DE102007047586A1 - Coating compositions - Google Patents

Abstract

The invention relates to coating compositions comprising at least one binder, a formaldehyde-free, carbonyl-hydrogenated ketone-aldehyde resin based on formaldehyde with low viscosity, very low color number and very high heat and light resistance, a colorant and optionally auxiliaries and additives, their preparation and their Use.

Description

The The invention relates to coating composition compositions from at least one binder, a formaldehyde-free, carbonyl-hydrogenated Ketone-aldehyde resin based on low viscosity formaldehyde, very low color number and very high heat and light resistance, a colorant and optionally auxiliaries and additives, their Production and its use

used the coating compositions for the Coating of different substrates, such. Metals, plastics, Paper, paper laminates, cardboard, cardboard, inorganic materials such as paper As ceramic, stone, concrete, plaster and / or glass, textiles, fibers, Tissue materials, leather and synthetic materials, such. B. Artificial leather, wood, foils of plastics and composites such as z. As aluminum-laminated films, the coating as far as possible is free from formaldehyde.

To The application of coating materials is a quick drying desirable to ensure rapid processing and defects caused by e.g. For example, dirt such as dust and dirt, etc., to avoid. It is also high Scratch resistance important to one over mechanical To obtain load insensitive coating.

It is known that ketones or mixtures of ketones and aldehydes can be converted to resinous products in the presence of basic catalysts or acids. Thus, it is possible to prepare resins from mixtures of cyclohexanone and methylcyclohexanone ( Ullmann Vol. 12, p. 551 ). The reaction of ketones and aldehydes usually leads to hard resins, which are often used in the paint industry. Technically important ketone-aldehyde resins are nowadays mostly produced using formaldehyde.

Ketone-formaldehyde resins have been known for a long time. Process for the preparation are for. B. described in DE 33 24 287 . US 2,540,885 . US 2,540,886 . DE 11 55 909 . DD 12 433 . DE 13 00 256 and DE 12 56 898 ,

to Usually, ketones and formaldehyde are produced in the presence reacted by bases with each other.

Ketone-aldehyde be in coating materials z. B. as a film-forming additional components used to control certain properties, such as drying rate, To improve gloss, hardness or scratch resistance. Because of their relatively low molecular weight have conventional Ketone-aldehyde resins have a low melt and solution viscosity and therefore serve in coating materials u. a. as a film-making Functional fillers.

The Carbonyl groups of the ketone-aldehyde resins are subject to z. B. irradiation with z. B. sunlight classic degradation reactions such. From the Norrish Type I or II [Laue, Plagens, Names and Keyword Reactions, Teubner Studienbücher, Stuttgart, 1995].

The use of unmodified ketone-aldehyde or ketone resins is therefore for high-quality applications such. B. outdoors, in which high resistance properties, in particular to weathering and heat are required, not possible. These disadvantages can be improved by hydrogenation of the carbonyl groups. The conversion of the carbonyl groups into secondary alcohols by hydrogenation of ketone-aldehyde resins has been practiced for a long time ( DE 826 974 . DE 870 022 . JP 11012338 . US 6,222,009 ).

The preparation of carbonyl- and ring-hydrogenated ketone-aldehyde resins based on ketones containing aromatic groups is also possible. Such resins are used in DE 33 34 631 described.

As Comprehensive own findings prove that all these are hydrogenated Products have a relatively high content of free formaldehyde in common. By the hydrogenation process described by the prior art Although the proportion of free formaldehyde over the unhydrogenated ketone-formaldehyde resins, it remains however, significant amounts of free formaldehyde in the hydrogenation products back. Higher temperatures during the Hydrogenation can lead to a further reduced formaldehyde content However, this can be detrimental to other resin properties such as As color, melting ranges, OH numbers, etc. impact.

Formaldehyde can cause health problems. An exact classification, however, is not yet done. The International Agency for Research in 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 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.

A method of lowering the formaldehyde content of non-hydrogenated acetone-formaldehyde resins without reducing the carbonyl groups is disclosed in US Pat US 5,247,066 described. Here a content of free formaldehyde is reached below 0.4%, which is significantly too high by today's standards. The carbonyl groups present impair the properties described above.

The in the patents DE 826 974 . DE 870 022 . JP 11012338 . US 6,222,009 and DE 33 34 631 The processes listed lead to products which have improved properties relative to the starting materials in terms of color, heat and light resistance. From today's point of view these products are no longer sufficient despite their improvement.

