DE102014000613A1 - Polyester compositions - Google Patents

Abstract

The invention relates to compositions comprising polyethylene terephthalate (PET), poly (1,4-cyclohexanedimethanol terephthalate (PCT) glass fibers and talc, the use of these compositions for the production of short-time thermoforming products, and a process for the preparation of short-term heat-resistant polyester-based products, in particular polyester-based optoelectronic products.

Description

The invention relates to compositions comprising polyethylene terephthalate (PET), poly (1,4-cyclohexanedimethanol terephthalate (PCT), talc and glass fibers, the use of these compositions for the production of short-time thermoforming products, and a process for the production of short-term heat-resistant polyester-based products for electrical or electronic applications.

Many electronic and electrical assemblies and components include temperature sensitive electrical and / or electronic products, particularly heat sensitive integrated circuits, lithium batteries, oscillator crystals, and optoelectronic products. In the course of assembly of such an assembly provided on the products electrical contacts must be reliably connected to tracks of a board and / or electrical contacts with other products. This assembly is often done with the aid of a soldering process, in which provided on the product solder terminals are soldered to the board. For each product, this results in a safe range for the soldering and soldering temperature, can be made in the good solder joints. In order to achieve a good soldering result, the products must be exposed to elevated temperatures during soldering for long periods of time. So z. B. when wave soldering the product placed on the board initially heated slowly to about 100-130 ° C degrees. This is followed by the actual soldering, which typically takes place at 260 to 285 ° C degrees and lasts for at least 5 seconds, followed by the solidification phase while the product cools slowly over several minutes.

According to "Http://de.wikipedia.org/wiki/Wellenl%C3%Böten" is the wave soldering, also referred to as wave soldering, a soldering process, with the electronic assemblies (printed circuit boards, printed circuit boards) are semi- or fully automatically soldered after loading. The solder side of the circuit board is first wetted in the Fluxer with a flux. Thereafter, the circuit board by means of convection heating (turbulence of heat, which practically everywhere, even on the top, the same temperature is applied), coil heating or infrared radiators preheated. This happens on the one hand to evaporate the solvent content of the flux (otherwise blistering during soldering), to increase the chemical effect of the activators and to avoid a temperature delay of the assembly and damage to the components by a too steep temperature increase during subsequent soldering. As a rule, a temperature difference of less than 120 ° C is required. This means that at a soldering temperature of 250 ° C, the board must be warmed up to at least 130 ° C.

Exact data results from temperature profiles. Temperature sensors are attached to relevant points on a sample board and recorded with a measuring device. Thus one obtains temperature curves for the upper and lower board sides for selected components. Subsequently, the assembly is driven over one or two solder waves. The solder wave is generated by pumping liquid solder through an opening. The soldering temperature is around 250 ° C for lead-containing solders, and around 10 ° C to 35 ° C higher for solders preferred for the prevention of lead-containing vapors, ie at 260 ° C to 285 ° C.

The soldering time should be selected so that the heating neither damages the printed circuit board nor the heat-sensitive components. The soldering time is the contact time of the liquid solder per solder joint. The guideline times are less than one second for single-sided printed circuit boards and no more than two seconds for double-sided printed circuit boards. For multi-circuit boards, individual soldering times of up to six seconds apply. To DIN EN 61760-1: 1998 is the maximum time for one or even two waves together 10 seconds. More details can be found in the above-mentioned literature. After soldering, it is advisable to cool the module in order to quickly reduce the thermal load again. This is done via direct cooling by a refrigeration unit (air conditioning) immediately after the soldering area and / or by conventional fans in the lowering station or a cooling tunnel in the return belt.

This results in high demands on the short-term heat resistance of the materials used, in particular for the more frequently used for environmental reasons lead-free solders with increased melting ranges. Furthermore, such materials must have very good aging resistance under the temperatures encountered in the application.

Thermoplastic polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are particularly suitable because of their good processability, low water absorption and the associated high dimensional stability, color stability at high temperatures, but especially because of their outstanding electrical properties for electrical and electronic applications. However, come across thermoplastic polyesters such as PBT and PET because of their melting points of 220 ° C and 260 ° C, especially in soldering processes with short-term peak temperatures above these melting points quickly to their limits.

As a thermoplastic polyester having a melting point of 285 ° C would be for wave soldering in principle, the poly (1,4-cyclohexylendimethylene) terephthalate (PCT) into consideration.

So describes WO 2007/033129 A1 Temperature-resistant compositions for LED sockets based on PCT, as well as titanium dioxide and glass fibers. The problem here, however, are the lower mechanical properties of the PCT compared to PBT or PET and, due to the slower crystallization, its more difficult processability. Also, one is very limited in the choice of suitable additives due to the high melting temperatures determined by the choice of suitable additives, which is especially true for the field of flame retardants, especially the thermally often sensitive halogen-free flame retardants based on nitrogen and phosphorus.

