EP3931247A1 - Matière à mouler thermoplastique - Google Patents

Matière à mouler thermoplastique

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Publication number
EP3931247A1
EP3931247A1 EP20704552.7A EP20704552A EP3931247A1 EP 3931247 A1 EP3931247 A1 EP 3931247A1 EP 20704552 A EP20704552 A EP 20704552A EP 3931247 A1 EP3931247 A1 EP 3931247A1
Authority
EP
European Patent Office
Prior art keywords
weight
polyamide
component
thermoplastic
fibers
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
EP20704552.7A
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German (de)
English (en)
Inventor
Jens Cremer
Sebastian Wagner
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3931247A1 publication Critical patent/EP3931247A1/fr
Pending 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
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • 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
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • 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
    • C08K3/16—Halogen-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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming

Definitions

  • the invention relates to the use of special glass fibers to increase the weld seam strength of injection molded articles made from thermoplastic molding compounds containing thermoplastic polyamides, as well as corresponding thermoplastic molding compounds, processes for their Fier ein, their use and fibers, films or molded articles made from thermoplastic molding compound.
  • Polyamides are among the polymers produced on a large scale around the world and, in addition to the areas of application for flakes, films, fibers and moldings (materials), serve a multitude of other uses.
  • polyamide 6 Polycapro lactam, PA 6
  • polyamide 66 nylon, polyhexamethylene adipamide, PA 66
  • Most of the technically important polyamides are semi-crystalline thermoplastic polymers that are characterized by high temperature resistance.
  • Moldings made from polyamides can be produced, for example, by injection molding. This usually creates (dynamic) weld lines.
  • Static weld lines arise e.g. B. during the welding process when joining thermoplastic molded parts.
  • a dynamic weld line is created in a plastic component in the injection molding process through the confluence of at least two mass flows, e.g. B. behind flea spaces, through wall thickness differences or through multiple gates or injection points of the tool. When two flow fronts meet, a weld line is created at the point of confluence, too
  • Called weld line or flow line These seams appear optically as lines. A binding seam is therefore a surface effect that is often visible on injection molded parts.
  • a weld line is a potential weak point in the component.
  • the flow fronts meet each other perpendicularly due to a volume expansion and weld.
  • the lower the pressure and temperature the lower the strength of the weld line.
  • Reinforcing fibers are often oriented parallel to the weld line due to the shear acting during the injection molding process and the flow conditions. If the melt has already cooled down so much that the meeting melt fronts can no longer be welded completely, the weld line on the surface can often be seen as a V-shaped notch. If tensile stresses occur in this area, the notch effect leads to excessive stress on the weld line, which then functions as a predetermined breaking point.
  • E-glass fibers consist of 52 to 62% silicon dioxide, 12 to 16% aluminum oxide, according to ASTM D578-00,
  • E-glass fibers 16 to 25% calcium oxide, 0 to 10% borax, 0 to 5% magnesium oxide, 0 to 2% alkali oxides, 0 to 1.5% titanium dioxide and 0 to 0.3% iron oxide.
  • E-glass fibers have a density of 2.54 to 2.62 g / cm 3 , a tensile modulus of elasticity of 70 to 75 GPa, a tensile strength of 3000 to 3500 MPa and an elongation at break of 4.5 to 4.8% , the mechanical properties of single fibers with a diameter of 10 mm and a length of 12.7 mm at 23 ° C and a relative humidity of 50% were determined.
  • E-glass is an aluminum borosilicate glass with a low proportion of alkali oxides ( ⁇ 2% by weight) and good electrical insulation properties. E-glass fibers are particularly well suited for the manufacture of printed circuits and for plastic reinforcement. A major disadvantage of e-glasses is their low acid resistance. E-glasses are described, inter alia, in US Pat. No. 3,876,481.
  • R-glass fibers are used in areas of application with high mechanical and thermal requirements and have a fairly high tensile strength even at elevated temperatures.
  • ECR-Glass E-Glass Corrosion Resistance
  • No. 5,789,329 is a boron-free aluminum-lime-silicate glass with a low proportion of alkali oxides.
  • ECR glass fibers have high acid resistance and good mechanical and electrical properties.
  • EP 2 703 436 A1 describes polyamide molding compounds which, in addition to particulate fillers, contain high-strength glass fibers which are essentially composed of silicon dioxide, aluminum oxide and magnesium oxide. Preferred glass fibers contain at least 5% by weight of magnesium oxide and at most 10% by weight of calcium oxide.
  • EP 3 130 663 A1 relates to reinforced polyamides, in particular long glass fiber reinforced polyamides, which have good mechanics and better shrinkage during processing.
  • the polyamides contain special glass fibers made from 57.5 to 59.5 wt.% S1O2, 17 to 20 wt.% Al2O3, 11 to 13.5 wt.% CaO and 8.5 to 12.5 wt. -% MgO.
  • the object of the invention is to provide thermoplastic molding compositions containing thermoplastic polyamides which, while at the same time having high rigidity and strength, have increased weld line strength. Furthermore, the thermoplastic molding compositions should have a low density.