The DE-10 2006 00 9079.9 describes the preparation of formaldehyde-free, carbonyl-hydrogenated ketone-aldehyde resins. However, the use in coating materials is not described.

Ketone-aldehyde have always been used to make the content non-volatile Increase constituents in coating materials. Under the compulsion of new guidelines such. Eg Directive 1999/13 / EC of the EU Council on the limitation of emissions of volatile substances Organic compounds must continue with these properties be improved.

task The present invention was to paint compositions for coating different substrates, which are free from free formaldehyde. The coating material compositions should have a high drying rate, water resistance and having scratch resistance and a low solution viscosity at high solids content. In addition, the films should have a have good adhesion to the ground, a low haze, a high color stability and a high heat and light resistance have.

The The object underlying the invention was able to surprisingly through the use of special coating compositions, which are described in more detail below, solved become.

• A) 5 bis 75 Gew.-% mindestens eines carbonylhydrierten Keton-Aldehydharzes auf Basis von Formaldehyd, mit einem Gehalt an freiem Formaldehyd von weniger als 3 ppm, das im Wesentlichen die Strukturelemente gemäß Formel I enthält
  
  mit R = aromatisch mit 6–14 Kohlenstoffatomen, (cyclo-)aliphatisch mit 1–12 Kohlenstoffatomen, R' = H, CH₂OH, k = 2 bis 15, bevorzugt 3 bis 12, besonders bevorzugt 4 bis 12, m = 0 bis 13, bevorzugt 0 bis 9, l = 0 bis 2, wobei die Summe aus k + l + m zwischen 5 und 15 und k > m ist, bevorzugt zwischen 5 und 12 liegt, die drei Strukturelemente alternierend oder statistisch verteilt sein können und wobei die Strukturelemente über CH₂-Gruppen linear und/oder über CH-Gruppen verzweigend verknüpft sind, und
• B) 20 bis 90 Gew.-% mindestens eines Bindemittels, und
• C) 0 bis 50 Gew.-% mindestens eines Farbmittels und/oder Füllstoffs und
• D) 5 bis 75 Gew.-% mindestens eines Zusatzstoffes, wobei die Summe der Gewichtsangaben von Komponente A) bis D) 100 Gew.-% beträgt.

The invention relates to coating compositions containing free formaldehyde below 100 ppm, essentially containing

• A) 5 to 75 wt .-% of at least one carbonyl-hydrogenated ketone-aldehyde resin based on formaldehyde, having a content of free formaldehyde of less than 3 ppm, which contains substantially the structural elements of formula I.
  
  with R = aromatic having 6-14 carbon atoms, (cyclo) aliphatic having 1-12 carbon atoms, R '= H, CH ₂ OH, k = 2 to 15, preferably 3 to 12, particularly preferably 4 to 12, m = 0 to 13, preferably 0 to 9, l = 0 to 2, wherein the sum of k + l + m is between 5 and 15 and k> m, preferably between 5 and 12, the three structural elements can be distributed alternately or statistically and wherein the structural elements via CH ₂ groups are linearly and / or branched via CH groups, and
• B) 20 to 90 wt .-% of at least one binder, and
• C) 0 to 50 wt .-% of at least one colorant and / or filler and
• D) 5 to 75 wt .-% of at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%.

It It was found that the combination of the below described Coating composition of components A) to D) meet all required criteria.

Component A)

The carbonyl-hydrogenated ketone-aldehyde resins essential to the invention are in amounts of 5 to 75 wt .-%, preferably from 5 to 50 wt .-% used.

mit
R = aromatisch mit 6–14 Kohlenstoffatomen, (cyclo-)aliphatisch mit 1–12 Kohlenstoffatomen,
R' = H, CH₂OH,
k = 2 bis 15, bevorzugt 3 bis 12, besonders bevorzugt 4 bis 12;
m = 0 bis 13, bevorzugt 0 bis 9,
l = 0 bis 2,
wobei die Summe aus k + l + m zwischen 5 und 15 und k > m ist, bevorzugt zwischen 5 und 12 liegt, die drei Strukturelemente alternierend oder statistisch verteilt sein können und wobei die Strukturelemente über CH₂-Gruppen linear und/oder über CH-Gruppen verzweigend verknüpft sind.As component A) are suitable carbonyl-hydrogenated ketone-aldehyde resins based on formaldehyde, having a content of free formaldehyde of less than 3 ppm, which contain substantially the structural elements of formula I.

