Polyamide compositions with inclined surface tracking resistance

Abstract

The present invention relates to a method for improving inclined plane tracking (IPT) properties at voltages higher than 1 kV by using a polyamide composition comprising: a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3-5 carbon atoms per amide group, excluding the carbon atom of the carbonyl group; b) 1-40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atom of the carbonyl group; c) 0-35% by weight of a flame retardant; d) 0-50% by weight of a fibrous and / or particulate filler; e) 1-25% by weight of an impact modifier; and f) 0-20% by weight of other additives.

Description

[Technical Field]

[0001] The present invention relates to a method for improving inclined plane tracking (IPT) properties at voltages above 1 kV by using a polyamide composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbonyl carbon atom; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbonyl carbon atom; c) 0 to 35% by weight of a flame retardant; d) 0 to 50% by weight of a fibrous and / or particulate filler; e) 1 to 25% by weight of an impact modifier; and f) 0 to 20% by weight of other additives. The present invention also relates to the polyamide composition and articles made from the polyamide composition. [Background technology]

[0002] The widespread use of polymeric materials as high-voltage insulation began after the introduction of epoxy resins in the 1950s. Initially, polymers were used for indoor conditions. Rosenthal introduced silicone composite insulators in 1976. Polymer insulator profiles can be complex, and parts can be thinner than ceramic counterparts. Unfortunately, polymers are many times less resistant to surface discharges than ceramic materials. Therefore, several methods have been devised to improve the resistance of polymers to degradation under high voltages.

[0003] Polyamide 66 (PA66) is a very important engineering thermoplastic polymer because it combines several desirable properties, such as high strength and stiffness, high toughness, high heat resistance, excellent abrasion resistance, good electrical and chemical resistance, high flowability, and excellent processability. PA66 is widely used as an insulating material in automotive, electrical, and electronic applications.

[0004] The Comparative Tracking Index (CTI) is the most common test for estimating the sensitivity of plastics to surface tracking and provides an indication of insulating materials, according to IEC 60112. CTI is an accelerated test method under wet and dirty conditions, in which a voltage is applied between two electrodes placed on the surface of the material.

[0005] Inclined Plane Tracking (IPT) is an effective method for evaluating the erosion and tracking resistance of insulating materials under high voltage (>1 kV) conditions under humid conditions. Polymers are organic materials whose molecules are not as tightly bonded to one another as inorganic materials such as porcelain and glass. These polymers degrade at much lower temperatures than porcelain. Carbon formed during the degradation process makes the surface conductive and leads to electrical failure when the material can no longer withstand the applied voltage. The formation of carbon conductive paths on the surface is called tracking. The most common polymer materials used for high-voltage applications are silicone rubber, EPR rubber, cycloaliphatic epoxy, and polycarbonate, which have excellent properties in terms of tracking and erosion resistance, hydrophobicity, and UV stability. Factors such as the type of organic filler, filler size, filler conductivity, and carbon content of the base polymer affect the IPT value. Typically, the test voltage range for IPT is 1 kV or less.

[0006] CN102732002A discloses a glass fiber reinforced PA66 / PA11 alloy with a high CTI value. The CTI value is improved by combining non-ferrous red phosphorus, a migration inhibitor, and a high CTI value agent. However, this patent application does not disclose the definition of the high CTI value agent.

[0007] CN102105119A discloses the use of PA1010 and polypropylene resin to improve the toughness and flexibility of PA66. CN103224703A discloses that the toughness of polyamide composites containing PA66 and PA1212 can be improved by the addition of styrene-acrylonitrile. Such polyamide combinations focus on improving toughness, regardless of the tracking resistance of the polyamide resin. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] CN102732002A [Patent Document 2] CN102105119A [Patent Document 3] CN103224703A Summary of the Invention [Problem to be solved by the invention]

[0009] The photovoltaic ("PV") market is transitioning from a 1 kVA power grid to a 1.5 kVA power grid, and this movement has led to new regulations for PV connectors and junction boxes. Engineering plastics offers many products for use in PV applications. However, little attention has been paid to high-voltage applications, particularly those at voltages such as 1.2 kV, 1.5 kV, and 2 kV. Polyamides with low carbon numbers of dicarboxylic acids or lactams, such as PA6 and PA66, are widely used in the PV market due to their favorable mechanical and processing properties. However, these polyamides cannot meet the requirements for PV applications at voltages higher than 1.5 kV. [Means for solving the problem]

[0010] One object of the present invention is to provide a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a long chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the amide group.

[0011] Another object of the present invention is to provide a method for improving tilt plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 0 to 35% by weight of a flame retardant; d) 0 to 50% by mass of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0012] In a preferred embodiment, the long chain aliphatic polyamide is selected from polyamide 1212, polyamide 610, polyamide 612, polyamide 1010 and polyamide 6 / 6.36.

[0013] In a preferred embodiment, the flame retardant comprises (c1) 3 to 15 mass % of red phosphorus and (c2) 1 to 10 mass % of a triazine-based flame retardant, based on the total mass of the polyamide composition. The triazine-based flame retardant is preferably melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate, or melamine polyphosphate.

[0014] In a preferred embodiment, the filler is glass fiber, preferably alkali-free E-glass fiber. Other additives f) may include antioxidants, lubricating and dispersing agents.

[0015] In a preferred embodiment, the weight ratio of polyamide components a) and b) in the polyamide composition is from 5:1 to 1:1, and preferably from 4:1 to 1:1, and more preferably from 3.5:1 to 2.5:1, in particular 3:1.

[0016] Compared with the prior art, the polyamide composition provided by the present invention has a high Charpy notched strength (≥ 16 kJ / m at 23°C). 2 and ≥ 8 kJ / m at -40°C 2 ) and unnotched impact strength (≥ 75kJ / m at 23°C 2 and ≥ 65 kJ / m at -40°C 2 ), high CTI value (>600V), UL94 V0 at thickness of 1.6mm and 0.8mm, and high IPT value (≥60min at 1.5kV), and can be widely used in electrical applications such as photovoltaic connector nuts and bodies, outdoor insulating electrical plastic parts, etc.

[0017] Another object of the present invention is to provide an article made from a polyamide composition that exhibits excellent anti-tracking properties at voltages greater than 1 kV, for example, 1.2 kV or more, 1.5 kV or more, or 2 kV or less, the article being preferably a nut or body of a photovoltaic connector, or an electrically insulating plastic part.

[0018] Another object of the present invention is to provide a polyamide composition, the composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 4 to 25% by weight of a flame retardant comprising red phosphorus as component c1) and a triazine-based flame retardant as component c2), the triazine-based flame retardant being preferably melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate or melamine polyphosphate, d) 0 to 50% by mass of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes. DETAILED DESCRIPTION OF THE INVENTION

[0019] Unless otherwise defined, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, the following terms have the meanings set forth below unless specified otherwise.

[0020] The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element.

[0021] As used herein, the term "about" is understood to refer to a range of numbers that one of skill in the art would consider equivalent to the stated value, in the context of achieving the same function or result.

