WO2011009766A1

WO2011009766A1 - Highly functional, highly or hyper-branched polyester and the production and use thereof

Info

Publication number: WO2011009766A1
Application number: PCT/EP2010/060045
Authority: WO
Inventors: Monika Haberecht; Bernd Bruchmann; Darijo Mijolovic; Angelika Maria Steinbrecher; Oihana Elizalde
Original assignee: Basf Se
Priority date: 2009-07-24
Filing date: 2010-07-13
Publication date: 2011-01-27

Abstract

The present invention relates to specifically constructed, highly functional, highly or hyper-branched polyesters containing ß,ß,ß',ß'-tetra(hydroxymethyl)cycloalkanol as an integrated construction component, a method for the production thereof, and the use thereof.

Description

Highly functional, highly branched or hyperbranched polyesters and their preparation and use

description

The present invention relates to specifically constructed high-functionality, highly branched or hyperbranched polyesters which contain β, β, β ', β'-tetra (hydroxymethyl) -cycloalkanol incorporated as a synthesis component, processes for their preparation and their use.

The high-functionality, highly branched or hyperbranched polyesters according to the invention may i.a. used as adhesion promoters, for example in printing inks, as thixotropic agents or as building blocks for the preparation of polyaddition or polycondensation polymers, for example of paints, coatings, adhesives, sealants, cast elastomers or foams, and as component of binders, optionally with other components such as Isocyanates, epoxy group-containing binders or alkyd resins, in adhesives, printing inks, coatings, foams, coatings and varnishes. Polyesters are usually obtained from the reaction of carboxylic acids with alcohols. Technically significant are aromatic polyesters, i. A polyester having an acid component in which at least one carboxy group is bonded to an aromatic ring, for example, prepared from phthalic acid, isophthalic acid or terephthalic acid and ethanediol, propanediol or butanediol, and aliphatic polyesters, i. Polyester having an acid component in which all carboxy groups are bonded to aliphatic or cycloaliphatic carbon atoms, prepared from succinic acid, glutaric acid or adipic acid with ethanediol, propanediol, butanediol, pentanediol or hexanediol. These aromatic or aliphatic polyesters are usually linear, strictly difunctional, or constructed with a low degree of branching.

Hyperbranched polyesters based on dimethylolpropionic acid are known from WO 93/17060 (EP 630 389) and EP 799 279, in which dimethylolpropionic acid is condensed as an AB 2 building block (A = acid group, B = OH group) intermolecularly to give polyesters. The synthesis is very inflexible, since one relies on AB2 building blocks such as dimethylolpropionic acid as the sole starting material. Furthermore, dendritic polyesters based on AB2 building blocks for general use i. d. R. too costly, since already these starting materials are expensive and often have to be prepared by multi-step syntheses.

EP 1109775 describes the preparation of hyperbranched polyesters having a tetrafunctional central group. Here, starting from unsymmetrical tetrols, such as homopentaerythritol, as a central molecule, a dendrimer-like Built product that finds use in paints. However, such asymmetric tetrols are expensive specialty chemicals that are not commercially available in large quantities. DE 101 63 163 and DE 10219508 describe the preparation of hyperbranched polyesters based on an A2 + B3 approach. This principle is based on the use of dicarboxylic acids and triols or of tricarboxylic acids and diols. The flexibility of these syntheses is significantly higher, since one does not depend on the use of an AB2 building block.

WO 2005/118677 describes hyperbranched polyesters based on dicarboxylic acids, diols and an at least trifunctional building block, i. Acid or alcohol. The properties of the hyperbranched polyesters thus obtainable can be adjusted very flexibly, but in some applications an improved hardness is required.

Nevertheless, it was desirable to further increase the flexibility of the synthesis to give hyperbranched or hyperbranched polyesters, especially in the setting of functionalities, solubility behavior and also melting or glass transition temperatures. It is known from US Pat. No. 5,039,760 to produce polyester from an aromatic dicarboxylic acid, an aliphatic glycol and from 0.001 to 1.0 mol% of a branching component. As the latter component, 2,2,6,6-tetramethylolcyclohexanol is mentioned, but not used in the explicitly disclosed examples. The products described there have no or only a slight degree of branching, so that they are not highly branched or hyperbranched compounds in the context of the present invention.

This process essentially gives linear polyesters which contain only a small number of branches and therefore behave essentially like linear polyesters.

In Plast. Massy (1963), (6), 18-20 describes the reaction of adipic acid with 2,2,6,6-tetramethylolcyclohexanol in various stoichiometries. Under the reaction conditions described there is cleaved formaldehyde by ether formation, which is disadvantageous for toxicity reasons. Although the reaction is carried out only to low conversions, as can be seen from the high OH numbers of the products, the products usually show a strong gel formation, which should be avoided.

The invention was based on the object by means of a technically simple and inexpensive process aliphatic or aromatic, highly functional and highly branched te provide polyesters whose structures, degrees of branching, functionalities and properties, such as solubility or melting or glass transition temperatures, can be easily adapted to the needs of the application and the advantageous properties, such as high functionality and / or high reactivity, combine can. In particular, in coating compositions, the polyester should gel-free effect rapid drying and / or improved gloss retention.

The object has been achieved according to the invention by hyperbranched polyesters in which β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols or mixtures containing them are copolymerized as polyol components.

The invention thus relates to highly functional, highly branched or hyperbranched polyesters having a molecular weight M _n of at least 500 g / mol and

a polydispersity M _w / M _n of 1, 2 - 100 obtainable by

implementation

at least one aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof and optionally at least one divalent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B2) which has 2 OH groups,

at least one ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol or at least one ß, ß, ß', ß'-tetra (hydroxymethyl) cycloalkanol containing reaction mixture,

- Optionally at least one x-valent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (C _x ) having more than two OH groups and x is a number greater than 2, preferably between 3 and 8, more preferably between 3 and 6, very particularly preferably from 3 to 4 and in particular 3, where the alcohol (C _x ) differs from β, β, β ', β'-tetra (hydroxymethyl) -cycloalkanol,

optionally at least one aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid (D _y ) or derivatives thereof having more than two acid groups and y is a number greater than 2, preferably between 3 and 8, more preferably between 3 and 6, very particularly preferably from 3 to 4 and in particular 3,

- in each case optionally in the presence of further functionalized units E which carry, in addition to or instead of hydroxyl groups or carboxy groups, at least one further functional group or functional elements which react in an analogous manner as hydroxy groups or carboxy groups and

optionally followed by reaction with a monocarboxylic acid F wherein the ratio of the reactive groups in the reaction mixture is selected such that a molar ratio of OH groups to carboxy groups or derivatives thereof is from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, more preferably from 3: 1 to 1: 3 and most preferably from 2: 1 to 1: 2 sets, and the proportion of hydroxy groups in ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol based to the sum of the hydroxy groups in the components ß, ß, ß ', ß'- tetra (hydroxymethyl) cycloalkanol, (B2) and (C _x ) is 10 to 100 mol%, with the proviso that

- At least one of the components (B2), (C _x ) and (D _y ) in the reaction mixture to at least 0.1% by weight, preferably at least 0.5, more preferably at least 1, 0, most preferably at least 5 and in particular at least 10th Gew%, based on the sum of all components (A) to (F), is present and / or

- It is the aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof is a mixture of at least two aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acids (A2) or derivatives thereof.

The invention furthermore relates to a process for preparing such highly functional, highly branched or hyperbranched polyesters.

Hyperbranched polyesters in the context of this invention are understood as meaning uncrosslinked polyesters having hydroxyl and carboxyl groups which are structurally as well as molecularly nonuniform. Uncrosslinked in the context of this document means that a degree of crosslinking of less than 15% by weight, preferably less than

10% by weight, determined via the insoluble fraction of the polymer. The insoluble portion of the polymer was determined by extraction for 4 hours with the same solvent as used for gel permeation chromatography, ie tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, preferably tetrahydrofuran in a Soxhlet apparatus and subsequent drying of the residue until the weight balance of the remaining residue. Hyperbranched polyesters can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with nonuniform chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts. For the definition of dendrimers and hyperbranched polymers see also PJ. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chemistry - A European Journal, 2000, 6, no. 14, 2499.

"Hyperbranched" in the context of the present invention is understood to mean that the degree of branching (DB) is 10 to 99.9%, preferably 20 to 99%, particularly preferably 20 to 95%. The degree of branching DB is defined as DB (%) = (T + Z) / (T + Z + L) × 100, with

T average number of terminally bound monomer units,

Z mean number of branching monomer units,

L is the average number of linearly bound monomer units.

By "dendrimer" is meant, in the context of the present invention, 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, 30-35.

More specifically, the following is to be accomplished for the invention:

The dicarboxylic acids (A2) include, for example, aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,

Suberic acid, azelaic acid, sebacic acid, undecane-α, ω-dicarboxylic acid, dodecane-α, ω-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, cis- and trans-cyclopentane-1,3-dicarboxylic acid. Furthermore, it is also possible to use aromatic dicarboxylic acids, such as, for example, phthalic acid, isophthalic acid or terephthalic acid. It is also possible to use unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, mescaconic acid, glutaconic acid or citraconic acid. The dicarboxylic acids mentioned can also be substituted by one or more radicals selected from

C 1 -C 20 -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-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl, trimethylpentyl, n Nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, or n-eicosyl, C 2 -C 20 -alkenyl groups, for example butenyl, hexenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl or eicosenyl, 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 Phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

Examples which may be mentioned of substituted dicarboxylic acids or derivatives thereof are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, 3,3-dimethylglutaric acid, dodecenylsuccinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid and Reaction products of polyisobutylenes with an eopharyl selected from the group of fumaric acid, fumaric acid, maleic acid, maleic anhydride and / or maleic acid, preferably with maleic anhydride or maleic acid dichloride, more preferably maleic anhydride, to polyisobutylene-substituted succinic acid derivatives wherein the polyisobutylsilyl group has a number average molecular weight M _{n may be} from 100 to 100,000 daltons. This reaction takes place according to the processes known to the person skilled in the art and preferably as described in German Offenlegungsschriften DE-A 195 19 042, there preferably from p. 2, p. 39 to p. 4, p. 2 and particularly preferably p. 3, Z. 35-58, and DE-A 43 19 671, there preferably from p. 2, Z. 30 to Z. 68, and DE-A 43 19 672, there preferably from p. 2, Z. 44 to p. 3, Z. 19, for the reaction of polyisobutylenes with enophiles.

