EP4314140A1 - Compositions de polyamide - Google Patents

Compositions de polyamide

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Publication number
EP4314140A1
EP4314140A1 EP21805487.2A EP21805487A EP4314140A1 EP 4314140 A1 EP4314140 A1 EP 4314140A1 EP 21805487 A EP21805487 A EP 21805487A EP 4314140 A1 EP4314140 A1 EP 4314140A1
Authority
EP
European Patent Office
Prior art keywords
mass
parts
formula
particularly preferably
iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21805487.2A
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German (de)
English (en)
Inventor
Jochen Endtner
Matthias Bienmüller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP4314140A1 publication Critical patent/EP4314140A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to compositions and products based on at least one polyamide containing at least one aluminum salt of an organic phosphorus compound of the general formula (I) and at least one organic phosphinic acid salt and/or at least one diphosphinic acid salt, a process for their preparation and their uses.
  • polyamides Due to their good mechanical stability, chemical resistance and good processability, polyamides are an important material, for example for use in motor vehicles, in components for the electrical and electronics industry or in household appliances. When polyamides are used in the vicinity of live parts, flame-retardant materials are often used to counteract the risk of fire caused by overheated wires or contacts. Depending on the area of application, not only are good self-extinguishing properties, in particular a UL94 V-0 classification according to Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", p. 14 to p. 18 Northbrook 1998, but also low flammability.
  • IEC60335-1 stipulates a glow wire test on the finished part in accordance with IEC60695-2-11 for components in unattended household appliances that are within 3mm of live parts with currents >0.2A.
  • a glow wire temperature of 750°C there must be no flaming for more than 2 seconds.
  • test results on the finished part do not correspond directly to test results that were carried out on a defined round plate at the same glow wire temperature in accordance with IEC60695-2-13 due to the undefined geometry of finished parts or metal contacts that impair the heat flow, especially according to IEC60695-2-13 Specimen is still considered not to be ignited if it shows a flame appearance for less than 5 seconds.
  • the classification "GWIT 775°C" is awarded if 3 test panels measured in a row at 750°C show no flames > 5 seconds.
  • halogen-free flame-retardant polyamides In the field of polyamides, there has recently been an increasing demand for halogen-free solutions, which, in addition to ecological reasons, is also due to the fact that halogen-free flame-retardant polyamides generally have a lower density and higher tracking resistance according to IEC60112-2010 compared to halogen-containing systems. Both play an important role, especially in drive systems in electromobility.
  • a high impact strength combined with high strength and rigidity is also essential for widespread use in technical applications, which allows the designer to design a component that saves material and thus also weight and resources.
  • EP 0 792 912 A2 describes calcium or aluminum salts of ethylmethylphosphinic acid, of ethane-1,2-bismethylphosphinic acid and of methylpropylphosphinic acid and finally the aluminum salt of methyl-octylphosphinic acid.
  • Polyamide 66 and 30% by weight of calcium salt or aluminum salt of ethylmethylphosphinic acid were used to produce compounds reinforced with 30% by weight of glass fibers without further additives such as processing stabilizers. Both the calcium salt and the aluminum salt of ethylmethylphosphinic acid achieved a V0 classification with a wall thickness of 1.6 mm and 1.2 mm.
  • compositions according to the invention should even have the V0 classification according to Underwriters Laboratories Inc. Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, pp. 14-18 Northbrook 1998 achieve wall thicknesses of only 0.75 mm, or at least show no deterioration in direct comparison with the compositions of EP 0 792 912 A2.
  • the IZOD impact strength according to DIN EN ISO 180 used in the context of the present invention to obtain mechanical parameters can be used both for rigid thermoplastic injection molding and extrusion molding compounds, duroplastic materials and thermotropic liquid-crystalline polymers and for filled and reinforced materials.
  • test specimens to be used here can be produced according to the relevant molding compound standard or by pressing and injection molding, or they can be taken from multi-purpose test specimens (DIN EN ISO 527 [2]).
  • DIN EN ISO 527 [2] The dimensions of the unnotched test specimen used within the scope of the present invention according to DIN EN ISO 3167, Type A are:
  • Width b (10.0 ⁇ 0.2) mm
  • Thickness h (4.0 ⁇ 0.2) mm
  • a high laser transmission is a laser transmission of at least 30%, preferably at least 40%, particularly preferably at least 50% measured on small plates with a thickness of 0.75 mm using the LPKF TMG3 transmission measuring device from LPKF Laser & Electronics AG, Garbsen, Germany a laser wavelength of 980 nm.
  • the transmission meter LPKF TMG3 is a certified, traceably calibrated measuring instrument. Its measuring equipment capability was verified within the scope of a statistical measuring system analysis (MSA). The device also meets the specifications of the automotive standard IATF 16949 and is therefore directly qualified for standard-compliant quality assurance.
  • the measurements within the The present invention is based on DVS Guideline 2243 (01/2014) "Laser beam welding of thermoplastics” using round plates with a diameter of 80 mm and a thickness of 0.75 mm in the near infrared (NIR).
  • the transmission measuring device LPKF TMG3 from the company LPKF Laser & Electronics AG is calibrated before the measurements with a measurement standard generated according to DIN EN ISO/IEC 17025.
  • the measurements are carried out at a laser wavelength of 980 nm.
  • the invention relates to polymer compositions containing A) to 100 parts by mass of polyamide 66
  • R 1 , R 2 are identical or different and are linear or branched C1-C6-alkyl and / or C6-Ci4-aryl
  • R 3 is linear or branched CrCio-alkylene, C 6 -Cio-arylene or C1-C6-
  • M is aluminum, zinc or titanium, m is an integer from 1 to 4; n is an integer from 1 to 3, x is 1 and 2, where n, x and m in formula (III) can only be integers such that the diphosphinic acid salt of the formula (III) as a whole is uncharged, and
  • the invention also relates to products based on the compositions according to the invention, in particular products for electromobility, for household appliances and in the electronics and electrical sectors.
