DE10303171A1 - Biodegradable polyester with improved processing behavior - Google Patents

Abstract

The present invention relates to thermoplastic molding compositions containing DOLLAR A i) 90 to 99.99% by weight, based on the total weight of components i) to ii), of at least one polyester which is biodegradable in accordance with DIN V 54900, and DOLLAR A ii) 0.01 to 10 wt .-%, based on the total weight of components i) to ii), at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and DOLLAR A iii) in addition 0 to 80 wt. -%, based on the weight of component i), conventional additives, DOLLAR A and processes for the production of thermoplastic molding compositions, the use of thermoplastic molding compositions for the production of blends, moldings, films or fibers, blends, moldings, films or fibers containing thermoplastic Molding compositions and the use of polyesters based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds as nucleation agent for polyesters that are biodegradable according to DIN V 54900.

Description

• i) 90 bis 99,99 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i) bis ü), mindestens eines Polyesters, der gemäß DIN V 54900 biologisch abbaubar ist, und
• ii) 0,01 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i) bis ü) mindestens eines Polyesters auf Basis von aromatischen Dicarbonsäuren und einer aliphatischen oder aromatischen Dihydroxyverbindung und iii) darüber hinaus 0 bis 80 Gew.-%, bezogen auf das Gewicht von Komponente i), üblicher Zusatzstoffe.

The present invention relates to thermoplastic molding compositions containing

• i) 90 to 99.99% by weight, based on the total weight of components i) to ü), of at least one polyester which is biodegradable in accordance with DIN V 54900, and
• ii) 0.01 to 10% by weight, based on the total weight of components i) to ü) of at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and iii) moreover 0 to 80% by weight, based on the weight of component i), conventional additives.

Furthermore, the present concerns Invention Process for the production of thermoplastic molding compositions, the Use of thermoplastic molding compositions for the production of Blends, molded parts, films or fibers, blends, molded parts, films or fibers containing thermoplastic molding compositions and the use of Polyesters based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds as nucleating agents for polyesters, which according to DIN V 54900 are biodegradable.

Biodegradable polyesters are known. For example, describes EP-A 792 309 semi-aromatic polyesters which, in addition to good mechanical properties, have good biodegradability.

Such biodegradable polyesters tend to cool down often from the melt to a delayed or slow crystallization, which can lead to disadvantages in the processing of the melts. For example, tend to delay or slowly crystallizing polyester melts during processing, for example, foils, for gluing with the tools, whereby just a limited one Throughput possible is.

To be a less delayed or to achieve accelerated crystallization of polymer melts, is the use of nucleating agents, for example talc, known. The nucleating agents known to the person skilled in the art show in the biodegradable polyesters do not have a sufficient effect.

The present invention lies thus based on the task of thermoplastic molding compositions to provide biodegradable polyester compared to known ones Molding compounds a less delayed or have accelerated crystallization on cooling from the melt, which have a reduced tendency to stick compared to the Show tools and the increased throughput during processing enable.

This task is from the beginning defined thermoplastic molding compositions, which are described in more detail below are fulfilled.

Basically come for manufacturing the thermoplastic according to the invention Molding compounds as component i) are all polyesters that are organic are degradable. The statement "biological degradable polyester " include all polyesters that meet the definition given in DIN V 54900 of biodegradability, in particular compostable polyester.

In general, biodegradability means that the polyesters disintegrate in a reasonable and detectable period of time. The breakdown can take place hydrolytically and / or oxidatively and can be mainly caused by the action of microorganisms such as bacteria, yeasts, fungi and algae. Biodegradability can be determined, for example, by mixing polyester with compost and storing it for a certain time. According to ASTM D 5338, ASTM D 6400, EN 13432 and DIN V 54900, CO ₂ -free air is allowed to flow, for example, through matured compost during composting and this is subjected to a defined temperature program. Here, the biodegradability is determined by the ratio of the net CO ₂ release of the sample (after deducting the CO ₂ release by the compost without sample) to the maximum CO ₂ release of the sample (calculated from the carbon content of the sample) as the biodegradability Are defined. Biodegradable polyesters usually show clear signs of degradation such as fungal growth, cracking and pitting after just a few days of composting.

Examples of biodegradable polyesters are cellulose derivatives such as cellulose esters, e.g. cellulose acetate, Cellulose acetate butyrate, starch esters, and polyesters, especially aliphatic homo- and copolyesters and partially aromatic copolyesters. Of course, are also suitable Mixtures or blends of the aforementioned biodegradable polyesters.

The named biodegradable Poiyester i) can as biodegradable blend or blend components Natural polymers or synthetic origin. Natural polymers Are e.g. Shellac, starch or cellulose. You can use physical and / or chemical methods can be modified. To the preferred polymers natural Origin counts Strength, thermoplastically processable starch or starch compounds like starch ether. In general, the weight ratio of biodegradable Polyesters i) to further biodegradable blend or mixture components, e.g. Strength, freely chosen in wide areas , for example in the range from 1.2: 1 to 0.8: 1.2.

Polymeric reaction products of lactic acid can be used as biodegradable polyesters i) position of the thermoplastic molding compositions used. These are known per se or can be produced by processes known per se. In addition to polylactide, copolymers or block copolymers based on lactic acid and other monomers can also be used. Linear polylactides are mostly used. However, branched lactic acid polymers can also be used. For example, multifunctional acids or alcohols can serve as branching agents. Examples include polylactides which essentially consist of lactic acid or its C ₁ - to C ₄ -alkyl esters or mixtures thereof and at least one aliphatic C ₄ - to C ₁₀ -dicarboxylic acid and at least one C ₃ - to C ₁₀ -alkanol with three to five hydroxy groups are available.

