EP3122810A1 - Compositions ininflammables à base de polyamide - Google Patents

Compositions ininflammables à base de polyamide

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Publication number
EP3122810A1
EP3122810A1 EP15711120.4A EP15711120A EP3122810A1 EP 3122810 A1 EP3122810 A1 EP 3122810A1 EP 15711120 A EP15711120 A EP 15711120A EP 3122810 A1 EP3122810 A1 EP 3122810A1
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EP
European Patent Office
Prior art keywords
weight
compositions
components
compositions according
group
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.)
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EP15711120.4A
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German (de)
English (en)
Inventor
Jochen Endtner
Matthias Bienmüller
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Priority to EP19181252.8A priority Critical patent/EP3578598A1/fr
Publication of EP3122810A1 publication Critical patent/EP3122810A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to polyamide-based compositions having at least one filler from the group of aluminum oxide, boron nitride and aluminum silicate and the use of these compositions for the production of products with increased flame retardance requirements, particularly preferably products with increased filament requirements, in particular components for current and voltage-carrying components in household appliances.
  • Polyamide compositions are used in a variety of applications ranging from automotive to electrical and electronics, due to their excellent strength, toughness, processability, and solvent resistance properties. Especially in the electrical and electronics sector, there are often increased requirements with regard to the flame retardance of the non-metallic insulating materials, materials or products used in these applications due to the increased risk of ignition, triggered for example by short circuits, electric arcs or damaged lines.
  • the non-metallic, insulating materials used must meet the normative requirements regarding their fire resistance according to IEC60335-1, if the distance of the material to live parts is less than 3 mm (see Plastischen, 56th cen ., 2005, No. 4, 66-67).
  • the GWFI is measured according to IEC60695-2-12 on a test plate (round disc) and is a measure of the self-extinguishing behavior of a sample under the influence of a glowing wire.
  • the specimen is pressed against a heated filament with a Newton force for 30 seconds.
  • the penetration depth of the filament is limited to 7 mm.
  • the test is passed if the specimen burns for less than 30 seconds after removal of the filament and if a tissue paper lying under the specimen does not ignite.
  • plastics due to their chemical composition, many plastics, such as polyamide, are highly flammable. In order to be able to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislator, plastics are therefore generally equipped with flame retardants.
  • halogen-containing flame retardants such as e.g. brominated polystyrenes or decabromodiphenylethane, which are most often used in combination with a flame retardant synergist such as e.g. Antimony trioxide, are used.
  • non-halogenated flame retardants nitrogen-containing derivatives, in particular melamine cyanurate, water-releasing compounds, in particular magnesium hydroxide, or phosphorus-containing components, in particular red phosphorus, melamine polyphosphate or the salts of phosphinic acids (phosphinates) are frequently used for polyamides (DE-A-2 252 258 and US Pat DE-A-2 447 727).
  • a disadvantage of the use of these flame retardants is in particular their systemic low decomposition temperature and, consequently, a small processing window of such flame retardant-containing molding compositions in compounding, in injection molding or in extrusion.
  • the compounding takes place in at least one mixing tool, preferably in extruders, particularly preferably in co-rotating twin-screw extruders, counter-rotating twin-screw extruders, by planetary roller extruder or co-kneader, and comprises the processing operations conveying, melting, dispersing, mixing, degassing and pressure build-up.
  • halogen-containing flame retardants may accumulate in organisms when introduced into the environment because of their high persistence.
  • halogen-free flame retardants based on phosphorus u.a. the energy-intensive production of disadvantage.
  • Example II herein relates to a molding compound of polyamide 46 and boron nitride. The composition is mixed in an extruder and subjected to an injection molding process for the production of test plates. Glow wire resistance was determined using the GWFI glow wire test to IEC 60695-2, which was passed at both 650 ° C and 960 ° C.
  • WO 2013/045426 A1 discloses a composition comprising a polyamide, a metal oxide such as aluminum oxide and a nitride compound such as boron nitride.
  • Other components include fibers such as glass fibers, flame retardants and thermal stabilizers.
  • CN 103 304 992 A describes a flame retardant polyamide composition containing polyamide 66, a flame retardant, a lower carbon accelerator, an antioxidant, and 1 to 3 wt% of a GWIT aid such as alumina.
  • US 4399246 A describes a polyamide composition containing a mineral filler, an aminosilane and a sulfonamide compound.
  • Examples 2 and Figure 3 describes compositions of polyamide and aluminum silicate. The compositions are mixed in an extruder at 270-280 ° C and extruded into test samples by injection molding.
  • polyamide-based compositions and products made therefrom which contain at least one electrically insulating thermally conductive filler from the group aluminum oxide, boron nitride or aluminum silicate, preferably aluminum silicate, fulfill increased flameproofing requirements, in particular increased glow wire resistance, without while the usual restrictions on the use of flame retardants processing windows or ecology must be taken into account.
  • compositions comprising a) at least one polyamide and b) at least one electrically insulating, thermally conductive filler selected from the group of aluminum oxide, boron nitride and aluminum silicate.
  • compositions comprising a) at least one polyamide and b) triclinic pinacoidal aluminosilicate.
  • compositions comprising a) 20 to 90% by weight, preferably 30 to 70% by weight of at least one polyamide and b) 10 to 80% by weight, preferably 15 to 75% by weight, especially preferably 30 to 70% by weight of at least one electrically insulating, thermally conductive filler selected from the group b1) aluminum oxide, b2) boron nitride and b3) aluminum silicate, the sum of all percentages by weight always being 100.
  • compositions comprising a) 20 to 90 wt .-%, preferably 30 to 70 wt .-% of at least one polyamide and b) 10 to 80 wt .-%, preferably 15 to 75 wt .-%, particularly preferably from 30 to 70% by weight of triclinic pinacoidal aluminum silicate, the sum of all percentages by weight always being 100.
