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    • 专利摘要:
    POLYAMIDE COMPOUND FOR MOLDING, AND MOLDED ARTICLE PRODUCED FROM A POLYAMIDE COMPOUND FOR MOLDING The present invention relates to polyamide compound for molding, which is characterized by the excellent flame retardant characteristic and a resistance to long-term heat aging. very good run. The molding compounds of the invention comprise a partially aromatic polyamide, caprolactam, a heat stabilizer, optionally a flame retardant and, optionally, additional additives. The polyamide molding compound is free of metal salts and / or metal oxides of a transition metal of Group VB, VIB, VIIB or VIIIB from the periodic table.
    公开号:BR102015002100B1
    申请号:R102015002100-3
    申请日:2015-01-29
    公开日:2020-06-30
    发明作者:Oliver Thomas；Nikolai Lamberts；Botho Hoffmann；Georgi BESCHIASCHVILI
    申请人:Ems-Patent Ag；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to polyamide molding compounds which are distinguished by excellent flame retardant properties and very good long-term resistance to heat aging. The molding compounds according to the invention comprise a partially aromatic polyamide, caprolactam, a heat stabilizer, possibly a flame retardant and, optionally, other additives and adjuvants. The polyamide molding compound is, therefore, free of metal salts and / or metal oxides of a transition metal of the VB, VIB, VIIB or VIIIB group in the periodic table.
    [0002] [002] Thermoplastic polyamides can be used as building materials for components that are subjected to higher temperatures during their lifetime. As the result here is thermo-oxidative damage, heat stabilizers are used that delay the occurrence of thermo-oxidative damage.
    [0003] [003] Long-term heat-stabilized polyamide molding compounds are known from EP 2 535 365 A1, where molding compounds based on a partially aromatic polyamide and caprolactam are processed, the molding compounds of which are provided with stabilizers of copper or with mixtures of copper and / or organic stabilizers. These molding compounds, however, have no flame retardant effect.
    [0004] [004] Document W02006 / 074934A1 also refers to long term heat stabilized molding compounds. Long-term heat stabilization is achieved here by using at least two special heat stabilizers (for example, copper iodide and iron oxide) and by using two polyamides, which differ at the melting point at least 20 ° C.
    [0005] [005] WO2012 / 168442A1 describes long-term heat-stabilized molding compounds which, in addition to a partially aromatic polyamide, also comprise PA 6 or PA 66, mixtures of copper and elemental iron stabilizers used as heat stabilizers.
    [0006] [006] Basically, there is a market demand for polyamides that are free from inorganic salts (containing halides), as these can be used to contact electrically conductive parts or metallic parts at risk of corrosion, without causing contact corrosion. The salts in the polyamide can be washed out of it by water or other polar solvents. By enriching the surface, unwanted electrical conductive tracks can be formed, which in turn can cause short circuits.
    [0007] [007] In parallel, there is also a demand for highly heat stabilized polyamides (> 220 ° C).
    [0008] [008] Until the present date, stabilization of polyamides to heat has been carried out for high temperatures (> 160 ° C), in particular by stabilization with copper iodide / potassium iodide, generally using approximately 0.5% by weight, in relation to the polymeric matrix. For lower temperatures, up to approximately 160 ° C, in particular, organic stabilizers are used. Typical levels of, for example, phenolic stabilizers are approximately 0.1% to 0.5% by weight, based on the polymeric matrix. For higher temperatures, this stabilization, according to the state of the art, was not effective enough.
    [0009] [009] From the state of the art it was, therefore, the object of the present invention to provide a polyamide molding compound with very good long-term heat aging resistance, without causing corrosion by contact or by conductive bridges.
    [0010] [010] This object is achieved by the polyamide molding compound according to claim 1 and the molded article according to claim 16. The dependent claims thus represent advantageous configurations.
    [0011] [011] According to the invention, therefore, a polyamide molding compound consisting of:
    [0012] [012] a) 22% to 99.99% by weight of a polyamide mixture, consisting of,
    [0013] [013] (A1) at least one partially aromatic, partially crystalline polyamide with a melting point in the range of 255 ° C to 330 ° C,
    [0014] [014] (A2) at least one polyamide containing caprolactam which differs from at least one partially aromatic, partially crystalline polyamide (A1) and which has a caprolactam content of at least 50% by weight,
    [0015] [015] the total caprolactam content of the caprolactam contained in polyamide (A1) and polyamide (A2), in relation to the polyamide mixture, being 3% and 35% by weight,
    [0016] [016] b) 0% to 25% by weight of at least one flame retardant,
    [0017] [017] c) 0.01% to 3.0% by weight of at least one heat stabilizer based on sterically hindered phenols and
    [0018] [018] d) 0 to 50% by weight of at least one additive,
    [0019] [019] the components a) to d) totaling up to 100% by weight, The polyamide compound for molding is, therefore, free of metal salts and / or metal oxides of a transition metal of the group VB, VIB, VIIB or VIIIB of the periodic table.
    [0020] [020] The polyamide molding compound according to the invention is distinguished by having a good resistance to long-term heat aging. In this way, the use of metallic salts and / or metallic oxides of a transition metal of the group VB, VIB, VIIB or VIIIB of the periodic table can be completely dispensed with. Optionally, a halide-free flame retardant can be added to the polyamide molding compound, which results in obtaining excellent flame retardant properties at the same time.
    [0021] [021] Surprisingly, it was found that high thermal stabilization can be achieved by high levels of an organic stabilizer in combination with a component containing caprolactam, with the halide salts being completely dispensable. Likewise, the polyamide molding compound according to the invention reaches a wider range of organic thermal stabilization temperatures.
    [0022] [022] According to the invention, a partially aromatic and at the same time partially crystalline polyamide, with a melting point in the range of 255 ° C to 330 ° C is used as a component (Al) of the polyamide mixture or of polyamide matrix A. Thus, the melting point of polyamides depends, essentially, only to a certain degree, on the molecular weight or intrinsic viscosity of the polyamides, however instead, it is caused by the chemical composition due to the choice of the corresponding monomers.
    [0023] [023] Thus, the polyamides usable for the invention can vary within a wide range, with the precondition that their melting point is in the range mentioned above. The melting points for the respective partially aromatic and partially crystalline polyamides are standard tabulated values for the respective polyamides, but they can also be understood with simple tests.
    [0024] [024] It should be understood as a polyamide containing caprolactam according to the invention, a polyamide which can be produced by polymerizing caprolactam or copolymerizing / polycondensing caprolactam with other monomers. The caprolactam-containing polymer therefore comprises at least 50% by weight of repeating units that are derived from caprolactam.