Out WO 2010/049531 A1 are known as example of electrical and electronic applications so-called power LEDs based on aromatic polyester or wholly aromatic polyester, which is to prevent the degradation of the thermoplastic material by heat or radiation. The use of these aromatic polyesters or completely aromatic polyesters, in particular based on p-hydroxybenzoic acid, terephthalic acid, hydroquinone or 4,4'-bisphenol and optionally isophthalic acid leads to a longer-lasting luminosity of those power LEDs. A disadvantage of the polyesters of WO 2010/049531 A1 However, here too, the high processing temperature in the melt, which is due to the high melting points of the polymers described at temperatures of 355 ° C and higher, as well as the high mold temperatures of 175 ° C and higher. High processing and mold temperatures limit the selection of other additives, in particular the selection of usable flame retardants, and also require special and costly equipped injection molding machines, especially for temperature control and cooling of the tools. In addition, high processing temperatures lead to increased wear of the injection unit.

The object of the present invention was therefore to provide compositions based on thermoplastic polyesters which, on the one hand, have improved PBT and PET-improved short-time heat distortion resistance but, on the other hand, can be processed at low temperatures for PBT or PET Selection of additives, in particular flame retardants, have and have good mechanical properties.

Good mechanical properties in the sense of the present invention are distinguished in the case of products to be produced by high values of Izod impact strength, high flexural strength and marginal fiber elongation. Impact strength describes the ability of a material to absorb impact energy and impact energy without breaking. The test of Izod impact resistance after ISO 180 is a standard method for determining the impact strength of materials. Here, an arm is initially held at a certain height (= constant potential energy) and finally released. The arm hits the test and breaks. From the energy absorbed by the sample, the impact energy is determined. The impact strength is calculated as the ratio of impact energy and specimen cross section (unit of measurement kJ / m ² ). The flexural strength in engineering mechanics is a value for a bending stress in a component subject to bending, beyond which failure occurs due to breakage of the component. It describes the resistance of a workpiece, which is opposed to its deflection or its fracture. In the short-term bending test after ISO 178 bar-shaped specimens are preferably placed with the dimensions 80 mm x 10 mm x 4 mm at the ends of two supports and loaded in the middle with a punch. From the determined forces and deflections, the characteristic values for the bending stress and the marginal fiber strain are calculated. ( Bodo Carlowitz: Tabular overview of the examination of plastics, 6th edition, Giesel-Verlag for publicity, 1992, pp. 16-17 ).

• a) 3 bis 30 Gew.-%, bevorzugt 5 bis 25 Gew.-%, besonders bevorzugt 10 bis 20 Gew.-% Poly(1,4-cyclohexylendimethylen)terephthalat (PCT), wobei der Anteil an PCT bezogen auf die Summe aller enthaltener thermoplastischen Polymere in der Zusammensetzung im Bereich von 5 bis 40 Gew.-%, bevorzugt 7 bis 30 Gew.-%, besonders bevorzugt bei 10–25% Gew.-% liegt.
• b) 15 bis 90 Gew.-%, bevorzugt 20 bis 70 Gew.-%, besonders bevorzugt 30 bis 60 Gew.-% Polyethylenterephthalat (PET),
• c) 5 bis 70 Gew.-%, bevorzugt 10 bis 45 Gew.-%, besonders bevorzugt 15 bis 35 Gew.-% Glasfasern, und
• d) 0,01 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-%, besonders bevorzugt 0,1 bis 2 Gew.-% Talkum, bevorzugt mikrokristalliner Talkum, wobei die Summe aller Gewichtsprozente der Komponenten stets 100 ergibt.

Solution to the problem and subject matter of the present invention are compositions containing

• a) 3 to 30 wt .-%, preferably 5 to 25 wt .-%, particularly preferably 10 to 20 wt .-% poly (1,4-cyclohexylenedimethylene) terephthalate (PCT), wherein the proportion of PCT based on the sum all thermoplastic polymers contained in the composition in the range of 5 to 40 wt .-%, preferably 7 to 30 wt .-%, particularly preferably 10-25% by weight.
• b) from 15 to 90% by weight, preferably from 20 to 70% by weight, particularly preferably from 30 to 60% by weight, of polyethylene terephthalate (PET),
• c) 5 to 70 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 35 wt .-% glass fibers, and
• d) 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-% talc, preferably microcrystalline talc, wherein the sum of all weight percent of the components always gives 100 ,

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 a preferred embodiment, the present invention relates to compositions comprising in addition to the components a), b), c) and d) still e) 1 to 50 wt .-%, preferably 5 to 30 wt .-%, particularly preferably 10 to 20 % By weight of at least one flame retardant, the components a, b, c) and d) being reduced to such an extent that the sum of all percentages by weight always equals 100.

In a preferred embodiment, in addition to the components a) to e) or instead of e), the compositions according to the invention additionally contain f) 0.01 to 10% by weight, preferably 0 to 1 to 7% by weight, particularly preferably 0, 5 to 5 wt .-% of at least one additive having at least two epoxy groups per molecule, wherein the remaining components are reduced so that the sum of all weight percent always 100.

In a preferred embodiment, in addition to components a) to f) or instead of components e) and / or f), the compositions according to the invention also contain g) 0.01 to 30% by weight, preferably 1 to 25% by weight, particularly preferably from 5 to 20% by weight of titanium dioxide, with the other components being reduced to such an extent that the sum of all percentages by weight always equals 100.

