DE102007034866A1 - Unsaturated polyester - Google Patents

Abstract

The invention relates to yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, and a process for their preparation and their use as adhesive component in coating compositions z. As for metallic, mineral substrates or for substrates made of wood and plastics, whereby the adhesion of these coating compositions is improved even under critical climatic conditions.

Description

The Invention relates to yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, and a process for their preparation and their use as adhesive component in coating compositions z. B. for metallic, mineral substrates or for substrates made of wood and plastics, whereby the adhesion of these coating compositions also is improved under critical climatic conditions.

unsaturated Polyester resins (UP resins) are known. They are by condensation of saturated and unsaturated dicarboxylic acids or their anhydrides prepared with diols. Your characteristics depend largely on type and quantity ratio of the starting materials.

As a carrier of the polymerizable double bonds usually α, β-unsaturated acids are used, primarily maleic acid or its anhydride or fumaric acid; Unsaturated diols are of minor importance. The higher the content of double bonds, ie the shorter the distance between the double bonds in the chain molecules, the more reactive is the polyester resin. It polymerizes very rapidly with high heat development and high volume shrinkage to a highly crosslinked and therefore relatively brittle end product. The reactive double bonds in the polyester molecule are therefore "diluted" by condensing in them saturated aliphatic or aromatic dicarboxylic acids. [Alkohol Als] Alcohol components used are straight-chain and / or branched diols The individual UP resin types differ not only by the components used for their preparation but also by the quantitative ratio of saturated to unsaturated acids, which determines the crosslink density in the polymerization, the degree of condensation, ie the molecular weight, the acid and OH number, ie the nature of the end groups in the chain molecules, the monomer content, the nature of the additives ( Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, p. 217 et seq., 1992 ).

UP resins based on dicidol as diol component are z. B. from known DE 924 889 . DE 953 117 . DE 22 45 110 . DE 27 21 989 . EP 114 208 . EP 934 988 such as WO 03/080703 ,

Coating compositions containing unsaturated polyesters as the adhesion-promoting component are known DE 24 09 800 . EP 114 208 and EP 934 988 such as DE 102 42 265 ,

benzene is according to the Technical Rules for Hazardous Substances (TRGS 905, directory carcinogenic, mutagenic or toxic substances) with K1 and M2. Consequently, it is desirable to benzene-containing products to renounce.

formaldehyde can cause health damage. An exact However, classification is not yet in progress. The "International Agency for Research on Cancer "(IARC), an institution of the World Health Organization (WHO), has recently determined on the basis of a study that Formaldehyde spontaneously very rarely occurring nasopharyngeal cancer (nasopharyngeal cancer) in humans.

Although the IARC rating is purely scientific and not yet direct legal consequences, but in the sense of a "sustainable Development "and a" responsible handling of chemical Substances "the provision of formaldehyde-free products is essential. In addition, it can be assumed that in the medium term only formaldehyde-free Products in the market will exist.

By EU directives are accelerating the need for high-quality polymers with low solution viscosity in the last Years, since in this way the proportion of volatile organic constituents (VOC) in coating materials (eg organic Solvent) can be reduced.

In high quality applications is the need for non-yellowing products high, which gives a very good adhesion to the substrate even under critical Climatic conditions such. B. warm and humid climate or very cold Climate or industrial atmosphere (resistance z. B. compared to salt solutions).

task The present invention was to provide yellowing-resistant, to find low-viscosity, unsaturated, amorphous polyesters which are largely free of benzene and formaldehyde, and the as an adhesive component in coating compositions z. B. for metallic, mineral substrates or suitable for substrates made of wood and plastics are.

The The objects underlying the invention were able to surprisingly by the synthesis and use of special, unsaturated Polyester, which are described in more detail below, solved become.

• I. einer Säurekomponente aus A) 10 bis 100 mol-%, bevorzugt 15 bis 90 mol-% mindestens einer α,ß-ungesättigten Dicarbonsäure, B) 0 bis 90 mol-%, bevorzugt 10 bis 85 mol-% mindestens einer linearen und/oder verzweigten, aliphatischen und/oder cycloaliphatischen und/oder aromatischen di- und/oder polyfunktionellen Carbonsäure, die über keine α,β-ungesättigten Gruppierungen verfügt, wobei die Summe aus A) und B) 100 mol-% ergibt,
• II. einer Alkoholkomponente aus C) 5 bis 100 mol-% eines Dicidolgemisches, D) 0 bis 95 mol-% mindestens eines di- und/oder polyfunktionellen Alkohols, wobei die Summe aus C) und D) 100 mol-% ergibt, dadurch gekennzeichnet, dass – der Gehalt an Benzol und 10 mg/kg und der Gehalt an Formaldehyd unter 10 mg/kg liegt, bezogen auf den Polyester, – die Polydispersität der Molekulargewichtsverteilung des Polyesters zwischen 1,3 und 4,5 liegt, und – der Gehalt an Tricyclodecan(mono-/di-)aldehyd in dem Dicidolgemisch C) unter 2 Gew.-% liegt, – der Gehalt an Mono(hydroxymethyl)tricyclo[5.2.1.0^2,6]decan in dem Dicidolgemisch C) unter 10 Gew.-% liegt, – der Gehalt an den Metallen Chrom, Nickel, Kupfer, Cadmium, Blei und Rhodium in dem Dicidolgemisch C) jeweils für sich unter 2 mg/kg liegt.

The invention relates to yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters which are largely free of benzene and formaldehyde, consisting of

• I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, ß-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol% of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) giving 100 mol%,
• II. An alcohol component from C) 5 to 100 mol% of a mixture of diclide, D) 0 to 95 mol% of at least one difunctional and / or polyhydric alcohol, the sum of C) and D) giving 100 mol% in that - the content of benzene and 10 mg / kg and the content of formaldehyde are below 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and - Content of tricyclodecane (mono- / di) aldehyde in the dicidol mixture C) is less than 2% by weight, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the mixture of diclides C) below 10% by weight The content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the Dicidol mixture C) is in each case less than 2 mg / kg.

• I. einer Säurekomponente aus A) 10 bis 100 mol-%, bevorzugt 15 bis 90 mol-% mindestens einer α,β-ungesättigten Dicarbonsäure, B) 0 bis 90 mol-%, bevorzugt 10 bis 85 mol-% mindestens einer linearen und/oder verzweigten, aliphatischen und/oder cycloaliphatischen und/oder aromatischen di- und/oder polyfunktionellen Carbonsäure, die über keine α,β-ungesättigten Gruppierungen verfügt, wobei die Summe aus A) und B) 100 mol-% ergibt,
• II. einer Alkoholkomponente aus C) 5 bis 100 mol-% eines Dicidolgemisches, D) 0 bis 95 mol-% mindestens eines di- und/oder polyfunktionellen Alkohols, wobei die Summe aus C) und D) 100 mol-% ergibt, dadurch gekennzeichnet, dass – der Gehalt an Benzol und 10 mg/kg und der Gehalt an Formaldehyd unter 10 mg/kg liegt, bezogen auf den Polyester, – die Polydispersität der Molekulargewichtsverteilung des Polyesters zwischen 1,3 und 4,5 liegt, und – der Gehalt an Tricyclodecan(mono-/di-)aldehyd in dem Dicidolgemisch C) unter 2 Gew.-% liegt, – der Gehalt an Mono(hydroxymethyl)tricyclo[5.2.1.0^2,6]decan in dem Dicidolgemisch C) unter 10 Gew.-% liegt, – der Gehalt an den Metallen Chrom, Nickel, Kupfer, Cadmium, Blei und Rhodium in dem Dicidolgemisch C) jeweils für sich unter 2 mg/kg liegt,

durch Umsetzung der Ausgangskomponenten bei einer Temperatur von 150 bis 270°C, bevorzugt 160 bis 230°C, besonders bevorzugt 160 bis 200°C in ein- oder mehrstufiger Fahrweise.Another object of the invention is a process for the preparation of yellowing resistant, low-viscosity, unsaturated, amorphous polyester, which are largely free of benzene and formaldehyde, consisting of

• I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol% of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) giving 100 mol%,
• II. An alcohol component from C) 5 to 100 mol% of a mixture of diclide, D) 0 to 95 mol% of at least one difunctional and / or polyhydric alcohol, the sum of C) and D) giving 100 mol% in that - the content of benzene and 10 mg / kg and the content of formaldehyde are below 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and - Content of tricyclodecane (mono- / di) aldehyde in the dicidol mixture C) is less than 2% by weight, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the mixture of diclides C) below 10% by weight %, the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the mixture Dicidol C) is in each case below 2 mg / kg,

by reacting the starting components at a temperature of 150 to 270 ° C, preferably 160 to 230 ° C, particularly preferably 160 to 200 ° C in one or more stages.

in the The following are the yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, the are largely free of benzene and formaldehyde, closer described.