[0022] The term "additive," as used herein, refers to additives included in a formulated system to improve its physical or chemical properties and provide a desired result. Such additives include, but are not limited to, dyes, pigments, tougheners, impact modifiers, rheology modifiers, plasticizers, thixotropic agents, natural or synthetic rubbers, fillers, reinforcing agents, thickeners, compatibilizers, inhibitors, fluorescent or other markers, thermal degradation reducers, heat resistance agents, surfactants, wetting agents, defoamers, dispersants, flow or slip aids, biocides, and stabilizers.

[0023] Unless otherwise specified, all percentages (%) are "percent by weight."

[0024] The underlying definitions or explanations given above within the general terms or preferred ranges apply to the final products and, correspondingly, to the starting materials and intermediates. These underlying definitions can be combined with one another as desired, i.e., including combinations between the general definitions and / or preferred ranges and / or embodiments, respectively.

[0025] All of the embodiments and preferred embodiments disclosed herein can be combined as desired and are considered to be within the scope of the present invention.

[0026] The "AB" in AB-polyamide indicates that one nitrogen atom and one carbonyl group are present in the repeating unit of the AB-polyamide. The "AABB" in AABB-polyamide indicates that there are two nitrogen atoms and two carbonyl groups in the repeating unit of the AABB-polyamide.

[0027] Unless otherwise specified, temperature refers to room temperature and pressure refers to ambient pressure.

[0028] Unless otherwise specified, solvent refers to any organic or inorganic solvent known to those skilled in the art and does not include monomer molecules of any kind.

[0029] The inventors of the present invention have surprisingly found that the inclined plane tracking properties of polyamide compositions at voltages greater than 1 kV can be improved by using long chain aliphatic polyamides having an average of 6 or more carbon atoms per amide group, excluding the carbon atom of the carbonyl group.

[0030] The present invention provides a method for improving tilt plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 0 to 35% by weight of a flame retardant; d) 0 to 50% by mass of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0031] The high voltage is higher than 1 kV, and preferably 1.2 kV or higher, more preferably 1.5 kV or higher, and even 2 kV or lower.

[0032] Number of carbon atoms per amide group In the case of AB-polyamides, the number of carbon atoms per amide group is defined as the number of carbon atoms between the nitrogen atom and the carbonyl group per amide group. An example of an AB-polyamide is polyamide 6 derived from caprolactam, where the number of carbon atoms between the nitrogen atom and the carbonyl group is 5, so the number of carbon atoms per amide group of polyamide 6 is 5. Another example of an AB-polyamide is polyamide 11 derived from laurinlactam, where the number of carbon atoms per amide group of polyamide 11 is 10.

[0033] In the case of AABB-polyamides derived from diamines and dicarboxylic acids, the number of carbon atoms per amide group is determined by the number of carbon atoms between the two nitrogen atoms of the diamine (C DA ) and the number of carbon atoms between the two carbonyl groups of the dicarboxylic acid (C DS ) is the average value of the number of carbon atoms per amide group. DA and C DS The sum of these divided by 2, i.e. (C DA +C DS) / 2. The division by 2 is necessary because two amide groups are formed by two nitrogen atoms and two carboxyl groups. The carbon atom (C DA ) includes the carbon atoms in the branched chains of the diamine. The carbon atom between the two carbonyl groups (C DS ) includes the carbon atoms in the branched chains of the dicarboxylic acid. An example of an AABB-polyamide is polyamide 610, which is made from hexamethylenediamine and sebacic acid. Polyamide 610 has 6 carbon atoms between the two nitrogen atoms and 8 carbon atoms between the two carbonyl groups, resulting in (6 + 8) / 2 = 7 carbon atoms per amide group in polyamide 610.

[0034] The number of carbon atoms per amide group of a mixture of polyamides (a) or (b) is the average number of carbon atoms in all polyamides (a) or (b), taking into account the mass ratio of polyamides (a) or (b) in the mixture.

[0035] a) semi-crystalline aliphatic polyamides having an average of 3 to 5 carbon atoms per amide group Component a) in the present invention is derived from an aliphatic dicarboxylic acid and an aliphatic diamine, a lactam, and / or an amino acid, wherein the aliphatic dicarboxylic acid preferably has 4 to 6 carbon atoms, the aliphatic diamine preferably has 4 to 6 carbon atoms, and the lactam preferably has 4 to 6 carbon atoms, and the carbon atoms include all carbon atoms constituting the dicarboxylic acid, diamine, or lactam.

[0036] Component a) according to the present invention comprises a copolyamide or blend of at least one semi-crystalline aliphatic polyamide (a) according to the present invention.

[0037] Examples of component a) in the present invention include PA4, PA6, PA56, PA46, PA66, and / or PA6 / 66, with PA66 being preferred. PA66 has excellent flame retardancy, and conventional PA66 products commonly used in the polyamide industry can be suitably selected in the present invention. Preferably, PA66 suitable for use as component a) may have a viscosity number of 90 to 300 ml / g, preferably 110 to 200 ml / g, and more preferably 110 to 170 ml / g, as measured in accordance with ISO 307-2007 using a 0.005 g / ml polyamide solution in 96% by weight sulfuric acid. Suitable PA66 is commercially available as Zytel® 101 NC010 from DuPont, Akromid® A from AKRO-PLASTIC, Durethan® A30S from LANXESS, and Ultramid® A from BASF.

[0038] PA6 has excellent flame retardancy, and conventional PA6 products commonly used in the polyamide industry can be suitably selected in the present invention. Preferably, the PA6 suitable for use as component a) may have a viscosity number of 90 to 260 ml / g, preferably 110 to 200 ml / g, as measured in a 96% by weight polyamide solution at a concentration of 0.005 g / ml in sulfuric acid according to ISO 307-2007. Suitable PA6s are commercially available as Zytel® 7301 NC010 from DuPont, Akromid® B from AKRO-PLASTIC, Durethan® B30SFN30 from LANXESS, and Ultramid® B from BASF.

[0039] The polyamide component a) is present in an amount of 10 to 50% by weight, preferably 15 to 45% by weight, and in particular 20 to 40% by weight, based on the total weight of the polyamide composition.

[0040] b) Long-chain aliphatic polyamides with an average of 6 or more carbon atoms per amide group Component b) in the present invention is derived from an aliphatic dicarboxylic acid and an aliphatic diamine, a lactam, and / or an amino acid, wherein the aliphatic dicarboxylic acid preferably has 6 or more carbon atoms, the aliphatic diamine preferably has 6 or more carbon atoms, and the lactam preferably has 6 or more carbon atoms, and the carbon atoms include any carbon atoms that constitute the dicarboxylic acid, diamine, or lactam.

[0041] The polyamide component b) is present in an amount of 1 to 40% by weight, preferably 5 to 30% by weight, more preferably 8 to 25% by weight, and especially 10 to 25% by weight, based on the total weight of the polyamide composition.

[0042] The aliphatic dicarboxylic acid for forming the long-chain aliphatic polyamide of the present invention is a conventional diacid used in the production of polyamides, preferably an aliphatic dicarboxylic acid having 6 to 40 carbon atoms, more preferably 6 to 36 carbon atoms, even more preferably 6 to 20 or 36 carbon atoms, and most preferably 6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and / or 36 carbon atoms. The aliphatic diamine for forming the long-chain aliphatic polyamide of the present invention is a conventional diamine used in the production of polyamides, preferably an aliphatic diamine having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably 6, 8, 9, 10, 11, 12, 13, and / or 14 carbon atoms. Here, the carbon atoms include all carbon atoms constituting the dicarboxylic acid or diamine.