In a preferred embodiment, in addition to the components a) to g) or instead of the components e) and / or f) and / or g), the compositions according to the invention also contain h) 0.01 to 15% by weight, preferably 0.1 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-% of at least one other, of the components c) to g) different additive, wherein the remaining components are reduced so that the sum of all weight percent always 100.

wobei c die Konzentration des gelösten Stoffs in g/ml, _0 die Viskosität des reinen Lösungsmittel und η_sp = η / η₀ – 1 die spezifische Viskosität ist.According to the invention, a blend of component a) PCT (CAS No. 24936-69-4) and component b) PET is used. Preferably used PCT has an intrinsic viscosity in the range of about 30 cm ³ / g to 150 cm ³ / g, more preferably 40 cm ³ / g to 130 cm ³ / g, particularly preferably 60 cm ³ / g to 120 cm ³ / g measured in analogy to ISO1628-1 in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. The intrinsic viscosity [η] is also called intrinsic viscosity or Staudinger index, since it is first a substance constant and secondly in a context of molecular weight. It indicates how the viscosity of the solvent is affected by the solute. The following definition is used to determine the intrinsic viscosity:

where c is the concentration of the solute in g / ml, _0 the viscosity of the pure solvent and η _sp = η / η₀ - 1 the specific viscosity is.

The PET to be used as component b) is a reaction product of aromatic dicarboxylic acids or their reactive derivatives, preferably dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these starting materials. PET can be prepared from terephthalic acid (or its reactive derivatives) and the respective aliphatic diols having 2 or 4 C atoms by known methods ( Plastics Handbook, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973 ).

Preferably used as component b) PET contains at least 80 mol%, preferably at least 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.

In addition to terephthalic acid residues, PET preferably used as component b) may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or radicals of aliphatic Dicarboxylic acids having 4 to 12 carbon atoms, preferably residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, or cyclohexanedicarboxylic acid.

In addition to ethylene or butane-1,4-glycol radicals, PET preferably used as component b) may contain up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms. Preference is given to radicals of 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, 1,6-hexanediol, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2, 2,4-trimethylpentanediol-1,3 or -1,6,2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (3-β-hydroxyethoxyphenyl) -propane or 2,2-bis- (4-hydroxypropoxyphenyl) -propane ( DE-A 24 07 674 (= US Pat. No. 4,035,958 ) DE-A 24 07 776 . DE-A 27 15 932 (= US 4,176,224 )).

In one embodiment, the PET to be used according to the invention as component b) can be prepared by incorporating relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, as described, for example, in US Pat. B. in the DE-A 19 00 270 (= US-A 3,692,744 ) are branched. Preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.

The PET to be used according to the invention preferably has an intrinsic viscosity of about 30 cm ³ / g to 150 cm ³ / g, particularly preferably 40 cm ³ / g to 130 cm ³ / g, particularly preferably 50 cm ³ / g to 100 cm ³ / g each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C using a Ubbelohde viscometer.

The polyesters of component a) PCT and component b) PET may, in one embodiment, if appropriate, also be used in a mixture with other polyesters, in particular PBT, and / or further polymers. The preparation of polyesters of the components a) and b) is also for example in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pages 65 ff, Verlag Chemie, Weinheim 1980 , described.

The glass fibers to be used according to the invention as component c) preferably have a fiber diameter in the range from 7 to 18 μm, particularly preferably in the range from 9 to 15 μm, and are added as continuous fibers or as cut or ground glass fibers. The fibers are preferably provided with a suitable sizing system and a primer or adhesion promoter system, particularly preferably based on silane.

q: eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4,
r: eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2,
k: eine ganze Zahl von 1 bis 3, bevorzugt 1.Very 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 ₂ r + 1) ₄ -k (I) in which the substituents have the following meanings:
X: NH ₂ -, HO-,

q: an integer from 2 to 10, preferably 3 to 4,
r: an integer from 1 to 5, preferably 1 to 2,
k: an integer of 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 finishing of the glass fibers, the silane compounds are preferably used in amounts of from 0.05 to 2% by weight, more preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight, based on the glass fibers used for surface coating.

Due to the processing into the molding composition or the product to be produced therefrom, the glass fibers may have a smaller d97 or d50 value in the molding compound or in the product than the originally used glass fibers. The glass fibers may have shorter length distributions than originally used due to the processing of the molding compound or molding in the molding compound or in the molding.

According to the invention as component d) talc, preferably microcrystalline talc used. Talc, also referred to as talc, is a layered silicate with the chemical composition Mg ₃ [Si ₄ O ₁₀ (OH) ₂ ], which, depending on the modification, crystallizes as talc 1A in the triclinic or as talc 2M in the monoclinic crystal system ( http://de.wikipedia.org/wiki/Talkum ). According to the invention to be assigned microcrystalline talc can be obtained, for example, as Mistron ^® R10 Imerys Talc Group, Toulouse, France (Rio Tinto Group).

According to the invention, at least one flame retardant is used as component e). Preferred flame retardants are commercially available organic halogen compounds with or without synergists or commercially available halogen-free flame retardants based on organic or inorganic phosphorus compounds or organic nitrogen compounds, individually or in a mixture.