With
R = aromatic with 6-14 carbon atoms, (cyclo) aliphatic with 1-12 carbon atoms,
R '= H, CH ₂ OH,
k = 2 to 15, preferably 3 to 12, particularly preferably 4 to 12;
m = 0 to 13, preferably 0 to 9,
l = 0 to 2,
where the sum of k + l + m is between 5 and 15 and k> m, preferably between 5 and 12, the three structural elements can be distributed alternately or randomly and wherein the structural elements are linear and / or via CH ₂ groups via CH ₂ groups Groups are branching linked.

• • der Gehalt an freiem Formaldehyd unter 3 ppm, bevorzugt unter 2,5 ppm, besonders bevorzugt unter 2,0 ppm liegt,
• • die Carbonylzahl zwischen 0 und 100 mg KOH/g, bevorzugt zwischen 0 und 50 mg KOH/g, besonders bevorzugt zwischen 0 und 25 mg KOH/g liegt,
• • die Hydroxylzahl zwischen 50 und 450 mg KOH/g, bevorzugt zwischen 150 und 400 mg KOH/g, besonders bevorzugt zwischen 200 und 375 mg KOH/g liegt,
• • die Farbzahl nach Gardner (50% in Ethylacetat) unter 1,5, bevorzugt unter 1,0, besonders bevorzugt unter 0,75 liegt,
• • die Farbzahl nach Gardner (50% in Ethylacetat) nach thermischer Belastung des Harzes (24 h, 150°C) unter 2,0, bevorzugt unter 1,5, besonders bevorzugt unter 1,0 liegt,
• • die Polydispersität (Mw/Mn) der Harze zwischen 1,35 und 1,6, besonders bevorzugt zwischen 1,4 und 1,58 liegt,
• • die Lösungsviskosität, 40%ig in Phenoxyethanol, zwischen 5000 und 12000 mPa·s, besonders bevorzugt zwischen 6000 und 10000 mPa·s liegt,
• • der Schmelzpunkt/-bereich zwischen 50 und 150°C, bevorzugt zwischen 75 und 140°C, besonders bevorzugt zwischen 100 und 130°C liegt und
• • der Gehalt an nicht flüchtigen Bestandteilen nach Temperung über 24 h bei 150°C über 97,0%, bevorzugt über 97,5% liegt.

Particular preference is given to carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde
characterized in that

• The content of free formaldehyde is below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm,
• The carbonyl number is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g,
• The hydroxyl number is between 50 and 450 mg KOH / g, preferably between 150 and 400 mg KOH / g, more preferably between 200 and 375 mg KOH / g,
• The Gardner color number (50% in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75,
• The Gardner color number (50% in ethyl acetate) after thermal loading of the resin (24 h, 150 ° C.) is below 2.0, preferably below 1.5, particularly preferably below 1.0,
• The polydispersity (Mw / Mn) of the resins is between 1.35 and 1.6, more preferably between 1.4 and 1.58,
• The solution viscosity, 40% in phenoxyethanol, is between 5000 and 12000 mPa.s, more preferably between 6000 and 10000 mPa.s,
• The melting point / range is between 50 and 150 ° C, preferably between 75 and 140 ° C, more preferably between 100 and 130 ° C, and
• • The content of non-volatile constituents after tempering for 24 h at 150 ° C over 97.0%, preferably above 97.5%.

• I. durch Herstellung der Grundharze durch Kondensation von mindestens einem Keton mit mindestens einem Aldehyd in Gegenwart mindestens eines basischen Katalysators und ggf. mindestens eines Phasentransferkatalysators, lösemittelfrei oder unter Verwendung eines wassermischbaren organischen Lösemittels,

und anschließend

• II. durch kontinuierliche, halb- oder diskontinuierlicher Hydrierung der Carbonylgruppen der Keton-Aldehydharze aus I. in der Schmelze oder in Lösung eines geeigneten Lösemittels mit Wasserstoff in Gegenwart eines Katalysators bei Drücken zwischen 50 und 350 bar, bevorzugt zwischen 100 und 300 bar, besonders bevorzugt zwischen 150 und 300 bar und Temperaturen zwischen 40 und 140°C, bevorzugt zwischen 50 und 140°C.

The production of the formaldehyde-free, formaldehyde-free, carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde, which essentially contain the structural elements according to formula I, is preferably carried out

• I. by preparation of the base resins by condensation of at least one ketone with at least one aldehyde in the presence of at least one basic catalyst and optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic solvent,

and subsequently

• II. By continuous, semi- or discontinuous hydrogenation of the carbonyl groups of the ketone-aldehyde resins from I. in the melt or in solution of a suitable solvent with hydrogen in the presence of a catalyst at pressures between 50 and 350 bar, preferably between 100 and 300 bar, especially preferably between 150 and 300 bar and temperatures between 40 and 140 ° C, preferably between 50 and 140 ° C.