  • the present invention additionally relates to the use of a) at least one polyamide and b) at least one electrically insulating, thermally conductive filler selected from the group consisting of aluminum oxide, boron nitride and triclinic aluminum silicate for the production of products with increased flame retardance requirements, preferably without additional flameproofing agents based on halogenated Nitrogen- or phosphorus-containing organic compounds or red phosphorus.
  • compositions comprising a) from 20 to 90% by weight, preferably from 30 to 70% by weight, of at least one polyamide and b) from 10 to 80% by weight, preferably from 15 to 75% by weight, particularly preferably 30 to 70% by weight of at least one electrically insulating thermally conductive filler selected from the group b1) aluminum oxide, b2) boron nitride and b3)
  • Aluminum silicate the sum of all percentages by weight always being 100, for the production of products with increased flame retardance requirements, preferably without additional flame retardants based on halogen-nitrogen or phosphorus-containing organic compounds or red phosphorus.
  • the invention preferably relates to the use of compositions comprising a) 20 to 90% by weight, preferably 30 to 70% by weight of at least one polyamide and b) 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 30 to 70
  • Wt .-% triclinic pinacoidal aluminosilicate the sum of all percentages by weight always being 100, for the production of products with increased flame retardance requirements, preferably without additional flame retardants based on halogen-nitrogen or phosphorus-containing organic compounds or red phosphorus.
  • compositions of the invention for further use are prepared by mixing the components a) and b) to be used as starting materials in at least one mixing tool.
  • molding compositions are obtained as intermediates, based on the compositions of the invention.
  • These molding compositions can either consist exclusively of components a) and b), or else contain other components in addition to components a) and b).
  • components a) and b) are to be varied within the specified quantity ranges so that the sum of all weight percentages always equals 100.
  • the invention therefore furthermore relates to polyamide molding compositions intended for use in extrusion, blow molding or injection molding, preferably in granular form, containing the compositions according to the invention which are from 50 to 100% by weight, preferably from 60 to 100% by weight preferably from 70 to 100 wt .-% of the invention or according to the invention for the production of equipped with increased flame retardant requirements, in particular equipped with increased glow wire resistance, make polyamide molding compounds, without taking the usual flame retardants restrictions in terms of processing window or ecology accepted Need to become.
  • the present invention relates to compositions comprising in addition to components a) and b) still c) 5 to 70 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 35 wt .-%, each based on the total composition of glass fibers, the remaining components are reduced so that the sum of all weight percentages always 100.
  • the present invention still further relates to compositions containing in addition to components a) to c), or instead of component c) d) 0.01 to 3 wt .-%, preferably 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 0.8 wt .-%, each based on the total composition, of at least one heat stabilizer, wherein the remaining components are reduced so far that the sum of all weight percentages always equals 100.
  • the present invention relates to compositions comprising in addition to the components a) to d) or instead of c) and / or d) to increase the flame retardancy e) 1 to 40 wt .-%, preferably 2 to 30 wt. -%, particularly preferably 5 to 20 wt .-%, each based on the total composition, of at least one flame retardant, wherein the other components are reduced so far that the sum of all weight percent always 100.
  • the present invention relates to compositions comprising in addition to the components a) to e) or instead of c) and / or d) and / or e) still f) 0.01 to 20 wt .-%, preferably 0.01 up to 10% by weight, particularly preferably 0.01 to 5% by weight, in each case based on the total composition, of at least one other additive which is different from components b) to e), the other components being reduced to such an extent that Sum of all weight percent always equals 100.
  • the polyamides to be used as component a) are preferably amorphous or semicrystalline polyamides.
  • Semicrystalline polyamides having a melting point of at least 180 ° C. or amorphous polyamides having a glass transition temperature of at least 150 ° C. are particularly preferred.
  • semicrystalline polyamides According to DE 10 201 1 084 519 A1, semicrystalline polyamides have a melting enthalpy of 4 to 25 J / g, measured by the DSC method according to ISO 1 1357 during the second heating and integration of the melt peak.
  • amorphous polyamides have a melting enthalpy of less than 4 J / g, measured by the DSC method according to ISO 1 1357 at the 2nd heating and integration of the melting peak.
  • a blend of different polyamides is also used as component a).
  • Preferred as component a) is aliphatic polyamide, more preferably polyamide 6 (PA 6), polyamide 4.6 (PA 46) or polyamide 66 (PA 66) or semi-aromatic polyamide, more preferably PA 6T / 6 and PA 6T / 66, or a co-polyamide of PA 6 or PA 66 used. Most preferably, PA 6 or PA 66 is used. Particular preference is given to using PA 6.
  • the used in the present application marking the polyamides corresponds to international standard, wherein the first digit (s) indicate the C atomic number of Trustdiamins and the last digit (s) the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA 6, this means that an ⁇ , ⁇ -aminocarboxylic acid or the lactam derived therefrom, in the case of PA 6, ie ⁇ -caprolactam, has been used as starting material; Incidentally, reference is made to H. Domininghaus, The Plastics and their properties, pages 272 et seq., VDI-Verlag, 1976.
  • the polyamide to be used as component a) preferably has a viscosity number determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 in the range from 80 to 180 ml / g, particularly preferably in the range from 90 to 170 ml / g, very particularly preferably in the range from 95 to 160 ml / g.
  • the polyamide 6 to be used as component a) has a viscosity number determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307 in the range from 100 to 135 ml / g on.
  • the viscosity number is the indicative size for the average molecular weight (molecular chain length) and is expressed by the K value.
  • the K value is calculated from the viscosity ratio according to an equation given by Fikentscher in 1929 (see: http://en.wikipedia.org/wiki/K-value_after_Fikentscher). The latter is the experimental basis for the calculation of viscosity numbers.
  • the ranking of a group of products in terms of molecular weight labeling is thus the same for K value and viscosity number. Conversion tables for the viscosity number and the K value can be found in EN ISO 1628-2.
  • polyamides to be used as component a) in the compositions according to the invention can be prepared by various processes and synthesized from different building blocks.
  • For the preparation of polyamides a variety of procedures are known, depending on the desired end product different monomer units and various chain regulators for adjusting a aspired molecular weight or monomers with reactive groups for later intended post-treatments can be used.