    [0025] [025] In order to provide reinforced or loaded molding compounds with adequate heat aging resistance, a caprolactam-containing polyamide is added to the partially aromatic, partially crystalline polyamide, so that the caprolactam content of the polyamide matrix is from 3 to 35, preferably from 10 to 28 and, particularly preferably, from 15 to 25% by weight. The use of a higher concentration of caprolactam does not substantially improve the resistance to heat aging, but it considerably reduces the thermal stability of the molding compounds and also the resistance to high temperatures. Below a caprolactam concentration of 3% by weight, in relation to the sum of the polyamides (A1) and (A2), the desired high resistance to heat aging can no longer be guaranteed.
    [0026] [026] In the case of a preferred polyamide molding compound according to the present invention, the polyamide A mixture consists of:
    [0027] [027] (A1) 70% to 78% by weight of at least one partially aromatic, partially crystalline polyamide with a melting point in the range of 255 ° C to 330 ° C, and
    [0028] [028] (A2) at least one caprolactam-containing polyamide with a caprolactam content of at least 50% by weight,
    [0029] [029] the component (A1) being free of caprolactam and aminocaproic acid, that is, it does not include repetition units derived from these.
    [0030] [030] The parameters or contents of other compounds mentioned above are, in this way, maintained.
    [0031] [031] The polyamide molding compounds according to the invention comprise from 22% to 94.99% by weight, preferably from 30% to 79.9% by weight, particularly preferably from 35% to 60% by weight of a polyamide matrix consisting of partially aromatic, partially crystalline polyamides with a melting point in the range of 255 ° C to 330 ° C (A1) and polyamides other than Al, based on caprolactam (A2).
    [0032] [032] The polyamide component (A2) consists of at least 50% by weight, preferably at least 60% by weight, and particularly preferably at least 70% by weight of caprolactam. The polyamide component (A2) is preferably a partially crystalline aliphatic polyamide.
    [0033] [033] The total content of caprolactam, that is, the sum of caprolactam contained in polyamide (A1) and polyamide (A2) is therefore 10% to 30% by weight, preferably 12% to 29% by weight, and particularly preferably, from 15% to 28% by weight, based on the mixture of polyamide (A1) and (A2).
    [0034] [034] Preferably, the molding compound according to the invention is free of polyolefins, in particular, free of polyethylene-D-olefin copolymers. COMPONENT (A1)
    [0035] [035] Component (Al) refers to partially aromatic, partially crystalline polyamides which preferably have a glass transition temperature in the range of 90 ° C to 140 ° C, preferably in the range of 110 ° C to 140 ° C and, in particular, in the range of 115 ° C to 135 ° C.
    [0036] [036] The melting point of polyamide (Al) is in the range of 255 ° C to 330 ° C, preferably in the range of 270 ° C to 325 ° C and, in particular, in the range of 280 ° C to 320 ° C.
    [0037] [037] Preferably partially aromatic, partially crystalline polyamides are therefore produced from:
    [0038] [038] a) 30% to 100% by mol, in particular 50% to 100% by mol, of terephthalic acid and / or naphthalene dicarboxylic acid and also from 0% to 70% by mol, in particular 0% at 50 mol% of at least one aliphatic dicarboxylic acid with 6 to 12 carbon atoms, and / or from 0 to 70 mol%, in particular from 0 to 50 mol% of at least one cycloaliphatic dicarboxylic acid with 8 to 20 carbon atoms, and / or 0 to 50 mol% of isophthalic acid, based on the total amount of dicarboxylic acids,
    [0039] [039] b) 80% to 100 mol% of at least one aliphatic diamine with 4 to 18 carbon atoms, preferably with 6 to 12 carbon atoms and also 0% to 20 mol%, at least at least one cycloaliphatic diamine, preferably with 6 to 20 carbon atoms, and / or 0 to 20 mol% of at least one araliphatic diamine such as, for example, PACM, MACM, IPDA, MXDA and PXDA , in relation to the total amount of diamines, and also possibly
    [0040] [040] c) aminocarboxylic acids and / or lactams with 6 to 12 carbon atoms, respectively.
    [0041] [041] According to a preferred configuration, the partially aromatic polyamide of component (A1) is formed on the basis of at least 30 mol%, in particular at least 50 mol% of terephthalic acid and at least 80 mole% of aliphatic diamines with 4 to 18 carbon atoms, preferably with 6 to 12 carbon atoms and possibly other aliphatic, cycloaliphatic and aromatic dicarboxylic acids and also lactams and / or aminocarboxylic acids. Isophthalic acid and naphthalene-dicarboxylic acid, in addition to terephthalic acid, can be used as additional aromatic dicarboxylic acids. Suitable aliphatic and cycloaliphatic dicarboxylic acids, which can be used in addition to terephthalic acid, have 6 to 36 carbon atoms and are used in a proportion of at most 70% by mol, in particular in a proportion of at most 50 mol% in relation to the total amount of dicarboxylic acids.
    [0042] [042] Furthermore, it is preferable that the mentioned aromatic dicarboxylic acids of the partially aromatic polyamide of component (A1) are selected from the group of: terephthalic acid, isophthalic acid and also mixtures thereof.
    [0043] [043] According to another preferred configuration, for example, the mentioned aliphatic dicarboxylic acids of the partially aromatic polyamide of component (A1), which can be used in addition to terephthalic acid, are selected from the group of adipic acid, submeric acid, acid azelaic, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid and fatty acid dimer (C36). Among dicarboxylic acids, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid or a mixture of such dicarboxylic acids, in particular adipic acid and isophthalic acid, and particularly adipic acid alone, are preferred.
    [0044] [044] According to another preferred configuration, the mentioned aliphatic diamines of the partially aromatic polyamide of component (A1) are selected from the group of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7- heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, or a mixture of such diamines, with preference being given to 1,6-hexanediamine, 1,10-decanediamine, 1,12-dodecanediamine, or a mixture of such diamines, and 1,6-hexanediamine and 1,10-decanediamine are particularly preferred. In addition to aliphatic diamines, cycloaliphatic and / or araliphatic diamines can be replaced at a concentration of 0% to 20% by mol, in relation to the total amount of diamines.
    [0045] [045] Preferably, high melting point polyamides are formed from the following components:
    [0046] [046] a) (Ala) dicarboxylic acids:
    [0047] [047] 50% - 100 mol% of aromatic terephthalic acid and / or naphthalene-dicarboxylic acid, in relation to the total amount of dicarboxylic acids present,
    [0048] [048] 0% - 50 mol% of an aliphatic dicarboxylic acid, preferably with 6 to 12 carbon atoms, and / or a cycloaliphatic dicarboxylic acid, preferably with 8 to 20 carbon atoms, and / or isophthalic acid;
    [0049] [049] b) (Alb) diamines:
    [0050] [050] 80 to 100 mol% of at least one aliphatic diamine with 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms, in relation to the total amount of diamines present,
    [0051] [051] 0% to 20 mol% of cycloaliphatic diamines, preferably with 6 to 20 carbon atoms, and / or aliphatic diamines such as, for example, PACM, MACM, IPDA, MXDA and PXDA, the molar content of which percentage of dicarboxylic acids in high melting polyamides totals 100% and the percentage molar content of diamines totals 100% and possibly from:
    [0052] [052] c) (A1c) aminocarboxylic acids and / or lactams, comprising lactams with preferably 6 to 12 carbon atoms, and / or aminocarboxylic acids with preferably 6 to 12 carbon atoms.
