DE202010017765U1 - Compositions filled with ground glass - Google Patents

Abstract

Compositions containing A) 5 to 95% by weight, preferably 20 to 90% by weight, particularly preferably 30 to 80% by weight of a thermoplastic, B) 5 to 80% by weight, preferably 10 to 60% by weight. -% of a non-fibrous and non-foamed ground glass with a d90 of 10 to 300 microns.

Description

The present invention relates to compositions based on a thermoplastic containing non-fibrous and non-foamed, ground glass with a specific particle size distribution and the preparation and use of the compositions according to the invention for the production of products, preferably fibers, films and moldings of any kind.

To modify the treatment, processing and application behavior, plastics are mostly provided with auxiliaries and with fillers and reinforcing materials. The latter improve properties such as stiffness, strength, heat resistance, dimensional stability and reduce thermal expansion.

Of particular importance for compositions in the art are fillers and reinforcing materials of minerals or glass, in particular borosilicate glass or silicate glass, which is used in the form of glass fibers, hollow or filled glass beads, glass flakes or in the form of expanded glass or foam glass.

Out DE 103 29 583 A1 and DE 103 34 875 A1 Materials are known for moldings containing, among other things as a thermoplastic polyamide and as a filler glass powder.

DE 10 2004 005 642 A1 . DE 10 2004 017 350 A1 and DE 10 2004 038 162 A1 all deal with food casings of thermoplastic constituents, inter alia, based on (co) polyamide (s) with, inter alia, glass flour as an inorganic particulate substance which can be added advantageously in particular in the outer layer of the shell, wherein the average particle size of the inorganic particles d50 greater than 10 μm, preferably in the range of 15 to 100 microns, more preferably in the range of 20 to 75 microns.

Finally revealed DE 10 2009 022 893 A1 Powder formulations with adsorbent particles based on polyester or polyamides which can also be added as filler glass powder.

However, a well-known drawback with the use of fillers and reinforcing materials lies in the negative impact on the fire, in particular the self-extinguishing behavior, so that to achieve a certain fire classification according to UL94 or in the glow wire after IEC60695-2-12 (GWFI) usually an increased effort in the use of flame retardants is required.

It was therefore an object of the present invention to provide a filler and reinforcing material for thermoplastic molding compositions in which the self-extinguishing behavior is less adversely affected by comparable flameproofing equipment than with conventional glass-based fillers and reinforcing materials.

It has now surprisingly been found that compositions based on a thermoplastic in the use of non-fibrous and unfoamed, ground glass in the form described in more detail below are less adversely affected in their fire behavior despite comparable flame retardant, as compared to conventional glass-based filling and Reinforcing would be the case, or that can be implemented with the glass described in more detail below, a comparable fire behavior with a less strong or less concentrated flame retardant than would be the case with conventional fillers and reinforcing materials.

• A) 5 bis 95 Gew.-%, bevorzugt 20 bis 90 Gew.-%, besonders bevorzugt 30 bis 80 Gew.-% eines Thermoplasten,
• B) 5 bis 80 Gew.-%, bevorzugt 10 bis 60 Gew.-%, besonders bevorzugt 15 bis 50 Gew.-% eines nicht-faserförmigen und nicht-geschäumten, gemahlenen Glases mit einem d90 von 10 bis 300 μm, bevorzugt 20 bis 150 μm, besonders bevorzugt 35 bis 80 μm.

The invention thus relates to compositions containing

• A) 5 to 95 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-% of a thermoplastic,
• B) 5 to 80 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 15 to 50 wt .-% of a non-fibrous and non-foamed, ground glass with a d90 of 10 to 300 .mu.m, preferably 20 to 150 microns, more preferably 35 to 80 microns.

For the sake of clarification, it should be noted that all general or preferred definitions and parameters listed below are included in any combination within the scope of the present invention.

In an alternative preferred embodiment, in addition to the components A) and B), the compositions may also contain C) 0.01 to 60% by weight, preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight, at least a halogen-containing or halogen-free flame retardant.

In a further preferred embodiment, the compositions may contain, in addition to components A) to C) or instead of C), also D) 0.01 to 50% by weight, preferably 1 to 25% by weight, particularly preferably 2 to 20% by weight .-% of at least one elastomer modifier included.

In a further preferred embodiment, in addition to components A) to D) or instead of C) and / or D), the compositions may also contain E) 0.01 to 5% by weight, preferably 0.05 to 3% by weight. , Particularly preferably 0.1 to 2 wt .-% of at least one lubricant and / or mold release agent.

In a further preferred embodiment, the compositions in addition to the components A) to E) or instead of C), D) and / or E) nor the component F) 0.01 to 50 wt .-%, preferably 1 to 30 wt .-%, more preferably 2 to 15 wt .-% of at least one filler different from component B).

In a further preferred embodiment, in addition to components A) to F) or instead of components C), D), E) and / or F), the compositions may also contain G) 0.01 to 20% by weight, preferably 0, 05 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-% in each case based on the total composition at least one further additive.

In a preferred embodiment, the sum of the proportions of the components in each case adds to 100 wt .-%. It is also possible that the composition consists only of A) and B).

As component A), the compositions according to the invention comprise at least one thermoplastic.

The thermoplastic is preferably at least one thermoplastic polyamide. Under thermoplastic polyamides are based on Hans Domininghaus in "The Plastics and their properties", 5th edition (1998), p. 14 , Understood polyamides whose molecular chains have no or more or less long and in number different side branches, which soften in the heat and are almost arbitrarily malleable.

The inventively preferred polyamides can be prepared by various methods and synthesized from very different building blocks and in special application alone or in combination with processing aids, stabilizers or polymeric alloying partners, preferably elastomers, are equipped to materials with specially selected property combinations. Also suitable are blends with proportions of other polymers, preferably of polyethylene, polypropylene, ABS, it being possible where appropriate to use one or more compatibilizers. The properties of the polyamides can be improved by adding elastomers, for. In terms of impact strength, especially if they are reinforced polyamides. The multitude of possible combinations enables a very large number of products with different properties.

For the preparation of polyamides, a variety of procedures have become known, depending on the desired end product different monomer units, various chain regulators for setting a desired molecular weight or monomers with reactive groups are used for later intended post-treatments.