Examples of biodegradable polyester i), from which the thermoplastic molding compositions according to the invention available are, are about aliphatic polyester. These include homopolymers more aliphatic hydroxy or lactones but also copolymers or block copolymers of different types hydroxy or lactones or mixtures thereof. This aliphatic polyester can also contain diols and / or isocyanates as building blocks. Furthermore can the aliphatic polyesters also contain building blocks that differ from trifunctional or multifunctional compounds such as epoxides, acids or triols derived. The latter building blocks can individually or it can several of them or together with the diols and / or isocyanates be contained in the aliphatic polyesters.

Methods for producing aliphatic polyesters are known to the person skilled in the art. The aliphatic polyesters generally have molecular weights M _n in the range from 1,000 to 100,000 g / mol.

Among the most preferred aliphatic Polyester matters Polycaprolactone.

Poly-3-hydroxybutanoic acid esters and copolymers of 3-hydroxybutanoic acid or their mixtures with 4-hydroxybutanoic acid and 3-hydroxyvaleric acid, in particular up to 30, preferably up to 20% by weight of the latter acid, are particularly preferred aliphatic polyesters , Suitable polymers of this type also include those with an R-stereospecific configuration, as are known from WO 96/09402. Polyhydroxybutanoic acid esters or their copolymers can be produced microbially:
Processes for the production from different bacteria and fungi are for example the message Chem Tech. Lab. 39, 1112-1124 (1991), a method for producing stereospecific polymers is known from WO 96/09402.

Furthermore, block copolymers can also be made from the hydroxycarboxylic acids mentioned or lactones, their mixtures, oligomers or polymers become.

Other aliphatic polyesters are those consisting of aliphatic or cycloaliphatic dicarboxylic acids or their mixtures and aliphatic or cycloaliphatic diols or their mixtures are constructed. According to the invention, both statistical as well as block copolymers can be used.

The aliphatic suitable according to the invention dicarboxylic acids generally have 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms. You can be both linear and branched. The under the present Cycloaliphatic dicarboxylic acids which can be used according to the invention usually those with 7 to 10 carbon atoms and in particular those with 8 carbon atoms. In principle, however, dicarboxylic acids can also be used a larger number on carbon atoms, for example with up to 30 carbon atoms, be used.

Examples include: malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, acelic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1 , 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornanedicarboxylic, including adipic acid is preferred.

The ester-forming derivatives of the above-mentioned aliphatic or cycloaliphatic dicarboxylic acids, which can also be used, are in particular the di-C ₁ -C ₆ -alkyl esters, such as dimethyl, diethyl, di-n-propyl, di-isopropyl, di-n -butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters. Anhydrides of the dicarboxylic acids can also be used.

The dicarboxylic acids or their ester-forming derivatives, individually or as a mixture of two or more of them are used.

Examples of eligible aliphatic polyesters are aliphatic copolyesters such as those in the WO 94/14870 are described, in particular aliphatic copolyesters from succinic acid, its diesters or their mixtures with other aliphatic acids or

Diesters such as glutaric acid and Butanediol or mixtures of this diol with ethylene glycol, propanediol or hexanediol or mixtures thereof.

Aliphatic polyesters of this type generally have molecular weights M _n in the range from 1000 to 100000 g / mol.

Likewise, the aliphatic polyester random or block copolyesters containing other monomers. The proportion of the other monomers is usually up to 10% by weight. Preferred comonomers are hydroxycarboxylic acids or lactones or their Mixtures.

Mixtures of two can of course also be used or more comonomers and / or other building blocks, such as epoxides or polyfunctional aliphatic or aromatic acids or polyfunctional alcohols for the production of aliphatic polyesters be used.

Furthermore, the thermoplastic according to the invention Molding compositions based on partially aromatic polyesters as component i). According to the invention, this also includes polyester derivatives are understood as polyether esters, polyester amides or polyether ester amides. To the suitable biodegradable partially aromatic polyesters belong linear not chain extended Polyester (WO 92/09654). Chain-extended and / or are preferred branched partially aromatic polyester. The latter are from the above Writings, WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which express reference is made. Mixtures of different partially aromatic polyesters also come considered as blends of partially aromatic polyesters with starch or modified starch, cellulose esters or polylactide.

• A) eine Säurekomponente aus a1) 30 bis 95 mol-% mindestens einer aliphatischen oder mindestens einer cycloaliphatischen Dicarbonsäure oder deren esterbildende Derivate oder Mischungen davon a2) 5 bis 70 mol-% mindestens einer aromatischen Dicarbonsäure oder deren esterbildendem Derivat oder Mischungen davon und a3) 0 bis 5 mol-% einer sulfonatgruppenhaltigen Verbindung,
• B) eine Diolkomponente ausgewählt aus mindestens einem C₂-bis C₁₂-Alkandiol und mindestens einem C₅- bis C₁₀-Cycloalkandiol oder Mischungen davon und gewünschtenfalls darüber hinaus eine oder mehrere Komponenten ausgewählt aus
• C) einer Komponente ausgewählt aus c1) mindestens einer Etherfunktionen enthaltenden Dihydroxyverbindung der Formel I HO-[(CH₂)_n-O]_m-H (I)in der n für 2, 3 oder 4 und m für eine ganze Zahl von 2 bis 250 stehen c2) mindestens einer Hydroxycarbonsäure oder Formel IIa oder IIb
  
