Polyamide molding material having high fracture strength, and molded parts manufactured therefrom.

Abstract

To provide a polyamide molding material with high fracture strength, and molded parts produced therefrom.SOLUTION: The present invention relates to a polyamide molding material with high fracture energy and molded parts produced therefrom which are particularly suitable for visible parts for automotive parts or for electronic devices. The polyamide molding material may comprise: a mixture M of a polyamide X and a polyamide Y; an additive; a coloring agent; and other ingredients. Thereby, the polyamide molding material also has, in addition to excellent fracture energy, excellent piano lacquer finish and high rubbing resistance.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamide molding material having high fracture energy and a molded product produced therefrom, and is particularly suitable for automotive parts and visible parts of electronic devices. The polyamide molding material has excellent piano lacquer finish and high abrasion resistance in addition to excellent fracture energy.

Background Art

[0002] Patent Document 1 relates to a transparent molded part formed from a selected polyamide molding material, and its physical properties, particularly transparency and dynamic resistance, are superior to those of polycarbonate. The transparent polyamide that forms the basis of these molding materials is formed from at least two aliphatic diamines and at least two aromatic dicarboxylic acids, and optionally lactam. However, mixtures of these transparent polyamides with other polyamides are not used in the examples.

[0003] Patent Document 2 relates to a transparent polyamide molding material based on a transparent cycloaliphatic polyamide, and may be used, for example, in the fields of housing parts, household sectors, sports goods or toys, and has a high elongation at break. The molding material may contain other polymers, particularly polyamides.

[0004] Patent Document 3 relates to a polyamide molding material having high gloss and high notch impact strength. This molding material is thereby based on an amorphous or microcrystalline copolyamide 6I / 6T / MACMI / MACMT / PACMT / Y or PA6I / 6T / MACMI / MACMT / Y. Here, Y represents lactam or ω-amino acid, and is impact-modified with a functionalized copolymer made from ethylene, propylene, and 1-butene. Aliphatic polyamides as blend components are not mentioned.

[0005] Patent Document 4 relates to a polyamide molding material, which is based on a mixture of a specific amorphous polyamide and a specific semicrystalline polyamide, and is characterized by excellent stress cracking resistance and excellent optical properties, particularly high light transmittance and low haze. The semicrystalline polyamide is a long-chain aliphatic polyamide.

[0006] Patent Document 5 relates to a polyamide molding material, which is based on a mixture of specific amorphous or microcrystalline polyamides and semicrystalline polyamides PA616, PA516, and PA1016, and is characterized by very good stress cracking resistance and very good optical properties.

[0007] Patent Document 6 describes the use of a molding material made from a polyamide mixture comprising an aliphatic homo- or copolyamide and a transparent homo- or copolyamide, and optionally fillers, reinforcing materials, and additives. The proposed application is the manufacture of molded parts for drinking water, particularly containers or conduits, in which at least a portion of the processed molding material is substantially directly exposed to drinking water. In the examples, only PA12 is used as the aliphatic polyamide.

[0008] Fully aliphatic polyamides like polyamide 66 certainly have high mechanical resistance, but they are crystalline. Because crystals refract or scatter light, the molded material takes on a silky or striped appearance due to the Tyndall effect. Therefore, crystalline polyamide molded materials are too opaque and have too much haze to produce parts that are aesthetically pleasing, high-quality, and visible when installed. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] European Patent Application Publication No. 1930373 [Patent Document 2] European Patent Application Publication No. 3336131 [Patent Document 3] European Patent Application Publication No. 3450481 [Patent Document 4] European Patent Application Publication No. 3502164 [Patent Document 5] European Patent Application Publication No. 3502191 [Patent Document 6] European Patent Application Publication No. 2055743 [Overview of the project] [Problems that the invention aims to solve]

[0010] Conventional techniques only result in a loss of dimensional stability after high energy absorption (which can be determined based on fracture energy). Therefore, the problem of providing a polyamide molding material that is both safe and aesthetically pleasing, especially against mechanical loads such as impacts, has not been solved. Molded parts made from such molded materials are used particularly as visible components in automotive parts and electronic devices. At the same time, the polyamide molding material preferably has a so-called piano lacquer finish, conveying the impression of the darkest black, paired with high gloss. Furthermore, the polyamide molding material is preferably abrasion resistant, as it has high stability against the effects of abrasives, both additionally and simultaneously. [Means for solving the problem]

[0011] This problem is solved by the molding material according to claim 1 and the molded part according to patent claim 13. [Effects of the Invention]

[0012] This results in a favorable improvement for the dependent patent claims. [Modes for carrying out the invention]

[0013] [Definition of Terms] <Notation and abbreviations for polyamides and their monomers> In the context of this invention, the term "polyamide" (abbreviation: PA) is understood as a comprehensive term encompassing homopolyamides and copolyamides. Selected names and abbreviations for polyamides and their monomers correspond to those defined in DIN EN ISO standard 16396-1:2015. The abbreviations used herein are synonyms for the IUPAC names of the monomers, and in particular, the following monomer abbreviations are observed. MACM: Bis(4-amino-3-methylcyclohexyl)methane (also written as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane; CAS number: 6864-37-5) PACM: Bis(4-aminocyclohexyl)methane (also written as 4,4'-diaminodicyclohexylmethane; CAS number: 1761-71-3) TMDC: Bis(4-amino-3,5-dimethylcyclohexyl)methane (also written as 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane; CAS number: 65962-45-0) T: Terephthalic acid (CAS number: 100-21-0) I: Isophthalic acid (CAS number: 121-95-5) BAC: 1,4-bis(aminomethyl)cyclohexane (CAS number: 2549-93-1).