The technically relevant processes for the preparation of polyamides usually run via the polycondensation in the melt. In this context, the hydrolytic polymerization of lactams is understood as a polycondensation.

Polyamides to be used preferably as component A) are partially crystalline polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.

Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bis-aminomethylcyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams. Copolyamides of several of the monomers mentioned are included.

Particularly preferred are caprolactams, most preferably ε-caprolactam is used.

Also most suitable are most compounds based on PA6, PA66 and other aliphatic and / or aromatic polyamides or copolyamides, in which 3 to 11 methylene groups are present on a polyamide group in the polymer chain.

Most preferred are PA6 and PA66.

The polyamides preferably used according to the invention can also be used in a mixture with other polyamides and / or further polymers.

In an alternative embodiment, thermoplastic polyesters are used as component A), particularly preferably partially aromatic polyesters.

The partially aromatic polyesters to be used according to the invention are selected from the group of polyalkylene terephthalates, preferably selected from the group of polyethylene terephthalates, polytrimethylene terephthalates and polybutylene terephthalates, more preferably polybutylene terephthalates and polyethylene terephthalates, most preferably polybutylene terephthalate.

Partly aromatic polyesters are understood to mean materials which, in addition to aromatic moieties, also contain aliphatic moieties. Polyalkylene terephthalates in the sense of the invention are reaction products of aromatic dicarboxylic acid or its reactive derivatives, in particular. Dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates can be prepared from terephthalic acid or its reactive derivatives and aliphatic or cycloaliphatic diols having 2 to 10 C atoms by known methods ( Plastics Handbook, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973 ).

Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or propane diol 1,3 and / or 1,4-butanediol residues.

The preferred polyalkylene terephthalates may contain, in addition to terephthalic acid radicals, up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.

In addition to ethylene or 1,3-propanediol or 1,4-glycol butanediol radicals, the preferred polyalkylene terephthalates may contain up to 20 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms , especially. Residues of 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, 1,6-hexanediol, cyclohexanedimethanol-1,4, 3-methylpentanediol-2,4, 2-Methy-1-pentanediol-2,4, 2,2,4-trimethyl-pentanediol-1,3 and -1,6,2-ethyl-hexanediol-1,3 2,2-diethyl-1,3-propanediol, hexanediol-2, 5, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2, 2-bis- (3-β-hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane ( DE-A 24 07 674 . 24 07 776 . 27 15 932 ).

The polyalkylene can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, as z. B. in the DE A 19 00 270 and the U.S. Patent 3,692,744 are described to be branched. Preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

It is advisable to use no more than 1 mol% of the branching agent, based on the acid component.

Particular preference is given to using polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives, in particular their dialkyl esters, and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol and mixtures of these polyalkylene terephthalates. In particular, very particular preference is given to using polyethylene terephthalate or polybutylene terephthalate.

Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.

(G entspricht dem Geschwindigkeitsgefälle) definiert. Wobei sich die spezifische Viskosität η_s aus der Viskosität der Lösung η und der Viskosität des Lösungsmittels η_L ergibt und [η] der Grenzwert der reduzierten Viskosität für c = 0 und G = 0 ist.

The polyalkylene terephthalates generally have an intrinsic viscosity of about 0.3 cm ³ / g to 1.5 cm ³ / g, preferably 0.4 cm ³ / g to 1.3 cm ³ / g, particularly preferably 0.5 cm ³ / g to 1.0 cm ³ / g as measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. The viscosity is determined in a measuring device, the viscometer, by measuring the flow rate through a defined volume, usually in a capillary, for a defined amount of the substance to be determined. In the art, a flow sensor is often used. The Staudinger index, often referred to as the intrinsic viscosity or intrinsic viscosity, is obtained by extrapolating the concentration to zero and is thus over:

(G corresponds to the speed gradient). Where the specific viscosity η _s results from the viscosity of the solution η and the viscosity of the solvent η _L and [η] is the limit value of the reduced viscosity for c = 0 and G = 0.

gegen η_s aufträgt. Auf diese Weise erhält man häufig einen linearen Zusammenhang. Diese Extrapolationsweise wird Extrapolation nach Schulz-Blaschke genannt. Üblich ist auch eine Auftragung von

gegen c welche Extrapolation nach Huggins heißt.The extrapolation to c = 0 can be performed graphically by

applies against η _s . In this way you often get a linear relationship. This extrapolation method is called extrapolation according to Schulz-Blaschke. Also common is a plot of

against c which extrapolation after Huggins is called.

r ist der Radius und l die Länge der Kapillare. Δp ist die Druckdifferenz zwischen den Kapillarenden und V das Flüssigkeitsvolumen, das während der Zeit t durch die Kapillare strömt. Alle Parameter können konstant gehalten werden, da die Schwerebeschleunigung g und die Höhe der Kapillare h = l konstant sind und der Dichteunterschied (Dichte = ρ) zwischen Lösungsmittel und verdünnter Lösung vernachlässigt werden kann. Somit ergibt sich eine Proportionalität η α t und mit Hilfe von Gleichung 3 ergibt sich:

The extrapolation of G → 0 can usually be dispensed with by selecting suitable viscometers, since the value of G is thus kept small and constant. The measurement is carried out with a viscometer, of which there are different versions. When measured with a capillary viscometer, the use of an Ubbelohde viscometer is the least expensive. The basis for the measurement of viscosity is provided by the Hagen-Poiseuille law:

r is the radius and l is the length of the capillary. Δp is the pressure difference between the capillary ends and V is the volume of fluid flowing through the capillary during time t. All parameters can be kept constant, since the gravitational acceleration g and the height of the capillary h = l are constant and the density difference (density = ρ) between solvent and dilute solution can be neglected. This results in a proportionality η α t and with the help of equation 3 it follows:

The actual measurands are the throughput times for a polymer-solvent mixture.

The polyesters to be used according to the invention as component A) can also be used in a mixture with other polyesters and / or further polymers.

The polyesters conventional additives, especially mold release agents, stabilizers and / or flow aids can be added in the melt or applied to the surface.