  • polyamides are those which are prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • Suitable starting materials are preferably aliphatic and / or aromatic dicarboxylic acids, particularly preferably adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines, particularly preferred Tetramethylenediamine, hexamethylenediamine, 2-methylpentan-1, 5-diamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomers diaminodicyclohexylmethane, diaminodicyclohexylpropane, bis-aminomethylcyclohexane, phenylened
  • Polyamides to be used in accordance with the invention particularly preferably as component a) are prepared from caprolactam, very particularly preferably from ⁇ -caprolactam.
  • PA 6 PA 66 and other based on aliphatic or / and aromatic polyamides or copolyamides compounds in which come to a polyamide group in the polymer chain 3 to 1 1 methylene groups.
  • Component b) PA 6, PA 66 and other based on aliphatic or / and aromatic polyamides or copolyamides compounds in which come to a polyamide group in the polymer chain 3 to 1 1 methylene groups.
  • the components boron nitride and aluminum oxide are used in a preferred embodiment in the form of fine needles, platelets, spheres or irregularly shaped particles.
  • Preferred average particle sizes of the boron nitride and of the aluminum oxide are in the range from 0.1 to 300 ⁇ m, particularly preferably in the range from 0.5 to 100 ⁇ m.
  • the thermal conductivity of the boron nitride and of the aluminum oxide is preferably in the range from 10 to 400 W / mK, particularly preferably in the range from 30 to 250 W / mK.
  • Suitable examples of alumina are the Martoxid® MPS-2 [CAS no. 1344-28-1] of Martinswerk GmbH, Bergheim, Germany. According to the invention Boronitrides to be used [CAS no. 10043-1 1 -5] are available, for example, as Polartherm® PT from Momentive Performance Materials Inc., Strongville, USA.
  • triclinic pinacoidal aluminosilicate is used in the context of the present invention.
  • the mineral kyanite used as triclinic pinacoidal aluminum silicate [CAS no. 1302-76-7] is an alumino-silicate in the form of a triclinic crystal with the chemical composition Al 2 [0 Si0 4 ].
  • Kyanite can be contaminated with iron and / or chromium compounds.
  • triclinic pinacoidal aluminum silicate or kyanite is preferably used with less than 1% by weight, more preferably less than 0.5% by weight, of impurities.
  • the Al 2 [0 Si0 4 ] or kyanite, used as a powder have an average particle size d 50 of at most 500 ⁇ m, preferably an average particle size in the range from 0.1 to 250 ⁇ m, more preferably in the range from 0.5 to 150 ⁇ m, very particularly preferably in the range from 0.5 to 70 ⁇ , whereby the fine distribution is ensured in the molding compositions obtainable from the compositions according to the invention and the products to be produced therefrom.
  • the size is determined by the equivalent spherical diameter (Stokes diameter). All these d50 and d95 diameter measurements are made with a "Sedigraph” (trade mark) device by gravity sedimentation in accordance with the AFNOR X1 1 -683 standard.
  • the Al 2 [0 Si0 4 ] particles or kyanite particles to be used according to the invention as component b) can be present in different forms, which are described by the aspect ratio. It is preferred to use kyanite particles having an aspect ratio in the range from 1 to 100, particularly preferably in the range from 1 to 30, very particularly preferably in the range from 1 to 10.
  • the Al 2 [0 Si0 4 ] particles or kyanite particles to be used according to the invention as component b) can be used with and / or without surface modification.
  • Surface modification refers to organic coupling agents which are intended to improve the binding of the particles to the thermoplastic matrix.
  • preference is given to using aminosilanes or epoxysilanes.
  • the Al 2 [0 Si0] particles or kyanite particles to be used according to the invention are used without surface modification used.
  • One supplier of kyanite is, for example, Quarzwerke GmbH, Frechen, which markets the kyanite as Al 2 [0 Si0 4 ] under Silatherm ® .
  • the triclinic pinacoidal aluminum silicate, kyanite, to be used as component b) is used in a preferred embodiment as a mixture with at least one of the components boron nitride or aluminum oxide.
  • the invention in this case preferably relates to compositions comprising at least one polyamide, triclinic pinacoidal aluminosilicate and boron nitride.
  • the invention furthermore preferably relates to compositions comprising at least one polyamide, triclinic pinacoidal aluminosilicate and aluminum oxide.
  • the invention also preferably relates to compositions comprising at least one polyamide, triclinic pinacoidal aluminum silicate, boron nitride and aluminum oxide.
  • the present invention preferably relates to compositions containing a) 20 to 90 wt .-%, preferably 30 to 70 wt .-% of at least one polyamide and b) 10 to 80 wt .-%, preferably 15 to 75 wt .-%, particularly preferably 30 to 70 wt .-% triclinic pinacoidal aluminosilicate and boron nitride.
  • the present invention furthermore preferably relates to compositions comprising a) 20 to 90% by weight, preferably 30 to 70% by weight of at least one polyamide and b) 10 to 80% by weight, preferably 15 to 75% by weight, especially preferably from 30 to 70% by weight of triclinic pinacoidal aluminosilicate and alumina.
  • the present invention furthermore preferably relates to compositions comprising a) 20 to 90% by weight, preferably 30 to 70% by weight of at least one polyamide and b) 10 to 80% by weight, preferably 15 to 75% by weight, especially preferably 30 to 70 wt .-% triclinic pinacoidal aluminosilicate, boron nitride and alumina.
  • cut fibers also called short fibers, with a length in the range of 0.1 to 1 mm, long fibers with a length in the range of 1 to 50 mm and continuous fibers with a length L> 50 mm.
  • Short fibers are used in injection molding technology and can be processed directly with an extruder.
  • Long fibers can also be processed in extruders. They are widely used in fiber spraying. Long fibers are often added to thermosets as a filler.
  • Continuous fibers are used as rovings or fabrics in fiber-reinforced plastics. Products with continuous fibers achieve the highest stiffness and strength values.