  • the present invention also relates to the use of 2 to 100 parts by mass, preferably 5 to 60 parts by mass, particularly preferably 7 to 40 parts by mass, particularly preferably 8 to 20 parts by mass, of at least one aluminum salt of the general formula (I) where R is Ci-Ci2-alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl, and 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to
  • R 1 , R 2 are identical or different and are linear or branched Ci-C 6 -alkyl and/or C6-Ci4-aryl,
  • R 3 is linear or branched CrCio-alkylene, C 6 -Cio-arylene or C1-C6-alkyl-C 6 - Cio-arylene or C 6 -Cio-aryl-Ci-C 6 -alkylene,
  • M is aluminum, zinc or titanium, m is an integer from 1 to 4; n is an integer from 1 to 3, x is 1 and 2, where n, x and m in formula (III) can only be integers such that the diphosphinic acid salt of the formula (III) as a whole is uncharged, in each case based on 100 parts by mass of polyamide 66 with 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 15 to 120 parts by mass, in particular preferably 20 to 90 parts by mass of at least one filler and/or reinforcing material, for the production of laser-transparent compositions or products, preferably also with a GW IT for 0.75 mm wall thicknesses of at least 775 e C.
  • inventive polyamide 66-based polymer compositions for use in products in electromobility, in household appliances and in the electronics and electrical sector is carried out by mixing the components A), B), C) and D) to be used as starting materials in at least one mixing tool in the mass ratios given above.
  • molding materials based on the polymer compositions according to the invention are obtained as intermediates.
  • These molding compositions can either consist exclusively of components A), B), C) and D), or they can also contain at least one further component. If laser-transparent polymer compositions are to be provided, further components should be selected in such a way that laser-absorbing additives are not used.
  • the subject of the present invention is a process for the production of products, preferably products for electromobility, for household appliances and in the electronics and electrical sector, by combining component A) with 100 parts by weight of polyamide 66
  • R 1 , R 2 are identical or different and are linear or branched Ci-C 6 -alkyl and/or C6-Ci4-aryl,
  • R 3 is linear or branched CrCio-alkylene, C 6 -Cio-arylene or C1-C6-alkyl-C 6 - Cio-arylene or C 6 -Cio-aryl-Ci-C 6 -alkylene,
  • M is aluminum, zinc or titanium, m is an integer from 1 to 4; n is an integer from 1 to 3, x is 1 and 2, where n, x and m in formula (III) can only be integers such that the diphosphinic acid salt of the formula (III) as a whole is uncharged, as well as with
  • the components are preferably kneaded, compounded, extruded or rolled to form a molding compound. This mixing preferably takes place at a temperature in the range from 270 to 300° C., particularly preferably by compounding on a co-rotating twin-screw extruder or Buss kneader. It can be advantageous to pre-mix individual components.
  • aryl group (abbreviated: Ar) is an organic chemical radical with an aromatic backbone.
  • Aryl is thus the general term for a monovalent atomic group derived from aromatic hydrocarbons by removing a hydrogen atom bonded to the ring.
  • aryl groups are derived from benzene (C 6 H 6 ), the simplest aryl group is phenyl (Ph), (-C 6 H 5 ).
  • Aryl groups can occur either as a fragment of a molecule or as an unstable free radical.
  • the invention also relates to polymer compositions containing, in addition to components A) to D), at least one other additive different from components B), C) and D), preferably at 0.01 to 100 parts by mass, particularly preferably 0.05 to 50 parts by mass, very particularly preferably 0.1 to 30 parts by mass, based in each case on 100 parts by mass of component A), with the proviso that laser absorbers are not used to obtain laser transparency.
  • the polyamide 66 [CAS No. 32131-17-2] to be used according to the invention as component A) in the context of the present invention preferably has a 0.5% by weight solution in 96% by weight sulfuric acid according to ISO 307 at 25
  • the viscosity number to be determined °C is in the range from 90 to 180 ml/g, particularly preferably in the range from 100 to 165 ml/g and very particularly preferably in the range from 110 to 140 ml/g.
  • Polyamide 66 poly(/V,/V-hexamethylene adipamide)poly(hexamethylene adipamide) to be used with preference according to the invention as component A) is available, for example, as Ultramid® A24E01 from BASF SE, Ludwigshafen.
  • the identification of the polyamides used in the context of the present application corresponds to the international standard ISO 1874-1, the first digit(s) being the number of carbon atoms in the starting diamine and the last digit(s) being the number of carbon atoms in the Specify dicarboxylic acid. If two numbers are given, as in the case of polyamide 66 (PA66), this means that the starting point is a dicarboxylic acid, in the case of PA 66 adipic acid, which has been reacted with flexamethylenediamine.
  • PA66 polyamide 66
  • the polyamide 66 to be used according to the invention as component A) can also be used in a mixture with at least one other polyamide and/or at least one other polymer. Therefore, all are included according to the invention Polyamide 66 based copolyamides.
  • Preferred other polymers are selected from the group consisting of polyethylene, polypropylene and acrylonitrile-butadiene-styrene copolymer (ABS). If at least one other polyamide or at least one other polymer is used, this is preferably or optionally done using at least one compatibilizer.
  • additives preferably mold release agents, stabilizers and/or flow aids known to those skilled in the art, can be admixed to the polyamide 66 to be used as component A) in the melt.
  • Component B) At least one aluminum salt of the general formula (I) is used as component B) to be used according to the invention, where R is Ci-Ci2-alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl.
  • These aluminum salts of organic phosphorus compounds of the general formula (I) to be used according to the invention as component B) in the context of the present invention can be prepared by various processes and synthesized from different building blocks.
  • a reaction kettle is charged with 83 g of methylphosphonic acid and heated to 120°C.