  in der p eine ganze Zahl von 1 bis 1500 und r eine ganze Zahl von 1 bis 4 bedeuten, und G für einen Rest steht, der ausgewählt ist aus der Gruppe bestehend aus Phenylen, -(CH₂)_q-, wobei q eine ganze Zahl von 1 bis 5 bedeutet, -C(R)H- und -C(R)HCH₂, wobei R für Methyl oder Ethyl steht c3) mindestens einem Amino-C₂- bis C₁₂-alkanol oder mindestens einem Amino-C₅-bis C₁₀-cycloalkanol oder Mischungen davon c4) mindestens einem Diamino-C₁-bis C₈-Alkan c5) mindestens einem 2,2'-Bisoxazolins der allgemeinen Formel III
  
  wobei R¹ eine Einfachbindung, eine (CH₂)_z Alkylengruppe, mit z = 2, 3 oder 4, oder eine Phenylengruppe bedeutet c6) mindestens einer Aminocarbonsäure ausgewählt aus der Gruppe, bestehend aus den natürlichen Aminosäuren, Polyamiden mit einem Molekulargewicht von höchstens 180008/mol, erhältlich durch Polykondensation einer Dicarbonsäure mit 4 bis 6 C-Atomen und einem Diamin mit 4 bis 10 C-Atomen, Verbindungen der Formeln IVa und IVb
  
  in der s eine ganze Zahl von 1 bis 1500 und t eine ganze Zahl von 1 bis 4 bedeuten, und T für einen Rest steht, der ausgewählt ist aus der Gruppe bestehend aus Phenylen, -(CH₂)_u-, wobei u eine ganze Zahl von 1 bis 12 bedeutet, -C(R²)H- und -C(R²)HCH₂, wobei R² für Methyl oder Ethyl steht, und Polyoxazolinen mit der wiederkehrenden Einheit V
  
  in der R³ für Wasserstoff, C₁-C₆-Alkyl, C₅-C₈-Cycloalkyl, unsubstituierten oder mit C₁-C₄-Alkylgruppen bis zu dreifach substituiertes Phenyl oder für Tetrahydrofuryl steht, oder Mischungen aus c1 bis c6 und
• D) einer Komponente ausgewählt aus d1) mindestens einer Verbindung mit mindestens drei zur Esterbildung befähigten Gruppen, d2) mindestens eines Isocyanates d3) mindestens eines Divinylethers oder Mischungen aus d1) bis d3) enthalten.

The particularly preferred partially aromatic polyesters include polyesters, which are essential components

• A) an acid component from a1) 30 to 95 mol% of at least one aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof a2) 5 to 70 mol% of at least one aromatic dicarboxylic acid or its ester-forming derivative or mixtures thereof and a3) 0 to 5 mol% of a compound containing sulfonate groups,
• B) a diol component selected from at least one C _{2 to} C ₁₂ alkanediol and at least one C ₅ to C ₁₀ cycloalkanediol or mixtures thereof and, if desired, one or more components selected from
• C) a component selected from c1) at least one dihydroxy compound of the formula I containing ether functions HO - [(CH ₂ ) _n -O] _m -H (I) where n is 2, 3 or 4 and m is an integer from 2 to 250 c2) at least one hydroxycarboxylic acid or formula IIa or IIb
  
  in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical which is selected from the group consisting of phenylene, - (CH ₂ ) _q -, where q is an integer Number from 1 to 5 denotes -C (R) H- and -C (R) HCH ₂ , where R is methyl or ethyl (c3) at least one amino-C ₂ -C ₁₂ -alkanol or at least one amino-C _{5 to} C ₁₀ cycloalkanol or mixtures thereof c4) at least one diamino C _{1 to} C ₈ alkane c5) at least one 2,2'-bisoxazoline of the general formula III
  
  where R ^{1 is} a single bond, a (CH ₂ ) _z alkylene group with z = 2, 3 or 4, or a phenylene group c6) at least one aminocarboxylic acid selected from the group consisting of the natural amino acids, polyamides with a molecular weight of at most 180008 / mol, obtainable by polycondensation of a dicarboxylic acid with 4 to 6 C atoms and a diamine with 4 to 10 C atoms, compounds of the formulas IVa and IVb
  
  in which s is an integer from 1 to 1500 and t is an integer from 1 to 4, and T is a radical which is selected from the group consisting of phenylene, - (CH ₂ ) _u -, where u is an integer Number from 1 to 12 means -C (R ² ) H- and -C (R ² ) HCH ₂ , where R ^{2 is} methyl or ethyl, and polyoxazolines with the repeating unit V
  
  in which R ^{3 represents} hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₈ cycloalkyl, unsubstituted or substituted by C ₁ -C ₄ alkyl groups up to triple substituted phenyl or tetrahydrofuryl, or mixtures of c1 to c6 and
• D) a component selected from d1) at least one compound with at least three groups capable of ester formation, d2) at least one isocyanate d3) at least one divinyl ether or mixtures of d1) to d3).

The acid component A of the partially aromatic Contains polyester preferably from 30 to 70, in particular from 40 to 60 mol% of a1 and from 30 to 70, in particular from 40 to 60 mol% a2.

As aliphatic or cycloaliphatic acids and the corresponding derivatives a1 come in above Consideration. Adipic acid or sebacic acid is particularly preferred respective ester-forming derivatives or mixtures thereof. Adipic acid is particularly preferred or their ester-forming: derivatives, such as their alkyl esters or their Mixtures used.

Aromatic dicarboxylic acids a2 are generally those with 8 to 12 carbon atoms and preferably those with 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid and ester-forming derivatives thereof. In particular, the di-C ₁ -C ₆ -alkyl esters, for example dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-iso-butyl, di-t -butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters. The anhydrides of dicarboxylic acids a2 are also suitable ester-forming derivatives.

In principle, however, aromatic dicarboxylic acids a2 with a larger number on carbon atoms, for example up to 20 carbon atoms, be used.