The yellowing-resistant, low-viscosity, unsaturated, amorphous polyes according to the invention ter, which are largely free of benzene and formaldehyde, are obtained by reacting the alcohol component and the acid component.

The inventive yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, the are largely free of benzene and formaldehyde, as included Acid component I. At least one α, β-unsaturated Dicarboxylic acid A). Preferably, the unsaturated Polyester resins Citracon, fumar, itaconic, maleic and / or mesaconic acid or their derivatives such. As anhydrides and / or low molecular weight Alkyl esters such. For example, methyl and / or ethyl esters. It can also mixtures are used.

Next the α, β-unsaturated dicarboxylic acids A) the acid component I. further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic Di- and / or polycarboxylic acids B) contain the above no α, β-unsaturated groups feature. Suitable are all di- and / or higher functional Carboxylic acids such. Phthalic acid, isophthalic acid, Terephthalic acid, 1,4-cyclohexanedicarboxylic acid, Succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, Hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, Adipic acid, azelaic acid, pyromellitic acid and / or trimellitic acid and derivatives thereof such. B. Anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or Ethyl ester. Preference is given to phthalic acid, trimellitic acid, Methylhexahydrophthalic acid, hexahydrophthalic acid, Tetrahydrophthalic acid, adipic acid and / or azelaic acid and their derivatives such. As anhydrides and / or low molecular weight Alkyl esters such. For example, methyl and / or ethyl esters. Especially preferred are phthalic acid, trimellitic acid, methylhexahydrophthalic acid, Hexahydrophthalic acid and / or adipic acid as well their derivatives such. As anhydrides and / or low molecular weight alkyl esters such as For example, methyl and / or ethyl esters. It can also be mixtures be used.

Monocarboxylic acids as acid component I. B), such as. B. isononanoic acid, 2-ethylhexanoic acid, benzoic acid, derivatives of benzoic acid such as B. tert-butyl benzoic acid are maximum in the subordinate Frame in amounts below 10 mol%, based on the acid component I., because they represent chain terminators, the OH or Reduce COOH functionality.

mixtures different acids A) and / or acids B) are also suitable.

As alcohol component II. According to the invention a Dicidolgemisch C) is used. Preferred is a Dicidolgemisch C) of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane and 5.8 Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, wherein each isomer may be contained in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-% , preferably 95 to 100 wt.%, and the mixture is at least 5 mol.% in the alcohol component II of the polyester. The isomer content of the Dicidolgemisches C) can qualitatively and quantitatively z. B. by GC analysis or quantitatively determined by separation by preparative GC or HPLC and subsequent NMR spectroscopy. All corresponding isomers of the dicidol in the 9-position are just as suitable, but due to the mirror symmetry of the above isomers, as well as the cis and trans isomers, indistinguishable under normal, practical circumstances.

Furthermore the dicidol mixture C) can contain up to 10% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product from cyclopentadiene.

Preferably, the alcohol component II. From 20 mol%, from 50 mol%, preferably from 90 mol%, more preferably from 100 mol% Dicidolgemisch C), this particularly preferably 95 to 100 wt .-% of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2. 1.0 contains ^2.6 ] decane.

For the preparation of dicidol, the Diels-Alder product of cyclopentadiene, dicyclopentadiene, is used, which is converted into the dialdehyde in an oxo synthesis using CO / H ₂ at elevated temperature and pressure. The catalysts used are transition metal compounds of the metals of group VIII of the Periodic Table of the Elements (cf. EP 1 529 768 . DE 103 57 718 ). Subsequently, the dialdehyde is converted by hydrogenation in the diol.

in the It was in view of a high yellowing resistance decisive for the invention that the invention essential Dicidol mixture C) contains a small proportion of production-related Has metals.

In particular, the content of the metals chromium, nickel, copper, cadmium, lead and rhodium, especially the content of rhodium must be less than 2 mg / kg, preferably less than 1.5 mg / kg, more preferably less than 1 mg / kg, in each case, ie each individual metal, in order to avoid color and yellowing problems. A check of the metal content can z. B. by atomic absorption spectroscopy (AAS).

Besides it is essential that the content of aldehydes in the Dicidolgemisch C), which contain an incomplete hydrogenation may be low, since aldehydes to a large extent the color and the yellowing resistance of the products influence negatively. According to the invention is a Dicidol C) used that less than 2, preferably less than 1 wt .-% Tricyclodecane (mono- / di-) aldehyde contains. The salary can by gas chromatographic analysis (GC) optionally in coupling determined qualitatively and / or quantitatively by mass spectrometry (MS) become.

Depending on the method of preparation, the dicidol mixture C) may also contain monoalcohols (cf. DE 103 57 718 P. 4 [0014]). Since these represent chain terminators and thus reduce the content of functional end groups, which adhesion properties can be adversely affected (poor interaction with the substrate (eg, enter acid groups interactions with metal substrates)) and optionally desired crosslinking reactions with z. As polyisocyanates and / or melamine-formaldehyde resins and / or epoxide-containing compounds due to the lack of crosslinkable functional end groups can not or only to a small extent, it is essential to the invention that the content of the mono (hydroxymethyl) tricyclo [5.2.1.0 ^{2 , 6} ] detan less than 10, preferably less than 5, especially less than 3 mol% based on the alcohol component Dicidolgemisch C). The content can be determined qualitatively and / or quantitatively by gas chromatographic analysis (GC) optionally in combination with mass spectrometry (MS).

In addition, it is essential to the invention that the content of benzene in the inventive Dicidolgemisch C) and thus in the inventive polyester less than 10 mg / kg, preferably less than 5 mg / kg, more preferably less than 3 mg / kg and the content of formaldehyde below 10 mg / kg, preferably less than 5 mg / kg, more preferably less than 2 mg / kg. That this is not trivial is shown in Example 1 of the DE-AS-1 618 384 in which dicyclopentadiene is hydroformylated as a 25% strength by weight benzene solution.

Next the Dicidolgemisch C), the alcohol component II. further diols and / or polyfunctional alcohols D) having more than two OH groups in amounts from 0 to 95 mol%, preferably from 0 to 80 mol%, preferred from 0 to 10 mol%. Suitable are all linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. Preferred are as additional alcohols D) ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene dipropylene, Triethylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol, Hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and also bisphenol A, B, C, F, norbornylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol used. It can also mixtures are used.

monoalcohols such as As hexanol are at most in the subordinate frame in quantities below 10 mol% based on the alcohol component, since they Chain terminators represent the OH or COOH functionality to reduce.

in the In general, the alcohol component II. In the molar ratio from 0.5 to 2.0 to 1 to acid component I. preferably 0.8 to 1.5 to 1. Particularly preferred is the reaction the alcohol component in the molar ratio of 1.0 to 1.1 to 1 to the acid component instead.

In a preferred embodiment I consist of the invention yellowing, low viscosity, unsaturated, amorphous polyester, which is largely free of benzene and formaldehyde are preferred, from an alcohol component of at least 90 mol% 95 mol%, particularly preferably 100 mol% of the described Dicidolgemisches C) and from fumaric acid and / or maleic acid (anhydride).

