graft polymers: E.1: 5% to 95% by weight, preferably 30% to 90% by weight, at least one vinyl monomer. E.2: One or more graft bases having a glass transition temperature of less than 10°C, preferably less than 0°C, and more preferably less than -20°C, in an amount of 95% to 5% by weight, preferably 70% to 10% by weight. In this case, the weight percentage is based on 100% by weight of component E).

[0093] The graft base E.2 generally has a median particle size (d50) in the range of 0.05 to 10 μm, preferably in the range of 0.1 to 5 μm, and more preferably in the range of 0.2 to 1 μm.

[0094] Monomer E.1 is preferably a mixture of the following: E.1.1: 50% to 99% by weight of vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds, particularly styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or (C1-C8)-alkyl methacrylates, particularly methyl methacrylate, ethyl methacrylate, and E.1.2: 1% to 50% by weight of vinyl cyanides, especially unsaturated nitriles, such as acrylonitrile and methacrylonitrile and / or (meth)acrylic (C1-C8)-alkyl, especially methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, t-butyl acrylate and / or derivatives of unsaturated carboxylic acids, especially anhydrides and imides, especially maleic anhydride or N-phenylmaleimide. In this case, the weight percentage is based on 100% by weight of component E).

[0095] Preferred monomer E.1.1 is selected from at least one monomer of styrene, α-methylstyrene, and methyl methacrylate, and preferred monomer E.1.2 is selected from at least one monomer of acrylonitrile, maleic anhydride, glycidyl methacrylate, and methyl methacrylate.

[0096] Particularly preferred monomers are styrene in E.1.1 and acrylonitrile in E.1.2.

[0097] Suitable graft bases E.2 for use in graft polymers in elastomer modifiers include, for example: diene rubber, EPDM rubber, i.e., ethylene / propylene and optionally diene-based rubbers, as well as acrylic esters, polyurethanes, silicones, chloroprene, and ethylene / vinyl acetate rubber. EPDM stands for ethylene-propylene-diene rubber.

[0098] A preferred graft base E.2 is a mixture of diene rubber, particularly butadiene, isoprene, etc., or diene rubber or a copolymer of diene rubber or a mixture thereof, with further copolymerizable monomers, particularly E.1.1 and E.1.2, provided that the glass transition temperature of component E.2 is less than 10°C, preferably less than 0°C, and more preferably less than -10°C.

[0099] A particularly preferred graft base E.2 is ABS polymer (emulsion, bulk, and suspension ABS), where ABS represents acrylonitrile-butadiene-styrene, as described, for example, in the following publications: German Patent Application Publication No. A2 035 390 or German Patent Application Publication No. A2 248 242 or Ullmann, Enzyklopaedie der Technischen Chemie [Encyclopaedia of Industrial Chemistry], vol.19(1980), p.280ff.

[0100] These elastomer modifiers / graft polymers are produced by free radical polymerization, preferably emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, particularly emulsion polymerization or bulk polymerization.

[0101] A particularly suitable graft rubber is ABS polymer, which is produced by a redox initiation method using a polymerization initiator system consisting of an organic peroxide and ascorbic acid, in accordance with U.S. Patent No. A4 937 285.

[0102] As is well known, in grafting reactions, the graft monomers do not necessarily have to be grafted entirely onto the graft base. Therefore, in this invention, the graft polymer is understood to mean the reaction product obtained by (co)polymerizing the graft monomers in the presence of the graft base and further finishing work.

[0103] Similarly, suitable acrylate rubbers are preferably based on a graft base E.2, which is a polymer of alkyl acrylate, and may be combined with other polymerizable ethylenically unsaturated monomers up to 40% by weight relative to E.2. Preferred polymerizable acrylic acid esters include: C1-C8 alkyl esters, e.g., methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo C1-C8 alkyl esters, preferably chloroethyl acrylate, glycidyl ester and mixtures thereof of monomers. Particularly preferred in this regard are graft polymers containing butyl acrylate as the core and methyl methacrylate as the shell, especially Paraloid® EXL2300 (manufactured by Dow Corning Corporation (Midland Michigan, USA)).