  • An intermediate prepared from 50 g methylphosphonic acid and 35.4 g aluminum tris(isopropoxide) is added to the reaction kettle in the presence of water.
  • the resulting solution which contains methylphosphonic acid and aluminum methylphosphonate in a molar ratio of 5:1 as intermediates, is heated to 240° C. with mechanical stirring.
  • the empirical formula (Ia) represents repeating monomer units (ie coordination units) of a coordination polymer which is in crystal form.
  • Component B) of the formula (Ia) with a molar ratio of phosphorus to aluminum of 4:1, to be determined by ICP-OES elemental analysis, is particularly preferred, needle-shaped crystals being particularly preferred. See Example 3 in WO 2021/076169 A1 and ICP-OES see: https://www.itmc.rwth-aachen.de/go/id/gden
  • compositions according to the invention contain at least one phosphinic acid salt of the formula (II) and/or at least one diphosphinic acid salt of the formula (III) and/or their polymers.
  • phosphinic acid salts of the formula (II) and diphosphinic acid salts of the formula (III) are also referred to as phosphinates.
  • M in the formulas (II) or (III) is preferably aluminum.
  • R 1 , R 2 in the formulas (II) and (III) are preferably identical or different and are linear or branched C 1 -C 6 -alkyl and/or phenyl.
  • R 1 , R 2 are particularly preferably identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl.
  • R 3 in formula (III) is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene , tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.
  • R 3 is particularly preferably phenylene or naphthylene.
  • Suitable phosphinates are described in WO-A 97/39053, the content of which in relation to the phosphinates is also covered by the present application.
  • Particularly preferred phosphinates for the purposes of the present invention are aluminum and zinc salts of dimethyl phosphinate, ethyl methyl phosphinate, diethyl phosphinate and methyl n-propyl phosphinate, and mixtures thereof.
  • n in formula (II) is preferably 2 and 3, particularly preferably 3.
  • n in formula (III) is preferably 1 and 3, particularly preferably 3.
  • x in formula (III) is 1 and 2, particularly preferably 2.
  • Aluminum tris(diethylphosphinate) [CAS No. 225789-38-8], which is available, for example, from Clariant International Ltd. Muttenz, Switzerland under the trade name Exolit® OP1230 or Exolit® OP1240 .
  • Component C) is preferably used in lower proportions by mass than component B).
  • Polymer compositions according to the invention contain at least one filler and/or reinforcing material as component D). Mixtures of two or more different fillers and/or reinforcing materials can also be used here. At least one filler and/or reinforcing material from the group consisting of carbon fibers [CAS No. 7440-44-0], glass beads or solid or hollow glass beads, glass fibers, ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content is preferably used as component D). 1% (E-Glass) [CAS No. 65997-17-3], Amorphous Silica [CAS No. 7631-86-9], Quartz Flour [CAS No. 14808-60-7], Calcium Silicate [CAS No.
  • glass fibers and wollastonite are particularly preferred, with glass fibers being most preferred.
  • carbon fibers can also be used as a filler or reinforcing material.
  • glass as filler and/or reinforcing material as component D.
  • Glass according to DIN1259-1 is preferably used.
  • Glass in the form of solid or hollow glass beads, glass fibers, ground glass or aluminum borosilicate glass with an alkali content of 1% (E glass) [CAS No. 65997-17-3] is very particularly preferably used.
  • short fibers with a length in the range from 0.1 to 1 mm
  • long fibers with a length in the range from 0.1 to 1 mm Length in the range of 1 to 50 mm and continuous fibers with a length L > 50 mm.
  • Short fibers are preferably used in injection molding technology and can be processed directly with an extruder.
  • Long fibers can also be processed in extruders.
  • Endless fibers are used as rovings or fabrics in fiber-reinforced plastics. Products with continuous fibers achieve the highest stiffness and strength values.
  • ground glass fibers are offered, the length of which after grinding is typically in the range from 70 to 200 ⁇ m.
  • preferred glass fibers to be used as component D) are cut long glass fibers with an average initial length in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm, very particularly preferably in the range from 2 to 7 mm.
  • Preferred glass fibers to be used as component D) have an average fiber diameter in the range from 7 to 18 gm, particularly preferably in the range from 9 to 15 gm. Scanning electron microscopy (SEM) can be used as a possible method for determining the fiber diameter
  • the glass fibers to be used preferably as component D) are finished with a suitable sizing system or a flaking agent or flaking agent system.
  • a sizing system or a silane-based flattening agent is preferably used.
  • Particularly preferred silane-based flattening agents for the treatment of the glass fibers to be used preferably as component D) are silane compounds of the general formula (IV)
  • X is NFI 2 -, carboxyl, FIO or HsC CH CHs 0
  • q in formula (IV) is an integer from 2 to 10, preferably 3 to 4
  • r in formula (IV) is an integer of 1 to 5, preferably 1 to 2
  • k in formula (IV) is an integer from 1 to 3, preferably 1.
  • Particularly preferred flattening agents are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or carboxyl group as substituent X in formula (IV), carboxyl groups being particularly preferred.
  • the flattening agent preferably the silane compounds of the formula (IV) is used in amounts of 0.05 to 2% by weight, particularly preferably in amounts of 0.25 to 1.5% % by weight and very particularly preferably in amounts of from 0.5 to 1% by weight, based in each case on 100% by weight of component D).
  • the glass fibers preferably to be used as component D) can be shorter in the composition or in the product than the glass fibers originally used due to the processing to the composition or to the product. That's how it is After processing, the arithmetic mean value of the glass fiber length, which can be determined using high-resolution X-ray computed tomography, is often only in the range of 150 gm to 300 gm.
  • glass fibers are manufactured using the melt spinning process (jet drawing, rod drawing and jet blowing processes).
  • the hot glass mass flows through hundreds of jet holes in a platinum spinning plate using gravity.