In a further preferred embodiment II included the polyesters o. g. Starting components as under embodiment I, but in addition a further acid B), selected from adipic acid or phthalic acid (anhydride), wherein the ratio of α, β-unsaturated Acid A) to the additional acid B) of 2 to 1 to 1 to 4 may vary. Preference is given to ratios from about 1 to 1 to 1 to 3.

The polyesters generally have acid numbers of 1 to 200 mg KOH / g, preferably 1-100 mg KOH / g, more preferably 1-50 mg KOH / g, OH numbers of 1 to 500 mg KOH / g, preferably 1-200 mg KOH / g, more preferably 1-100 mg KOH / g and a glass transition temperature (Tg) of -30 to + 90 ° C, preferably -20 to + 80 ° C, more preferably -10 to + 75 ° C on.

Polymers usually do not have an exact molecular weight but a molecular weight distribution (dimer, trimer, tetramer, etc.). The breadth of the distribution is described by the polydispersity, which is the ratio of weight average (Mw) and number average molecular weight (Mn) [ Odian, George, Principles of Polymerization, Third Edition, John Wiley & Sons, New York, 1991, page 86, ]. For a given Mn, the higher the polydispersity (broad distribution), the higher the viscosity of a polymer. This can be explained by the fact that high molecular weight fractions of a polymer have a significantly higher influence on the viscosity than low molecular weight fractions.

The number average molecular weight (Mn) of the polyesters according to the invention is between 500 and 6000, preferably 700 and 5000 g / mol and the weight-average molecular weight (Mw) between 900 and 27000, preferably 1000 and 15000 g / mol. The polydispersity of the molecular weight distribution of the polyesters according to the invention is between 1.3 and 4.5, preferably between 1.6 and 4.0, so that the polyesters have a low solution viscosity measured at 23 ° C. in accordance with US Pat DIN EN ISO 3219 , as a 60% solution in xylene between 50 and 5000 mPa · s, preferably between 50 and 3500, more preferably between 100 and 2500 mPa · s have.

The polyesters of the invention are amorphous, therefore have no crystalline components in the DSC heating curve. In this way, on the one hand, high transparency and clarity, on the other hand a flexible mechanical behavior can be obtained. Also, the compatibility with other components of a coating is positively influenced by the lack of crystallinity. The verification is carried out by differential scanning calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min.

The polyesters according to the invention can also Contain auxiliaries and additives, preferably selected from inhibitors, water and / or organic solvents, Neutralizing agents, surfactants, Oxygen and / or radical scavengers, catalysts, light stabilizers, Color brighteners, photosensitizers and initiators, additives to influence rheological properties such. B. thixotropic agents and / or thickening agents, leveling agents, skin-preventing agents, Defoamers and deaerators, antistatic agents, thermoplastic Additives, fire retardants, internal release agents, lubricants, Wetting and dispersing agents, plasticizers, preservatives such as B. fungicides and / or biocides, matting agents, Fillers and / or blowing agents.

Produced the polyesters according to the invention by (semi) continuous or discontinuous esterification and condensation of the acid components I. and the alcohol components II. In single-stage or multi-stage Driving.

The inventive yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, the are largely free of benzene and formaldehyde, can as an adhesive component in coating compositions, in particular for metallic and / or mineral substrates and / or for substrates made of wood and / or plastics, be used.

• I. einer Säurekomponente aus A) 10 bis 100 mol-%, bevorzugt 15 bis 90 mol-% mindestens einer α,β-ungesättigten Dicarbonsäure, B) 0 bis 90 mol-%, bevorzugt 10 bis 85 mol-% mindestens einer linearen und/oder verzweigten, aliphatischen und/oder cycloaliphatischen und/oder aromatischen di- und/oder polyfunktionellen Carbonsäure, die über keine α,β-ungesättigten Gruppierungen verfügt, wobei die Summe aus A) und B) 100 mol-% ergibt,
• II. einer Alkoholkomponente aus C) 5 bis 100 mol-% eines Dicidolgemisches, D) 0 bis 95 mol-% mindestens eines di- und/oder polyfunktionellen Alkohols, wobei die Summe aus C) und D) 100 mol-% ergibt, dadurch gekennzeichnet, dass – der Gehalt an Benzol und 10 mg/kg und der Gehalt an Formaldehyd unter 10 mg/kg liegt, bezogen auf den Polyester, – die Polydispersität der Molekulargewichtsverteilung des Polyesters zwischen 1,3 und 4,5 liegt, und – der Gehalt an Tricyclodecan(mono-/di-)aldehyd in dem Dicidolgemisch C) unter 2 Gew.-% liegt, – der Gehalt an Mono(hydroxymethyl)tricyclo[5.2.1.0^2,6]decan in dem Dicidolgemisch C) unter 10 Gew.-% liegt, – der Gehalt an den Metallen Chrom, Nickel, Kupfer, Cadmium, Blei und Rhodium in dem Dicidolgemisch C) jeweils für sich unter 2 mg/kg liegt, als Haupt- oder Nebenkomponente in Kleb- und/oder Beschichtungsstoffen sowie als Haftkomponente in Beschichtungsstoffzusammensetzungen, insbesondere für metallische und/oder mineralische Untergründe und/oder für Untergründe aus Holz, Glas, Papier, Karton, Textilien, Fasern, Gewebematerialien und/oder Kunststoffen.

The invention also provides the use of the polyester consisting of

• I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol% of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) giving 100 mol%,
• II. An alcohol component from C) 5 to 100 mol% of a mixture of diclide, D) 0 to 95 mol% of at least one difunctional and / or polyhydric alcohol, the sum of C) and D) giving 100 mol% in that - the content of benzene and 10 mg / kg and the content of formaldehyde are below 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and - Content of tricyclodecane (mono- / di-) aldehyde in the diclidol mixture C) is less than 2% by weight, The content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the dicidol mixture C) is less than 10% by weight, the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the Dicidol mixture C) in each case less than 2 mg / kg, as a main or minor component in adhesives and / or coating materials and as an adhesive component in coating compositions, in particular for metallic and / or mineral substrates and / or substrates made of wood, glass, paper , Cardboard, textiles, fibers, fabric materials and / or plastics.

Furthermore the subject of the invention is the use as aqueous, solvent-based (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid) thermosetting, radiation-curable and / or air-drying (oxidative and / or physical) coating materials, Fillers, sealants and / or adhesives.

The polyesters of the invention can be used be, especially in solvent-containing and / or aqueous Coating materials and / or in solvent-free coating materials (For example, radiation-curable coating materials and / or Powder coatings) especially in fillers, primers, fillers, base, Topcoats and / or clearcoats, printing inks, ballpoint pen pastes, pigment preparations, Inks, polishes, glazes, laminations, cosmetics, such as z. As nail polishes, sealants and insulating materials and adhesives.

there can substrates from z. As metals, plastics, paper, Cardboard, inorganic materials such. As ceramic, stone, concrete and / or Glass, textiles, fibers, fabric materials, leather and synthetic Materials, such. B., imitation leather, wood, films made of plastics and / or composites such. B. aluminum-laminated films with the coating material composition are coated. The compositions can be used for all conceivable applications both in the Used indoors as well as outdoors, such. B. as Bautenschutzfarben / -lacke, road marking paints, Automotive Finishing (OEM, Refinish), Coil-Coatings, Can-Coatings, Textile Finishing, Wood coatings, plastic coatings and decorative applications, etc. Also for use in adhesives, such. For example the bonding of textiles, leather, paper, plastics, metals and similar materials, are such compositions suitable.

there can the coating materials of the invention be applied by all known methods, for. Roll, brush, Diving, Flooding, Spraying, Pouring, Rolling, Spraying, Printing, wiping, washing, tumbling, centrifuging.

The Property of the polyester, the adhesion of coating compositions To improve it predestines them for corrosion protection. In addition to increasing the adhesion to the substrate will also the interlayer adhesion to overlying boundary layers improved.

One Another advantage of the polyester is the high resistance to hydrolysis. Coating composition compositions comprising a Polyesters also have a high gloss and a good course. In spray paints is also the spray mist recording significantly increased.