Preferred halogen-containing compounds, in particular brominated or chlorinated compounds, are ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ether. As phosphorus compounds, the phosphorus compounds are according to WO A 98/17720 (= US Pat. No. 6,538,024 ), preferably metal phosphinates, in particular aluminum phosphinate or zinc phosphinate, metal phosphonates, in particular aluminum phosphonate, calcium phosphonate or zinc phosphonate and the corresponding hydrates of the metal phosphonates, furthermore derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxides (DOPO derivatives ), triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP), including oligomers and bisphenol-A-bis-diphenyl phosphate (BDP), including oligomers, polyphosphonates (such. as Nofia ^® HM1100 Fa. FRX polymer, Chelmsford, USA) also zinc bis (diethylphosphinate), aluminum tris (diethylphosphinate), melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine poly (aluminum phosphate), melamine poly (zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof. As nitrogen compounds, in particular melamine or melamine cyanurate and reaction products of trichlorotriazine, piperazine and morpholine according to CAS no. 1078142-02-5 (eg MCA PPM triazine HF from MCA Technologies GmbH, Biel-Benken, Switzerland). Preferred synergists are antimony compounds, in particular antimony trioxide or antimony pentoxide, zinc compounds, tin compounds, in particular zinc stannate, or borates, in particular zinc borates, it also being possible to use synergistically combinations of different flame retardants.

Also, the flame retardant so-called carbon formers such. As polyphenylene ethers and anti-dripping agents such as tetrafluoroethylene polymers are added

Among the halogen-containing flame retardants are particularly preferably ethylene-1,2-bistetrabromophthalimide, tetrabromobisphenol A oligo-carbonate, polypentabromobenzyl acrylate or brominated polystyrene such. B. Fire Master ^® PBS64 (Great Lakes, West Lafayette, USA) (dietylphosphinat) each in combination with antimony trioxide and / or aluminum-tris used.

Among the halogen-free flame retardants, aluminum tris are particularly preferred (diethylphosphinate) in combination with melamine polyphosphate (z. B. Melapur ^® 200/70 BASF SE, Ludwigshafen, Germany) and / or melamine cyanurate (z. B. Melapur ^® MC25 BASF SE, Ludwigshafen , Germany) and / or Phenoxyphosphazenoligomere (z. B. Rabitle ^® FP110 Fushimi Pharmaceutical Co.m Ltd., Kagawa, Japan) was used.

As a flame retardant aluminum tris (diethylphosphinate) that as Exolit ^® OP1240 (CAS No 225789-38-8) is sold by Clariant International Ltd, Muttenz, Switzerland is especially preferably used.

According to the invention, at least one additive having at least two epoxy groups per molecule is used as component f). Preferred additives of component f) are selected from the series of bisphenol diglycidyl ethers. Bisphenol diglycidyl ethers are obtained by reactions of bisphenol derivatives with epichlorohydrin. Preferred bisphenol components are 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) -1-phenyl-ethane (bisphenol AP), bis (4-hydroxyphenyl) sulfone ( Bisphenol S) and bis (4-hydroxydiphenyl) methane (bisphenol F), diglycidyl ether based on bisphenol A being particularly preferred are. Very particular preference is given to solid bisphenol A diglycidyl ethers having a softening point above 60 ° C such as. As the Araldite ^® GT7071 Fa. Huntsman, Everberg, Belgium.

The titanium dioxide to be used as component g) preferably has an average particle size in the range from 90 nm to 2000 nm. For the titanium dioxide to be used according to the invention as component g), titanium dioxide pigments are suitable whose basic structure after sulfate (SP) or chloride (CP ) Method can be prepared and have the anatase and / or rutile structure, preferably rutile structure. The main body need not be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0 wt .-% (calculated as Al ₂ O ₃ ) and an excess of oxygen in the gas phase at the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z. Particularly preferred in order to obtain a sufficiently high brightness of the products to be prepared from the compositions, a "light" stabilization with Al is preferred, or at higher Al doping amounts compensation with antimony. When using titanium dioxide as white pigment in paints and varnishes, plastics, etc., it is known that unwanted photocatalytic reactions produced by UV absorption lead to the decomposition of the pigmented material. Titanium dioxide pigments absorb light in the near ultraviolet range, creating electron-hole pairs that generate highly reactive radicals on the titanium dioxide surface. The radicals formed in organic media result in a binder degradation. According to the invention, to lower the photoactivity of the titanium dioxide, it is preferably after-treated in an inorganic form, particularly preferably with oxides of Si and / or Al and / or Zr and / or by the use of Sn compounds.

The surface of pigmentary titanium dioxide is preferably covered with amorphous precipitates of oxide hydrates of the compounds SiO ₂ and / or Al ₂ O ₃ and / or zirconium oxide. The Al ₂ O ₃ sheath facilitates pigment dispersion in the polymer matrix, the SiO ₂ sheath impedes the charge exchange on the pigment surface and thus prevents polymer degradation.

According to the invention, the titanium dioxide is preferably provided with hydrophilic and / or hydrophobic organic coatings, in particular with siloxanes or polyalcohols.

Titanium dioxide to be used according to the invention as component g) preferably has an average particle size in the range from 90 nm to 2000 nm, preferably in the range from 200 nm to 800 nm.

Commercially available products are, for example, Kronos ^® 2230, Kronos ^® 2225 and Kronos ^® vlp7000 of Messrs. Kronos, Dallas, United States.

According to the invention, at least one additive which differs from components c), d), e), f) and g) can be used as component h).

