WO2009013064A2

WO2009013064A2 - Coating material compositions

Info

Publication number: WO2009013064A2
Application number: PCT/EP2008/057370
Authority: WO
Inventors: Patrick GLÖCKNER; Andreas Wenning
Original assignee: Evonik Degussa Gmbh
Priority date: 2007-07-24
Filing date: 2008-06-12
Publication date: 2009-01-29
Also published as: CN101353546A; WO2009013064A3; DE102007034865A1

Abstract

The invention relates to coating material compositions for, for example, metallic, mineral substrates or for substrates of wood, paper and plastics, which comprise yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters which are very largely free of benzene and formaldehyde, as a result of which the adhesion of these coating material compositions is improved even under critical ambient conditions, and to a preparation process and use of said compositions.

Description

Coating compositions

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

Unsaturated polyester resins (UP resins) are known. They are prepared by condensation of saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties depend largely on the type and amount ratio of the starting materials.

The carriers of the polymerizable double bonds are generally α, β-unsaturated acids, primarily maleic acid or its anhydride or fumaric acid; Unsaturated diols are of minor importance. The higher the content of double bonds, d. H. the shorter the distance of 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 in the components used for their preparation but also in the quantitative ratio from 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 Encyclopaedia of Industhal Chemistry, VOL A21, page 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 and WO 03/080703.

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

Benzene is listed in accordance with the Technical Rules for Hazardous Substances (TRGS 905, list of carcinogenic, mutagenic or reprotoxic substances) with K1 and M2. Accordingly, it is desirable to dispense with benzene-containing products.

Formaldehyde can cause health problems. However, an exact classification is not yet made. The International Agency for Research on Cancer (IARC), an institution of the World Health Organization (WHO), recently determined on the basis of a study that formaldehyde causes spontaneously very rare nasopharyngeal cancer in humans.

Although the lARC assessment is purely scientific and does not yet produce any direct legal consequences, the provision of formaldehyde-free products is indispensable in the sense of "sustainable development" and "responsible handling of chemical substances". In addition, it can be assumed that in the medium term only formaldehyde-free products will exist on the market.

Accelerated by EU directives, the demand for high-quality polymers with low solution viscosity has risen sharply in recent years, as it can reduce the level of volatile organic compounds (VOC) in coating materials (eg organic solvents).

In high quality applications, the need for non-yellowing Products that have 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 to, for example, salt solutions) have.

The object of the present invention was

Coating substance compositions which are suitable for metallic, mineral substrates or for substrates made of wood, paper and plastics.

The coating compositions should also have a very good adhesion, even under critical climatic conditions high corrosion protection, high gloss, high solids content or a low viscosity at a given solids content and a very good stone chip resistance and resistance to salt solutions and be largely free of benzene and formaldehyde ,

The objects underlying the invention have surprisingly been achieved by the use of special, unsaturated polyesters, which are described in more detail below.

The invention relates to coating compositions essentially containing

1. 0.1 to 80 wt .-% of a yellowing-resistant, low-viscosity, unsaturated, amorphous polyester, which is largely free of benzene and formaldehyde, consisting of I. an acid component

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 having no α, ß-unsaturated groups, the sum of A) and B) being 100 mol%, II. an alcohol component

C) 5 to 100 mol% of a mixture of diclidols,

D) 0 to 95 mol% of at least one di- and / or polyfunctional alcohol, wherein the sum of C) and D) gives 100 mol%, and wherein

the content of benzene is less than 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, relative to the polyester,

the polydispersity of the molecular weight distribution of the polyester is between 1, 3 and 4.5, and

the tricyclodecane (mono- / di-) aldehyde content in the dicidol mixture C) is less than 2% by weight,

the content of mono (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] 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 mixture of diclides C) is in each case less than 2 mg / kg, and

2. 99.9 to 20 wt .-% of at least one further binder, 3. 0 to 80 wt .-% of at least one excipient and / or additive, 4. 0 to 70 wt .-% of at least one colorant and / or filler,

wherein the sum of the weights of the components is 1. to 4. 100 wt .-%.

It has been found that the combination of the coating material compositions described below from components 1 to 4 fulfill all the required criteria.

The coating material compositions thus obtained are characterized in that they • have very good adhesion to metallic, mineral substrates and / or to substrates made of wood, paper and / or plastics, even under critical climatic conditions,

• protect the surfaces from corrosion, • have a very good resistance to stone chips,

• resistant to yellowing,

• have a high gloss,

• have a high solids content or a low viscosity at a given solids content and • have a high resistance to salt solutions.

A very good adhesion to metallic, mineral substrates and / or substrates made of wood and / or plastics even under critical climatic conditions, a high corrosion protection effect, a high resistance to salt solutions and a very good stone chip resistance is surprisingly achieved significantly by adjusting the following parameters:

• Substrate wetting The surface tension of the coating material composition must always be lower than that of the substrate to be coated, so that the substrate can be optimally wetted by the coating material.

The surface tension of the coating composition according to the invention can be adjusted by the addition of the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyester 1, which are largely free of benzene and formaldehyde.

Adsorption between film and substrate

The higher the number of interactions between coating and substrate, and the stronger these interactions are, the better the adhesion. Depending on the substrate, this can be realized by polymers in the coating material, the hydrogen bridge forming groups z. As urethane groups, OH groups (metals, plastic substrates) or salt-forming groups (eg., Carbonsäuregruppen) (metal substrates) in the molecular structure. The lowest possible glass transition temperature of the film formers, which during processing and crosslinking is below the processing / regeneration temperature, supports the orientation of the functional groups to the substrate.

The adsorption between film and substrate can be improved by the addition of the invention essential, yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde.