Starting materials for the thermoplastics of component A) may be synthetically z. B. from petrochemical raw materials and / or biochemical processes resulting from renewable resources.

As component B), the compositions contain non-fibrous and unfoamed milled glass having a particle size distribution having a d90 of 10 to 300 μm, preferably 20 to 150 μm, particularly preferably 35 to 80 μm. In this case, preferably such non-fibrous and non-foamed ground glass is used, which furthermore has a d10 of 0.6 to 10 .mu.m, preferably 0.8 to 6 .mu.m, particularly preferably 1.0 to 5 microns. In this case, such non-fibrous and non-foamed ground glass is particularly preferred, which further has a d50 of 3 to 50 microns, preferably 5 to 40 microns, more preferably 7 to 30 microns.

Concerning the d10, d50 and d90 values, their purpose and their meaning is on Chemie Ingenieur Technik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000 referenced, according to which d10 value the particle size is below which 10% of the particle amount, d50 the particle size below which 50% of the particle quantity is (median value) and the d90 the particle size is below which 90% of the particle amount.

Preferably, such non-fibrous and unfoamed, ground glass has an average particle size of 5 to 50 μm, more preferably 15 to 30 μm.

The details of the particle size distribution or of the particle sizes here relate to so-called surface-based particle sizes, in each case before incorporation into the thermoplastic molding composition. Here, the diameters of the surfaces of the respective glass particles are related to the areas of imaginary spherical particles (spheres). This is done by operating according to the principle of laser obscuration particle size of Fa. Ankersmid (Eye Tech ^® with the containing therein EyeTech ^® software and ACM-104 cell, Ankersmid Lab, Oosterhout, Netherlands).

The non-fibrous and non-foamed ground glass is of particulate, non-cylindrical shape and has a length to thickness ratio of less than 5, preferably less than 3, more preferably less than 2.

To distinguish from the present invention is called foamed glass, often called expanded glass, a glass enclosed in the gas bubbles, for example, from air or carbon dioxide. However, this inclusion of gas, in contrast to the inventively used non-foamed glass leads to a reduction in density.

By way of distinction from the present invention, fibrous glass is understood to mean a glass geometry with a cylindrical or oval cross-section which has a length-to-thickness ratio (L / D ratio) greater than 5.

The non-foamed and non-fibrous ground glass to be used in the present invention may preferably be obtained by grinding glass with a mill, more preferably. a ball mill and most preferably with subsequent screening or sieving are obtained. The starting material is all geometric shapes of solidified glass into consideration.

Preferred starting materials for grinding to ground glass according to the invention are also glass waste, as incurred in particular in the production of glass products as undesirable by-product and / or as unspecified main product, so-called off-spec product. This includes, in particular, waste and cullet glass, as may occur in particular in the production of window or bottle glass, and in the production of glass-containing fillers and reinforcing materials, in particular in the form of so-called melt cake. The glass may be colored, with non-colored glass being the preferred starting material.

As a starting glass for grinding come in principle all types of glass into consideration as they are for. In DIN1259-1 are described. Preference is given to soda-lime glass, float glass, quartz glass, lead crystal glass, borosilicate glass and E glass, soda-lime glass, borosilicate glass and E glass being particularly preferred and E glass being very particularly preferred. Likewise particularly preferred for the preparation of the non-foamed and non-fibrous ground glass to be used according to the invention are types of glass in which the content of K ₂ O is less than or equal to 2% by weight, based on all components of the glass. The non-foamed and non-fibrous ground glass to be used according to the invention can be obtained, for example, from VitroMinerals, Covington, GA, USA. It is offered as so-called CS Glass Powder in specifications CS-325, CS-500 and CS-600 (see also www.glassfillers.com or Chris DeArmitt, Additives Feature, Mineral Fillers, COMPOUNDING WORLD, February 2011, pages 28-38 respectively. www.compoundingworld.com ). Alternatively, MF7900 of Lanxess Germany GmbH can be used, a non-fibrous and non-foamed ground glass based on E glass containing about 0.1 wt .-% triethoxy (3-aminopropyl) silane Sizing C ') with a d90 of 54 μm, a d50 of 14 μm, a d10 of 2.4 μm and an average particle size of 21 μm, in each case based on the particle surface.

The non-foamed and non-fibrous ground glass to be used according to the invention is preferably provided with a silane or siloxane-based surface modification or coating, where aminoalkyl, glycidyl, alkenyl, acryloyloxyalkyl and / or methacryloxyalkyl-functionalized trialkoxysilanes and their aqueous hydrolysates and combinations from these are particularly preferred.

Very particular preference is given to surface modifications with aminoalkyltrialkoxysilanes, in particular aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane or their aqueous hydrolysates.

The silane compounds are preferably used in amounts of from 0.01% by weight to 1.5% by weight, more preferably in amounts of from 0.05% by weight to 1.0% by weight and in particular in amounts of 0, 1 wt .-% to 0.5 wt .-% based on the ground glass used for surface coating.

The starting glass for milling can already be treated with the surface modification or sizing. Likewise, the non-foamed and non-fibrous ground glass to be used according to the invention can be treated after the grinding with the surface modification or sizing.

The inventively used non-foamed and non-fibrous, ground glass can due to the processing of the composition of the invention or to moldings from the composition of the invention or in the molding a smaller d90 or d50 value or d10 value or a smaller mean particle size than the originally used ground particles.

In a preferred embodiment, the compositions according to the invention may contain as component C) at least one halogen-containing or halogen-free flame retardant. As flame retardants, phosphorus-containing flame retardants selected from the groups of mono- and oligomeric phosphoric and phosphonic acid esters, Phosphonatamine, phosphonates, phosphinates, more preferably metal dialkylphophinates, especially aluminum tris [dialkylphosphinates] and zinc bis [dialkylphosphinates], phosphites, hypophosphites , Phosphine oxides and phosphazenes in question. In this case, metal dialkylphosphinates are preferred, with aluminum tris [dialkylphosphinate] and zinc bis [dialkylphosphinate] being very particularly preferred.