[0014] <amount> The polyamide molding material according to the present invention preferably contains components (a) to (d) or consists only of components (a) to (d). This specifies that the sum of components (a) to (d) is 100% by weight. The indicated range for the amounts of individual components (a) to (d) should be understood to mean that any amount of each individual component can be selected within the specified range, as long as the strict requirement that the sum of components (a) to (d) is 100% by weight is met.

[0015] <Amorphous or microcrystalline polyamide> Amorphous or microcrystalline polyamide exhibits a heat of fusion at a heating rate of 20 K / min in differential scanning calorimetry (DSC) according to DIN EN ISO 11357-3 (2018), preferably 25 J / g or less, particularly preferably 22 J / g or less, and most preferably 0 to 20 J / g.

[0016] Microcrystalline polyamide also has a melting point in addition to the glass transition temperature. However, when measured according to ASTM D1003-21 (2021), a plate made of microcrystalline polyamide with a thickness of 2 mm is still transparent, that is, microcrystalline polyamide has a form with small dimensions such that the light transmittance is at least 88% or at least 90%, and the haze is at most 3%.

[0017] Amorphous polyamide, compared with microcrystalline polyamide, has no heat of fusion or has a very low heat of fusion that is hardly detectable. In differential scanning calorimetry (DSC) according to DIN EN ISO 11357-3 (2018), the heat of fusion of amorphous polyamide at a heating rate of 20 K / min is preferably 5 J / g or less, particularly preferably 3 J / g or less, and most preferably 0 to J / g. Amorphous polyamide has no melting point because it is amorphous.

[0018] In the context of the present invention, semi-crystalline polyamide refers to a polyamide that exhibits a heat of fusion at a heating rate of 20 K / min in differential scanning calorimetry (DSC) based on DIN EN ISO 11357-3 (2018), preferably 25 J / g or more, particularly preferably 30 J / g or more, and most preferably 35 J / g or more. A plate made of semi-crystalline polyamide with a thickness of 2 mm is not transparent, that is, its light transmittance measured according to ASTM D1003-21 (2021) is less than 88%, and / or the haze is greater than 5%.

[0019] <Transparent polyamide> In the sense of the present invention, transparent polyamide is defined as having a light transmittance of at least 88% or at least 90% as measured on a 2 mm thick plate according to ASTM D1003-21 (2021), and a haze of up to 5%, preferably up to 3%. Hereinafter, when referring to transparent polyamide, it always means amorphous or microcrystalline polyamide, which satisfy the above definition with respect to transparency and heat of fusion.

[0020] <Summary of the Invention> Therefore, the present invention relates to a polyamide molding material comprising, or preferably comprising, the following components. (a) M is a mixture consisting of the following in a weight of 93.0 to 99.9%, X is at least one polyamide in an amount of 15.0 to 50.0% by weight, and Y is at least one polyimide in a weight of 50.0-85.0%. The aforementioned Y is selected from the group consisting of PA6, PA66, PA6 / 66, PA610, PA612, PA614, PA616, PA6 / 12, and mixtures thereof. (b) 0.05 to 5.0% by weight of additives, (c) At least one coloring agent in an amount of 0.01 to 2.0% by weight, (d) It may contain ingredients other than those in (a) to (c), Here, X, which is at least one polyamide, is selected from the group consisting of polyamides comprising at least AC, BC and E, or AC, BC, AD and BD, or AC and E, which are amide-bonded polyamide units derived from monomer units A, B, C, D and / or E. Monomer units A, B, C, D, and E have the following definitions: A: At least one cyclic aliphatic diamine, B: At least one acyclic aliphatic diamine, C: at least one aromatic dicarboxylic acid, D: at least one aliphatic dicarboxylic acid, E: at least one α,ω-aminocarboxylic acid or at least one lactam, The sum of X and Y is 100% by weight of M, and the sum of components (a) to (d) is 100% by weight.

[0021] Surprisingly, the polyamide molding material according to the present invention exhibits extremely high energy absorption under the influence of tensile stress and impact mechanical loads, and therefore, it has been found to fracture later under mechanical load than conventionally known polyamide compositions. Thus, the polyamide molding material according to the present invention is superior in terms of safety to conventional compositions. At the same time, the composition has an excellent appearance and can be used in high-quality applications, such as parts that are visible when installed, such as the interior of a vehicle.

[0022] <Polyamide mixture> The polyamide mixture M contained in the polyamide molding material according to the present invention contains 15.0 to 50.0% by weight of polyamide X and 50.0 to 85.0% by weight of polyamide Y. Thus, the weight ratio of components X and Y is added to 100% by weight of mixture M. It is preferable that the amount of polyamide X in the mixture is less than the amount of polyamide Y, i.e., the amount of polyamide X is less than 50% by weight of the mixture. Similarly, it is preferable that the amount of polyamide Y is greater than 50% by weight.

[0023] The polyamide mixture M preferably contains at least one polyamide X in an amount of 15.0 to 45.0% by weight, more preferably 20.0 to 42.0% by weight, and particularly preferably 25.0 to 38.0% by weight. That is, the complementary proportion of at least one polyamide Y is preferably 55.0 to 85.0% by weight, more preferably 58.0 to 80.0% by weight, and particularly preferably 62.0 to 75.0% by weight.

[0024] <Polyamide X> Polyamide X is a transparent polyamide, and preferably contains at least 50 mol% of monomers having only aliphatic structural units relative to the total amount of monomers in polyamide X. Polyamide X is preferably amorphous or microcrystalline.

[0025] At least 50 mol% of the monomers having only aliphatic structural units are aliphatic diamines, aliphatic dicarboxylic acids, aliphatic lactams, or aliphatic aminocarboxylic acids. Therefore, polyamide X consists of at least 50 mol% of monomers having only aliphatic structural units and 50 mol% or less of monomers containing aromatic structural units.

[0026] Furthermore, the polyamide X is transparent, more preferably having a transparency of at least 88% or at least 90%, and a haze of up to 5%, preferably 3% (determined, respectively, using the measurement methods described later).