The The following examples are intended to further explain the invention but do not limit their scope:

Analytical methods

1. Analytical methods of the invention essential polyester

Determination of the content formaldehyde

The formaldehyde content is determined by the lutidine method by HPLC ( Official collection of examination procedures according to § 64 LFGB K 84.00 7 (EG): "Detection and quantitative determination of free formaldehyde" )
Device: HP IC system with two isocratic pumps, thermostatically controlled reactor, variable UV / VIS detector and evaluation unit, eg. B. Hewlett-Packard HP 1100 with PC-based evaluation software ChemStation.
Stationary phase C18 reversed phase, 5 μm, 250 × 4.0 mm
Mobile phase Milli-Q water
Injection volume 20 μl
Post-column derivatization of acetylacetone solution
Flow 1.0 ml / min
Detection UV detection at 420 nm
Sample preparation Dissolve 250 mg in 3 ml THF and make up to 25 ml with water
Calibration solution 100 mg formaldehyde solution / 100 ml water
1: 1000 dilution in water
Evaluation against external standard

Determination of the content benzene

The benzene content was determined by headspace GC / FID analysis.
Device: Capillary gas chromatograph with 2 × FID, e.g. Perkin-Elmer 8500 and headspace sampler, e.g. Perkin-Elmer HS101
Separation columns: 2 capillary columns
Column 1
Stationary phase: CP-Sil 08
Length: 50 m
Inner diameter: 0.53 mm
Column 2
Stationary phase: DB-Wax
Length: 60 m
Inner diameter: 0.53 mm
Carrier gas: nitrogen
Column admission pressure: 70 kPa
High pressure dosage: 150 kPa
GC method:
Oven temperature: 50 ° C; 4 minutes; 5 ° / min -130 ° C; 30 ° / min -180 ° C; 10 min
Injector temperature: 160 ° C
Detector temperature: 230 ° C
Injection time: approx. 0.04-0.2 min
Sample preparation: approx. 300 mg original sample in 5 ml DMF (mixed with internal standard n-butylbenzene)
Evaluation: The evaluation is carried out against an internal standard taking into account experimentally determined calibration factors

Determination of the metal content

Of the Content of the metals chromium, nickel, copper, cadmium, lead and Rhodium was determined by atomic absorption spectroscopy (AAS).

digestion:

0.3-0.7 g of sample material are weighed, treated with 3 ml of water and 6 ml of HNO ₃ (65%) and digested in a microwave autoclave at 255 ° C and 130-140 bar for 30 min. Then the digestion solution is made up to 50 ml with water.

The Measurement of Cr, Ni, Cu, Cd, Pb is carried out with ICP-OES (inductively plasma optical emission spectroscopy, type Jobin-Yvon Ultima2, with radial argon plasma). The meter is from 0.1 calibrated to 5 mg / l.

Rh is measured by flame AAS (atomic absorption spectrometry, Varian SpectrAA 220FS, with acetylene / air flame). The meter is calibrated from 0 to 4 mg / L. NaHSO ₄ is added as a matrix modifier to the measurement solution.

Determination of the content of tricyclodecane (mono- / di-) aldehyde and mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane

The determination is carried out by mass spectroscopy by means of GC-MS. For this purpose, the sample is analyzed by gas chromatography and then the detected components are identified by GC / MS analysis. The quantification is carried out from the gas chromatogram by normalization to 100 areas%.
Device: Capillary gas chromatograph with FID or MSD, eg. B. Agilent HP5890 or 6890 (MSD with EI + and CI option)
Separation columns: capillary column
Stationary phase: MDN-5S
Length: 30 m
Inner diameter: 0.32 mm
Carrier gas: helium
Column admission pressure: 100 kPa (init Pressure)
Mode: constant flow
GC method:
Oven temperature: 60 ° C; 8 ° / min - 250 ° C; 10 min
Injector temperature: 275 ° C
Detector temperature: 250 ° C
Injection volume: 0.6 μl
Sample preparation: The original sample was diluted 1:10 in methyl tert-butyl ether.
Evaluation: The GC evaluation was carried out from the gas chromatogram by standardization to 100 area percent.

The GC / MS evaluation was initially against an NBS spectra library. Molmassen- and structural suggestions were made by self-interpretation.

In addition, the determination of aldehydes by FT IR spectroscopy. For this purpose, the Dicidolgemisch is prepared on NaCl disks and recorded the FT IT spectrum. The absence of a carbonyl band in the range 1600-1800 cm ^-1 proves that no aldehydes are present.

Determination of the glass transition temperature and the content of crystalline components

The determination of the glass transition temperature (Tg) is carried out by differential scanning calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min. The absence of crystalline peaks characterizes the amorphous character of the polyester.

Determination of the hydroxyl number (OH number)

The determination is based on the DIN EN ISO 4629 "Determination of the hydroxyl number".

Determination of the acid number (SZ number)

The determination is based on the DIN EN ISO 2114 "Determination of the acid number".

Determination of the content of non-volatile Shares (nfA)

The content of non-volatile substances is determined by the DIN EN ISO 3251 , It is given as the mean of a duplicate determination. 2 g of the sample are weighed into a cleaned aluminum dish (tare mass m ₁ ) on an analytical balance (mass m _{2 of} the substance). Subsequently, the aluminum dish is placed for 24 h at 160 ° C in a convection oven. The dish is cooled to room temperature and weighed to the nearest 0.1 mg (m ₃ ). The nonvolatile fraction (nfA) is calculated according to the following equation:

Determination of color number according to Gardner and after thermal stress

The Gardner color number is determined in 60% solution of the resin in xylene based on DIN EN ISO 4630 ,

Also, the color number after thermal stress is determined in this way. For this purpose, the resin is first stored for 24 hours at 160 ° C. in an air atmosphere (see Determination of the non-volatile content). Then the Gardner color number is determined in 50% solution of the thermally loaded resin in xylene based on DIN EN ISO 4630 ,

Determination of the solution viscosity

The determination of the solution viscosity takes place after DIN EN ISO 3219 , If there is a solid resin, is previously dissolved in a suitable solvent, such as xylene, with a solids content of, for example, 60%. The viscosity is measured at 23 ° C using a plate / cone rotation viscometer (1/40 s).

Determination of molecular weight and polydispersity

The Measurement of the molecular weight distribution of the invention Polyester takes place by means of gel permeation chromatography in tetrahydrofuran against polystyrene as standard. The polydispersity D is calculated from the ratio of weight average (Mw) to number average (Mn).

2. Analytical Methods of Inventive coating materials

Determinations of benzene content and formaldehyde are identical to the methdods described above.

Determination of hardness-elasticity balance

The hardness was determined by means of pendulum damping ( DIN EN ISO 1522 ), the elasticity by Erichsentiefung ( DIN EN ISO 1520 ).

Determination of relative volume shrinkage ΔV

The measurement was carried out by determining the density of the formulation before (d _M ) and after UV curing (d _P ) by means of gas pycnometer ( Jeffrey Stansbury, Junhao Ge, RadTech Report, May / June 2003, p. 56-62 ):

Determination of stone chip resistance

The test was carried out according to DIN 55996-1 , 500 g pebbles; Rating 0 = very good; 5 bad.

Determination of yellowing resistance

To determine the resistance to yellowing, the polyesters according to the invention were used as a 60% strength solution in xylene in a 1-component alkyd-melamine baking finish. The lacquers were mounted on aluminum sheets with a 100 .mu.m pull frame and cured at 140.degree. C. for 30 min. The formulation is shown in Table 1. Table 1: 1-component burn-in system based on alkyd / melamine (%) feedstock comparison With inventive polyester VIALKYD AR 340 / 60X (alkyd resin) 25.0 20.7 SOLVESSO 100 2.3 2.3 methoxypropylacetate 3.2 3.2 Polyester according to the invention, 60% in xylene - 4.3 TEGO DISPERS 710 2 2 TEGO DISPERS 652 0.3 0.3 AEROSIL 200 1 1 KRONOS 2160 27.4 27.4 VIALKYD AR 340 / 60X 8.0 8.0 SOLVESSO 100 2 2.0 Grist 1h Skandex 1: 1 with beads (⌀ = 3 mm) Auflacksystem VIALKYD AR 340 / 60X 10 10 CYMEL 301 (98% pure) (melamine resin) 8.6 8.6 methoxypropylacetate 2.6 2.6 n-butanol 7.6 7.6 total 100.0 100.0

The coated panels were then subjected to a Westher O-meter test. The CIE-Lab color differences between the comparative film without inventive polyester and the film with polyester according to the invention were after DIN 6174 / DIN 5033 determined with the measuring device x-rite 8200 spectrophotometer (measuring parameters: without gloss / aperture 12.7 mm / illuminant D65 / 10 °).