  • the object of the invention is also to provide an additive which allows an increase in the bond seam strength and preferably at the same time a reduction in the density of moldings made from thermoplastic molding compositions containing thermoplastic polyamides, the molding compositions additionally containing at least one elastomer.
  • the object is achieved according to the invention by using glass fibers which have a tensile strength according to DIN ISO 527-5 from 86.0 to 92.0 GPa, a tensile modulus of elasticity according to DIN ISO 527-5 from 2600 to 3200 MPa and a Have a softening point according to DIN ISO 7884-1 of 900 to 950 ° C, preferably by using glass fibers of the following composition
  • the glass fibers have a tensile strength according to DIN ISO 527-5 of 86.0 to 92.0 GPa, a tensile modulus of elasticity according to DIN ISO 527-5 of 2600 to 3200 MPa and a softening point according to DIN ISO 7884-1 of 900 up to 950 ° C.
  • the standards refer to the 2019 version.
  • thermoplastic molding composition containing a) 30.0 to 90.0% by weight of at least one thermoplastic polyamide as component A),
  • glass fibers which have a tensile strength according to DIN ISO 527-5 of 86.0 to 92.0 GPa, a tensile modulus of elasticity according to DIN ISO 527-5 from 2600 to 3200 MPa and a softening point according to DIN ISO 7884-1 of 900 to 950 ° C, preferably of the following composition
  • component C 0 to 3.0% by weight of at least one heat stabilizer as component C
  • component D further additives and processing aids as component D
  • the sum of the percentages by weight of components A) to D) being 100% by weight.
  • thermoplastic molding composition by mixing components A), B) and, if appropriate, C) and D).
  • thermoplastic molding compositions by producing fibers, foils and moldings, by using the corresponding fibers, foils or moldings and by methods for their production. Moldings are preferred.
  • the weld line strength is a special criterion for moldings produced by injection molding, with at least two flow fronts of the molten polyamide composition meeting during injection molding and forming at least one weld line.
  • weld line is understood to mean a dynamic weld line, as described at the beginning.
  • the term “weld line” can also be replaced by “flow line” or “weld line”. It is essential that the weld line is obtained by injection molding the polyamide composition.
  • the weld lines are often the weak points of the injection molded body. In particular, if the polyamide composition on the mold wall of the injection molding tool cools down too quickly, the confluent mass flow can no longer combine optimally. It comes to the formation of weld lines or small notches, which then represent a weak point in the injection molded part. In the event of mechanical stress, a break often occurs along the weld line / flow line, or a break begins in this area. Therefore, the weld line strength is important for the strength of the injection molded body as a whole.
  • thermoplastic molding compositions according to the invention are explained in more detail below.
  • thermoplastic molding compositions contain 30.0 to 90.0% by weight, preferably 40.0 to 85.0% by weight, preferably 50.0 to 80.0% by weight, in particular 60, 0 to 74.9% by weight of at least one thermoplastic polyamide.
  • component C) is also used, the maximum possible amount is reduced by the minimum amount of component C) used, so that the sum of all parts by weight
  • component C) heat stabilizer results in ranges of 30.0 to 89.99% by weight, preferably 40.0 to 84.98% by weight, in particular 50.0 to 79.95% by weight. -%, especially 60.0 to 74.90% by weight.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 210, preferably 110 to 160 ml / g, determined in a 0.5% by weight solution in 96.0% by weight sulfuric acid at 25 ° C according to ISO 307.
  • Examples include polyamides derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and polyamides obtained by reacting dicarboxylic acids with diamines.
  • Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned here as acids.
  • diamines are alkanediamines with 6 to 12, in particular 6 to 9, carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2.2- Di- (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2-methyl-pentane.
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacic acid amide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95.0% by weight of caprolactam units.
  • polyamides can be obtained from w-aminoalkylnitriles such as, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by what is known as direct polymerization in the presence of water, for example in DE-A-10313681, EP-A- 1 198 491 and EP 9 220 65 described.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of several polyamides are suitable, the mixing ratio being as desired.
  • Suitable polyamides preferably have a melting point of less than 265 ° C.
  • PA 1 1 1 1-aminoundecanoic acid
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1.12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1.13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA MXD6 m-xylylenediamine, adipic acid
  • PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
  • PA 6 / 6T (see PA 6 and PA 6T)
  • PA 6/66 (see PA 6 and PA 66)
  • PA 6/12 see PA 6 and PA 12
  • PA 66/6/610 see PA 66, PA 6 and PA 610) (see PA 61 and PA 6T)
  • Component A) is optionally a blend of at least one aliphatic polyamide and at least one partially aromatic or aromatic polyamide.
  • component A) which contain polyamide-6 and polyamide-6.6 and optionally additionally polyamide-6l / 6T. It is preferred to work with a major amount of polyamide-6.6.
  • the amount of polyamide-6 is preferably 5.0 to 50.0% by weight, particularly preferably 10.0 to 30.0% by weight, based on the amount of polyamide-6.6. If polyamide-6l / 6T is also used, its proportion is preferably 10.0 to 25.0% by weight, based on the amount of polyamide-6.6.