Preference is given to using nitrogen-containing flame retardants individually or in a mixture. Particularly noteworthy are melamine oxalate, melamine phosphate prim., Melamine phosphate sec. And melamine pyrophosphate sec., Reaction products of melamine with condensed phosphoric acids or reaction products of condensation products of melamine with phosphoric acid or condensed phosphoric acids, in particular melamine polyphosphate, and the reaction products of melamine and polyphosphoric acid with basic aluminum, Magnesium and / or zinc compounds, as well as melamine cyanurate and Neopentylglycolborsäuremelamin. Also suitable are guanidine salts such as guanidine carbonate, guanidine cyanurate prim., Guanidine phosphate prim., Guanidine phosphate sec., Guanidine sulfate prim., Guanidine sulfate sec., Pentaerythritol boric acid, neopentyl glycol borohydride, urea phosphate and urea cyanurate. In addition, condensation products of melamine, in particular melem, melam, melon or higher condensed compounds of this type and their reaction products with condensed phosphoric acids can be used. Also suitable are tris (hydroxyethyl) isocyanurate or its reaction products with carboxylic acids, benzoguanamine and its adducts or salts and its nitrogen-substituted products and their salts and adducts. Other nitrogen-containing components are allantoin compounds, and their salts with phosphoric acid, boric acid or pyrophosphoric acid and glycolurils or their salts in question.

It is also possible to use inorganic nitrogen-containing compounds, preferably ammonium salts, in particular ammonium polyphosphate.

Particularly preferred nitrogen-containing flame retardants are melamine cyanurate and melamine polyphosphate, with melamine cyanurate being particularly preferred. Melamine cyanurate is understood to mean the reaction product of preferably equimolar amounts of melamine and cyanuric acid or isocyanuric acid. These include all commercially available and commercially available product qualities. Examples include Melapur ^® MC25 and MC50 Melapur (Fa. BASF, Ludwigshafen, Germany). The melamine cyanurate used consists of particles having average particle diameters of 0.1 .mu.m to 100 .mu.m, preferably from 0.1 .mu.m to 30 .mu.m, more preferably 0.1 .mu.m to 7 .mu.m and may be surface-treated or coated with known agents. These include, inter alia, organic compounds which may be applied in monomeric, oligomeric and / or polymeric form to the melamine cyanurate. For example, coating systems based on silicon-containing compounds such as organofunctionalized silanes or organosiloxanes can be used. Coatings with inorganic components are also possible.

Commercially available organic halogen compounds with synergists can be used individually or in admixture as halogen-containing flame retardants. In particular, the following brominated and chlorinated compounds may be mentioned as examples: ethylene-1,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated polystyrene, bis (pentabromophenyl) ethane. As synergists z. As antimony compounds, especially sodium antimonate, antimony trioxide and antimony pentoxide suitable.

Other flame retardants or flame retardant synergists not specifically mentioned here can also be used. These include purely inorganic phosphorus compounds, in particular red phosphorus or boron phosphate hydrate. Furthermore, salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives such as aluminum and / or magnesium hydroxide, Ca-Mg-carbonate hydrates (eg. DE-A 4 236 122 ) are used. Also suitable are flame retardant synergists from the group consisting of the oxygen-nitrogen or sulfur-containing metal compound, preferably zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide, molybdenum oxide, titanium dioxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, boron nitride, magnesium nitride, zinc nitride, zinc phosphate, Calcium phosphate, calcium borate, magnesium borate or mixtures thereof.

Further suitable flame retardant additives are carbon formers, preferably phenol-formaldehyde resins, polycarbonates, polyphenyl ethers, polyimides, polysulfones, polyethersulfones, polyphenylsulfides and polyether ketones, and also anti-dripping agents, in particular tetrafluoroethylene polymers.

The flame retardants can be added in pure form, as well as masterbatches or compactates.

The elastomer modifiers to be used as component D) in a preferred embodiment of the compositions according to the invention include, inter alia, one or more graft polymers of D.1 5 to 95 wt .-%, preferably 30 to 90 wt .-%, of at least one vinyl monomer on D.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, more preferably <-20 ° C.

The graft base D.2 generally has an average particle size (d50 value) of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m, particularly preferably 0.2 to 1 .mu.m.

Monomers D.1 are preferably mixtures of D.1.1 50 to 99% by weight of vinylaromatics and / or ring-substituted vinylaromatics (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8) -alkyl esters (such as, for example, methyl methacrylate, ethyl methacrylate ) and D.1.2 From 1 to 50% by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8) -alkyl esters (such as, for example, methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives, in particular anhydrides and imides, unsaturated carboxylic acids, in particular maleic anhydride or N-phenyl-maleimide.

Preferred monomers D.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers D.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.

Particularly preferred monomers are D.1.1 styrene and D.1.2 acrylonitrile.

Suitable graft bases D.2 for the graft polymers to be used in the elastomer modifiers are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, furthermore acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.

Preferred grafting principles D.2 are diene rubbers, in particular based on butadiene, isoprene, etc., or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers, preferably according to D.1.1 and D.1.2, with the proviso that the glass transition temperature the component 0.2 at <10 ° C, preferably at <0 ° C, more preferably at <-10 ° C.

Particularly preferred graft bases D.2 are ABS polymers (emulsion, bulk and suspension ABS), as described, for. B. in the DE-A 2 035 390 (= US Pat. No. 3,644,574 ) or in the DE-A 2 248 242 (= GB-A 1 409 275 ) or in Ullmann, Enzyklopadie der Technischen Chemie, Vol. 19 (1980), p. 280 ff. are described. The gel content of the grafting base D.2 is preferably at least 30% by weight, more preferably at least 40% by weight (measured in toluene).

The elastomer modifiers or graft polymers are prepared by free-radical polymerization, for. B. by emulsion, suspension, solution or bulk polymerization, preferably prepared by emulsion or bulk polymerization.

Particularly suitable graft rubbers are also ABS polymers obtained by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US-A 4,937,285 getting produced.

Since, in the grafting reaction, the grafting monomers are not necessarily grafted completely onto the grafting base, graft polymers according to the invention are also understood as those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during the workup.

Also suitable acrylate rubbers based on grafting D.2 preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on D.2 other polymerizable, ethylenically unsaturated monomers. Preferred polymerizable acrylic esters include C1-C8 alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters, such as chloroethyl acrylate, glycidyl esters and mixtures of these monomers. In this case, graft polymers with butyl acrylate as a core and methyl methacrylate as a shell (z. B. Paraloid EXL2300 ^®, Fa. Dow Corning Corporation, Midland Michigan, USA) are particularly preferred.