The aromatic dicarboxylic acids or their ester-forming derivatives a2 can be used individually or as a mixture out of two or more of them. Particularly preferred becomes terephthalic acid or their ester-forming derivatives such as dimethyl terephthalate.

As a compound containing sulfonate groups you usually place an alkali or alkaline earth metal salt of a sulfonate group-containing dicarboxylic acid or their ester-forming derivatives, preferably alkali metal salts of 5-sulfoisophthalic or their mixtures, particularly preferably the sodium salt.

According to one of the preferred embodiments contains the acid component A from 40 to 60 mol% a1, from 40 to 60 mol% a2 and from 0 to 2 mol% a3. According to a further preferred embodiment, the acid component contains A from 40 to 59.9 mol% a1, from 40 to 59.9 mol% a2 and from 0.1 up to 1 mol% a3, in particular from 40 to 59.8 mol% a1, from 40 to 59.8 mol% a2 and from 0.2 to 0.5 mol% a3.

In general, the diols B under branched or linear alkane diols with 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkane diols with 5 up to 10 carbon atoms selected.

Examples of suitable alkanediols are Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl- 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol. It can mixtures of different alkanediols can also be used.

Depending on whether an excess of acid or OH end groups desired is used, either component A or component B in excess become. According to a preferred embodiment, the molar ratio of components A to B used in the range from 0.4: 1 to 1.5: 1, are preferably in the range from 0.6: 1 to 1.1: 1.

In addition to components A and B, the Polyesters on which the molding compositions according to the invention are based, further Components included.

The dihydroxy compounds c1 used are preferably diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran (poly-THF), particularly preferably diethylene glycol, triethylene glycol and polyethylene glycol, with mixtures of these or compounds which differ Have variables n (see formula 1), for example polyethylene glycol which contains propylene units (n = 3), for example obtainable by polymerization according to known methods of first ethylene oxide and then with propylene oxide, particularly preferably a polymer based on polyethylene glycol, with different variables n, with units formed from ethylene oxide predominating. The molecular weight (M _n ) of the polyethylene glycol is generally chosen in the range from 250 to 8000, preferably from 600 to 3000 g / mol.

According to one of the preferred embodiments can for example from 15 to 98, preferably 60 to 99.5 mol% of the diols B and 0.2 to 85, preferably 0.5 to 30 mol% of the dihydroxy compounds c1, based on the molar amount of B and c1, for the preparation of the partially aromatic Polyester are used.

In a preferred embodiment, the hydroxycarboxylic acid c2) used is: glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, its cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D -, L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione), p-hydroxybenzoic acid as well as their oligomers and polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (for example, as EcoPLA ^® (from Cargill. ) available) as well as a mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter is available under the name Biopol ^® from Zeneca), particularly preferred for the production of partially aromatic polyester the low molecular weight and cyclic derivatives thereof.

The hydroxycarboxylic acids can for example in quantities of 0.01 to 50, preferably 0.1 to 40,% by weight to be used on the amount of A and B.

Amino-C ₂ -C ₁₂ -alkanol or amino-C ₅ -C ₁₀ -cycloalkanol (component c3), which should also include 4-aminomethylcyclohexane-methanol, are preferably amino-C ₂ -C ₆ -alkanols such as 2-aminoethanol , 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and amino-C ₅ -C ₆ -cycloalkanols such as aminocyclopentanol and aminocyclohexanol or mixtures thereof.

The diamino-C ₁ -C ₈ -alkane (component c4) is preferably a diamino-C ₄ -C ₆ -alkane such as 1,4-diminobutane, 1,5-diaminopentane and 1,6-diaminohexane (hexamethylene diamine, "HMD ").

According to a preferred embodiment can be from 0.5 to 99.5 mol%, preferably 0.5 to 50 mol%, c3 to the molar amount of B, and from 0 to 50, preferably from 0 to 35 mol%, c4, based on the molar amount of B, for the preparation of the partially aromatic Polyester are used.

The 2,2'-bisoxazolines c5 of the general formula III are generally obtainable by the process from Angew. Chem. Int. Edit., Vol. 11 (1972), pp. 287-288. Particularly preferred bisoxazolines are those in which R 'is a single bond, a (CH ₂ ) ₂ alkylene group with z = ₂ , 3 or 4, such as methylene, ethane-1,2-diyl, propane-1,3-diyl, propane 1,2-diyl, or a phenylene group. Particularly preferred bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1,2-bis (2-oxazolinyl) ethane, 1,3-bis (2-oxazolinyl) propane or 1 , 4-bis (2-oxazolinyl) butane, in particular 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazolinyl) benzene or 1,3-bis (2-oxazolinyl) benzene.

For the production of the partially aromatic Polyester can for example from 70 to 98 mol% B, up to 30 mol% c3 and 0.5 to 30 mol% c4 and 0.5 to 30 mol% c5, each based on the sum the molar amounts of components B, c3, c4 and c5 can be used. According to another preferred embodiment it is possible from 0.1 to 5, preferably 0.2 to 4 wt .-% c5, based on the total weight of A and B to use.

Natural aminocarboxylic acids can be used as component c6 become. These include Valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, Lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, Histidine, proline, serine, tryosine, asparagine or glutamine.

Preferred aminocarboxylic acids of the general formulas IVa and IVb are those in which s is an integer from 1 to 1000 and t is an integer from 1 to 4, preferably 1 or 2 and T is selected from the group consisting of phenylene and - (CH ₂ ) _u -, where u is 1, 5 or 12.

Furthermore, c6 can also be a polyoxazoline of the general formula V. C6 can also be a mixture of different aminocarboxylic and / or polyoxazolines.

According to a preferred embodiment can be c6 in amounts from 0.01 to 50, preferably from 0.1 to 40% by weight, based on the total amount of components A and B used become.