[0043] The lactam for forming the long chain aliphatic polyamide in the present invention may be decanelactam, caprylactam, and / or laurinlactam.

[0044] The long-chain aliphatic polyamide is preferably at least one selected from the group consisting of PA7, PA8, PA9, PA11, PA12, PA68, PA610, PA612, PA614, PA618, PA88, PA810, PA812, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PA1313, PA1410, PA1412, PA1414, PA1418 and PA6.36, more preferably PA610, PA1010, PA1012, PA1210 and / or PA1212. In a preferred embodiment, component b) is PA1212.

[0045] Component b) in the present invention comprises a blend of at least two long chain aliphatic polyamides and / or long chain aliphatic polyamide copolymer copolyamides.

[0046] A long-chain aliphatic polyamide copolymer is a polyamide copolymer in which the building blocks of the polyamide copolymer contain at least one long-chain aliphatic polyamide segment (segment A), and the remaining segments of the polyamide copolymer are non-long-chain aliphatic polyamide segments or other long-chain segments other than segment A. Examples of the remaining segments include PA6 or PA66. An example that may be mentioned is PA6 / 6.36, which is a copolymer of PA6 and PA6.36, the latter formed from hexamethylenediamine and C36 dicarboxylic acid. Other examples include PA66 / 610, PA6 / 610, and PA66 / 6 / 610.

[0047] There is no limitation on the type of copolymer, and for example, block copolymers, random copolymers, graft copolymers or alternating copolymers are suitable for the present invention.

[0048] The long-chain aliphatic polyamide in the present invention has a molecular weight conventional in polyamide compositions, and the intrinsic viscosity of the long-chain polyamide is preferably 90 to 200 ml / g, measured in a polyamide solution at a concentration of 0.005 g / ml in 96% by weight sulfuric acid at 25°C according to ISO 307.

[0049] In a preferred embodiment, the weight ratio of polyamide components a) and b) in the polyamide composition is 5:1 to 1:1, preferably 4:1 to 1:1, and more preferably 3.5:1 to 2.5:1, in particular 3:1.

[0050] c) Flame retardants The flame retardant c) is preferably a phosphorus-based flame retardant, a halogenated flame retardant, a nitrogen-based flame retardant, and / or a mineral-based flame retardant. It can be used in untreated form.

[0051] Examples of mineral-based flame retardants include antimony trioxide, alkaline earth metal oxides such as zinc oxide or magnesium oxide, metal hydroxides such as magnesium hydroxide or aluminum hydroxide, metal borates such as zinc borate.

[0052] Phosphorus-based flame retardants include inorganic and organic phosphorus-containing flame retardants.

[0053] Examples of inorganic phosphorus-containing flame retardants include red phosphorus, zinc phosphate, ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate, with red phosphorus being preferred.

[0054] Examples of organic phosphorus-containing flame retardants include ethylenediamine phosphate, piperazine phosphate, piperazine pyrophosphate, dialkyl phosphates or combinations of dialkyl phosphates and metal salts of phosphoric acid.

[0055] The dialkyl phosphate may be aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl-n-propyl phosphinate, calcium dimethyl phosphinate, magnesium dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, magnesium ethyl methyl phosphinate, zinc ethyl methyl phosphinate, calcium diethyl phosphinate, magnesium diethyl phosphinate, zinc diethyl phosphinate, calcium methyl-n-propyl phosphinate, magnesium methyl-n-propyl phosphinate, and / or zinc methyl-n-propyl phosphinate. Among these, aluminum diethyl phosphinate, zinc diethyl phosphinate, aluminum dimethyl phosphinate, and zinc dimethyl phosphinate are more preferred.

[0056] The metal salt of phosphorus may be Al(H2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3·4H2O and / or Al(OH)(H2PO3)2·2H2O. Suitable organophosphorus based flame retardants are commercially available from Clariant as OP1230, OP1400.

[0057] The nitrogen-based flame retardant is preferably a triazine-based flame retardant. Examples of triazine-based flame retardants include melamine or its derivatives, such as melam, melem, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, silicate melamine, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate or melamine polyphosphate, melam pyrophosphate, melam polyphosphate, melem phosphate, melem pyrophosphate, melem polyphosphate, and phosphates, pyrophosphates, melamine neopentyl glycol borate and polyphosphates of higher condensates of melamine and / or melem. Melamine polyphosphate salts derived from 1,3,5-triazine compounds are preferred, having an average condensation degree n of 20 to 200, and a 1,3,5-triazine content per mole of phosphorus atom of 1.1 to 2.0 moles of a 1,3,5-triazine compound selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, and diaminophenyltriazine. The n value of this type of salt is generally 40 to 150, and the molar ratio of 1,3,5-triazine compound to phosphorus atom is preferably 1.2 to 1.8.

[0058] An example of a halogenated flame retardant is brominated polystyrene.

[0059] The flame retardant as component c) is present in an amount of 0 to 35% by weight, preferably 4 to 25% by weight, and in particular 8 to 18% by weight, based on the total weight of the polyamide composition.

[0060] In one preferred embodiment, the flame retardant in the present invention is selected from the group consisting of red phosphorus, antimony trioxide, dialkyl phosphates, combinations of metal salts of dialkyl phosphates and phosphoric acid, and triazine-based flame retardants.

[0061] In one preferred embodiment, the flame retardant in the present invention may be red phosphorus.

[0062] The red phosphorus may be used in the form of a red phosphorus masterbatch. The content of red phosphorus in the masterbatch may be 30% by mass to 60% by mass. The base resin in the masterbatch may be the impact modifier e) of the present invention.

[0063] In a preferred embodiment, the flame retardant of the present invention comprises red phosphorus as component c1) and a triazine-based flame retardant as component c2), preferably melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate, or melamine polyphosphate. Component c1) is preferably present in an amount of 3 to 20% by mass, more preferably 10 to 15% by mass, of the polyamide composition. Component c2) is preferably present in an amount of 1 to 10% by mass, more preferably 3 to 8% by mass, of the polyamide composition.

[0064] In one preferred embodiment, the flame retardant according to the present invention comprises, as component c1), red phosphorus in an amount of 3 to 20% by weight, preferably 10 to 15% by weight, and as component c2), melamine phosphate and / or dimelamine phosphate in an amount of 1 to 10% by weight, preferably 3 to 8% by weight, based on the total weight of the polyamide composition.

[0065] In a preferred embodiment, the flame retardant in the present invention comprises 15 to 35 mass % of an organic phosphorus-containing flame retardant based on the total mass of the polyamide composition.

[0066] In a preferred embodiment, the flame retardant in the present invention comprises 15 to 35 mass % of a dialkyl phosphate, or a combination of a dialkyl phosphate and a metal salt of phosphorus, based on the total mass of the polyamide composition.

[0067] In one preferred embodiment, the flame retardant in the present invention comprises 20 to 25 mass % of a dialkyl phosphate, or a combination of a dialkyl phosphate and a metal salt of phosphorus, based on the total mass of the polyamide composition.

