DE102005027822A1 - Marking of molded articles based on thermoplastic polymers or their mixture, additive materials, and further additives such as high- or hyper- branched polycarbonate or hyper-branched polyester, for improving the marking ability - Google Patents

Abstract

Marking of molded articles on the basis of thermoplastic polyesters or their mixture (up to 70 wt.%), additive materials by high-energy radiation, and further additives such as high- or hyper- branched polycarbonate with hydroxy number of 1-600 mg potassium hydroxide (KOH)/g, according to DIN 53240 or at least a hyper-branched polyester, for the improving the marking ability. Marking of molded articles on the basis of thermoplastic polyesters or their mixture (up to 70 wt.%), additive materials by high-energy radiation, and further additives such as high- or hyper- branched polycarbonate with hydroxy number of 1-600 mg KOH/g, according to DIN 53240 or at least a hyper-branched polyester of type of formula (AxBy), for the improving the marking ability. x : 1.1; and y : 2.1. Independent claims are included for: (1) a thermoplastic molded mass comprising a thermoplastic polyester (10-99.9 wt.%), polycarbonate and/or polyester (0.01-50 wt.%), secondary inorganic group metal salt (0.01-10 wt.%); soot and/or graphite (0-10 wt.%) and additional materials (0-50 wt.%); and (2) molded articles, semi-finished product or finished materials that are obtained by the above procedure.

Description

The The present invention relates to an improved method for labeling of thermoplastic polyesters by means of high-energy radiation, Polyester molding compounds and the labeled moldings of any kind.

plastics can be labeled by printing process. Has in recent years However, the laser lettering prevailed largely. The advantages lie in the simple, fast and precise feasible, non-contact (neither mechanical stress nor contamination of the workpiece), flexible (computer-controlled), clean and chemical-free processing. Leave laser systems easily integrate into automated production lines; Plastic components can individually labeled, because a layout change computer-aided easy and fast possible is. The lettering is non-contact even on hard to reach Put. Across from Conventional printing techniques thus yield considerable advantages.

The most important characterization of the achieved Labeling is the readability that quantifies with the contrast can be. In addition to high contrast are sufficient color depth and as smooth as possible surface required. The font should be resistant to abrasion and chemicals.

In order to on a plastic molding A high quality mark is created, the absorption of laser light must cause a color change reaction. Depending on the wavelength, irradiated Power, pulse length etc. are each different interactions between laser light and plastic dominate and one therefore distinguishes a number various laser-induced mechanisms leading to a permanent Guide the marker: Thermochemical reaction, surface carbonization, melting, Remelting, evaporation, sublimation, engraving, discoloration, foaming, photochemical Reaction, ablation (material removal), fading of dyes, Removal of a coating layer.

At the Laser marking distinguishes two methods, the masks (projection) and beam deflection labeling (scanning the laser beam). Masking uses pulsed lasers. A laser beam with sufficiently large Aperture illuminates a mask representing all the information to be transmitted contains. The mask is imaged with a lens on the surface to be labeled, The information can be applied to the workpiece with a single laser pulse become. For big ones Images, the mask can be scanned with multiple pulses. The maximum size of the label field is limited by the necessary energy density. The projection method allows fast labels; because a mask is created but it is not so flexible. In the beam deflection inscription the laser beam is over two movable mirrors and a plane field lens on the label workpiece directed.

To date, mainly the CO ₂ laser (10.6 mm wavelength) and especially the Nd: YAG laser (1.06 mm) or the frequency-doubled Nd: YAG laser (532 nm) are used. Often, however, the absorption coefficient of the plastics to be processed at these wavelengths is not high enough to induce a color change in the polymeric material. For this reason, plasticizers and fillers are usually added to the plastic during its production which strongly absorb at the wavelength used and transfer the absorbed energy to the surrounding polymer matrix (eg addition of sensitizing dyes in the form of pigments, addition of toxic arsenic or Cd compounds , Addition of suitable monomers in the copolymerization, coating of the substrate with special paint and color films, inks, etc.). Known is the incorporation of carbon black (DE-A 2936926) or bone carbon (EP-A 522370) or of antimony trioxide in thermoplastic elastomers. Special plastic additives with high absorbency, in particular for the wavelength of the Nd: YAG laser, allow markings with high contrast, good sharpness and good abrasion resistance (C. Herkt-Maetzky, Kunststoffe 81 (1991) 4). Other methods work with radiation-sensitive bleachable additives (and possibly additional, less radiation-sensitive non-discolourable compounds). Irradiation then destroys the radiation-sensitive dyes and the background or complementary color of the polymer matrix then remains at the irradiated points, resulting in a visual, colorful contrast marking. Such color changes lead to good contrasts ( EP 327508 ). Plastics containing commercial colored pigments can be partially labeled with the frequency-doubled Nd: YAG laser, as a large number of pigments and dyes absorb at 532 nm. The pigments are bleached resulting in a color change. By adding modified mica pigments molding compositions can be prepared which can be labeled with the CO ₂ laser (C. Herkt-Maetzky, Kunststoffe 81 (1991) 4). Also described was a method in which On a carrier material pigments are applied, which are melted by means of the laser by thermal means in the surface (EP-A 419 377).

In DE-A 4133124 describes high-polymers which can be labeled with laser light Materials containing as additive inorganic Nebengruppenmetallsalze contain. From EP-A 592942 PA-masses are known, the iron oxide pigments as fillers contain.

To improve the contrast in the labeling of black-colored polymers (white writing on black background) were in the literature additives such as copper salts (eg US 5489639 ; EP-A 764683), titanium dioxide (EP-A 330689), tetrazoles (EP-A 572178 and EP-A 566312) or antimony trioxide (EP-A 796743) described ben. Furthermore, additives of boron, zinc and tin salts are described (WO 99/55773).

plastics to modify is complicated. The added fillers can change the material properties of the plastic adversely affect. So can additives to improve Of writability often not intended side effects such as reduced strength of the material or unwanted Colors when using pigments result. Therefore, it was after special laser-sensitive additives that are sought in the plastic incorporated, other performance material properties do not influence. The sensitization is often only for one Wavelength, to which the system has been optimized.

task The present invention was therefore a method of labeling of moldings the basis of thermoplastic polyesters available provide, which does not have the disadvantages described above and the creation of durable high-contrast fonts on technical easy to implement way and during processing an improved flowability exhibit.

This object is achieved by a method according to the preamble of claim 1, wherein at least one highly branched or hyperbranched polycarbonate B1) with an OH number of 1 to 600 mg KOH / g polycarbonate (according to DIN 53240, Part 2), or at least one highly branched or hyperbranched polyester B2) of the type A _x B _y with x at least 1.1 and y at least 2.1 or mixtures thereof.

The in the method according to the invention used high-energy radiation generally has a wavelength in the range from 150 to 1500, preferably in the range of 150-1100 nm.

For example, mention may be made here of CO ₂ lasers (10.6 mm) and Nd: YAG lasers (1064 or 532 nm) or UV lasers, the latter in particular being excimer lasers having the following wavelengths:
F ₂ excimer laser 157 nm
ArF excimer laser 193 nm
KrCl excimer laser 222 nm
KrF excimer laser 248 nm
XeCl excimer laser 308 nm
XeF excimer laser 351 nm
as well as frequency-multiplied Nd: YAG lasers with wavelengths of 355 nm (frequency tripled) or 266 nm (frequency-quadrupled).

Especially preferred are Nd: YAG lasers (1064 or 532 nm), KrF lasers (248 nm) and XeCl laser (308 nm).

The energy densities of the lasers used are generally in the range from 0.3 mJ / cm ² to 50 J / cm ^2, preferably 0.5 mJ / cm ² to 20 J / cm ² and particularly preferably 1 mJ / cm ² to 10 J / cm ² .

at the use of pulsed lasers is the pulse rate in general in the range of 0.1 to 10,000, preferably from 0.5 to 5000 and in particular from 1 to 1000 Hz and the pulse lengths (duration of the individual Pulse) in the range of 0.1 to 1000, preferably from 0.5 to 500 and more preferably from 1 to 100 ns.

Depending on the energy density of the laser used, the pulse length and the type of the irradiated molded article are sufficient to achieve good inscriptions generally 1 to 20,000, preferably 1 to 5000 and in particular 1 to 3000 pulses.