On This way, the content of harmful formaldehyde be greatly reduced. Formaldehyde-free means that the invention essential carbonyl-hydrogenated ketone-aldehyde resins have a content of free formaldehyde below 3 ppm, preferably below 2.5 ppm, more preferably below 2.0 ppm.

It was found to have a low color number and a high thermal Resistance the result of a low carbonyl number (l <2 of I-c) is. The carbonyl number of the invention essential carbonyl-hydrogenated ketone-aldehyde resins A) is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g, so that the Gardner color number (50% in ethyl acetate) of the invention essential carbonyl-hydrogenated ketone-aldehyde resins below 1.5, preferably below 1.0, more preferably below 0.75 and the color number after Gardner (50% in ethyl acetate) after thermal stress (24 h, 150 ° C) less than 2.0, preferably less than 1.5, more preferably less than 1.0.

A As low as possible solution viscosity desired, so that the proportion of organic solvents, which is necessary, among other things, to the solution viscosity to lower in the desired processing area, due the economy and due to environmental considerations as possible is low. The solution viscosity of the invention essential carbonyl-hydrogenated ketone-aldehyde resins, 40% in phenoxyethanol, between 5000 and 12000 mPa · s, more preferably between 6000 and 10,000 mPa · s.

at given molecular weight (Mn) is the solution viscosity the higher, the less uniform the dissolved polymer is (high polydispersity). The invention essential carbonyl-hydrogenated ketone-aldehyde resins A) have low polydispersities (Mw / Mn) between 1.35 and 1.6, more preferably between 1.4 and 1.58.

One highest possible melting range of the invention essential carbonyl-hydrogenated ketone-aldehyde resins A) is desired, thus z. B. the drying rate of the coating materials and the hardness of the coatings as high as possible are.

One high melting point / range can on the one hand on a high Molecular weight (sum of k + l + m in formula I) can be obtained. However, the higher the molecular weight, the higher is also the solution viscosity. That's why it was desired to raise the melting point / range without the Increase molecular weight. This could be achieved in which k in formula I always predominates and preferably prefers is high. The value for k is 2 to 15, preferably 3 to 12, particularly preferably 4 to 12. Die carbonyl-hydrogenated ketone-aldehyde resins essential to the invention have melting points / ranges between 50 and 150 ° C, preferably between 75 and 140 ° C, more preferably between 100 and 13000 A high k according to formula I also has a positive effect on the solubility of the invention essential carbonyl-hydrogenated Ketone-aldehyde resins A) in polar solvents such. B. Alcohols, which is especially important for coating materials, since here often alcohols such. As ethanol can be used. Also, the compatibility with polar binders such as z. B. nitrocellulose thereby positively influenced. Therefore, k chosen so that k is greater than m and the hydroxyl number is between 50 and 450 mg KOH / g, preferably between 150 and 400 mg KOH / g, more preferably between 200 and 375 mg KOH / g lies.

The Solubility properties can be adjusted by the ratio of k, l and m. The higher for example k is and the lower m and l the better carbonyl-hydrogenated ketone-aldehyde resins essential to the invention soluble in polar solvents such as Alcohols and the better the compatibility with polar Binders such. B. nitrocellulose. On the other side must that ratio of k, l and m be chosen so that further properties such. B. the water resistance not be adversely affected.

The Values for k, l and m as well as the sum of the values can whole numbers, z. B. 2, but also intermediate values, such. B. 2.4 assume.

Components for the preparation of carbonyl-containing Base resins, process step I.

Ketones and aldehydes

When Ketones for the preparation of the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde are all ketones, in particular all α-methyl ketones in α'-position to the carbonyl group have no reaction possibility or in α'-position have only a low reactivity, such as. As acetophenone, derivatives of acetophenone such as. As hydroxyacetophenone, alkyl-substituted Acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, Methoxyacetophenone, 3,3-dimethylbutanone, methyl isobutyl ketone but also Propiophenone alone or in mixtures. These ketones, in particular the α-methyl ketones are from 70 to 100 mol% based on the ketone component in the resins of the invention contain.

Prefers become carbonyl-hydrogenated ketone-aldehyde resins A) based on the ketones Acetophenone, 3,3-dimethylbutanone and methyl isobutyl ketone alone or in mixture.