  • the fiber length is in the range of 70 to 200 ⁇ .
  • Short glass fibers, long glass fibers or continuous glass fibers can be used according to the invention.
  • Long glass fibers or continuous glass fibers are preferably used, particularly preferably long glass fibers.
  • the glass fibers can also be used as ground glass fibers.
  • the glass fibers preferably have a mean fiber diameter in the range of 7 and 18 ⁇ , particularly preferably in the range of 9 and 15 ⁇ , wherein the average fiber diameter of a single fiber by length and thickness measurement semiautomatic by means of scanning electron microscopic images (SEM) by means of graphics tablet and computer-aided data acquisition.
  • SEM scanning electron microscopic images
  • the glass fibers to be used as component c) are preferably provided with a suitable sizing system or an adhesion promoter or adhesion promoter system, particularly preferably silane-based.
  • silane-based adhesion promoters are silane compounds of the general formula (I)
  • adhesion promoters are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyl triethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are preferably used in amounts ranging from 0.05 to 2% by weight, more preferably in the range from 0.25 to 1.5% by weight and in particular in the range of 0.5 to 1 wt .-%, based on the amount of glass fiber, used for surface coating.
  • the glass fibers Due to the processing / compounding into the molding compound or the product to be produced therefrom, the glass fibers may have a smaller d97 or d50 value in the molding composition or in the product than the glass fibers originally used. As a result of the processing into the molding compound (compounding) or molding (injection molding or extrusion), the glass fibers can have shorter length distributions than originally used in the molding composition or in the molding.
  • Thermostabilisatoren be selected from the group of sterically hindered phenols, which are compounds having a phenolic structure having on the phenolic ring at least one sterically demanding group.
  • Particularly preferred sterically hindered phenols are compounds of the formula (II)
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals 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 represents a substituted amino group.
  • a steric hindrance in organic chemistry is the term used to describe the influence of the spatial extent of a molecule on the course of a reaction, first invented by Victor Meyer in 1894 for observation that some reactions occur only slowly or not at all when there are large and bulky groups in the vicinity of the reacting atoms, a well-known example of the influence of the steric ones Disruption or a sterically demanding group is the presence of very bulky terf-butyl groups.
  • thermostabilizers of the formula (II) are described as antioxidants, for example in DE-A 27 02 661, the content of which is fully encompassed by the present application.
  • Another group of preferred sterically hindered phenols is derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.
  • Particularly preferred compounds of this class are compounds of the formula (III)
  • R 4 , R 5 , R 7 and R 8 independently of one another represent C 1 -C 8 -alkyl groups, which in turn may be substituted and of which at least one of them is a sterically demanding group
  • R 6 is a bivalent aliphatic radical having 1 to 10 C atoms means that may also have CO bonds in the main chain.
  • Particularly preferred compounds of the formula (III) are compounds of the formulas (IV), (V) and (VI).
  • VI (Irganox ® 1098 from BASF SE)
  • Very particularly preferred heat stabilizers are selected from the group consisting of 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert. -butyl-4-hydroxyphenyl) -propionate], pentaerythritol tetrakis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], distearyl-3,5-di-tert-butyl 4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphodicyclo [2.2.2] oct-4-ylmethyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3.5 -Di-tert-butyl-4-hydroxyphenyl-3,5-distearyl-thiotriazylamine, 2- (2'-hydroxy-3'-hydroxy-3 ', 5'-di
  • Particularly preferred heat stabilizers are selected from the group consisting of 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 N, N'-hexamethylene-bis- 3,5-di-tert-butyl-4-hydroxyhydro- cinnamide (Irganox ® 1098), and Irganox ® 245 from BASF SE, Ludwigshafen, Germany described above.
  • N N'-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide, [CAS. 23128-74-7], used as thermal stabilizer, available as Irganox® 1098 from BASF SE, Ludwigshafen, Germany.
  • Preferred flame retardants e) are commercially available organic halogen compounds with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds which are used individually or mixed with one another, but also mineral flame retardant additives, preferably magnesium hydroxide or Ca-Mg carbonate hydrates (eg. A 4 236 122).
  • Preferred organic halogen compounds are ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachloro bisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ethers.
  • Suitable organic / inorganic phosphorus compounds are the phosphorus compounds according to WO-A 98/17720, preferably red phosphorus, metal phosphinates, in particular aluminum phosphinate or zinc phosphinate, metal phosphonates, in particular aluminum phosphonate, calcium phosphonate or zinc phosphonate, derivatives of 9,10-dihydro-9-oxa-10 phosphophenanthrene-10-oxide (DOPO derivatives)], triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP), including oligomers, and bisphenol A bis diphenyl phosphate (BDP), including oligomers, bis (diethylphosphinate), aluminum tris (diethylphosphinate), melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine poly (aluminum phosphate), melamine poly (zinc phosphate) or phenoxypho
  • the organic nitrogen compounds used are, in particular, melamine or melamine cyanurate, reaction products of trichlorotriazine, piperazine and morpholine according to CAS no. 1078142-02-5 (eg MCA PPM triazine HF from the company MCA Technologies GmbH, Biel-Benken, Switzerland) in question.
  • Preferred synergists are antimony compounds, in particular antimony trioxide or antimony pentoxide, zinc compounds, tin compounds, in particular zinc stannate or various borates, in particular zinc borates. It is also possible to add so-called carbon formers and tetrafluoroethylene polymers to the flame retardant.
  • brominated polystyrenes such as e.g. Firemaster® PBS64 (Great Lakes, West Lafayette, USA), or brominated phenylene ethers, in each case particularly preferably used in combination with antimony trioxide and / or zinc stannates as synergists.
  • halogen-free flame retardants it is particularly preferred to use aluminum tris (diethylphosphinate) in combination with IVIelamine polyphosphate (eg Melapur® 200/70 from BASF SE, Ludwigshafen, Germany) and zinc borate (eg Firebrake® 500 or Firebrake® ZB from RioTinto Minerals, Greenwood Village, USA) or aluminum tris (diethylphosphinate) in combination with aluminum phosphonate and / or aluminum phosphonate hydrate.