As additional components, the optional be used to produce the partially aromatic polyesters can, counting Compounds d1, the at least three groups capable of ester formation contain.

The compounds d1 preferably contain three to ten functional groups which are capable of forming ester bonds. Particularly preferred compounds d1 have three to six functional groups of this type in the molecule, in particular three to six hydroxyl groups and / or carboxyl groups. Examples include:
Tartaric acid, citric acid, malic acid;
Trimethylolpropane, trimethylolethane;
pentaerythritol;
polyether triols;
glycerol;
trimesic;
Trimellitic acid, anhydride;
Pyromellitic acid, dianhydride and
Hydroxyisophthalic.

The connections d1 are in the Usually in amounts of 0.01 to 15, preferably 0.05 to 10, particularly preferably 0.1 to 4 mol%, based on component A used.

As component d2, a or a mixture of different isocyanates used. It can be aromatic or aliphatic diisocyanates can be used. But it can also higher functional isocyanates are used.

Under an aromatic diisocyanate In the context of the present invention, d2 is primarily tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, Naphthylene-1,5-diisocyanate or xylylene diisocyanate understood.

These include 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate particularly preferred as component d2. In general, the latter diisocyanates used as a mixture.

The trinuclear isocyanate d2 comes also tri (4-isocyanophenyl) methane. The multi-core aromatic diisocyanates are used, for example, in the production of or dinuclear diisocyanates.

In minor quantities, e.g. to 5% by weight, based on the total weight of component d2 component d2 also urethione groups, for example for capping of the isocyanate groups.

Taking an aliphatic diisocyanate In the context of the present invention, d2 are primarily linear or branched alkylene diisocyanates or cycloalkylene diisocyanates with 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, e.g. 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), Roger that. Particularly preferred aliphatic diisocyanates d2 are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.

Among the preferred isocyanurates counting the aliphatic isocyanurates, which differ from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferred 3 to 12 carbon atoms, e.g. Isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), derived. You can the alkylene diisocyanates can be both linear and branched. Especially Isocyanurates based on n-hexamethylene diisocyanate are preferred based, for example cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate.

Generally the component d2 in amounts of 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol% based on the sum of the molar amounts of A and B used.

In general, the divinyl ether d3 can be all usual and commercially available Use divinyl ether. 1,4-butanediol divinyl ether are preferably used, 1,6-hexanediol divinyl ether or 1,4-cyclohexanedimethanol divinyl ether or mixtures thereof.

The divinyl ethers are preferred in amounts of 0.01 to 5, in particular from 0.2 to 4 wt .-%, based on the Total weight of A and B used.

Examples of preferred partially aromatic polyesters are based on the following components
A, B, d1
A, B, d2
A, B, d1, d2
A, B, d3
A, B, c1
A, B, c1, d3
A, B, c3, c4
A, B, c3, c4, c5
A, B, d1, c3, c5
A, B, c3, d3
A, B, c3, d 1
A, B, c1, c3, d3
A, B, c2

Among them are partially aromatic polyesters, those based on A, B, d1 or A, B, d2 or on A, B, d1, d2 are special prefers. According to another preferred embodiment, the partially aromatic are based Polyester on A, B, c3, c4, c5 or A, B, d 1, c3, c5.

The production of semi-aromatic Polyester is known per se or can be made by methods known per se respectively.

The preferred partially aromatic polyesters are characterized by a molecular weight (M _n ) in the range from 1000 to 100000, in particular in the range from 9000 to 75000 g / mol, preferably in the range from 10000 to 50,000 g / mol and a melting point in the range from 60 to 170 , preferably in the range from 80 to 150 ° C.

The aliphatic and / or partially aromatic polyester can Hydroxy and / or Have carboxyl end groups in any ratio. The above aliphatic and / or partially aromatic polyesters can also end group modified. For example, OH end groups Reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic or pyromellitic anhydride acid-modified become.

In general, as components ii) of the thermoplastic molding compositions known polyester Basis of aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds. These polyesters suitable as component ii) are due to their high proportion of aromatic units not biodegradable.

A first group of preferred polyesters ii) are polyalkylene terephthalates, in particular with 2 to 10 carbon atoms in the alcohol section.

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can 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- or t-butyl groups ,

These polyalkylene terephthalates can by Implementation of aromatic dicarboxylic acids, their esters or others ester-forming derivatives with aliphatic dihydroxy compounds be produced in a manner known per se.

Preferred dicarboxylic acids are 2,6- terephthalic acid and isophthalic acid or to name their mixtures. Up to 20 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids become.

Of the aliphatic dihydroxy compounds diols with 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 prefers.

As a particularly preferred polyester ii) are polyalkylene terephthalates which differ from alkanediols Derive 2 to 6 carbon atoms. Of these, primarily Polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof, in particular polybutylene terephthalate, are preferred. Also preferred are PET and / or PBT, which also up to 1 % By weight of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further May contain monomer units.

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

Furthermore, component u) of the molding compositions according to the invention PET recyclates (also called scrap PET), optionally in a mixture use 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 to mean:

• 1) So-called post industrial recyclate: this is production waste in the case of polycondensation or in processing, for example sprues in injection molding processing, start-up goods in injection molding processing or extrusion or edge sections of extruded sheets or foils.
• 2) Post consumer recyclate: these are plastic items that are collected and processed by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recyclate can either available as regrind or in the form of granules. In the latter case the tube cyclates are separated and cleaned in one Extruder melted and granulated. This usually becomes Handling, the flowability and the dosability for further processing steps facilitated.

Both granulated and as regrind existing recyclates can are used, the maximum edge length 6 mm, preferably smaller Should be 5 mm.