Typical additives of component h) are preferably stabilizers, mold release agents, UV stabilizers, heat stabilizers, gamma ray stabilizers, antistatic agents, flow aids, flame retardants, elastomer modifiers, acid scavengers, emulsifiers, nucleating agents, plasticizers, lubricants, dyes or pigments. The above-mentioned and further suitable additives are described, for example, in Gächter, Müller, Kunststoff-Additive, 3rd edition, Hanser Verlag, Munich, Vienna, 1989 and in the Plastics Additives Handbook, 5th Edition, Hanser Verlag, Munich, 2001. Die Additives can be used alone or in mixture or in the form of masterbatches.

The stabilizers used are preferably sterically hindered phenols and 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.

Preferred phosphites are selected from the series tris (2,4-di-tert-butyl-phenyl) phosphite (Irgafos ^® 168, BASF SE, CAS 31570-04-4), bis (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphite (Ultranox ^® 626, Chemtura, CAS 26741-53-7), bis (2,6-di-ter-butyl-4-methylphenyl) pentaerythritol diphosphite (ADK Stab PEP-36, Adeka, CAS 80693-00 (-1), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228 ^®, Dover Chemical Corporation, CAS 154862-43-8), tris nonylphenyl) phosphite (Irgafos ^® TNPP, BASF SE, CAS 26523- 78-4), (2,4,6-tri-t-butylphenol) 2-butyl-2-ethyl-1,3-propane-ediol phosphite (Ultranox ^® 641, Chemtura, CAS 161717-32-4), or Hostanox ^® P-EPQ used.

At least Hostanox ^® P-EPQ (CAS No. 119345-01-6) of Clariant International Ltd., Muttenz, Switzerland is particularly preferably used as phosphite stabilizer. This contains the invention In particular, most preferably used as component d) tetrakis (2,4-di-tert-butylphenyl) -1,1-biphenyl-4,4'-diylbisphosphonit (CAS No. 38613-77-3).

Hydrotalcite, chalk, zinc stannate and boehmite are preferably used as acid scavengers.

Preferred mold release agents are at least one selected from ester wax (s), pentaerythritol tetrastearate (PETS), long-chain fatty acids, long-chain fatty acid salt (s), long-chain fatty acid amide derivative (s), montan waxes and low molecular weight polyethylene or polypropylene wax (s). or ethylene homopolymer wax (s).

Preferred long-chain fatty acids are stearic acid or behenic acid. Preferred salts of long-chain fatty acids are calcium stearate or zinc stearate. Preferred amide derivative of long-chain fatty acids is ethylene-bis-stearylamide. Preferred montan waxes are mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.

As dyes or pigments, regardless of the titanium dioxide of component c) further dyes or pigments are used, for. B. to give in the case of an optoelectronic product to be emitted by this light a hue or to improve the light to be emitted by means of an optical brightener.

The nucleating agent used is preferably sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide.

The plasticizers used are preferably dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.

As an elastomer modifier to be used additive is preferably one or more graft polymer (s) E of

E.1 5 to 95 wt .-%, preferably 30 to 90 wt .-%, of at least one vinyl monomer on

E.2 95 to 5 wt .-%, preferably 70 to 10 wt .-% of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C used.

The graft base E.2 generally has an average particle size (d ₅₀ value) of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m, particularly preferably 0.2 to 1 .mu.m.

Monomers E.1 are preferably mixtures of

E.1.1 50 to 99 wt .-% vinyl aromatics and / or ring-substituted vinyl aromatics (such as styrene, α-methyl styrene, p-methyl styrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters (such B. methyl methacrylate, ethyl methacrylate) and / or glycidyl (meth) acrylate and

E.1.2 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, n-butyl acrylate, t-butyl) Butyl acrylate) and / or glycidyl methacrylate and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example, maleic anhydride and N-phenyl-maleimide).

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

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

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

Preferred grafting principles E.2 are diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (for example according to E.1.1 and E.1.2), with the proviso that the glass transition temperature of component E.2 is below <10 ° C., preferably <0 ° C., particularly preferably <-10 ° C. ,

Particularly preferred as the grafting E.2. pure polybutadiene rubber.

Particularly preferred polymers E are ABS polymers (emulsion, bulk and suspension ABS), as z. 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 graft base E.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene). ABS means acrylonitrile-butadiene-styrene copolymer with the CAS number 9003-56-9 and is a synthetic terpolymer of the three different monomer types acrylonitrile, 1,3-butadiene and styrene. It belongs to the amorphous thermoplastics. The proportions may vary from 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene.

The elastomer modifiers or graft copolymers E are prepared by free-radical polymerization, for. 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 E according to the invention are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during workup.

Suitable acrylate rubbers are based on grafting bases E.2 which are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on E.2 of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable Acrylsäureestern include C ₁ -C ₈ -alkyl, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C ₁ -C ₈ -alkyl esters, particularly preferably chloroethyl acrylate and mixtures of these monomers.

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 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

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

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 grafting E.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 graft base E.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft base E.2 are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-C ₁ -C ₆ -alkyl ethers, methyl methacrylate, butadiene , Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.

Further suitable grafting principles according to E.2 are silicone rubbers 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.

Independently of component c), additives and / or reinforcing substances may be present in the compositions according to the invention as additives.