[0027] According to one preferred embodiment of the present invention, the polyamide X is amorphous.

[0028] According to another preferred embodiment of the present invention, the polyamide X comprises at least one monomer having an aromatic structural unit.

[0029] The polyamide X is preferably in a solution prepared by dissolving 0.5 g of the polymer in 100 ml of m-cresol, where the relative viscosity at 20°C, measured according to ISO 307:2007, is in the range of 1.35 to 2.40, particularly 1.40 to 1.90, and more particularly 1.45 to 1.80. For example, the relative viscosity of a polyamide having at least polyamide units AC, BC, and E is preferably in the range of 1.50 to 1.75, and particularly 1.59 to 1.64. For example, the relative viscosity of a polyamide having at least polyamide units AC, BC, AD, and BD is preferably in the range of 1.60 to 1.85, and particularly 1.70 to 1.75. For example, the relative viscosity of a polyamide having at least polyamide units AC and E is preferably in the range of 1.40 to 1.65, and particularly 1.51 to 1.57.

[0030] In the case of polyamide X, monomer units A to E are preferably independently selected from the group consisting of the following. A: (Cyclic aliphatic diamines) bis(4-amino-3-methyl-cyclohexyl)methane (MACM), bis(4-amino-cyclohexyl)methane (PACM), bis(4-amino-3,5-dimethyl-cyclohexyl)methane (TMDC), and mixtures thereof. B: (Acyclic aliphatic diamine) 1,6-hexanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, preferably selected from 1,6-hexanediamine and 1,10-decanediamine. C: (Aromatic dicarboxylic acid) Selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, preferably a mixture of terephthalic acid and isophthalic acid. D: (Aliphatic dicarboxylic acids) Adipic acid, azelaic acid, 1,10-decanediic acid, 1,12-dodecanediic acid, 1,14-tetradecanediic acid, 1,16-hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and mixtures thereof. E: (α,ω-aminocarboxylic acid or lactam) Selected from the group consisting of α,ω-aminohexanoic acid, α,ω-aminoundecanoic acid, α,ω-aminododecanoic acid, caprolactam, laurolactam, and mixtures thereof.

[0031] According to another preferred embodiment, the polyamide unit AC of polyamide X comprises at least two different, preferably exactly two different cyclic aliphatic diamines, in particular bis(4-amino-3-methyl-cyclohexyl)methane (MACM) and bis(4-amino-cyclohexyl)methane (PACM).

[0032] Furthermore, it is preferable that polyamide X contains polyamide units AC and BC as essential components.

[0033] Similarly, it is preferable that the polyamide X does not contain monomer units D.

[0034] In particular, it is preferable that polyamide X contains polyamide units AC, BC, and E, and most preferably that polyamide X consists of polyamide units AC, BC, and E.

[0035] Furthermore, it is even more advantageous that the polyamide X contains 30 mol% or more, preferably 40 mol% or more, particularly 42 mol% or more, relative to the total amount of monomers, with monomers having aromatic structural units in the range of 30-50 mol%, 40-50 mol%, or 42-50 mol%.

[0036] In particular, polyamide X includes PA6I / 6T / MACMI / MACMT / PACMT / 12, PA6I / 6T / MACMI / MACMT / MACMT / 12 / 612, PAMACMI / 12, PAMACMT / 12, PA10I / MACMI / MACM10 / 1010, PA10T / MACMT / MACM10 / 1010, PA10I / 10T / MACMI / MAMT / MACM10 / 1010PAMACMI / MACMT, PAMACMI / MACMT Selected from the group consisting of / 12, PAMACMI / MACMT / MACM12, PA6I / 6T / MACMI / MACMT, PA6I / 6T / MACMI / MACMT / 12, PA6I / 612 / MACMI / MACM12, PA6T / 12 / MACMT / MACM12, PA6I / 6T / 612 / MACMI / MACMT / MACM12, PA6I / 6T / MACMI / MACMT / -PACMI / PACMT / MACM12 and mixtures thereof.

[0037] <Polyamide Y> Polyamide Y is at least one acyclic aliphatic polyamide. Polyamide Y is selected from the group consisting of PA6, PA66, PA6 / 66, PA610, PA612, PA614, PA616, PA6 / 12, and mixtures thereof.

[0038] The polyamide Y preferably has a relative viscosity in the range of 2.10 to 3.60, particularly 2.30 to 3.50, and even more particularly 2.40 to 2.80, measured at 20°C in a solution prepared by dissolving 1.0 g of the polymer in 100 ml of sulfuric acid, according to ISO 307:2007.

[0039] Remarkably, the observed improvement in fracture energy is first achieved through the selection and combination of specific polyamides X and Y, while simultaneously obtaining an appearance that allows for the high-quality fitting of the molded material into parts.

[0040] <Additive (b)> The molding material according to the present invention comprises, as component (b), at least one additive preferably selected from the group consisting of organic stabilizers and inorganic stabilizers, particularly antioxidants, anti-ozone agents, heat stabilizers, light stabilizers, UV stabilizers, UV absorbers or UV blockers, lubricants, demolding agents, and mixtures and combinations thereof.

[0041] The amount of at least one additive is 0.05 to 5.0% by weight, preferably 0.10 to 3.0% by weight, more preferably 0.20 to 2.5% by weight, and particularly preferably 0.25 to 2.3% by weight, relative to the total of components (a) to (d).