[0104] A more preferred graft base as E.2 is a silicone rubber having active graft sites as described in the following patents: German Patent Application Publication A3 704 657, German Patent Application Publication A3 704 655, German Patent Application Publication A3 631 540, and German Patent Application Publication A3 631 539.

[0105] Preferred graft polymers containing a silicone fraction include methyl methacrylate or styrene-acrylonitrile as the shell and a silicone / acrylic acid ester graft as the core. An example of a usable graft polymer having styrene-acrylonitrile as the shell is Metablen® SRK200. Examples of usable graft polymers having methyl methacrylate as the shell are Metablen® S2001, Metablen® S2030 and / or Metablen® SX-005. The use of Metablen® S2001 is particularly preferred. Products bearing the trade name Metablen® are available from Mitsubishi Rayon Ltd. (Tokyo, Japan).

[0106] Crosslinking can be achieved by copolymerizable monomers having two or more polymerizable double bonds. Preferred examples of crosslinkable monomers include: 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 trivinyl cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, preferably divinylbenzene and trivinylbenzene; and further, triallyl phosphate and diallyl phthalate.

[0107] Preferred crosslinkable monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds having at least three ethylenically unsaturated groups.

[0108] Particularly preferred crosslinkable monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloyl hexahydro-s-triazine, and triallylbenzene. The amount of the monomer to be crosslinked is preferably 0.02% to 5% by weight, and particularly 0.05% to 2% by weight, based on 100% by weight of graft base E.2.

[0109] For cyclic crosslinkable monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight based on 100% by weight of graft base E.2.

[0110] In addition to acrylic esters, preferred "other" polymerizable and ethylenically unsaturated monomers that can optionally be used to produce graft base E.2 include: acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C1-C6 alkyl ethers, methyl methacrylate, glycidyl methacrylate, and butadiene. The preferred acrylate rubber as graft base E.2 is an emulsion polymer having a gel content of at least 60% by weight.

[0111] In addition to elastomer modifiers based on graft polymers, it is also possible to use elastomer modifiers that are not based on graft polymers and have a glass transition temperature of less than 10°C, preferably less than 0°C, and more preferably less than -20°C. Preferably, these include elastomers having a block copolymer structure and, in addition, elastomers that can be thermoplastically melted, particularly EPM, EPDM, and / or SEBS rubbers (EPM = ethylene-propylene copolymer, EPDM = ethylene-propylene-diene rubber, SEBS = styrene-ethene-butene-styrene copolymer).

[0112] The preferred flame retardant used as component E) is halogen-free.

[0113] Suitable phosphorus-containing flame retardants for use as component E) include, for example, phosphorus-containing compounds from the following group: organometallic phosphinates, particularly metal diethylphosphinates; inorganic metal phosphinates, particularly aluminum phosphinate and zinc phosphinate; mono and oligomeric phosphate esters and phosphonic acid esters, particularly triphenyl phosphate (TPP); resorcinol bis(diphenyl phosphate) (RDP); bisphenol A bis(diphenyl phosphate) (BDP) (including oligomers); polyphosphonates, particularly bisphenol A-diphenylmethyl phosphate copolymer, such as Nofia(trademark) HM1100 [CAS No. 68664-06-2] (FRX Polymers (manufactured by Chelmsford, USA) and further derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO derivatives), phosphonate amine salts, metal phosphonates, particularly aluminum phosphates and aluminum alkyl phosphates and zinc phosphates, and zinc alkyl phosphates, as well as further phosphine oxides and phosphazenes. Particularly preferred phosphazenes are phenoxyphosphazene oligomers. Further phosphorus-containing flame retardants suitably used as component E) include: melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminum phosphate), melamine poly(zinc phosphate), and reaction products of melem, melam, melon with concentrated phosphoric acid.