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

As another group of as a component ii) suitable compounds are fully aromatic polyesters, which differ from aromatic dicarboxylic acids and aromatic dihydroxy compounds derived.

Suitable as aromatic dicarboxylic acids the ones already described for polyalkylene terephthalates Links. Are preferred for fully aromatic polyester mixtures of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, especially mixtures of about 80% terephthalic acid 20% isophthalic acid to about equivalents 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 (V1)

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

Examples of these are the parent bodies of these compounds
dihydroxydiphenyl,
Di (hydroxyphenyl) alkane,
Di (hydroxyphenyl) cycloalkane,
Di (hydroxyphenyl) sulfide,
Di (hydroxyphenyl) ether,
Di (hydroxyphenyl) ketone,
di- (hydroxyphenyl) sulfoxide,
a, a'-di- (hydroxyphenyl) -dialkylbenzol,
Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene
Resorcinol and
Hydroquinone and their nuclear alkylated or nuclear halogenated derivatives called.

Of these will be
4,4'-dihydroxydiphenyl,
2,4-di- (4'-hydroxyphenyl) -2-methylbutane
a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and
2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,
as well as 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'-dihydroxydiphenyl sulfone and
2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane
or mixtures thereof are preferred.

Of course you can as a component ii) also mixtures of polyalkylene terephthalates and fully aromatic Use polyesters. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.

Of course, polyester block copolymers such as copolyether esters can also be used as component ii). Such products are known per se and in the literature, for example in the US-A 3,651,014 , described. Corresponding products are also commercially available, for example 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 n' eine ganze Zahl von 0 bis 2 ist.According to the invention, polyester ii) should also be understood to mean polycarbonates. Suitable polycarbonates are, for example, those based on diphenols of the general formula (VII)

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 - means and n 'is an integer from 0 to 2.

The diphenols can 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 formula VII 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. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferred, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Both homopolycarbonates as well Copolycarbonates are suitable as component ii), are preferred in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A.

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

Polycarbonates which have relative viscosities η _rel of 1.10 to 1.50, in particular of 1.25 to 1.40, have proven to be particularly suitable. 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 VII are known per se or can be produced by known processes.

The polycarbonates can be produced, for example, by reacting the diphenols with phosgene by the interfacial process or with phosgene by the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by an appropriate amount of known chain terminators. (See, for example, for polydiorganosiloxane-containing polycarbonates DE-OS 33 34 782 ).

Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with 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, pt-outylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol.

Amorphous polyester carbonates may be mentioned as further suitable components ii), with phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production. For further details, please refer to the EP-A 711 810 directed.

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

Bisphenol A can also be replaced by Bisphenol TMC. Such polycarbonates are available under the trademark APEC HT ^® from Bayer AG.

The thermoplastic molding compositions according to the invention usually contain from 90 to 99.99% by weight, preferably from 95 to 99.95% by weight, particularly preferably from 99 to 99.9% by weight of component i) and from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight of component ii), the percentages by weight each refer to the total weight of components i) to ii).

The thermoplastic molding compositions according to the invention and / or the polyester i) Contain additives iii), which one during the polymerization process in any stage or afterwards, for example in a melt of the polyester, or together with the incorporation of component ii). exemplary stabilizers, neutralizing agents, lubricants and release agents, Antiblocking agents, dyes or fillers called.

Based on the polyester i) can to add from 0 to 80 wt .-% additives. Suitable additives are for example fillers, Stabilizers or lubricants and mold release agents. Such additives are e.g. in plastic manual, vol. 3/1, Carl Hanser Verlag, Munich, 1992, Pp. 24 to 28 in detail described.

Examples of fillers are particulate substances such as calcium carbonate, clay minerals, calcium sulfate, barium sulfate, Titanium dioxide, soot, Lignin powder, iron oxide, which also act as coloring components can, as well as fiber materials, e.g. Cellulose fibers, sisal and hemp fibers. The proportion of fillers is usually not more than 40 wt .-%, based on the total weight the molding composition according to the invention, in particular not more than 20% by weight.

Stabilizers are e.g. tocopherol (Vitamin E), organic phosphorus compounds, mono-, di- and polyphenols, Hydroquinones, diarylamines, thioethers, melamine or urea. As Antiblocking agents come e.g. Talc, chalk, mica or silicon oxide into consideration. Lubricants and mold release agents are usually substances based on hydrocarbons, fatty alcohols, higher carboxylic acids, metal salts higher carboxylic acids such as calcium or zinc stearate, fatty acid amides such as erucic acid amide and wax types, e.g. Paraffin waxes, beeswax, montan waxes and like. Preferred release agents are erucic acid amide and / or wax types and particularly preferably combinations of these two types of release agents. Preferred wax types are beeswaxes and ester waxes, in particular Glycerol. Those for production are particularly preferred the molding compositions of the invention used polyester i) with 0.05 to 2.0 wt .-% erucic acid amide or 0.1 to 2.0 wt .-% wax types, each based on the plastic content of the molding compounds. Those for the production of the molding compositions according to the invention are very particularly preferred used polyester i) with 0.05 to 0.5 wt .-% erucic acid amide and 0.1 to 1.0% by weight of wax types, in particular glycerol monostearate, each based on the plastic content of the molding compounds.

The polyesters which can be used according to the invention as component ii) can be introduced into the polyesters i) to be stabilized by various methods. For example, the polyester ii) can be admixed with one or more of the monomer components for the preparation of the polyester i), for example the dicarboxylic acids and / or diols, already during the preparation of component i). According to another ver the polyesters ii) can be incorporated into the melt of the fully reacted polyesters i).