Determination of substrate wetting and the course

The Determination of the substrate wetting and the course takes place visually. Good wetting is achieved when the applied paint a closed film without defects such. B. crater results. One good flow is achieved when the applied, closed film a low intrinsic structure (eg orange peel, too deep penetration in the substrate at z. B. wood, o. Ä.) Has.

Determination of compatibility

The Determination of compatibility is done in the way that the polyester of the invention with the examined Binder in the mass ratio 1: 4 and 1: 2 (based on Solid resin) in 50% solution In the solvent, in which the resin to be examined is dissolved is mixed. By optically assessing the solution, this becomes turbid and intolerances examined. After mounting the Solutions on glass plates and evaporation of the solvent Then the visual assessment of the film is done on turbidity and incompatibilities.

Determination of liability

The adhesion of the coatings was examined before and after loading by cross-hatch testing ( DIN EN ISO 2409 ).

stress test

• Tropentest: Storage of the test panels at 40 ° C and 95% humidity
• Water Storage: DIN EN ISO 2812-2 (Storage of the test panels at 40 ° C in demineralised water)

Determination of corrosion resistance

• Salt spray test ( DIN EN 13523-8 )

Determination of gloss level

The determination was made according to DIN EN ISO 2813 at 20 ° / 60 °.

Determination of the content of non-volatile Shares (nfA)

The content of non-volatile substances is determined by the DIN EN ISO 3251 , It is given as the mean of a duplicate determination. 2 g of the sample are weighed into a cleaned aluminum dish (tare mass m ₁ ) on an analytical balance (mass m _{2 of} the substance). Subsequently, the aluminum dish is placed for 24 h at 160 ° C in a convection oven. The dish is cooled to room temperature and weighed to the nearest 0.1 mg (m ₃ ). The nonvolatile fraction (nfA) is calculated according to the following equation:

Examples

Starting component Dicidol mixture C) im Isomer ratio of approximately 1: 1: 1 [3.8: 4.8: 5.8 isomers]

The content of tricyclodecane (mono- / di-) aldehyde in the Dicidolgemisch used was less than 2 wt .-%, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane was below 10 wt .-%, and the Content of rhodium below 2 mg / kg. The content of the metals chromium, nickel, copper, cadmium and lead was less than 1 mg / kg. The content of benzene and the content of formaldehyde were below 10 mg / kg each.

Example 1 (polyester)

3.3 mol of the Dicidolgemisches, 2.1 moles of phthalic anhydride and 1.1 moles of maleic anhydride are reacted in a reaction flask with distillation head, stirrer and thermometer in a nitrogen atmosphere at 210 ° C until an acid number of 15.9 mg KOH / g and a OH number of 36.0 mg KOH / g is reached.
M _n = 2100 g / mol M _w = 7200 g / mol, polydispersity = 3.4, glass transition temperature 62 ° C (no crystalline peak), viscosity as a 60% solution in xylene: 960 mPa · s, Gardner color number as 60 % solution in xylene before / after thermal exposure: 0.1 / 0.2, content of benzene: <2 mg / kg, content of formaldehyde: <1 mg / kg.

Example 2 (polyester)

5.3 mol of Dicidolgemisches, 2.5 mol of adipic acid and 2.5 moles of maleic anhydride are reacted in a reaction flask with distillation head, stirrer and thermometer in a nitrogen atmosphere at 210 ° C until an acid number of 28 mg KOH / g and an OH Number of 29 mg KOH / g is reached.
M _n = 2000 g / mol M _W = 5200 g / mol, polydispersity = 2.6, glass transition temperature 9 ° C (no crystalline peak), viscosity as a 60% solution in xylene: 780 mPa · s, color number according to Gardner than 60 % solution in xylene before / after thermal exposure: 0.1 / 0.1, content of benzene: <2 mg / kg, content of formaldehyde: <1 mg / kg.

The Compatibility of the two invention Polyesters from Examples 1 and 2 were investigated. They point, for example a good compatibility with PVC, chlorinated rubber, nitrocellulose, Ketone-aldehyde resins, alkyd resins, acrylate resins, polyesters, melamine resins, Urea resins and polyisocyanates.

The yellowing resistance under weathering conditions was checked by the Westher O-meter test. The test procedure was already explained in the chapter Determination of yellowing resistance. The following Table 2 shows the results which prove that the yellowing resistance is very good. Table 2: Results of the WOM investigations irradiation time ΔE comparison ΔE resin from Example 1 ΔE resin from Example 2 250 h 1.93 2.01 2.43 500 h 1.87 2.10 2.42 750 h 1.95 2.10 2.42 1000 h 1.97 2.13 2.44

Example 3 (Polyester)

9.9 mol of Dicidolgemisches, 5.0 mol of phthalic anhydride, 2.0 mol of adipic acid and 3.0 moles of maleic anhydride are reacted in a reaction flask with distillation head, stirrer and thermometer in a nitrogen atmosphere at 210 ° C until an acid number of 32 mg KOH / g and an OH number of 27 mg KOH / g is reached.
M _n = 2000 g / mol M _W = 5900 g / mol, polydispersity = 3.0, glass transition temperature 46 ° C (no crystalline peak), viscosity as a 60% solution in xylene: 850 mPa · s, color number according to Gardner than 60 % solution in xylene before / after thermal exposure: 0.1 / 0.2, content of benzene: <2 mg / kg, content of formaldehyde: <1 mg / kg.

The polyester according to the invention thus prepared is melted in a closed container at about 120 ° C, treated with dimethylethanolamine corresponding to a degree of neutralization of 1.0 and provided with vigorous stirring with water. After cooling to room temperature, a storage-stable dispersion having a solids content of about 38.5% is obtained.
Viscosity _{D = 200} : <30 mPas, pH value: 7.8, solids content: 38.5%.

applications

In a red anticorrosive paint based on a soluble vinyl chloride (VC) copolymer (V1) are in each case 2.2 wt .-% of the inventive polyesters according to Example 1 and 2 in the form of their 60% solutions in Xylene used (see Table 3). The original poor adhesion before loading on galvanized sheets, measured as cross cut value "G5", is improved by the added polyesters to the very good values of "G0" each. At the same time, the adhesion improves significantly according to the different types of stress. Table 3: Formulation of a red anti-corrosion varnish (%) feedstock V1 B1 B2 VILIT MB 30 (vinyl chloride copolymer) 13.4 13.1 13.1 HORDARESIN NP 70 9.2 9.0 9.0 VESTINOL AH 4.1 4.0 4.0 ARALDIT GY 250 0.5 0.5 0.5 butyl 2.0 2.0 2.0 xylene 13.3 13.0 13.0 SOLVESSO 100 12.6 12.2 12.2 Polyester according to Example 1 - 60% in xylene 0 2.2 0 Polyester according to Example 2 - 60% in xylene 0 0 2.2 THIXOTROL ST 10% in xylene 9.2 9.0 9.0 PERENOL F 1 0.3 0.3 0.3 BAYFERROX 130 5.1 5.0 5.0 Zinc oxide resin seal S - NT 2.3 2.3 2.3 Blanc fixe N 14.0 13.7 13.7 Micro Talk AT 1 14.0 13.7 13.7 total 100.0 100.0 100.0

• Untergrund: verzinkter Stahl
• Schichtdicke (trocken): ca. 30 μm
• Trocknung: 24 h Raumtemperatur

Tabelle 4: Ergebnisse der Haftung und der Unterwanderung Art der Belastung V1 B1 B2 Vor Belastung GT 5 GT 0 GT 0 14 d 40°C, Wasserlagerung GT 5 GT 1 GT 0–1 Tropentest (40°C/95% rel. Luftfeuchtigkeit) GT 5 GT 0–1 GT 0–1 Salzsprühtest 240 h: Gitterschnitt Unterwanderung (in mm) GT 5 > 10 GT 0 0 GT 0 0 The content of benzene and content of formaldehyde in compositions B1 and 62 was below 10 mg / kg each.