[0114] As a further flame retardant for component E), phosphorus-free nitrogen-containing flame retardants may also be used alone or in mixtures. Preferred nitrogen-containing flame retardants include: trichlorotriazine, piperazine and reaction products of morpholine of CAS No. 1078142-02-5, particularly MCA PPM Triazine HF (manufactured by MCA Technologies GmbH (Biel-Benken, Switzerland)) and further condensation reaction products of melamine cyanurate and melamine, specifically melem, melam, melon or compounds of this type with a higher degree of condensation. Preferred inorganic nitrogen-containing compounds are ammonium salts.

[0115] Other flame retardants or flame retardant synergies 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-perfluorobutanesulfonic acid, may also be used. Equally preferred are flame retardant synergies from the following group: oxygen-containing, nitrogen-containing or sulfur-containing metal compounds whose 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.

[0116] Further flame retardant additives suitable and preferred for use as component E) include: carbonization agents, more preferably poly(2,6-diphenyl-1,4-phenyl) ether, particularly poly(2,6-dimethyl-1,4-phenylene) ether [CAS No. 25134-01-4], phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyetherketones, and further anti-sagging agents, particularly tetrafluoroethylene polymers. Tetrafluoroethylene polymers may be used in pure form or in combination with other resins, preferably styrene-acrylonitrile (SAN) or acrylates, preferably methyl methacrylate / butyl acrylate.

[0117] For the intended use, halogen-containing flame retardants may be used as needed. These include commercially available organic halogen compounds, either in the presence or absence of synergistic agents. Preferred halogenated compounds, particularly brominated and chlorinated compounds, include: ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene, and brominated polyphenylene ether.

[0118] A flame retardant for additional use as component E) may be added to polyalkylene terephthalate or polycycloalkylene terephthalate in pure form, or further via a masterbatch or as a high-density preparation.

[0119] Preferred heat stabilizers for use as component E) are selected from the following group: sulfur-containing stabilizers, particularly sulfides, dialkylthiocarbamates or thiodipropionic acids, further selected from the group of iron salts and copper salts, particularly the latter, preferably copper(I) iodide used in combination with potassium iodide and / or sodium hypophosphite (NaH2PO2); further sterically hindered amines, particularly tetramethylpiperidine derivatives; aromatic secondary amines, particularly diphenylamines, hydroquinones, substituted resorcinols, salicylates, benzotriazoles and benzophenones; and further sterically hindered phenols and aliphatic or aromatically substituted phosphates, as well as various typical substituted products of these groups.

[0120] Among sterically hindered phenols, the preferred use is one having at least one 3-tert-butyl-4-hydroxy-5-methylphenyl unit and / or at least one 3,5-di(tert-butyl-4-hydroxyphenyl) unit, and particularly preferred are: hexane-1,6-diolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][CAS No.35074-77-2] (Irganox® 259 (manufactured by BASF SE (Ludwigshafen, Germany))), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][CAS No.6683-19-8] (Irganox® 1010, BASF (Manufactured by SE) 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 Stab® AO 80). ADK Stab® AO 80 is commercially available from Adeka-Palmerole SAS (Mulhouse, France).

[0121] Among aliphatic or aromatically substituted phosphates, preferred for use are bis(2,4-dicumylphenyl)pentaerythritol diphosphate [CAS No. 154862-43-8] (available, for example, from Dover Chemical Corp. (Dover, USA) under the trade name Doverphos® S9228) and tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4'-diylbisphosphonite [CAS No. 38613-77-3] (which can be obtained, for example, from Clariant International Ltd. (Muttenz, Switzerland) as Hostanox® P-EPQ).

[0122] Particularly preferred use The present invention more preferably relates to the use of polyamide 6 to reduce the melt viscosity, measured at 260°C according to ISO 11443, and / or the filling pressure, measured according to EN ISO 294-1, of compositions and molding compounds containing 10 to 115 parts by mass of glass fibers and 0.5 to 30 parts by mass of ethylene-butyl acrylate copolymer per 100 parts by mass of polybutylene terephthalate.