Appropriate Lasers in the process of the invention can be used are commercially available.

excimer are particularly suitable for the projection (mask method). But it is also possible, the Beam with moving mirrors to lead (scanning). With homogeneous Beam cross-section is the irradiation of a mask of about 2 cm × 2 cm possible. By Use of suitable optics, the beam cross section but also be widened further.

With Excimer lasers can be well labeled with just one pulse (at correspondingly adjusted energy density), so that in comparison to Nd: YAG lasers also very fast labels can be produced. at the mass production of injection molded parts e.g. must be the labeling time smaller than the injection molding time (<approx. 30 s) divided by the number of mold cavities. It follows, that in these cases the injection molded molds labeled at high speeds Need to become. Such high speeds are partial with the Nd: YAG laser not possible, but achievable only with 1-pulse mask bombardment.

Yet higher Labeling speed requirements are continuous Processes such as the profile extrusion with material speeds of several m / s. Therefor Even high write speeds of Nd: YAG lasers are not enough more out.

When Radiation sources can Continuous UV lamps such as Hg, Xe or Deuterium lamps be used. Such products are also commercially available.

To the method according to the invention become shaped bodies on the basis of thermoplastic polyesters A) or mixtures this polyester with up to 70 wt .-%, based on the total weight the components and other additives C) by means of high-energy Radiation labeled.

When Component (A) contains the molding compositions 10 to 99.9 according to the invention, preferably 30 to 99.5 and in particular 30 to 99.3 wt .-% at least a thermoplastic polyester other than B).

Generally are polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound used.

A first group of preferred polyesters are polyalkylene terephthalates, especially those having 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example by halogen, such as chlorine and bromine, or by C ₁ -C ₄ -alkyl groups, such as methyl, ethyl, i- or n-propyl and n, i and t-butyl groups ,

These Polyalkylene terephthalates can by reaction of aromatic dicarboxylic acids, their esters or others ester-forming derivatives with aliphatic dihydroxy compounds be prepared in a conventional manner.

When preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or to name their mixtures. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic, azelaic, sebacic, dodecanedioic and cyclohexanedicarboxylic be replaced.

From the aliphatic dihydroxy compounds are diols having 2 to 6 Carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.

Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, in particular, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred. Further preferred are PET and / or PBT, which up to 1 wt .-%, preferably up to 0.75 wt .-% 1,6-hexanediol and / or 2-Me Thyl-1,5-pentanediol as further monomer units.

The viscosity the polyester (A) is generally in the range of 50 to 220, preferably from 80 to 160 (measured in a 0.5 wt .-% solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to ISO 1628.

Especially preferred are polyesters whose carboxyl end group content up to 100 meq / kg, preferably up to 50 meq / kg and especially up to 40 meq / kg polyester. Such polyesters can For example, according to the method of DE-A 44 01 055 produced become. The carboxyl end group content is usually by titration (e.g., potentiometry).

Especially preferred molding compositions contain as component A) a mixture of polyesters other than PBT, such as Polyethylene terephthalate (PET). The proportion e.g. of polyethylene terephthalate is preferably in the mixture up to 50, in particular 10 to 35 wt .-%, based on 100 wt .-% A).

Farther Is it advantageous to recycle PET (also called scrap-PET) if necessary in mixture with polyalkylene terephthalates such as PBT.

• 1) sog. Post Industrial Rezyklat: hierbei handelt es sich um Produktionsabfälle bei der Polykondensation oder bei der Verarbeitung z.B. Angüsse bei der Spritzgussverarbeitung, Anfahrware bei der Spritzgussverarbeitung oder Extrusion oder Randabschnitte von extrudierten Platten oder Folien.
• 2) Post Consumer Rezyklat: hierbei handelt es sich um Kunststoffartikel, die nach der Nutzung durch den Endverbraucher gesammelt und aufbereitet werden. Der mengenmäßig bei weitem dominierende Artikel sind blasgeformte PET Flaschen für Mineralwasser, Softdrinks und Säfte.

Recyclates are generally understood as:

• 1) so-called post-industrial recyclate: this is production waste during polycondensation or during processing, for example, sprues in injection molding, starting goods in injection molding or extrusion or edge sections of extruded sheets or foils.
• 2) Post Consumer Recyclate: These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices.

Both Types of recyclate can either as regrind or in the form of granules. In the latter Case become the tube cyclates after separation and cleaning melted in an extruder and granulated. This will usually the handling, the flowability and the dosability for facilitates further processing steps.

Either Granulated as well as regrind present recyclates can for Use come, the maximum edge length 10 mm, preferably smaller Should be 8 mm.

by virtue of the hydrolytic cleavage of polyesters during processing (by traces of moisture) it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

When Another group are fully aromatic polyesters to name each other of aromatic dicarboxylic acids and aromatic dihydroxy compounds.

When aromatic dicarboxylic acids are those already described in the polyalkylene terephthalates Links. Preference is given to mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid bis about equivalent Mixtures of these two acids used.

in der Z eine Alkylen- oder Cycloalkylengruppe mit bis zu 8 C-Atomen, eine Arylengruppe mit bis zu 12 C-Atomen, eine Carbonylgruppe, eine Sulfonylgruppe, ein Sauerstoff- oder Schwefelatom oder eine chemische Bindung darstellt und in der m den Wert 0 bis 2 hat. Die Verbindungen können an den Phenylengruppen auch C₁-C₆-Alkyl- oder Alkoxygruppen und Fluor, Chlor oder Brom als Substituenten tragen.The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is the value 0 to 2 has. The compounds may also carry C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds his example
dihydroxydiphenyl,
Di (hydroxyphenyl) alkane,
Di (hydroxyphenyl) cycloalkane,
Di (hydroxyphenyl) sulfide,
Di (hydroxyphenyl) ether,
Di (hydroxyphenyl) ketone,
di- (hydroxyphenyl) sulfoxide,
α, α'-di (hydroxyphenyl) -dialkylbenzol,
Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene
Resorcinol and
Hydroquinone and their nuclear alkylated or ring-halogenated derivatives called.

Of these will be
4,4'-dihydroxydiphenyl,
2,4-di- (4'-hydroxyphenyl) -2-methylbutane
α, α'-di (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and
2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,
and in particular
2,2-di- (4'-hydroxyphenyl) propane
2,2-di- (3 ', 5-dichlordihydroxyphenyl) propane,
1,1-di- (4'-hydroxyphenyl) cyclohexane,
3,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenylsulfone and
2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane
or mixtures thereof are preferred.

Of course you can also mixtures of polyalkylene terephthalates and wholly aromatic polyesters deploy. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the wholly aromatic polyester.

Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. Also in the trade corresponding products are available, eg Hytrel ^® (DuPont).

worin Q eine Einfachbindung, eine C₁- bis C₈-Alkylen-, eine C₂- bis C₃-Alkyliden-, eine C₃- bis C₆-Cycloalkylidengruppe, eine C₆- bis C₁₂-Arylengruppe sowie -O-, -S- oder -SO₂- bedeutet und m eine ganze Zahl von 0 bis 2 ist.As a polyester to be understood according to the invention also halogen-free polycarbonates. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula

wherein Q is a single bond, a C ₁ to C ₈ alkylene, a C ₂ to C ₃ alkylidene, a C ₃ to C ₆ cycloalkylidene group, a C ₆ to C ₁₂ arylene group, and -O- , -S- or -SO ₂ - and m is an integer from 0 to 2.

The diphenols may also have substituents on the phenylene radicals, such as C ₁ - to C ₆ -alkyl or C ₁ - to C ₆ -alkoxy.

preferred Diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane. Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Either Homopolycarbonates as well as copolycarbonates are as component A. suitable, are preferred in addition to the bisphenol A homopolymer Copolycarbonates of bisphenol A.

The suitable polycarbonates be branched in a known manner, preferably by the Incorporation of 0.05 to 2.0 mol%, based on the sum of the used Diphenols, on at least trifunctional compounds, for example those with three or more than three phenolic OH groups.

Particularly suitable polycarbonates have proven, the relative viscosities η _rel from 1.10 to Have 1.50, in particular from 1.25 to 1.40. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.

The Diphenols of the general formula are known per se or according to produced by known methods.