For 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 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate ; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, 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 graft D.2.

For cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the grafting base D.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for preparing the graft base D.2 are preferably acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C1-C6-alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene , Preferred acrylate rubbers as grafting base D.2 are emulsion polymers which have a gel content of at least 60% by weight.

Further suitable grafting principles according to D.2 are silicone gums with graft-active sites as described in US Pat DE-A 3 704 657 (= US 4,859,740 ) DE-A 3 704 655 (= U.S. 4,861,831 ) DE-A 3 631 540 (= US 4,806,593 ) and DE-A 3 631 539 (= U.S. 4,812,515 ) to be discribed.

In addition to elastomer modifiers based on graft polymers, graft polymer-based elastomer modifiers which have glass transition temperatures <10 ° C., preferably <0 ° C., particularly preferably <-20 ° C., can likewise be used. For this purpose, z. For example, elastomers having a block copolymer structure. For this purpose, z. B. thermoplastic meltable elastomers include. By way of example and with preference, EPM, EPDM and / or SEBS rubbers are mentioned here.

The lubricants and / or mold release agents to be used in a preferred embodiment of the compositions according to the invention as component E) may be, for example, long-chain fatty acids, in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, and their ester derivatives or amide derivatives, in particular ethylene-bis Stearylamide, montan waxes and low molecular weight polyethylene or polypropylene waxes. Montan waxes for the purposes of the present invention are mixtures of straight-chain, saturated carboxylic acids having chain lengths of 28 to 32 carbon atoms. According to the invention are preferably lubricants and / or mold release agents from the group of esters, or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols or amines having 2 to 40 carbon atoms and metal salts of saturated or unsaturated aliphatic carboxylic acids 8 to 40 carbon atoms used, ethylene-bis-stearylamide, calcium stearate and / or Ethylenglycoldimontanat, here in particular Licowax ^® E Fa. Clariant, Muttenz, Basel, is particularly preferred and ethylene-bis-stearylamide is very particularly preferred. The alternatives mentioned here are only suitable if they are not already used as one of the components A) and C) to G).

As component F), in a further preferred embodiment, the compositions may contain at least one further filler or reinforcing agent which is different from component B).

Mixtures of two or more different fillers and / or reinforcing materials, preferably based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmite, magnesium carbonate, chalk, may also be used , Feldspar, barium sulfate, glass beads and / or fibrous fillers and / or reinforcing materials based on carbon fibers and / or glass fibers. Preference is given to using mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate and / or glass fibers. Particular preference is given to using mineral particulate fillers based on talc, wollastonite, kaolin and / or glass fibers, with glass fibers being very particularly preferred.

Furthermore, needle-shaped mineral fillers are also used with particular preference. According to the invention, needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced needle-like character. Needle-shaped wollastonites are preferably mentioned. Preferably, the mineral has a length: diameter ratio of 2: 1 to 35: 1, particularly preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1. The mean particle size of the needle-shaped invention Minerals are preferably less than 20 microns, more preferably less than 15 microns, more preferably less than 10 microns, determined with a CILAS GRANULOMETER.

The filler and / or reinforcing agent other than component B) may be surface-modified in a preferred embodiment, preferably with a primer or adhesion promoter system, particularly preferably based on silane. However, pretreatment is not essential. In particular, when using glass fibers, polymer dispersions, film formers, branching agents and / or glass fiber processing aids may be used in addition to silanes.

The glass fibers very particularly preferably used according to the invention as component F), which generally have a fiber diameter of between 7 and 18 μm, preferably between 9 and 15 μm, are added as continuous fibers or as cut or ground glass fibers. Fiber-shaped milled glass fibers can be obtained when continuous fibers or cut glass fibers are subjected to an additional grinding process, in particular in a ball mill. The fibers may be provided with a suitable sizing system and a primer or adhesion promoter system, preferably based on silane.

steht,
a für eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4 steht,
r für eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2 steht und
k für eine ganze Zahl von 1 bis 3, bevorzugt 1 steht.Particularly preferred silane-based adhesion promoters for the pretreatment are silane compounds of the general formula (I) (X- (CH ₂ ) q) k -si- (O-CrH 2r + 1) 4-k (1) wherein
X for NH ₂ , carboxyl, HO or

stands,
a is an integer from 2 to 10, preferably 3 to 4,
r is an integer from 1 to 5, preferably 1 to 2, and
k is an integer from 1 to 3, preferably 1.

Particularly preferred adhesion promoters are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

For the equipment of the fillers, the silane compounds are generally used in amounts of 0.05 to 2 wt .-%, preferably 0.25 to 1.5 wt .-% and in particular 0.5 to 1 wt .-% based on the mineral Filler used for surface coating. The particulate fillers may have a smaller d97 or d50 value due to the processing to form the composition or shaped bodies from the composition or in the shaped body than the fillers originally used. The glass fibers may have shorter length distributions than originally used due to the processing to the composition or molded articles from the composition or in the molding. Preference is given to using fillers and reinforcing agents other than B) in amounts of from 1 to 30% by weight, more preferably from 2 to 15% by weight and very particularly preferably from 3 to 7% by weight, based in each case on the overall molding composition.

As component G), the compositions according to the invention may contain, in addition to the components C) to F) or instead of C), D), E) and / or F), further additives. Additives for the purposes of the present invention include UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, heat stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers other than component D), dyes and pigments. The additives can be used alone or mixed or in the form of masterbatches.

UV stabilizers which may be mentioned are various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

Suitable colorants may be inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, zinc sulfide or carbon black, furthermore organic pigments, preferably phthalocyanines, quinacridones, perylenes and dyes, preferably nigrosine and anthraquinones.

As thermostabilizer sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these groups or mixtures thereof can be used. Preference is given to using sterically hindered phenols, alone or in combination with phosphites, wherein the use of N, N'-bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamines (e.g. as Irganox ^® 1098 Fa. BASF SE, Ludwigshafen, Germany. Germany) is particularly preferred.