  • polyamide-6l / 6T polyamide-6l or polyamide-6T or mixtures thereof can also be used.
  • polyamide-6, polyamide-66 and copolymers or mixtures thereof are used according to the invention.
  • the polyamide-6 or polyamide-66 preferably has a viscosity number in the range from 80 to 180 ml / g, in particular 85 to 160 ml / g, in particular 90 to 140 ml / g, determined at 0.5% by weight Solution in 96% strength by weight sulfuric acid at 25 ° C according to ISO 307.
  • a suitable polyamide-66 preferably has a viscosity number in the range from 1 10 to 170 ml / g, particularly preferably 130 to 160 ml / g.
  • suitable partially crystalline and amorphous polyamides reference can also be made to DE 10 2005 049 297. They have a viscosity number of 90 to 210, preferably 110 to 160 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. in accordance with ISO 307.
  • polyamide-6 or polyamide-66 0 to 10% by weight, preferably 0 to 5% by weight, can be replaced by partially aromatic polyamides. Partly aromatic polyamides are particularly preferably not used.
  • the thermoplastic polyamide is preferably selected from polyamide-6, polyamide-66, polyamide-6.10, polyamide-6T / 6l, polyamide-6T / 6, polyamide-6T / 66 and copolymers or mixtures thereof.
  • the molding compositions according to the invention contain 10.0 to 70.0, preferably 15.0 to 55.0 and in particular 20.0 to 40.0% by weight, especially 25.0 to 35.0% by weight.
  • % Glass fibers that have a tensile strength according to DIN ISO 527-5 of 86.0 to 92.0 GPa, a tensile modulus of elasticity according to DIN ISO 527-5 from 2600 to 3200 MPa and a softening point according to DIN ISO 7884-1 of 900 to 950 ° C, preferably with the following composition B1) 55.5 to 62.0 wt .-% Si0 2 ,
  • oxides B5) are to be understood as meaning oxides of the elements Li, Zn, Mn, Le, V, Ti, Be, Sn, Ba, Zr, Sr, Fe, B, Na, K or mixtures thereof.
  • the glass fibers can contain up to 1, preferably up to 0.5% by weight of Li 2 O and / or Ti0 2 .
  • Fe 2 0 3 and / or B 2 0 3 can, if they are present, be contained in amounts of 0.1 to 3, preferably 0.2 to 3% by weight.
  • Oxides of the elements Zn, Mn, Le, V, Be, Sn, Ba, Zr, Sn can, if they are present, according to the invention in amounts from 0.05 to 3% by weight, preferably from 0.2 to 1, 5 wt .-% be contained th.
  • Suitable amounts for Na 2 0 and / or K 2 0, if they are present, are at least
  • the ratio MgO (B4): Al 2 0 3 (B2) is preferably at least 1.4 to a maximum of 3.0, in particular from 1.5 to 2.8,
  • the MgO (B4): CaO (B3) ratio is preferably from 1.4 to 2.7, in particular from 1.2 to 2.6.
  • the sums of MgO + CaO and MgO + AI2O3 are particularly limited to the following areas:
  • glass fibers B which have a fiber length of 2 to 20 mm, in particular 3 to 10 mm, and / or an L / D ratio of 200 to 2000, preferably 200 to 800.
  • the glass fibers B) can be surface-pretreated with a silane compound for better compatibility with the thermoplastics.
  • Suitable silane compounds are those of the general formula
  • n an integer from 2 to 10, preferably 3 to 4,
  • n an integer from 1 to 5, preferably 1 to 2,
  • k an integer from 1 to 3, preferably 1.
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as the X substituent.
  • the silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1.0 and in particular 0.05 to 0.5% by weight (based on B)) for surface coating.
  • Suitable coating agents are based on isocyanates, phenolic resins or acrylic acid derivatives.
  • the polyamide molding compounds according to the invention can be produced by the known processes for the production of long fiber-reinforced rod granules, in particular by pultrusion processes in which the endless fiber strand (roving) is completely soaked with the polymer melt and then cooled and cut.
  • the long fiber-reinforced rod granulate obtained in this way which preferably has a granulate length of 3 to 25 mm, in particular from 4 to 12 mm, can go with the usual processing methods, such.
  • B. injection molding or pressing can be processed into molded parts.
  • the compositions according to the invention contain 0 to 3.0% by weight, preferably 0 to 2.0% by weight, particularly preferably 0 to 1.0% by weight, in particular 0 to 0.3% by weight % of at least one heat stabilizer. If a heat stabilizer is present, the amounts are 0.01 to 3.0% by weight, preferably 0.02 to 2.0% by weight, particularly preferably 0.05 to 1.0% by weight, in particular 0 , 1 to 0.3 wt%.
  • the upper limit of component A) is reduced accordingly.
  • the upper limit of the amount of component A) is 89.99% by weight.
  • the heat stabilizers are preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof.