Furthermore, mixtures of two or more of the aforementioned dicarboxylic acids can be used. For example, one to six, preferably one to four, more preferably one to three, most preferably one to two and in particular a dicarboxylic acid can be used.

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

Derivatives are preferably understood the relevant anhydrides in monomeric or polymeric form,

Mono- or dialkyl esters, preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters,

furthermore mono- and divinyl esters as well

mixed esters, preferably mixed esters with different C1-C4

Alkyl components, more preferably mixed methyl ethyl esters. Among these, preferred are the anhydrides and the mono- or dialkyl esters, particularly preferred are the anhydrides and the mono- or di-C 1 -C 4 -alkyl esters, and most preferably the anhydrides.

Ci-C4-alkyl in this document means methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, particularly preferably methyl and ethyl, and most preferably methyl.

In the context of the present invention, it is also possible to use a mixture of a dicarboxylic acid and one or more of its derivatives. Likewise, it is within the scope of the present invention possible to use a mixture of several different derivatives of one or more dicarboxylic acids.

Particular preference is given to using malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, octadecenylsuccinic anhydride, 1, 2-, 1, 3- or 1,4-cyclohexanedicarboxylic acids (hexahydrophthalic acids as cis- or trans-compounds or mixtures thereof), phthalic acid, isophthalic acid , Terephthalic acid or its anhydrides or mono- or dialkyl esters.

It is a preferred embodiment of the present invention to use as dicarboxylic acids (A2) at least partially, preferably exclusively those compounds in which the two carboxy groups are bonded to a ring system, preferably a cycloaliphatic or aromatic ring system. Examples thereof are 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, cis- and trans-cyclopentane-1, 3-dicarboxylic acid, phthalic acid, isophthalic acid or terephthalic acid, preferred are cis- and trans-cyclohexane-1, 2-dicarboxylic acid, phthalic acid or terephthalic acid or derivatives thereof, preferably their anhydrides or Mono or dialkyl ester. It is an inventive feature that at least one of the components (B2), (C _x ) and (Dy) in the reaction mixture to at least 0.1% by weight, preferably at least 0.5, more preferably at least 1, 0, most preferably at least 5 and in particular at least 10% by weight, based on the sum of all components (A) to (F), is present. This feature and / or the presence of the component (A2) must be realized according to the invention. It is an advantage of this embodiment that the hyperbranched polyesters based on the dicarboxylic acids containing a ring system and β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol give polyesters having a particularly high glass transition temperature, so that they are, for example, very good suitable for coating systems.

Reactable tricarboxylic acids or polycarboxylic acids (D _y ) are, for example, aconitic acid, 1,3,5-cyclohexanetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid ( Pyromellitic acid) as well as mellitic acid and low molecular weight polyacrylic acids.

Conceivable tricarboxylic acids or polycarboxylic acids (D _y ) are also those which contain further functional groups, such as hydroxyl groups or tert. Amino groups, except Carboxygruppen wear. Examples include citric acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Tricarboxylic acids or polycarboxylic acids (D _y ) can be used in the reaction according to the invention either as such or in the form of derivatives.

Derivatives are preferably understood

"the relevant anhydrides in monomeric or polymeric form,

Mono-di- or trialkyl, preferably mono-, di- or tri-C 1 -C 4 -alkyl esters, more preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or triethyl esters,

furthermore mono-, di- and trivinyl esters as well

mixed esters, preferably mixed esters with different

C 1 -C 4 -alkyl components, more preferably mixed methyl ethyl esters.

Among these, preference is given to the anhydrides and the mono- or dialkyl esters; the anhydrides and the mono- or di-C 1 -C 4 -alkyl esters are particularly preferred, and the anhydrides are very particularly preferred.

In the context of the present invention, it is also possible to use a mixture of a triester of polycarboxylic acid and one or more of its derivatives, for example a mixture of pyromellitic acid and pyromellitic dianhydride. For example, one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular a tricarboxylic or polycarboxylic acid can be used. Likewise, it is within the scope of the present invention, to use a mixture of several different derivatives of one or more tri- or polycarboxylic acids, for example a mixture of 1, 3,5-cyclohexanetricarboxylic acid and pyromellitic dianhydride. Examples of diols (B2) according to 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, 2-decanediol , 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, 1, 5-hexadiene-3,4-diol, 1, 2 and 1, 3-cyclopentanediols, 1, 2, 1, 3 - And 1, 4-cyclohexanediols, 1, 1, 1, 2, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexanes, 1, 1, 1, 2, 1, 3 and 1 , 4-bis (hydroxyethyl) cyclohexane, neopentyl glycol, (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 l, tripropylene glycol, polyethylene glycols HO (CH 2 CH 2 O) _n -H or polypropylene glycols HO (CH [CH 3] CH 2 O) _n -H, where n is an integer and n> 4, polyethylenepolypropylene glycols, the sequence being the ethylene oxide - The propylene oxide units may be blockwise or random, polytetramethylene glycols, preferably up to a molecular weight of up to 5000 g / mol, poly-1, 3-propanediols, preferably having a molecular weight of up to 5000 g / mol, polycaprolactones or mixtures of two or more representatives of the above compounds. For example, one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular a diol can be used. In this case, one or both hydroxy groups in the abovementioned diols can be substituted by SH groups. Preferably used diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2, 1, 3 - And 1, 4-cyclohexanediol, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

The dihydric alcohols B2 may optionally contain further functionalities such as, for example, carbonyl, carboxy, alkoxycarbonyl or sulfonyl, for example dimethylolpropionic acid or dimethylolbutyric acid, and their C 1 -C ₄ -alkyl esters, but the alcohols B 2 preferably have no further functionalities.

It is an embodiment of the present invention that at least one compound B2 is present in the hyperbranched polyesters.

According to the invention, the hyperbranched polyesters contain, as compound C _{x, at} least one β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol. It is also possible to use a mixture of a plurality of β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols, for example up to four, preferably up to three, particularly preferably up to two. Quite It is especially preferred to use exactly one β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol.

The β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols are cycloalkano-1e which carry hydroxymethyl groups in the β position relative to the secondary hydroxy group.

The name of the atomic groups in the cycloalkanol is as follows:

These are preferably based on cyclolalkanols having a ring size of 4 to 12, preferably from 5 to 12, most preferably from 6 to 12.

Preferred β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols are 2,2,6,6-tetrakis (hydroxymethyl) cyclohexan-1-ol, 2,2,5,5-tetrakis (hydroxymethyl) cyclopentane 1-ol, 2,2,8,8-tetrakis (hydroxymethyl) cyclooctan-1-ol and 2,2,12,12-tetrakis (hydroxymethyl) cyclododecan-1-ol. Particular preference is given to 2,2,6,6-tetrakis (hydroxymethyl) cyclohexan-1-ol, 2,2,5,5-tetrakis (hydroxymethyl) cyclopentan-1-ol and 2,2,12,12-tetrakis (hydroxymethyl) cyclododecan-1-ol, very particularly preferably 2,2,6,6-tetrakis (hydroxymethyl) cyclohexan-1-ol and 2,2,5,5-tetrakis (hydroxymethyl) cyclopentan-1-ol and in particular 2,2,6,6-tetrakis (hydroxymethyl) cyclohexan-1-ol.

The preparation of these compounds can be carried out, for example, by an aldol reaction of the corresponding cycloalkanone with formaldehyde, followed by a crossed Cannizzaro reaction with formaldehyde. The reaction can preferably be based on cyclopentanone, cyclohexanone, cyclooctanone or cyclododecanone. A possible production of some ß, ß, ß ', ß'-

Tetra (hydroxymethyl) cycloalkanols is described in DE-OS 2223136 and can be analogously to the production of other ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanols transferred.

It is also possible to use β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols containing reaction mixtures in which not all four possible β-positions of the cycloalkanol are hydroxymethylated, but which only account for a certain proportion of three or even more contain less hydroxymethylated product. Examples of such products are β, β, β'-tri (hydroxymethyl) -cycloalkanol, β, β'- Di (hydroxymethyl) cycloalkanol or β, β-di (hydroxymethyl) cycloalkanol. It is also conceivable that a carbonyl group is present instead of the secondary hydroxy group, so that the reaction mixture has a proportion of .alpha., .Alpha., .Alpha. ', .Alpha.'

Tetra (hydroxymethyl) cycloalkanone, α, α, α'-tri (hydroxymethyl) cycloalkanone, α, α'-di (hydroxymethyl) cycloalkanone or α, α-di (hydroxymethyl) cycloalkanone may contain. The products mentioned are generally contained in the reaction mixture to not more than 10% by weight, preferably to not more than 5% by weight. Conceivable are such reaction mixtures which have a mean hydroxymethylation of at least 3.5, preferably at least 3.6, more preferably at least 3.8 and most preferably at least 3.9. According to the invention, these reaction mixtures can likewise be used instead of the β, β, β ', β'-tetra (hydroxymethyl) -cycloalkanols. The statements made in this document for ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanols can be readily transferred to the reaction mixtures containing them.