Component ii) can according to known Method and using known mixing devices in the previously produced polyester i) are introduced (see for example Saechtling, plastic paperback, Hanser Verlag, Munich, Vienna, Issue 26, 1995, pages 191 to 246). Component ii) can, for example with the help of a screw machine, e.g. an extruder, either can be mixed in in pure form or as a so-called "master batch", in component i).

In general, it is these masterbatches around special molding compounds, in which the required additives or additives, for example component ü), in a matrix of, for example thermoplastic polymer, for example component i), embedded are, however, the additive content compared to conventional additive molding compounds significantly higher, for example in the area from 10 to 70% by weight. By adding appropriate amounts a master batch to a non-additive fourth, for example Thermoplastics can then molding compounds with usual Additive contents can be produced.

The thermoplastic molding compositions according to the invention are particularly suitable for the production of blends, molded parts, films or Fibers suitable.

Can be particularly preferred the molding compositions according to the invention Blends with polysaccharides or polysaccharin derivatives, in particular Strength, are produced, which in turn to films, molded parts or fibers are processable.

A special area of application of the Molding compositions according to the invention relates to the use as a compostable film or a compostable Coating, for example as a mulch film.

Another preferred field of application of the molding compositions according to the invention relates to the production of completely degradable blends with starch mixtures (preferably with thermoplastic starch as described in WO 90/05161) analogously to that in US Pat DE-A 42 37 535 described method. The molding compositions according to the invention can be mixed both as granules and as a polymer melt with starch mixtures, mixing being preferred as a polymer melt, since one process step (granulation) can be saved (direct assembly). According to previous observations, the thermoplastic molding compositions according to the invention can advantageously be used as a synthetic blend component on account of their hydrophobic nature, their mechanical properties, their biodegradability, their good compatibility with thermoplastic starch and not least because of their cheap raw material base.

Other areas of application concern for example the use of the molding compositions according to the invention in agricultural Mulch, packaging material for Seeds and nutrients, Substrate in adhesive films, baby panties, Bags, sheets, Bottles, boxes, dust bags, labels, pillow cases, protective clothing, Hygiene items, handkerchiefs, Toys and wipers.

Another use of the molding compositions according to the invention relates to the production of foams, the procedure generally being known (see EP-A 372,846 ; Handbook of Polymeric foams and Foam Technology, Hanser Publisher, Munich, 1991, pp. 375 to 408). Usually, the molding composition according to the invention is first melted, then mixed with a blowing agent and the mixture thus obtained is subjected to reduced pressure by extrusion, the foaming being produced.

With the help of the thermoplastic according to the invention Molding compounds are made available from biodegradable polyesters, the opposite already known thermoplastic molding compositions based on biology degradable polyester a less delayed or accelerated crystallization when cooling have from the melt, which is reduced during processing Tendency to stick to the tools and which show increased throughput during processing enable.

Examples: application technology measurements:

The molecular weight M _{n of} the polymers was determined as follows: 15 mg of the polymers were dissolved in 10 ml of hexafluoroisopropanol (HFIP). In each case 125 μl of this solution were analyzed by means of gel permeation chromatography (GPC). The measurements were carried out at room temperature. HFIP + 0.05% by weight of trifluoroacetic acid Ka salt was used for the elution. The elution rate was 0.5 ml / min. The following column combination was used (all columns manufactured by Showa Denko Ltd., Japan): Shodex ^® HFIP-800P (diameter 8mm, length 5 cm), Shodex ^® HFIP-803 (diameter 8mm, length 30 cm), Shodex ^® HFIP-803 (diameter 8mm, length 30 cm). The polymers were detected using an RI detector (differential refractometry). The calibration was carried out using narrowly distributed polymethyl methacrylate standards with molecular weights from M _n = 505 to M _n = 2,740,000. Elution ranges outside this interval were determined by extrapolation.

The melting and crystallization temperatures of the molding compositions were determined by DSC measurements with an Exstet DSC 6200R from Seiko: 10 to 15 mg of the respective samples were heated from -70 ° C to 200 under a nitrogen atmosphere with a heating rate of 20 ° C / min ° C heated. The peak temperatures of the melting peak observed were stated as the melting temperatures of the samples. The samples were then immediately cooled from 200 ° C to -70 ° C at a cooling rate of 20 ° C / min.

As crystallization temperatures of the samples became the peak temperatures of the crystallization peak observed specified. An empty sample pan was used as a reference.

Input materials: component i):

P-i-1: For the production of the biological degradable polyester P-i-1 were 87.3 kg of dimethyl terephthalate, 80.3 kg adipic acid, 117 kg of 1,4-butanediol and 0.2 kg of glycerin together with 0.028 kg of tetrabutyl orthotitanate (TBOT) mixed, the molar ratio between alcohol components and acid component Was 1.30. The reaction mixture was brought to a temperature of Heated 180 ° C and reacted at this temperature for 6 hours. Then was the temperature to 240 ° C elevated and the excess dihydroxy compound under Vacuum over distilled off for a period of 3 hours. Then 0.9 kg at 240 ° C. Hexamethylene diisocyanate slowly metered in over 1 hour.

The polyester Pi-1 thus obtained had a melting temperature of 119 ° C. and a molecular weight (M _n ) of 23,000 g / mol.

Components ii):

The following were used as component ii):
P-ü-1: Polybutylene terephthalate (PBT) with a viscosity number of 107 ml / g (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene, 1: 1 mixture, at 35 ° C according to EN ISO 1628-1).