  • the filaments can be drawn in unlimited length at a speed of 3 - 4 km/minute.
  • E-glass the most used material with an optimal price-performance ratio (E-glass from R&G) with a composition according to https://www.r-g.de/wiki/Glass fibers of 53-55% S1O 2 , 14-15 % Al 2 O 3 , 6-8% B 2 O 3 , 17-22% CaO, ⁇ 5% MgO, ⁇ 1% K 2 0 or Na2Ü and approx. 1% other oxides;
  • H-Glass, hollow glass fibers for reduced weight R&G glass hollow fiber fabrics 160 g/m 2 and 216 g/m 2 );
  • Quartz glass with high temperature resistance.
  • E-glass fibers have gained the greatest importance for plastic reinforcement.
  • the "E” in E-glass stands for electrical glass, as it was originally used primarily in the electrical industry.
  • glass melts are made from pure quartz with additions of limestone, kaolin and boric acid. In addition to silicon dioxide, they contain varying amounts of various metal oxides.
  • the composition determines the properties of the products. According to the invention, preference is given to using at least one type of glass fiber from the group E glass, H glass, R,S glass, D glass, C glass and quartz glass, particularly preferably glass fibers made from E glass. Glass fibers from E-glass are the most widely used reinforcement material. The strength properties correspond to those of metals (e.g. aluminum alloys), although the specific gravity of laminates containing E-glass fibers is lower than that of metals. E-glass fibers are non-flammable, heat-resistant up to approx. 400°C and resistant to most chemicals and weather influences.
  • needle-shaped, mineral fillers are understood to mean a mineral filler with a strongly pronounced needle-shaped character.
  • Wollastonite is the preferred acicular mineral filler to be used as component D).
  • the needle-shaped, mineral filler preferably has a length:diameter ratio, which can be determined for example by means of scanning electron microscopy, in the range from 2:1 to 35:1, particularly preferably in the range from 3:1 to 19:1, particularly preferably in the range of 4:1 up to 12:1.
  • the mean particle size of the acicular, mineral fillers which can be determined, for example, by means of scanning electron microscopy, is preferably less than 20 ⁇ m, particularly preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m.
  • d90 values their determination and their significance, reference is made to Chemie Ingenieurtechnik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d90 value is the particle size below which 90% of the particles are located.
  • the non-fibrous and non-foamed ground glass is of particulate, non-cylindrical shape and has a length-to-thickness ratio to be determined by means of laser diffractometry in accordance with ISO 13320 of less than 5, preferably less than 3, particularly preferably less than 2. The value is zero of course excluded.
  • the non-foamed and non-fibrous ground glass to be used as component D) in one embodiment is also characterized in that it does not have the glass geometry with a cylindrical or oval cross section that is typical for fibrous glass having a length-to-diameter ratio (L/D ratio) greater than 5, which can be determined, for example, by means of scanning electron microscopy.
  • L/D ratio length-to-diameter ratio
  • the non-foamed and non-fibrous ground glass to be used according to the invention as component D) in one embodiment is preferably obtained by grinding glass with a mill, preferably a ball mill, and particularly preferably with subsequent classification or sieving.
  • Preferred starting materials for grinding the non-fibrous and non-foamed, ground glass to be used as component D) in one embodiment are also glass waste, such as is particularly the case in the manufacture of glass products as an undesirable by-product and/or as a main product that does not meet specifications (so-called off-spec goods ) attack.
  • the glass can be colored, with non-colored glass being preferred as the starting material for use as component D).
  • At least one further additive different from components B), C) and D) is used as component E).
  • Preferred additives to be used as component E) are antioxidants, heat stabilizers, UV stabilizers,
  • Gamma radiation stabilizers can be used alone or in a mixture or in the form of masterbatches.
  • additives to be used as component E) are to be selected in such a way that no laser absorbers, such as soot in particular, are used.
  • Laser-absorbing additives are sufficiently known to those skilled in the art.
  • Preferred thermal stabilizers of component E) are sterically hindered phenols, in particular those containing at least one 2,6-di-tert-butylphenyl group and/or 2-tert-butyl-6-methylphenyl group, particularly preferably N,N'- 1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide] [CAS No.
  • phosphites available for example as Irganox 1098 from BASF, Ludwigshafen, Germany, also phosphites , hypophosphites, especially sodium hypophosphite NaH 2 P0 2, hydroquinones, aromatic secondary amines, substituted resorcinols, Salicylates, benzotriazoles and benzophenones, 3,3'-thiodipropionic acid esters and variously substituted representatives of these groups or mixtures thereof.
  • copper salts preferably in combination with sodium hypophosphite NaH 2 PC>2, can also be used as thermal stabilizers of component E).
  • Copper(I) iodide [CAS No. 7681-65-4] and/or copper(triphenylphosphino)iodide [CAS No. 47107-74-4] is preferably used as the copper salt.
  • the copper salts are preferably used in combination with sodium hypophosphite NahhPC ⁇ or with at least one alkali metal iodide.
  • Preferred alkali metal iodide is potassium iodide [CAS No. 7681-11-0].
  • Heat stabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 parts by weight, particularly preferably 0.05 to 1 part by weight, based in each case on 100 parts by weight of component A).
  • UV stabilizers to be used as component E) are preferably substituted resorcinols, salicylates, benzotriazoles and benzophenones, HALS derivatives (“Hinderd Amine Light Stabilizers”) containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit or benzophenones deployed.
  • UV stabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 parts by weight, particularly preferably 0.1 to 1 part by weight, based in each case on 100 parts by weight of component A).