  • IVIelamine polyphosphate eg Melapur® 200/70 from BASF SE, Ludwigshafen, Germany
  • zinc borate eg Firebrake® 500 or Firebrake® ZB from RioTinto Minerals, Greenwood Village, USA
  • aluminum tris (diethylphosphinate) in combination with aluminum phosphonate and / or aluminum phosphonate hydrate.
  • flame retardants is aluminum tris (diethylphosphinate) (for example Exolit® OP1230 from Clariant International Ltd. Muttenz, Switzerland) [CAS no. 225789-38-8] in a combination with IVIelaminpolyphosphat [CAS no. 41583-09-9 or CAS no. 255-449-7] (Melapur® 200/70) and zinc borate [CAS no. 51201 -70-8] (Firebrake® 500).
  • aluminum tris diethylphosphinate
  • Typical additives of component f) are preferably stabilizers, mold release agents, UV stabilizers, gamma ray stabilizers, laser absorbers, antistatic agents, flow aids, elastomer modifiers, emulsifiers, nucleating agents, acid scavengers, plasticizers, lubricants, dyes, laser marking additives or pigments.
  • the additives can be used alone or mixed or in the form of masterbatches.
  • Stabilizers used are preferably hydroquinones, aromatic secondary amines, in particular diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as variously substituted representatives of these groups or mixtures thereof.
  • Preferred mold release agents are selected from the group ester waxes, pentaerythritol tetrastearate (PETS), long-chain fatty acids, fatty acid salts, amide derivatives, montan waxes, low molecular weight polyethylene or polypropylene waxes and ethylene homopolymer waxes.
  • PETS pentaerythritol tetrastearate
  • long-chain fatty acids long-chain fatty acids
  • fatty acid salts fatty acid salts
  • amide derivatives amide derivatives
  • montan waxes low molecular weight polyethylene or polypropylene waxes and ethylene homopolymer waxes.
  • Preferred long-chain fatty acids are stearic acid or behenic acid.
  • Preferred fatty acid salts are Ca or Zn stearate.
  • Preferred amide derivative is ethylene-bis-stearylamide.
  • Preferred montan waxes are mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.
  • titanium dioxide As pigments or dyes, preference is given to using zinc sulfide, titanium dioxide, ultramarine blue, iron oxide, carbon black, phthalocyanines, quinacridones, perylenes, nigrosine and anthraquinones.
  • titanium dioxide pigments are suitable whose basic structure is based on the sulfate (SP) or chloride (CP). Can be prepared and have the anatase and / or rutile structure, preferably rutile structure.
  • the main body need not be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0 wt .-% (calculated as Al 2 0 3 ) and an excess of oxygen in the gas phase at the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by a doping z. B. with Al, Sb, Nb or Zn. Particularly preferred is a "slight" stabilization with Al, or at higher Al doping amounts compensation with antimony.
  • Titanium dioxide pigments absorb light in the near ultraviolet range, creating electron-hole pairs that generate highly reactive radicals on the titanium dioxide surface.
  • the radicals formed in organic media result in a binder degradation.
  • the titanium dioxide is preferably after-treated in an inorganic form, particularly preferably with oxides of Si and / or Al and / or Zr and / or by the use of Sn compounds.
  • the surface of pigmentary titanium dioxide is preferably covered with amorphous precipitates of oxide hydrates of the compounds SiO 2 and / or Al 2 O 3 and / or zirconium oxide.
  • the Al 2 O 3 sheath facilitates pigment dispersion in the polymer matrix, the Si0 2 sheath impedes the charge exchange on the pigment surface and thus prevents polymer degradation.
  • the titanium dioxide is preferably provided with hydrophilic and / or hydrophobic organic coatings, in particular with siloxanes or polyalcohols.
  • Titanium dioxide to be used particularly preferably according to the invention has an average particle size in the range from 90 nm to 2000 nm, preferably in the range from 200 nm to 800 nm.
  • Commercially available products include, for example, Kronos® 2230, Kronos® 2225 and Kronos® vlp7000 from Kronos, Dallas, USA.
  • the nucleating agents used are preferably talc, sodium or calcium phenylphosphate or silicon dioxide, talc being particularly preferred.
  • Talc is a powdered magnesium magnesium hydrate having the chemical composition Mg 3 [Si 4 Oio (OH) 2], ([CAS No. 14807-96-6]).
  • Hydrotalcite, chalk, boehmite or zinc stannates are preferably used as acid scavengers.
  • the plasticizers used are preferably dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
  • an elastomer modifier to be used additive is preferably one or more graft polymer (s) E of
  • E.2 95 to 5 wt .-%, preferably 70 to 10 wt .-% of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C used.
  • the graft base E.2 generally has an average particle size (d 50 value) of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • Monomers E.1 are preferably mixtures of
  • E.1.11 50 to 99% by weight of vinylaromatics and / or ring-substituted vinylaromatics, preferably styrene, oc-methylstyrene, p-methylstyrene, p-chlorostyrene, and / or methacrylic acid (C 1 -C 8 ) -alkyl ester, preferably methyl methacrylate , Ethyl methacrylate, and
  • E.1 .2 1 to 50% by weight of vinyl cyanides, preferably unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid (C 1 -C 8 ) -alkyl esters, preferably methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or Derivatives, preferably anhydrides and imides, unsaturated carboxylic acids, preferably maleic anhydride and N-phenyl-maleimide.
  • vinyl cyanides preferably unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid (C 1 -C 8 ) -alkyl esters, preferably methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or Derivatives, preferably anhydrides and imides, unsaturated carboxylic acids
  • Preferred monomers E.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers E.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride 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 preferably diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate. rubbers.
  • Preferred grafting principles 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 further copolymerizable monomers (for example according to E.1.1 and E.1.2), with with the proviso that the glass transition temperature of component E.2 below ⁇ 10 ° C, preferably ⁇ 0 ° C, more preferably ⁇ -10 ° C.