The Production of the polycarbonates can be carried out, for example, by reaction the diphenols with phosgene by the interfacial method or with phosgene according to the method in homogeneous phase (the so-called pyridine method) be carried out, wherein the particular molecular weight to be set in known Way through an appropriate amount of known chain terminators is achieved. (In terms of polydiorganosiloxane-containing polycarbonates see, for example DE-OS 33 34 782).

suitable Chain terminators are, for example, phenol, but p-t-butylphenol also long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or Monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-t-butylphenol, p-t-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol.

halogen-free Polycarbonates in the sense of the present invention means that the polycarbonates of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents are constructed, wherein the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the production of the polycarbonates with phosgene by the interfacial process, not halogenated is to be considered within the meaning of the invention. Such polycarbonates with ppm levels of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.

When Further suitable components A) are amorphous polyestercarbonates called phosgene against aromatic dicarboxylic acid units like isophthalic acid and / or terephthalic acid units, was replaced during manufacture. For more details, see this Reference is made to EP-A 711 810.

Further suitable copolycarbonates with cycloalkyl radicals as monomer units are described in EP-A 365 916.

Furthermore, bisphenol A can be replaced by bisphenol TMC. Such polycarbonates are available under the trademark APEC ^HT® from Bayer.

When Component B) contain the molding compositions 0.01 to 50, preferably 0.5 to 20 and in particular 0.7 to 10 wt .-% B1) at least a high or hyperbranched polycarbonate; with an OH number of 1 to 600, preferably 10 to 550 and in particular from 50 to 550 mgKOH / g Polycarbonate (according to DIN 53240, Part 2) or at least one hyperbranched polyester as a component B2) or mixtures thereof as explained below.

Under hyperbranched polycarbonates B1) are used in the context of this invention uncrosslinked macromolecules with hydroxyl and carbonate groups, which are both structurally as well as molecularly disparate. You can start on the one hand from a central molecule analogous to dendrimers, but constructed with uneven chain length of the branches be. You can on the other hand also linear, with functional side groups, be constructed or, as a combination of the two extremes, linear and branched parts of the molecule exhibit. For the definition of dendrimeric and hyperbranched polymers see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

Under "hyperbranched" is related understood with the present invention that the degree of branching (Degree of Branching, DB), that is, the mean number of dendritic connections plus average number of end groups per molecule, 10 to 99.9%, preferred 20 to 99%, more preferably 20-95%.

(wobei T die mittlere Anzahl der terminalen Monomereinheiten, Z die mittlere Anzahl der verzweigten Monomereinheiten und L die mittlere Anzahl der linearen Monomereinheiten in den Makromolekülen der jeweiligen Stoffe bedeuten).In the context of the present invention, "dendrimer" is understood to mean that the degree of branching is 99.9-100% For the definition of the "degree of branching" see H. Frey et al., Acta Polym. 1997, 48, 30 and is defined as

(where T is the average number of terminal monomer units, Z is the average number of branched monomer units and L is the average number of linear monomer units in the macromolecules of the respective substances).

Preferably, component B1) has a number average molecular weight M _{n of} from 100 to 15,000, preferably from 200 to 12,000 and in particular from 500 to 10,000 g / mol (GPC, standard PMMA).

The Glass transition temperature Tg is especially from -80 ° C to +140, preferably from -60 to 120 ° C (according to DSC, DIN 53765).

Especially is the viscosity (mPas) at 23 ° C (according to DIN 53019) from 50 to 200,000, especially from 100 to 150,000 and especially preferably from 200 to 100,000.

• a) Umsetzung mindestens eines organischen Carbonats (A) der allgemeinen Formel RO[(CO)]_nOR mit mindestens einem aliphatischen, aliphatisch/aromatisch oder aromatischen Alkohol (B), welcher mindestens 3 OH-Gruppen aufweist, unter Eliminierung von Alkoholen ROH zu einem oder mehreren Kondensationsprodukten (K), wobei es sich bei R jeweils unabhängig voreinander um einen geradkettigen oder verzweigten aliphatischen, aromatisch/aliphatisch oder aromatischen Kohlenwasserstoffrest mit 1 bis 20 C-Atomen handelt, und wobei die Reste R auch unter Bildung eines Ringes miteinander verbunden sein können und n eine ganze Zahl zwischen 1 und 5 darstellt, oder
• ab) Umsetzung von Phosgen, Diphosgen oder Triphosgen mit o.g. Alkohol (B) unter Chlorwasserstoffeliminierung sowie
• b) intermolekulare Umsetzung der Kondensationsprodukte (K) zu einem hochfunktionellen, hoch- oder hyperverzweigten Polycarbonat,

wobei das Mengenverhältnis der OH-Gruppen zu den Carbonaten im Reaktionsgemisch so gewählt wird, dass die Kondensationsprodukte (K) im Mittel entweder eine Carbonatgruppe und mehr als eine OH-Gruppe oder eine OH-Gruppe und mehr als eine Carbonatgruppe aufweisen.Component B1) is preferably obtainable by a process comprising at least the following steps:

• a) reacting at least one organic carbonate (A) of the general formula RO [(CO)] _n OR with at least one aliphatic, aliphatic / aromatic or aromatic alcohol (B) which has at least 3 OH groups, with elimination of alcohols ROH one or more condensation products (K), wherein each R is independently a straight-chain or branched aliphatic, aromatic / aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms, and wherein the radicals R are also connected together to form a ring and n represents an integer between 1 and 5, or
• ab) reaction of phosgene, diphosgene or triphosgene with the abovementioned alcohol (B) with elimination of hydrogen chloride and
• b) intermolecular conversion of the condensation products (K) to a highly functional, highly branched or hyperbranched polycarbonate,

wherein the quantitative ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (K) have on average either a carbonate group and more than one OH group or one OH group and more than one carbonate group.

When Starting material can be phosgene, diphosgene or triphosgene used with organic carbonates being preferred.

The radicals R used as starting material organic carbonates (A) of the general formula RO (CO) _n OR are each independently a straight-chain or branched aliphatic, aromatic / aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms. The two radicals R can also be linked together to form a ring. It is preferably an aliphatic hydrocarbon radical and particularly preferably a straight-chain or branched alkyl radical having 1 to 5 C atoms, or a substituted or unsubstituted phenyl radical.

In particular, simple carbonates of the formula RO (CO) _n OR are used; n is preferably 1 to 3, in particular 1.

Dialkyl or diaryl carbonates can be prepared, for example, from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols with phosgene. Furthermore, they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO _x . For preparation methods of diaryl or dialkyl carbonates, see also "Ullmann's Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, Verlag Wiley-VCH.

Examples of suitable carbonates include aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1,2- or 1,3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, di propyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecylacarbonate or didodecyl carbonate.

Examples for carbonates, where n is greater than 1, include dialkyl dicarbonates such as di (-t-butyl) dicarbonate or dialkyl tricarbonates such as di (-t-butyltricarbonate).

Prefers Aliphatic carbonates are used, in particular those in the radicals 1 to 5 comprise C atoms, for example dimethyl carbonate, Diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.

The Organic carbonates are at least one aliphatic Alcohol (B), which has at least 3 OH groups or mixtures implemented two or more different alcohols.

Examples for connections with at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, Trimethylolpropane, 1,2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, Pentaerythritol, diglycerol, triglycerol, polyglycerols, bis (tri-methylolpropane), Tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, phloroglucinol, Trihydroxytoluene, trihydroxydimethylbenzene, phloroglucide, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1-tris (4'-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, Bis (tri-methylolpropane) or sugars, such as glucose, tri- or higher Polyetherols based tri- or higher functional Alcohols and ethylene oxide, propylene oxide or butylene oxide, or polyesterols. These are glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, Pentaerythritol, and their polyetherols based on ethylene oxide or propylene oxide is particularly preferred.

These polyfunctional alcohols can also be used in a mixture with difunctional alcohols (B '), with the proviso that the average OH functionality of all alcohols used together bigger than 2 is. Examples of suitable compounds having two OH groups include Ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, Dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, hexanediol, cyclopentanediol, Cyclohexanediol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, Bis (4-hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1'-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, Resorcinol, hydroquinone, 4,4'-dihydroxyphenyl, Bis (4-bis (hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (hydroxymethyl) benzene, Bis (hydroxymethyl) toluene, bis (p-hydroxyphenyl) methane, bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) propane, 1,1-bis (p-hydroxyphenyl) cyclohexane, Dihydroxybenzophenone, difunctional polyether polyols based on Ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran, Polycaprolactone or polyesterols based on diols and dicarboxylic acids.