  • Colorants to be used as component E) are preferably inorganic pigments, in particular ultramarine blue, bismuth vanadate, iron oxide, titanium dioxide, zinc sulfide, tin-titanium-zinc oxides [CAS No. 923954-49-8], also organic colorants, preferably phthalocyanines, quinacridones, benzimidazoles, in particular Ni-2-hydroxy-napthyl-benzimidazole [CAS no. 42844-93-9] and/or pyrimidine-azo-benzimidazole [CAS no. 72102-84-2] and/or Pigment Yellow 192 [CAS No. 56279-27-7], also perylenes, anthraquinones, in particular C.I. Solvent Yellow 163 [CAS No. 13676-91-0] is used, although this list is not exhaustive and the colorants must be selected with particular consideration of the requirements for laser transmission or laser absorption behavior.
  • carbon black and/or nigrosine are also used as colorants.
  • Nucleating agents to be used as component E) are preferably sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide and very particularly preferably talc, although this list is not exhaustive.
  • Flow aids to be used as component E) are preferably copolymers of at least one ⁇ -olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol. Particular preference is given to copolymers in which the ⁇ -olefin is composed of ethene and/or propene and the methacrylic acid ester or acrylic acid ester contains linear or branched alkyl groups having 6 to 20 carbon atoms as the alcohol component. Acrylic acid (2-ethyl)hexyl ester is very particularly preferred.
  • Copolymers suitable as flow aids are distinguished not only by their composition but also by their low molecular weight. Accordingly, for the compositions to be protected from thermal degradation according to the invention, above all copolymers are suitable which have an MFI value measured at 190° C. and a load of 2.16 kg of at least 100 g/10 min, preferably at least 150 g/10 min , particularly preferably at least 300 g / 10 min.
  • the MFI, melt flow index is used to characterize the flow of a melt of a thermoplastic and is subject to the standards ISO 1133 or ASTM D 1238.
  • a particularly preferred flow aid is a copolymer of ethene and 2-ethylhexyl acrylate with MFI 550, known as Lotryl® 37EH550.
  • Chain-extending additives to be used as component E) and hydrolysis stabilizers are preferably difunctional or polyfunctional additives with a branching or chain-extending action, containing at least two functional groups with a branching or chain-extending action per molecule.
  • Low molecular weight or oligomeric compounds which have at least two chain-extending functional groups per molecule which can react with primary and/or secondary amino groups and/or amide groups and/or carboxylic acid groups are preferred as branching or chain-extending additives.
  • Functional groups having a chain-extending action are preferably isocyanates, carbodiimides, alcohols, epoxides, maleic anhydride, oxazolines, oxazines, oxazolones, preference being given to epoxides.
  • Particularly preferred difunctional or polyfunctional branching or chain-extending additives are diepoxides based on diglycidyl ether (bisphenol and epichlorohydrin), based on amine epoxy resin (aniline and epichlorohydrin), based on diglycidyl ester (cycloaliphatic dicarboxylic acids and epichlorohydrin) individually or in mixtures, and 2,2 -Bis[p-hydroxyphenyl]propane diglycidyl ether, bis[p-(N-methyl-N-2,3-epoxypropylamino)phenyl]methane and epoxidized fatty acid esters of glycerol containing at least two epoxide groups per Molecule.
  • diglycidyl ether bisphenol and epichlorohydrin
  • amine epoxy resin aniline and epichlorohydrin
  • diglycidyl ester cycloaliphatic dicarboxylic acids and epichlorohydrin
  • Particularly preferred di- or polyfunctional additives with a branching or chain-extending effect are glycidyl ethers, very particularly preferably bisphenol A diglycidyl ether [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, and also very particularly preferably epoxidized soybean oil [CAS No. 8013- 07-8] and/or epoxidized linseed oil.
  • Plasticizers preferably used as component E) are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oils or N-(n-butyl)benzenesulfonamide.
  • Elastomer modifiers to be used with preference as component E) include, inter alia, one or more graft polymers of
  • the graft base E.2 generally has an average particle size d50 value, to be determined by means of laser diffractometry in accordance with ISO 13320, of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • Monomers for E.1 are preferably mixtures of
  • E.1 .1 50 to 99 wt. especially. methyl methacrylate, ethyl methacrylate and
  • Preferred monomers E.1.1 are to be selected from at least one of the monomers styrene, a-methylstyrene and methyl methacrylate
  • preferred monomers E.1.2 are selected selects from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.
  • Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.
  • Suitable graft bases E.2 for the graft polymers to be used in the elastomer modifiers are diene rubbers, EPDM rubbers, ie those based on ethylene/propylene and optionally diene, and also acrylate, polyurethane, silicone, chloroprene and ethylene/vinyl acetate rubbers.
  • EPDM stands for ethylene propylene diene rubber.
  • Preferred graft bases E.2 are diene rubbers, in particular based on butadiene, isoprene, etc. or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers, in particular according to E.1.1 and E.1.2, with the proviso that the glass transition temperature of the Component E.2 is ⁇ 10°C, preferably ⁇ 0°C, particularly preferably ⁇ -10°C.
  • Particularly preferred grafting bases E.2 are ABS polymers (emulsion, bulk and suspension ABS), where ABS stands for acrylonitrile-butadiene-styrene, as z. 19 (1980), pp. 277-295.
  • the gel content of the graft base E.2 is preferably at least 30% by weight, particularly preferably at least 40% by weight (measured in toluene).
  • the elastomer modifiers or graft polymers to be used as component E) are prepared by free-radical polymerization, preferably by emulsion, suspension, solution or bulk polymerization, in particular by emulsion or bulk polymerization.
  • graft rubbers are ABS polymers which are produced by redox initiation using an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • graft polymers are also understood according to the invention as products which are obtained by (co)polymerization of the graft monomers in the presence of the graft base and are also obtained during work-up.
  • Acrylate rubbers which are also suitable are based on graft bases E.2, which are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include Ci-Cs-alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl ester; Haloalkyl esters, preferably halo-Ci-Cs-alkyl esters such as chloroethyl acrylate, glycidyl esters and mixtures of these monomers.