    [0053] [053] While the components (A1a) and (A1b) are used extensively in equimolar form, the concentration of (A1c) is a maximum of 20% by weight, preferably a maximum of 15% by weight in maximum of 12% by weight, respectively in relation to the sum of (A1a) to (A1c).
    [0054] [054] In addition to the components (A1a) and (A1b) used extensively in equimolar form, dicarboxylic acids (A1a) or diamines (A1b) can be used to control the molar mass or to compensate for the losses of monomers during the production of the polyamide so that, in its entirety, the concentration of the component (A1a) or (A1b) may predominate.
    [0055] [055] Suitable cycloaliphatic dicarboxylic acids are cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA).
    [0056] [056] The aliphatic diamines mentioned above, which are mandatorily used, can be replaced by different diamines in a secondary amount of, not more than 20 mol%, preferably not more than 15 mol%, and in particular , not more than 10 mol%, in relation to the total amount of diamines. As cycloaliphatic diamines, for example, cyclohexanediamine, 1,3-bis- (aminomethyl) -cyclohexane (BAC), isophoronadiamine, norbornane-dimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2- ( 4,4'-diaminodicyclohexyl) propane (PACP) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM). As araliphatic diamines, m-xylylenediamine (MXDA) and p-xylylenediamine (PXDA) can be mentioned.
    [0057] [057] In addition to the dicarboxylic acids and diamines described above, lactams and / or aminocarboxylic acids can also be used as polyamide forming components (component (A1c)). Suitable compounds are, for example, caprolactam (CL), a, m-aminocaproic acid, a, w-aminonanoic acid, a, w-aminoundecanoic acid (AUA), laurolactam (LL) and a, w-aminododecanoic acid (ADA) . The concentration of aminocarboxylic acids and / or lactams that are used together with the components (Ala) and (Alb) is a maximum of 20% by weight, preferably a maximum of 15% by weight and, particularly preferably maximum 12% by weight based on the sum of components (A1a) to (A1c). Lactams or a, w-amino acids with 4, 6, 7, 8, 11 or 12 carbon atoms are especially preferred. These are the lactam pyrrolidin-2-one (4 atoms of C), E-caprolactam (6 atoms of C), oenantolactam (7 atoms of C), caprylactam (8 atoms of C), laurolactam (12 atoms of C) or a, W-amino acids, 1,4-aminobutanoic acid, 1,6-aminohexanoic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid and 1,12-aminododecanoic acid.
    [0058] [058] In a particularly preferred configuration, the Al component is free of caprolactam or aminocaproic acid.
    [0059] [059] Regulators can be added to control molar mass, relative viscosity or fluidity or MVR (melt flow index), in the form of monocarboxylic acids or monoamines, to batch and / or pre-condensate (before post-condensation). Aliphatic, cycloaliphatic or aromatic monocarboxylic acids or monoamines suitable as regulators are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3 - (3-5-di-tert-butyl-4-hydroxyphenyl) -propanoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3- (3-tert-butyl-4-hydroxy-5- methylphenyl) propanoic acid, 2- (3,5-di-tert-butyl-4-hydroxybenzylthio) acetic acid, 3,3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid, butylamine, pentylamine, hexylamine, 2 -ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, 3- (cyclohexylamino) -propylamine, methylcyclohexylamine, dimethylcyclohexylamine, benzylamine, 2,2,6 , 6-tetramethylpiperidine-4-amine, 1,2,2,6,6-pentamethylpiperidine-4-amine, 4-amino-2,6-di-tert-butylphenol, among others. These regulators can be used individually or in combination. Other monofunctional compounds can also be used as regulators that can react with an amino or acid group, such as anhydrides, isocyanates, acid halides or esters. The normal amount of regulator use is between 10 and 200 mmol per kg of polymer.
    [0060] [060] Partially aromatic co-polyamides (A1) can be produced with methods that are known per se. The appropriate methods have been described in several passages and, consequently, some of the possible methods discussed in the patent literature are indicated, whose content of the disclosure of the documents mentioned below is included, in relation to the method for the production of the component polyamide ( A) of the present invention, expressly in the content of the disclosure of the present patent application: DE-A-195 13 940, EP-A-0 976 774, EP-A-0 129 195, EP-A-0 129 196, EP -A-0 299 444, US 4,831,106, US 4,607,073, DE-A-14 95393 and US 3,454,536.
    [0061] [061] Specific representatives of polyamides (Al) according to the invention are: PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / 6, PA 6T / 6I, PA 6T / 61/6, PA 6T / 66, 6T / 610, 6T / 612, PA 6T / 10T, PA 6T / 10I, PA 9T, PA10T, PA 12T, PA 10T / 10I, PA 10T / 106, PA 10T / 12, PA 10T / 11, PA6T / 9T, PA 6T / 12T, PA 6T / 10T / 6I, PA 6T / 6I / 6, PA 6T / 6I / 12 and also mixtures thereof, particularly preferably the partially aromatic polyamide of component (A) is selected from among the group: PA 6T / 6I, PA6T / 66, PA 6T / 10T, PA 6T / 10T / 6I and also mixtures of these. Polyamides (Al) comprising 6T units are preferred, in particular at least 10% by weight of 6T units.