In addition to the β, β, β ', β'-tetra (hydroxymethyl) cycloalkanols according to the invention, it is also possible optionally to use further at least trifunctional alcohols C _x :

At least trifunctional alcohols (C _x ) include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolpentane, 1, 2,4-butanetriol, 1, 2,6-hexanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine,

Tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol or higher condensation products of glycerol, di (trimethylolpropane), di (pentaerythritol), trishydroxymethyl isocyanurate, tris (hydroxyethyl) isocyanurate (THEIC), tris (hydroxypropyl) isocyanurate, inositols or sugars, such as glucose, fructose or sucrose, sugar alcohols such as Sorbitol, mannitol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol, isomalt, trifunctional or higher polyetherols based on trifunctional or higher alcohols and ethylene oxide, propylene oxide and / or butylene oxide. These are glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, di (trimethylolpropane), 1, 2,4-butanetriol, 1, 2,6-hexanetriol, pentaerythritol,

Tris (hydroxyethyl) isocyanurate and their polyetherols based on ethylene oxide and / or propylene oxide are particularly preferred. It is also possible to use mixtures of at least trifunctional alcohols (C _x ). For example, one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular an at least trifunctional alcohol can be used. It represents a further feature according to the invention that the aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof is a mixture of at least two aliphatic, cycloaliphatic see, araliphatic or aromatic dicarboxylic acids (A2) or derivatives thereof. This feature and / or the presence of at least one component (B2), (Cx) and / or (D _y ) in the reaction mixture must be realized according to the invention. If component (A2) is used as a mixture of two dicarboxylic acids, their molar ratio may be from 5:95 to 50:50, preferably from 10:90 to 50:50 and particularly preferably from 20:80 to 50:50 ,

The process according to the invention can be carried out in bulk or in the presence of a solvent. Suitable solvents 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 a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, particularly suitable solvents in the absence of acidic catalysts are ethers, such as, for example, dioxane or tetrahydrofuran and ketones, for example methyl ethyl ketone and methyl isobutyl ketone.

The amount of solvent added is according to the invention at least 0.1% by weight, based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and particularly preferably at least 10 wt .-%. 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.

In a preferred embodiment, the reaction is carried out free of solvent.

For carrying out the process according to the invention, it is possible to work as an additive in the presence of a water-removing agent which is added at the beginning of the reaction. Suitable examples are molecular sieves, in particular molecular sieve 4A, 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, for example, to use a water separator in which the water is removed by means of an entraining agent. Furthermore, the separation can be effected by stripping, for example by passing a gas which is inert under the reaction conditions through the reaction mixture. mixed, if appropriate in addition to a distillation. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases.

The process according to the invention can be carried out in the absence of catalysts. However, it is preferable to work in the presence of at least one catalyst. These are preferably acidic inorganic, organometallic or organic catalysts or mixtures of several acidic inorganic, organometallic or organic catalysts. For the purposes of this document, acidic catalysts are Lewis acids, ie compounds according to Rompps Chemie-Lexikon, keyword "acid-base term", which can take up an electron pair in the valence shell of one of its atoms. Examples of acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, sulfates and hydrogen sulfates, such as sodium hydrogensulfate, 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 AI (OR ¹ ) 3 and titanates of the general formula Ti (OR ¹ ) 4 can be used as acidic inorganic catalysts, wherein the radicals R ^{1 may be} the same or different and are independently selected from each other

C 1 -C 20 -alkyl radicals, 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, n -Decyl, n-dodecyl, n-hexadecyl or n-octadecyl.

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 ¹ in Al (OR ¹ ) 3 or Ti (OR ¹ ) 4 are preferably identical and selected from n-butyl, isopropyl, 2-ethylhexyl, n-octyl, decyl or dodecyl.

Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R ¹ 2 SnO or Dialkylzinndiestern R ¹ 2 Sn (OR ²⁾ 2 wherein R ¹ is as defined above standing and can be identical or different. R ² may have the same meanings as R ¹ and additionally C 6 -C 12 aryl, for example phenyl, o-, m- or p-tolyl, xylyl or naphthyl. Each R ² may be the same or different. Examples of tin-organic catalysts are tin (II) n-octanoate,

Tin (II) 2-ethylhexanoate, tin (II) laurate, dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate. Also conceivable are antimony, bismuth. or organoaluminum catalysts.

Particularly preferred representatives of acidic organometallic catalysts are dibutyltin oxide, diphenyltin oxide and dibutyltin dilaurate.

Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as para-toluene sulfonic acid. It is also possible to use acidic ion exchangers as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups, which are crosslinked with about 2 mol% of divinylbenzene.

It is also possible to use combinations of two or more of the aforementioned catalysts. It is also possible to use those organic or organometallic or else inorganic catalysts which are present in the form of discrete molecules in immobilized form, for example on silica gel or on zeolites.

If it is desired to use acidic inorganic, organometallic or organic catalysts, preference is given to using from 1 to 10,000 ppm by weight of catalyst, more preferably from 2 to 5,000 ppm by weight, based on the total mass of the hydroxyl- and carboxy-containing compounds.

It is also possible according to the invention to use enzymes as catalysts, if their use is also less preferred.

Correspondingly usable enzymes are, for example, selected from hydrolases (EC 3.-.-.-), and among these, especially among the esterases (EC 3.1.-.-), lipases (EC 3.1.1.3), glycosylases (EC 3.2.-. -) and proteases (EC 3.4.-.-) in free or on a support chemically or physically immobilized form, preferably lipases, esterases or proteases and particularly preferably esterases (EC 3.1.-.-). Very particular preference is given to Novozyme 435 (lipase from Candida antarctica B) or lipase from Alcaligenes sp., Aspergillus sp., Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp., Burkholderia sp., Candida sp. Pseudomonas sp., Thermomyces sp. or porcine pancreas, particularly preferred are lipase from Candida antarctica B or from Burkholderia sp. The enzyme content in the reaction medium is generally in the range of about 0.1 to 10 wt .-%, based on the sum of the components used (A2), (B2), ß, ß, ß ', ß'-tetra (hydroxymethyl ) cycloalkanol, (C _x ) and (Dy). The process according to the invention is preferably carried out under an inert gas atmosphere, ie a gas which is inert under the reaction conditions, for example under carbon dioxide, combustion gases, nitrogen or noble gases, of which in particular argon can be mentioned. The inventive method is carried out at temperatures of 60 to 250 ⁰ C. If an enzyme is used as the catalyst, the reaction temperature is generally not more than 120 ^° C., preferably not more than 100 ^° C., and more preferably not more than 80 ^° C. If other than enzymes are used as catalysts, the reaction temperature is at least 160 ^° C., preferably 160 to 220 ^° C., and particularly preferably 160 to 190 ^° C.

The pressure conditions of the method according to the invention are generally uncritical. You can work at significantly reduced pressure, for example at 10 to 500 mbar. The process according to the invention can also be carried out 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. Preferably, the reaction is at reduced or atmospheric pressure, more preferably at atmospheric pressure.

The reaction time of the process according to the invention is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours and more preferably 1 to 12 hours.

If the reaction is carried out enzymatically, it is generally carried out at 0 to 100 ° C, preferably 20 to 80 ° C, particularly preferably 20 to 70 ⁰ C, most preferably 20 to 60 ° C. The reaction time depends, inter alia, on the temperature, the amount used and the activity of the enzyme catalyst and the required conversion and of the components. As a rule, 1 to 72 hours, preferably 3 to 36 and particularly preferably 3 to 24 hours are sufficient for this.

When reacting the components A2, B2, β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol, C _x and / or D _y , the ratio of the reactive groups in the reaction mixture is chosen such that a molar ratio of OH - Groups of carboxy groups or derivatives thereof from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, more preferably from 3: 1 to 1: 3 and most preferably from 2: 1 to 1: 2 sets.

The proportion of carboxy groups in component A2, based on the sum of the carboxy groups in components (A2) and (D _y ), is generally from 50 to 100 mol%, preferably from 70 to 100 mol%, particularly preferably from 80 to 100 mol%, most preferably 90 to 100 mol% and in particular 100 mol%. Of course, the latter is only true if component (Dy) is not present in the reaction mixture following the above proviso.

When calculating the proportion of hydroxy groups in the reaction, it should be taken into account that in the component according to the invention β, β, β ', β'-

Tetra (hydroxymethyl) cycloalkanol the secondary hydroxy group on the cycloalkanol under the specified reaction conditions is not or only slightly. Thus, for the reaction, β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol are in fact only to be regarded as tetrafunctional polyol.

The proportion of hydroxy groups of ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol based on the sum of the hydroxy groups in the components ß, ß, ß', ß'- tetra (hydroxymethyl) cycloalkanol, (B2) and ( C _x ) is generally 10 to 100 mol%, preferably 20 to 100 mol%, particularly preferably 30 to 100 mol%, very particularly preferably 40 to 100 mol% and in particular 50 to 100 mol%. Of course, 100 mol% of the component β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol can only be used if the above proviso is followed by the aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof is a mixture of at least two aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acids (A2) or derivatives thereof.

The proportion of hydroxyl groups in component (B2) based on the sum of the hydroxyl groups in the components β, β, β ', β'-tetra (hydroxymethyl) -cycloalkanol, (B2) and (Cx) is generally 0 to 50 mol %, preferably 0 to 40 mol%, particularly preferably 0 to 30 mol%, very particularly preferably 0 to 20 mol% and in particular 0 to 10 mol%. The proportion of hydroxyl groups in the component (C _x ) based on the sum of the hydroxyl groups in the components β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol, (B2) and (Cx) is generally 0 to 90 mol%, preferably 0 to 80 mol%, particularly preferably 0 to 70 mol%, very particularly preferably 0 to 60 mol% and in particular 0 to 50 mol%.

It should be noted that the sum of hydroxyl groups is always 100 mol%. After completion of the reaction, the highly functional highly branched and hyperbranched polyester can be easily isolated, for example by filtering off the catalyst and optionally removing the solvent, wherein the removal of the solvent is usually carried out at reduced pressure. Further suitable work-up methods are precipitation of the polymer after addition of water and subsequent washing and drying.