Of Further, further CH-acidic ketones in the subordinate Scale in mixture to the above mentioned ketones up to 30 mol%, preferably up to 15 mol% based on the ketone component be used, such as. Acetone, methyl ethyl ketone, heptanone-2, Pentanone-3, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, Cyclohexanone and all alkyl-substituted cyclohexanones with a or more alkyl radicals containing a total of 1 to 8 carbon atoms have, individually or in mixture. As examples alkyl-substituted Cyclohexanones can be 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone. To be favoured Cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone.

Next Formaldehyde are suitable as additional aldehyde components the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde in principle, unbranched or branched aldehydes, such as. Acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and Dodecanal. In general, all in the literature used for ketone resin synthesis as suitable called aldehydes become. Preferably, however, formaldehyde is used alone. The further aldehydes may be present in proportions between 0 and 75 mol%, preferably 0 and 50 mol%, more preferably between 0 and 25 mol% based on the aldehyde component. Aromatic aldehydes, such as. As benzaldehyde, in Mixture with formaldehyde up to 10 mol% may also be included.

The required formaldehyde is usually used as approx. From 20 to 40% by weight aqueous or alcoholic (eg methanol or butanol) solution. Other uses of the Formaldehyde are formaldehyde-donating compounds such. For example, para-formaldehyde and / or trioxane.

All are particularly preferred as starting compounds for the carbonyl-hydrogenated ketone-aldehyde resins acetophenone, 3,3-dimethylbutanone and methyl isobutyl ketone and optionally CH-acidic ketones from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone alone or in mixture and formaldehyde used. It is also possible to mix different Ketone-aldehyde resins A).

The molar ratio between the ketone and the aldehyde component is between 1: 0.25 to 1 to 15, preferably between 1: 0.9 to 1: 5 and more preferably between 1: 0.95 to 1: 4.

Process for the preparation of the carbonyl group-containing Base resins, process step I.

to Preparation of the carbonyl-containing base resins I. is the respective Ketone or a mixture of different ketones with formaldehyde or a mixture of formaldehyde and additional aldehydes in the presence of at least one basic catalyst for the reaction brought. Especially when using formaldehyde as aqueous Solution and ketones whose water solubility is limited is, can advantageously water-miscible organic solvents be used. Because of the better associated with it among other things Phase mixing is the reaction conversion then faster and more complete. In addition, optionally at least one phase transfer catalyst additionally be used, making it z. B. possible is to reduce the amount of alkali compound. After completion the reaction becomes the aqueous phase of the resin phase separated. The crude product is washed with acidic water while until a melt sample of the resin appears clear. Then the resin will dried by distillation.

The reaction to produce the base resins from ketone and aldehyde is carried out in a basic medium. In general, all in the literature for ketone resin syntheses mentioned as suitable basic catalysts such. As alkali compounds are used. Preference is given to hydroxides such. As the cations NH ₄ , NR ₄ , Li, Na, K. Very particularly preferred are hydroxides of the cations NH ₄ , NR ₄ , Li, Na.

The Reaction for the preparation of the base resins from ketone and aldehyde can performed using an auxiliary solvent become. As suitable, alcohols such. For example, methanol or Ethanol proved. It is also possible as an auxiliary solvent to use water-soluble ketones, which are then in the resin to react with.

to Purification of the base resins I. must the basic catalyst used be removed. This can easily be done by washing with water Use of acids for neutralization happen. in the Generally, all acids are for neutralization such as B. all organic and / or inorganic acids, suitable. Preference is given to organic acids having 1 to 6 Carbon atoms, more preferably organic acids with 1 to 4 carbon atoms.

In the polycondensation mixture for the preparation of the base resins Ketone and aldehyde may optionally be phase transfer catalysts additionally used.

eingesetzt, wobei
X: ein Stickstoff- oder Phosphoratom,
R₁, R₂, R₃, R₄: gleich oder verschieden sein können und einen Alkylrest mit 1 bis 22 C-Atomen in der Kohlenstoffkette und/oder einen Phenyl- und/oder einen Benzylrest
und
Y: das Anion einer (an)organischen Säure oder ein Hydroxidion
bedeuten.When using a phase transfer catalyst, 0.01 to 15% by weight, based on the ketone, of a phase transfer catalyst of the general formula (II)

used, where
X: a nitrogen or phosphorus atom,
R ₁ , R ₂ , R ₃ , R ₄ : may be the same or different and is an alkyl radical having 1 to 22 C atoms in the carbon chain and / or a phenyl and / or a benzyl radical
and
Y: the anion of an organic acid or a hydroxide ion
mean.