[0042] When a stabilizer is used as at least one additive, it can be selected from the group consisting of the following, according to one preferred embodiment. Compounds of monovalent or divalent copper, particularly salts of monovalent or divalent copper with organic or inorganic acids, or monovalent or divalent phenols, oxides of monovalent or divalent copper, or complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides, or phosphines, preferably Cu(I) or Cu(II) salts of copper salts of hydrohalic acid, hydrocyanic acid, or aliphatic carboxylic acids. Here, the monovalent copper compound is preferably CuCl, CuBr, CuI, CuCN, and Cu2O, and the divalent copper compound is preferably CuCl2, CuSO4, CuO, copper(II) acetate, or copper(II) stearate, or a mixture of these compounds. These copper compounds are used as is or, preferably, in the form of concentrates, the concentrates being polymers having the same or substantially the same chemical properties as polyamide X or Y, the concentrates containing copper salts or copper compounds at high concentrations (masterbatch), and the copper compounds are more preferably used in combination with additional metal halides, including alkali halides such as Na, KI, NaBr, and KBr. Here, the molar ratio of metal halide to copper is 0.5 to 20, preferably 1 to 10, and particularly preferably 2 to 7. • Stabilizers based on secondary aromatic amines, • Stabilizers based on sterically hindered phenols, • Phosphites and phosphonates, • N,N'-oxamide, hydroxyphenyltriazine, hydroxyphenylbenzotriazole, dibenzoylmethane, aminohydroxybenzoylbenzoate, hydroxybenzophenone, hindered amine light stabilizers (HALS), and • A mixture of the above-mentioned stabilizers.

[0043] Particularly preferred examples of usable stabilizers based on secondary aromatic amines according to the present invention are adducts of phenylenediamine and acetone (Naugard A), adducts of phenylenediamine and linoleic acid, Naugard 445, N,N'-dinaphthyl-p-phenylenediamine, N,N'-dinaphthyl-p-phenylenediamine, or mixtures of two or more of these.

[0044] Particularly preferred examples of sterically hindered phenol-based stabilizers usable according to the present invention are N,N'-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionamide, bis(3,3-bis(4'-hydroxy-3'-tert-butylphenyl)-butanoic acid)-glycol ester, 2,1'-thioethyl-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid ester, 4-4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionic acid ester, or mixtures of two or more of these stabilizers.

[0045] Preferred phosphates and phosphates include triphenyl phosphate, diphenylalkyl phosphate, dialkyl phosphate, tris(nonylphenyl) phosphate, trilauryl phosphate, trioctadecyl phosphate, distearyl pentaerythritol phosphate, tris(2,4-di-tert-butylphenyl) phosphate, diisodecyl pentaerythritol phosphate, bis(2,4-di-tert-butylphenyl) pentaerythritol phosphate, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphate, diisodecyl-oxy-pentaerythritol phosphate, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol phosphate, bis(2,4,6-tris-(tert-butylphenyl)) pentaerythritol phosphate, Tristearyl sorbitol phosphate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz-[d,g]-1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz[d,g]-1,3,2-dioxaphosphosine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, particularly preferably tris(2,4-di-tert-butylphenyl)phenyl phosphite and tris(Hostanox(R) PAR24: Clariant, Basel commercial product).

[0046] A preferred embodiment of the heat stabilizer consists of a combination of IrgatecNC66 (available from BASF) and a copper stabilizer based on CuI and KI. In particular, a heat stabilizer based solely on CuI and KI is preferred.

[0047] In another preferred embodiment, the heat stabilizer of component (b) is selected from the group consisting of phenolic heat stabilizers, phosphite heat stabilizers, amine heat stabilizers, or mixtures or combinations thereof, and in particular, component C is preferably selected from the following group. Triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide], tris-(2,4-di-tert-butylphenyl)phosphate, tris-(2,4-di-tert-butylphenyl)phosphate, or mixtures thereof.

[0048] Preferred organic stabilizers are phenol and / or phosphate compounds such as Irganox245, Irganox1010, Irganox1098, HostanoxPAR24, or Irgafos168. Particularly preferred as component (D) is a mixture of Irganox1010 (CAS 6683-19-8, phenolic antioxidant) and Anox20 (CAS 6683-19-8, phenolic antioxidant) in a ratio of 7:3 and HostanoxPAR24 (CAS:31570-04-4, tris(2,4-ditate-butylphenyl)) in a ratio of 2 parts by weight, totaling 10 parts by weight.

[0049] Preferred UV stabilizers include, for example, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)oxamide (Tinuvin 312), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol (Tinuvin 1577), 2-(4,6-diaryl-1,3,5-triazine-2-yl)-5-(alkoxy substituent)-phenol (Tinuvin 1600), and 2-tert- Tinuvin 326, 2-(benzotriazol-2-yl)-4-methylphenol, 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropane-2-yl)phenol, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(2-hydroxyphenyl)-benzotriazole derivatives Carboprotect), 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol (Tinuvin328), 2-(benzotriazol-2-yl)-6-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol (Tinuvin360), poly[[6-[( [1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diol][(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]](Chimasorb 944FD, 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione (Parsol 1577), and mixtures thereof.

[0050] A preferred embodiment of the processing aid is an aluminum salt, alkali salt, alkaline earth metal salt, or an ester or amide of a fatty acid having 10 to 44 carbon atoms, preferably 14 to 44 carbon atoms, with the metal ions being Na, Mg, Ca, and Al, and Ca or Mg being particularly preferred. Particularly preferred metal salts are magnesium stearate, calcium stearate, and calcium montanate, as well as aluminum stearate. The fatty acid is monovalent or divalent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanediic acid, behenic acid, particularly preferably stearic acid, capric acid, and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms). According to another preferred embodiment, suitable processing aids include calcium stearate, glyceryl monostearate, Abrill1033, or ACRAWAXC.