[0068] In a preferred embodiment, the flame retardant in the present invention contains 15 to 35 mass % of a dialkyl phosphate selected from the group consisting of aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl-n-propyl phosphinate, zinc diethyl phosphinate, and zinc dimethyl phosphinate, based on the total mass of the polyamide composition.

[0069] In a preferred embodiment, the flame retardant of the present invention comprises 15 to 35 mass % of a combination of a dialkyl phosphate and a metal salt of phosphorus, based on the total mass of the polyamide composition, where the dialkyl phosphate is selected from the group consisting of aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl-n-propyl phosphinate, zinc diethyl phosphinate, and zinc dimethyl phosphinate, and the metal salt of phosphorus is selected from the group consisting of Al(H2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3·4H2O, and / or Al(OH)(H2PO3)2·2H2O.

[0070] The average particle size (d 50 ) is preferably in the range of 0.0001 to 0.5 mm, particularly 0.001 to 0.2 mm.

[0071] In a preferred embodiment, the flame retardant of the present invention comprises 5 to 15 mass %, preferably 5 to 10 mass %, of a mineral-based flame retardant and 10 to 30 mass %, preferably 15 to 25 mass %, of a halogenated flame retardant, based on the total mass of the polyamide composition. The mineral-based flame retardant is preferably antimony trioxide. The halogenated flame retardant is preferably brominated polystyrene.

[0072] Those skilled in the art will recognize other suitable nitrogen-containing flame retardants.

[0073] d) Fibrous and / or particulate fillers The fibrous and / or particulate fillers in the present invention can be conventional fillers used in polyamide compositions. The filler may include, for example, fibers selected from the group consisting of glass fibers, carbon fibers, and mineral fibers. Preferably, the composition contains at least glass fibers, carbon fibers, or a combination thereof. The glass fibers may be selected from, for example, A-glass, C-glass, D-glass, E-glass, H-glass, M-glass, R-glass, and S-glass fibers, or any mixture thereof. Alkali-free E-glass fibers or glass fiber mixtures containing E-glass fibers and one or more other glass fibers are preferred. These can be used in the commercially available form of roving or chopped glass. The glass fibers may have an average length of 2 to 7 mm, and more preferably 3 to 6 mm. The diameter of the glass fibers is preferably 3 to 20 μm, more preferably 7 to 13 μm. Examples of cross-sectional shapes of the fibrous reinforcing agent include circular, rectangular, elliptical, and other non-circular cross sections, with circular being preferred.

[0074] The fillers used are any particulate fillers known to those skilled in the art, including in particular particulate fillers selected from the group consisting of minerals, talc, mica, dolomite, silicates, quartz, wollastonite, kaolin, silicic acid, magnesium, carbonate, magnesium hydroxide, chalk, ground glass, glass flakes, glass beads, hollow glass beads and mixtures thereof.

[0075] In one preferred embodiment, the fibrous and / or particulate filler in the present invention is chopped glass fiber and / or carbon glass fiber.

[0076] The polyamide composition of the present invention comprises 0 to 50 mass %, preferably 10 to 40 mass %, more preferably 15 to 30 mass % of component d), based on the total mass of the polyamide composition.

[0077] e) Impact modifiers The polyamide composition comprises as component e) an impact modifier (often also called elastomeric polymer, elastomer or rubber) in an amount of 1 to 25% by weight, preferably 5 to 20% by weight, in particular 8 to 15% by weight, based on the total weight of the polyamide composition.

[0078] The impact modifier is preferably derived from at least two monomers selected from the group consisting of alpha-olefins, dienes, ethylenically unsaturated nitriles, and ethylenically unsaturated carboxylic acids and epoxy compounds, esters and acid anhydrides thereof, and more preferably derived from at least one of alpha-olefins, dienes, ethylenically unsaturated carboxylic acids, esters of unsaturated carboxylic acids and ethylenically unsaturated nitriles, and at least one of epoxy compounds or acid anhydrides of unsaturated carboxylic acids.

[0079] The alpha-olefin preferably has 2 to 20 carbon atoms, more preferably 4 to 10. Examples of the alpha-olefin include ethylene, propylene, 1-butylene, isobutene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-decene, and mixtures thereof, more preferably ethylene, propylene, 1-butene, 1-hexene, isobutene, a mixture of ethylene and propylene, a mixture of ethylene and 1-octene, a mixture of ethylene and 1-butene, a mixture of propylene and 4-methyl-1-pentene, a mixture of propylene and 1-butene, a mixture of ethylene, propylene and 1-butene, a mixture of 1-decene and 1-methyl-1-pentene, and most preferably a mixture of ethylene, 1-butene, 1-propylene, 1-pentene, and a mixture of ethylene and 1-octene.

[0080] The dienes are preferably conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene and mixtures thereof, non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene and mixtures thereof, cyclic dienes such as cyclopentadiene, Preferred are cyclohexadiene, cyclooctadiene, dicyclopentadiene, alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes such as 3-methyltricyclo[5.2.1.0.2.6]-3,8-decadiene, and mixtures thereof. 1,3-Butadiene, 1,3-pentadiene and / or isoprene are preferred, with 1,3-butadiene being more preferred.

[0081] The ethylenically unsaturated nitrile monomer is preferably selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and α-cyanoethylacrylonitrile, more preferably acrylonitrile and / or methacrylonitrile, and most preferably acrylonitrile.

[0082] The ethylenically unsaturated carboxylic acid has at least one carbon-carbon double bond and at least one carboxyl group. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, 2-ethylacrylic acid, 2-chloroacrylic acid, crotonic acid, isocrotonic acid, angelic acid, sorbic acid, methaconic acid, and cinnamic acid, and more preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid, and / or citraconic acid.

[0083] The epoxy compound of an ethylenically unsaturated carboxylic acid may be a carboxylic acid glycidyl ester, a glycidyl ether, and / or the like. Examples of the epoxy compound of an ethylenically unsaturated acid include glycidyl acrylate, glycidyl methacrylate, 1-glycidyl maleate, diglycidyl maleate, monoglycidyl itaconic acid, diglycidyl itaconic acid, monoglycidyl citraconic acid, diglycidyl citraconic acid, monoglycidyl butenecarboxylic acid, preferably glycidyl acrylate and / or glycidyl methacrylate.

[0084] The ester of an ethylenically unsaturated carboxylic acid is preferably an ester of acrylic acid and / or acetic acid, more preferably an alkyl ester and / or a hydroxyalkyl ester of acrylic acid and / or acetic acid, for example, a C1-C6 alkyl ester of acrylic acid and / or acetic acid. 18 , more preferably C1 to C 12 , most preferably C1 to C4 alkyl esters and / or C1 to C 18 , more preferably C1 to C 12Examples of esters of ethylenically unsaturated carboxylic acids include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, dimethyl maleate, monomethyl maleate, and hydroxyethyl methacrylate. (HEMA), stearyl methacrylate, stearyl acrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypropyl methacrylate, and vinyl acetate, more preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate, and most preferably methyl methacrylate, methyl acrylate, butyl acrylate, and / or butyl methacrylate.