If necessary, the reaction mixture of a decolorization, for example by treatment with activated carbon or metal oxides, such as alumina, silica, magnesia, zirconia, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50 wt%, preferably 0.5 to 25 wt %, more preferably 1-10 wt% at temperatures of for example 10 to 200 ⁰ C, preferably 20 to 180 ⁰ C and particularly preferably 30 to 160 ⁰ C are subjected.

This can be done by adding the powdery or granular decolorizing agent to the reaction mixture and subsequent filtration or by passing the reaction mixture through a bed of decolorizing agent in the form of any suitable shaped body.

The decolorization of the reaction mixture can be carried out at any point in the work-up procedure, for example at the stage of the crude reaction mixture or after any pre-wash, neutralization, washing or solvent removal.

The reaction mixture can furthermore be subjected to prewashing and / or neutralization and / or after-washing, preferably only to neutralization. Optionally, neutralization and pre-wash can also be reversed in the order.

From the aqueous phase of the washes and / or neutralization, the desired products of value can be at least partially recovered by acidification and extraction with a solvent and used again. For pre-washing or washing the reaction mixture in a washing machine with a washing liquid, for example water or a 5 to 30 wt%, preferably 5 to 20, particularly preferably 5 to 15 wt% saline, potassium chloride, ammonium chloride, Sodium sulfate or ammonium sulfate solution, preferably water or saline.

The quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7. The washing or neutralization can be carried out, for example, in a stirred tank or in other conventional apparatuses, for example in a column or mixer-settler apparatus.

Processually, for washing or neutralization in the process according to the invention, all extraction and washing processes and apparatuses known per se can be used, e.g. those described in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed, 1999 Electronic Release, Chapter: Liquid - Liquid Extraction - Apparatus. For example, these can be one-stage or multistage, preferably single-stage extractions, and those in cocurrent or countercurrent mode, preferably countercurrent mode.

Preferably Siebboden- or packed packed columns, stirred or mixer-settler apparatuses, as well as pulsed columns or those are used with rotating internals.

Prewash is preferably used when metal salts, preferably organotin compounds, are used as catalyst (with).

A post-wash may be advantageous for removing base or salt traces from the neutralized reaction mixture.

For neutralization, the optionally prewashed reaction mixture, which may still contain small amounts of catalyst and / or carboxylic acid, with a 5 to 25, preferably 5 to 20, particularly preferably 5 to 15 wt% aqueous solution of a base such as alkali or Alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, preferably sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium hydrogencarbonate, calcium hydroxide, milk of lime, ammonia, ammonia or potassium carbonate, optionally containing 5-15% by weight of common salt, potassium chloride, ammonium chloride or ammonium sulfate may be added, particularly preferably with sodium hydroxide or sodium hydroxide solution, are neutralized. The degree of neutralization is preferably 5 to 60 mol%, preferably 10 to 40 mol%, particularly preferably 20 to 30 mol%, based on the monomers containing acid groups.

The addition of the base takes place in such a way that the temperature in the apparatus does not rise above 60 ⁰ C, preferably between 20 and 35 ⁰ C and the pH is 4-13. The removal of the heat of neutralization is preferably carried out by cooling the container by means of internal cooling coils or via a double wall cooling. The quantitative ratio of reaction mixture: neutralizing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7.

With regard to the apparatus, the above applies.

In a preferred embodiment, however, can be dispensed with a wash, neutralization and decolorization.

If a solvent is present in the reaction mixture, this can essentially be removed by distillation. Preference is given to optionally removed solvent after washing and / or neutralization from the reaction mixture, if desired, this can also be done before washing or neutralization. For this purpose, the reaction mixture can be mixed with such an amount of storage stabilizer that after removal of the solvent 100 - 500, preferably

200-500 and more preferably 200-400 ppm thereof are contained in the target ester (residue). The distillative removal of the main amount of optionally used solvent or low-boiling by-products takes place for example in a stirred tank with double wall heating and / or internal heating coils under reduced pressure, for example at 20-700 mbar, preferably 30-500 and more preferably 50-150 mbar and a temperature of 40-120 ^° C.

Of course, the distillation can also take place in a falling film or thin film evaporator. For this purpose, the reaction mixture, preferably several times in the circulation, under reduced pressure, for example at 20 - 700 mbar, preferably 30 to 500 and more preferably 50 - 150 mbar and a temperature of 40 - 80 ⁰ C passed through the apparatus.

Advantageously, an inert gas under the reaction conditions may be introduced into the distillation apparatus, for example, 0.1 to 1, preferably 0,2 - 0,8 and more preferably from 0.3 to 0.7 m ³ oxygen containing gas per m ³ reaction mixture and per hour.

The residual solvent content in the residue after distillation is generally below 5% by weight, preferably 0.5-5% and particularly preferably 1 to 3% by weight.

The separated solvent is condensed and preferably reused.

If necessary, in addition to or in place of the distillation, solvent stripping may be carried out. For this purpose, the product, which may still contain small amounts of solvent or low-boiling impurities, heated to 50 - 150 ⁰ C, preferably 80 - 150 ⁰ C and removed the remaining amounts of solvent with a suitable gas in a suitable apparatus. If necessary, a vacuum can also be applied to assist.

Suitable apparatuses are, for example, columns of a type known per se which contain the usual internals, e.g. Soils, beds or directed packings, preferably have beds. In principle, all standard installations are suitable as column internals, for example trays, packings and / or random packings. Of the trays, bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred; of the trays are those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids, preferred.

Also conceivable here is a falling film, thin film or wiped film evaporator, such as e.g. a Luwa, Rotafilm or Sambay evaporator, which can be equipped as a splash guard, for example, with a demister.

Suitable gases are inert under the stripping gases, especially those that are temperature-controlled at 50 to 100 ⁰ C.

The amount of stripping gas is for example 5 to 20, more preferably 10 to 20 and most preferably 10 to 15 m ^{3 of} stripping gas per m ^{3 of} reaction mixture and hour.

If necessary, the esterification mixture may be subjected to filtration at any stage of the work-up procedure, preferably after scrubbing / neutralization and any solvent removal, if necessary, to remove any precipitated traces of salts and any decolorizing agent present. Pre-washing or post-washing is preferably dispensed with, only one filtration step may be expedient. Likewise, neutralization is preferably dispensed with. The sequence of the steps prewash, after-wash, and solvent removal and filtration is arbitrary.

A further subject of the present invention are the highly functional, highly branched or hyperbranched polyesters obtainable by the process according to the invention. The polyesters according to the invention have a molecular weight M _n of at least 500, preferably at least 600 and more preferably at least 700 g / mol. The upper limit of the molecular weight M _n is preferably 100,000 g / mol, more preferably not more than 80,000 and most preferably not more than 30,000 g / mol.

The polydispersity and the number-average and weight-average molecular weight M _n and M w relate here to gel permeation chromatographic measurements using polymethyl methacrylate as standard and tetrahydrofuran, dimethyl acetamide or hexafluoroisopropanol as eluent. The method is described in the Analyst Taschenbuch Vol. 4, pages 433 to 442, Berlin 1984.

The polydispersity of the polyesters according to the invention is generally at least 1, 2, preferably at least 1, 4 and more preferably at least 1.5.

The polydispersity of the polyesters according to the invention is generally not more than 100, preferably not more than 75, more preferably not more than 50, very preferably not more than 40, in particular not more than 30 and especially not more than 15.

The polyesters according to the invention are usually very readily soluble, ie, at 25 ^° C., clear solutions with a content of up to 50% by weight, in some cases even up to 80% by weight, of the polyester according to the invention in tetrahydrofuran (THF), Ethyl acetate, n-butyl acetate, ethanol and many other solvents without the naked eye gel particles are detectable. This shows the low degree of crosslinking of the polyesters according to the invention.

The high-functionality hyperbranched and high-branched polyesters according to the invention are carboxy-terminated, carboxy- and hydroxy-terminated and are preferably hydroxy-terminated and can be used for the preparation of e.g. of adhesives, inks, coatings, foams, coatings and paints can be used advantageously.

A further aspect of the present invention is the use of the highly functional, highly branched and hyperbranched polyesters according to the invention for the preparation of polyaddition or polycondensation products, for example polycarbonates, polyurethanes, polyesters and polyethers. The use of the hydroxy-terminated high-functionality, highly branched and hyperbranched polyesters according to the invention for the production of polycarbonates, polyesters or polyurethanes is preferred. A further aspect of the present invention is the use of the highly functional highly branched and hyperbranched polyesters according to the invention and of the polyaddition or polyfunctional polyesters prepared from highly functional, highly branched and hyperbranched polyesters Polycondensation products as a component of printing inks, adhesives, coatings, foams, coatings and varnishes.

A further aspect of the present invention are printing inks, adhesives, laminations, foams, coatings and paints containing at least one high-functionality hyperbranched polyester according to the invention or polyaddition or polycondensation products prepared from the high-functionality, highly branched and hyperbranched polyesters of the invention characterized by good performance properties.

Another preferred aspect of the present invention are printing inks, in particular packaging inks for flexographic and / or gravure printing, comprising at least one solvent or a mixture of different solvents, at least one colorant, at least one polymeric binder and optionally further additives, wherein at least one of the polymeric binders is a highly branched and hyperbranched high-functionality polyester according to the invention.

The highly branched and hyperbranched polyesters according to the invention can also be used in admixture with other binders in the context of the present invention. Examples of further binders for the printing inks according to the invention include polyvinyl butyral, nitrocellulose, polyamides, polyurethanes, polyacrylates or polyacrylate copolymers. The combination of highly branched and hyperbranched polyesters with nitrocellulose has proved particularly advantageous. The total amount of all binders in the printing ink of the invention is usually 5 to 35 wt .-%, preferably 6 to 30 wt .-% and particularly preferably 10 to 25 wt .-% based on the sum of all components. The ratio of highly branched and hyperbranched polyester to the total amount of all binders is usually in the range of 30 wt .-% to 100 wt .-%, preferably at least 40 wt .-%, but the amount of highly branched and hyperbranched polyester as a rule 3% by weight, preferably 4% by weight and especially preferably 5% by weight should not be less than the sum of all constituents of the printing ink.