Components iii):

The following were used as component iii):
P-iii-1: erucic acid amide, commercial product from Sigma-Aldrich Chemie GmbH
P-iii-2: talcum powder <10 μl, commercial product from Sigma-Aldrich Chemie GmbH

Production of the molding compositions according to the invention:

To produce the molding compositions according to the invention, the starting materials listed in Table 1 were mixed in a twin-screw extruder (ZSK30) at 230 ° C. The melting and crystallization temperatures of the molding compositions thus obtained are also shown in Table 1. Table 1:

sThe examples prove that the Molding compound F-V1 less delayed or the accelerated crystallization of the molding compositions according to the invention F-3 and F-5 when cooling from the melt.

Film Production:

To produce further molding compositions according to the invention, the starting materials listed in Table 2 were mixed in a twin-screw extruder (ZSK30) at 230 ° C. and granulated. The molding compositions were then processed into films as follows: on a chill-roll system from Reifenhäuser with an extruder diameter of 90 mm, an extruder length of 2250 mm and two chill-roll rollers (diameter of the first roller: 400 mm; diameter the second roller 150 mm) were from the molding compositions at a melt temperature of 175 ° C, a throughput of 38 kg / h, a drawing speed of 15 m / min, at the roller temperature shown in Table 2 of both chill-roll rollers and under otherwise the same conditions in each case were produced using the chill-roll extrusion process. Table 2 is also shown the frequency with which the molding compounds were stuck to the chill-roll rollers during film production. The sticking can be recognized by the fact that the film initially adheres to the first rotating roller beyond the normal detachment point and then detaches abruptly (in contrast, a non-sticking film detaches from the first rotating roller without jerking at the same detaching point) ). The frequency of the bonding shown in Table 2 is the number of visually detectable jerky detachment processes of the film from the first rotating roller per minute. Table 2:

The from the molding compositions of the invention F-1 to F-4 produced films had a processing reduced tendency to stick to the tools and enabled increased throughput in processing than those made from molding compounds F-V1 to F-V3 Films.

They also owned from the molding compositions according to the invention F-1 through F-4 manufactured films have better transparency than that Films made from the molding compounds F-V1 to F-V3.

Claims (10)

Thermoplastic molding composition containing i) 90 to 99.99% by weight, based on the total weight of components i) to ii), of at least one polyester which is biodegradable in accordance with DIN V 54900, and ii) 0.01 to 10% by weight .-%, based on the total weight of components i) to ii) of at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and iii) moreover 0 to 80% by weight, based on the weight of component i), of conventional additives. Thermoplastic molding composition according to claim 1, wherein the polyester i) is composed of: A) an acid component from a1) 30 to 95 mol% of at least one aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof a2) 5 to 70 mol% at least one aromatic dicarboxylic acid or its ester-forming derivative or mixtures thereof and a3) 0 to 5 mol% of a compound containing sulfonate groups, the molar percentages of components a1) to a3) together giving 100% and B) a diol component from at least one C ₂ -bis C ₁₂ alkanediol or a C ₅ to C ₁₀ cycloalkanediol or mixtures thereof and, if desired, moreover one or more components selected from C) a component selected from c1) at least one dihydroxy compound of the formula I containing ether functions HO - [(CH ₂ ) _n -O] _m -H (I) in which n is 2, 3 or 4 and m is an integer from 2 to 250, c2) at least one hydroxycarboxylic acid of the formula IIa or IIb

in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical which is selected from the group consisting of phenylene, - (CH ₂ ) _q -, where q is an integer Number from 1 to 5 denotes -C (R) H- and -C (R) HCH ₂ , where R is methyl or ethyl (c3) at least one amino-C ₂ -C ₁₂ -alkanol or at least one amino-C _{5 to} C ₁₀ cycloalkanol or mixtures thereof c4) at least one diamino-C ₁ to C ₈ alkane c5) at least one 2,2'-bisoxazoline of the general formula III

where R ^{1 is} a single bond, a (CH ₂ ) ₂ alkylene group, with z = 2, 3 or 4, or a phenylene group, c6) at least one aminocarboxylic acid selected from the group consisting of the natural amino acids, polyamides with a molecular weight of at most 18000 g / mol, obtainable by polycondensation of a dicarboxylic acid with 4 to 6 C atoms and a diamine with 4 to 10 C atoms, compounds of the formulas IV a and IVb

in which s is an integer from 1 to 1500 and t is an integer from 1 to 4, and T is a radical which is selected from the group consisting of phenylene, - (CH ₂ ) _u -, where u is an integer Number from 1 to 12 means -C (R ² ) H- and -C (R ² ) HCH ₂ , where R ^{2 is} methyl or ethyl, and polyoxazolines with the repeating unit V

in the R ³ for hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₈ cycloalkyl, unsubstituted or with C ₁ -C ₄ alkyl groups up to trisubstituted phenyl or tetrahydrofuryl, or mixtures of c1) to c6) and D) of a component selected from d1) at least one compound with at least three groups capable of ester formation, d2) at least one isocyanate d3) at least one divinyl ether or mixtures of d1 ) to d3). Thermoplastic molding composition according to claims 1 to 2, wherein component ii) is at least one polyalkylene terephthalate. Thermoplastic molding composition according to claims 1 to 3, wherein component ii) polyethylene terephthalate or polybutylene terephthalate is. Thermoplastic molding composition according to claims 1 to 4, wherein component ii) is polybutylene terephthalate. Process for the production of molding compositions according to claims 1 to 5, characterized in that the Components i) to iii) are mixed. Process for the production of molding compositions according to claims 1 to 5, characterized in that component ii) is admixed in the production of component i). Use of the molding compositions according to claims 1 to 5 for the production of blends, molded parts, foils or fibers. Blends, molded parts, foils or fibers, available from the molding compositions according to claims 1 to 5th Use of polyesters based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds as nucleating agents for polyester, which according to DIN V 54900 are biodegradable.