[0123] The present invention relates more particularly to the use of 0.5 to 15 parts by mass of polyamide 6 to reduce the melt viscosity, measured at 260°C according to ISO 11443, and / or the filling pressure, measured according to EN ISO 294-1, of compositions and molding compounds containing 10 to 115 parts by mass of glass fiber and 0.5 to 30 parts by mass of ethylene-butyl acrylate copolymer per 100 parts by mass of polybutylene terephthalate.

[0124] Particularly preferred method The present invention relates to a method for reducing the melt viscosity, measured at 260°C according to ISO 11443 and / or the filling pressure, measured according to EN ISO 294-1, of a composition and molding compound containing 10 to 115 parts by mass of glass fiber and 0.5 to 30 parts by mass of ethylene-butyl acrylate copolymer per 100 parts by mass of polybutylene terephthalate, by adding polyamide 6, preferably in an amount ranging from 0.5 to 15 parts by mass.

[0125] Particularly preferred compositions, molding compounds, and manufactured articles In one preferred embodiment, the present invention further relates to compositions, molded compounds, and manufactured articles comprising A) polybutylene terephthalate per 100 mass, B) 10 to 115 parts by mass of glass fiber, C) 0.5 to 15 parts by mass of polyamide 6, and D) 0.5 to 30 parts by mass of ethylene-butyl acrylate copolymer.

[0126] Preferred manufactured articles are manufactured articles for the electrical or electronic industry, and more preferably manufactured articles for electric mobility.

[0127] The molding compound of the present invention is formulated for further use by mixing the components to be used in at least one mixing device, preferably a compounder, particularly by injection molding or extrusion molding. This yields a molding compound based on the composition of the present invention as an intermediate. The molding compound is ultimately used to manufacture articles by appropriate methods.

[0128] The present invention also relates, instead, to a process for manufacturing articles, preferably for the electrical industry, electric mobility or electronics industry, more preferably for electronic or electrical components and parts, the process of which involves mixing the compositions of the present invention to obtain a molding compound, ejecting it in the form of an extruded product, cooling the extruded product until it can be pelletized, pelletizing it, and finally subjecting the pelletized product to an injection molding or extrusion operation, preferably an injection molding operation, to form a matrix material. In one embodiment, the molding compound can also be sent directly to the injection molding or extrusion without ejecting it, molding it into an extruded product, or pelletizing it.

[0129] Mixing is preferably carried out in a molten state at a temperature in the range of 240 to 310°C, preferably in the range of 260 to 300°C, and particularly preferably in the range of 270 to 295°C. For this purpose, the use of a twin-screw extruder is particularly preferred.

[0130] In one embodiment, a pellet material containing the composition according to the present invention is dried in a vacuum drying cabinet or a drying air dryer at a temperature in the range of about 120°C for a period of time in the range of 2 hours, and then subjected to an injection molding or extrusion molding process as a matrix material to produce a manufactured article according to the present invention.

[0131] Methods for injection molding and extrusion molding of thermoplastic molding compounds are known to those skilled in the art. The present invention's method for producing polyester-based articles by extrusion or injection molding is carried out at a melting temperature in the range of 240°C to 330°C, preferably 260°C to 300°C, and particularly preferably 270°C to 290°C, and optionally further at a pressure of 2500 bar or less, preferably 2000 bar or less, particularly preferably 1500 bar or less, and most particularly preferably 750 bar or less.

[0132] Sequential co-extrusion molding involves extruding two different materials in a continuous, alternating sequence. This results in the formation of preforms having alternatingly different material compositions in the extrusion direction. By selecting appropriate materials, it is possible to obtain articles that impart particularly desired properties in specific cross-sections, such as articles with soft ends and hard middle sections, or integrated soft bellows sections (Thielen, Harwig, Gust, “Blasformen von Kunststoffhohlkoerpern” [Blow-Moulding of Hollow Plastics Bodies], Carl Hanser Verlag, Munich, 2006, pp. 127-129).

[0133] In injection molding, a molding compound containing the composition according to the present invention, preferably in pellet form, is melted (i.e., plasticized) in a heated cylindrical cavity and injected as an injection molding material into a heated cavity under pressure. After the material is cooled (solidified), the injection molded product is demolded.