    [0062] [062] According to the invention, in particular, therefore, the following partially aromatic co-polyamides are preferred as high melting point polyamides (A1):
    [0063] [063] • partially crystalline polyamide 6T / 6I with 50% to 80% by mol of hexamethylene-terephthalamide units and 20% to 50% by mol of hexamethylene-isophthalamide units;
    [0064] [064] • partially crystalline polyamide 6T / 6I with 55% to 75% by mol of hexamethylene-terephthalamide units and 25% to 45% by mol of hexamethylene-isophthalamide units;
    [0065] [065] • partially crystalline polyamide 6T / 6I with 62% to 73% by mol of hexamethylene-terephthalamide units and 25% to 38% by mol of hexamethylene-isophthalamide units;
    [0066] [066] • partially crystalline polyamide 6T / 6I with 70 mol% of hexamethylene-terephthalamide units and 30 mol% of hexamethylene-isophthalamide units;
    [0067] [067] • partially crystalline polyamide 6T / 66 with 30% to 80 mol% of hexamethylene-terephthalamide units and 20% to 70 mol% of hexamethylene-adipamide units;
    [0068] [068] • partially crystalline polyamide 6T / 66 with 50% to 70 mol% of hexamethylene-terephthalamide units and 30% to 50 mol% of hexamethylene-adipamide units;
    [0069] [069] • partially crystalline polyamide 6T / 66 with 50 to 60 mol% of hexamethylene-terephthalamide units and 40 to 50 mol% of hexamethylene-adipamide units;
    [0070] [070] • partially crystalline polyamide 6T / 66 with 55% to 60% by mol of hexamethylene-terephthalamide units and 40% to 45% by mol of hexamethylene-adipamide units;
    [0071] [071] • partially crystalline polyamide, produced from at least 50 mol% of terephthalic acid and a maximum of 50 mol% of isophthalic acid and also a mixture of at least two diamines, selected from the group of hexamethylenediamine , nonanediamine, methyloctanediamine and decanediamine;
    [0072] [072] • partially crystalline polyamide, produced from at least 70 mol% of terephthalic acid and a maximum of 30 mol% of isophthalic acid and also a mixture of hexamethylenediamine and dodecanediamine;
    [0073] [073] • partially crystalline polyamide, produced from at least 50 mol% of terephthalic acid and a maximum of 50 mol% of dodecanedioic acid and also a mixture of at least two diamines, selected from the group of hexamethylenediamine , nonanediamine, methyloctanediamine and decanediamine;
    [0074] [074] • 6T / 10T partially crystalline polyamide with 10% to 60% by mol, preferably with 10% to 40% by mol of hexamethylene-terephthalamide- (6T) units - and with 40% to 90% by mol, preferably 60 to 90 mole% of decamethylene-terephthalamide- (10T) units;
    [0075] [075] • partially crystalline polyamide 6T / 10T / 6I with 50% to 90% by mol, preferably with 50% to 70% by mol of hexamethylene-terephthalamide- (6T) units - and with 5% to 45% in mol, preferably with 10% to 30% by mol of hexamethylene-isophthalamide- (6I) units and 5% to 45% by mol, preferably 20% to 40 mol% of decamethylene-terephthalamide- ( 10T)
    [0076] [076] • partially crystalline polyamide 6T / 6I / 6 with 60% to 85 mol% of hexamethylene-terephthalamide- (6T) units - and 15% to 40 mol% of hexamethylene-isophthalamide- (6I) units - which additionally comprises 5% to 15% by weight of caprolactam;
    [0077] [077] The partially aromatic, partially crystalline polyamide (A1) has a viscosity of ƞrel solution, measured according to DIN EN ISO 307 in solutions of 0.5 g of polymer in 100 ml of m-cresol at a temperature of 20 ° C of a maximum of 2.6, preferably of a maximum of 2.3, in particular of a maximum of 2.0. Preferably, the polyamides (A1) have a ƞrel solution viscosity in the range of 1.45 to 2.3, in particular in the range of 1.5 to 2.0 or 1.5 to 1.8.
    [0078] [078] The polyamides (A1) according to the invention can be produced in normal polycondensation plants via the pre-condensation and post-condensation process sequence. For polycondensation, preferably, the chain regulators described are used to control viscosity. In addition, viscosity can be adjusted by using an excess of diamine or diacid. COMPONENT (A2)
    [0079] [079] Component (A2) refers to caprolactam-containing polyamides with a caprolactam content of at least 50% by weight, preferably at least 60% by weight, and particularly preferably at least 70% by weight. In particular, (A2) refers to PA 6 polyamide.
    [0080] [080] In the case where component (A2) refers to a copolymer, the preferred co-monomers for (A2), which are used in addition to caprolactam, are, on the one hand, combinations of diamines and dicarboxylic acids which are preferably used equimolarly or almost equimolarly, and, on the other hand, lactams and aminocarboxylic acids.
    [0081] [081] Suitable diamines are, in particular, linear or branched aliphatic diamines with 4 to 18 carbon atoms. Suitable dicarboxylic acids are aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 6 to 36 carbon atoms.
    [0082] [082] According to a first preferred configuration, diamine C4-C18 refers to a diamine selected from the group of 1,4-butanediamine, 1,5-pentanediamine, 2-methylpentanediamine, 1,6-hexanediamine, 1,7 -heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, methyl-1,8-octanediamine, 2,2,4-trimethylhexanediamine, 2,4,4-trimethylhexanediamine, 1,10-decanediamine, 1,11- undecanediamine , 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 4,4-diaminodicyclohexylmethane (PACM ), 2,2- (4,4'-diaminodicyclohexyl) propane (PACP), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), mxylylene diamine, p-xylylene diamine or a mixture of such diamines, 1, 6-hexanediamine, 1,10-decanediamine, 1,12-dodecanediamine, or a mixture of such diamines, 1,6-hexanediamine and 1,10-decanediamine are preferred, and 1,6-hexanediamine alone is particularly preferred.
    [0083] [083] Suitable aliphatic dicarboxylic acids are adipic acid, butyric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanic acid and hexadecanic acid. Suitable cycloaliphatic dicarboxylic acids are cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA). Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Among the dicarboxylic acids, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid or a mixture of such dicarboxylic acids are preferred, preferably adipic acid and terephthalic acid and, in particular, adipic acid alone.
    [0084] [084] Other preferred co-monomers for polyamide (A2) are possibly lactams or aminocarboxylic acids with 7 to 12 carbon atoms, with laurolactam and aminoláuric acid being particularly preferred.
    [0085] [085] Particularly preferred polyamides of type (A2) are co-polyamides produced from the monomers caprolactam and laurolactam or caprolactam, hexanediamine and adipic acid or caprolactam, hexanediamine and terephthalic acid, that is, co-polyamides PA 6/12 or PA 6/66 or PA 6/6 or PA 6/12/66 or PA 6/66/610, whose caprolactam content is at least 50% by weight.
    [0086] [086] The polyamide containing caprolactam (A2) has a viscosity of ƞrel solution, measured according to DIN EN ISO 307 in solutions of 0.5 g of polymer dissolved in 100 ml of m-cresol at a temperature of 20 ° C in the range of 1.6 to 3.0, preferably in the range of 1.7 to 2.5, in particular, in the range of 1.8 to 2.2.
    [0087] [087] Preferably, the at least one heat stabilizer is selected from the group consisting of N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) - propionamide, ester bis- (3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid, 2,1'-thioethylbis- (3- (3,5-di-tert-butyl-4) glycolic acid -hydroxyphenyl) -propionate, 4,4'- butylidene-bis- (3-methyl-6-tert-butylphenol), triethylene glycol- 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionate, octadecyl -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, Brüggolen TP-H7005 or mixtures of two or more of these, preferably of the heat stabilizers mentioned above, stabilizers based on sterically hindered phenols are used, in particular Brüggolen TP-H7005.
    [0088] [088] The at least one heat stabilizer based on sterically hindered phenols is preferably contained in an amount of 0.1% to 1.5% by weight, particularly preferably from 0.2% to 1% by weight. Weight.
    [0089] [089] It is particularly preferred that the polyamide molding compound is free of inorganic stabilizers based on transition metals and metals of the main group III to V, and it is particularly preferred that they are completely free of inorganic stabilizers.