[0051] <Coloring agent (c)> Component (c) is a colorant or mixture of colorants suitable for coloring polyamide molding materials black. The black coloring and appearance are based on visual evaluation. The colorant is an organic or inorganic dye or pigment. Dyes are colorants that do not scatter light but instead absorb light of a certain visible wavelength. Dyes often dissolve in the polymer matrix at a certain concentration. Pigments are organic or inorganic dyes and generally exist as insoluble discontinuous particles in the polymer matrix. Whether a particular dye is designated as a pigment or a dye depends on the polymer matrix, the concentration of the dye, its crystallinity, temperature, and other factors. With respect to the present invention, preferred colorants are soluble in the polyamide molding material at the concentration required for coloring the molded article, and these can also be used in combination with carbon black.

[0052] According to the present invention, the colorants are used in an amount and combination sufficient to color the molding material black and mostly opaque. The specific amount of colorants used depends, in particular, on their solubility and extinction coefficient in the thermoplastic matrix, and on whether they are used in combination with one or more additional colorants.

[0053] The ratio of component (c) to the sum of components (a) to (d) is preferably in the range of 0.05 to 2.0% by weight. According to a preferred embodiment of the present invention, the ratio of component (c) to the sum of components (a) to (d) is preferably 0.08 to 1.5% by weight, and particularly preferably 0.10 to 1.0% by weight.

[0054] Suitable colorants generally possess high absorption coefficients and high thermal stability in the visible wavelength range. Therefore, the high thermal stability of a colorant is evident when no significant discoloration or thermal degradation is observed during the manufacturing and processing of colored molded materials during injection molding or extrusion in the temperature range of 230°C to 300°C. Furthermore, the colorant does not affect or degrade the polymer during molding, which could lead to unacceptable loss of mechanical properties or the formation of gaseous byproducts.

[0055] Synthetic colorants are generally obtained from coal tar or petroleum intermediates. Many different types of dyes are available for use in thermoplastic materials. The color index lists many different chemical classes of colorants, such as nitroso, nitro, monoazo, diazo, triazo, polyazo, azo, stilbene, carotenoids, diphenylmethane, triarylmethane, xanthene, quinoline, acridine, methine, thiazole, indamine, indophenol, azine, oxazine, thiazine, sulfur, lactone, aminoketone, hydroxyketone, anthraquinone, indigloid, phthalocyanine, nigrosine, carbon black, and inorganic pigments.

[0056] The colorants or combinations of colorants are preferably selected from the group consisting of pyrazolone, perinone and anthraquinone, methine, azo and coumarin colorants and / or inorganic pigments and metal-containing pigments such as metal complexes of azo, azomethine or methine colorants, azomethine, quinacridone, dioxazine, isoindoline, isoindolinone, perylene, phthalocyanine, pyrrolopyrrole, and thioindigo colorants, and carbon black may be added.

[0057] Examples of inorganic pigments include antimony trioxide, antimony pentoxide, basic lead carbonate, basic lead sulfate or lead silicate, lithopone, titanium dioxide (anatase, rutile), zinc oxide, zinc sulfide, metal oxides such as Prussian blue, lead chromate, lead sulfochromate, chromium antimony titanate, chromium oxide, ferric oxide, cobalt blue, cobalt chromite blue, cobalt nickel gray, manganese blue, manganese violet, molybdate orange, molybdate red, nickel antimony titanate, ultramarine blue, and metal sulfides such as antimony trisulfide, cadmium sulfide, cadmium selenide, zirconium silicate, zirconium vanadium blue, and zirconium praseodymium yellow. Suitable disperse dyes include polymer-soluble dyes such as anthraquinones, such as alkylamino, amino, arylamino, cyclohexylamino, hydroxy, hydroxyamino, or phenylmercaptoanthraquinone. Metal complexes of azo dyes, particularly 1:2 chromium or cobalt complexes of monoazo dyes, and fluorescent dyes of the benzthiazole, coumarin, oxaline, or thiazine type are also suitable.

[0058] At least one colorant is preferably selected from the group consisting of organic dyes, particularly anthraquinone dyes, perinone dyes, nigrosine, carbon black, and mixtures and combinations thereof.

[0059] Preferably, at least one colorant (c) contains at least one colorant listed below as a Color Index Common Name (CIGN): Solvent Green 3 (CAS No.: 128-80-3), Solvent Green 28 (CAS No.: 28198-05-2), Solvent Red 52 (CAS No.: 81-39-0), Solvent Red 111 (CAS No.: 82-38-2), Solvent Red 135 (CAS No.: 20749-68-2), Solvent Red 169 (CAS No.: 27354-18-3), Solvent Red 179 (CAS No.: 89106-94-5), Solvent Red 207 (CAS No.: 10114-49-5), Disperse Red 22 (CAS No.: 2944-28-7), Vat Red 41 (CAS number: 522-75-8), Solvent Orange 60 (CAS number: 61969-47-9), Solvent Orange 63 (CAS number: 16294-75-0), Solvent Violet 13 (CAS number: 81-48-1), Solvent Violet 14 (CAS number: 8005-40-1), Solvent Violet 50, Disperse Blue 73 (CAS number: 12222-78-5), Solvent Blue 97 (CAS number: 61969-44-6), Solvent Blue 101 (CAS number: 6737-68-4), Solvent Blue 104 (CAS No.: 116-75-6), Solvent Blue 138 (CAS No.: 110157-96-5), Disperse Yellow 160 (CAS No.: 75216-43-2), Solvent Yellow 84 (CAS No.: 12239-76-8), Solvent Yellow 93 (CAS No.: 4702-90-3), Solvent Yellow 98 (CAS No.: 12671-74-8), Solvent Yellow 163 (CAS No.: 13676-91-0), Solvent Yellow 160:1 (CAS No.: 35773-43-4), and mixtures thereof. These colorants have good heat stability.

[0060] Preferred phthalocyanine colorants include, for example, Pigment Blue 15:1 (CAS No.: 147-14-8), Pigment Blue 15:3 (CAS No.: 147-14-8), Pigment Blue 16 (CAS No.: 574-93-6), and Pigment Green 7 (CAS No.: 1328-53-6).