• Substrate: galvanized steel
• Layer thickness (dry): approx. 30 μm
• Drying: 24 h room temperature

Table 4: Results of liability and infiltration Type of load V1 B1 B2 Before stress GT 5 GT 0 GT 0 14 d 40 ° C, water storage GT 5 GT 1 GT 0-1 Tropical test (40 ° C / 95% relative humidity) GT 5 GT 0-1 GT 0-1 Salt spray test 240 h: cross-hatch infiltration (in mm) GT 5> 10 GT 0 0 GT 0 0

The Values show the different adhesion of the paints before and after the salt spray test. While V1 per se a bad one Liability already possesses before the load, is the adhesion in the Examples B1 and B2 very good.

As a result, is the adhesion even under critical climatic conditions (high water resistance) and improved by the action of saline solutions. Also is the anti-corrosion effect in contrast to the formulation significantly improved without the addition of the polyester essential to the invention. While in V1 an infiltration of> 10 mm occurs, there is no infiltration in the case of B1 and B2.

• Trocknung: 24 h Raumtemperatur
• Schichtdicke: 25–30 μm

Tabelle 6: Ergebnisse der Haftung auf verschiedenen Untergründen Untergrund V2 B3 B4 Stahl GT5 GT0 GT0 Verlauf Orangenhaut Gut Gut verzinkter Stahl GT3 GT0 GT0 Verlauf Orangenhaut Gut Gut Aluminium GT5 GT0 GT0 Verlauf Orangenhaut Gut Gut Comparative Example C2 and Inventive Use Examples 83 and 84 2.8% by weight of the inventive polyesters according to Examples 1 and 2 in the form of their 60% strength solutions in xylene are used in a white anticorrosion paint based on chlorinated rubber (V2) (Table 5) , These additives significantly improve the adhesion of such paints to untreated steel, galvanized steel and aluminum. In addition, the substrate wetting and the course are markedly improved by the polyester added to the invention. Table 5: Formulation of a white anticorrosion paint (%) feedstock V2 B3 B4 PERGUT S 10 (chlorinated rubber) 24.0 22.8 22.8 xylene 43.2 42.1 42.1 VESTINOL AH 7.6 7.2 7.2 EDENOL D 81 1.5 1.4 1.4 TiO ₂ KRONOS 2059 23.7 23.7 23.7 Polyester according to Example 1 60% in xylene 0 2.8 0 Polyester according to Example 2 60% in xylene 0 0 2.8 total 100.0 100.0 100.0

• Drying: 24 h room temperature
• Layer thickness: 25-30 μm

Table 6: Results of adhesion on different substrates underground V2 B3 B4 stole GT5 GT0 GT0 course orange peel Well Well galvanized steel GT3 GT0 GT0 course orange peel Well Well aluminum GT5 GT0 GT0 course orange peel Well Well

Comparative Example C3 and inventive Application examples B5 and B6

• Einbrennbedingungen: 30 min 130°C
• Untergrund: verzinkter Stahl
• Schichtdicke (trocken): 25–30 μm

Tabelle 8: Ergebnisse der lacktechnischen Eigenschaften Messmethode V3 B5 B6 Gitterschnittwert (GT) 2–3 0 0 Glanz (60°) 73 95–99 93–98 Pendelhärte (s) 154 173 166 Erichsentiefung (mm) 6,2 7,5 8,6 Steinschlagbeständigkeit 5 1–2 0–1 3.2% by weight of the inventive polyesters according to Examples 1 and 2 in the form of their 60% strength solutions in xylene are used in a white stoving lacquer based on a hydroxyl-containing polyacrylate resin crosslinked with a fully methyl-etherified melamine resin (V3) (Table 7). The only moderate adhesion to galvanized steel in the blank sample V3 is significantly improved. Also, the gloss level is increased and improved hardness and elasticity values are obtained by the added polyester according to the invention. It can be seen that these additives according to the invention improve the course, making the film surface appear smoother. This can be explained by an improved substrate wetting. In addition, one finds by the added polyester according to the invention significantly improved stone impact resistance again. Table 7: Formulation of a white acrylate / melamine stoving lacquer (%) feedstock V3 B5 B6 PARALOID AT 410 (acrylic resin) 43.0 40.5 40.5 CYMEL 303 (melamine resin) 8.2 7.8 7.8 methoxypropanol 5.3 5.1 5.1 butanol 2.1 2.0 2.0 DYNAPOL catalyst 1203 2.0 2.0 2.0 TiO ₂ KRONOS 2059 39.4 39.4 39.4 Polyester according to Example 1 60% in xylene 0 3.2 0 Polyester according to Example 2 60% in xylene 0 0 3.2 total 100.0 100.0 100.0

• Baking conditions: 30 min 130 ° C
• Substrate: galvanized steel
• Layer thickness (dry): 25-30 μm

Table 8: Results of the coating properties measurement method V3 B5 B6 Cross-hatch value (GT) 2-3 0 0 Gloss (60 °) 73 95-99 93-98 Pendulum hardness (s) 154 173 166 Erichsentiefung (mm) 6.2 7.5 8.6 Chip resistance 5 1-2 0-1

Comparative Example C4 and Inventive Application examples B7 and B8

• Einbrennbedingungen: 15 min 170°C
• Untergrund: verzinkter Stahl
• Schichtdicke (trocken): 25–30 μm

Tabelle 10: Ergebnisse der Haftung Messmethode V4 B7 B8 Gitterschnittwert [GT] 2–3 0–1 0 In a white stoving lacquer based on a hydroxyl-containing, saturated polyester resin crosslinked with a blocked polyisocyanate (V4), in each case 3.0% by weight of the inventive polyesters according to Examples 1 and 2 are used in the form of their 60% strength solutions in xylene (Table 9) ). The initial moderate adhesion to galvanized steel is greatly improved. Table 9: Formulation of a white PUR stoving lacquer (%) feedstock V4 B7 B8 DYNAPOL H 905-07 (OH-Polyester) 42.5 40.3 40.3 VESTANAT B 1370 (isocyanate) 15.5 14.8 14.8 Dibutyltin dilaurate (DBTL), 10% in xylene 1.0 1.0 1.0 xylene 4.1 4.0 4.0 butyl 1.9 1.9 1.9 KRONOS 2059 (TiO ₂ ) 35.0 35.0 35.0 Polyester according to Example 1, 60% in xylene 0 3.0 0 Polyester according to Example 2, 60% in xylene 0 0 3.0 total 100.0 100.0 100.0

• Stoving conditions: 15 min 170 ° C
• Substrate: galvanized steel
• Layer thickness (dry): 25-30 μm

Table 10: Results of liability measurement method V4 B7 B8 Cross-hatch value [GT] 2-3 0-1 0

Comparative Example C5 and Inventive Application Example B9

• Untergrund: ABS
• Spritzviskosität: 20 s im Ford 4 Becher

Tabelle 12: Ergebnisse der Haftung nach Tesaabriss Messmethode V5 B9 Gitterschnittwert [GT] 4–5 0 In a metallic plastic varnish (V5), 2% by weight of the thermoplastic acrylate resin is replaced by the polyester of the invention according to Example 2 in the form of its 60% strength solution in xylene (Table 11). The originally bad fixation of the aluminum plates on ABS is optimized, the adhesion to ABS improved. Table 11: Formulation of a metallic plastic paint (%) feedstock V5 B9 DEGALAN LP 64/12 (50% in toluene / xylene 1/1) (acrylate resin) 60.0 58.0 CAB 381-0.1 (25% in ethyl acetate) (cellulose acetobutyrate) 15.0 15.0 METALLUX R 678 5.0 5.0 methyl ethyl ketone 6.0 6.0 xylene 6.0 6.0 methoxypropylacetate 3.0 3.0 isopropanol 5.0 5.0 Polyester according to Example 2, 60% in xylene 0 2.0 total 100.0 100.0