    [0090] [090] PA compounds for molding which comprise organic stabilizers have, compared to PA compounds for molding supplied with inorganic stabilizers such as, for example, copper based stabilizers, better behavior with respect to contact corrosion.
    [0091] [091] In a preferred configuration of the polyamide molding compound according to the invention, at least one other heat stabilizer is an organic stabilizer selected from the group consisting of:
    [0092] [092] • stabilizers based on aromatic secondary amines, in particular adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linolene, Naugard 445, N, N'-dinaftyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine or mixtures of two or more of these,
    [0093] [093] • phosphite and phosphonite group stabilizers, in particular triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, di-stearyl-pentahydrite -isodecyl-pentaerythritoldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritoldiphosphite, di-isodecyloxy-pentaerythritoldiphosphite, bis ( di-tert-butyl-6-methylphenyl) -pentaerythritoldiphosphite, bis (2,4,6-tris- (tert-butylphenyl)) pentaerythritoldiphosphite, tristearyl-sorbitoltriphosphite, tetquis (2,4-di-tert-butylphenyl) -4, 4'- biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo- [d, g] -1,3,2-dioxaphosphocine, 6-fluoro-2,4 , 8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite and bis ( 2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, tris [2-tert-butyl-4-thio phosphate (2'-methyl-4'-hydroxy-5'-te rc-butyl) -phenyl-5-methyl] phenyl-phosphite and tris (2,4-di-tert-butylphenyl) phosphite, (Hostanox® PAR24: commercial product manufactured by Clariant, Basel) Brüggolen TP-H7005, 2, 6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazian-2-ylamino) phenol (Irganox® 565: commercial product of BASF), bis (3-tert -butyl-4-hydroxy-5-methylphenyl) triethylene glycol propionate (Irganox® 245: commercial product from BASF), tetrakismethylene (3,5-di-tert-butyl-4-hydroxyhydrocinamate) methane (Irganox® 1010: commercial product from BASF), 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (Irganox® 1310: commercial product from BASF), 2,2 '' monoacrylate - methylenebis- (6 -tert-butyl-p-cresol) (Irganox® 3052: commercial product of BASF),
    [0094] [094] • mixtures of these.
    [0095] [095] Furthermore, it is preferable that the polyamide molding compound comprises 0.2% to 2% by weight, preferably from 0.2% to 1.5% by weight of stabilizers based on secondary amines and / or 0.1% to 1.5% by weight, preferably from 0.2% to 1% by weight of stabilizers based on sterically hindered phenols and / or 0.1% to 1.5% by weight, of preferably, from 0.2% to 1% by weight of phosphite and phosphonite group stabilizers, the total proportion of stabilizers in the polyamide molding compound being no more than 3% by weight.
    [0096] [096] The behavior of contact corrosion plays an important role if molded articles made from the molding compounds according to the invention are brought into contact with metals. If the molded articles have purely organic stabilizers, the corrosion of metals on contact can be almost completely suppressed, in particular, completely suppressed. The behavior of contact corrosion can be quantified through the electrical conductivity of the PA compound for molding, which is from 1 * 10 -6 to 0.5 * 10 -11 S, preferably from 1 * 10 -8 to 8 * 10 -10 S and particularly preferably from 3 * 10 -9 to 3 * 10 -10 S, determined as described in the experimental part.
    [0097] [097] In general, halogen-free flame retardants are possible in the present invention. As a result, it becomes possible that the polyamide molding compounds according to the invention have excellent flame retardant properties, in addition to very good long-term heat aging resistance.
    [0098] [098] A preferred configuration of the polyamide molding compound according to the invention provides that the at least one flame retardant is halogen-free. The halogen-free flame retardant is therefore selected from the group consisting of melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melem phosphate, melem pyrophosphate, dimelamine pyrophosphate, dimelamine phosphate, polyphosphate of melem, phosphaphenanthrenes, metal hydroxides, phosphinic acid salts, diphosphinic acid salts and combinations thereof.
    [0099] [099] Furthermore, it is preferable that the flame retardant additionally comprises at least one synergist, such as at least one synergist being preferably selected from the group consisting of nitrogen-containing compounds, phosphorus-containing compounds and nitrogen, metal borates, metal carbonates, metal hydroxides, metal hydroxy-oxides, metal nitrides, metal oxides, metal phosphates, metal sulfides, metal stannates, metal hydroxy stannates, silicates, zeolites, basic zinc silicates, silicic acids and combinations of these , in particular triazine derivatives, melamine, guanidine, guanidine derivatives, biuret, triuride, tartrazine, glycoluryl, acetoguanamine, butyroguanamine, caprinoguanamine, benzoguanamine, cyanuric acid melamine derivatives, isocyanuric acid melamine derivatives, melamine cyanurate, melamine products condensation of melamine, melamine pyrophosphate, pyrophosphates of the condensation products of melamine, dimelamine phosphate, dimelamine pyrophosphate, melamine polyphosphate, dicyandiamide, ammonium polyphosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, polyphosphates from melamine condensation products, melamine sulphate, allantoin, aluminum hydroxide, meta synthetic aluminum hydroxide (synthetic aluminum hydroxy-oxide), natural aluminum meta-hydroxide (natural aluminum hydroxy-oxide), aluminum oxide, calcium borate, calcium carbonate, calcium and magnesium carbonate, calcium oxide, sulfide calcium, iron oxide, magnesium borate, magnesium carbonate, magnesium hydroxide, magnesium nitride, magnesium oxide, magnesium sulfide, manganese hydroxide, manganese oxide, titanium nitride, titanium dioxide, zinc borate , zinc metaborate, zinc carbonate, zinc hydroxide, zinc nitride, zinc oxide, zinc phosphate, zinc sulfide, zinc stannate, zinc hydroxy stannate, basic silicate zinc, tin oxide hydrate, and combinations thereof.
    [0100] [0100] However, it is also possible that the flame retardant is free of synergists.
    [0101] [0101] Furthermore, it is preferable that the at least one flame retardant is a salt of the phosphonic acid of general formula (I)
    [0102] [0102] and / or formula (II)
    [0103] [0103] and / or one of its polymers, R1 and R2 being the same or different and being selected from the group consisting of Cl-C8 alkyl and / or linear or branched aryl, R3 being selected from the group consisting of C1-Cl0 alkylene straight or branched chain, C6-C10 arylene, alkylarylene and arylalkylene, M being a metal ion of the 2nd or 3rd main group or auxiliary group of the periodic table, preferably A1, Ba, Ca or Zn, m being 2 or 3, n 1 or 3 and ex 1 or 2.
    [0104] [0104] The flame retardant Exolit OP 1230, marketed by the company Clariant, which refers to the aluminum salt of diethylphosphonic acid (CAS-No. 225789-38-8), is particularly preferred.