For this purpose, the polyesters essential to the invention have an acid number between 1 and 200 mg KOH / g, preferably between 1 and 100, more preferably between 1 and 50 mg KOH / g and an OH number between 1 and 500 mg KOH / g, preferably between 1 and 200, more preferably between 1 and 100 mg KOH / g. The Tg of the unsaturated amorphous polyester 1 varies from -30 to +90 ⁰ C, preferably from -20 to +80 ⁰ C, more preferably - 10 to + 75 ⁰ C.

Also, low viscosity assists the

Coating composition in absorbent substrates such. As wood or paper penetration of the coating material in the ground. Since there is thus a "gearing" between the coating material and the substrate, the adsorption and thus the adhesion is further improved.

Therefore, the inventively essential, yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters 1, which are largely free of benzene and formaldehyde, solution viscosities measured at 23 ° C according to DIN EN ISO 3219, as 60% solutions in xylene between 50 and 5,000 mPa -s, preferably between 50 and 3,500, more preferably between 100 and 2,500 nnPa-s.

Volume shrinkage / internal stress Particularly in the case of solvent-borne coating compositions (hot-seal coatings, hot melt adhesives, radiation-curable coating compositions), the volume shrinkage that occurs during crosslinking reduces adhesion to a particular degree. It can be explained by the fact that the distance of the film former in the uncured state is greater than after the chemical cross-linking, in which covalent single bonds are formed. The volume shrinkage is the more pronounced, the higher the functionality and the lower the molecular weight and the standing claim of the film former. Since low molecular weight film formers have a very high functionality in relation to their molecular weight, their influence on the volume shrinkage is correspondingly high.

Depending on the type of drying, the temperature during curing varies between room temperature (about 20 ° C) and 250 ° C. As long as the glass transition temperature (Tg) of the forming film is below the cure temperature, the film may change shape, i. H. relax, whereby the influence of the volume shrinkage on the adhesion is rather low. However, if the Tg of the film forming rises above the curing temperature, internal tensions arise due to the crosslinking and the volume shrinkage associated therewith, which can lead to delamination of the coating from the substrate (delamination). Accordingly, it must be ensured that the coating can reduce these internal stresses (relax), what z. B. by adjusting the Tg of the binder 2nd and the film succeeds.

Often these parameters can not be adjusted due to the desired mechanical properties of the film. [Meichsner, G., Maday, M., Paulus, L / V., Schwalm, R., Beck, £., Menzel, K., Shrinkage and Inner Tensions of UV Cured Paints, Polymers & Coatings 2006, 24. September 26, 2006, 29].

By adding the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, the mechanical properties (eg hardness-elasticity balance) are improved, the glass transition temperature of the forming Films optimally adjusted to the selected curing temperature and reduces the volume shrinkage.

• Compatibility of the components If the compatibility of the components of the coating material composition is not optimal, this incompatibility leads to a loss of adhesion.

It has been found that there is a very broad compatibility of the polyesters 1 according to the invention with other constituents of coating materials and / or adhesives and / or sealants. For example, the polyesters 1 according to the invention can be homogeneously mixed in solution or melt with binders 2. Polyacrylates, saturated and / or unsaturated polyesters and copolyesters, derivatives of cellulose such. Cellulose nitrate, cellulose ethers and / or cellulose acetobutyrates, casein, phenolic and / or melamine-formaldehyde resins, benzoguanamine resins, phenolic resins, alkyd resins, acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, polyvinyl acetates, polyvinylpyrolidones, polyamides, ketone-aldehyde resins, ketone resins, Urea-aldehyde resins, polyurethanes, polyureas, epoxy resins, resoles, rosin resins, resinates,

Polyvinyl alcohols and derivatives, polyethers, natural resins, hydrocarbon resins such. As coumarone, indene, cyclopentadiene, terpene resins, silicone resins, rubbers, cyclo rubber, Maleinatharzen, silicic acid esters and alkali metal silicates (eg., Water glass) and / or chlorine and / or fluorine-containing polymers such. Example, polyvinyl chloride and its derivatives such as copolymers and terpolymers, chlorinated rubbers, chlorinated polyesters, PVDF and give after application and evaporation of any solvents present clear and transparent films.

The property of polyesters 1, to improve the adhesion of coating compositions, predestines them for corrosion protection. In addition to increasing adhesion to the substrate, intercoat adhesion to overlying boundary layers is also improved. Another advantage of the polyester is the high resistance to hydrolysis. Coating compositions which contain a polyester 1 according to the invention also have a high gloss and a good flow. In spray paints, the spray mist absorption is also significantly increased.

Component 1.

The constituent polyester 1 according to the invention can be present in amounts of from 0.1 to 80, preferably from 1 to 50, particularly preferably from 1 to 20,% by weight in the coating material compositions according to the invention.

In the following, the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, described in more detail.

The inventively essential yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, are obtained by reacting the alcohol component and the acid component.

The essential to the invention, yellowing, low viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, contain as acid component I. At least one α, ß-unsaturated dicarboxylic acid A). Preferably, the unsaturated polyester resins contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid or their derivatives such as. As anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters. It can also be used mixtures.

In addition to the α, β-unsaturated dicarboxylic acids A), the acid component I may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acids B) which have no α, β-unsaturated Have groupings. 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. As anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters. Preference is given to phthalic acid, trimellitic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid and derivatives thereof such as. As anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters. Particularly preferred are phthalic acid, trimellitic acid, methylhexahydrophthalic acid, hexahydrophthalic acid and / or adipic acid and derivatives thereof such. As anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters. It can also be used mixtures.

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 contained in a subordinate framework in amounts below 10 mol%, based on the acid component I., since they represent chain terminators, which reduce the OH or COOH functionality.