[0085] The acid anhydride of an ethylenically unsaturated carboxylic acid is preferably selected from the group consisting of maleic anhydride (MAH), acrylic anhydride, methacrylic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, nadic anhydride, methylnadic anhydride, himic anhydride, and methylhimic anhydride, more preferably maleic anhydride, (meth)acrylic anhydride, and / or fumaric anhydride.

[0086] The monomers of the impact modifier are preferably selected from the group consisting of ethylene, 1-butene, 1-propylene, 1-pentene, 1-octene, 1,3-butadiene, acrylonitrile, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, maleic anhydride, acrylic anhydride, glycidyl acrylate and glycidyl methacrylate.

[0087] Impact modifier polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, volume 14 / 1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392-406, and in the monograph "Toughened Plastics" by C.B. Bucknall (Applied Science Publishers, London, 1977).

[0088] Some preferred classes of these impact modifiers are described below.

[0089] In one embodiment of the present invention, the impact modifier is derived from a combination of at least two monomers of an alpha-olefin or an alpha-olefin and a conjugated diene.

[0090] In one embodiment of the present invention, the impact modifier is derived from two monomers: ethylene, propylene, and / or octene. The impact modifier is preferably an ethylene-propylene (EPM) rubber or an ethylene-octene copolymer.

[0091] In one embodiment of the present invention, the impact modifier is derived from an alpha-olefin and a diene, and is preferably an ethylene-propylene-diene (EPDM) rubber.

[0092] EPM rubbers generally have substantially no residual double bonds, while EPDM rubbers may have 1 to 20 double bonds per 100 carbon atoms.

[0093] Examples of diene monomers for EPDM rubber that may be mentioned are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes such as 3-methyltricyclo[5.2.1.0.2.6]-3,8-decadiene, and mixtures thereof. 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubber is preferably 0.5 to 50 mass %, particularly 1 to 8 mass %, based on the total mass of the rubber.

[0094] The EPM and EPDM rubbers may preferably be grafted with an ethylenically unsaturated carboxylic acid and / or its epoxy compound, ester, and acid anhydride. Examples of grafting monomers include acrylic acid, methacrylic acid, glycidyl (meth)acrylate, and maleic anhydride.

[0095] In one embodiment of the present invention, the impact modifier is derived from an alpha-olefin, an epoxy compound of an ethylenically unsaturated carboxylic acid, and styrene. The alpha-olefin here is preferably ethylene, butylene, and / or propylene, more preferably ethylene and butylene. Examples of the epoxy compound of an ethylenically unsaturated carboxylic acid here include preferably glycidyl acrylate and / or glycidyl methacrylate (GMA). The epoxy compound of an ethylenically unsaturated carboxylic acid here is preferably grafted to a polyolefin / polystyrene coblock or copolymerized to a polyolefin / polystyrene coblock.

[0096] In one preferred embodiment of the present invention, the impact modifier is a GMA grafted polypropylene or a GMA grafted styrene-ethylene-butylene (SEBS) copolymer.

[0097] In one embodiment of the present invention, the impact modifier is derived from at least one alpha-olefin, at least one ethylenically unsaturated carboxylic acid, and at least one epoxy compound of the ethylenically unsaturated carboxylic acid. Examples of the alpha-olefin include ethylene, butylene, and propylene. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and fumaric acid, preferably acrylic acid and methacrylic acid. Examples of the epoxy compound of the ethylenically unsaturated carboxylic acid include glycidyl acrylate and / or glycidyl methacrylate (GMA). The impact modifier is preferably an ethylene / acrylic / GMA ternary copolymer.

[0098] In one embodiment of the present invention, the impact modifier is derived from at least one alpha-olefin, at least one ester of an ethylenically unsaturated carboxylic acid, and at least one polyester ether elastomer. Examples of the alpha-olefin include ethylene and / or butylene. Examples of the ester of an ethylenically unsaturated carboxylic acid include methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and / or butyl methacrylate.

[0099] Copolymers of (e-1) alpha-olefins and (e-2) ethylenically unsaturated carboxylic acids, epoxy compounds, esters, and / or acid anhydrides of ethylenically unsaturated carboxylic acids are another group of preferred rubbers. The copolymers may be block, alternating, random, or graft copolymers, and are preferably block and / or graft copolymers. The (e-1) alpha-olefin is preferably ethylene, butylene, propylene, and / or octene. The component (e-2) is preferably one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, maleic anhydride, (meth)acrylic anhydride, fumaric anhydride, glycidyl acrylate, and glycidyl methacrylate.

[0100] In one embodiment of the present invention, the impact modifier is derived from at least one monomer (e-1) of an alpha-olefin and at least one monomer (e-2) of an epoxy compound of an ethylenically unsaturated carboxylic acid and / or an acid anhydride of an ethylenically unsaturated carboxylic acid. The alpha-olefin here is preferably ethylene, butylene, propylene, and / or octene. Examples of the epoxy compound of an ethylenically unsaturated carboxylic acid here include glycidyl acrylate and / or glycidyl methacrylate (GMA). The acid anhydride of an ethylenically unsaturated carboxylic acid here is preferably maleic anhydride. The monomer (e-2) here is preferably grafted to a polyolefin block or copolymerized to a polyolefin block. The impact modifier is preferably GMA-grafted ethylene, GMA-grafted polypropylene, GMA-grafted ethylene-butylene copolymer, or GMA-grafted ethylene-octene.

[0101] In one preferred embodiment, the impact modifier in the present invention is derived from ethylene and octene.

[0102] The copolymer is advantageously composed of 50 to 98% by weight of (e-1) alpha-olefin and 0.1 to 20% by weight of component (e-2).

[0103] Particularly preferred copolymers are: 50 to 98% by weight, in particular 55 to 95% by weight, of ethylene and / or octene, 0.1 to 20% by weight, in particular 0.3 to 20% by weight, of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic anhydride and / or maleic anhydride, and 1 to 45% by weight, in particular 5 to 40% by weight, of (meth)acrylic acid, n-butyl acrylate and / or 2-ethylhexyl acrylate It consists of:

[0104] The ethylene copolymers described above may be prepared by processes known per se, preferably by random copolymerization at high pressure and temperature. Suitable processes are well known.

[0105] Particularly preferred impact modifiers are selected from maleic anhydride functionalized polyolefins, maleic anhydride functionalized polyethylene copolymers, glycidyl methacrylate functionalized ethylene and methyl acrylate terpolymers, or combinations thereof.

[0106] The molar mass of the impact modifier is preferably between 10,000 and 500,000 g / mol, more preferably between 15,000 and 400,000 g / mol (Mn, determined by GPC in 1,2,4-trichlorobenzene with PS calibration).

[0107] Of course, it is also possible to use mixtures of the above types of impact modifiers.

[0108] f) Additives The polyamide composition may contain 0 to 20% by mass of other additives, including antioxidants, lubricating and dispersing agents, UV stabilizers, pigments, colorants, antistatic agents, thickeners, thixotropic agents, surfactants, viscosity modifiers, plasticizers, or nucleating agents.

[0109] Suitable antioxidants that may be mentioned are hindered phenol antioxidants with phosphate antioxidant lipid compound system.Suitable hindered phenols are in principle all compounds that have a phenol structure and have at least one bulky group on the phenol ring.