  • the amount of copper is preferably 0.003 to 0.5% by weight, in particular 0.005 to 0.3% by weight and particularly preferably 0.01 to 0.2% by weight, based on the Total weight of the composition.
  • the amount of these stabilizers is preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1.5% by weight, based on the total weight of the composition.
  • the amount of these stabilizers is preferably 0.1 to 1.5% by weight, particularly preferably 0.2 to 1% by weight, based on the total weight of the composition.
  • the amount of these stabilizers is preferably 0.1 to 1.5% by weight, particularly preferably from 0.2 to 1% by weight, based on the Total weight of the composition.
  • Suitable compounds C) of monovalent or divalent copper are, for. B. salts of mono- or divalent copper with inorganic or organic acids or mono- or dihydric phenols, the oxides of mono- or divalent copper or the complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides or phosphines, before given Cu (I) - or Cu (II) salts of hydrohalic acids, hydrocyanic acids or the copper salts of the aliphatic carboxylic acids.
  • the monovalent copper compounds CuCI, CuBr, Cul, CuCN and CU2O and the divalent copper compounds CuCh, CuSC> 4, CuO, copper (II) acetate or copper (II) stearate are particularly preferred.
  • the copper compounds are commercially available or their production is known to the person skilled in the art.
  • the copper compound can be used as such or in the form of concentrates.
  • Concentrate is a polymer, preferably of the same chemical nature as component A), which contains the copper salt in high concentration.
  • the use of concentrates is a common process and is used particularly frequently when very small amounts of an input material have to be dosed.
  • the copper compounds are advantageously used in combination with other metal halides, in particular alkali halides such as Nal, Kl, NaBr, KBr, the molar ratio of metal halide to copper halide being 0.5 to 20, preferably 1 to 10 and particularly preferably 3 to 7 , is.
  • stabilizers based se kundärer aromatic amines include adducts of phenylenediamine with acetone (Naugard ® A), adducts of phenylenediamine with linolenic acid, 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (Nau gard ® 445 ), N, N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine or mixtures of two or more thereof.
  • Preferred examples of stabilizers based on sterically hindered phenols which can be used according to the invention are N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, bis- (3,3-bis - (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid) glycol ester, 2,1'-thioethylbis (3- (3,5-di.tert-butyl-4-hydroxyphenyl) propionate, 4, 4'-Butylidene bis (3-methyl-6-tert-butylphenol), tri-ethylene glycol 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, or mixtures of two or more of these Stabilizers.
  • Preferred phosphites and phosphonites are triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphentaerythritol diphosphite, tris (2,4-di-tertyl-butylphenyl) phosphite, bis-pentaerythritol, bisphosphite (2, 4-di-tertyl-butylphenyl) phosphite 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisode
  • a preferred embodiment of the heat stabilizer consists of a combination of organic heat stabilizers (in particular Hostanox PAR 24 and Irganox 1010), a bi sphenol A based epoxide (in particular Epikote 1001) and a copper stabilization on the basis of Cul and KI.
  • organic heat stabilizers in particular Hostanox PAR 24 and Irganox 1010
  • a bi sphenol A based epoxide in particular Epikote 1001
  • a copper stabilization on the basis of Cul and KI.
  • a commercially available stabilizer mixture consisting of African orga stabilizers and epoxides is, for example Irgatec NC66 ® of BASF SE. Heat stabilization based exclusively on Cul and Kl is particularly preferred.
  • further transition metal compounds in particular metal salts or metal oxides from group VB, VIB, VI IB or VIIIB of the periodic table, is possible or alternatively locked out.
  • the molding composition according to the invention can preferably not contain any transition metals from group VB, VIB, VI IB or VIIIB of the periodic table, such as. B. iron or steel powder, are added or not.
  • Irganox ® 1098 N, N'-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphe- nyl) propionamide]
  • compositions according to the invention contain, as component D), 0 to 30.0% by weight, preferably 0 to 20.0% by weight, in particular 0 to 10.0% by weight, especially 0 to 5.0% by weight , other additives.
  • component D 0 to 30.0% by weight, preferably 0 to 20.0% by weight, in particular 0 to 10.0% by weight, especially 0 to 5.0% by weight , other additives.
  • the minimum amount is 0.1% by weight, preferably 0.5% by weight, in particular 0.8% by weight.
  • component D) is also used, the upper limit of component A) is reduced accordingly.
  • the upper limit of the amount of component A) is 88.9% by weight.
  • additives are glass fibers different from component B), fillers and reinforcing materials different from glass fibers, thermoplastic polymers different from component A), or further additives.
  • thermoplastic molding compositions can contain 0 to 20% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight, of glass fibers other than component B).
  • component D comprises glass fibers, short fibers preferably being used. These preferably have a length in the range from 2 to 50 mm and a diameter of 5 to 40 ⁇ m.
  • continuous fibers rovings
  • Fibers with a circular and / or non-circular cross-sectional area are suitable, in the latter case the dimension ratio of the main cross-sectional axis to the secondary cross-sectional axis is in particular> 2, preferably in the range from 2 to 8 and particularly preferably in the range from 3 to 5.