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

The acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.

As alcohol component II. Essentially essential 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 ²⁶ ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and 5,8-bis (hydroxymethyl ) Tricyclo [5.2.1.0 ²⁶ ] decane, wherein each isomer may be present 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 by separation by preparative GC or HPLC and subsequent NMR spectroscopy can be determined. All corresponding isomers of 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.

In addition, the Dicidolgemisch C) may contain up to 10% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of 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 ²⁶ ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane contains.

Dicidol is produced from the Diels-Alder product of cyclopentadiene, dicyclopentadiene, 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.

With regard to a high yellowing resistance, it was decisive for the invention that the dicidol mixture C) essential to the invention has a small proportion of metals contained in the preparation.

In particular, the content of the metals chromium, nickel, copper, cadmium, lead and rhodium, especially the content of rhodium, each alone, so each metal, below 2 mg / kg, preferably below 1, 5 mg / kg, particularly preferred below 1 mg / kg to avoid color and yellowing problems. A check of the metal content can z. B. by atomic absorption spectroscopy (AAS). In addition, it is essential that the content of aldehydes in the Dicidolgemisch C), which may be contained by an incomplete hydrogenation, is low, since aldehydes have a negative effect on the color and the yellowing resistance of the products adversely. Essential to the invention, a Dicidolgemisch C) is used which contains less than 2, preferably less than 1 wt .-% tricyclodecane (mono- / di-) aldehyde. The content can be determined qualitatively and / or quantitatively by gas chromatographic analysis (GC) optionally in combination with mass spectrometry (MS).

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 epoxy-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 ²⁶ ] decane is below 10, preferably below 5, especially below 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 dicidol mixture C) essential to the invention and thus in the polyester essential to the invention is below 10 mg / kg, preferably below 5 mg / kg, more preferably below 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 DE-AS-1 618 384, according to which dicyclopentadiene is hydroformylated as a 25 wt .-% benzene solution.

In addition to the Dicidolgemisch C), the alcohol component II. Other diols and / or polyfunctional alcohols D) having more than two OH groups in amounts of 0 to 95 mol%, preferably from 0 to 80, 0 to 50, preferably 0 to 10 mol%. Suitable are all linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. Preferred additional alcohols D) are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3

Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 2,4-dimethyl-2-ethylhexane -1, 3-diol used. It can also be used mixtures.

Monoalcohols such. B. hexanol are contained in the subordinate frame in amounts below 10 mol% based on the alcohol component, since they represent chain terminators that reduce the OH or COOH functionality.

In general, the alcohol component II. In a molar ratio of 0.5 to 2.0 to 1 to the acid component I., preferably 0.8 to 1, 5 to 1. Particularly preferably the reaction of 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, the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters 1, which are largely free of benzene and formaldehyde, consist of an alcohol component having at least 90 mol%, preferably 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, the polyesters 1 contain the o. G. Starting components as in embodiment I, but additionally a further acid B), selected from adipic acid or phthalic acid (anhydhd), wherein the ratio of the α, ß-unsaturated acid A) to the additional acid B) of 2 to 1 to 1 to 4 can vary , Ratios of about 1 to 1 to 1 to 3 are preferred.

The polyesters 1 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 from 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 ⁰ C, more preferably -10 to +75 ⁰ 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) to number average molecular weight (Mn) [Odian, George, Pήnciples of Polymeήzation, 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 1 according to the invention is between 500 and 6,000, preferably 700 and 5,000 g / mol and the weight-average molecular weight (Mw) between 900 and 27,000, preferably 1,000 and 15,000 g / mol. The polydispersity of the molecular weight distribution of the invention significantly en polyester is between 1, 3 and 4.5, preferably between 1, 6 and 4.0, so that the polyester has a low solution viscosity measured at 23 ⁰ C in accordance with DIN EN ISO 3219, as a 60% XyIoI solution between 50 and 5,000 nnPa-s, preferably between 50 and 3,500, more preferably between 100 and 2,500 mPa-s have.

The polyesters 1 according to the invention are amorphous and 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 test is carried out by differential 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 may also contain auxiliaries and additives, preferably selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for Influence rheological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers and deaerators, antistatic agents, thermoplastic additives, fire retardants, internal release agents, lubricants, wetting and dispersing agents, plasticizers, preservatives such. As well as fungicides and / or biocides, matting agents, fillers and / or blowing agents.

The polyesters 1 according to the invention are produced by (semi) continuous or discontinuous esterification and condensation of the acid components I. and the alcohol components II. In a one-stage or multi-stage procedure.

Component 2.

The binders 2 are used in amounts of 99.9 to 20, preferably 99 to 50, particularly preferably 99 to 80 wt .-%. Preference is given to binders from the group of polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyamides, casein, polyureas, derivatives of cellulose such as. As cellulose nitrate, cellulose ethers and / or Celluloseacetobutyrate, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinylpyrolidones, (cyclo) rubbers, natural resins, hydrocarbon resins such. Coumarone, indene, cyclopentadiene resins, terpene resins, maleate resins, phenolic resins, phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, ketone resins, aminoplasts (e.g., melamine, benzoguanamine resins), polyolefins, acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, epoxy resins, resoles, rosin resins, resinates, silicic acid esters and

Alkali metal silicates (eg waterglass) and / or silicone resins and / or chlorine- and / or fluorine-containing polymers, such as, for example, As polyvinyl chloride and its derivatives, chlorinated rubber, chlorinated polyester, PVDF used. It can too Mixtures are used. The binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.

The binders may be soluble in organic solvents but also in reactive diluents and / or soluble in water, mixed or dispersible. In principle, all binders which are used in the paint, paints, adhesives and printing inks industry are suitable.