[0134] They are distinguished as follows: 1. Plasticization / Melting, 2. Injection phase (filling operation), 3. Pressure holding phase (due to thermal shrinkage during crystallization), 4. Demolding.

[0135] For more information on this, see http: / / de.wikipedia.org / wiki / Spritzgie%C3%9Fen. An injection molding machine includes a clamping unit, an injection unit, a drive system and a control system. The clamping unit includes fixed and movable heat plates and end plates for the mold, and a drive system (toggle mechanism or hydraulic clamping unit) for the tie bars and movable heat plates.

[0136] The injection unit includes an electrically heated barrel, a drive mechanism (motor, transmission) for the screw, and a hydraulic system for moving the screw and the injection unit. The injection unit performs the functions of melting, metering, injecting, and pressure holding (for contraction) of powdered / pelletized raw materials. The problem of backflow (leakage) of molten material inside the screw is solved by a check valve.

[0137] In injection molding, the molten material that flows in is then separated and cooled to create the manufactured product. For this purpose, a two-part mold is always required. Injection molding can be classified into the following functional systems: - Runner type, - Molded insert system, - Bent type, - Machine mount and force absorption system, - De-molding systems and mobile transmission, - Temperature control system.

[0138] In contrast to injection molding, extrusion molding involves using an extruder to produce an infinite number of plastic extrusions of the molding compound according to the present invention, and the extruder is a machine for producing shaped thermoplastic molded products. For more information on this, see http: / / de.wikipedia.org / wiki / Extrusionsblasformen. There are distinctions between single-screw extruders and twin-screw extruders, and further distinctions between their sub-classifications: ordinary single-screw extruders, transport single-screw extruders, counter-clockwise twin-screw extruders, and co-clockwise twin-screw extruders.

[0139] An extrusion molding system consists of the following elements: extruder, mold, downstream equipment, and extrusion blow mold. An extrusion molding system for producing shaped materials consists of the following elements: extruder, shaped material mold, calibration unit, cooling zone, caterpillar and roller take-up, separation equipment, and inclined chute.

[0140] As a result, the present invention also relates to halogen-free manufactured articles, particularly halogen-free manufactured articles with leakage current resistance, which can be obtained by extruding, preferably by extruding or injection molding, a molding compound that can be obtained from the composition of the present invention. [Examples]

[0141] For the purpose of illustrating the improvements related to melt viscosity and / or filling pressure described in this invention, the corresponding molding compounds were first prepared by compounding. For this purpose, the individual components were mixed in a twin-screw extruder (ZSK 26 Mega Compounder) from Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature in the range of 260-290°C, discharged in the form of extruded material, cooled until they could be pelletized, and then pelletized (typically in a vacuum drying cabinet at 120°C for 2 hours). After drying, the pellets were processed to prepare test specimens.

[0142] The test specimens for the study reported in Table 1 were injection molded on an Arburg 320-210-500 injection molding machine at a melting temperature of 260°C and a mold temperature of 80°C.

[0143] Reactant: Component A): Linear polybutylene terephthalate (Pocan® B1300, commercially available from Lanxess Deutschland GmbH (Leverkusen, Germany)), intrinsic viscosity 93 cm³ 3 / g (measured at 25°C in a phenol:1,2-dichlorobenzene = 1:1 ratio) Component B): Glass fiber (CS 7967(26 / 1493)D, commercially available from Lanxess Deutschland GmbH (Leverkusen, Germany)) Component C): Polyamide 6 (Durethan® B26, commercially available from Lanxess Deutschland GmbH (Leverkusen, Germany)) Component D): Ethylene-butyl acrylate copolymer (Lotryl® 28BA700T, SK Functional Polymer) Component E): E1) Nucleating agent: Talc E2) Heat stabilizer: Additive DP0001 [CAS No. 649560-74-7] (Lanxess Deutschland GmbH).

[0144] [Table 1]

[0145] To measure the filling pressure as defined in EN ISO 294-1, dumbbell-shaped test specimens with dimensions according to ISO 527-2 / Type 1A were injection molded, and the pressure required by the injection molding machine was recorded. The melting temperature was set to 260°C, and the mold temperature was set to 80°C.