The Diols serve to finely adjust the properties of the polycarbonate. If difunctional alcohols are used, the ratio of difunctional alcohols B ') to the at least trifunctional alcohols (B) from the skilled person ever according to the desired Properties of the polycarbonate set. As a rule, the amount is of the alcohol or alcohols (B ') 0 to 50 mol% with respect the total amount of all alcohols (B) and (B ') together. The amount is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, and especially preferably 0 to 30 mol%.

The Reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture is usually carried out with elimination of Hydrogen chloride, the reaction of the carbonates with the alcohol or Alcohol mixture for the invention highly functional highly branched polycarbonate takes place with elimination of the monofunctional Alcohol or phenol from the carbonate molecule.

The according to the inventive method formed highly functional highly branched polycarbonates after the reaction, ie without further modification, with hydroxyl groups and / or terminated with carbonate groups. They dissolve well in different Solvents for example, in water, alcohols, such as methanol, ethanol, butanol, Alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, Methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, Dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.

In the context of this invention, a high-functionality polycarbonate is to be understood as meaning a product which, in addition to the carbonate groups which form the polymer backbone, also has at least three, preferably at least six, more preferably at least ten functional groups. The functional groups are carbonate groups and / or OH groups. The number of terminal or pendant functional groups is not limited in principle but may be Products with a very high number of functional groups have undesirable properties, such as high viscosity or poor solubility. The high-functionality polycarbonates of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.

In the preparation of the high-functionality polycarbonates B1), it is necessary to adjust the ratio of the compounds containing OH groups to phosgene or carbonate so that the resulting simplest condensation product (hereinafter called condensation product (K)) on average either a carbonate group or carbamoyl group and contains more than one OH group or one OH group and more than one carbonate group or carbamoyl group. The simplest structure of the condensation product (K) of a carbonate (A) and a di- or polyalcohol (B) gives the arrangement XY _n or Y _n X, where X is a carbonate group, Y is a hydroxyl group and n usually one Number between 1 and 6, preferably between 1 and 4, particularly preferably between 1 and 3 represents. The reactive group, which results as a single group, is referred to hereinafter generally "focal group".

Lies for example, in the production of the simplest condensation product (K) from a carbonate and a dihydric alcohol, the conversion ratio at 1: 1, the average result is a molecule of type XY, illustrated by the general formula 1.

In the preparation of the condensation product (K) from a carbonate and a trihydric alcohol at a conversion ratio of 1: 1 results in the average molecule of the type XY ₂ , illustrated by the general formula 2. Focal group here is a carbonate group.

In the preparation of the condensation product (K) from a carbonate and a tetrahydric alcohol also with the conversion ratio 1: 1 results in the average molecule of the type XY ₃ , illustrated by the general formula 3. Focal group here is a carbonate group.

In the formulas 1 to 3, R has the meaning defined above and R ¹ is an aliphatic or aromatic radical.

Furthermore, the preparation of the condensation product (K) can be carried out, for example, also from a carbonate and a trihydric alcohol, illustrated by the general formula 4, wherein the reaction ratio is at molar 2: 1. This results in the average molecule of type X ₂ Y, focal group here is an OH group. In the formula 4, R and R ^{1 have} the same meaning as in the formulas 1 to 3.

If the components additionally difunctional compounds, such as a dicarbonate or a diol given, this causes an extension of the chains, as illustrated for example in the general formula 5. The result is again on average a molecule of the type XY ₂ , focal group is a carbonate group.

In formula 5, R ^{2 is} an organic, preferably aliphatic radical, R and R ¹ are defined as described above.

It is also possible to use a plurality of condensation products (K) for the synthesis. In this case, on the one hand, several alcohols or more carbonates can be used. Furthermore, mixtures of different condensation products of different structure can be obtained by selecting the ratio of the alcohols used and the carbonates or phosgene. This is exemplified by the example of the reaction of a carbonate with a trihydric alcohol. If the starting materials are used in a ratio of 1: 1, as shown in (II), one molecule XY _{2 is obtained} . If the starting materials are used in the ratio 2: 1, as shown in (IV), one obtains a molecule X ₂ Y. At a ratio between 1: 1 and 2: 1, a mixture of molecules XY ₂ and X ₂ Y is obtained ,

The by way of example in the formulas 1-5 described simple condensation products (K) react according to the invention preferably intermolecular to form highly functional polycondensation products, im called following polycondensation products (P). The implementation to Condensation product (K) and the polycondensation product (P) is usually carried out at a temperature of 0 to 250 ° C, preferably at 60 to 160 ° C in substance or in solution. It can generally all solvents to be used opposite are inert to the respective starting materials. Preference is given to using organic Solvent, such as decane, dodecane, benzene, toluene, chlorobenzene, xylene, Dimethylformamide, dimethylacetamide or solvent naphtha.

In a preferred embodiment the condensation reaction is carried out in bulk. The at the reaction released monofunctional alcohol ROH or the Phenol, can be used to accelerate the reaction by distillation, if necessary at reduced pressure, removed from the reaction equilibrium become.

If Distillation is provided, it is regularly recommended such Carbonates, which in the reaction alcohols with ROH release a boiling point of less than 140 ° C.

To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze the esterification or transesterification reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, preferably of sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, zirconium - or bismuth-organic compounds, also called double metal cyanide (DMC) catalysts, such as in the DE 10138216 or in the DE 10147712 described.

Preferably potassium hydroxide, potassium carbonate, potassium bicarbonate, diazabicyclooctane (DABCO), Diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles, such as Imidazole, 1-methylimidazole or 1,2-dimethylimidazole, titanium tetrabutylate, Titanium tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, Zirkonacetylacetonat or mixtures thereof used.

The Addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight based on the Amount of alcohol or alcohol mixture used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, can be on the composition of the starting components and the residence time, the average Molekularge adjust the weight of the polymer (P).

The Condensation products (K) or the polycondensation products (P), the at elevated Temperature are usually at room temperature over a longer Period stable.

by virtue of the nature of the condensation products (K), it is possible that from the condensation reaction polycondensation (P) with different structures, the branches, but can result have no crosslinks. Furthermore, the polycondensation products (P) ideally either a car bonatgruppe as a focal group and more than two OH groups or an OH group as a focal group and more than two carbonate groups on. The number of reactive groups gives this is due to the nature of the condensation products used (K) and the degree of polycondensation.

For example may be a condensation product (K) according to the general formula 2 by triple intermolecular condensation to two different ones Polycondensation products (P), which in the general formulas 6 and 7, react.

In formulas 6 and 7, R and R ^{1 are} as defined above.

To the Termination of the intermolecular polycondensation reaction, there are various Options. For example the temperature can be lowered to an area where the Reaction comes to a standstill and the product (K) or the polycondensation product (P) is stable on storage.

Farther it is possible to deactivate the catalyst, with basic e.g. by Addition of Lewis acids or Proton acids.

In a further embodiment can, as soon as due to the intermolecular reaction of the condensation product (K) a polycondensation product (P) with the desired degree of polycondensation is present, the product (P) to stop the reaction, a product with across from be added to the focal group of (P) reactive groups. So For example, in the case of a carbonate group as a focal group, one may Mono-, di- or Polyamine are added. For a hydroxyl group as a focal Group may, for example, a mono-, di- or polyisocyanate, the product (P), an epoxy group-containing compound or one having OH groups reactive acid derivative be added.

The Preparation of the highly functional Polycarbonates are usually in a pressure range of 0.1 mbar to 20 bar, preferably 1 mbar to 5 bar, in reactors or reactor cascades, the operated in batch mode, semi-continuous or continuous become.

By the aforementioned adjustment of the reaction conditions and optionally by choosing the appropriate solvent can the products of the invention be processed after production without further purification.

In a further preferred embodiment the product is stripped, that is, of low molecular weight, volatile Compounds released. This can be done after reaching the desired Degree of conversion of the catalyst is optionally deactivated and the low molecular weight volatile Ingredients, e.g. Monoalcohols, phenols, carbonates, hydrogen chloride or volatile oligomeric or cyclic compounds by distillation, if appropriate introducing a gas, preferably nitrogen, carbon dioxide or air, optionally at reduced pressure.