Component 3.

The component 3 may optionally be present and is used in amounts of 0 to 80, preferably 0.1 to 70, particularly preferably 0.1 to 60 wt .-%. Suitable as component 3 are auxiliaries and additives such as, for example, inhibitors, organic solvents, water, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners,

Photosensitizers and initiators, additives for influencing rheological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers and deaerators, antistatic agents, lubricants, wetting and dispersing agents, crosslinking agents such. As melamine-formaldehyde resins, blocked and / or unblocked (poly) isocyanates, (poly) amines and / or

Poly (carboxylic acids), preservatives such. As well as fungicides and / or biocides, thermoplastic additives, plasticizers, matting agents, fire retardants, internal release agents and / or blowing agents.

Suitable solvents are those used in the paint, paint, adhesive and

Used in the printing ink industry. For example, z. As alcohols, acetates, ketones, ethers, glycol ethers, aliphatic, aromatic, alone or in mixture. However, it is also possible to use so-called reactive diluents which are commonly used in radiation-curing coating materials, such as, for example, B. mono-, or higher functional acrylate monomers, which may also be alkoxylated, and / or vinyl ethers.

Component 4. Component 4 may optionally be present and is used in amounts of from 0 to 70, preferably from 0.1 to 60, particularly preferably from 1 to 50,% by weight. In principle, all colorants and / or fillers which are used in the paint, paints, adhesives and printing inks industry are suitable. They are selected according to coloristic aspects and requirements such. B. hue, brightness, saturation, color intensity, compatibility, transparency, hiding power, light fastness, bleeding fastness, etc., as well as mechanical aspects and requirements such. B. Corrosion protection, hardness-elasticity balance, etc ..

There are inorganic pigments and fillers such. B. Milohblau, titanium dioxide, iron oxides, metal pigments (eg., Spinel, bismuth vanadate, nickel titanium, chromium oxide), carbon blacks and carbonates such. As chalk, limestone, calcite, dolomite, barium carbonate, sulfates, such as. As baryte, blanc fixe, calcium sulfates, silicates, such as. As talc, pyrophyllite, chlorite, mica, kaolin, slate, field column, precipitated Ca, Al, Ca / Al, Na / Al silicates, silicic acids, such as. As quartz, quartz, cristobalite, kieselguhr, precipitated and / or fumed silica, glass flour and oxides such. For example, magnesium and aluminum oxides and hydroxides and organic pigments such. As isoindoline, azo, Chinachdon-, perylene, dioxazine, phthalocyanine pigments used. In addition, metallic effect pigments such. Aluminum, copper, copper / zinc and zinc pigments, fire-colored bronzes, iron oxide-aluminum pigments,

Interference or pearlescent effect pigments such. Example, metal oxide mica pigments, bismuth oxychloride, basic lead carbonate, fish silver or micronized titanium dioxide, platelet-shaped graphite, platelet-shaped iron oxide, multi-layer effect pigments from PVD films or produced by the CVD process (Chemical Vapor Deposition) and Flüssigkhstall- (polymer) Pigments are used. In addition, dyes are used. A list of pigments, fillers and / or dyes used is described in "Römpp Lexikon, Lacke und Druckfarben, publisher Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 "or" Pigment and Füllstofftabellen, published by Olaf Lückert, Vincentz Verlag, Hannover, 2002 ".

The invention also provides a process for the preparation of coating compositions comprising substantially 1. 0.1 to 80 wt .-% of a yellowing-resistant, low-viscosity, unsaturated, amorphous polyester, which is largely free of benzene and formaldehyde, consisting of

1. 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 having no α, ß-unsaturated groups where the sum of A) and B) is 100 mol%, II. an alcohol component

C) 5 to 100 mol% of a mixture of diclidols,

the content of mono (hydroxymethyl) thcyclo [5.2.1.0 ²⁶ ] decane in the dicidol mixture C) is less than 10% by weight,

2. 99.9 to 20 wt .-% of at least one further binder, 3. 0 to 80 wt .-% of at least one adjuvant, and / or additive, 4. 0 to 70 wt .-% of at least one colorant and / or filler . wherein the sum of the weights of the components is 1. to 4. 100 wt .-%, by intensive mixing of the components at temperatures of 20 to 80 ° C.

The compositions are prepared by intensive mixing of the components at temperatures of 20 to 80 ° C ("Textbook of Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, Page 229 ff.) Non-liquid components are optionally first dissolved in suitable solvents or water before mixing, then the remaining components are added with stirring, in the case of pigments and / or fillers, for example, dispersion takes place.

The subject matter is also the use of the coating material compositions.

The subject matter is substantially containing the use of coating compositions

A) 10 to 100 mol%, preferably 15 to 90 mol% of at least one α, β-unsaturated dicarboxylic acid,

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) gives 100 mol%, and wherein the content of benzene is below 10 mg / kg and the content of formaldehyde is 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) thcyclo [5.2.1.0 ²⁶ ] decane in the

Dicidol mixture C) is less than 10 wt .-%, - the content of the metals chromium, nickel, copper, cadmium, lead and

Each rhodium in the Dicidol mixture C) is less than 2 mg / kg, and

2. 99.9 to 20% by weight of at least one further binder,

3. 0 to 80% by weight of at least one adjuvant and / or additive, 4. 0 to 70% by weight of at least one colorant and / or filler,

where the sum of the weights of the components is 1. to 4. 100% by weight,

for metallic and / or mineral substrates and / or for substrates made of wood, paper, cardboard, glass, textiles and / or plastics.