[0061] As component (c), Solvent Brown 53 (CAS No.: 64696-98-6), Pigment Brown 23 (CAS No.: 35869-64-8), Pigment Brown 24 (CAS No.: 68186-90-3), Pigment Brown 25 (CAS No.: 6992-11-6), Pigment Orange 68 (CAS No.: 42844-93-9), Solvent Orange 60 (CAS No.: 61969-47-9), Solvent Orange 63 (CAS No.: 16294-75-0), and Pigment Brown 6 (CAS No.: 52357-70-7) are more preferred.

[0062] Particularly preferred dyes are Solvent Red 52, Solvent Red 135, Solvent Red 179, Solvent Violet 13, Solvent Violet 14, Solvent Violet 36, Solvent Violet 50, Disperse Blue 73, Solvent Yellow 93, Solvent Green 3, Disperse Yellow 160, Solvent Blue 97, and mixtures containing at least one of these dyes.

[0063] In particular, a coloring agent selected from the following group of dye mixtures is preferred. Solvent Green 3 and Solvent Red 179 Solvent Red 52 and Solvent Blue 97 Solvent Green 3, Solvent Blue 97, and Solvent Red 179 Solvent Green 3, Solvent Red 52, and Solvent Red 179 Here, the dye mixture may further contain carbon black. Preferably, the dye mixture contains up to 50% by weight of carbon black relative to the dye mixture, and more preferably 20 to 50% by weight.

[0064] A mixture of the following components is most preferred as a coloring agent. • 20-40% by weight of Solvent Green 3 • 0-20% by weight of Solvent Red 52 • 15-35% by weight of Solvent Red 179 40-60% by weight of carbon black Here, the sum of each component is 100% by weight of the mixture (component c). The amount of this colorant mixture (c) relative to the sum of components (a) to (d) is preferably 0.7 to 0.8% by weight.

[0065] Carbon black preferably has a particle size distribution d 90 Types with a particle size of <200 nm (meaning at least 90% of the particles are smaller than 200 nm) are used. The particle size distribution can be determined, for example, by scanning transmission electron microscopy (STEM). Examples of these types of carbon black include Color Black FW 1 beads, Corax N115, Black Pearls 1100, Black Pearls 1150, or Black Pearls 880.

[0066] The presence of colorants, particularly in terms of the aforementioned quantity and quality, can provide polyamide molding materials based on transparent polyamide that feature a black piano lacquer finish.

[0067] <Additive (d)> The polyamide molding material according to the present invention may further contain an additive (component d) in a proportion of, for example, 0 to 10% by weight relative to the total of components (a) to (d).

[0068] According to a preferred embodiment of the present invention, the proportion of component (d) in the polyamide molding material is preferably in the range of 0 to 5.0% by weight, particularly 0.10 to 2.0% by weight, relative to the total of components (a) to (d).

[0069] In another preferred embodiment, at least one additive (d) is selected from the group consisting of monomers, particularly lactams, softeners, impact strength modifiers, condensation catalysts, chain modifiers, particularly monofunctional carboxylic acids or amines, defoamers, antiblocking agents, natural layered silicates, synthetic layered silicates, nanoscale fillers, and mixtures thereof.

[0070] Molded parts can be manufactured from the polyamide molding material according to the present invention, and these molded parts are selected from the group consisting particularly of interior and exterior parts for automobiles, motorcycles, camping vehicles or mobile homes, building and facade parts, decorative structural frames, operating buttons or levers, covers, visible surfaces, backlight parts, openings for mobile phones, tablets, housings for electronic devices, decorative parts for vehicles, household appliances, containers, vehicle keys, leisure and outdoor products.

[0071] The subject matter of the present invention is not limited to the specific embodiments shown herein, but will be described in more detail based on the following examples. Within the scope of this application, the following measurement methods were used.

[0072] <Haze, Transparency> In accordance with ASTM D1003-21, clarity and haze were measured on a 2 mm thick plate (60 mm × 60 mm surface) at 23°C using a BYK Gardner Haze Gard Plus measuring instrument with CIE light source C.

[0073] <Relative viscosity, η rel > The relative viscosity at 20°C was measured according to ISO 307 (2007). For this purpose, 0.5 g of polymer granules was weighed into 100 ml of m-cresol, and the relative viscosity (RV) was calculated using the formula RV = t / t0 based on Section 11 of the standard.

[0074] <Tensile modulus> In accordance with ISO 527 (2012), the tensile modulus and tensile strength were determined using an ISO test rod (Type A1, dimensions 170 × 20 / 10 × 4 mm) manufactured according to the ISO / CD3167 (2003) standard, at a temperature of 23°C and a tensile speed of 1 mm / min.

[0075] <Yield stress and yield elongation> In accordance with ISO 527 (2012), the yield stress and yield elongation were determined using an ISO test rod (Type A1, dimensions 170 × 20 / 10 × 4 mm) manufactured according to ISO / CD 3167 (2003), at a temperature of 23°C and a tensile speed of 50 mm / min.

[0076] <Fracture stress and fracture elongation> In accordance with ISO 527 (2012), the fracture stress and elongation at break were determined using an ISO test rod (Type A1, dimensions 170 × 20 / 10 × 4 mm) manufactured according to ISO / CD 3167 (2003), at a temperature of 23°C and a tensile speed of 50 mm / min.

[0077] <Charpy impact strength> In accordance with ISO179 / 2*eU (1997, *2 = mounted), the Charpy impact strength was determined at a temperature of 23°C using an ISO test rod (Type B1, dimensions 80 × 10 × 4 mm) manufactured in accordance with ISO / CD3167 (2003).