[0110] Examples of compounds that can be preferably used are those of formula I: [ka] (In the formula, R 1 and R 2 is an alkyl group, a substituted alkyl group, or a substituted triazole group, where the group R 1 and R 2 may be the same or different, and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group. It is of the type.

[0111] Another group of preferred hindered phenols is provided by those derived from substituted benzenecarboxylic acids, especially substituted benzeneepropionic acids.

[0112] Particularly preferred compounds from this class are of formula II: [ka] (In the formula, R 4 , R 5 , R 7 and R 8 are, independently of one another, C1-C8 alkyl groups which themselves may have a substituent (at least one of which is a bulky group), and R 6 is a divalent aliphatic group having 1 to 10 carbon atoms, the main chain of which may also have a CO bond. is a compound of

[0113] Compounds which have proven particularly effective and are therefore preferably used are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and also N,N'-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and the above-mentioned product Irganox® 245 from BASF SE, which has particularly good suitability.

[0114] Suitable flame retardant accelerators include zinc oxide, modified zinc oxide, Zn borate, Zn stannate, MgO, Mg(OH)2, ZnCO3, MgCO3, CaCO3 and AlOOH, with zinc oxide and modified zinc oxide being particularly preferred.

[0115] Suitable lubricating dispersants include zinc stearate, calcium stearate, ethylene bisstearic acid amine, oleic acid amide, erucic acid amide, polyethylene wax, or combinations thereof.

[0116] Suitable colorants include inorganic pigments, such as titanium dioxide, iron oxide, and carbon black.

[0117] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 25% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36; c) 3 to 20% by weight of red phosphorus and 1 to 10% by weight of a triazine-based flame retardant; d) 10 to 40% by mass of fibrous and / or particulate fillers; e) 0 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0118] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 25% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36; c) 3 to 20% by weight of red phosphorus and 1 to 10% by weight of a triazine-based flame retardant; d) 10 to 40% by mass of fibrous and / or particulate fillers; e) 5 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0119] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 15% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36, wherein the weight ratio of components a) to b) is 3.5:1 to 2.5:1, c) 4 to 25% by mass of a flame retardant; d) 20 to 40% by mass of fibrous and / or particulate fillers; e) 5 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0120] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 15% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36, wherein the weight ratio of components a) to b) is 3.5:1 to 2.5:1, c) 3-20% by weight of red phosphorus, or a combination of 3-20% by weight of red phosphorus and 1-10% by weight of a triazine-based flame retardant; d) 20 to 40% by mass of fibrous and / or particulate fillers; e) 5 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0121] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 15% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36, wherein the weight ratio of components a) to b) is 3.5:1 to 2.5:1, c) 15 to 35% by mass of a dialkyl phosphate or a combination of a dialkyl phosphate and a metal salt of phosphorus (the dialkyl phosphate is preferably selected from the group consisting of aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl-n-propyl phosphinate, zinc diethyl phosphinate and zinc dimethyl phosphinate, and the metal salt of phosphorus is preferably selected from the group consisting of Al(H2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3·4H2O and / or Al(OH)(H2PO3)2·2H2O), d) 20 to 40% by mass of fibrous and / or particulate fillers; e) 0 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0122] In one preferred embodiment, a method for improving inclined plane tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising, based on the total weight of the polyamide composition: a) 20 to 40% by weight of at least one semi-crystalline aliphatic polyamide selected from the group consisting of PA6, PA66 and PA6 / 66, b) 8 to 15% by weight of at least one long-chain aliphatic polyamide selected from the group consisting of PA1212, 610, 612, 1010 and PA6 / 6.36, wherein the weight ratio of components a) to b) is 3.5:1 to 2.5:1, c) 5 to 15% by weight of a mineral-based flame retardant and 10 to 30% by weight of a halogenated flame retardant, based on the total weight of the polyamide composition (the mineral-based flame retardant is preferably antimony trioxide and the halogenated flame retardant is preferably brominated polystyrene); d) 20 to 40% by mass of fibrous and / or particulate fillers; e) 0 to 15% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0123] Preparation of polyamide compositions The polyamide compositions of the present invention can be produced by processes known per se, by mixing the components in conventional mixing equipment, such as a screw extruder, Brabender mixer, or Banbury mixer, followed by extrusion. The extrudate can be cooled and pelletized. It is also possible to premix the individual components and then add the remaining components individually and / or in the form of a mixture. Typically, the screw diameter is 20-40 mm, the screw speed is 300-500 rpm, the throughput is 25-35 kg / h, and the melt temperature is 230-320°C.

[0124] In one preferred embodiment, the polyamide composition is produced by (1) introducing the semi-crystalline aliphatic polyamide (a), the long-chain aliphatic polyamide (b), the impact modifier (e) and the additive (f) into an extruder, and (2) introducing the fibrous and / or particulate filler (d) and the flame retardant (c) into the extruder from a downstream feeding zone, followed by compounding and extrusion.

[0125] The polyamide compositions of the present invention are characterized by good mechanical properties and a highly reproducible flame retardant classification according to UL 94, and further by very good electrical properties at high voltages, for example high IPT and CTI values ​​at voltages above 1 kV, 1.2 kV, 1.5 kV or even as high as 2 kV.

[0126] Polyamide compositions are suitable for the manufacture of any type of fiber, film, and molded article. Some examples are plug connectors, plugs, plug parts, cable harness components, circuit mounts, circuit mount components, three-dimensional injection molded circuit mounts, electrical connection elements, and mechatronic components. Due to their excellent electrical properties at high voltages, these materials are particularly suitable for the manufacture of photovoltaic connector nuts and bodies, and outdoor insulating electrical plastic parts.

[0127] Another object of the present invention is to provide an article made from a polyamide composition that exhibits excellent anti-tracking properties at voltages exceeding 1 kV, for example, 1.2 kV or more, 1.5 kV or more, or 2 kV or less, preferably a nut or body of a photovoltaic connector, or an electrically insulating plastic part.

[0128] Another object of the present invention is to provide a polyamide composition, the composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the amide groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the amide groups, in which the weight ratio of components a) and b) in the polyamide composition is 3.5:1 to 2.5:1, c) 4 to 25% by weight of a flame retardant comprising red phosphorus as component c1) and a triazine-based flame retardant as component c2), which is preferably melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate or melamine polyphosphate, d) 0 to 50% by mass of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by mass of other additives Includes.

[0129] Component a) is preferably present in an amount of 15 to 45% by weight, and in particular 20 to 40% by weight, based on the total weight of the polyamide composition. Component b) is preferably present in an amount of 5 to 30% by weight, more preferably 8 to 25% by weight, and in particular 10 to 20% by weight, based on the total weight of the polyamide composition. In component c), component c1) is preferably present in an amount of 3 to 15% by weight, more preferably 5 to 10% by weight, of the polyamide composition, and component c2) is preferably present in an amount of 1 to 10% by weight, more preferably 3 to 8% by weight, of the polyamide composition. [Example]

[0130] The present invention will now be described with reference to examples and comparative examples, which are not intended to limit the present invention.