[0146] The melt viscosity was measured at 260°C at a predetermined shear rate in accordance with ISO 11443.

[0147] Heat strain resistance was measured on 80 mm × 10 mm × 4 mm test specimens according to ISO 75-2 Method A (bending stress, 1.80 MPa).

[0148] The tensile modulus, tensile strength, and elongation at break were measured according to ISO 527.

[0149] Tracking resistance is expressed as CTI (Relative Tracking Index) and determined by the method described in standard ISO 60112:2003. A voltage was applied to the surface of a test specimen (60 mm × 40 mm × 4 mm) using two electrodes, and the surface was treated with droplets of an electrolyte solution (simulating dust and moisture) between the electrodes. After 50 droplets, if no defects (short circuits or ignition) were observed, the CTI was considered to be at the maximum voltage.

[0150] Table 1 shows that, in particular, when comparing Example 1 with Comparative Example 2 (an example in International Publication No. 2005 / 121245A1), the addition of polyamide 6 results in a significant reduction in both melt viscosity and filling pressure.

Claims

1. Poly-C １ ~C ６ Use of polyamide 6 to reduce the melt viscosity, measured at 260°C according to ISO 11443, and / or the packing pressure, measured according to EN ISO 294-1, of compositions and molding compounds in which 10 to 115 parts by weight of glass fibers are present per 100 parts by weight of alkylene terephthalate.

2. The poly-C used １ ~C ６ Use according to claim 1, characterized in that the alkylene terephthalate is polyethylene terephthalate or polybutylene terephthalate, in particular polybutylene terephthalate.

3. Poly-C １ ~C ６ per 100 parts by weight of alkylene terephthalate, 10 to 115 parts by weight of glass fibers, and 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one methacrylic or acrylic ester of an aliphatic alcohol; 3. Use according to claim 1 or 2, characterized in that:

4. Use according to any one of claims 1 to 3, characterized in that the amount of polyamide 6 used is between 0.5 and 15 parts by weight.

5. 5. Use according to claim 3 or 4, characterized in that the copolymer of at least one α-olefin and at least one acrylic ester used is a copolymer of ethene and 2-ethylhexyl acrylate or a copolymer of ethene and butyl acrylate.

6. Poly-C １ ~C ６ - Method for reducing the melt viscosity, measured at 260°C according to ISO 11443, and / or the packing pressure, measured according to EN ISO 294-1, of compositions and moulding compounds in which 10 to 115 parts by weight of glass fibres are present per 100 parts by weight of alkylene terephthalate, preferably polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), in particular polybutylene terephthalate, characterized in that polyamide 6, preferably in an amount ranging from 0.5 to 15 parts by weight, is added.

7. The poly-C used １ ~C ６ 7. The method according to claim 6, characterized in that the alkylene terephthalate is polyethylene terephthalate or polybutylene terephthalate, in particular polybutylene terephthalate.

8. 8. The method according to claim 6 or 7, characterized in that the composition or molding compound further contains from 0.5 to 30 parts by weight of at least one copolymer of at least one α-olefin and at least one methacrylic or acrylic ester of an aliphatic alcohol.

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

10. Compositions, molding compounds and articles of manufacture comprising: A) Poly-C １ ~C ６ per 100 parts by weight of alkylene terephthalate, B) 10 to 115 parts by weight of glass fibers; 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 methacrylic or acrylic ester of an aliphatic alcohol. Compositions, molding compounds and articles of manufacture comprising:

11. 11. Compositions, molding compounds and manufactured articles according to claim 10, characterized in that the component A) used is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), in particular polybutylene terephthalate.

12. Compositions, moulding compounds and articles of manufacture according to claims 10 or 11, characterized in that the copolymer used is an ethylene-butyl acrylate copolymer.

13. Compositions, moulding compounds and manufactured articles according to any one of claims 10 to 12, characterized in that they are used in the electrical or electronic industry, preferably in electric mobility.