In this case, the coating compositions of the invention are used as aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid) thermosetting, radiation-curable and / or air-drying (oxidatively and / or physically) sweeping agents, fillers -, sealants and / or adhesives.

The coating material compositions according to the invention can be used, in particular as solvent-containing and / or aqueous coating materials and / or as solvent-free coating materials (eg radiation-curable coating materials and / or powder coatings) such as fillers, primers, fillers, basecoats, topcoats and / or clearcoats, Printing inks, ballpoint pen pastes, Pigment preparations, inks, polishes, glazes, laminations, cosmetics, such. As nail polishes, sealants and insulating materials and adhesives.

In this case, substrates of z. As metals, plastics, paper, cardboard, inorganic materials such. As ceramics, stone, concrete and / or glass, textiles, fibers, fabric materials, leather and synthetic materials, such as. B., imitation leather, wood, films of plastics and / or composites such. B. aluminum-laminated films with the invention

Coating material composition are coated. The compositions can be used for all conceivable applications both indoors and outdoors, such. B. as Bautenschutzfarben / -Iacke, road marking paints, automotive coatings (OEM, Refinish), coil coatings, can coatings, textile finishing, wood coatings, plastic coatings, and for decorative applications, etc. Also suitable for use in adhesives, such. As for the bonding of textiles, leather, paper, plastics, metals and similar materials, such compositions are suitable.

The coating materials of the invention can be applied by any known method, e.g. Rolling, brushing, dipping, flooding, spraying, pouring, rolling, spraying, printing, wiping, washing, tumbling, centrifuging.

The coating compositions of the invention are characterized by a high solids content. The coating compositions according to the invention have a solids content of from 10% to 99.9%, preferably from 20% to 99.9%, particularly preferably from 50% to 99.9%. The content of volatile organic compounds (VOC) is between 0 and 60 wt .-%, preferably between 0 and 40 wt .-%, particularly preferably between 0 and 30 wt .-%.

The dried, cured or crosslinked films which are obtained from the coating compositions according to the invention are distinguished by particularly good adhesion to metallic, mineral substrates or to substrates made of wood and plastics critical climatic conditions with high corrosion protection, a high gloss and a very good stone chip resistance and resistance to salt solutions.

The coating compositions according to the invention have very good adhesion properties to underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.

The course is perfect and the surfaces are free of disturbances, such as craters and wetting disorders. Also, the water resistance is very good. Also, the compositions of the invention have a high yellowing resistance and a very good hardness elasticity balance.

The invention also relates to objects coated with the coating material compositions.

The following examples are intended to further illustrate the invention but not to limit its scope:

Analytical Methods of the Substances Essential to the Invention 1.

Determination of the content of formaldehvd

The formaldehyde content is determined by the lutidine method by HPLC

(Official Collection of Investigation Proceedings under § 64 LFGB K 84.00 7 (EC): "Detection and Quantitative Determination of Free Formaldehyde")

Device: HPLC system with two isocratic pumps, thermostatically controlled reactor, variable UVA / IS detector and evaluation unit, eg. B. Hewlett-Packard HP 1100 with

PC-based evaluation software ChemStation.

Stationary phase C18-reversed-phase, 5 μm, 250 x 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 of benzene

The benzene content was determined by headspace GC / FID analysis.

Device: Capillary gas chromatograph with 2xFID, z. Perkin-Elmer 8500 and headspace sampler, e.g. Perkin-Elmer HS101

Separation columns: 2 capillary columns

Column 1

Stationary phase: CP-SiI 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 pre-pressure: 70 kPa high-pressure dosage: 150 kPa GC method: oven temperature: 50 ⁰ C; 4 minutes; 57min - 130 ⁰ C; 307min - 180 ⁰ 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 takes place against an internal standard under

Consideration of experimentally determined calibration factors Determination of the metal content

The content of the metals chromium, nickel, copper, cadmium, lead and rhodium was determined by means of atomic absorption spectroscopy (AAS).

digestion:

From 0.3 to 0.7 g of sample material are weighed, with 3 ml of water and 6 ml of HNO ₃ was added (65%) and in the microwave autoclave at 255 ⁰ C and 130 - 140 bar digested 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 coupled plasma optical emission spectroscopy, type Jobin-Y by Ultima2, with radial argon plasma). The meter is calibrated from 0.1 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 (hvdroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ldecan

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 El + and Cl option)

Separation columns: capillary column

Stationary phase: MDN-5S

Length: 30 m

Inner diameter: 0.32 mm Carrier gas: helium

Column pressure: 100 kPa (init pressure)

Mode: constant flow

GC method: Oven temperature: 60 ^° C .; 87min - 250 ⁰ C; 10 min

Injector temperature: 275 ° C

Detector temperature: 250 ⁰ 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

Standardization to 100 area percent.

The GC / MS evaluation was initially performed 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 slices and recorded the FT IR 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) by means of Differentialkalorimethe (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 made in accordance with DIN EN ISO 4629 "Determination of the Hydroxyl Number".

Determination of the acid number (SZ number)

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

Determination of the content of nonvolatile matter (nfA) The content of nonvolatile matter is determined in accordance with DIN EN ISO 3251. It is given as the mean value from a duplicate determination. In a cleaned aluminum dish (Taramasse nrπ) are weighed on an analytical balance about 2 g of the sample (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:

nfaJ " ^{3 ffll} - i00 [mass%]

Determination of Gardner color number before and after thermal exposure

The Gardner color number is determined in 60% solution of the resin in

XyIoI 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). The Gardner color number is then determined in 50% strength solution of the thermally stressed resin in xylene based on DIN EN ISO 4630.