[0131] The following starting materials were used: Polyamide 66, BASF, Ultramid A27, ISO 307, 1157 viscosity number 150 cm 3 / g. Polyamide 66, BASF, Ultramid A24, ISO 307, 1157 viscosity number 125 cm 3 / g. Polyamide 1212, poly(dodecamethylene dodecanoamide), Shandong Dongchen New Technology Co., Ltd., PA1212 Type II. Polyamide 610, poly[imino-1,6-hexanediylimino(1,10-dioxo-1,10-decanediyl)], Shandong Dongchen New Technology Co., Ltd., PA610 Type II. Polyamide 6 / 6·36, BASF, Ultramid Flex F29. Polyamide 6I / 6T, DuPont, Selar 3426. Glass fiber, Nippon Electric Glass Co., Ltd., NEG-T251H, length = 4.5 mm, diameter = 10 um. Red phosphorus masterbatch containing 50% by weight of red phosphorus having an average particle size (d50) of 20-25 μm and 50% by weight of an olefin polymer, Italmatch Chemicals, Masterbatch 11452-1270, olefin polymer: 59.8% by weight of ethylene, 35% by weight of n-butyl acrylate, 4.5% by weight of acrylic acid, and 0.7% by weight of maleic anhydride. Melamine phosphate, BASF, Melapur 200-70. OP1400, a mixture of 80% by weight of OP1230 (aluminum diethylphosphinate) and 20% by weight of PHOPHAL (aluminum phosphate), Clariant. Brominated polystyrene, Shandong Brother Science & Technology Co., Ltd., XZ-6700H. Antimony trioxide masterbatch, 90% by weight of Sb2O3 in low-density polyethylene (LDPE), Dongguan Jiefu Flame-Retarded Materials Co., Ltd., LDPE90B. MAH-grafted ethylene octene copolymer, DuPont, Fusabond N493. Lotader AX8900, random terpolymer of ethylene, acrylic ester and glycidyl methacrylate, 8% by weight glycidyl methacrylate, 24% by weight acrylic ester, Arkema.

[0132] Wax ester, lubricant, Emery Oleochemicals Co., Ltd., Loxiol G32. Irganox 1098, antioxidant, BASF. Zinc oxide, Shenlong, ZnO 99.8%. UB434, Colloids Ltd, black colorant masterbatch (MB).

[0133] Measurement method Inclined Plane Tracking (IPT) values ​​were measured according to ASTM D2303. The flame retardancy classification was measured according to UL94, and the sample dimensions were 127mm*12.7mm*1.6mm (length*width*thickness). Comparative Test Index (CTI) values ​​were measured according to IEC60112. Tensile strength, breaking strain and E-modulus were measured according to ISO 527-2 using 1A type test specimens with Z050 (Zwick Roell GmbH, Germany). Notched Charpy impact was measured using a HIT25P (Zwick Roell, Germany) in accordance with ISO179 / 1eA. Unnotched Charpy impact was measured using a HIT25P (Zwick Roell, Germany) in accordance with ISO179 / 1eU.

[0134] Example 1: Procedure: (1) 31.9% by mass of polyamide 66 (Ultramid A27), 10.5% by mass of polyamide 1212, 8.7% by mass of impact modifier (Fusabond N493), 2% by mass of AX8900, 0.35% by mass of lubricant (Loxiol G32), 0.35% by mass of antioxidant (Irganox 1098), 0.7% by mass of flame retardant accelerator (ZnO), and 2.5% by mass of black colorant MB (UB434) were blended in a high-speed mixer. (2) The mixture was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 15% by mass of red phosphorus masterbatch and 3% by mass of Melapur 200-70 were fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0135] Example 2: Procedure: (1) The components in the following mass ratios were blended in a high-speed mixer: 31.9 mass% polyamide 66 (Ultramid A27), 10.5 mass% polyamide 610, 8.7 mass% impact modifier (Fusabond N493), 2 mass% AX8900, 0.35 mass% lubricant (Loxiol G32), 0.35 mass% antioxidant (Irganox 1098), 0.7 mass% flame retardant accelerator (ZnO), and 2.5 mass% black colorant MB (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 15% by mass of red phosphorus masterbatch and 3% by mass of Melapur 200-70 were fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0136] Example 3: Procedure: (1) The components in the following mass ratios were blended in a high-speed mixer: 31.9 mass% polyamide 66 (Ultramid A27), 10.5 mass% polyamide 6 / 636, 8.7 mass% impact modifier (Fusabond N493), 2 mass% AX8900, 0.35 mass% lubricant (Loxiol G32), 0.35 mass% antioxidant (Irganox 1098), 0.7 mass% flame retardant accelerator (ZnO), and 2.5 mass% black colorant MB (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 15% by mass of the flame retardant red phosphorus masterbatch and 3% by mass of Melapur 200-70 were fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0137] Comparative Example 1: Procedure: (1) The components in the following mass ratios were blended in a high-speed mixer: 46.9 mass% polyamide 66 (Ultramid A27), 12.2 mass% impact modifier (Fusabond N493), 0.35 mass% lubricant (Loxiol G32), 0.35 mass% antioxidant (Irganox 1098), 0.7 mass% flame retardant accelerator (ZnO), and 2.5 mass% black colorant MB (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 12% by mass of red phosphorus masterbatch was fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0138] Comparative Example 2: Procedure: (1) The components in the following mass ratios were blended in a high-speed mixer: 31.9 mass% polyamide 66 (Ultramid A27), 10.5 mass% Selar 3426, 8.7 mass% impact modifier (Fusabond N493), 2 mass% AX8900, 0.35 mass% lubricant (Loxiol G32), 0.35 mass% antioxidant (Irganox 1098), 0.7 mass% flame retardant accelerator (ZnO), and 2.5 mass% black colorant MB (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 15% by mass of the flame retardant red phosphorus masterbatch and 3% by mass of Melapur 200-70 were fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0139] The articles produced from the above examples were tested for flame retardancy, electrical properties and mechanical properties, and the results are summarized in Table 1 below.

[0140] [Table 1]

[0141] From the table above, it can be seen that using PA66 alone as the polyamide component results in a composition with poor performance at high voltages above 1 kV, i.e., a very low IPT value, making it unsuitable for applications in the electrical technology field. In contrast, the polyamide compositions of the present invention combine excellent electrical properties at high voltages with a high level of flame retardancy and good mechanical properties, making these compositions ideal materials for applications such as photovoltaic connector nuts and bodies, outdoor insulating electrical plastic parts, etc. Among these aliphatic long-chain polyamides, PA1212 exhibits high IPT values ​​at both 1.5 kV and 2.0 kV, demonstrating better overall properties.

[0142] In particular, as shown in Comparative Example 2, when the long-chain aliphatic polyamide is replaced with an aromatic polyamide, the IPT value at 1.5 kV is significantly lower than that obtained with the long-chain aliphatic polyamide, and cannot meet the requirements for PV applications at higher voltages.