It can be used a single solvent or a mixture of several solvents. Suitable solvents in principle are the customary solvents for printing inks, in particular for packaging printing inks. Particularly suitable as solvents for the printing ink of the invention are alcohols such as ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol, substituted alcohols such as ethoxypropanol, esters such as ethyl acetate, isopropyl acetate, n-propyl or n-butyl acetate. As a solvent, water is also suitable in principle. Particularly preferred solvents are ethanol or mixtures, which consist predominantly of ethanol, and ethyl acetate. Among the solvents which are possible in principle, the person skilled in the art, depending on the solubility shade of the polyester and the desired properties of the ink a suitable choice. Usually, 40 to 80% by weight of solvent are used with respect to the sum of all constituents of the printing ink. As colorants, the usual dyes, in particular conventional pigments can be used. Examples are inorganic pigments such as titanium dioxide pigments or iron oxide pigments, interference pigments, carbon blacks, metal powders such as in particular aluminum, brass or copper powder, and organic pigments such as azo, phthalocyanine or isoindoline pigments. It is of course also Gemi- see various dyes or colorants can be used as well as soluble organic dyes. Usually, 5 to 25% by weight of colorant are used with respect to the sum of all constituents.

The packaging printing ink according to the invention may optionally comprise further additives and auxiliaries. Examples of additives and hydrogens are fillers such as calcium carbonate, aluminum oxide hydrate or aluminum or magnesium silicate. Waxes increase the abrasion resistance and serve to increase the lubricity. Examples are in particular polyethylene waxes, oxidized polyethylene waxes, petroleum waxes or ceresin waxes. Fatty acid amides can be used to increase the surface smoothness. Plasticizers serve to increase the elasticity of the dried film. Examples are phthalic acid esters such as dibutyl phthalate, diisobutyl phthalate, di-octyl phthalate, citric acid esters or esters of adipic acid. Dispersing agents can be used to disperse the pigments. In the case of the printing ink according to the invention, it is advantageously possible to dispense with adhesion promoters without the use of adhesion promoters being excluded therefrom. The total amount of all additives and auxiliaries usually does not exceed 20% by weight with respect to the sum of all constituents of the printing ink and is preferably 0-10% by weight.

The production of the packaging printing ink according to the invention can be carried out in a manner known in principle by intensive mixing or dispersion of the constituents in customary apparatuses, for example dissolvers, stirred ball mills or a three-roll mill. Advantageously, a concentrated pigment dispersion with a portion of the components and a portion of the solvent is first prepared, which is further processed later with other ingredients and further solvent to the finished ink.

A further preferred aspect of the present invention is printing inks which comprise at least one solvent or a mixture of different solvents, at least one polymeric binder and optionally further additives, at least one of the polymeric binders being a highly branched and hyperbranched high-functionality polyester according to the invention, as well as the use of the Inventive printing lacquers for priming, as a protective lacquer and for producing multilayer materials.

Naturally, the printing varnishes according to the invention contain no colorants, but apart from that they have the same constituents as the already described printing inks according to the invention. The quantities of the other components increase accordingly.

Surprisingly, by the use of printing inks, in particular packaging printing inks, and printing varnishes with binders based on highly branched and hyperbranched polyesters, multilayer materials with outstanding adhesion between the individual layers are obtained. The addition of adhesion agents is no longer necessary. It is particularly surprising that without adhesion promoters even better results can be achieved than if adhesion promoters are added. Especially on polar films the adhesion could be significantly improved.

The polyesters according to the invention can be used as binder component, for example in coating compositions, optionally together with other hydroxyl- or amino-containing binders, for example with hydroxy (meth) acrylates, hydroxystyryl (meth) acrylates, linear or branched polyesters, polyethers, polycarbonates, Melamine resins or urea-formaldehyde resins, together with carboxy- and / or hydroxyl-functional compounds, for example with isocyanates, capped isocyanates, epoxides, carbonates and / or aminoplasts, preferably isocyanates, epoxides or aminoplasts, particularly preferably with isocyanates or epoxides, and most preferably with isocyanates.

Isocyanates are, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an average NCO functionality of at least 1, 8, preferably 1, 8 to 5 and particularly preferably 2 to 4, and their isocyanurates, oxadiazinetriones, iminooxadiazinediones, ureas, biurets, amides , Urethanes, allophanates, carbodiimides, uretonimines and uretdiones.

The diisocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates, such as 1, 4-, 1 , 3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-iso-cyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) , 1, 3 or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methyl- thylcyclohexane and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their mixtures of isomers, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and mixtures of isomers thereof, mixtures of 2,4 ^' , 4,4 ^' - and oligomeric diisocyanatodiphenylmethanes (polymer-MDI), 1, 3 or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, diphenyl-4,4'- diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate. There may also be mixtures of said diisocyanates.

Suitable polyisocyanates are polyisocyanates having isocyanurate groups, uretdione diisocyanates, biisocyanate-containing polyisocyanates, polyisocyanates containing urethane or allophanate groups, oxadiazinetrione groups or iminooxadiazinedione-containing polyisocyanates, carbodiimide- or uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates, cycloaliphatic Diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The diisocyanates and polyisocyanates which can be used preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of from 1 to 60% by weight, based on the diisocyanate and polyisocyanate (mixture), preferably from 2 to 60% by weight and especially preferably 10 to 55% by weight.

Preferred are aliphatic or cycloaliphatic di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof. Particularly preferred are hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) - cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, very particularly preferred are isophorone diisocyanate and hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate. Further preferred

1) isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl Isocyanurates, which are cyclic trimers of diisocyanates, or mixtures with their higher, more than one isocyanurate homologues. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average

NCO functionality from 2.6 to 4.5.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).

3) biuret-containing polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs. These biuret polyisocyanates generally have an NCO content of 18 to 23 wt .-% and an average NCO functionality of 2.8 to 4.5.

4) polyisocyanates containing urethane and / or allophanate groups with aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with monohydric or polyhydric alcohols, e.g. Methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol

(Lauryl alcohol), 2-ethylhexanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1, 3-Propandiolmono- methyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol or polyhydric alcohols, as listed above in the polyesterols, or their Mixtures can be obtained. These urethane and / or allophanate polyisocyanates generally have a

NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5. 5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetri onocyanate-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.

7) carbodiimide and / or uretonimine-modified polyisocyanates.

The polyisocyanates 1) to 7) can be used in a mixture, if appropriate also in a mixture with diisocyanates.

The isocyanate groups of the di- or polyisocyanates may also be present in capped form. Suitable capping agents for NCO groups are e.g. Oximes, phenols, imidazoles, pyrazoles, pyrazolinones, triazoles, diketopiperazines, caprolactam, malonic acid esters or compounds as mentioned in the publications of Z.W. Wicks, Prog. Org. Coat. 3 (1975) 73-99 and Prog. Org. Coat 9 (1981), 3-28, by DA Wicks and Z.W. Wicks, Prog. Org. Coat. 36 (1999), 148-172 and Prog. Org. Coat. 41 (2001), 1-83 and in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 2, 61 ff. Georg Thieme Verlag, Stuttgart 1,963th

By blocking or blocking agents are meant compounds which convert isocyanate groups into blocked (capped or protected) isocyanate groups, which then do not exhibit the usual reactions of a free isocyanate group below the so-called deblocking temperature. Such compounds having blocked isocyanate groups are commonly used in dual-cure or powder coatings which are finally cured by isocyanate group cure.

Epoxy compounds are those having at least one, preferably having at least two, particularly preferably two to ten epoxide groups in the molecule.

Suitable examples include epoxidized olefins, glycidyl esters (eg glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or aromatic polyols. Such products are commercially available in large numbers. Polyglycidyl compounds of the bisphenol A, F or B type and glycidyl ethers of polyhydric alcohols, for example of butanediol, of 1,6-hexanediol, of glycerol and of pentaerythritol, are particularly preferred. Examples of such polyepoxide compounds are Epikote® 812 (epoxy value: approx. 0.67 mol / 100g) and Epikote® 828 (epoxy value: approx. 0.53 mol / 100g), Epikote® 1001, Epikote® 1007 and Epikote® 162 (Epoxy value: approx. 0.61 mol / 100g) from the company Resolution, Rutapox® 0162 (epoxy value: about 0.58 mol / 100 g), Rütapox® 0164 (epoxy value: about 0.53 mol / 100 g) and Rütapox® 0165 (epoxy value: about 0.48 mol / 100 g) from Bakelite AG, Araldit® DY 0397 (epoxy value: about 0.83 mol / 100 g) from Vantico AG. Carbonate compounds are those having at least one, preferably having at least two, preferably two or three carbonate groups in the molecule, which preferably contain terminal C 1 -C 20 -alkyl carbonate groups, particularly preferably terminal C 1 -C 4 -alkyl carbonate groups, very particularly preferably terminal methyl carbonate, ethyl carbonate or n-butyl carbonate ,

Also contemplated are compounds having active methylol or alkylalkoxy groups, especially methylalkoxy groups, such as etherified reaction products of formaldehyde with amines such as melamine, urea, etc., phenol / formaldehyde adducts, siloxane or silane groups, and anhydrides, e.g. in US 5,770,650 are described.

Among the technically widespread and known, preferred aminoplasts are particularly preferred urea resins and melamine resins, such. Urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-urea-formaldehyde resins, usable.

Suitable urea resins are those which are obtainable by reacting ureas with aldehydes and can be modified if appropriate. As ureas, urea, N-substituted or N, N'-disubstituted ureas are suitable, e.g. N-methylurea, N-phenylurea, N, N'-dimethylurea, hexamethylenediurea, N, N'-diphenylurea, 1,2-ethylenediurea, 1,3-propylenediurea, diethylenetriurea, dipropylenetriurea, 2-hydroxypropylenediurea, 2- imidazolidinone (ethyleneurea), 2-oxohexahydropyrimidine (propyleneurea) or 2-oxo-5-hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).