Determination of the solution viscosity

The solution viscosity is determined according to DIN EN ISO 3219. If a solid resin is present, it is first dissolved in a suitable solvent, such as, for example, xylene, with a solids content of, for example, 60%. The viscosity is measured at 23 ⁰ C using a plate / cone viscometer (1 / 4OS).

Determination of the molecular weight and the polvdispersity The measurement of the molecular weight distribution of the polyesters essential to the invention is carried out by means of gel permeation chromatography in tetrahydrofuran against polystyrene as standard. The polydispersity D is calculated from the ratio of the weight average (Mw) to the number average (Mn). 2. Analytical Methods of the Inventive Coating Compositions

The content of benzene and formaldehyde content are identical to those described above.

Determination of hardness-elasticity balance

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

Determination of relative volume shrinkage AV

The measurement was carried out by determining the density of the formulation before (CI _M ) and after UV curing (dp) by means of a 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 yellowing resistance, the polyesters were used as a 60% solution in xylene in a 1K alkyd melamine stoving lacquer. 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.

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

Determination of substrate wetting and course

The determination of the substrate wetting and the course takes place visually. A good Wetting is achieved when the applied paint a closed film without defects such. B. crater results. A good course is achieved if the applied, closed film has a low intrinsic structure (eg, orange peel, too deep penetration into the substrate in, for example, woods, or the like).

Determination of compatibility

The determination of the compatibility is carried out in such a way that the polyester essential to the invention 1 with the binder to be tested in a mass ratio of 1: 4 and 1: 2 (based on solid resin) dissolved in 50% solution in the solvent in which the resin to be tested is, is mixed. By optically assessing the solution, it is examined for turbidity and incompatibilities. After mounting the solutions on glass plates and evaporation of the solvent then the visual assessment of the film is carried out for turbidity and incompatibilities.

Determination of liability

The adhesion of the coatings was examined before and after loading by means of a cross-cut test (DIN EN ISO 2409).

Stress tests 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 ⁰ C in demineralised water)

Determination of corrosion resistance Salt spray test (DIN EN 13523-8)

Determination of gloss level

The determination was carried out according to DIN EN ISO 2813 at 20760 °.

Determination of the content of nonvolatile matter (nfA)

The determination of the content of non-volatile components is carried out according to DIN EN ISO 3251. It is given as the mean value of a duplicate determination. Place in a cleaned aluminum dish (Taramasse nrπ) on an analytical balance Approximately 2 g of the sample weighed (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 non-volatile fraction (nfA) is calculated according to the following equation: - 100 [mass%]

Examples Starting component Dicidol mixture C) in an 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 ²⁶ ] 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 (Inventive Polyester)

3.3 mol of Dicidolgemisches, 2.1 mol of phthalic anhydride and 1, 1 mol of maleic anhydride are reacted in a reaction flask with distillation head, stirrer and thermometer in a nitrogen atmosphere at 210 ° C to 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 of 62 ⁰ C (no crystalline peak), viscosity as a 60% solution in xylene 960 mPa · s, Gardner color number 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.

Example 2 (Inventive Polyester)

5.3 mol of the Dicidolgemisches, 2.5 moles of adipic acid and 2.5 moles of maleic anhydride are in a reaction flask with distillation head, stirrer and thermometer reacted 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 60% solution in xylene: 780 mPa s, Gardner color number as 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 inventive polyesters from Examples 1 and 2 were investigated. They have 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 Weather-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 since almost no additional yellowing is caused by the polyesters essential to the invention.

Table 2: Results of the WOM investigations

Example 3 (Inventive 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 60% solution in xylene: 850 rnPa 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.

The thus prepared, essential to the invention polyester 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 = 200: <30 mPas, pH: 7.8, solids content: 38.5%.

applications

Comparative Example C1 and Inventive Use Examples B1 to B2

In a red anticorrosion paint based on a soluble vinyl chloride (VC) copolymer (V1), in each case 2.2% by weight of the polyesters according to the invention according to Examples 1 and 2 are used in the form of their 60% strength solutions in xylene (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 (%)

The content of benzene and formaldehyde content in the compositions B1 and B2 was less than 10 mg / kg.

Substrate: galvanized steel / layer thickness (dry): approx. 30 μm / drying: 24 h

room temperature

Table 4: Results of liability and infiltration

The values show the different adhesion of the paints before and after the salt spray test. While V1 per se has poor adhesion even before loading, the adhesion in Examples B1 and B2 is very good.

Consequently, the adhesion is improved even under critical climatic conditions (high water resistance) and under the action of salt solutions. The corrosion protection effect, in contrast to the formulation without the addition of the invention essential polyester significantly improved. While an infiltration of> 10 mm occurs in V1, there is no infiltration in the case of B1 and B2.

Comparative Example C2 and Inventive Application Examples B3 and B4

2.8% by weight of the polyesters according to Examples 1 and 2 in the form of their 60% strength solutions in xylene are used in each case in a white corrosion protection varnish 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 (%)

Drying: 24 h room temperature / layer thickness: 25 - 30 μm

Table 6: Results of adhesion on different substrates

Comparative Example C3 and inventive use examples B5 and B6

In a white stoving lacquer based on a hydroxyl-containing polyacrylate resin crosslinked with a fully methyl-etherified melamine resin (V3), in each case 3.2% by weight of the polyesters according to Examples 1 and 2 are used in the form of their 60% strength solutions in xylene (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 polyesters. 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 through the polyester significantly improved stone impact resistance again.