  • graft polymers with butyl acrylate as the core and methyl methacrylates as the shell in particular.
  • Paraloid® EXL2300 from Dow Corning Corporation, Midland Michigan, USA, is particularly preferred.
  • crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups.
  • Very particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinked monomers is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the graft base E.2.
  • Preferred “other” polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base E.2, are acrylonitrile, styrene, ⁇ -methylstyrene, acrylamide, vinyl C 1 -C 6 -alkyl ether, methyl methacrylate, glycidyl methacrylate , butadiene.
  • Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • suitable graft bases according to E.2 are silicone rubbers with graft-active sites, as described in DE-A 3,704,657, DE-A 3,704,655, DE-A 3,631,540 and DE-A 3,631,539.
  • Preferred graft polymers with a silicone component are those which have methyl methacrylate or styrene-acrylonitrile as the shell and a silicone/acrylate graft as the core.
  • Styrene-acrylonitrile to be used preferably as the shell is Metabien® SRK200 .
  • Methyl methacrylate to be used preferably as the shell is Metabien® S2001 or Metabien® S2030 or Metabien® SX-005. Metabien® S2001 is particularly preferably used.
  • the products with the trade name Metabien ® are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate ; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinked monomers is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the graft base E.2.
  • Preferred “other” polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base E.2, are acrylonitrile, styrene, ⁇ -methylstyrene, acrylamide, vinyl C 1 -C 6 -alkyl ether, methyl methacrylate, glycidyl methacrylate, butadiene .
  • Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • elastomer modifiers which are not based on graft polymers and have glass transition temperatures ⁇ 10° C., preferably ⁇ 0° C., particularly preferably ⁇ 20° C., can also be used.
  • Lubricants and/or mold release agents to be used as component E) are preferably long-chain fatty acids, in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, and their ester derivatives, in particular those based on pentaerythritol, in particular fatty acid esters of pentaerythritol or amide derivatives , in particular ethylene-bis-stearylamide, montan waxes and low molecular weight polyethylene or polypropylene waxes.
  • long-chain fatty acids in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, and their ester derivatives, in particular those based on pentaerythritol, in particular fatty acid esters of pentaerythritol or amide derivatives , in particular ethylene-bis-stearylamide, montan waxes and low molecular weight polyethylene or polypropylene waxes.
  • montan waxes are mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.
  • lubricants and/or mold release agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with saturated aliphatic alcohols or amides of amines having 2 to 40 carbon atoms with unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms C atoms or, instead of the carboxylic acids, metal salts of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms are used.
  • Lubricants and/or mold release agents to be used with particular preference as component E) are to be selected from the group consisting of pentaerythritol tetrastearate [CAS No. 115-83-3], ethylene bisstearylamide, calcium stearate and ethylene glycol dimontanate. Calcium stearate [CAS No. 1592-23-0] or ethylene-bis-stearylamide [CAS No. 110-30-5] is particularly preferably used. Ethylene-bis-stearylamide (Loxiol® EBS from Emery Oleochemicals) is particularly preferably used.
  • Components to be used with preference as component E) to reduce water absorption are preferably polyesters, polybutylene terephthalate and/or polyethylene terephthalate being preferred and polyethylene terephthalate being very particularly preferred.
  • the polyesters are preferably used in concentrations of 5 to 20% by weight and particularly preferably in concentrations of 7 to 15% by weight, based in each case on the entire polymer composition and with the proviso that the sum of all percentages by weight of the polymer composition is always 100% by weight % results.
  • Further flame retardants to be used with preference as component E) are mineral flame retardants different from component B) and C), nitrogen-containing flame retardants or phosphorus-containing flame retardants.
  • flame retardants which, as laser absorbers, have a negative effect on the laser transmission of a product based on polymer compositions according to the invention, if the need requires it, taking into account the disadvantages caused by the loss of laser transparency.
  • magnesium hydroxide is particularly preferred.
  • Magnesium hydroxide [CAS No. 1309-42-8] can be contaminated due to its origin and production method. Typical impurities are, for example, species containing silicon, iron, calcium and/or aluminum, which can be embedded in the magnesium hydroxide crystals, for example in the form of oxides.
  • the magnesium hydroxide to be used as a mineral flame retardant can be uncoated or provided with a size.
  • the magnesium hydroxide to be used as a mineral flame retardant is preferably provided with sizes based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes.
  • Magnesium hydroxide to be used preferably as a mineral flame retardant has an average particle size d50 to be determined by laser diffractometry according to ISO 13320 in the range from 0.5 ⁇ m to 6 ⁇ m, with a d50 in the range from 0.7 ⁇ m to 3.8 ⁇ m being preferred and a d50 in the range from 1.0 pm to 2.6 pm is particularly preferred.
  • Mineral flame retardants to be used according to the invention as component E) are suitable types of magnesium hydroxide, in particular Magnifin® H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag® Q2015 TC from Penoles, Mexico City, Mexico.
  • Preferred nitrogen-containing flame retardants to be used as component E) are the reaction products of trichlorotriazine, piperazine and morpholine according to CAS no Melamines, in particular Meiern, melam, melon or more highly condensed compounds of this type.
  • Preferred inorganic nitrogen-containing compounds are ammonium salts.
  • salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives in particular aluminum hydroxide or Ca-Mg carbonate hydrates (DE-A 4 236 122) as component E) to be used flame retardants.
  • flame retardant synergists from the group of oxygen-, nitrogen- or sulphur-containing metal compounds.
  • Zinc-free compounds are preferred, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, magnesium nitride, calcium phosphate, calcium borate, magnesium borate or mixtures thereof.
  • zinc-containing compounds can also be used as flame retardants of component E)—if required.
  • Flierzu preferably include zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.
  • calcium stannate and calcium hydroxystannate can also be used as flame retardants of component E) if required.