  • component D) includes so-called “flat glass fibers”. These specifically have an oval or elliptical or an elliptical (so-called “cocoon” or “cocoon” fiber) or rectangular or almost rectangular cross-sectional area provided with constriction (s). Glass fibers with a non-circular cross-sectional area and a dimensional ratio of the main cross-sectional axis to the secondary cross-sectional axis of more than 2, preferably from 2 to 8, in particular from 3 to 5, is preferably used.
  • the proportion of flat glass fibers predominates, as defined above, i.e. H. they make up more than 50% by weight of the total mass of the fibers.
  • rovings of glass fibers are used as component D), these preferably have a diameter of 10 to 20 ⁇ m, preferably 12 to 18 ⁇ m.
  • the cross section of the glass fibers can be round, oval, elliptical, almost rectangular or rectangular. So-called flat glass fibers with a ratio of the cross-sectional axes of 2 to 5 are particularly preferred.
  • E-glass fibers are used. But all other types of fiberglass, such as. B. A-, C-, D-, M-, S-, R-glass fibers, or any mixtures thereof or mixtures with E-glass fibers can be used.
  • fillers and reinforcing material is understood broadly within the scope of the invention and includes particulate fillers, fibers other than glass fibers and any transition forms.
  • Particulate fillers can have a wide range of particle sizes, ranging from powdery to coarse-grained particles.
  • Organic or inorganic fillers and reinforcing materials can be used as fillers.
  • inorganic fillers such as kaolin, chalk, wollastonite, talc, calcium carbonate, silicates, titanium dioxide, zinc oxide, graphite, glass particles, eg. B.
  • nanoscale fillers such as carbon nanotubes (carbon nanotubes), nanoscale layered silicates, nanoscale aluminum oxide (AI2O3), nanoscale titanium dioxide (T1O2), graphene, permanently magnetic or magnetizable metal compounds and / or alloys, phyllosilicates and na Noscale silicon dioxide (S1O2) can be used.
  • the fillers can also be surface treated.
  • sheet silicates in the molding compositions according to the invention for. B. kaolins, serpentines, talc, mica, vermiculite, lllite, smectite, montmorillonite, hectorite, double hydroxides or mixtures thereof can be used.
  • the sheet silicates can be surface-treated or untreated.
  • one or more fibrous materials can be used. These are preferably selected from known inorganic reinforcing fibers such as boron fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers; organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • inorganic reinforcing fibers such as boron fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers
  • organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • carbon fibers aramid fibers, boron fibers, metal fibers or potassium titanate fibers is particularly preferred.
  • no glass fibers other than component B) and no other fillers and reinforcing materials are used.
  • thermoplastic polymers different from component A) can be used.
  • thermoplastic polymers different from component A) are preferably selected from
  • Homopolymers or copolymers that contain at least one monomer in copolymerized form which is selected from C2-C10 monoolefins, such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C2 -Cio-alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched and unbranched Ci-Cio alcohols, vinyl aromatics, such as styrene, acrylonitrile, methacrylonitrile, a, b- ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride,
  • C2-C10 monoolefins such as ethylene or propylene, 1,3-butadiene, 2-ch
  • PC Polycarbonates
  • Polyesters such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA),
  • thermoplastic polyurethanes TPU
  • Examples include polyacrylates with the same or different alcohol residues from the group of C ⁇ Cs alcohols, especially butanol, hexanol, octanol and 2-ethylhexanol, polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrile-butadiene-styrene Copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene Butadiene-methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMA), polyoxymethylene (POM), polyviny
  • the at least one thermoplastic polymer optionally additionally contained in the molding composition according to the invention is preferably polyvinyl chloride (PVC), Polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.
  • thermoplastic molding compositions 1.0 to 30.0 wt.%, Preferably 2.0 to 20.0 wt.%, Particularly preferably 3.0 to 10.0 wt.%, In particular 3 , 5 to 7.0 wt .-%, contain at least one elastomer.
  • the elastomer is preferably selected from
  • d1) copolymers of ethylene with at least one comonomer selected from C3-12 olefins, Ci-12-alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride, as component D1),
  • components D1) and D2) can also be grafted with maleic anhydride.
  • One or more different comonomers can be present in component D1), preferably one to three different copolymers, particularly preferably one or two different comonomers.
  • the C3-12 olefins are preferably terminal, linear C3-12 olefins, particularly preferably C3-8 olefins. Examples of suitable olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.
  • Ci-12-alkyl (meth) acrylates there are Ci-12-alkyl residues, preferably C2-6-alkyl residues, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl residues. It is preferably an alkyl acrylate.
  • the proportion of basic ethylene building blocks is preferably 1 to 99% by weight, particularly preferably 60 to 98% by weight, particularly preferably 84 to 96% by weight.