Table 7: Formulation of a white acrylate / melamine stoving lacquer (%)

Baking conditions: 30 min 130 ° C Substrate: galvanized steel

Layer thickness (dry): 25 - 30 μm

Table 8: Results of the coating properties

Comparative Example C4 and inventive use examples B7 and B8

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 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 (%)

Stoving conditions: 15 min 170 ⁰ C Substrate: galvanized steel Layer thickness (dry): 25 - 30 μm

Table 10: Results of liability

Comparative Example C5 and Inventive Application Example B9

In a metallic plastic paint (V5), 2% by weight of the thermoplastic acrylate resin is replaced by the polyester of Example 2 in the form of its 60% 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 (%)

Substrate: ABS Spray Viscosity: 20 seconds in the Ford 4 cup

Table 12: Results of adhesion after Tesa tear

Comparative Example C6 and Inventive Application Example BIO To a road marking color (V6) of the invention essential polyester 1 according to Example 1 is given (Table 13). The adhesion to mineral substrate is greatly improved.

Table 13: Formulation of a road marking color (%)

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 ⁰ C) for about 80 Substrate: Asphalt wet coating layer thickness about 500 microns Table 14: Results of liability

Comparative Example V7 and inventive application examples B11 and B12

In a radiation-curable clearcoat based on an epoxy acrylate (V7), in each case 10% by weight of the binder is replaced by the polyesters according to Examples 1 and 2 in the form of their 50% solutions in tripropylene glycol diacrylate (TPGDA) (Table 15). The initial moderate adhesion to galvanized steel is greatly improved. In addition, the viscosity is lowered, the volume shrinkage significantly reduced and the hardness-elasticity balance improved. 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

Substrate: galvanized steel Layer thickness (dry): 20 - 30 μm Table 16: Results of the coating properties

Comparative Example C8 and Inventive Application Example B13 The aqueous polyester according to Example 3 was used in an aqueous plastic paint (V8). It significantly improves adhesion to EPDM.

Table 17: Formulation of a PUR plastic paint for EPDM

Substrate: EPDM

Layer thickness (wet): 100 μm Drying: 24 h room temperature Table 18: Results of liability

Claims

Patent claims

1. Essentially containing coating material compositions

1. 0.1 to 80% by weight of a yellowing-resistant, low-viscosity, unsaturated, amorphous polyester that is largely free of benzene and

Formaldehyde is composed of

I. an acid component

A) 10 to 100 mol% of at least one α, ß-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 from A) and B) gives 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 di- and/or polyfunctional

Alcohol, where the sum of C) and D) is 100 mol%, and where - the benzene content is less than 10 mg/kg and the formaldehyde content 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

C) is less than 2% by weight,

- the content of mono(hydroxymethyl)thcyclo [5.2.1.0 ²⁶ ]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) is each less than 2 mg/kg, and

2. 99.9 to 20% by weight of at least one further binder,

3. 0 to 80% by weight of at least one auxiliary and/or additive,

4. 0 to 70% by weight of at least one colorant and/or filler,

where the sum of the weights of components 1 to 4 is 100% by weight.

2. Coating material compositions according to claim 1, characterized in that in component 1. α, ß-unsaturated acids A) selected from citraconic, fumaric, itaconic, maleic and / or mesaconic 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.

3. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. as α, ß-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 contained.

4. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. acids B) selected from phthalic acid, isophthalic acid, terephthalic acid, 1 ^-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, whose derivatives such as anhydrides and/or low molecular weight alkyl esters such as methyl and/or ethyl esters, alone or in mixtures, are contained.

5. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. 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.

6. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. a dicidol mixture 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 ²⁶ ]decane and 5,8-bis(hydroxymethyl)tricyclo [5.2.1.0 ²⁶ ]decane, each isomer being able to be present in the mixture in a proportion of 20 to 40% by weight and the sum of the three isomers is 90 to 100% by weight, preferably 95 to 100% by weight, and the mixture is present at least 5 mol% in the alcohol component II of the polyester.

7. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. alcohols D) 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, cyclohexyldimethanol, glycehn, hexanediol, neopentyl glycol,

Trimethylolethane, trimethylolpropane and/or pentaerythritol as well as bisphenol A, B, C, F, norbornylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, alone or in mixtures, are included.

8. Coating material compositions according to at least one of the preceding claims, characterized in that component 1. contains the alcohol component II. in a molar ratio of 0.5 to 2 to 1, preferably from 0.8 to 1.5 to 1, to the acid component I.

9. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. the content of the metals chromium, nickel, copper,

Cadmium, lead and/or rhodium are each less than 1.5 mg/kg.

10. Coating material compositions according to at least one of the previous ones

Claims, characterized in that the polyesters 1. have an acid number between 1 and 200 mg KOH/g, preferably between 1 and 100, particularly preferably between 1 and 50 mg KOH/g.

11. Coating material compositions according to at least one of the preceding claims, characterized in that the polyesters 1. have an OH number between 1 and 500 mg KOH/g, preferably between 1 and 200 mg KOH/g, particularly preferably between 1 and 100 mg KOH/g. g.

12. Coating material compositions according to at least one of the preceding claims, characterized in that the polyesters 1. have a Tg of -30 to +90 ⁰ C, preferably -20 to +80 ⁰ C, particularly preferably -10 to 75 ° C.

13. Coating material compositions according to at least one of the preceding claims, characterized in that the polyesters 1. have an M _n between 500 and 6000, preferably 700 and 5000 g/mol and an M _w between 900 and 27000, preferably 1000 and 15000 g/mol.

14. Coating material compositions according to at least one of the preceding claims, characterized in that the polydispersity of the molecular weight distribution of the polyesters 1. is between 1.3 and 4.5, preferably between 1.6 and 4.0.

15. Coating material compositions according to at least one of the preceding claims, characterized in that the solution viscosity of the polyester 1., measured at 23 ° C according to DIN EN ISO 3219, as a 60% solution in XyIoI is between 50 and 5000 mPa-s, preferably between 50 and 3500, particularly preferably between 100 and 2500 nnPa-s.