In a further preferred embodiment can the polycarbonates of the invention in addition to the already obtained by the reaction functional groups received additional functional groups. The functionalization can while of molecular weight building or subsequently, i. after completion the actual polycondensation take place.

Gives one before or during the molecular weight structure to components, in addition to hydroxyl or Carbonate groups further functional groups or functional elements own, so receives a polycarbonate polymer with random distribution of the Carbonate or hydroxyl groups different functionalities.

such Effects can be, for example, by adding compounds during the Achieve polycondensation, in addition to hydroxyl groups, carbonate groups or carbamoyl groups further functional groups or functional Elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, Derivatives of carboxylic acids, Derivatives of sulphonic acids, Derivatives of phosphonic acids, Silane groups, siloxane groups, aryl radicals or long-chain alkyl radicals wear. For modification by means of carbamate groups, for example Ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2'-aminoethoxy) ethanol or higher alkoxylation products of ammonia, 4-hydroxy-piperidine, 1-hydroxyethylpiperazine, diethanolamine, Dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, Tris (hydroxyethyl) aminomethane, ethylene diamine, propylene diamine, hexamethylene diamine or use isophorone diamine.

For the modification with mercapto groups For example, mercaptoethanol began. Tertiary amino groups can be, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine produce. ether can for example by condensation of di- or higher functional Polyetherols are generated. By reaction with long-chain Alkanediols can introduce long-chain alkyl radicals, the reaction with alkyl or aryl diisocyanates generates alkyl, aryl and urethane groups or urea group-containing polycarbonates.

By Addition of dicarboxylic acids, tricarboxylic acids, e.g. dimethyl terephthalate or tricarboxylic acid ester can be produced ester groups.

A subsequent Functionalization can be obtained by using the resulting high-functionality, high-functionality or hyperbranched polycarbonate in an additional process step (Step c)) with a suitable functionalizing reagent, which with the OH and / or carbonate groups or carbamoyl groups of Polycarbonates can react.

hydroxyl containing high-functionality, high or hyperbranched polycarbonates can to Example by adding acid group or molecules containing isocyanate groups. For example can be acid groups containing polycarbonates by reaction with anhydride-containing Obtained connections.

Farther can Hydroxyl-containing high-functionality polycarbonates also by reaction with Alkylenaxiden, for example ethylene oxide, propylene oxide or butylene oxide, into highly functional polycarbonate polyether polyols.

One greater Advantage of the method lies in its economy. Either the reaction to a condensation product (K) or polycondensation product (P) and the reaction of (K) or (P) to polycarbonates with Other functional groups or elements may be present in a reaction device done, which is technically and economically advantageous.

As component B2) of the mixture according to the invention, the molding compositions according to the invention contain at least one hyperbranched polyester of the type A _x B _y,
in which
x is at least 1.1, preferably at least 1.3, in particular at least 2
y is at least 2.1, preferably at least 2.5, in particular at least 3
is.

Of course, as Units A and B are also mixtures used.

A polyester of the type A _x B _y is understood to mean a condensate which is composed of an x-functional molecule A and a y-functional molecule B. For example, mention may be made of a polyester of adipic acid as molecule A (x = 2) and glycerol as molecule B (y = 3).

Under hyperbranched polyesters B2) are used in the context of this invention uncrosslinked macromolecules with hydroxyl and carboxyl groups which are both structurally as well as molecularly disparate. You can start on the one hand from a central molecule analogous to dendrimers, but constructed with uneven chain length of the branches be. You can on the other hand also linear, with functional side groups, be constructed or, as a combination of the two extremes, linear and branched parts of the molecule exhibit. For the definition of dendrimeric and hyperbranched polymers see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

Under "hyperbranched" is related understood with the present invention that the degree of branching (Degree of Branching, DB), that is, the mean number of dendritic Links plus average number of end groups per molecule, 10 to 99.9%, preferred 20 to 99%, more preferably 20-95%.

Under "dendrimer" is related understood with the present invention that the degree of branching 99.9 to 100% is. To define the "Degree of Branching "see H. Frey et al., Acta Polym. 1997, 48, 30.

The component B2) preferably has an M _n of 300 to 30,000, in particular from 400 to 25,000 and very particularly from 500 to 20,000 g / mol, determined by means of GPC, standard PMMA, mobile phase dimethylacetamide.

Preferably B2) has an OH number of 0 to 600, preferably 1 to 500, in particular from 20 to 500 mg KOH / g of polyester according to DIN 53240 and preferred a COOH number of 0 to 600, preferably from 1 to 500 and especially from 2 to 500 mg KOH / g polyester.

The T _g is preferably from -50 ° C to 140 ° C and in particular from -50 to 100 ° C (by DSC, according to DIN 53765).

Especially such components B2) are preferred in which at least one OH or COOH number greater than 0, preferably greater than 0.1 and in particular greater than 0.5 is.

• (a) eine oder mehrere Dicarbonsäuren oder eines oder mehrere Derivate derselben mit einem oder mehreren mindestens trifunktionellen Alkoholen oder
• (b) eine oder mehrere Tricarbonsäuren oder höhere Polycarbonsäuren oder eines oder mehrere Derivate derselben mit einem oder mehreren Diolen

in Gegenwart eines Lösemittels und optional in Gegenwart eines anorganischen, metallorganischen oder niedermolekularen organischen Katalysators oder eines Enzyms umsetzt. Die Umsetzung im Lösungsmittel ist die bevorzugte Herstellmethode.In particular, by the method described below, the component B2) of the invention is available, uz by

• (A) one or more dicarboxylic acids or one or more derivatives thereof with one or more at least trifunctional alcohols or
• (b) one or more tricarboxylic acids or higher polycarboxylic acids or one or more derivatives thereof with one or more diols

in the presence of a solvent and optionally in the presence of an inorganic, organometallic or low molecular weight organic catalyst or an enzyme. The reaction in the solvent is the preferred method of preparation.

highly functional hyperbranched polyester B2) in the context of the present invention are molecularly and structurally inconsistent. They differ through their molecular heterogeneity of dendrimers and are therefore to produce with considerably less effort.

The dicarboxylic acids which can be reacted according to variant (a) include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a, w-dicarboxylic acid, dodecane-a, w-dicarboxylic acid, cis- and trans- Cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, and cis- and trans-cyclopentane-1,3-dicarboxylic acid,
wherein the above-mentioned dicarboxylic acids may be substituted with one or more radicals selected from
C ₁ -C ₁₀ -alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n decyl,
C ₃ -C ₁₂ cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;
Alkylene groups such as methylene or ethylidene or
C ₆ -C ₁₄ aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

When exemplary representatives for substituted dicarboxylic acids may be mentioned: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.

Farther belong to the according to variant (a) convertible dicarboxylic acids ethylenically unsaturated acids such as for example, maleic acid and fumaric acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic or terephthalic acid.

Farther Mixtures of two or more of the aforementioned representatives can be deploy.

The dicarboxylic acids can be used either as such or in the form of derivatives.

• – die betreffenden Anhydride in monomerer oder auch polymerer Form,
• – Mono- oder Dialkylester, bevorzugt Mono- oder Dimethylester oder die entsprechenden Mono- oder Diethylester, aber auch die von höheren Alkoholen wie beispielsweise n-Propanol, iso-Propanol, n-Butanol, Isobutanol, tert.-Butanol, n-Pentanol, n-Hexanol abgeleiteten Mono- und Dialkylester,
• – ferner Mono- und Divinylester sowie
• – gemischte Ester, bevorzugt Methylethylester.

Derivatives are preferably understood

• The relevant anhydrides in monomeric or polymeric form,
• Mono- or dialkyl esters, preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols, for example n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol-derived mono- and dialkyl esters,
• - Further mono- and divinyl esters as well
• Mixed esters, preferably methyl ethyl esters.

in the Within the scope of the preferred preparation, it is also possible to use a mixture of one Dicarboxylic acid and to use one or more of their derivatives. Likewise it is possible a mixture of several different derivatives of one or more dicarboxylic acids use.

Especially you prefer to use succinic acid, glutaric, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters. Very particularly preferred if adipic acid is used one.