However, preference is also given to a mixture of two or more different fillers and / or reinforcing substances, in particular based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate, glass spheres and / or fibrous fillers and / or reinforcing materials based on carbon fibers used. Preference is given to using mineral particulate fillers based on mica, silicate, quartz, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar or barium sulfate. Mineral particulate fillers based on wollastonite or kaolin are particularly preferably used according to the invention.

Furthermore, acicular mineral fillers are also particularly preferably used as an additive. According to the invention, needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced needle-like character. As an example, needle-shaped wollastonites are mentioned. Preferably, the mineral has a length: diameter ratio of from 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, most preferably from 4: 1 to 12: 1. The mean particle size of the acicular minerals according to the invention is preferably less than 20 .mu.m, more preferably less than 15 .mu.m, particularly preferably less than 10 .mu.m determined with a CILAS GRANULOMETER.

As already described above for component c), in a preferred use form, the filler and / or reinforcing material may be surface-modified, particularly preferably with an adhesion promoter or adhesion promoter system, particularly preferably based on silane. However, pretreatment is not essential.

For the finishing of fillers to be used as an additive, the silane compounds are generally purchased in amounts of from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight used on the mineral filler for surface coating.

The particulate fillers may have a smaller d97 or d50 value than the originally used fillers due to the processing into the molding compound or molding in the molding compound or in the molding.

In a preferred embodiment, the present invention relates to compositions comprising a) poly (1,4-cyclohexylenedimethylene) terephthalate, preferably having a viscosity of 110 g / cm ³ , PET, c) glass fibers, d) talc and e) aluminum tris (diethylphosphinate).

In a preferred embodiment, the present invention relates to compositions comprising a) poly (1,4-cyclohexylenedimethylene) terephthalate (PCT), preferably having a viscosity of 110 g / cm ³ , b) polyethylene terephthalate (PET), c) glass fibers, d) talc , preferably microcrystalline talc, e) aluminum tris (diethylphosphinate) and h) pentaerythritol tetrastearate.

However, the present invention also relates to the use of the compositions according to the invention in the form of molding compositions for the production of short-time thermoforming products, preferably electronic and electronic assemblies and components, particularly preferably optoelectronic products.

For the preparation according to the invention for injection molding or for extrusion to be used molding compositions obtained by mixing the individual components of the compositions according to the invention mixed, discharged into a strand, cooled to Granulierfähigkeit and granulated.

Preferably, the mixing takes place at temperatures in the range of 260 to 310 ° C, preferably 270-300 ° C particularly preferably at 280-295 ° C in the melt. Particularly preferred for this purpose, a twin-screw extruder is used.

In a preferred embodiment, the granules containing the composition according to the invention are dried at 120 ° C. in a vacuum drying oven or in a dry air dryer for about 2 hours before being subjected to injection molding or an extrusion process for the production of products.

However, the present invention also relates to a process for the production of products, preferably short-time thermoforming products for the electrical or electronics industry, more preferably electronic or electrical assemblies and components, wherein the matrix material as a molding composition containing the compositions according to the invention by injection molding or extrusion, preferably by injection molding becomes.

However, the present invention also relates to a process for improving the short-time heat distortion resistance of polyester-based products, characterized in that one processes compositions of the invention in the form of molding compositions by injection molding or extrusion.

The methods of injection molding and the extrusion of thermoplastic molding materials are known in the art.

Processes according to the invention for the production of products by extrusion or injection molding work at melt temperatures in the range from 260 to 330 ° C., preferably from 270 to 300 ° C., more preferably from 280 to 290 ° C. and optionally additionally at pressures of at most 2500 bar, preferably at Pressing a maximum of 2000 bar, more preferably at pressures of up to 1500 bar and most preferably at pressures of at most 750 bar.

In sequential coextrusion, two different materials are ejected in succession in succession. In this way, a preform with sections of different material composition in the extrusion direction. Certain article sections may be provided with specific required properties by appropriate material selection, for example for soft-end and hard-centered article or integrated soft-bellows regions ( Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Munich 2006, pages 127-129 ).

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 injected as a spray mass under pressure into a tempered cavity. After cooling (solidification) of the mass, the injection molded part is removed from the mold.

• 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 platens for the tool, a face plate and columns and drive of the moving platen. (Toggle joint or hydraulic clamping unit).

An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit. The task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (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 product 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

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 of conventional single-screw extruders, conveying-effective single-screw extruders, counter-rotating twin-screw extruders and co-rotating twin-screw extruders.

Extrusion lines consist of extruder, tool, follower, extrusion blow molding. Extrusion lines for the production of profiles consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, separating device and tilting channel.

The present invention accordingly also relates to products, in particular short-term dimensionally stable products, obtainable by extrusion, preferably profile extrusion, or injection molding of the molding compositions obtainable from the compositions according to the invention.

However, the present invention also relates to a process for the production of short-term heat-resistant products, characterized in that PCT and PET and titanium dioxide-containing compositions are processed in the form of molding materials by injection molding or in extrusion.