    [0105] [0105] Metal-free flame retardants are particularly preferred.
    [0106] [0106] The polyamide molding compound preferably comprises from 5% to 24% by weight, preferably from 6% to 23% by weight, particularly preferably from 7% to 21% by weight of at least a flame retardant. If more than 25% by weight of component b) is added, the mechanical properties suffer a lot, below 5% by weight, in contrast, the flame retardant properties are negatively affected.
    [0107] [0107] In a preferred configuration, the molding compound is classified according to the IEC 60695-11-10 standard (UL94) as V-0.
    [0108] [0108] In another preferred configuration of the polyamide molding compound according to the invention, the at least one additive is selected from the group consisting of light stabilizers, UV stabilizers, UV absorbers or UV blockers, lubricants, dyes , nucleating agents, antistatic agents, conductivity additives, release agents, fillers, reinforcing agents, optical brighteners or mixtures thereof.
    [0109] [0109] The fillers, in particular, are selected from the group consisting of hair crystals, talc, mica, silicates, quartz, titanium dioxide, volastonite, kaolin, silicic acids, magnesium carbonate, magnesium hydroxide, chalk, carbonate precipitated or ground calcium, lime, feldspar, barium sulphate, glass balls, hollow glass balls, loads of hollow silicate balls, natural layered silicates, synthetic layered silicates and mixtures thereof,
    [0110] [0110] Reinforcing agents are preferably fibers, in particular glass fibers and / or carbon fibers. In addition, it is preferable that the fibers refer to fibers with a circular cross-sectional area, fibers with a non-circular cross-sectional area or to a mixture of fibers with a circular cross-sectional area and fibers with a cross-sectional area non-circular, the proportion of fibers with a non-circular cross-sectional area in the mixture, preferably at least 50% by weight and, in the case of fibers with a non-circular cross-sectional area, the dimensional ratio of the main axis of the cross section for the auxiliary axis of the cross section being preferably> 2, particularly preferably in the range 2 to 8, very particularly preferably in the range 3 to 5. Preferably the fibers are short fibers preferably with a length in the range of 2 to 50 mm and a diameter of 5 to 40 µm, and / or endless fibers (fibers for weaving).
    [0111] [0111] If flat glass fibers with a non-circular cross-sectional area are used, these are preferably used as short glass fibers (glass cut to a length of 0.2 to 20 mm, preferably 2 to 12 mm).
    [0112] [0112] Another preferred configuration provides that the reinforcing agents are glass fibers with an area of non-circular cross section and a dimensional ratio of the main axis of the cross section to the auxiliary axis of the cross section of more than 2, preferably from 2 to 8, particularly preferably from 3 to 5, with the glass fibers having an oval, elliptical, rectangular, or almost rectangular cross-sectional area provided with nips or nips, with the fibers of glass preferably from 0.2 to 20 mm, especially preferably from 2 to 12 mm in length, the length of the main axis of the cross section being preferably in the range of 6 to 40 µm, particularly preferably , in the range of 15 to 30 µm, and the length of the secondary axis of the cross section being preferably in the range of 3 and 20 pm, particularly preferably in the range of 4 to 10 pm.
    [0113] [0113] In another preferred configuration of the polyamide molding compound according to the invention, it is free of metallic pigments.
    [0114] [0114] For use in applications where the behavior of contact corrosion is relevant, a molding compound as follows is preferred:
    [0115] [0115] a) 22% to 99.99% by weight of a polyamide mixture, consisting of,
    [0116] [0116] (A1) at least one partially aromatic, partially crystalline polyamide with a melting point in the range of 255 ° C to 330 ° C,
    [0117] [0117] (A2) at least one polyamide containing caprolactam which differs from at least one partially aromatic, partially crystalline polyamide (A1) and which has a caprolactam content of at least 50% by weight,
    [0118] [0118] the total caprolactam content of caprolactam contained in polyamide (A1) and polyamide (A2), in relation to the polyamide mixture, being 3% and 35% by weight,
    [0119] [0119] b) 0.01% to 3.0% by weight of at least one heat stabilizer, in particular, sterically hindered phenol based stabilizers and
    [0120] [0120] d) 0 to 50% by weight of at least one additive,
    [0121] [0121] components a) to d) totaling up to 100% by weight. The polyamide molding compound is therefore free from metal salts and / or metal oxides.
    [0122] [0122] Of particular preference, for applications in which the behavior of contact corrosion is relevant, a compound for molding is provided as follows:
    [0123] [0123] a) 27% to 84.99% by weight of a polyamide mixture, consisting of,
    [0124] [0124] (A1) at least one partially aromatic, partially crystalline polyamide with a melting point in the range of 255 ° C to 330 ° C,
    [0125] [0125] (A2) at least one caprolactam-containing polyamide which differs from at least one partially aromatic, partially crystalline polyamide (A1) and which has a caprolactam content of at least 50% by weight, the total caprolactam content of the caprolactam contained in polyamide (A1) and polyamide (A2), compared to the polyamide mixture, being 3% and 35% by weight,
    [0126] [0126] b) 15% to 65% by weight of fillers and reinforcing agents,
    [0127] [0127] c) 0.1% to 3.0% by weight of at least one stabilizer to organic heat, in particular stabilizers based on sterically hindered phenols and
    [0128] [0128] d) 0% to 5.0% by weight of at least one additive,
    [0129] [0129] components a) to d) totaling up to 100% by weight. The polyamide molding compound is therefore free from metal salts and / or metal oxides.
    [0130] [0130] Furthermore, the present invention relates to a method for the production of such a polyamide molding compound. It also refers to molded articles that are produced with such polyamide molding compounds. APPLICATIONS
    [0131] [0131] Furthermore, the invention relates to the uses of molded parts that consist, at least partially, of such polyamide compounds for molding. Molded parts that are placed, at least partially, in contact with metals are preferred.
    [0132] [0132] For the automotive sector, the following can be mentioned by way of example: cylinder head covers, engine covers, combustion air cooler housings, flange for combustion air coolers, feed tubes, in particular, kegs supply, connectors, gears, fan rotors, cooling water housings, housings or parts of housings for heat exchangers, coolants for coolants, combustion air coolers, thermostat, water pump, heating body, parts fixing. In the electrical / electronic sector, such uses are, for example, parts of starting assistance points, circuit boards, housings, sheets, tubes, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors , connectors, regulators, tanks and sensors.
    [0133] [0133] The present invention is explained in more detail with reference to the following examples, without restricting the invention to the specific configurations represented here. EXAMPLES
    [0134] [0134] In Table 1, the materials used for the examples are compiled.