When At least trifunctional alcohols can be implemented, for example: Glycerine, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, trimethylolbutane, trimethylolpropane or di-trimethylolpropane, Trimethylolethane, pentaerythritol or dipentaerythritol; sugar alcohols such as mesoerythritol, threitol, sorbitol, mannitol or mixtures the above at least trifunctional alcohols. Prefers Glycerol, trimethylolpropane, trimethylolethane and Pentaerythritol.

To Variant (b) are convertible tricarboxylic acids or polycarboxylic acids for example, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and Mellitic.

Tricarboxylic acids or polycarboxylic can be in the reaction of the invention either as such or in the form of derivatives.

• – die betreffenden Anhydride in monomerer oder auch polymerer Form,
• – Mono-, Di- oder Trialkylester, bevorzugt Mono-, Di- oder Trimethylester oder die entsprechenden Mono-, Di- oder Triethylester, aber auch die von höheren Alkoholen wie beispielsweise n-Propanol, iso-Propanol, n-Butanol, Isobutanol, tert.-Butanol, n-Pentanol, n-Hexanol abgeleiteten Mono- Di- und Triester, ferner Mono-, Di- oder Trivinylester
• – sowie gemischte Methylethylester.

Derivatives are preferably understood

• The relevant anhydrides in monomeric or polymeric form,
• Mono-, di- or trialkyl esters, preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or triethyl esters, but also those of higher alcohols, for example n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol-derived mono- di- and triesters, and also mono-, di- or trivinyl esters
• - and mixed methyl ethyl esters.

in the Within the scope of the present invention, it is also possible to use a mixture of a Tri- or polycarboxylic acid and to use one or more of their derivatives. Likewise It is possible in the context of the present invention, a mixture of several to use various derivatives of one or more tri- or polycarboxylic acids, to obtain component B2).

Examples of diols used for variant (b) of the present invention are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1 , 4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3 -diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol , Hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2- Decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, cyclopentanediols, cyclohexanediols, inositol and derivatives, (2) -methyl-2,4-pentanediol, 2,4- Dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, diethylene glycol, triethylene glycol, Dipropylene glycol, tripropylene glycol, polyethylene glycols HO (CH ₂ CH ₂ O) _n -H or polypropylene glycols HO (CH [CH ₃ ] CH ₂ O) _n -H or mixtures of two or more of the above compounds in which n is an integer and n = 4-25. One or both hydroxyl groups in the abovementioned diols can also be substituted by SH groups. Preference is given to ethylene glycol, propane-1,2-diol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

The molar ratio of molecules A to molecules B in the A _x B _y polyester in variants (a) and (b) is 4: 1 to 1: 4, in particular 2: 1 to 1: 2.

The according to variant (a) of the method reacted at least trifunctional Alcohols can Hydroxyl groups each have the same reactivity. Preferred are here also at least trifunctional alcohols, their OH groups first are reactive, but which react by reacting with at least one acid group a drop in reactivity, due to steric or electronic influences, with the remaining OH groups induce. This is for example when using trimethylolpropane or pentaerythritol the case.

The according to variant (a) reacted at least trifunctional alcohols can but also hydroxyl groups with at least two chemically different reactivities exhibit.

The different reactivity of the functional groups may be either chemical (e.g., primary / secondary / tertiary OH group) or based on steric causes.

For example For example, the triol may be a triol having primary and secondary hydroxyl groups preferred example is glycerol.

at the implementation the reaction of the invention according to variant (a), preference is given to working in the absence of diols and monofunctional alcohols.

at the implementation the reaction of the invention variant (b) is preferably carried out in the absence of mono- or dicarboxylic acids.

The inventive method is in the presence of a solvent carried out. Suitable are, for example, hydrocarbons such as paraffins or Aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, as solvents in Absence of acidic catalysts very suitable: ethers such as dioxane or tetrahydrofuran and ketones such as Methyl ethyl ketone and methyl isobutyl ketone.

The amount of solvent added is according to the invention at least 0.1 wt .-%, based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and be especially preferably at least 10% by weight. It is also possible to use excesses of solvent, based on the mass of reacted starting materials to be reacted, for example 1.01 to 10 times. Solvent amounts of more than 100 times, based on the mass of reacted starting materials to be reacted, are not advantageous because significantly lower concentrations of the reactants, the reaction rate decreases significantly, resulting in uneconomical long reaction times.

To carry out the process preferred according to the invention, it is possible to work as an additive in the presence of a dehydrating agent which is added at the beginning of the reaction. Suitable examples are molecular sieves, in particular molecular sieve 4 Å, MgSO ₄ and Na ₂ SO ₄ . It is also possible during the reaction to add further de-watering agent or to replace de-watering agent with fresh de-watering agent. It is also possible to distill off water or alcohol formed during the reaction and to use, for example, a water separator.

you The process can be carried out in the absence of acidic catalysts. Preferably one works in the presence of an acid inorganic, organometallic or organic catalyst or mixtures of several acidic ones inorganic, organometallic or organic catalysts.

Examples of acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH = 6, in particular = 5) and acidic aluminum oxide. Furthermore, for example, aluminum compounds of the general formula Al (OR) ₃ and titanates of the general formula Ti (OR) ₄ can be used as acidic inorganic catalysts, wherein the radicals R may be the same or different and are independently selected from each other
C ₁ -C ₁₀ -alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n decyl,
C ₃ -C ₁₂ cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.

The radicals R in Al (OR) ₃ or Ti (OR) ₄ are preferably identical and selected from isopropyl or 2-ethylhexyl.

Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R ₂ SnO, where R is as defined above. A particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin, or di-n-butyltin dilaurate.

preferred Acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or Phosphonic. Particularly preferred are sulfonic acids such as para-toluenesulfonic acid. you can also use acidic ion exchangers as acidic organic catalysts use, for example, sulfonic acid-containing polystyrene resins, which are crosslinked with about 2 mol% divinylbenzene.

you may also be combinations of two or more of the foregoing Use catalysts. It is also possible to use such organic or organometallic or inorganic catalysts in the form discrete molecules be present in immobilized form.

Do you wish acidic inorganic, organometallic or organic catalysts to use, it is according to the invention 0.1 to 10 wt .-%, preferably 0.2 to 2 wt .-% catalyst.

The inventive method is under inert gas atmosphere carried out, this means for example, under carbon dioxide, nitrogen or inert gas, under in particular argon should be mentioned.

The inventive method is carried out at temperatures of 60 to 200 ° C. Preferably works at temperatures of 130 to 180, especially to 150 ° C or less. Particularly preferred are maximum temperatures up to 145 ° C, very particular preferably up to 135 ° C.

The pressure conditions of the method according to the invention are not critical per se. You can work at significantly reduced pressure, for example at 10 to 500 mbar. The inventive method can also be performed at pressures above 500 mbar. For reasons of simplicity, the reaction is preferably at atmospheric pressure; but it is also possible to carry out at slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar. The reaction is preferably at atmospheric pressure.

The Reaction time of the method according to the invention is usually 10 minutes to 25 hours, preferably 30 minutes to 10 hours and more preferably one to 8 hours.

To When the reaction is over, the highly functional hyperbranched can be obtained Easily isolate polyester, for example by filtering off the Catalyst and concentration, where the concentration usually at Performs reduced pressure. Other well-suited processing methods are failures Add water and then Washing and drying.

Farther Component B2) may be in the presence of enzymes or decomposition products produced by enzymes (according to DE-A 101 63163). It includes the implemented according to the invention dicarboxylic acids not to the acidic organic catalysts in the sense of the present Invention.

Prefers is the use of lipases or esterases. Well suited lipases and esterases are Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geolrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor mihei, pig pancreas, pseudomonas spp., pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or esterase from Bacillus spp. and Bacillus thermoglucosidasius. Particularly preferred is Candida antarctica Lipase B. The listed Enzymes are commercially available, for example, at Novozymes Biotech Inc., Denmark.

Is preferable to use the enzyme in an immobilized form, for example on silica gel or Lewatit ^®. Processes for the immobilization of enzymes are known per se, for example from Kurt Faber, "Biotransformations in Organic Chemistry", 3rd edition 1997, Springer Verlag, Chapter 3.2 "Immobilization" page 345-356. Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.