• Substrate: ABS
• Spray viscosity: 20 seconds in the Ford 4 cup

Table 12: Results of adhesion after Tesa tear measurement method V5 B9 Cross-hatch value [GT] 4-5 0

Comparative Example C6 and Inventive Application example B10

To a road marking color (V6) the polyester according to the invention according to Example 1 is given (Table 13). The adhesion to mineral substrate is greatly improved. Table 13: Formulation of a road marking color (%) feedstock V6 B10 VILIT MC 31 (VC copolymer) 130.0 130.0 Synthetic resin AP (ketone-aldehyde resin) 50.0 50.0 Polyester according to Example 1 0.0 15.0 VESTINOL AH 35.0 35.0 acetone 125.0 125.0 ethyl acetate 40.0 40.0 Special fuel 80/110 from Aug. Hedinger GmbH 95.0 95.0 Butyl acetate 99/100% 34.0 34.0 AEROSIL 380 6.0 6.0 DICALITE GPE 18 60.0 60.0 BAYERTITAN R-KB-2 90.0 90.0 BAYERTITAN A 40.0 40.0 SIKRON SH 300 130.0 130.0 Cristobalite flour M 0010 100.0 100.0 Minigrain No. 4 50.0 50.0 total 985.0 1000.0

• Viskosität nach Verdünnung (Krebs Units bei 23°C) ca. 80
• Untergrund: Asphalt
• Nassauftragsschichtdicke ca. 500 μm

Tabelle 14: Ergebnisse der Haftung Messmethode V6 B10 Gitterschnittwert [GT] 3 0 For a reflective coating, 2 parts by mass of marker color are mixed with 1 part of the size reflex glass beads type A (8) and diluted with 5% diluent (composition: same solvent mixture in the formulation).

• Viscosity after dilution (Krebs Units at 23 ° C) approx. 80
• Substrate: asphalt
• Wet application layer thickness approx. 500 μm

Table 14: Results of liability measurement method V6 B10 Cross-hatch value [GT] 3 0

Comparative Example V7 and inventive Application examples B11 and B12

In a radiation-curable clearcoat based on an epoxy acrylate (V7) are each 10 wt .-% of the binder by the inventive Polyester according to Example 1 and 2 in the form of their 50% solutions in tripropylene glycol diacrylate (TPGDA) (Table 15). The original moderate adhesion to galvanized Steel is greatly improved. In addition, the viscosity decreased, the volume shrinkage significantly reduced and the hardness-elasticity balance improved.

• Untergrund: verzinkter Stahl
• Schichtdicke (trocken): 20–30 μm

Tabelle 16: Ergebnisse der lacktechnischen Eigenschaften Messmethode V7 B11 B12 Viskosität (mPas) 1265 925 890 Pendelhärte (s) 169 175 167 Erichsentiefung (mm) 2,3 3,4 4,6 MEK-Test > 150 > 150 > 150 Dichte (g/cm³, Feststoff) 1,21 1,19 1,15 Dichte (g/cm³, flüssig) 1,1149 1,1157 1,0741 Volumenschrumpf (%) 8,5 6,7 7,1 Volumenschrumpf Differenz zu V7 (%) - –1,9 –1,5 Gitterschnitt [GT] 4–5 2 1–2 It was also surprising that the speed and completeness of the reaction of the double bonds (determined by means of FT infrared measurement) are increased by adding the polyesters according to the invention. Table 15: Formulation of a UV clearcoat feedstock V7 B11 B12 CRAYNOR CN 104 (epoxy acrylate) 50.0 45.0 45.0 TPGDA 40.0 35.0 35.0 DAROCUR 1173 5.0 5.0 5.0 EBECRYL P 115 5.0 5.0 5.0 Polyester according to Example 1, 50% in TPGDA 0 10.0 0 Polyester according to Example 2, 50% in TPGDA 0 0 10.0 total 100.0 100.0 100.0

• Substrate: galvanized steel
• Layer thickness (dry): 20-30 μm

Table 16: Results of the coating properties measurement method V7 B11 B12 Viscosity (mPas) 1265 925 890 Pendulum hardness (s) 169 175 167 Erichsentiefung (mm) 2.3 3.4 4.6 MEK test > 150 > 150 > 150 Density (g / cm ³ , solid) 1.21 1.19 1.15 Density (g / cm ³ , liquid) 1.1149 1.1157 1.0741 Volume shrinkage (%) 8.5 6.7 7.1 Volume shrinkage difference to V7 (%) - -1.9 -1.5 Cross-hatch [GT] 4-5 2 1-2

Comparative Example C8 and Inventive Application example B13

In an aqueous plastic varnish (V8) was the aqueous Resin used according to Example 3. It improves adhesion to EPDM significant.

• Untergrund: EPDM
• Schichtdicke (nass): 100 μm
• Trocknung: 24 h Raumtemperatur

Tabelle 18: Ergebnisse der Haftung Messmethode V8 B13 Gitterschnittwert [GT] 3 1 Table 17: Formulation of a PUR plastic paint for EPDM feedstock V8 B13 Alberdingk U 5200 VP 80.0 80.0 methoxypropanol 2.0 2.0 Butydiglykol 2.5 2.5 VE water 15.5 15.5 Polyester according to Example 3 0.0 5.0 total 100.0 105.0

• Substrate: EPDM
• Layer thickness (wet): 100 μm
• Drying: 24 h room temperature

Table 18: Results of liability measurement method V8 B13 Cross-hatch value [GT] 3 1

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• DE 924889 [0004]
• - DE 953117 [0004]
• - DE 2245110 [0004]
• - DE 2721989 [0004]
• - EP 114208 [0004, 0005]
• - EP 934988 [0004, 0005]
• WO 03/080703 [0004]
• - DE 2409800 [0005]
• - DE 10242265 [0005]
• - EP 1529768 [0024]
• - DE 10357718 [0024, 0028]
• - DE 618384 [0029]

Cited non-patent literature

• Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, p. 217 et seq., 1992 [0003]
• Odian, George, Principles of Polymerization, Third Edition, John Wiley & Sons, New York, 1991, page 86, [0036]
• - DIN EN ISO 3219 [0037]
• - DIN 53 765 [0038]
• - Official Collection of Examination Procedures according to § 64 LFGB K 84.00 7 (EC): "Detection and Quantitative Determination of Free Formaldehyde" [0050]
• - DIN 53 765 [0059]
• - DIN EN ISO 4629 [0060]
• - DIN EN ISO 2114 [0061]
• - DIN EN ISO 3251 [0062]
• - DIN EN ISO 4630 [0063]
• - DIN EN ISO 4630 [0064]
• - DIN EN ISO 3219 [0065]
• - DIN EN ISO 1522 [0067]
• - DIN EN ISO 1520 [0067]
• - Jeffrey Stansbury, Junhao Ge, RadTech Report, May / June 2003, p. 56-62 [0068]
• - DIN 55996-1 [0069]
• - DIN 6174 [0071]
• - DIN 5033 [0071]
• - DIN EN ISO 2409 [0074]
• - DIN EN ISO 2812-2 [0074]
• - DIN EN 13523-8 [0074]
• - DIN EN ISO 2813 [0075]
• - DIN EN ISO 3251 [0076]

Claims (23)