The nucleating agent used may preferably be sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide and particularly preferably talc, although this list is not exhaustive.

As flow aids it is possible with preference to use copolymers of at least one α-olefin with at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol. Particular preference is given to copolymers in which the α-olefin is synthesized from ethene and / or propene and the methacrylic acid ester or acrylic ester contains, as alcohol component, linear or branched alkyl groups having 6 to 20C atoms. Very particular preference is given to acrylic acid (2-ethyl) hexyl ester. Suitable flow aids according to the invention suitable copolymers in addition to the composition also by the low molecular weight. Accordingly, copolymers which are to be stored according to the invention prior to thermal degradation are especially suitable copolymers having an MFI value measured at 190 ° C. and a load of 2.16 kg of at least 100 g / 10 min, preferably of at least 150 g / 10 min , more preferably at least 300 g / 10 min. The MFI, melt flow index, is used to characterize the flow of a melt of a thermoplastic and is subject to the standards ISO 1133 or ASTM D 1238 , The MFI or all information on the MFI in the context of the present invention relate or have become uniform ISO 1133 measured or determined at 190 ° C and a test weight of 2.16 kg.

Preferably plasticizers to be used as component G) are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.

• A) 5 bis 95 Gew.-%, bevorzugt 20 bis 90 Gew.-%, besonders bevorzugt 30 bis 80 Gew.-% Polyamid,
• B) 5 bis 80 Gew.-%, bevorzugt 10 bis 60 Gew.-%, besonders bevorzugt 15 bis 50 Gew.-% eines nicht-faserförmigen und nicht-geschäumten, gemahlenen Glases mit einem d90 von 10 bis 300 μm, bevorzugt 20 bis 150 μm, besonders bevorzugt 35 bis 80 μm welches mit
• B') mindestens einem Aminoalkyltrialkoxysilan, bevorzugt in Mengen von 0,01 Gew.-% bis 1,5 Gew.-% bezogen auf die Menge des gemahlenen Glases beschlichtet ist.

In a preferred embodiment, the present invention relates to compositions containing

• A) 5 to 95 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-% polyamide,
• B) 5 to 80 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 15 to 50 wt .-% of a non-fibrous and non-foamed, ground glass with a d90 of 10 to 300 .mu.m, preferably 20 to 150 microns, more preferably 35 to 80 microns which with
• B ') at least one aminoalkyltrialkoxysilane, preferably in amounts of 0.01 wt .-% to 1.5 wt .-% coated based on the amount of the ground glass.

• A) 5 bis 95 Gew.-%, bevorzugt 20 bis 90 Gew.-%, besonders bevorzugt 30 bis 80 Gew.-% Polyamid,
• B) 5 bis 80 Gew.-%, bevorzugt 10 bis 60 Gew.-%, besonders bevorzugt 15 bis 50 Gew.-% eines nicht-faserförmigen und nicht-geschäumten, gemahlenen Glases mit einem d90 von 10 bis 300 μm, bevorzugt 20 bis 150 μm, besonders bevorzugt 35 bis 80 μm und
• C) 0,01 bis 60 Gew.-% Melamincyanurat.

In an alternative preferred embodiment, the present invention relates to compositions containing

• A) 5 to 95 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-% polyamide,
• B) 5 to 80 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 15 to 50 wt .-% of a non-fibrous and non-foamed, ground glass with a d90 of 10 to 300 .mu.m, preferably 20 to 150 microns, more preferably 35 to 80 microns and
• C) 0.01 to 60 wt .-% melamine cyanurate.

• A) 5 bis 95 Gew.-%, bevorzugt 20 bis 90 Gew.-%, besonders bevorzugt 30 bis 80 Gew.-% Polyamid,
• B) 5 bis 80 Gew.-%, bevorzugt 10 bis 60 Gew.-%, besonders bevorzugt 15 bis 50 Gew.-% eines nicht-faserförmigen und nicht-geschäumten, gemahlenen Glases mit einem d90 von 10 bis 300 μm_' bevorzugt 20 bis 150 μm, besonders bevorzugt 35 bis 80 μm welches mit
• B') mindestens einem Aminoalkyltrialkoxysilan, bevorzugt in Mengen von 0,01 Gew.-% bis 1,5 Gew.-% bezogen auf die Menge des gemahlenen Glases beschlichtet ist. und
• C) 0,01 bis 60 Gew.-% Melamincyanurat.

In a particularly preferred embodiment, the present invention relates to compositions containing

• A) 5 to 95 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-% polyamide,
• B) 5 to 80 wt .-%, preferably 10 to 60 wt .-%, particularly preferably 15 to 50 wt .-% of a non-fibrous and non-foamed, ground glass having a d90 of 10 to 300 microns _' preferably 20 to 150 microns, more preferably 35 to 80 microns which with
• B ') at least one aminoalkyltrialkoxysilane, preferably in amounts of 0.01 wt .-% to 1.5 wt .-% coated based on the amount of the ground glass. and
• C) 0.01 to 60 wt .-% melamine cyanurate.

However, the present invention also relates to products, preferably fibers, films or moldings, obtainable from the compositions according to the invention by injection molding or extrusion.

The compositions according to the invention are preferably used in injection molding, including the special processes GIT (gas injection technology), WIT (water injection technology) and PIT (projectile injection technology), in the extrusion process in profile extrusion, in blow molding, particularly preferably standard extrusion blow molding, 3D extrusion blow molding or suction blow molding to produce from it inventive products.

Process for the production of products by extrusion or injection molding operate at melt temperatures in the range of 230 to 330 ° C, preferably from 250 to 300 ° C and optionally additionally at pressures of at most 2500 bar, preferably at pressures of at most 2000 bar, more preferably at pressures of a maximum of 1500 bar and most preferably at pressures of a maximum of 750 bar.

The method of injection molding is characterized in that the raw material, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and sprayed as a spray mass under pressure in a tempered cavity. After cooling (solidification) of the mass, the injection molded part is removed from the mold.

• 1. Plastifizieren/Aufschmelzen
• 2. Einspritzphase (Füllvorgang)
• 3. Nachdruckphase (wegen thermischer Kontraktion bei der Kristallisation)
• 4. Entformen.