  • Flame retardants to be used as component E) are preferably also aluminum salts of phosphonic acid.
  • phosphonic acid is the substance with the molecular formula H 3 PO 3 [CAS no. 13598-36-2] (http://de.wikipedia.org/wiki/Phosphons%C3%A4ure).
  • the salts of phosphonic acid are called phosphonates.
  • AF Holleman, E. Wiberg Textbook of Inorganic Chemistry. 101st edition.
  • phosphorous acid or "phosphite” should only be used for the tautomeric species with a free pair of electrons on the phosphorus.
  • phosphorous acid and “phosphites” were previously also used for the tautomeric forms with double-bonded oxygen to phosphorus, so that in the present invention the terms phosphonic acid and phosphorous acid or phosphonates and phosphites are used synonymously with one another.
  • Preferred aluminum salts of phosphonic acid are at least one from the group consisting of primary aluminum phosphonate [AI(H 2 PO 3 ) 3 ], basic aluminum phosphonate [AI(0H)H 2 R03) 2 2H2O],
  • Preferred alkali metals in formula (VI) are sodium and potassium.
  • the aluminum salts of phosphonic acid described have high laser transmission in polyamides and can be used individually or as a mixture.
  • Particularly preferred aluminum salts of phosphonic acid are selected from the group consisting of primary aluminum phosphonate [AI(H 2 PO 3 ) 3 ], secondary aluminum phosphonate [AI 2 (HP0 3 ) 3 ], basic aluminum phosphonate [AI(OH)H 2 PO 3 ) 2 -2H 2 0],
  • Preferred other phosphorus-containing flame retardants other than component B) and C) are other organic metal phosphinates, red phosphorus, inorganic metal hypophosphites, other metal phosphonates, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO derivatives ), resorcinol bis(diphenyl phosphate) (RDP) including oligomers, bisphenol A bis diphenyl phosphate (BDP) including oligomers, 4,4'-biphenyl bis(diphenyl phosphate), melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminium phosphate ), melamine-poly(zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof.
  • RDP resorcinol bis(diphenyl phosphate)
  • BDP bisphenol A bis diphenyl phosphate
  • BDP including
  • flame retardants to be used as component E) are char formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyether sulfones or polyether ketones, and also anti-drip agents, in particular tetrafluoroethylene polymers.
  • the flame retardants to be used as component E) can be added in pure form or via masterbatches or compacts.
  • halogen-containing flame retardants can also be used as flame retardants—if required, taking into account the disadvantages, inter alia, due to the loss of the flame retardants being halogen-free.
  • Preferred halogen-containing flame retardants are commercially available organic halogen compounds, particularly preferably ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate,
  • Brominated polystyrene is preferably used in an amount of 10-30% by weight, particularly preferably in an amount of 15-25% by weight, in each case based on the total composition, with at least one of the other components being reduced to such an extent that the sum of all percentages by weight is always 100.
  • Brominated polystyrene is commercially available in various product qualities. Examples of these are, for example, Firemaster® PBS64 from Lanxess, Cologne, Germany, and Saytex® HP-3010 from Albemarle, Baton Rouge, USA.
  • At least one laser absorber selected from the group consisting of antimony trioxide, tin oxide, tin orthophosphate, barium titanate, Aluminum oxide, copper hydroxyphosphate, copper orthophosphate, potassium copper diphosphate, copper hydroxide, antimony tin oxide, bismuth trioxide and anthraquinone can be used.
  • Tin oxide, antimony trioxide or antimony tin oxide are particularly preferred.
  • Antimony trioxide is very particularly preferred.
  • the laser absorber in particular the antimony trioxide, can be used directly as a powder or in the form of masterbatches.
  • Preferred masterbatches are those based on polyamide and/or polyolefins, preferably polyethylene.
  • Antimony trioxide is very particularly preferably used in the form of a polyamide 6-based masterbatch.
  • the laser absorber can be used individually or as a mixture of several laser absorbers.
  • Laser absorbers can absorb laser light of a specific wavelength. In practice, this wavelength is in the range from 157 nm to 10.6 pm. Examples of lasers of these wavelengths are described in WO2009/003976 A1. Nd:YAG lasers, with which wavelengths of 1064, 532, 355 and 266 nm can be realized, and CO2 lasers are preferably used.
  • Component C) is preferably used in lower proportions by mass than component B).
  • a preferred subject matter of the present invention is a process for the production of products, preferably products for electromobility, for household appliances and in the electronics and electrical field, wherein the components A) 100 parts by mass of polyamide 66 with
  • the components are preferably kneaded, compounded, extruded or rolled to form a molding compound.
  • This mixing preferably takes place at a temperature in the range from 270 to 300° C., particularly preferably by compounding on a co-rotating twin-screw extruder or Buss kneader. It can be advantageous to pre-mix individual components.
  • a particularly preferred subject matter of the present invention is a process for the production of products, preferably products for electromobility, for household appliances and in the electronics and electrical sectors, where components A) are mixed with 100 parts by weight of polyamide 66
  • Component C) is preferably used in lower proportions by mass than component B).
  • the injection molding process is characterized in that the raw material, preferably in the form of granules, is melted (plasticized) in a heated cylindrical cavity and injected as an injection mass under pressure into a temperature-controlled cavity. After the mass has cooled down (solidified), the injection molded part is removed from the mold.
  • An injection molding machine consists of a clamping unit, the injection unit, the drive and the control.
  • the clamping unit includes fixed and movable clamping plates for the tool, a front plate as well as columns and drive of the moving tool platen. (Toggle joint or hydraulic clamping unit).
  • An injection unit includes the electrically heatable cylinder, the screw drive (motor, gearbox) and the hydraulics for moving the screw and injection unit.
  • the task of the injection unit is to melt the powder or granules, dose them, inject them and push them down (because of contraction).
  • the problem of backflow of the melt within the screw is solved by non-return valves.