• a) 3 bis Gew.-% bevorzugt 5 bis 25 Gew.-%, besonders bevorzugt 10 bis 20 Gew.-% Poly(1,4-cyclohexylendimethylen)terephthalat (PCT), wobei der Anteil an PCT bezogen auf die Summe aller enthaltener thermoplastischen Polymere in der Zusammensetzung im Bereich von 5 bis 40 Gew.-%, bevorzugt 7 bis 30 Gew.-%, besonders bevorzugt bei 10–25% Gew.-% liegt.
• b) 15 bis 90 Gew.-%, bevorzugt 20 bis 70 Gew.-%, besonders bevorzugt 30 bis 60 Gew.-% Polyethylenterephthalat (PET),
• c) 5 bis 70 Gew.-%, bevorzugt 10 bis 45 Gew.-%, besonders bevorzugt 15 bis 35 Gew.-% Glasfasern, und
• d) 0,01 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-%, besonders bevorzugt 0,1 bis 2 Gew.-% Talkum, bevorzugt mikrokristalliner Talkum,

wobei die Summe aller Gewichtsprozente stets 100 ergibt, zu Formmassen verarbeitet werden und diese einem Spritzguss oder einer Extrusion unterzogen werden.The present invention preferably relates to a process for the preparation of short-time thermoforming products, characterized in that the above-mentioned compositions, preferably containing compositions

• a) 3 to wt .-%, preferably 5 to 25 wt .-%, particularly preferably 10 to 20 wt .-% poly (1,4-cyclohexylenedimethylene) terephthalate (PCT), wherein the proportion of PCT based on the sum of all contained thermoplastic polymers in the composition in the range of 5 to 40 wt .-%, preferably 7 to 30 wt .-%, particularly preferably 10-25% by weight.
• b) from 15 to 90% by weight, preferably from 20 to 70% by weight, particularly preferably from 30 to 60% by weight, of polyethylene terephthalate (PET),
• c) 5 to 70 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 35 wt .-% glass fibers, and
• d) 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-% talc, preferably microcrystalline talc,

the sum of all weight percentages always being 100, being processed into molding compositions and subjected to injection molding or extrusion.

The products obtainable by the mentioned processes surprisingly show excellent short-term heat resistance, in particular in soldering processes, as well as optimized properties in the mechanical properties. In addition, the molding compositions for injection molding and extrusion to be produced from the compositions according to the invention are distinguished by good processability compared with the prior art.

However, the present invention also relates to the use of the compositions according to the invention for increasing the short-time heat distortion resistance of products, preferably of products of the electrical or electronics industry, in particular electronic products for printed circuit boards such. B. Housing for bobbins, connectors or capacitors and power transistors and optoelectronic products.

The products produced in accordance with the invention are therefore also outstandingly suitable for electrical or electronic products, preferably optoelectronic products, in particular LEDs or OLEDs. A light-emitting diode (also luminescence diode, English light-emitting diode, German light-emitting diode, LED) is an electronic semiconductor device. If current flows through the diode in the forward direction, it emits light, infrared radiation (as an infrared light-emitting diode) or else ultraviolet radiation with a wavelength dependent on the semiconductor material and the doping. An organic light emitting diode (OLED) is a thin-film luminous component made of organic Semiconducting materials, which differs from the inorganic light-emitting diodes (LED) in that current density and luminance are lower and no single-crystalline materials are required. Compared to conventional (inorganic) light-emitting diodes, organic light-emitting diodes can therefore be produced less expensively, but their service life is currently lower than that of conventional light-emitting diodes.

Examples

For the preparation of the compositions according to the invention, the individual components in a twin-screw extruder (ZSK 26 Mega Compounder Fa. Coperion Werner & Pfleiderer (Stuttgart, Germany with 3-hole nozzle plate and a nozzle hole diameter of 3 mm) at temperatures between 280 and 295 ° C in After further steps, the granules were dried in a vacuum drying oven at 120 ° C. for about 2 hours, whereby the processability was rated qualitatively as a function of the temperature: "+" stands for the melt for trouble-free processing, "o" for limited processability, eg because of a sharp increase in nozzle pressure or the decomposition of sensitive additives.

The plates and test specimens for the tests listed in Table 1 were sprayed on a commercial injection molding machine at a melt temperature of 280-290 ° C and a mold temperature of 80-120 ° C. A parameter for the quality of the injection molding process was in the context of the present invention, the mold release: For the mold release rapid crystallization is advantageous in order to eject the product from the tool as quickly as possible and without deformation can. In the examples and comparative examples shown in Table 1, "+" stands for a good, "o" for a satisfactory and "-" for a poor mold release.

Short-term heat resistance

The test for determining the short-time heat distortion resistance or solder bath resistance simulates the conditions of the wave soldering as follows:
From a plate having a thickness of 1.0 mm, test specimens of dimensions 20 × 10 × 1 mm were cut out. These were spent for 15 min in a commercial hot air oven heated at the temperature indicated in Table 1. Subsequently, the melting behavior of the specimens was visually inspected. "+" Stands for a sample without visually observable melting, "o" for a sample with rounded edges and "-" for a sample melted over the entire surface.

feedstocks

• Component a: PCT [CAS no. 24936-69-4] with a viscosity of 110 g / cm ³ ]
• Component b: PET: polyethylene terephthalate (polyester chips PET V004, Invista, Wichita, USA)
• Component c: Glass fibers with a diameter of 10 μm, sized with silane-containing compounds (CS 7967, commercial product of Lanxess N.V., Antwerp, Belgium)
• Component d: talc: Mistron ^® R10 Imerys Talc Group, Toulouse, France (Rio Tinto Group)
• Component e: aluminum tris (diethylphosphinate) Exolit ^® OP1240 of Clariant International Ltd., Muttenz, Switzerland
• Component h: further additives customary for use in polyesters, such as, for example, mold release agents (for example pentaerythritol tetrastearate (PETS)), heat stabilizers (for example based on phenyl phosphites). The type and amount of the additives summarized as component H are identical in type and amount for examples and comparative examples.