    [0135] [0135] a) determined in accordance with ISO 307 (0.5 g of polyamide in 100 ml of m-cresol), with the calculation of relative viscosity (RV) according to RV = t / t0 following section 11 the standard; b) determined according to the ISO 307 standard (0.5 g of polyamide in 100 ml of formic acid), with the calculation of the relative viscosity (RV) according to RV = t / t0 following section 11 of the standard; c) supply of KI mixture with Ca stearate performed at EMS. PRODUCTION OF MOLDING COMPOUNDS AND COMPOUNDS
    [0136] [0136] The molding compounds for examples E1 to E4 according to the invention and also for comparative examples CE1 to CE3 were produced in a twin screw extruder from the company of Werner and Pfleiderer of type ZSK25. The proportions of the quantities of starting materials in percent by weight (% by weight), relative to 100% by weight of the total molding compound mixed in the twin screw extruder are shown in Table 2.
    [0137] [0137] The polyamide granules were dosed together with the additives in the feed zone, while the glass fiber was dosed into the melted polymer through the side feeder 3 located in front of the nozzle. The housing temperature was adjusted with a profile rising to 320 ° C. A yield of 15 kg was achieved at a speed of 150 to 250 rpm. After cooling the strands in a water bath, granulating and drying at 120 ° C for 24 hours, injection molding of the compounds was performed to form the pieces for the ISO test. Injection molding was performed on an Arburg Allrounder 320-210-750 injection molding equipment with cylinder temperatures of 300 ° C to 325 ° C in zones 1 to 4 and a mold temperature of 135 ° C.
    [0138] [0138] Mechanical properties are compiled in Table 3 after storage under heat at 220 ° C.
    [0139] [0139] The determination of the properties indicated in Tables 2 and 3 was carried out according to the following methods. IMPLEMENTATION OF UNDER HEAT STORAGE
    [0140] [0140] Heat storage was implemented in individual electrically heated chambers and ventilated heated cabinets, according to IEC 60216-4-1, at 220 ° C in the form of ISO bars for tensile testing (standard: ISO 3167 , Type A, 170 x 20/10 x 4 mm). After the times indicated in Table 3, the specimens were removed from the oven and tested, after cooling to 23 ° C, according to the methods indicated below. DETERMINATION OF BREAKING STRENGTH AND BREAKING STRETCH
    [0141] [0141] The determination of the breaking strength and elongation at break was carried out in accordance with ISO 527, with a tensile speed of 5 mm / min in an ISO tensile specimen in accordance with ISO 3167, Type A with dimensions of 170 x 20/10 x 4 mm at a temperature of 23 ° C. DETERMINATION OF FLAME RETARDANT PROPERTIES
    [0142] [0142] The flame retardant properties were determined in the vertical fire test according to the IEC 60695-11-10 (UL94) standard on specimens with a wall thickness of 0.8 mm. The specimens were stored, before the test, for 7 days at 70 ° C. EVALUATION OF RESISTANCE TO HEAT AGING
    [0143] [0143] Resistance to heat aging has been assessed with (+) if the mechanical properties determined as described above after 2000 hours are still greater than 50% of the initial values, that is, before storage under heat. EVALUATION OF CORROSION BEHAVIOR BY CONTACT DESCRIPTION OF VISUAL EVALUATION INCLUDED
    [0144] [0144] Sheets of materials (80 * 80 * 3 mm, film molding) were initially stored for 500 hours at 85 ° C and 85% humidity. A copper sheet (10 * 80 * 1 mm) was subsequently pressed onto the pre-positioned sheets. The leaves in contact with the copper foil were stored for another 1000 hours under ambient conditions and, subsequently, the copper foil was removed and the corrosion evaluated visually. DETERMINATION OF CONDUCTIVIPAPE
    [0145] [0145] Sheets of materials (80 * 80 * 3 mm, film molding) were initially stored for 500 hours at 85 ° C and 85% humidity. Subsequently, the sheets were supplied diagonally, with two conductive silver strips (200N Hans Wolbring GmbH) with a spacing of one centimeter. The surface was placed in contact with the conductive silver strips and the surface resistance was tested and measured. The indicated conductivity corresponded to the reciprocal surface resistance. DETERMINATION OF THE TREATMENT RESISTANCE INDEX (CTI)
    [0146] [0146] The determination of the CTI was carried out according to standard IEC60112.
    权利要求:
    Claims (16)
    [0001]
    POLYAMIDE COMPOUND FOR MOLDING, consisting of; a) 22% to 99, 99% by weight of a polyamide mixture, consisting of, (Al) at least one partially aromatic, partially crystalline polyamide with a melting point in the range of 255 ° C to 330 ° C, (A2) at least one caprolactam-containing polyamide which differs from at least one partially aromatic, partially crystalline (Al) polyamide and which has a caprolactam content of at least 50% by weight, the total caprolactam content of the caprolactam contained in the polyamide (Al) and polyamide (A2), in relation to the polyamide mixture, being 3% and 35% by weight, (b) 0% to 25% by weight of at least one flame retardant, (c) 0.01% to 3.0% by weight of at least one organic heat stabilizer based on sterically hindered phenols and d) 0 to 50% by weight of at least one additive, components a) to d) totaling up to 100% by weight, characterized by the polyamide molding compound being free of metal salts and metal oxides of a transition metal of the group VB, VIB, VIIB or VIIIB of the periodic table.
    [0002]
    POLYAMIDE COMPOUND FOR MOLDING, according to the previous claim, characterized in that the electrical conductivity of the compound for molding is from 1 * 10 - 6 to 0.5 * 10 -11 S, preferably from 1 * 10 -8 to 8 * 10 -10 S and particularly preferably from 3 * 10 -9 to 3 * 10 -10 S.
    [0003]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the polyamide compound for molding is free of inorganic stabilizers based on transition metals and metals of the main group III to V.
    [0004]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one heat stabilizer based on sterically hindered phenols is selected from the group consisting of N, N'-hexamethylene-bis-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) -propionamide, bis- (3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid glycolic ester, 2.1 ' -tioethylbis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), triethylene glycol- 3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) -propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, or mixtures of two or more of these.
    [0005]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one heat stabilizer based on sterically hindered phenols is contained in an amount of 0.1% to 1.5% by weight, particularly preferably from 0.2% to 1% by weight.
    [0006]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one additional heat stabilizer is selected from the group of: • stabilizers based on secondary aromatic amines, in particular adducts of phenylenediamine with acetone, adducts of phenylenediamine with linolene, N, N'-dinafty-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine or mixtures of two or more of these, • phosphite and phosphonite group stabilizers, in particular triphenylphosphite, diphenylalkylphosphite, phenylalkylphosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecylphosphite, di-styryl-pentaerythrityl-trisphite-trifold-tertiary-trifold-tertiary-trifold-tertiary isodecyl pentaerythritoldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritoldiphosphite, di-isodecyloxy pentaerythritoldiphosphite, bis (2,4-di-ter-tert -butyl-6-methylphenyl) - pentaerythritoldiphosphite, bis (2,4,6-tris- (tertbutylphenyl)) pentaerythritoldiphosphite, tri-stearyl-sorbitoltriphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'- biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo- [d, g] -1,3,2-dioxaphosphocine, 6-fluoro-2,4,8, 10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite and bis (2,4 -di-tert-butyl-6-methylphenyl) ethylphosphite, tris [2-tert-butyl-4-thio phosphate (2'-methyl-4'-hydroxy-5'-tert-but yl) -phenyl-5-methyl] phenyl-phosphite and tris (2,4-di-tert-butylphenyl) phosphite, 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1 , 3,5-triazian-2-ylamino) phenol, triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, tetrakis-methylene (3,5-di-tert-butyl-4-hydroxyhydrocinamate ) methane, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 2.2 '' - methylenebis- (6-tert-butyl-p-cresol) monoacrylate, and also • mixtures of these.