  • grafting E.2. pure polybutadiene rubber.
  • Particularly preferred polymers E are ABS polymers (emulsion, bulk and suspension ABS), as z.
  • DE-A 2 035 390 US Pat. No. 3,644,574
  • DE-A 2 248 242 DE-A 1 409 275
  • the gel content of the graft base E.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
  • ABS means acrylonitrile-butadiene-styrene copolymer with the CAS number 9003-56-9 and is a synthetic terpolymer of the three different monomer types acrylonitrile, 1, 3-butadiene and styrene. It belongs to the amorphous thermoplastics. The proportions may vary from 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene.
  • the elastomer modifiers or graft copolymers E are prepared by free-radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
  • Particularly suitable graft rubbers are also ABS polymers which are prepared by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285. Since, in the grafting reaction, the grafting monomers are not necessarily completely grafted onto the grafting base, graft polymers E according to the invention are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are added during workup ,
  • Suitable acrylate rubbers are based on grafting 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.
  • Preferred polymerizable acrylic acid esters include C 1 -C 8 -alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen-C 1 -C 8 -alkyl esters, in particular preferably chloroethyl acrylate, and also mixtures of these monomers.
  • 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, such as. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallylcyanate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the grafting E.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft base E.2 are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinylCrC 6 - alkyl ethers, methyl 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.
  • additives and / or reinforcing substances may be present in the compositions according to the invention as additives.
  • mineral particulate fillers based on mica, silicate, quartz, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar or barium sulfate are particularly preferably used according to the invention.
  • needle-shaped mineral fillers are also used with particular preference as an additive. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character. In particular, acicular wollastonites are mentioned.
  • the mineral has a length: diameter ratio in the range of 2: 1 to 35: 1, more preferably in the range of 3: 1 to 19: 1, most preferably in the range of 4: 1 to 12: 1.
  • the average particle size of the acicular minerals according to the invention is preferably less than 20 ⁇ m, more preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m determined with a CILAS GRANULOMETER.
  • the filler and / or reinforcing material to be used as component f) may also be surface-modified, particularly preferably with a bonding agent or adhesion promoter system, particularly preferably silane-based.
  • a bonding agent or adhesion promoter system particularly preferably silane-based.
  • pretreatment is not essential.
  • the silane compounds are generally used in amounts of from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight. %, based on the mineral filler used for surface coating.
  • the particulate fillers to be used as component f) may have a smaller d97 or d50 value due to the processing, preferably already in the compounding, to the molding compound or in the subsequent processing to the molded article / product in the molding compound or in the molded article / article have, as the fillers originally used.
  • laser absorbers are laser light absorbers, preferably for labeling plastic products.
  • Preferred laser absorbers are 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. Particularly preferred are antimony trioxide and antimony tin oxide. Very particular preference is given to antimony trioxide.
  • 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 or those based on polybutylene terephthalate, polyethylene, polypropylene, polyethylene-polypropylene copolymer, maleic anhydride-grafted polyethylene and / or maleic anhydride grafted polypropylene, wherein the polymers for the antimony trioxide masterbatch individually or im Mixture can be used.
  • 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 between 157 nm and 10.6 ⁇ . Examples of lasers of these wavelengths are described in WO2009 / 003976 A1. Preference is given to Nd: YAG lasers, with which wavelengths of 1064, 532, 355 and 266 nm can be realized, and C0 2 lasers are used.
  • Molding compounds to be used for injection molding or for extrusion are obtained by mixing components a) and b) and optionally c) and / or d) and / or e) in the stated percentages by weight in at least one mixing unit, preferably at least one extruder. mixed or compounded.
  • the mixed composition is then discharged as a molding composition into a strand, cooled to granulation capability and granulated.
  • the granulation is followed by a drying step.
  • the mixing / compounding of the above-listed components in the stated weight percent at temperatures ranging from 240 to 300 ° C in the melt, preferably in an extruder, more preferably in a twin-screw extruder.
  • the granules obtained in the extruder containing the composition according to the invention are dried at 80 ° C. in a dry air dryer or vacuum drying oven for about 2-6 hours before being subjected to injection molding or an extrusion process for the production of products.
  • the present invention therefore also relates to a process for the production of products with increased flame retardance requirements, preferably of products for the electrical or electronics industry, more preferably of electronic or electrical assemblies and components, by compositions according to the invention as a molding compound in injection molding or in extrusion used, preferably in injection molding.
  • Processes according to the invention for the production of products by extrusion or injection molding preferably operate at melt temperatures in the range from 230 to 330 ° C., more preferably in the range from 240 to 300 ° C., very preferably in the range from 250 to 280 ° C. and optionally additionally at pressures of a maximum of 2500 bar, preferably at pressures of at most 2000 bar, more preferably at pressures of at most 1500 bar and most preferably at pressures of at most 750 bar.
  • sequential coextrusion a variant of extrusion, two different materials are ejected in succession in an alternating sequence. In this way, a preform with sections of different material composition in the extrusion direction.
  • Certain article sections can be equipped with specific required properties by appropriate material selection, for example for articles with soft ends and hard middle part or integrated soft bellows areas (Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Kunststoff 2006, page 127-129).
  • the method of injection molding is characterized in that the raw material based on a composition according to the invention, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and injected as a spray mass under pressure into a tempered cavity. After cooling (solidification) of the mass, 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 controller.
  • the clamping unit includes fixed and movable platens for the tool, a face plate and columns and drive of the moving platen. (Toggle joint or hydraulic clamping unit).
  • An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit.
  • the task of the injection unit is to melt the powder or the granules containing at least the components a) and b), to dose, to inject and to press (because of contraction).
  • the problem of backflow of the melt inside the screw is solved by backflow stops.
  • an endlessly shaped plastic strand containing the composition according to the invention is used in the extruder during extrusion, the extruder being a machine for producing thermoplastic molded pieces.