Table 1 shows that with thermally sensitive flame retardants such as component e, both in the case of the polyester blends according to the invention both good processability and thus good mechanical data and increased short-term heat resistance at temperatures above the melting point of component a is given. This is an important requirement for applications such. B. electronic components, short solder bath temperatures may be exposed to 285 ° C. Table 1: Polyester Blends with Thermally Sensitive Flame Retardants All quantities of the components in Table 1 are in% by weight. See 1 See 2 See 3 Example 1 Ex. 2 Component a) 53 13 43 38 Component b) 40 53 10 15 Component c) 30 30 30 30 30 Component d) 0.5 0.5 0.5 0.5 0.5 Component e) 15 15 15 15 15 Component h) 1.5 1.5 1.5 1.5 1.5 Processability at 290 ° C + O O + + demouldability + - O + + Melt stiffness at 265 ° C + + + + + Melt stiffness at 275 ° C O + + + + Melt stiffness at 285 ° C - + + + + IZOD [kJ / m ² ] + - - + + Bending strength [Mpa] + - - + + Outer fiber strain + - - + +

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.

Cited patent literature

• WO 2007/033129 A1 [0009]
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Cited non-patent literature

• "Http://en.wikipedia.org/wiki/Wave_Coats" [0003]
• DIN EN 61760-1: 1998 [0005]
• ISO 180 [0012]
• ISO 178 [0012]
• Bodo Carlowitz: Tabular Review of the Testing of Plastics, 6th Edition, Giesel Publishing, 1992, pp. 16-17 [0012]
• ISO1628-1 [0019]
• Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973 [0020]
• Ullmanns Enzyclopädie der technischen Chemie, 4th Edition, Volume 19, pages 65 ff, Verlag Chemie, Weinheim 1980 [0026]
• http://en.wikipedia.org/wiki/Talkum [0032]
• Ullmann, Enzyklopadie der Technischen Chemie, Vol. 19 (1980), p. 280 ff. [0064]
• Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Munich 2006, pages 127-129 [0091]

Claims (10)

Containing compositions a) 3 to 30 wt .-% poly (1,4-cyclohexylenedimethylene) terephthalate (PCT), wherein the proportion of PCT based on the sum of all contained thermoplastic polymers in the composition in the range of 5 to 40 wt .-% is. b) 15 to 90% by weight of polyethylene terephthalate (PET), c) 5 to 70 wt .-% glass fibers, and d) 0.01 to 10 wt .-% talc, wherein the sum of all weight percentages of the components always gives 100. Compositions according to claim 1, characterized in that these contain, in addition to the components a), b), c) or d) still e) 5 to 50 wt .-% of at least one flame retardant, wherein the components a, b, c) and d) reduced to the extent that the sum of all weight percentages always equals 100. Compositions according to Claim 2, characterized in that the flame retardants used are organic halogen compounds with or without synergists or halogen-free flame retardants based on organic or inorganic phosphorus compounds or organic nitrogen compounds, individually or in a mixture. Compositions according to Claim 3, characterized in that ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ether are used as the organic halogen compounds. Compositions according to claim 3, characterized in that as organic or inorganic phosphorus compounds, metal phosphinates, in particular aluminum phosphinate or zinc phosphinate, metal phosphonates, in particular aluminum phosphonate, calcium phosphonate or zinc phosphonate and the corresponding hydrates of the metal phosphonates, as well as derivatives of 9,10-dihydro-9-oxa-10 phosphophenanthrene-10-oxides (DOPO derivatives), triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) (RDP), including oligomers, and bisphenol A bis diphenyl phosphate (BDP) including oligomers, polyphosphonates, and zinc bis (diethylphosphinate), aluminum tris (diethylphosphinate), melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine poly (aluminum phosphate), melamine poly (zinc phosphate) or Phenoxyphosphazenoligomere and mixtures thereof can be used. Compositions according to Claim 3, characterized in that the organic nitrogen compounds used are melamine or melamine cyanurate and reaction products of trichlorotriazine, piperazine and morpholine. Compositions according to Claim 3, characterized in that antimony compounds, in particular antimony trioxide or antimony pentoxide, zinc compounds, tin compounds, in particular zinc stannate, or bristles, in particular zinc borates, are used as synergists. Compositions according to Claim 5, characterized in that aluminum tris (diethylphosphinate) is used. Compositions according to one of claims 1 to 8, characterized in that these contain in addition to the components a) to e) or in place of the components e) still f) 0.01 to 15 wt .-% of at least one additive having two epoxy groups per molecule , wherein the remaining components are reduced so far that the sum of all weight percent always equals 100. Compositions according to claim 9, characterized in that component f) from the series of bisphenol diglycidyl ethers, preferably 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenyl-ethane , Bis (4-hydroxyphenyl) sulfone and bis (4-hydroxydiphenyl) methane.