  • C3-12 olefins preferably 99 to 1% by weight, particularly preferably 40 to 10% by weight,
  • Ci-12-alkyl (meth) acrylates preferably 40 to 2% by weight, particularly preferably 30 to 5% by weight,
  • (Meth) acrylic acid preferably 40 to 2% by weight, particularly preferably 30 to 5% by weight,
  • Maleic anhydride preferably 3 to 0.01% by weight, particularly preferably 2 to 0.1% by weight.
  • the total amount of comonomers is preferably in the range from 1 to 99% by weight, particularly preferably from 2 to 40% by weight.
  • the copolymers of component D1) can be random or block copolymers.
  • the former consist of a crystallizing and thus physically crosslinking the main polymer (polyethylene), the degree of crystallization of which is reduced by a comonomer that is randomly incorporated along the chain, so that the crystallites in the finished molding compound do not exist have more direct contact. As in conventional elastomers, they then act as isolated cross-linking points.
  • the hard and soft segments are sharply separated in one molecule.
  • the material separates below a certain temperature into a continuous and a discontinuous phase. As soon as the latter falls below its glass temperature, it in turn acts as a networking point.
  • the copolymer of component D1) can also be grafted with maleic anhydride.
  • the maleic anhydride used for the grafting is preferably used in an amount of 5 to 0.005% by weight, particularly preferably 3 to 0.01% by weight, based on the copolymer of component D1).
  • the maleic anhydride content in the grafted copolymer of component D1) is preferably in the range from 2 to 0.1% by weight, based on the non-grafted copolymer of component D1).
  • Component D1) preferably has a melt flow index value (MVR) (190 ° C / 2.16 kg according to IS01 133) of 0.1 to 20 cm 3/10 min, particularly preferably 0.1 to 15 cm 3 / 10 min.
  • MVR melt flow index value
  • component D2 polyethylene or polypropylene or a mixture of both can be used as component D2).
  • This component D2) can also be grafted with maleic anhydride, the proportion of maleic anhydride, based on the polyolefin, being 5 to 0.005% by weight, particularly preferably 2 to 0.1% by weight.
  • Component D2) preferably has an MVR value (190 ° C / 2.16 kg according to IS01 133) of 0.1 to 20 cm 3/10 min, particularly preferably 0.1 to 15 cm 3/10 min.
  • elastomer describes components D1) and D2), which can optionally be grafted with maleic anhydride. They can preferably be thermoplastic elastomers (TPE). TPEs behave in a comparable way to classic elastomers at room temperature, but they can be plastically deformed when heat is applied and thus show a thermoplastic behavior.
  • mixtures of components D1) and D2) can also be used.
  • thermoplastic elastomers are mostly copolymers that consist of a “soft” elastomer component and a “hard” thermoplastic component. Their properties are between those of elastomers and thermoplastics.
  • Polyolefin elastomers are polymerized, for example, using metallocene catalysts; ethylene-propylene elastomers (EPR or EPDM) can be cited as examples.
  • EPR or EPDM ethylene-propylene elastomers
  • the most common polyolefin elastomers are copolymers of ethylene and butene or ethylene and octene.
  • Lucalen ® A2540D is a low density polyethylene containing n-butyl acrylate as a comonomer. It has a density of 0.923 g / cm 3 and a Vicat softening temperature of 85 ° C. with a butyl acrylate content of 6.5% by weight.
  • Lucalen ® A2700M is a low-density polyethylene that also contains a butyl acrylate comonomer. It has a density of 0.924 g / cm 3 , a Vicat softening temperature of 60 ° C and a melting temperature of 95 ° C.
  • ExxonMobil's Exxelor TM VA 1801 polymer resin is a semi-crystalline ethylene copolymer functionalized with maleic anhydride by reactive extrusion and has a medium viscosity. The polymer backbone is completely saturated. The density is
  • Suitable preferred additives D) are lubricants, but also flame retardants, light protection agents (UV stabilizers, UV absorbers or UV blockers), dyes and nucleating agents and optionally also metallic pigments, metal flakes, metal-coated particles, antistatic agents, conductivity additives, mold release agents, optical Brighteners, defoamers, etc.
  • the molding compositions according to the invention can contain 0 to 20.0% by weight, particularly preferably 0 to 10.0% by weight, based on the total weight of the composition, of at least one flame retardant as additive E). If the molding compositions according to the invention contain at least one flame retardant, then preferably in an amount from 0.01 to
  • Preferred halogen-free flame retardants are red phosphorus, phosphinic acid or diphosphinic acid salts, and / or nitrogen-containing flame retardants such as melamine, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, melamine phosphate (primary, secondary) or secondary melamine pyrophosphate and derivatives of these, guanane and neopentylglycolboron derivatives known to those skilled in the art, , as well as polymeric melamine phosphate (CAS No .: 56386- 64-2 or 218768-84-4 and EP-A-1 095 030), ammonium polyphosphate, trishydroxyethyl iso- cyanurate (optionally also ammonium polyphosphate in a mixture with trishydroxyethyl isocyanurate) (EP-A-058 456 7).
  • nitrogen-containing flame retardants such as melamine, mel
  • N-containing or P-containing flame retardants or PN condensates suitable as flame retardants can be found in DE-A-10 2004 049 342, as can the synergists customary for this, such as oxides or borates.