[0078] <Charpy Notch impact strength> In accordance with ISO179 / 2*eA (1997, *2 = installed), the Charpy notch impact strength was determined at a temperature of 23°C using an ISO test rod (Type B1, dimensions 80 × 10 × 4 mm) manufactured in accordance with ISO / CD3167 (2003).

[0079] <60% gloss> In accordance with ISO 2813 (2015), gloss was determined using a Minolta Multi Gloss 268 instrument on a 60 × 60 × 2 mm plate at an angle of 60° and a temperature of 23°C. Glossiness is expressed in dimensionless gloss units (GU). After injection molding, the dry test specimens were stored in a dry environment, i.e., on silica gel at room temperature for at least 48 hours.

[0080] <Temperature and humidity adjustment> Temperature and humidity control was carried out in accordance with ISO 527 (2012). As a result, the test specimens were stored for 16 hours at 23 ± 2°C and a relative humidity of 50 ± 10°C.

[0081] <Destructive Energy> According to ISO 527 (2012), the fracture energy is expressed on the lower surface of the stress-strain curve in a tensile test.

[0082] <Abrasion resistance> Test equipment: Clock meter compliant with DIN EN ISO105-X12, or other test equipment capable of setting the required test conditions (test force: 9N, test path: 104±3mm). Test head: Rubbing adapter C compliant with DIN55654:2015, Test equipment / rubbing medium: Abrasive paper compliant with DIN55654:2015, Abrasive grains: Made of aluminum oxide, semi-open spread, 5μm grain, grains fully resin-bonded to a flexible extruded PES film (e.g., 3M) TM 261X1), the abrasive paper is cut to a precise width of 25mm and a minimum length of 75mm. Gloss measurement device: Gloss measurement is performed using a reflectometer at a 20° angle (in accordance with DIN ENISO2813:2015). Sample preparation: The test requires a minimum sample size of 150mm x 100mm, and the conditions are set as described above.

[0083] <Test Management> 1. Temperature and humidity adjustment 2. Wash with running water or lukewarm water. 3. Gloss level measurement before scratching: Glossiness measurement should be performed at a measurement angle of 20°. 4. Rubbing / Scratching: Before each step, clamp a new rubbing medium, and the step consists of five double strokes performed under a load of 9N. If the rubbing marks are not uniform (striped, stained), repeat the test. 5. After rubbing, the sample is stored at room temperature for 24 hours. 6. Gloss measurement of rubbing marks: Position the gloss measuring device so that the measurement direction is 90° with respect to the friction direction. Ensure that the measuring opening of the gloss measuring device is in contact with the load surface, and in this case, do not measure the first and last 10 mm of the rubbing marks.

[0084] Friction resistance is expressed as a percentage change in gloss relative to the initial gloss level. The measurement angle is 20°. The relative change in gloss is calculated as follows: (Initial gloss level - Gloss level after rubbing) × 100 / Initial gloss level Table 1 summarizes the materials used in the usage examples and comparative examples. [Table 1]

[0085] Table 2 shows an example of a polyamide molding material according to the present invention, and Table 3 shows a compound not according to the present invention (a comparative example), with the measured values ​​obtained for each. The quantity information is shown as a weight ratio. [Table 2] [Table 3]

[0086] The measured values ​​obtained in Examples 1-11 and Comparative Examples 1-9 are shown in Tables 4 and 5. [Table 4] [Table 5]

[0087] As is evident from the examples, a specific combination of polyamides X and Y is required to obtain high fracture energy. At the same time, a desirable visual effect (piano black) can be obtained, and the abrasion resistance can also be increased in a remarkable way.

Claims

1. A polyamide molding material comprising the following components: (a) M is a mixture of the following components in an amount of 93.0 to 99.9% by weight, X is at least one polyamide in an amount of 15.0 to 50.0% by weight, and Y is at least one polyamide in an amount of 50.0 to 85.0% by weight. The aforementioned Y is selected from the group consisting of PA6, PA66, PA6 / 66, PA610, PA612, PA614, PA616, PA6 / 12, and mixtures thereof. (b) At least one additive in an amount of 0.05 to 5.0% by weight, (c) comprising 0.01 to 2.0% by weight of at least one coloring agent, (d) It may contain components other than those in (a) to (c), Here, X is selected from the group consisting of polyamides comprising at least AC, BC and E, or AC, BC, AD and BD, or AC and E, which are amide-bonded polyamide units derived from monomer units A, B, C, D and / or E. The monomer units A to E are, A: At least one cyclic aliphatic diamine, B: At least one acyclic aliphatic diamine, C: at least one aromatic dicarboxylic acid, D: at least one aliphatic dicarboxylic acid, E: at least one α,ω-aminocarboxylic acid or at least one lactam, The sum of X and Y is 100% by weight of M, and the sum of components (a) to (d) is 100% by weight. Polyamide molding material.

2. The product contains 0.10 to 3.0% by weight of at least one additive (b), and / or 0.05 to 2.0% by weight of at least one coloring agent (c), and / or 0 to 5.0% by weight of component (d). The polyamide molding material according to claim 1.

3. The monomer units A to E are each independent of each other. A: The cyclic aliphatic diamine is selected from the group consisting of bis(4-amino-3-methyl-cyclohexyl)methane (MACM), bis(4-amino-cyclohexyl)methane (PACM), bis(4-amino-3,5-dimethyl-cyclohexyl)methane (TMDC), and mixtures thereof. B: The acyclic aliphatic diamine is selected from the group consisting of 1,6-hexanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. C: The aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof. D: The aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, azelaic acid, 1,10-decanediic acid, 1,12-dodecanediic acid, 1,14-tetradecanediic acid, 1,16-hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and mixtures thereof. E: The α,ω-aminocarboxylic acid or lactam is selected from the group consisting of α,ω-aminohexanoic acid, α,ω-aminoundecanoic acid, α,ω-aminododecanoic acid, caprolactam, laurolactam, and mixtures thereof. The polyamide molding material according to claim 1 or 2.