One differentiates

• 1. plasticizing / melting
• 2nd injection phase (filling process)
• 3rd post-pressure phase (due to thermal contraction during crystallization)
• 4. Demoulding.

An injection molding machine consists of a clamping unit, the injection unit, the drive and the controller. The clamping unit includes fixed and movable clamping plates for the tool, a face plate as well as columns and drive of the moving tool clamping plate (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 granules, meter, inject and post-print (because of contraction). The problem of melt backflow within the screw (leakage flow) is solved by backflow stops.

• – Angusssystem
• – Formbildende Einsätze
• – Entlüftung
• – Maschinen- und Kraftaufnahme
• – Entformungssystem und Bewegungsübertragung
• – Temperierung

In the injection mold then the inflowing melt is dissolved, cooled and thus manufactured the component to be manufactured. Necessary are always two tool halves. In injection molding, the following functional complexes are distinguished:

• - Angus system
• - Forming inserts
• - venting
• - Machine and power consumption
• - Demoulding system and motion transmission
• - Temperature control

The injection molding special processes GIT (gas injection technology), WIT (water injection technology) and projectile injection technology (PIT) are specialized injection molding processes for the production of hollow workpieces. A difference to the standard injection molding consists in a special step towards the end of the tool filling phase or after a defined partial filling of the casting mold. In the process-specific working step, a process medium is injected via a so-called injector into the molten mass of the preform for the formation of cavities. These are gas - usually nitrogen - in the case of GIT and water in the case of. In the case of PIT a projectile is injected into the molten soul and formed in this way a cavity.

In contrast to injection molding, an endlessly shaped plastic strand, in this case a polyamide, is used in the extruder during the extrusion, the extruder being a machine for producing thermoplastic molded parts. A distinction is made between single-screw extruders and twin-screw extruders and the respective subgroups conventional single-screw extruders, conveying single-screw extruders, counter-rotating twin-screw extruders and co-rotating twin-screw extruders.

• 1. Plastifizieren und Bereitstellen der thermoplastischen Schmelze in einem Extruder,
• 2. Extrusion des thermoplastischen Schmelzestrangs durch eine Kalibrierhülse, die den Querschnitt des zu extrudierenden Profils aufweist,
• 3. Abkühlung des extrudierten Profils in einem Kalibriertisch,
• 4. Weitertransport des Profils mit einem Abzug hinter dem Kalibriertisch,
• 5. Ablängen des zuvor endlosen Profils in einer Schneideanlage,
• 6. Sammeln der abgelängten Profile an einem Sammeltisch.

Profiles in the sense of the present invention are (construction) parts which have an identical cross section over their entire length. They can be produced by profile extrusion. The basic process steps of the profile extrusion process are:

• 1. plasticizing and providing the thermoplastic melt in an extruder,
• 2. extrusion of the thermoplastic melt strand through a calibration sleeve having the cross-section of the profile to be extruded,
• 3. cooling the extruded profile in a calibration table,
• 4. further transport of the profile with a trigger behind the calibration table,
• 5. cutting to length the previously endless profile in a cutting machine,
• 6. Collect the cut profiles at a collecting table.

A description of the profile extrusion of polyamide 6 and polyamide 66 is given in Plastics Handbook 314, polyamides, Carl Hanser Verlag, Munich 1998, pages 374-384 ,

Blow molding processes according to the present invention are preferably standard extrusion blow molding, 3D extrusion blow molding, suction blow molding and sequential coextrusion.

• 1. Plastifizieren und Bereitstellen der thermoplastischen Schmelze in einem Extruder,
• 2. Umlenken der Schmelze in eine senkrechte Fließbewegung nach unten und das Ausformen eines schlauchförmigen Schmelze-„Vorformlings”,
• 3. Umschließen des frei unter dem Kopf hängenden Vorformlings durch eine in der Regel aus zwei Halbschalen bestehenden Form, dem Blasformwerkzeug,
• 4. Einschieben eines Blasdorns oder einer (ggf. mehrer) Blasnadel(n),
• 5. Aufblasen des plastischen Vorformlings gegen die gekühlte Wand des Blasformwerkzeugs, wo der Kunststoff abkühlt, erhärtet und die endgültige Form des Formteils annimmt,
• 6. Öffnen der Form und Entformen des blasgeformten Teils,
• 7. Entfernen der abgequetschten „Butzen”-Abfälle” an beiden Enden des Blasformteils.

The basic process steps of standard extrusion blow molding are described in ( Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Munich 2006, pages 15 to 17 ):

• 1. plasticizing and providing the thermoplastic melt in an extruder,
• 2. diverting the melt downwards in a vertical flow and forming a tubular melt "preform",
• 3. enclosing the freely hanging under the head preform by a generally consisting of two half-shells mold, the blow mold,
• 4. insertion of a blowing mandrel or a (possibly several) blowing needle (s),
• 5. inflating the plastic preform against the cooled wall of the blow molding tool where the plastic cools, hardens and assumes the final shape of the molding,
• 6. opening the mold and demolding the blow-molded part,
• 7. Remove the pinched "slug" waste at both ends of the blow molding.

Further post-processing steps can follow.

By means of standard extrusion blow molding, products with complex geometry and multiaxial curvatures can be produced. However, then products are obtained which contain a large proportion of excess, squeezed material and have a weld in large areas.

In the case of 3D extrusion blow molding, which is also referred to as 3D blow molding, a preform adapted in its diameter to the article cross section is therefore deformed and manipulated with special devices and then introduced directly into the blow mold cavity to avoid weld seams and to reduce the use of material. The remaining squish edge is thus reduced to a minimum at the article ends ( Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Manchen 2006, page 117-122 ).

In Saugblasformverfahren, also referred to as suction bubbles, the preform is fed directly from the nozzle of the hose head in the closed blow mold and "sucked" through an air flow through the blow mold. After exiting the lower end of the preform from the blow mold this is squeezed off by closing elements up and down, and the inflation and cooling process follow ( Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Munich 2006, page 123 ).

The products of the invention are used in the automotive, electrical, electronics, telecommunications, computer, sports, medical, household, construction or entertainment industries.