Urea resins may optionally be partially or fully modified, e.g. by reaction with mono- od. Polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionic modified urea resins), particularly suitable are the alcohol-modified urea resins.

Possible alcohols for the modification are C 1 -C 6 -alcohols, preferably C 1 -C 4 -alkyl alcohols and in particular methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol and sec-butanol. Suitable melamine resins are those which are obtainable by reacting melamine with aldehydes and which may optionally be partially or completely modified. Particularly suitable aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and glyoxal.

Melamine-formaldehyde resins are reaction products of the reaction of melamine with aldehydes, e.g. the o.g. Aldehydes, especially formaldehyde. Optionally, the resulting methylol groups are modified by etherification with the abovementioned monohydric or polyhydric alcohols. Furthermore, the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites. By the action of formaldehyde on mixtures of melamine and urea or on mixtures of melamine and phenol, melamine-urea-formaldehyde resins or melamine-phenol-formaldehyde resins which can also be used according to the invention are also produced according to the invention. The production of said aminoplasts is carried out according to known methods.

Particular examples are melamine-formaldehyde resins, including monomeric or polymeric melamine resins, and partially or fully alkylated melamine resins, urea resins, e.g. Methylol ureas such as formaldehyde-urea resins, alkoxy ureas such as butylated formaldehyde-urea resins, but also N-methylol acrylamide emulsions, isobutoxymethylacrylamide emulsions, polyanhydrides, such as. Polysuccinic anhydride, and siloxanes or silanes, e.g. Dimethyldimethoxysilanes.

Particularly preferred are aminoplast resins such as melamine-formaldehyde resins or formaldehyde-urea resins.

The paints in which the polyesters according to the invention can be used may be conventional basecoats, water-based paints, essentially solvent-free and water-free liquid basecoats (100% systems), essentially solvent-free and water-free solid basecoats (powder coatings and pigmented powder coatings ) or substantially solvent-free, possibly pigmented powder coating dispersions (powder slurry basecoats) act. They can be thermal, radiation or DuaICure-curable, and self-crosslinking or externally crosslinking. If the polyesters according to the invention are used in powder coatings, these powder coatings may contain, in addition to the hyperbranched polyesters, at least one binder (O) and at least one crosslinker (V) included. Optionally, the powder coatings may also contain other additives (F), such as in particular pigments.

As binders (O), crosslinkers (V) and additives (F) it is possible to use compounds such as described in WO 2007/134736, page 31, line 33 to page 32, line 9 and page 33, line 16 to page 57 , Line 3, which is hereby incorporated by reference into the present disclosure.

If the polyesters according to the invention are used in waterborne paints, the polyesters according to the invention are as a rule very particularly preferably present in an amount fraction of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight 0.4 to 5% by weight and in particular 0.5 to 3% by weight, based on the solids content of the aqueous basecoat materials. Furthermore, these aqueous basecoats may contain conventional lacquer solvents, for example in a proportion of preferably less than 20% by weight, more preferably less than 15% by weight.

These are conventional lacquer-based solvents, these can be obtained, for example, from the preparation of the binders or the polyesters or are added separately. Examples of such solvents are monohydric or polyhydric alcohols, e.g. Propanol, butanol, hexanol; Glycol ethers or esters, e.g. Diethylene glycol di-C 1 -C 5 alkyl ethers, dipropylene glycol di-C 1 -C 5 -alkyl ethers, ethoxypropanol, butylglycol; Glycols e.g. Ethylene glycol and / or propylene glycol, and their di- or trimers, N-alkylpyrrolidones, such as. N-methylpyrrolidone and ketones such as methyl ethyl ketone, acetone, cyclohexanone; aromatic or aliphatic hydrocarbons, e.g. Toluene, XyIoI or linear or branched aliphatic Cβ - Ci2 hydrocarbons.

The waterborne basecoats have, for example, solids contents of 10 to 50% by weight; for effect waterborne basecoats, for example, they are preferably 15 to 30% by weight; for unicolour waterborne basecoats, they are preferably higher, for example 20 to 45% by weight.

When calculating the ratio of pigment to binder, the sum of the proportions by weight of coloring pigments, effect pigments and / or fillers is related to the sum of the proportions by weight of solid binder, solid paste resin and solid crosslinker in the finished aqueous basecoat.

In addition to the hyperbranched polyester according to the invention, the aqueous basecoats also contain at least one binder (O) and at least one crosslinker (V). Optionally, the waterborne basecoats can additionally contain further additives (F) and / or pigments and / or effect pigments (G). As binders (O), crosslinkers (V), additives (F) and pigments (G), it is possible to use compounds such as described in WO 2008/009516, page 24, line 4 to page 44, line 10, which are hereby incorporated by reference Reference is part of the present disclosure.

The highly functional highly branched polyesters formed by the process according to the invention are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with acid groups. They usually dissolve well in various 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, di - methylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate. In the context of this invention, a highly functional polyester is to be understood as meaning a product which, in addition to the ester groups which link the polymer backbone, also has at least three, preferably at least six, particularly preferably at least ten functional groups end- and / or pendent. The functional groups are acid groups and / or OH groups. The number of terminal or pendant functional groups is in principle not limited to the top, but products with a very high number of functional groups may have undesirable properties, such as high viscosity. The high-functionality polyesters of the present invention generally have not more than 500 terminal and / or pendant functional groups, preferably not more than 100 terminal and / or pendant functional groups.

In one embodiment of the invention, the polyester of the present invention can be prepared by reacting in a first phase of the reaction, i. For example, during the first half of the total reaction time, preferably during the first quarter, and more preferably during the first 10% of the total reaction time, no or only a small portion of the total amount of the polyhydric alcohol in the reaction, for example 0 to 90%, preferably 0 to 75%, more preferably 10 to 66%, and most preferably 25 to 50%. Under polyhydric alcohol, the sum of ß, ß, ß ', ß'-

Tetra (hydroxymethyl) cycloalkanol and optionally the x-valent alcohol C _x denotes.

The remaining amount of polyhydric alcohol is not used in the reaction until the above first phase of the reaction has expired. In a further preferred embodiment of the invention, when at least one y-valent carboxylic acid D _{y is used} in the reaction, the polyester according to the invention can be prepared by preference in a first phase of the reaction, ie for example during the first half of the total reaction time during the first quarter, and more preferably during the first 10% of the total reaction time, no or only a small part of the total amount of the y-valent carboxylic acid D _{y is used} in the reaction, for example 0 to 90%, preferably 0 to 75%, more preferably 10 to 66%, and most preferably 25 to 50%.

The remaining amount of y-valent carboxylic acid D _y is only used in the reaction when the above-mentioned first phase of the reaction has expired.

In a further preferred embodiment of the invention, when at least one dihydric alcohol B2 is used in the reaction, the polyester of the invention may be prepared by reacting in a first phase of the reaction, i. For example, during the first half of the entire reaction time, preferably during the first quarter and more preferably during the first 10% of the total reaction time, no or only a small part of the total amount of dihydric alcohol B2 is used in the reaction, for example 0 to 90%. preferably 0 to 75%, more preferably 10 to 66% and most preferably 25 to 50%. The remaining amount of dihydric alcohol B2 is only used in the reaction when the above-mentioned first phase of the reaction has expired. In a further preferred embodiment of the invention, the polyester of the invention can be prepared by reacting in a first phase of the reaction, i. for example, during the first half of the total reaction time, preferably during the first quarter, and more preferably during the first 10% of the total reaction time, no or only a small portion of the total amount of dibasic carboxylic acid A2 in the reaction, for example 0 to 90%, is preferred 0 to 75%, more preferably 10 to 66% and most preferably 25 to 50%.

The remaining amount of dibasic carboxylic acid A2 is not used in the reaction until the abovementioned first phase of the reaction has run its course.

In a further preferred embodiment, the polyesters according to the invention may have, in addition to the functional groups already obtained by the reaction, further functional groups. Functionalization can take place during the molecular weight build-up or else subsequently, ie after completion of the actual reaction of the components A2, B2, β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol, C _x and / or D _y . This means that the conversion of the components A2, B2, ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol, C _x and / or D _y at least 75%, preferably at least 80, more preferably at least 85, most preferably at least 90, in particular at least 95 and specifically to at least 97% completed. Functionalization with saturated or unsaturated monocarboxylic acids during the molecular weight build-up is less preferred.

If components are added before or during the molecular weight build-up which have other functional groups or functional elements in addition to hydroxyl or carboxy groups, a polyester polymer having randomly distributed functionalities other than the carboxy or hydroxy groups is obtained.

For example, functional groups can also be ether groups, carbonate groups, urethane groups, urea groups, thiol groups, thioether groups, thioester groups, keto or aldehyde groups, mono-, di- or trisubstituted amino groups, nitrile or isonitrile groups, carboxamide groups, sulfonamide groups. groups, silane groups or siloxane groups, sulfonic acid, sulfenic acid or sulfinic acid groups, phosphonic acid groups, vinyl or allyl groups or lactone groups. Such effects can be achieved, for example, by addition of functionalized building blocks E as compounds during the polycondensation which, in addition to or instead of hydroxyl groups or carboxy groups, carry at least one further functional group or functional elements which react in an analogous manner as hydroxyl groups or carboxy groups. Examples thereof are mercapto groups, primary, secondary or tertiary amino groups, ether groups, carbonyl groups, sulfonic acids or derivatives of sulfonic acids, sulfinic acids or derivatives of sulfinic acids, phosphonic acids or derivatives of phosphonic acids, phosphinic acids or derivatives of phosphinic acids, silane groups, siloxane groups. Preference is given to the functional groups which react analogously to hydroxyl groups, selected from the group consisting of primary amino groups and secondary amino groups, preferably primary amino groups. Preference is given to the functional groups which react analogously to carboxy groups, selected from the group consisting of sulfonic acids and

Phosphonic acids, preferably sulfonic acids. For modification by means of amide groups, for example ethanolamine, propanolamine, Isopropano- can be in the esterification lamin, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2 ^'- aminoethoxy) ethanol or higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine additionally use. Mercaptoethanol can be used for the modification with mercapto groups, for example. Tertiary amino groups can be produced, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine. Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols. Long-chain alkyl radicals can be introduced by reaction with long-chain alkanediols, and the reaction with alkyl or aryl diisocyanates generates polyesters having aryl and urethane groups.

Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polyester in an additional process step with a suitable functionalizing reagent which can react with the OH and / or carboxy groups of the polyester.

A functionalization of hydroxyl-containing polyesters according to the invention with saturated or unsaturated, aliphatic, cycloaliphatic, araliphatic or aromatic monocarboxylic acids F may preferably be carried out subsequently, ie after completion of the actual reaction of the components A2, B2, C _x and / or D _y in a separate step. Suitable saturated monocarboxylic acids F may comprise 1 to 30 carbon atoms, preferably 2 to 30, particularly preferably 4 to 25, very particularly preferably 6 to 20 and in particular 8 to 20 carbon atoms.

Examples of suitable saturated monocarboxylic acids F are formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, 2-ethylhexanoic acid, octanoic acid, isononanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid , Arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, α- or ß-naphthalic acid or mixtures of these acids.

Suitable α, β-unsaturated monocarboxylic acids F may comprise 3 to 20 carbon atoms, preferably 3 to 10, particularly preferably 3 to 6, very particularly preferably 3 to 5 and in particular 3 to 4 carbon atoms. Examples of suitable α, ß-unsaturated monocarboxylic acids F are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid or crotonic acid, preferred are acrylic acid, methacrylic acid, particularly preferred is acrylic acid.

The reaction with saturated or unsaturated monocarboxylic acids F can be carried out instead of the carboxylic acids with their derivatives, for example with their anhydrides, chlorides or esters, preferably with their anhydrides or esters, especially that is preferred with their esters with C 1 -C 4 -alkyl alcohols, very particularly preferably with their methyl esters.

A reaction in the sense of esterification can be carried out, for example, in the presence of at least one esterification catalyst, for example sulfuric acid, aryl or alkylsulfonic acids or mixtures thereof. Examples of arylsulfonic acids are benzenesulfonic acid, para-toluenesulfonic acid or dodecylbenzenesulfonic acid, examples of alkylsulfonic acids are methanesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid. Strongly acidic ion exchangers or zeolites can also be used as esterification catalysts. Preference is given to sulfuric acid and ion exchanger.

The reaction temperature is generally from 40 to 160 ⁰ C, it may be sensible, while removing arising of the reaction water with the aid of an azeotroping solvent, such as n-pentane, n-hexane, n-heptane, cyclohexane, Methylcyclohexane, benzene, toluene or xylene.

If the water contained in the reaction mixture is not removed via an azeotroping solvent, it is possible to remove it by stripping with an inert gas, preferably an oxygen-containing gas, more preferably with air or lean air.

A reaction in the sense of a transesterification can be carried out, for example, in the presence of at least one transesterification catalyst, for example metal chelate compounds of, for example, As hafnium, titanium, zirconium or calcium, alkali metal and Magnesiumalkohola- te, organic tin compounds or calcium and lithium compounds, for example, oxides, hydroxides, carbonates or halides, but preferably titanium, magnesium or aluminum.

The alcohol released in the transesterification can be removed, for example, by distillation, stripping or applying a vacuum.

To suppress polymerization in the reaction of α, ß-unsaturated carboxylic acids or derivatives thereof, it may be useful to work in the presence of commercially available polymerization inhibitors, which are known in the art per se.

Such esters of α, β-unsaturated carboxylic acids with the polyesters according to the invention can be used, for example, in radiation-curable coating compositions. Hydroxy-containing high-functionality, high or hyperbranched polyesters can be obtained, for example, by addition of molecules containing isocyanate groups be modified. For example, polyesters containing urethane groups can be obtained by reaction with alkyl or aryl isocyanates.

Furthermore, hydroxyl-containing high-functionality polyesters can also be converted into highly functional polyester-polyether polyols by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or isobutylene oxide. These compounds can then be obtained, for example, water-soluble.

The polyesters obtainable according to the invention generally have a viscosity of not more than 100 Pa.s (measured at 80 ^° C. according to DIN EN 3219).

The polyesters obtainable according to the invention have a sum of acid number according to DIN 53402 and OH number according to DIN 53240, part 2 of up to 800 mg KOH / g, preferably up to 750, more preferably up to 700 and very particularly preferably up to 600 mg KOH /G.

The OH number according to this standard is preferably up to 400, particularly preferably up to 300 and very particularly preferably up to 250 mg KOH / g.

The polyesters obtainable according to the invention generally have a glass transition temperature of -40 to 140 ^° C., preferably -30 to 120 ^° C., particularly preferably -20 to 100 ^° C., and very particularly preferably -20 to 90 ^° C.

The glass transition temperature T ₉ is determined by DSC (Differential Scanning Calorimetry) according to ASTM 3418/82.

In a preferred embodiment of the present invention, polyesters according to the invention which have a T ₉ from -20 to 70 ^° C. are used in printing inks, since in this case a good adhesion of the printing ink to the substrate is obtained in combination with blocking resistance and optionally adhesion to a cover layer becomes.

In a preferred embodiment of the present invention, such polyesters according to the invention which have a glass transition temperature T ₉ of at least 0 ^° C. are used in coating compositions and paints. This range of glass transition temperature is advantageous for achieving, for example, sufficient paint hardness and chemical resistance.

Examples

General remarks: The molecular weights were determined by gel permeation chromatography (GPC) (eluent: THF standard: PMMA).

The acid number was determined in each case according to DIN 53402. The OH number (mg KOH / g) was determined on the basis of DIN 53240, Part 2.

The determination of the glass transition temperature was carried out by means of differential scanning calorimetry (DSC). The sample was cooled to -30 ⁰ C and heated in steps of 10 ° C / min. The second heating curve was evaluated. The octadecenylsuccinic anhydride used is a technical mixture of the positional isomers with respect to the double bond.

Comparative Example 1 Into a 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser-cooled condenser were added 110.1 g (0.50 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol and 109.6 g (0.75 mol) of adipic acid, and 0.02 g (91 ppm) of di-n-butyltin dilaurate. Under nitrogen gassing, the mixture was heated to 160 ⁰ C and kept under stirring for 1.5 h at this temperature, with water of reaction was deposited over the descending condenser. After an amount of 13.7 g of water had been separated, the reaction mixture was cooled to room temperature.

The polymer according to the invention was obtained in the form of a pale yellow resin.

The following key figures were determined:

Acid number = 123 mg KOH / g polymer

OH number = 202 mg KOH / g polymer

M _n = 695 g / mol, M _w = 66350 g / mol

T ₉ = 6.8 ⁰ C

Example 1 :

Into a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with condenser 70.0 g (0.32 mol)

2,2,6,6-tetramethylolcyclohexan-1-ol, 34.8 g (0.24 mol) of adipic acid and 83.2 g (0.24 mol) of octadecenyl succinic anhydride and 0.02 g (106 ppm) of n-butyltin dilaurate added. Under nitrogen the mixture was heated to 160 ⁰ C and kept under stirring for 100 min at this temperature, with reaction onswasser was deposited on the descending condenser. After a quantity of 4.2 g of water had been deposited, the reaction mixture was cooled to room temperature. The polymer according to the invention was obtained in the form of a yellow resin.

The following key figures were determined:

Acid number = 106 mg KOH / g polymer

OH number = 129 mg KOH / g polymer

M _n = 905 g / mol, M _w = 5980 g / mol

T ₉ = 9.5 ⁰ C

Example 2:

In a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with collector, 39.0 g (0.18 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol, 23.8 g (0 , 18 mol) of trimethylolpropane and 77.8 g (0.53 mol) of adipic acid and 0.02 g (142 ppm) of di-n-butyltin dilaurate.

Under nitrogen gassing, the mixture was heated to 160 ^° C. and maintained at this temperature with stirring for 1 h, with water of reaction being deposited via the descending condenser. After an amount of 3.6 g of water had been deposited, the reaction mixture was cooled to room temperature.

The following key figures were determined:

Acid number = 151 mg KOH / g polymer

OH number = 291 mg KOH / g polymer

M _n = 810 g / mol, M _w = 8160 g / mol

T ₉ = -16.3 ⁰ C

Example 3:

In a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with collector, 70.0 g (0.32 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol, 13.9 g (0 , 10 mol) of adipic acid and 58.8 g (0.38 mol) of hexahydrophthalic anhydride were admixed with 0.02 g (140 ppm) of di-n-butyltin dilaurate.

Under nitrogen and stirring the mixture for 3h at 160 was - heated 170 ⁰ C, wherein water of reaction was deposited on the descending condenser. After the acid value of the reaction mixture had fallen to 110 mg KOH / g polymer, the reaction was terminated by cooling to room temperature.

The polymer according to the invention was obtained in the form of a pale yellow solid. The following parameters were determined: acid number = 105 mg KOH / g polymer

OH number = 200 mg KOH / g polymer

M _n = 479 g / mol, M _w = 11454 g / mol T ₉ = 80 ^° C.

Example 4:

In a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with collector, 100.0 g (0.45 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol, 6.6 g (0.05 mol) of adipic acid and 98.0 g (0.63 mol) of hexahydrophthalic anhydride with 0.02 g (140 ppm) of di-n-butyltin dilaurate.

Under nitrogen and stirring the mixture for 2h at 160 was - 170 ⁰ C ER- hitzt wherein reaction water was deposited on the descending condenser.