Yellowing-resistant, low-viscosity unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, consisting of I. an acid component of A) 10 to 100 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol% at least a linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) giving 100 mol%, II. An alcohol component from C) 5 to 100 mol% of a mixture of diclide, D) 0 to 95 mol% of at least one difunctional and / or polyhydric alcohol, the sum of C) and D) giving 100 mol% in that - the content of benzene and 10 mg / kg and the content of formaldehyde are below 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and - Content of T ricyclodecan (mono- / di-) aldehyde in the Dicidol mixture C) below 2 wt .-% is located, - the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6] decan in the Dicidol mixture C) below 10 wt %, - the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the Dicidolgemisch C) is in each case below 2 mg / kg. Polyester according to claim 1, characterized in that α, β-unsaturated Acids A) selected from Citracon, Fumar, Itacon, Maleic and / or mesaconic acid and / or their derivatives we Anhydrides and / or low molecular weight alkyl esters such as methyl and / or Ethyl esters are included. Polyester according to at least one of the preceding claims, characterized in that as α, β-unsaturated Acid A) fumaric acid and / or maleic acid, and / or their derivatives such as anhydrides and / or low molecular weight Alkyl esters such as methyl and / or ethyl esters, alone or in mixtures, are included. Polyester according to at least one of the preceding claims, characterized in that acids B) selected phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, Methyltetra-, methylhexahydrophthalic, hexahydrophthalic, Tetrahydrophthalic acid, dodecanedioic acid, adipic acid, Azelaic acid, pyromellitic acid and / or trimellitic acid, and / or their derivatives such as anhydrides and / or low molecular weight Alkyl esters such as methyl and / or ethyl esters, alone or in mixtures, are included. Polyester according to at least one of the preceding claims, characterized in that as acid B) phthalic acid, Trimellitic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, Tetrahydrophthalic acid, adipic and / or azelaic acid, and / or their derivatives such as anhydrides and / or low molecular weight Alkyl esters such as methyl and / or ethyl esters, alone or in mixtures, are included. Polyester according to at least one of the preceding claims, characterized in that a Dicidolgemisch C) of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2. 1.0 ^2,6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, wherein each isomer may be contained in a proportion of 20 to 40% by weight in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100 wt .-% results, and the mixture is at least 5 mol% in the alcohol component II. Of the polyester is present. Polyester according to at least one of the preceding claims, characterized in that alcohols D) are selected from Ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, Triethylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexynedimethanol, glycerol, Hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and also bisphenol A, B, C, F, norbornylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol are included. Polyester according to at least one of the preceding claims, characterized in that the alcohol component II. In the molar ratio of 0.5 to 2 to 1, preferably from 0.8 to 1.5 to 1, to the acid component I is included. Polyester according to at least one of the preceding claims, characterized in that the content of the metals chromium, nickel, Copper, cadmium, lead and / or rhodium in each case less than 1.5 mg / kg. Polyester according to at least one of the preceding claims, characterized in that it has an acid number between 1 and 200 mg KOH / g, preferably between 1 and 100, more preferably between 1 and 50 mg KOH / g. Polyester according to at least one of the preceding claims, characterized in that it has an OH number between 1 and 500 mg KOH / g, preferably between 1 and 200, more preferably between 1 and 100 mg KOH / g. Polyester according to at least one of the preceding claims, characterized in that it has a Tg of -30 to + 90 ° C, preferably -20 to + 80 ° C, especially preferably have from -10 to 75 ° C. Polyester according to at least one of the preceding claims, characterized in that they have a M _n between 500 and 6,000, preferably 700 and 5,000 g / mol and an M _w between 900 and 27,000, preferably 1,000 and 15,000 g / mol. Polyester according to at least one of the preceding claims, characterized in that the polydispersity of the molecular weight distribution between 1.3 and 4.5 is preferably between 1.6 and 4.0. Polyesters according to at least one of the preceding claims, characterized in that the solution viscosity measured at 23 ° C according to DIN EN ISO 3219, as a 60% solution in xylene between 50 and 5,000 mPa · s, preferably between 50 and 3,500, more preferably between 100 and 2,500 mPa · s. Polyester according to at least one of the preceding claims, characterized in that auxiliaries and additives are included. Polyester according to at least one of the preceding claims, characterized in that the alcohol component II. Of at least 90% Dicidolgemisch C) and the acid component I. and from Fumaric acid and / or maleic acid (anhydride) consists. Polyester according to claim 17, characterized in that additionally adipic acid and / or phthalic acid (anhydride) contained as an acid component in a ratio α, β-unsaturated Acid A) to the additional acid B) of 2 to 1 to 1 to 4, especially from 1 to 1 to 1 to 3. A process for preparing yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters which are largely free of benzene and formaldehyde, consisting of I. an acid component of A) 10 to 100 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol% of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) 100 mol % gives, II. an alcohol component from C) 5 to 100 mol% of a dicidol mixture, D) 0 to 95 mol% of at least one difunctional and / or polyfunctional alcohol, the sum of C) and D) 100 mol% %, characterized in that - the content of benzene and 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester between 1.3 and 4.5 the content of tricyclodecane (mono- / di-) aldehyde in the dicidol mixture C) is below 2% by weight, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the mixture of diclidols C) less than 10% by weight, - the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the dicidol mixture C) in each case less than 2 mg / kg, by reacting the starting components at a temperature of 150 to 270 ° C, preferably 160 to 230 ° C, particularly preferably 160 to 200 ° C in one or more stages. Use of the polyesters consisting of I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol% % of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) being 100 mol% II, an alcohol component from C) 5 to 100 mol% of a Dicidolgemisches, D) 0 to 95 mol% of at least one di- and / or polyfunctional alcohol, wherein the sum of C) and D) 100 mol% , characterized in that - the content of benzene and 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and - The content of tricyclodecane (mono- / di-) aldehyde in the Dicidolgemis ch C) is below 2% by weight, - the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the mixture of diclides C) is less than 10% by weight, - the content of the metals chromium, Nickel, copper, cadmium, lead and rhodium in the Dicidolgemisch C) each alone is less than 2 mg / kg, as the main or minor component in adhesives and / or coating materials. Use of the polyesters consisting of I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol % of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) being 100 mol %, II. an alcohol component from C) 5 to 100 mol% of a dicidol mixture, D) 0 to 95 mol% of at least one difunctional and / or polyfunctional alcohol, the sum of C) and D) 100 mol% , characterized in that - the content of benzene and 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and the content of tricyclodecane (mono- / di-) aldehyde in the dicidol mixture ch C) is below 2% by weight, - the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the mixture of diclides C) is less than 10% by weight, - the content of the metals chromium, Nickel, copper, cadmium, lead and rhodium in the Dicidolgemisch C) each alone is less than 2 mg / kg, as an adhesive component in coating compositions, in particular for metallic and / or mineral substrates and / or substrates made of wood, glass, paper, cardboard , Textiles fibers, fabric materials and / or plastics. Use of the polyesters consisting of I. an acid component of A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid, B) 0 to 90 mol%, preferably 10 to 85 mol % of at least one linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acid which has no α, β-unsaturated groups, the sum of A) and B) being 100 mol %, II. an alcohol component from C) 5 to 100 mol% of a dicidol mixture, D) 0 to 95 mol% of at least one difunctional and / or polyfunctional alcohol, the sum of C) and D) 100 mol% reveals characterized in that - the content of benzene and 10 mg / kg and the content of formaldehyde are below 10 mg / kg, based on the polyester, - the polydispersity of the molecular weight distribution of the polyester is between 1.3 and 4.5, and the content of tricyclodecane (mono- / di-) aldehyde in the dicidol mixture C) is less than 2% by weight, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane in the diclidol mixture C) is below 10 % By weight, - the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the Dicidolgemisch C) each alone is below 2 mg / kg, in aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid) thermosetting, radiation-curable and / or air-drying (oxidative and / or physical) coating materials, fillers and / or sealants and / or adhesives. Use according to claim 20 to 22 as a modifying resin in putties, primers, fillers, base, top and / or Clearcoats, printing inks, ballpoint pies, pigment preparations, Inks, polyursts, glazes, laminations, cosmetics, such as z. As nail polishes, sealants and insulating materials and adhesives.