The Amount of immobilized enzyme used is 0.1 to 20 wt .-%, in particular 10 to 15 wt .-%, based on the mass of the total used to be converted starting materials.

The inventive method gets over at temperatures above 60 ° C performed. Preferably you work at temperatures of 100 ° C or below. Preferred are Temperatures up to 80 ° C, most preferably from 62 to 75 ° C and even more preferably from 65 to 75 ° C.

The inventive method is in the presence of a solvent carried out. Suitable are, for example, hydrocarbons such as paraffins or Aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, they are very special suitable: ethers such as dioxane or tetrahydrofuran and Ketones such as methyl ethyl ketone and methyl isobutyl ketone.

The Amount of added solvent is at least 5 parts by weight, based on the mass of the used to be reacted starting materials, preferably at least 50 parts by weight and more preferably at least 100 parts by weight. Quantities of over 10 000 Parts by weight of solvent are not wanted because at significantly lower concentrations, the reaction rate clearly wears off, which leads to uneconomic long implementation times.

The inventive method will be pressed performed above 500 mbar. Preferably, the reaction is at atmospheric pressure or slightly elevated pressure, for example, up to 1200 mbar. You can also under significantly elevated pressure work, for example when pressing up to 10 bar. The reaction is preferably at atmospheric pressure.

The Reaction time of the method according to the invention is usually 4 hours to 6 days, preferably 5 hours to 5 days and especially preferably 8 hours to 4 days.

To When the reaction is over, the highly functional hyperbranched can be obtained Isolate polyester, for example by filtering off the enzyme and concentration, wherein the concentration usually at reduced Pressure. Other well-suited processing methods are failures Add water and then Washing and drying.

The according to the inventive method available highly functional, hyperbranched polyester, are characterized by particularly low levels of discoloration and Verharzungen. For the definition of hyperbranched polymers see also: P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, no. 1, 1-8. Under "highly functional hyperbranched " understood in connection with the present invention, however that the degree of branching, that is the mean Number of dendritic links plus the average number of end groups per molecule is 10-99.9%, preferably 20-99%, more preferably 30-90% is (see H. Frey et al., Acta Polym., 1997, 48, 30).

The polyesters according to the invention have a molecular weight M _{w of} from 500 to 50 000 g / mol, preferably from 1000 to 20 000, particularly preferably from 1000 to 19 000. The polydispersity is from 1.2 to 50, preferably from 1.4 to 40, particularly preferably 1, 5 to 30 and most preferably 1.5 to 10. They are usually readily soluble, that is, clear solutions of up to 50 wt .-%, in some cases even up to 80 wt .-%, of the polyester according to the invention in tetrahydrofuran (THF), n-butyl acetate, ethanol and many other solvents without the naked eye gel particles are detectable.

The highly functional hyperbranched polyesters are carboxy-terminated, carboxy- and hydroxyl-terminated and preferably hydroxyl-terminated.

The conditions components B1) to B2) are preferably from 1:20 to 20: 1, in particular from 1:15 to 15: 1 and more particularly of 1: 5 to 5: 1.

at the hyperbranched polycarbonates B1) / polyesters used B2) are particles with a size of 20-500 nm. These nanoparticles are present in the polymer blend finely divided, the size of the particles in the compound is from 20 to 500 nm, preferably 50 to 300 nm.

Such compounds are commercially available as Ultradur ^® high speed available.

When Component C) can the molding compositions according to the invention 0 to 70, in particular up to 50 wt .-% of other additives and Contain processing aids which are different from B).

When Examples are fibrous or particulate fillers such as glass fibers or mineral fillers such as Wollastonite, elastomeric polymers (e.g., EP, EPDM rubbers, TPU's, core-shell polymers), UV stabilizers, Nucleating agents, flame retardants, plasticizers, antioxidants and heat stabilizers called.

In a preferred embodiment of the process according to the invention, an inorganic secondary group metal salt is additionally used as additive (better contrast in writing) in amounts of from 0.01 to 10% by weight, preferably from 0.005 to 5% by weight; preferably from 0.01 to 2 wt .-% and in particular from 0.02 to 1 wt .-%. A subgroup metal is generally understood to mean elements which have d electrons in their outer electron shell (d ¹ -d ¹⁰ ).

Of the inorganic minor group metal salts, those which have proved to be particularly suitable in which the subgroup metal has an electron configuration d ⁶ to d ¹⁰ , preferably d ⁹ , ie Cu, Ag, Au, in particular Cu and Ag. Further preferred inorganic subgroup metal salts are the halides, pseudohalides and sulfates. Pseudohalides include linear anions such as cyanide, fulminate, cyanate, thiocyanate and azide and non-linear anions such as dicyanamide, dicyanophosphide, tricyanomethane and nitrosodicyanomethane. Particularly preferred are the chlorides, bromides, thiocyanates and sulfates, as well as ZnO and ZnS.

Next optionally transition metal salts also come other additives, usually for labeling of moldings used with lasers, for the application; required is the However, adding additional additives is not.

As component C2), the inventive compositions A) 0.01 to 10, preferably example, 0.05 to 10 and in particular 0.1 to 5 wt .-% carbon black or graphite. Suitable are carbon blacks having a pore volume (DBP dibutyl phthalate adsorption) according to DIN 53 601 of at least 30 ml / g 100 g, preferably at least 50 ml / 100 g.

The DBP adsorption rate is generally according to DIN 53 601 or ASTM-D 2414 determines and provides a measure of the structure of the respective soot By structure is meant the linking of carbon black primary particles to aggregates. To determine this parameter, 10 g of soot, which is in a kneader with measurable power transmission (Plastographen) is submitted, as long dibutyl phthalate added dropwise, until the maximum torque (grid point of soot) is exceeded.

preferred Types of Carbon Black have an iodine value according to ASTM D-1510 in mg / g of at least 50, in particular of at least 70.

Component C) preferably has a BET specific surface area (according to DIN 60 132 or ASTM D 3037) of at least 20, preferably at least 30 m ² / g.

The average primary particle size is usually 5 to 50, preferably 12 to 35 nm.

Such types of carbon black are, for example under the trade name Printex ^® XE2 (Degussa AG) or Ketjen Black EC DJ 600 (Akzo) available and Furnace carbon blacks such as Printex ^® 90, 75, 80, 85, 95, and Raven ^® carbon blacks of Columbian Chem. Comp. ,

When Another additive to improve the writability of the according to the inventive method to be inscribed moldings an inorganic black pigment based on iron oxide as essential Ingredient in amounts of 0.01 to 4, preferably 0.02 to 3 and in particular 0.02 to 1 wt .-%. Preferred iron oxide pigments have a spinel or inverse spinel structure.

The unit cell of the spinel lattice contains 32 oxygen atoms, which form an approximately cubic dense sphere packing. In the normal spinel structure, 8 Me ²⁺ ions occupy the center of octahedra (octahedra) formed from 4 O ² ions. In the so-called inverse spinel structure, the distribution of cations is different. Half of the Me ³⁺ ions occupy the tetrahedral sites, the other half are distributed together with the Me ²⁺ ions on the octahedral sites. Also transitions between the two structures with unordered distribution of the cations are possible. The normal and inverse structures can be characterized by the formulas Me ²⁺ [Me ₂ ³⁺ ] O ₄ , and Me ³⁺ [Me ²⁺ Me ³⁺ ] O ₄ . Among the ferrites there are representatives of both structures: The zinc ferrite has the normal structure Zn [Fe ₂ ] O ₄ , whereas in magnesium ferrite the cations are predominantly distributed as in the inverse spinel: Fe ³⁺ [Mg ²⁺ Fe ³⁺ ] O ₄ ,

As examples of divalent metals, mention may be made of Mg, Fe (II), Zn, Mn, Co, Ni, Cu, Cd, trivalent metals being Al, Fe (III), V, Cr or titanium. Preferred iron oxide pigments are magnetite (inverse spinel Fe ³⁺ [Fe ²⁺ Fe ³⁺ ] O ₄ ), Cr ³⁺ [Cu ^II , Fe ^II ] O ₄ and mixed phase pigments of Fe ₂ O ₃ / Mn ₂ O ₃ .

at These mixed phase pigments become guest ions in certain host lattices built-in, which depending on the choice of Gastionen color effects targeted can be adjusted. The basic structure of the host lattice is through the installation is not changed. Only the dimension of the unit cell - the lattice constants - become changed by the incorporation of foreign ions. For the production more stable Pigments, it makes sense to start from structures that are particularly size stability exhibit. Which also includes in particular the spinel structure. By the partial or complete substitution of the metal ions in the spinel by coloring guest ions such as chromium and copper can lightfast black pigments are obtained.

at The preparation of the mixed phase pigments is based on the oxidic or hydroxide compounds of the components, which may be intermediates precipitation with alkalis from the appropriate metal salt solution. The intimate mixing of raw materials takes place in the wet phase. The actual education the mixed phase is a solid-state reaction and requires this high temperatures. This results in the coloring of all plastics more as sufficient temperature resistance of these pigments. The glow can be continuous or discontinuous.