  • Suitable halogen-containing flame retardants are z. B.
  • Oligomeric brominated polycarbonates BC 52 Great Lakes
  • polypentabromo benzyl acrylate with N greater than 4 FR 1025 Dead sea bromine
  • thermoplastic molding compositions according to the invention can contain 0 to 1.5% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1% by weight, of a lubricant.
  • the metal ions are preferably alkaline earth and Al, Ca or Mg being particularly preferred.
  • Preferred metal salts are Ca stearate and Ca montanate as well as Al stearate. Mixtures of different salts can also be used, the mixing ratio being as desired.
  • the carboxylic acids can be mono- or divalent. Examples are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 40 carbon atoms).
  • the aliphatic alcohols can be mono- to tetravalent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be monovalent to trivalent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate. Ethylenebisstearamide (EBS) is particularly preferred.
  • the polyamide compositions according to the invention can contain nigrosine as component D), preferably in an amount of 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight, in particular 0.2 to 0.4 % By weight, based on the molding compound.
  • Nigrosine (Solvent Black 7 - CAS: 8005-02-5) is a deep black organic dye. Nigrosine is a mixture of synthetic black colorants and is obtained by heating nitrobenzene, aniline and aniline hydrochloride in the presence of an iron or copper catalyst. Nigrosine occurs in different versions (water-soluble, alcohol-soluble and oil-soluble). A typical water-soluble nigrosine is Acid Black 2 (Cl 50420), a typical alcohol-soluble nigrosine is Solvent Black 5 (Cl 50415), and a typical oil-soluble nigrosine is Solvent Black 7 (Cl 50415: 1).
  • nigrosine is not harmless in terms of a potentially harmful effect.
  • nigrosine to the polyamide compositions according to the invention can further reduce the tendency of the polyamide composition to crystallize, since nigrosine interferes with crystallization. The addition thus leads to slower crystallization or to lowering the crystallization temperature.
  • Solvent Black 28 (CAS No. 12237-23-91) and, if necessary, to combine it with at least one other colorant.
  • Component D) is then preferably selected from non-nucleating colorants other than nigrosine. These include non-nucleating dyes, non-nucleating pigments and mixtures thereof. Examples of non-nucleating dyes are Solvent Yellow 21 (commercially available as Oracet Yellow ® FA 160 by the company BASF SE) or Solvent Blue 104 (commercially available as Solvaperm ® Blue 2B from the company Clariant). Examples of non-nucleating Pig ments are Pigment Brown 24 (commercially available as Sicotan ® Yellow K 201 1 FG from BASF SE).
  • the molding composition according to the invention contains as component E) 0.001 to 0.5% by weight of at least one white pigment.
  • the molding compound can contain 0.05% by weight of titanium dioxide from Kronos 2220 from Kronos.
  • Carbon black can also be used as component D).
  • the compositions according to the invention contain 0.05 to 3% by weight, preferably 0.07 to 1% by weight, preferably 0.1 to 0.2 wt.% carbon black.
  • Carbon black also known as industrial black, is a modification of carbon with a high surface-to-volume ratio and consists of 80 to 99.5% by weight of carbon.
  • the specific surface area of carbon black is about 10 to 1500 m 2 / g (BET).
  • the carbon black can be produced as gas black, furnace black, lamp black, split black or acetylene black.
  • the grain diameter is in the range from 8 to 500 nm, typically 8 to 110 nm.
  • Carbon black is also referred to as Pigment Black 7 or Lamp Black 6. Color carbon blacks are nano-sized carbon blacks which, due to their fineness, increasingly lose the brown base tone of conventional carbon blacks.
  • At least one additional colorant selected from anthraquinone colorants, benzimidazolone colorants and perinone colorants can also be used as component D) in addition to carbon black and nigrosine.
  • the colorants are preferably dyes, pigments or mixtures thereof.
  • the colorant is used in an amount of 10 to 1000 ppm, preferably 20 to 500 ppm, in particular 50 to 200 ppm, based on the total molding composition.
  • the polyamide molding compounds are produced by processes known per se. This includes mixing the components in the appropriate proportions by weight.
  • the components are preferably mixed at elevated temperatures by joint blending, mixing, kneading, extruding or rolling.
  • the temperature during mixing is preferably in a range from 220 ° C to 340 ° C, particularly preferably from 240 to 320 ° C and especially from 250 to 300 ° C.
  • the person skilled in the art is familiar with the suitable methods.
  • the present invention also relates to moldings which are produced using the polyamide molding compositions according to the invention.
  • the polyamide molding compounds can be used to produce molded parts using any suitable processing techniques. Suitable processing techniques are in particular injection molding, extrusion, coextrusion, deep drawing or any other known plastic molding method. These and other examples are e.g. B. in "Coloring of plastics", VDI-Verlag, ISBN 3-18-404014-3 to find.
  • the shaped bodies are preferably produced by means of a twin screw extruder.