After the acid value of the reaction mixture had fallen to 120 mg KOH / g polymer, the reaction was terminated by cooling to room temperature. The polymer according to the invention was obtained in the form of a pale yellow solid.

The following key figures were determined:

Acid number = 116 mg KOH / g polymer

OH number = 203 mg KOH / g polymer

M _n = 479 g / mol, M _w = 3704 g / mol

T ₉ = 80 ^° C.

Example 5:

In a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with collector, 100.0 g (0.45 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol, 33.2 g (0 , 23 mol) of adipic acid and 70.0 g (0.45 mol) of hexahydrophthalic anhydride were added with 0.02 g (100 ppm) of di-n-butyltin dilaurate.

Under nitrogen gassing and stirring, the mixture was heated to 170 ^° C for 3 hours, with water of reaction being deposited over the descending condenser. After the acid number in the reaction mixture had fallen to 16 mg KOH / g polymer, the reaction was terminated by cooling to room temperature.

The polymer according to the invention was obtained in the form of a pale yellow solid.

The following key figures were determined:

Acid number = 106 mg KOH / g polymer

OH number = 233 mg KOH / g polymer

M _n = 377 g / mol, M _w = 8579 g / mol

T ₉ = 66 ^° C.

Example 6:

100.0 g (0.45 mol) were placed in a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with receiver. 2,2,6,6-tetramethylolcyclohexan-1-ol, 165.8 g (1.13 mol) of adipic acid and 47.3 g (0.45 mol) of neopentyl glycol with 0.02 g (64 ppm) of di-n- butyltin dilaurate added.

Under nitrogen and stirring the mixture for 3h at 160 was - heated 170 ⁰ C, wherein water of reaction was deposited on the descending condenser. After the acid number in the reaction mixture had fallen to 72 mg KOH / g polymer, the reaction was terminated by cooling to room temperature.

The following parameters were determined: acid number = 68 mg KOH / g polymer

OH number = 236 mg KOH / g polymer

M _n = 826 g / mol, M _w = 11317 g / mol

T ₉ = -15 ⁰ C. Example 7

In a 500 ml round bottom flask equipped with stirrer, internal thermometer, gas inlet tube and descending condenser with collector, 100.0 g (0.45 mol) of 2,2,6,6-tetramethylolcyclohexan-1-ol, 39.1 g (0 , 23 mol) of cyclohexane-1, 4-dicarboxylic acid and 70.0 g (0.45 mol) of hexahydrophthalic anhydride with 0.02 g (96 ppm) of di-n-butyltin dilaurate.

Under nitrogen and stirring the mixture for 1, 5h at 160 was - 170 ⁰ C., whereby the reaction, water was deposited on the descending condenser. After the acid value in the reaction mixture had fallen to 120 mg KOH / g polymer, the reaction was terminated by cooling to room temperature.

The following key figures were determined:

Acid number = 119 mg KOH / g polymer

OH number = 214 mg KOH / g polymer

M _n = 322 g / mol, M _w = 3676 g / mol

T ₉ = 86 ⁰ C

Application Comparative Experiments: Test Method:

Lacquer films were stored for 24 h at 23 ± 2 ⁰ C and 50 ± 10% humidity.

Scratch Resistance: Scratch resistance was tested by rubbing with a 1-by-1-cm scotch-brite nonwoven (Scotchbrite®, 7448 type S ultrafine) at a load of 500 g over the paint surface. The gloss of the paint was determined by means of a micro TRI-Gloss measuring device. The decrease in gloss after 10 and 50 double strokes (dH) can be considered as a measure of the scratch resistance of the paints. After 50 double strokes, the coatings were incubated for 1 h stored and then the gloss is determined as a measure of the reflow capability again at 60 ⁰ C and 12 h at room temperature.

To determine the dust-drying time, the paint surface was touched with a cotton swab, the paint is then considered to be dust-dry, when no cotton sticks to the surface.

To test the drying behavior of the paints, a hopper filled with approx. 60-8Og of sand and equipped with wheels is pulled over a lacquer-coated glass plate at a constant feed rate. The feed rate is 1 cm / h. After completion of the tests, the plate is freed from loose sand. Sand drying is the period of time between the beginning of the test and the last permanent adhesion of the grains of sand. The through-drying is determined as the time in which the wheels of the funnel still leave a trace in the paint.

The block resistance was determined according to DIN EN 13523-24.

From the polyesters of the above examples, 60% solutions were prepared in butyl acetate and these formulations were used as such in the following performance tests in the amounts indicated in the table.

For this purpose, 60 g of polyester were mixed with 40 g of butyl acetate with stirring for about one hour. The sample according to Example 1 gave a homogeneous and

transparent solution. The sample according to Comparative Example 1 was hardly soluble and the final mixture was cloudy with gel-like particles and therefore could not be used further in the performance tests.

rt: room temperature

Joncryl® 922: Polyacrylatol from BASF with OH number 140 mg KOH / g Basonat® HL 100 from BASF SE, Ludwigshafen: polyisocyanate containing isocyanurate groups and based on hexamethylene diisocyanate having an NCO content in accordance with DIN EN ISO 1909 of 21.5- 22.5%

Claims

claims

1. Highly functional, highly branched or hyperbranched polyesters having a molecular weight M _n of at least 500 g / mol and

a polydispersity M _w / M _n of 1, 2 - 100 obtainable by

implementation

at least one aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof and

optionally at least one divalent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B2) which has 2 OH groups, - at least one β, β, β ', β'-tetra (hydroxymethyl) cycloalkanol or at least one β, β, β ', ß'-tetra (hydroxymethyl) cycloalkanol containing reaction mixture,

optionally at least one x-hydric aliphatic, cycloaliphatic, aliphatic or aromatic alcohol (C _x ) which has more than two OH groups and x is a number greater than 2, preferably between 3 and 8, particularly preferably between 3 and 6, very particularly preferably from 3 to 4 and in particular 3, where the alcohol (C _x ) differs from β, β, β ', β'-tetra (hydroxymethyl) -cycloalkanol,

optionally at least one aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid (D _y ) or its derivative having more than two acid groups and y is a number greater than 2, preferably between 3 and 8, more preferably between 3 and 6, most preferably of 3 to 4 and in particular 3,

- in each case optionally in the presence of further functionalized units E and

optionally followed by reaction with a monocarboxylic acid F, wherein the ratio of the reactive groups in the reaction mixture is selected such that a molar ratio of OH groups to carboxy groups or their derivatives of 5: 1 to 1: 5, preferably 4: 1 to 1: 4, particularly preferably from 3: 1 to 1: 3 and very particularly preferably from 2: 1 to 1: 2 represents, and the proportion of hydroxy groups of ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol based on the sum of the hydroxy groups in the components ß, ß, ß', ß'-tetra (hydroxymethyl) cycloalkanol, (B2 ) and (C _x ) is 10 to 100 mol%, with the proviso that

- At least one of the components (B2), (C _x ) and (D _y ) in the reaction mixture to at least 0.1% by weight, based on the sum of alller components (A) to (F), is present and / or

- It is in the aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof is a mixture of at least two aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acids (A2) or derivatives thereof.

2. Highly functional, highly branched or hyperbranched polyesters according to claim 1, characterized in that the compound (A2) is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, octadecenylsuccinic acid, maleic acid, sebacic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or their mono- or dialkyl esters or anhydrides.

3. Highly functional, highly branched or hyperbranched polyesters according to claim 1 or 2, characterized in that the compound (B2) is selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol , 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2, 1, 3 and

1, 4-cyclohexanediol, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

4. Highly functional, highly branched or hyperbranched polyesters according to any one of the preceding claims, characterized in that the ß, ß, ß ', ß'- tetra (hydroxymethyl) cycloalkanol is selected from the group consisting of 2,2,6,6- Tetrakis (hydroxymethyl) cyclohexan-1-ol, 2,2,5,5-tetrakis (hydroxymethyl) cyclopentan-1-ol, 2,2,8,8-tetrakis (hydroxymethyl) cyclooctan-1-ol and 2, 2,12,12-tetrakis (hydroxymethyl) cyclododecan-1-ol.

5. Highly functional, highly branched or hyperbranched polyesters according to any one of the preceding claims, characterized in that the compound (C _x ) is selected from the group consisting of glycerol, diglycerol, triglycerol,

Trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, 1, 2,6-hexanetriol, pentaerythritol, tris (hydroxyethyl) isocyanurate and their polyetherols based on of ethylene oxide and / or propylene oxide.

6. Highly functional, highly branched or hyperbranched polyester according to any one of the preceding claims, characterized in that the reaction at a temperature of 160 to 220 ⁰ C over a period of 10 minutes to

48 hours.

7. Highly functional, highly branched or hyperbranched polyesters according to any one of the preceding claims, characterized in that the proportion of carbo xygruppen in the component A2 based on the sum of the carboxy groups in the components (A2) and (D _y ) 50 bis 100 mol%.

8. Highly functional, highly branched or hyperbranched polyesters according to any one of the preceding claims, characterized in that the proportion of hydroxy xygruppen of ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol based on the

Sum of the hydroxy groups in the components ß, ß, ß ', ß'-tetra (hydroxymethyl) cycloalkanol, (B2) and (C _x ) 20 to 100 mol%.

9. Highly functional, highly branched or hyperbranched polyesters according to any one of the preceding claims, characterized in that the proportion of hydroxyl groups in the component (B2) based on the sum of the hydroxy groups in the components ß, ß, ß ', ß'-tetra ( hydroxymethyl) cycloalkanol, (B2) and (Cx) is 0 to 50 mol%.

10. Use of the highly functional highly branched and hyperbranched polyesters according to one of the preceding claims and the polyaddition or polycondensation products prepared from highly functional, highly branched and hyperbranched polyesters as a component of printing inks, adhesives, coatings, foams, coatings and paints.