  • the present invention consequently also relates to products obtainable by injection molding of the compositions according to the invention.
  • a preferred subject of the invention is also the use of polymer compositions containing
  • R 1 , R 2 are identical or different and are linear or branched C1-C6-alkyl and/or C6-Ci4-aryl,
  • R 3 is linear or branched CrCio-alkylene, C 6 -Cio-arylene or C1-C6-alkyl-C 6 -Cio-arylene or C 6 -Cio-aryl-Ci-C 6 -alkylene,
  • M is aluminum, zinc or titanium, m is an integer from 1 to 4; n is an integer from 1 to 3, x is 1 and 2, where n, x and m in formula (III) can only be integers such that the diphosphinic acid salt of the formula (III) as a whole is uncharged, and D) 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 15 to 120 parts by mass, particularly preferably 20 to 90 parts by mass of at least one filler and/or reinforcing material for the production of products for use in motor vehicles, in components for electrical and electronics industry or in household appliances.
  • the present invention also relates to the use of 2 to 100 parts by mass, preferably 5 to 60 parts by mass, particularly preferably 7 to 40 parts by mass, particularly preferably 8 to 20 parts by mass, of aluminum methylphosphonate of the formula (Ia) and 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass, particularly preferably 10 to 50 parts by mass aluminum tris (diethylphosphinate) and 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 15 to 120 parts by mass , Particularly preferably 20 to 90 parts by mass of glass fibers, based in each case on 100 parts by mass of polyamide 66, for the production of laser-transparent compositions or Products, preferably with a GWIT at 0.75mm wall thickness of at least 775°C.
  • the present invention also relates to the use of 2 to 100 parts by mass, preferably 5 to 60 parts by mass, particularly preferably 7 to 40 parts by mass, particularly preferably 8 to 20 parts by mass, of aluminum methylphosphonate of the formula (Ia) and 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass, particularly preferably 10 to 50 parts by mass aluminum tris (diethylphosphinate), 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 15 to 120 parts by mass , particularly preferably 20 to 90 parts by mass of glass fibers and 0.01 to 30 parts by mass, preferably 0.1 to 15 parts by mass, particularly preferably 0.3 to 5 parts by mass, particularly preferably 0.5 to 3 parts by mass /V,/ ⁇ /-1, 6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide and/or ethylene-bis-stearylamide, each based on 100 parts by
  • Component C) is preferably used in lower proportions by mass than component B).
  • polyamide 66-based polymer compositions were first prepared by compounding.
  • the individual components according to Tab granulated with the glass fibers being metered in with the aid of a side extruder in the rear area of the extruder (near the nozzle).
  • the granulate was processed by injection molding at temperatures in the range of 270 to 290°C to form standard test specimens for the respective tests, with an Arburg 320-type injection molding machine being used for the injection molding. 210-500 was used.
  • a reaction kettle was charged with 83 g of methylphosphonic acid and heated to 120°C.
  • An intermediate prepared from 50 g methylphosphonic acid and 35.4 g aluminum tris(isopropoxide) was added to the reaction kettle in the presence of water.
  • the resulting solution which contained as intermediates methylphosphonic acid and aluminum methylphosphonate in a 5:1 molar ratio, was heated to 240°C with mechanical stirring. Stirring was continued at 240°C for about 30 minutes until a solid formed. Then 500 ml of water were added and this mixture was stirred for 16 h, during which time a uniform slurry formed.
  • the product was finally filtered off, washed with 750 ml and dried.
  • the result was 64.3 g of the product of the formula (Ia) to be used as component B) as fine, colorless crystals, with a yield of 93%.
  • the glow-wire resistance was determined using the glow-wire ignition test GWIT (glow-wire-ignition-temperature) according to DIN EN 60695-2-13. In the GWIT test, the glow wire ignition temperature is specified, which is 25K (or 30K for temperatures in the range from 900°C to 960°C) higher than the maximum
  • Glow wire temperature which, in 3 consecutive tests, does not lead to ignition even during the exposure time of the glow wire.
  • a flame with a burning time of > 5 seconds is considered to be ignition.
  • Round plates with a diameter of 80mm and a thickness of 0.75mm were used for the tests.
  • the actual burning time at a test temperature of 750°C is also given as "GWIT burning time", independent of the maximum GWIT classification achieved.
  • GWIT burning time independent of the maximum GWIT classification achieved.
  • the highest individual burning time of the burning times determined in 3 consecutive tests is listed.
  • the flame retardance of the test specimens with dimensions of 125 mm x 13 mm x 0.75 mm was determined according to the UL94V method (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", p. 14 - 18 Northbrook 1998).
  • the IZOD impact strength was obtained in accordance with ISO180-A on test specimens measuring 80 mm ⁇ 10 mm ⁇ 4 mm.
  • Component A Polyamide 66 (Torzen U3501 NC01, Invista, Wichita, USA) with a viscosity number of 126 ml, measured according to ISO 307 in a 0.5% by weight solution in 96% by weight sulfuric acid at 25° C /G,
  • Component C) aluminum tris(diethylphosphinate), [CAS no. 225789-38-8] (Exolit ®
  • example 1 achieves a VO classification with 0.75 mm wall thicknesses in the UL94 test and also achieves a high GW IT of at least 775° C., with the burning time at a glow wire temperature being 0 seconds, i.e. above the requirement according to the DIN EN 60695-2-13 standard, there is no ignition at all.

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Abstract

La présente invention concerne des compositions à base d'au moins un polyamide contenant au moins un sel d'aluminium d'un composé organophosphoré de formule générale (I), et au moins un sel organique d'acide phosphinique et/ou au moins un sel d'acide diphosphinique, un procédé pour leur préparation et leur utilisation.
EP21805487.2A 2021-03-26 2021-11-02 Compositions de polyamide Pending EP4314140A1 (fr)

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