  • the present invention also relates to a process for the production of the molding compositions according to the invention, components A), B) and optionally C) and D) in the corresponding corresponding amounts are mixed, preferably by extrusion.
  • Commercially available twin-screw extruders of different sizes (shaft diameters) can be used in this process.
  • the temperature during the extrusion is 200 to 400.degree. C., preferably 250 to 350.degree. C., particularly preferably 250 to 320.degree.
  • the moldings produced from the molding compositions according to the invention are used for the Fierstel development of internal and external parts, preferably with a load-bearing or mechanical function, in the electrical, furniture, sports, mechanical engineering, sanitary and flygiene, medicine, energy and drive technology, automobile and other means of transport sectors or housing material for devices and apparatus for telecommunications, entertainment electronics, household appliances, mechanical engineering, in the area of fleizungs Symposium or for fastening parts for installations or for containers and ventilation parts of all kinds.
  • the mechanics, in particular the impact strength of the molded parts according to the invention, are significantly higher, with better shrinkage at the same time.
  • B. bearings or thread inserts from the poly ester molding compound according to the invention, encapsulated with other compatible or incompatible materials, such as. B. thermoplastics, thermosets or elastomers;
  • Outsert parts such as frames, housings or supports made of the polyamide molding compound according to the invention, in which functional elements made of other compatible or incompatible materials, such as.
  • Hybrid parts (elements made from the polyamide molding compound according to the invention combined with other compatible or incompatible materials, such as thermoplastics, thermosets or elastomers) produced by composite injection molding, injection welding. Assembly injection molding, ultrasonic, friction or laser welding, gluing, flanging or riveting;
  • the polyamide molding compound according to the invention can be the substrate itself or the substrate carrier or, in the case of FHybrid / bi-injection parts, a defined substrate area, which can also be achieved by subsequent chemical (e.g. etching) or physical treatment (e.g. machining or laser ablation) can be brought to the surface;
  • Moldings are preferably produced from the polyamide compositions used according to the invention by injection molding, with at least two flow fronts of the molten polyamide composition meeting during injection molding and forming at least one weld line.
  • the molded bodies thus have at least one weld line that results from the injection molding process.
  • Injection molding can take place according to known methods and is described, for example, in “Coloring of plastics”, VDI-Verlag, ISBN 3-18-404014-3.
  • At least two sprue points are provided in the tool, resulting in at least two flow fronts of the molten polyamide composition.
  • significantly more injection points can also be provided.
  • the at least two flow fronts can arise by flowing around a flea space or core in the mold.
  • the moldings produced according to the invention can be one-piece or multi-piece.
  • the individual molded bodies are to be connected to one another subsequently, for example by welding, such as friction welding, gas welding or laser beam welding.
  • Polyamide-6 Ultramid ® B27 from BASF SE, melting point: 220 ° C, viscosity number
  • Floch-resistant glass fiber Composition: SiC> 2: 60.8% by weight; AI2O3: 15.2% by weight, MgO:
  • Stabilizer Irganox ® 1098 from BASF SE (heat stabilizer)
  • Carbon black Printex 60 from Orion Engineered Carbons GmbHFI
  • EBS Ethylenebisstearamide
  • the molding compositions were produced by mixing the ingredients listed below in a ZE 25 A UTXi twin-screw extruder at temperatures of 260.degree.
  • the properties specified in Table 1 below were determined according to the specified standards, valid in 2019. The proportions of the ingredients are given in% by weight.
  • the granulate obtained was injected into standard ISO flound bones on an injection molding machine at a melt temperature of 290 ° C. and assessed both visually and by measurement.
  • the production of the standard ISO dog bones with a thickness of 4 mm and a length of 150 mm was carried out via injection points located opposite one another at the ends of the dog bone, so that the inflowing polyamide flowed from the outside into the center of the dog bone and was located in the center of the Molded body formed a weld line.
  • the weld line strength was determined by a standardized tensile strength test.
  • the mechanical properties were determined in accordance with DIN ISO 527 or 179-2 / 1 eU or 179-2 / 1 eAf in the 2019 version. The amounts given in the table are% by weight. Table 1

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Abstract

L'invention concerne l'utilisation de fibres de verre, lesquelles présentent une résistance à la rupture selon DIN ISO 527-5 de 86,0 à 92,0 GPa, un module d'élasticité en traction selon DIN ISO 527-5 de 2600 à 3200 MPa et un point de ramollissement selon DIN ISO 7884-1 de 900 à 950 °C, pour augmenter la résistance des joints de corps moulés composés de matières à mouler contenant des polyamides thermoplastiques.
EP20704552.7A 2019-02-25 2020-02-19 Matière à mouler thermoplastique Pending EP3931247A1 (fr)

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KR20210132145A (ko) 2021-11-03
JP7500592B2 (ja) 2024-06-17
BR112021014885A2 (pt) 2021-10-05
WO2020173766A1 (fr) 2020-09-03
US20220145046A1 (en) 2022-05-12
CN113474402B (zh) 2023-10-27
JP2022522673A (ja) 2022-04-20

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