[0143] Example 4: Procedure: (1) The components in the following weight ratios were blended in a high-speed mixer: 23.45% by weight of polyamide 66 (Ultramid A27), 23.45% by weight of polyamide 1212, 12.2% by weight of impact modifier (Fusabond N493), 0.35% by weight of lubricant (Loxiol G32), 0.35% by weight of antioxidant (Irganox 1098), 0.7% by weight of flame retardant accelerator (ZnO), and 2.5% by weight of black colorant masterbatch (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 12% by mass of a flame retardant (red phosphorus masterbatch) was fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0144] Example 5: Procedure: (1) The components in the following weight ratios were blended in a high-speed mixer: 31.4% by weight of polyamide 66 (Ultramid A27), 15.5% by weight of polyamide 1212, 12.2% by weight of impact modifier (Fusabond N493), 0.35% by weight of lubricant (Loxiol G32), 0.35% by weight of antioxidant (Irganox 1098), 0.7% by weight of flame retardant accelerator (ZnO), and 2.5% by weight of black colorant masterbatch (UB434). (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 12% by mass of a flame retardant (red phosphorus masterbatch) was fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0145] Example 6: Procedure: (1) The components in the following mass ratios were blended in a high-speed mixer: 35.1 mass% polyamide 66 (Ultramid A27), 11.8 mass% polyamide 1212, 12.2 mass% impact modifier (Fusabond N493), 0.35 mass% lubricant (Loxiol G32), 0.35 mass% antioxidant (Irganox 1098), 0.7 mass% flame retardant accelerator (ZnO), and 2.5 mass% black colorant masterbatch. (2) The mixer was fed into the throat zone of a twin-screw extruder. (3) 25% by mass of glass fiber (NEG-T251H) was fed into the extruder via a side fiber feeder. (4) 12% by mass of a flame retardant (red phosphorus masterbatch) was fed into the extruder via a side powder feeder. (5) Twin-screw extruder pelletization was added and the extrudate was cut into pellets. (6) The screw diameter was 26 mm, the screw speed was 300 rpm–500 rpm, the throughput was 25–35 kg / h, and the melt temperature was 280°C.

[0146] The articles produced from Examples 4-6 above were tested for flame retardancy and electrical properties, and the results are summarized in Table 2 below.

[0147] [Table 2]

[0148] Examples 7 to 12 and Comparative Examples 3 to 4 Examples 7-12 were carried out according to the processing procedures of Examples 1-6, and Comparative Examples 3-4 were carried out according to the processing procedures of Comparative Examples 1-2, except that the ingredients were added in the amounts shown in Tables 3-4 below. The articles produced from the above examples were tested for flame retardancy and electrical properties, and the results are summarized in Tables 3-4 below.

[0149] [Table 3]

[0150] [Table 4]

[0151] At a high voltage of 1.5 kV, the polyamide composition of the present invention achieved significantly improved IPT values, whereas the same amount of PA66 alone resulted in much lower IPT values ​​at such a high voltage.

[0152] It will be understood that the structures, materials, compositions, and methods described herein are intended to be exemplary of the invention, and that the scope of the invention is not limited by the scope of the examples. Those skilled in the art will recognize that the invention can be practiced with variations of the disclosed structures, materials, compositions, and methods, and that such variations are considered to be within the scope of the invention. Accordingly, the present invention is intended to cover such modifications and variations as come within the scope of the appended claims and their equivalents.

Claims

1. 1. A method for improving inclined surface tracking characteristics at voltages greater than 1 kV by using a polyamide composition, the composition comprising: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 0 to 35% by weight of a flame retardant; d) 0 to 50% by weight of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by weight of other additives A method comprising:

2. 2. The method of claim 1, wherein the semi-crystalline aliphatic polyamide is selected from polyamide 4, polyamide 6, polyamide 56, polyamide 46, polyamide 66 and / or polyamide 6 / 66.

3. 3. The method of claim 1, wherein component a) is present in an amount of 15 to 45% by weight, based on the total weight of the polyamide composition.

4. 4. The method according to any one of claims 1 to 3, wherein the at least one long chain aliphatic polyamide is selected from polyamide 1212, polyamide 610, polyamide 612, polyamide 1010 and polyamide 6 / 6.

36.

5. 5. The method according to claim 1, wherein component b) is present in an amount of 5 to 30% by weight, based on the total weight of the polyamide composition.

6. 6. The method of any one of claims 1 to 5, wherein the flame retardant comprises c1) 3 to 20% by weight of red phosphorus, and c2) 1 to 10% by weight of a triazine-based flame retardant, based on the total weight of the polyamide composition.

7. 7. The method of claim 6, wherein the triazine-based flame retardant is selected from melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, dimelamine pyrophosphate, dimerazine phosphate, or melamine polyphosphate.

8. 8. The method according to any one of claims 1 to 7, wherein the flame retardant c) is present in an amount of 4 to 25% by weight, based on the total weight of the polyamide composition.

9. 9. The method of claim 1, wherein the filler is glass fiber.

10. 10. The method of any one of claims 1 to 9, wherein the impact modifier is selected from maleic anhydride functionalized polyolefins, maleic anhydride functionalized polyethylene copolymers, glycidyl methacrylate functionalized ethylene terpolymers, or combinations thereof.

11. 11. The method according to any one of claims 1 to 10, wherein the weight ratio of components a) and b) in the polyamide composition is from 5:1 to 1:

1.

12. 12. The method according to any one of claims 1 to 11, wherein the weight ratio of components a) and b) in the polyamide composition is from 4:1 to 1:

1.

13. 13. The method of any one of claims 1 to 12, wherein the voltage is greater than or equal to 1.2 kV and less than or equal to 2 kV.

14. The polyamide composition a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 4 to 25 wt. % of a flame retardant comprising red phosphorus as component c1) and a triazine-based flame retardant as component c2), d) 0 to 50% by weight of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by weight of other additives 14. The method of any one of claims 1 to 13, comprising:

15. 15. The method according to any one of claims 1 to 14, wherein the polyamide composition is used for the manufacture of a nut or body of a photovoltaic connector, or an electrically insulating plastic part.

16. The following ingredients: a) 10 to 50% by weight of at least one semi-crystalline aliphatic polyamide having an average of 3 to 5 carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; b) 1 to 40% by weight of at least one long-chain aliphatic polyamide having an average of 6 or more carbon atoms per amide group, excluding the carbon atoms of the carbonyl groups; c) 4 to 25 wt. % of a flame retardant comprising red phosphorus as component c1) and a triazine-based flame retardant as component c2), d) 0 to 50% by weight of fibrous and / or particulate fillers; e) 1 to 25% by weight of an impact modifier, and f) 0 to 20% by weight of other additives Including, the at least one long chain aliphatic polyamide is selected from PA7, PA8, PA9, PA11, PA12, PA68, PA610, PA612, PA614, PA618, PA88, PA810, PA812, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PA1313, PA1410, PA1412, PA1414, PA1418, PA6.36, PA6 / 6.36, PA66 / 610, PA6 / 610 and PA66 / 6 / 610, Polyamide composition.

17. 17. The polyamide composition of claim 16, wherein the weight ratio of components a) and b) in the polyamide composition is from 5:1 to 1:

1.

18. 18. The polyamide composition according to claim 16 or 17, wherein component c1) is present in an amount of 3 to 15% by weight of the polyamide composition, and component c2) is present in an amount of 1 to 10% by weight of the polyamide composition.

19. 19. An article made from a polyamide composition as defined in any one of claims 1 to 18.

20. 20. The article of claim 19, which is a nut or body of a photovoltaic connector, or an electrically insulating plastic part(s).

21. 20. Use of a polyamide composition according to any one of claims 1 to 18 for improving inclined plane tracking properties at voltages above 1 kV and up to 2 kV.

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