Examples

To demonstrate the improvements according to the invention with regard to flame retardancy and mechanics, first of all corresponding plastic compositions were prepared by compounding. For this purpose, the individual components were mixed in a twin-screw extruder (ZSK 25 compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)) at temperatures between 240 and 310 ° C., as a strand discharged, cooled to Granulierfähigkeit and granulated. After drying (usually two days at 70 ° C in a vacuum oven), the processing of the granules was carried out at temperatures between 240 and 300 ° C to standard specimens for the respective tests.

The flame retardancy of the compositions was determined on the one hand by the method UL94V ( Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances," p. 14 to p. 18 Northbrook 1998 ) certainly. The thickness of the standard test specimen was 0.75 mm.

The glow-wire resistance was determined using the glow-wire test GWFI (Glow-Wire Flammability Index) according to [EC 60695-2-12 on round plates of 0.75 and / or 1.5 mm thickness.

The particle size determination of the ground glass particles was carried out using a laser-optical process ("Eye Tech") from Ankersmid Ltd, Oosterhout, The Netherlands in a cell of the "ACM-104 Liquid Flow (4 × 4 mm)" type. The measuring time was about 900 sec. The evaluation refers to the surface of the glass particle.

In the experiments were used:
Component A1: polyamide 6 (Durethan ^® B29, from Lanxess Germany GmbH, Leverkusen, Germany.)
Component A2: (Durethan ^® B26, from Lanxess Germany GmbH, Leverkusen, Germany.)
Component B: Non-fibrous and non-foamed ground glass (E-glass based glass containing about 0.1 wt% sizing based on triethoxy (3-aminopropyl) silane and a d90 of 54 μm, a d50 of 14 μm, a d10 of 2.4 μm and an average particle size of 21 μm, in each case based on the particle surface, Fa. Lanxess Deutschland GmbH, Leverkusen, Germany)
Component C: melamine, (Melapur ^® MC25, from BASF, Ludwigshafen, Germany.)
Component D: impact modifier (Paraloid ^® EXL-2300, from Dow Corning Corporation, Midland, Michigan, USA.)
Component E: mold release agents (N, N'-ethylene bis-stearyl amide or Licowax ^® E from Clariant GmbH, Muttenz, Switzerland.)
Component F1: chopped glass fiber CS 7928 coated, Fa. Lanxess Deutschland GmbH, Leverkusen, Germany)
Component F2: milled cut glass fiber MF 7982 coated, Fa. Lanxess Deutschland GmbH, Leverkusen, Germany)
Component F3: glass beads (Aminoalkyltrialkoxysilanschlichte 0.2 wt .-%) with a typical particle size in the range of 35 microns (Spheriglass ^® Potters 3000 CP 0302 of Potters Industries Inc., Valley Forge, USA)
Component F4: expanded glass granulate (Poraver ^® 0.04, from Bennert Poraver GmbH, Postbauer Heng, Germany.)
Component F5: mineral talcum (Luzenac A60H, Fa. Luzenac Europe SAS, Toulouse, France)
Component G1: Thermostabilizer (Irganox 1098, BASF, Ludwigshafen, Germany)
Component G2: nucleating agent (talc)

Angaben der Komponenten in Gew.-% bezogen auf die GesamtformmasseComponents E and G are the same in type and amount in the respective Examples and Comparative Examples. Table 1 Formulations without flame retardants component 1 C1.1 C1.2 2 C2 3 C3 A1 [%] 69.82 69.82 69.82 64.82 64.82 69.82 69.82 B [%] 30 30 18 F1 [%] 30 30 12 12 F2 [%] 30 F3 [%] 18 D [%] 5 5 e [%] 0.16 0.16 0.16 0.16 0.16 0.16 0.16 G2 [%] 0.02 0.02 0.02 0.02 0.02 0.02 0.02 GWFI (1.5 mm) ° C 930 700 700 750 650 700 650 Details of the components in% by weight based on the total molding compound Table 2 Formulations with flame retardant

Details of the components in wt .-% based on the total molding composition

The examples show that formulations 1 to 6 according to the invention containing component B show clear advantages in terms of fire behavior compared to comparative examples C to C6.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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• Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", p. 14 to p. 18 Northbrook 1998 [0128]

Claims (11)

Compositions containing A) 5 to 95 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-% of a thermoplastic, B) 5 to 80 wt .-%, preferably 10 to 60 wt .-% of a non-fibrous and non-foamed ground glass with a d90 of 10 to 300 microns. Compositions according to claim 1, characterized in that non-fibrous ground glass means that the glass when viewed under the microscope does not have any fragments having a well-shaped cylindrical shape with a diameter of 1 to 30 μ, the cylindrical shape being different Glass processing step results as grinding and non-foamed ground glass means that the glass when viewed under the microscope has no fragments that have a planar structure, wherein the flat structure does not result from the grinding process of the glass but has its origin of expanded glass as the starting material. Compositions according to claims 1 or 2, characterized in that in addition to A) and B) they also contain C) 0.01 to 60 wt .-% of at least one halogen-containing or halogen-free flame retardant. Compositions according to claims 1 to 3, characterized in that they contain in addition to component C) or instead of C) still D) 0.01 to 50 wt .-% of at least one elastomer modifier. Compositions according to claims 1 to 4, characterized in that these in addition to the components A) to D) or instead of C) and / or D) still E) 0.01 to 5 wt .-%, at least one sliding and or mold release agent. Compositions according to claims 1 to 5, characterized in that these in addition to the components A) to E) or instead of C), D) and / or E) nor the component F) 0.01 to 50 wt .-% at least a filler other than component B). Compositions according to claims 1 to 6, characterized in that these in addition to the components A) to F) or in place of the components C), D), E) and / or F) nor G) 0.01 to 20 wt. % contain at least one additional additive. Compositions according to claims 1 to 7, characterized in that they contain as component A) polyamide or polyester, preferably polyamide. Compositions according to claims 1 to 8, characterized in that component B) is coated with B ') at least one aminoalkyltrialkoxysilane. Compositions according to Claim 9, characterized in that they contain C) 0.01 to 60% by weight of melamine cyanurate. Products, preferably fibers, films or moldings, obtainable from the compositions according to claims 1 to 10 by injection molding or extrusion.