4. The polyamide unit AC comprises at least two different cyclic aliphatic diamines, particularly bis(4-amino-3-methyl-cyclohexyl)methane (MACM) and bis(4-amino-cyclohexyl)methane (PACM). The polyamide molding material according to claim 1 or 2.

5. The mixture M consists of 15.0 to 45.0% by weight, preferably 20.0 to 42.0% by weight, and particularly preferably 25.0 to 38.0% by weight of the at least one polyamide X, and 55.0 to 85.0% by weight, preferably 58.0 to 80.0% by weight, and particularly preferably 62.0 to 75.0% by weight of the at least one polyamide Y. The polyamide molding material according to claim 1 or 2.

6. The at least one polyamide X contains, with respect to the total amount of monomers, monomers having aromatic structural units in an amount of 30 mol% or more, preferably 40 mol% or more, particularly 42 mol% or more, particularly preferably 30 to 50 mol%, or 40 to 50 mol%, or 42 to 50 mol%, or 42 to 50 mol%, or 42 to 50 mol%, or 30 to 50 mol%, or 40 to 50 mol%, or 40 to 50 mol%, or 40 to 50 mol%, or 40 to 50 mol%, or 40 to 50 mol%, or 3 The polyamide molding material according to claim 1 or 2.

7. The at least one polyamide X is PA6I / 6T / MACMI / MACMT / PAMCT / 12, PA6I / 6T / MACMI / MACMT / MACM12 / 612, PAMACMI / 12, PAMACMT / 12, PA10I / MACMI / MACM10 / 1010, PA10T / MACMT / MACM10 / 1010, PA10I / 10T / MACMI / MAMT / MACM10 / 1010PAMACMI / MACMT, PAMACMI / MACMT / 12, PAMACMI / MACMT / MACM12, PA6I / 6T / MACMI / MACMT, PA6I / 6T / MACMI / MACMT / 12, PA6I / 612 / MACMI / MACM12, PA6T / 12 / MACMT / MACM12, PA6I / 6T / 612 / MACMI / MACMT / MACM12, PA6I / 6T / MACMI / MACMT / -PAMACMI / PAMACMT / MACM12, and mixtures thereof selected. The polyamide molding material according to claim 1 or 2.

8. PAMACMI / 12 not included The polyamide molding material according to claim 1 or 2.

9. The at least one polyamide X has, according to ASTM-D1003-21, at least 88% transparency and a maximum haze of 5% on a plate measuring 60 × 60 × 2 mm. The polyamide molding material according to claim 1 or 2.

10. The coloring agent (c) is selected from the group consisting of organic dyes, particularly anthraquinone dyes, perinone dyes, nigrosine, carbon black, and mixtures and combinations thereof. The polyamide molding material according to claim 1 or 2.

11. The colorant (c) comprises a combination of carbon black and at least one dye selected from the group consisting of pyrazolone, perinone and anthraquinone, methine, azo and coumarin dyes, and pigments containing metals. The metal-containing pigments include, for example, inorganic pigments, metal complexes of azo, azomethine, or methine dyes, azomethine, quinacridone, dioxazine, isoindoline, isoindolinone, perylene, phthalocyanine, pyrrolopyrrole, and thioindigo colorants, and nigrosine. The polyamide molding material according to claim 1 or 2.

12. The proportion of carbon black in the aforementioned combination is 20 to 50% by weight relative to the combination of dyes. The polyamide molding material according to claim 1 or 2.

13. The coloring agent (c) is It consists of carbon black, solvent green 3, solvent red 52, solvent red 179, or carbon black and polysynthene black H (solvent black 27, CAS number 72812-34-1), The ratio of carbon black to the coloring agent (c) is 20 to 50% by weight. The polyamide molding material according to claim 1 or 2.

14. The coloring agent (c) comprises at least two dyes selected from the group consisting of pyrazolone, perinone and anthraquinone, methine, azo and coumarin dyes, and / or pigments containing metals. The aforementioned metal-containing pigments include, for example, inorganic pigments, metal complexes of azo, azomethine, or methine dyes, azomethine, quinacridone, dioxazine, isoindoline, isoindolinone, perylene, phthalocyanine, pyrrolopyrrole, and thioindigo colorants, and nigrosine. Does not contain carbon black The polyamide molding material according to claim 1 or 2.

15. The aforementioned coloring agent (c) consists of a combination of solvent green 3, solvent red 179, and solvent blue 97. The polyamide molding material according to claim 1 or 2.

16. The at least one additive (b) is selected from the group consisting of organic and inorganic stabilizers, antioxidants, anti-ozone agents, heat stabilizers, light stabilizers, UV stabilizers, UV absorbers or UV blockers, lubricants, demolition agents, and mixtures and combinations thereof. The polyamide molding material according to claim 1 or 2.

17. It comprises at least one component different from the additive (b) and colorant (c), The aforementioned components are selected from the group consisting of softeners, impact strength modifiers, condensation catalysts, chain modifiers, particularly monofunctional carboxylic acids or amines, defoamers, antiblocking agents, natural layered silicates, synthetic layered silicates, nanoscale fillers, and mixtures thereof. The polyamide molding material according to claim 1 or 2.

18. Does not contain impact strength modifiers The polyamide molding material according to claim 1 or 2.

19. A molded part comprising the polyamide molding material according to claim 1 or 2, The molded parts are selected from the group consisting of interior and exterior parts for automobiles, motorcycles, camping vehicles or mobile homes, building and facade parts, decorative structural frames, operating buttons or levers, covers, visible surfaces, backlight parts, openings for mobile phones, tablets, housings for electronic devices, decorative parts for vehicles, household appliances, containers, vehicle keys, leisure and outdoor products. Molded parts.