  • Extrusion plants consist of extruders, tools, downstream equipment, extrusion blow molding.
  • Extrusion lines for the production of profiles consist of extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, separating device and tilting channel.
  • the present invention consequently also relates to products obtainable by extrusion or injection molding of the molding compositions according to the invention.
  • the mechanical properties of the products produced from the compositions according to the invention were determined in the bending test according to ISO 178 and in the IZOD impact test according to ISO 180/1 U.
  • the glow-wire resistance was determined using the glow-wire test GWFI (Glow-Wire Flammability Index) according to IEC 60695-2-12.
  • the flexural strength in engineering mechanics is a value for a bending stress in a component subject to bending, beyond which failure occurs due to breakage of the component. It describes the resistance of a workpiece, which is opposed to its deflection or its fracture.
  • beam-shaped specimens are preferably placed with the dimensions 80 mm x 10 mm x 4mm at the ends on two supports and loaded in the middle with a bending punch (Bodo Carlowitz: Tabular overview of the testing of plastics, 6. Edition, Giesel-Verlag for publicity, 1992, pp. 16-17).
  • the flexural modulus is determined in a 3-point bending test, whereby a test specimen is positioned on two supports and loaded with a test stamp in the middle, which is probably the most common
  • the bending modulus of a flat sample is then calculated as follows:
  • This method of heat deflection temperature (HDT) described in DIN EN ISO 75-1, -2, -3 uses standard test specimens with rectangular cross section, which are preferably exposed flat to a three-point bend under constant load. Depending on the specimen height is thereby to achieve a so-called edge fiber tension a f of 1, 80 (Method A), 0.45 (Method B) or 8.00 N / mm 2 (Method C) by weights or / and springs a force
  • the loaded samples are subjected to heating at a constant heating rate of 120 K / h (or 50 K / h). If the deflection of the sample reaches an edge fiber elongation of 0.2%, the associated temperature is the heat deflection temperature HDT (English, heat deflection temperature or heat distortion temperature). In the frequently used method HDT-A - also in the context of the present invention - the applied bending stress is 1, 8 MPa.
  • the ISO 180/1 U impact strength is a measure of a material's ability to absorb impact energy and impact energy without breaking it. A large number of factors determine the impact resistance of a component:
  • the impact resistance is measured with the aid of a percussion hammer.
  • the impact resistance is calculated as the ratio of impact energy and specimen cross section (unit of measure kJ / m 2 ).
  • Charpy or IZOD There are different methods of measurement, the methods according to Charpy or IZOD.
  • IZOD method used in the present invention the test specimen is edgewise and clamped only on one side.
  • thermogravimetric analysis TGA
  • the sample was heated in air in a TGA apparatus (Netzsch TG209 F1 Iris) at a heating rate of 20.0 K / min and the mass change was recorded over the temperature.
  • the temperature at which a cumulative loss of mass of 2% occurred was defined as the temperature T (Z) at which thermal stability is no longer sufficiently ensured.
  • Component a / 1 polyamide 6 (Durethan® B29, Lanxess Deutschland GmbH,
  • Component b / 1 kyanite, eg Silatherm ® -T 1360-400 AST quartz Werke GmbH,
  • Component b / 2 magnesium hydroxide, e.g. Magnifin® 5HIV, Martinswerk GmbH,
  • Component f) Further additives customary for use in polyamides, such as, for example, mold release agents (in particular ethylene bis (stearylamide), [CAS No. 1 10-30-5], nucleating agents (for example based on talcum) com- f) combined additives agree in type and amount for examples and comparative examples.
  • mold release agents in particular ethylene bis (stearylamide), [CAS No. 1 10-30-5]
  • nucleating agents for example based on talcum
  • compositions shown in Table 1 were all processed as described above.
  • a GWFI of 750 ° C already meets the normative requirements for use as insulating material for live parts> 0.5 A in supervised domestic appliances.
  • the result of the use of aluminum silicate at the same filler content significantly better mechanical properties.

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Abstract

La présente invention concerne des compositions à base de polyamide comportant au moins une charge choisi dans le groupe contenant l'oxyde d'aluminium, le nitrure de bore et le silicate d'aluminium triclinique, et l'utilisation de ces compositions pour fabriquer des produits présentant des exigences majorés en matière d'ignifugation, de façon particulièrement préférée des produits présentant des exigences accrues en termes de filament chauffant, en particulier de composants destinés à des éléments de conduction de courant et de tension dans des appareils ménagers.