    [0007]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one flame retardant is halogen-free, such a halogen-free flame retardant being preferably selected from the group consisting of cyanurate of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melem phosphate, melem pyrophosphate, dimelamine pyrophosphate, dimelamine phosphate, melem polyphosphate, phosphaphenanthrenes, metal hydroxides, phosphoric acid salts, phosphonic acid salts and combinations of these.
    [0008]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the flame retardant additionally comprises at least one synergist, such as at least one synergist being preferably selected from the group consisting of nitrogen-containing compounds, compounds containing phosphorus and nitrogen, metal borates, metal carbonates, metal hydroxides, metal hydroxides, metal nitrides, metal oxides, metal phosphates, metal sulphides, metal stannates, metal hydroxy stannates, silicates, zeolites, basic zinc silicates, silicic acids and combinations thereof, in particular triazine, melamine, guanidine derivatives, guanidine derivatives, biuret, triuride, tartrazine, glycoluryl, acetoguanamine, butyroguanamine, caprinoguanamine, benzoguanamine, cyanuric acid melamine derivatives, isocyanuric acid melamine derivatives, melamine cyanurate, condensation products from the blade, melamine pyrophosphate, pyrophosphates from melamine condensation products, dimelamine phosphate, dimelamine pyrophosphate, melamine polyphosphate, dicyandiamide, ammonium polyphosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, melanohydrate phosphate products melamine, allantoin, aluminum hydroxide, synthetic aluminum hydroxy-oxide such as synthetic aluminum meta-hydroxide, natural aluminum hydroxy-oxide such as natural aluminum meta-hydroxide, aluminum oxide, calcium borate, calcium carbonate, calcium and magnesium carbonate, calcium oxide, calcium sulfide, iron oxide, magnesium borate, magnesium carbonate, magnesium hydroxide, magnesium nitride, magnesium oxide, magnesium sulfide, manganese hydroxide, manganese oxide, titanium nitride, titanium dioxide, zinc borate, zinc metaborate, zinc carbonate, zinc hydroxide, zinc nitride, zinc oxide, z phosphate inco, zinc sulfide, zinc stannate, zinc hydroxy stannate, basic zinc silicate, tin oxide hydrate, and combinations thereof.
    [0009]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one flame retardant is a phosphonic acid salt of general formula (I)
    [0010]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized by 5% to 24% by weight, preferably 6% to 23% by weight, particularly preferably 7% to 21% by weight of the hair least one flame retardant are contained in the polyamide molding compound.
    [0011]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that the at least one additive is selected from the group consisting of: • light stabilizers, UV stabilizers, UV absorbers or UV blockers, • lubricants, • dyes, • nucleating agents, • anti-static agents, in particular selected from the group consisting of carbon black, carbon nanotubes or mixtures thereof, • conductivity additives, • release agents, • fillers, in particular selected from the group consisting of capillary crystals, talc, mica, silicates, quartz, titanium dioxide, volastonite, kaolin, silicic acids, magnesium carbonate, magnesium hydroxide, chalk, precipitated or ground calcium carbonate, lime, feldspar, barium sulfate, glass balls, hollow glass balls, loads of hollow silicate balls, natural layer silicates, synthetic layer silicates and mixtures thereof, • reinforcing agents, • optical brighteners or • mixtures of these.
    [0012]
    POLYAMIDE COMPOUND FOR MOLDING, according to the previous claim, characterized by containing fibers as reinforcing agents, in particular glass fibers and / or carbon fibers.
    [0013]
    POLYAMIDE COMPOUND FOR MOLDING, according to the previous claim, characterized in that the fibers refer to fibers with a circular cross-sectional area, fibers with a non-circular cross-sectional area or to a mixture of fibers with a circular cross-sectional area and fibers with a non-circular cross-sectional area, the proportion of fibers with a non-circular cross-sectional area in the mixture is preferably at least 50% by weight and, in the case of fibers with a non-circular cross-sectional area , the dimensional ratio of the main axis of the cross section to the auxiliary axis of the cross section being preferably> 2, particularly preferably in the range 2 to 8, most particularly preferably in the range 3 to 5.
    [0014]
    POLYAMIDE COMPOUND FOR MOLDING, according to claims 12 or 13, characterized in that the fibers are short fibers, preferably with a length in the range of 2 to 50 mm and a diameter of 5 to 40 pm, and / or fibers without end.
    [0015]
    POLYAMIDE COMPOUND FOR MOLDING, according to any one of the preceding claims, characterized in that it is free of metallic pigments.
    [0016]
    MOLDED ARTICLE PRODUCED FROM A POLYAMIDE COMPOUND FOR MOLDING, as defined in any of the preceding claims, characterized in that it is preferably in the form of a component for the automobile or for the electric / electronic field, in particular caps for heads of cylinder, engine covers, housings for combustion air coolers, flaps for combustion air coolers, supply tubes, feed barrels, connectors, gears, fan rotors, cooling water housings, housings or parts of housings for heat exchangers, coolers for refrigerants, combustion air coolers, thermostat, water pump, heating body, fastening parts, in the form of an electrical or electronic component, parts of starting points, a circuit, a part of a circuit board, a housing component, a sheet, a tube, in particular in the form of a switch, a distributor idor, a relay, a resistor, a capacitor, a coil, a lamp, a diode, an LED, a transistor, a connector, a regulator, a deposit and / or a sensor, with components that are, at least partially, preferred in contact with a metal.
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    同族专利:
    公开号 | 公开日
    EP2902444A1|2015-08-05|
    JP2015145496A|2015-08-13|
    EP2902444B1|2018-01-17|
    US20150218374A1|2015-08-06|
    BR102015002100A2|2015-12-08|
    CN105017766A|2015-11-04|
    KR20150091266A|2015-08-10|
    TW201533156A|2015-09-01|
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    法律状态:
    2015-12-08| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-22| B09A| Decision: intention to grant|
    2020-06-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP14153391.9|2014-01-31|
    EP14153391.9A|EP2902444B1|2014-01-31|2014-01-31|Polyamide moulding compounds with flame retardant properties and very good long-term heat ageing resistance|
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