16. Coating material compositions according to at least one of the preceding claims, characterized in that component 1 contains auxiliary substances and additives.

17. Coating material compositions according to at least one of the preceding claims, characterized in that in component 1. the alcohol component II. consists of at least 90% dicidol mixture C) and the acid component I. consists of fumaric acid and / or maleic acid (anhydride).

18. Coating material compositions according to claim 17, characterized in that component 1. additionally contains adipic acid and/or phthalic acid (anhydride) as an acid component in a ratio of α, ß-unsaturated acid A) to additional acid B) of 2 to 1 to 1 to 4, especially from 1 to 1 to 1 to 3.

19. Coating material compositions according to at least one of the preceding claims, characterized in that binders 2. from the group of polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins,

Polyamides, casein, polyureas, cellulose derivatives such as. B. cellulose nitrate, cellulose ethers and / or cellulose acetobutyrates, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinylpyrolidones, (cyclo) rubbers, natural resins, hydrocarbon resins such as. B. coumarone, indene, cyclopentadiene resins, terpene resins, maleic resins, phenolic resins,

Phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, ketone resins, aminoplasts such as. B. melamine, benzoguanamine resins, polyolefins, acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, epoxy resins, resoles, rosin resins, resinates, silicic acid esters and alkali metal silicates such as. B. water glass and / or silicone resins and / or chlorine and / or fluorine-containing polymers such as. B. polyvinyl chloride and its derivatives, chlorinated rubbers, chlorinated polyester, PVDF, alone or in mixtures.

20. Coating material compositions according to at least one of the preceding claims, characterized in that auxiliary substances and / or additives 3. selected from inhibitors, organic solvents, water, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners,

Photosensitizers and initiators, additives to influence rheological properties such as B. thixotropic agents and/or thickeners, leveling agents, anti-skinning agents, defoamers and deaerators, Antistatics, lubricants, wetting and dispersing agents, crosslinking agents such as B. melamine-formaldehyde resins, blocked and / or unblocked (poly) isocyanates, (poly) amines and / or (poly) carboxylic acids, preservatives such as. B. also fungicides and/or biocides, thermoplastic additives, plasticizers, matting agents,

Fire retardants, internal release agents and/or blowing agents, alone or in mixtures, are included.

21. Coating material compositions according to at least one of the preceding claims, characterized in that as component 3. alcohols, acetates, ketones, ethers, glycol ethers,

Aliphatics, aromatics, alone or in a mixture, are contained.

22. Coating material compositions according to at least one of the preceding claims, characterized in that reactive diluents are included as component 3.

23. Process for producing coating material compositions essentially containing 1. 0.1 to 80% by weight of a yellowing-resistant, low-viscosity, unsaturated, amorphous polyester, which is largely free of benzene and formaldehyde, consisting of I. an acid component

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 has, the sum of A) and B) being 100 mol%, II. an alcohol component C) 5 to 100 mol% of a dicidol mixture,

D) 0 to 95 mol% of at least one di- and/or polyfunctional alcohol, the sum of C) and D) being 100 mol%, and the benzene content being less than 10 mg/kg and the formaldehyde content being 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

C) is below 2% by weight, the content of mono(hydroxymethyl)thcyclo [5.2.1.0 ²⁶ ]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) is below 2 mg/kg, and

2. 99.9 to 20% by weight of at least one further binder,

3. 0 to 80% by weight of at least one auxiliary and/or additive, 4. 0 to 70% by weight of at least one colorant and/or filler,

where the sum of the weights of components 1 to 4 is 100% by weight,

by intensively mixing the components at temperatures of 20 to 80 °C.

24. Use of the coating material compositions essentially containing

Formaldehyde is consisting of I. an acid component 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 has, the sum of A) and B) being 100 mol%, II. an alcohol component

C) 5 to 100 mol% of a dicidol mixture, D) 0 to 95 mol% of at least one di- and/or polyfunctional

Alcohol, where the sum of C) and D) is 100 mol%, and where the benzene content is less than 10 mg/kg and the formaldehyde content 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 C) is less than 2% by weight, the content of mono(hydroxymethyl)thcyclo [5.2.1.0 ²⁶ ]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) is below 2 mg/kg, and

2. 99.9 to 20% by weight of at least one further binder,

3. 0 to 80% by weight of at least one auxiliary and/or additive,

4. 0 to 70% by weight of at least one colorant and/or filler,

where the sum of the weights of components 1 to 4 is 100% by weight, for metallic and/or mineral substrates and/or for substrates made of wood, paper, cardboard, glass, textiles and/or plastics.

25. Use of the coating material compositions as aqueous, solvent-based (normal, medium, high, very high solids) and/or solvent-free

(powder and/or liquid) heat-curable, radiation-curable and/or air-drying (oxidative and/or physical) coating materials, fillers and/or sealants and/or adhesives.

26. Use of the coating material compositions as fillers, primers, fillers, base coats, top coats and/or clear coats, printing inks, ballpoint pen pastes, pigment preparations, inks, polishes, glazes, laminations, cosmetic items, such as. E.g. nail polishes, sealants and insulation materials as well as adhesives.

27. Use of the coating material compositions on metals, plastics, paper, cardboard, inorganic materials such as ceramics, stone, concrete and/or glass, textiles, fibers, fabric materials, leather and synthetic materials such as artificial leather, wood, films made of plastics and/or composite materials such as aluminum-clad foils.

28. Use of the coating material compositions as building protection paints and dyes, road marking paints, automotive paints, coil coatings, can coatings, textile finishing paints, wood paints, plastic paints and paints for decorative applications.

29. Objects coated with the coating compositions.