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CN106163139B (zh) * 2016-08-31 2020-01-14 奥士康精密电路（惠州）有限公司 Pcb板边露铜焊盘的成型方法
CN106757503A (zh) * 2016-12-10 2017-05-31 钦州学院 一种阻燃纤维新材料及其制备方法
CN112940492A (zh) * 2021-03-30 2021-06-11 江苏江山红化纤有限责任公司 一种阻燃聚酰胺复合材料及其制备方法
WO2024091994A1 (fr) * 2022-10-26 2024-05-02 Celanese International Corporation Composition de polymère thermoplastique renforcée par des fibres contenant une enveloppe ignifuge

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014095984A1 (fr) * 2012-12-18 2014-06-26 Quarzwerke Gmbh Matériau synthétique thermoconductible
EP2862894A1 (fr) * 2013-10-15 2015-04-22 LANXESS Deutschland GmbH Masse de formage thermoplastique

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE28646E (en) * 1963-05-31 1975-12-09 einforced polyamides and process of preparation thereof
JPS543486B1 (fr) * 1968-12-30 1979-02-23
US3644574A (en) 1969-07-17 1972-02-22 Eastman Kodak Co Shaped articles of blends of polyesters and polyvinyls
US4013613A (en) 1971-10-01 1977-03-22 General Electric Company Reinforced intercrystalline thermoplastic polyester compositions
DE2252258A1 (de) 1972-10-25 1974-05-09 Hoechst Ag Schwerentflammbare thermoplastische polyester
DE2447727A1 (de) 1974-10-07 1976-04-08 Hoechst Ag Schwerentflammbare polyamidformmassen
CH626385A5 (fr) 1976-02-05 1981-11-13 Ciba Geigy Ag
US4399246A (en) * 1982-08-06 1983-08-16 E. I. Du Pont De Nemours & Co. Filled polyamide compositions with silanes and sulfonamides
DE3631540A1 (de) 1986-09-17 1988-03-24 Bayer Ag Thermoplastische formmassen mit hoher alterungsbestaendigkeit und guter tieftemperaturzaehigkeit
DE3631539A1 (de) 1986-09-17 1988-03-24 Bayer Ag Alterungsbestaendige thermoplastische formmassen mit guter zaehigkeit
DE3704655A1 (de) 1987-02-14 1988-08-25 Bayer Ag Teilchenfoermige mehrphasenpolymerisate
DE3704657A1 (de) 1987-02-14 1988-08-25 Bayer Ag Teilchenfoermige mehrphasenpolymerisate
DE3738143A1 (de) 1987-11-10 1989-05-18 Bayer Ag Verwendung von redoxpfropfpolymerisaten zur verbesserung der benzinbestaendigkeit von thermoplastischen, aromatischen polycarbonat- und/oder polyestercarbonat-formmassen
DE4236122A1 (de) 1992-10-27 1994-04-28 Bayer Ag Flammgeschützte, mineralgefüllte, thermoplastische Formmassen mit hoher Kriechstromfestigkeit
DE19643280A1 (de) 1996-10-21 1998-04-23 Basf Ag Flammgeschützte Formmassen
US20040194657A1 (en) * 2000-06-22 2004-10-07 Thomas Lally Fire-retardant coating, method for producing fire-retardant building materials
DE10241126A1 (de) 2002-09-03 2004-03-25 Clariant Gmbh Flammschutzmittel-Stabilisator-Kombination für thermoplastische Polymere
DE102004027872A1 (de) * 2004-06-08 2006-01-05 Lanxess Deutschland Gmbh Polyamid-Formmassen mit verbesserter Fließfähigkeit
ATE421554T1 (de) * 2004-06-08 2009-02-15 Lanxess Deutschland Gmbh Polyamid-formmassen mit verbesserter fliessfähigkeit
ATE546489T1 (de) * 2004-07-01 2012-03-15 Solvay Specialty Polymers Usa Aromatisches polyamid enthaltende zusammensetzung und daraus hergestellter gegenstand
JP5352947B2 (ja) * 2006-07-31 2013-11-27 テクノポリマー株式会社 放熱シャーシ
JP2008189855A (ja) * 2007-02-06 2008-08-21 Mitsubishi Engineering Plastics Corp 難燃性ポリアミド樹脂組成物
WO2009003976A1 (fr) 2007-06-29 2009-01-08 Dsm Ip Assets B.V. Microsphère comprenant un cœur polymère, une écorce et un absorbeur
DE102007037316A1 (de) * 2007-08-08 2009-02-12 Lanxess Deutschland Gmbh Thermisch leitfähige und elektrisch isolierende thermoplastische Compounds
JP5767809B2 (ja) * 2008-03-18 2015-08-19 株式会社カネカ 高熱伝導性樹脂成形体
CN101977976B (zh) * 2008-03-20 2014-08-27 帝斯曼知识产权资产管理有限公司 导热塑料材料的热沉
JP2010100682A (ja) * 2008-10-21 2010-05-06 Techno Polymer Co Ltd 放熱性樹脂組成物、ｌｅｄ実装用基板及びリフレクター
WO2011095208A1 (fr) * 2010-02-03 2011-08-11 Abb Research Ltd Système d'isolation électrique
JP5688409B2 (ja) * 2010-04-07 2015-03-25 電気化学工業株式会社 Ｌｅｄ照明筐体用の放熱性樹脂組成物及びそのｌｅｄ照明用放熱性筐体
JP2013001802A (ja) * 2011-06-16 2013-01-07 Unitika Ltd 熱伝導性樹脂組成物およびそれからなる成形体
JP2013053188A (ja) * 2011-09-01 2013-03-21 Unitika Ltd ポリアミド樹脂組成物およびそれからなる成形体
BR112014007243B1 (pt) * 2011-09-27 2022-04-19 Basf Se Composição, componentes e dispositivo de iluminação
DE102011084519A1 (de) 2011-10-14 2013-04-18 Evonik Industries Ag Verwendung einer Mehrschichtfolie für die Herstellung photovoltaischer Module
CA2867720A1 (fr) * 2012-03-20 2013-09-26 Rhodia Operations Compositions de polymere retardatrices de flamme
CN104364900A (zh) * 2012-04-17 2015-02-18 莫门蒂夫性能材料股份有限公司 用于减少成型周期时间的导热聚合物组合物
CN103073878B (zh) * 2012-09-26 2014-12-24 天津金发新材料有限公司 聚酰胺组合物、制备方法及其应用
CN103304992B (zh) * 2013-06-14 2015-11-18 慈溪金岛塑化有限公司 一种高灼热丝起燃温度阻燃尼龙组合物
EP2816082B1 (fr) * 2013-06-19 2018-09-19 3M Innovative Properties Company Eléments fabriqués par traitement thermoplastique de composés polymère - nitrure de bore, composés polymère - nitrure de bore pour la fabrication de tels éléments et leur utilisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014095984A1 (fr) * 2012-12-18 2014-06-26 Quarzwerke Gmbh Matériau synthétique thermoconductible
EP2862894A1 (fr) * 2013-10-15 2015-04-22 LANXESS Deutschland GmbH Masse de formage thermoplastique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2015144491A1 *

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HUE043312T2 (hu) 2019-08-28
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KR20160140636A (ko) 2016-12-07
US20200270417A1 (en) 2020-08-27
CN110452526A (zh) 2019-11-15
WO2015144491A1 (fr) 2015-10-01
JP2017508854A (ja) 2017-03-30
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CN106133043B (zh) 2019-07-12
US20170101519A1 (en) 2017-04-13

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