Afterwards, the Products are washed and wet ground intensively, as at The high-temperature solid-state reaction to an increased extent to the formation of aggregates and agglomerates. Drying in usual for pigments Dryers and final grinding to destroy the drying agglomerates shut down on.

Other Processes for the preparation of iron oxide pigments are those skilled in the art known; e.g. from Römpp Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, New York 1994, p. 1096.

The common Production method is the so-called aniline process. In the reduction from nitrobenzene to aniline in acidic solution is used as a reducing agent Cast iron in the form of fine chips used. This is oxidized to iron oxide, which is normally obtained with black-gray color. Through special process management and suitable additives such as iron (II) salts and aluminum salts, strong black oxide black sludges are obtained. These become black iron oxide after washing and filtration worked up.

In order to optimally develop the optical properties of the pigment, it is preferable to adhere to a narrowly limited primary particle size range, for example between 0.1 and 1 mm for Fe ₃ O ₄ . The particle size of suitable black pigments is adjusted by so-called micronization, ie a special grinding with superheated steam. In this case, a relatively homogeneous particle size distribution is achieved.

The Primary particle size and their Distribution becomes common through sieve analysis, sedimentation analysis and known counting methods (e.g., by electron microscopy).

As a preferred commercially available black pigments include Pigment Black 11, Black 100 Real and Bayferrox ^® black grades (Bayer AG).

The thermoplastic according to the invention Molding compounds can be prepared by methods known per se, in which the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and subsequently extruded. After extrusion, the extrudate can be cooled and be crushed. It can Also, individual components are premixed and then the remaining Starting materials are added individually and / or also mixed become. The mixing temperatures are usually 230 to 290 ° C.

To Another preferred procedure, the components B) and optionally C) mixed with a polyester prepolymer, formulated and granulated. The resulting granules are in solid phase subsequently under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity condensed.

The thermoplastic according to the invention Molding compounds are characterized by good writability and flowability with good mechanics at the same time.

Especially is the processing of the individual components (without clumping or caking) easily and in short cycle times possible, so that in particular thin-walled components as an application in question.

These are suitable for the production of labeled moldings any Kind, especially for Applications as keyboards etc., especially applications where a caption knows black background.

Component A / 1

• Polybutylene terephthalate having a viscosity number VN of 130 ml / g and a carboxyl end group of 34 meq / kg (Ultradur B 4520 ^® from BASF AG) (VN measured in 0.5 wt .-% solution of phenol / o-dichlorobenzene), 1: 1 mixture at 25 ° C, containing 0.65 wt .-% pentaerythritol tetrastearate (component C31 based on 100 wt .-% A)

Component A / 2

• PBT as under A / 1 with 24 wt .-% glass fibers (C32) and 27.5 Wt .-% of a mixture of Ca-phosphinate (C33) and melamine cyanurate (C34) in proportion 63: 37.

Component A / 3

• PBT as under A / 1 with 30 wt .-% glass fibers (C32).

Manufacturing specification for polycarbonates B1

General procedure:

In a three-necked flask equipped with stirrer, reflux condenser and internal thermometer according to the table 1 the polyfunctional alcohol equimolar mixed with diethyl carbonate and 250 ppm of catalyst (based on the amount of alcohol) was added. The mixture was then submerged stir at 100 ° C, at heated to 140 ° C with the experiment marked with *, and 2 h at this temperature touched. As the reaction progressed, the temperature was reduced the reaction mixture due to the incipient boiling of the liberated monoalcohols. Now the reflux cooler was against a descending cooler exchanged, ethanol distilled off and the temperature of the reaction mixture slowly up to 160 ° C elevated.

The distilled ethanol was collected in a chilled round bottom flask, balanced and the turnover so compared to the theoretically possible Full turnover determined as a percentage (see Table 1).

• TMP ⩠ Trimethylolpropan
• PO ⩠ Propylenoxid

The reaction products were then analyzed by gel permeation chromatography, eluent was dimethylacetamide, polymethyl methacrylate (PMMA) was used as standard.

• TMP ⩠ trimethylolpropane
• PO ⩠ propylene oxide

Component C11

• ZnO

Component C12

• Cerium (III) chloride

Component C13

• silver chloride

Component C21

• ^Raven® 880 from Columbian Chem. Comp.
• DBP absorption: 100.1 ^cm3 / 100 g ASTM D2414
• Iodine value: 81.4 ^cm3 / 100 g (ASTM D 1510)
• d ₅₀ = 30 nm

Component C22

• ^Raven® 2000 from Columbian Chem. Comp.
• DBP absorption: 65 ^cm3 / 100 g
• d ₅₀ = 18 nm

Component C23

• Black Pearls 700 from Cabot
• DBP absorption: 115.8 ^cm3 / 100 g
• Iodine number: 252.4 mg / g
• _d50: 18 nm

Processing conditions and measurement methods

Injection molding: Temp. Melting vessel: 260 ° C Temp. Form: 100 ° C Print: 13 bar (for A / 3 16 bar)

granules at 70 ° C overnight Pre-dry.

Assessment of laser inscribability (Contrast value)

• Laser: Nd: YAG, wavelength = 1064 nm
• With mode aperture 1.0 mm, writing speed = 500 mm / sec.
• With mode aperture 1.3 mm, writing speed = 400 mm / sec.

Comparative Experiments Table 1

For A / 3 had to the injection molding machine can be set to 16 bar, otherwise the Injection nozzle clogged.

Table 2

Table 3

Claims (10)

Process for labeling moldings based on thermoplastic polyesters A) or mixtures of these polyesters with up to 70 wt .-%, based on the total weight of the components, other additives C), by means of high-energy radiation, characterized in that as an additive B ) to improve the writability at least one hyperbranched or hyperbranched polycarbonate B1) having an OH number of 1 to 600 mg KOH / g polycarbonate (according to DIN 53240, Part 2), or at least one hyperbranched or hyperbranched polyester B2) of type A. _x B _y with x at least 1.1 and y at least 2.1 or mixtures thereof. A method according to claim 1, characterized in that the component B1) has a number average molecular weight M _w of 100 to 15,000 g / mol. Process according to claims 1 or 2, characterized the component B1) has a glass transition temperature Tg of -80 ° C to 140 ° C. Process according to claims 1 to 3, characterized component B1) has a viscosity (mPas) at 23 ° C. (according to DIN 53019) from 50 to 200,000. Process according to claims 1 to 4, characterized that one in addition uses an inorganic subgroup metal salt. Process according to claims 1 to 5, characterized that in addition Soot or Graphite or mixtures thereof are used. Process according to claims 1 to 6, characterized that as a source of high-energy radiation, a Nd: YAG laser with a wavelength of 1064 nm, which works according to the deflection method. Process according to claims 1 to 7, characterized that as a source of high-energy radiation, a Nd: YAG laser with Frequency doubling is used with a wavelength of 532 nm. Thermoplastic molding compositions containing A) 10 up to 99.9% by weight of at least one thermoplastic polyester, B) 0.01 to 50 wt .-% B / 1 or B / 2 or mixtures thereof according to claim 1 C1) from 0.01 to 10% by weight of inorganic minor group metal salt, C2) 0 to 10 wt .-% of carbon black or Graphite or mixtures thereof C3) 0 to 50% by weight of others additives where the sum of the weight percentages A) to C) always 100% results. Labeled moldings, semi-finished or finished parts, available according to the process conditions according to claims 1 to 8 or from the thermoplastic Molding compositions according to claim 9th