In the case of quaternary ammonium salts, alkyl radicals (R _1-4 ) having 1 to 22 C atoms, in particular those having 1 to 12 C atoms, in the carbon chain and / or phenyl and / or benzyl radicals and / or mixtures of both are preferred , As anions such strong (on) organic acids such. B. Cr ^- , Br ^- , J ^- but also hydroxides, methoxides or acetates in question. Examples of quaternary ammonium salts are cetyl dimethyl benzyl ammonium chloride, tributyl benzyl ammonium chloride, trimethyl benzyl ammonium chloride, trimethyl benzyl ammonium iodide, triethyl benzyl ammonium chloride or triethyl benzyl ammonium iodide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride. Benzyltributylammonium chloride, cetyldimethylbenzylammonium chloride and / or triethylbenzylammonium chloride is preferably used.

For quaternary phosphonium salts, alkyl radicals having 1 to 22 C atoms and / or phenyl radicals and / or benzyl radicals are preferred for R _1-4 . As anions such strong (on) organic acids such. B. Cl ^- , Br ^- , J ^- but also hydroxides, methoxides or acetates in question.

When quaternary phosphonium salts come z. B. triphenylbenzylphosphonium chloride or Triphenylbenzylphosphoniumjodid in question. It can However, mixtures are used.

Of the optionally contained phase transfer catalyst is in amounts from 0.01 to 15, preferably from 0.1 to 10.0, and in particular in amounts of from 0.1 to 5.0% by weight, based on the ketone used, of the polycondensation mixture used.

Particularly preferred embodiment

In a particularly preferred embodiment, the carbonyl-containing base is first Resin I. produced. For this purpose, 10 mol of ketone in a 50 to 90% strength methanolic solution, 0 to 5% by mass of a phase transfer catalyst and 1 to 5 mol of an aqueous formaldehyde solution are introduced and homogenized with stirring. Then, with stirring, the addition of 0.1 to 5 mol of an aqueous sodium hydroxide solution. At 70 to 115 ° C is then added with stirring, the addition of 4 to 10 moles of an aqueous formaldehyde solution for 30 to 120 min. The stirrer is stopped after further 0.5 to 5 h stirring at reflux temperature. Optionally, after about one third of the runtime, another 0.1 to 1 mol of an aqueous formaldehyde solution may be added. The aqueous phase is separated from the resin phase. The crude product is washed with water using an organic acid until a melt sample of the resin appears clear. Then, the resin is dried by distillation.

Process for the preparation of the invention essential Ketone-aldehyde resins according to process step II.

The resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen. The carbonyl groups of the ketone-aldehyde resin are converted into a secondary hydroxy group. Depending on the reaction conditions, a part of the hydroxy groups can be split off, so that methylene groups result. The reaction conditions are chosen so that the proportion of unreduced carbonyl groups is low. For illustrative purposes, the following simplified scheme is used:

When Catalysts can be used in principle all compounds which are the hydrogenation of carbonyl groups as well as the hydrogenation catalysing free formaldehyde to methanol with hydrogen. It can use homogeneous or heterogeneous catalysts be particularly preferred are heterogeneous catalysts.

Around the formaldehyde-free products according to the invention In particular, metal catalysts have been selected of nickel, copper, copper-chromium, palladium, platinum, ruthenium and Rhodium alone or in mixture proved to be suitable, especially preferred are nickel, copper-chromium and ruthenium catalysts.

To increase the activity, selectivity and / or lifetime, the catalysts may additionally contain doping metals or other modifiers. Typical dopants are z. B. Mo, Fe, Ag, Cr, Ni, V, Ga, In, Bi, Ti, Zr and Mn and the rare earths. Typical modifiers are for. For example, those with which the acid-base properties of the catalysts can be influenced, such. As alkali and alkaline earth metals or their compounds and phosphoric acid or sulfuric acid and their compounds. The catalysts may be in the form of powders or moldings, such as. As extrudates or pressed powders are used. Full contacts, Raney type catalysts or supported catalysts can be used. Preference is given to Raney type and supported catalysts. Suitable carrier materials are, for. For example, diatomaceous earth, silica, alumina, aluminosilicates, titanium dioxide, zirconium dioxide, aluminum-silicon mixed oxides, magnesium oxide and activated carbon. The active metal can be applied in a manner known to those skilled in the carrier material, such as. B. by impregnation, spraying or precipitation. Depending on the nature of the catalyst preparation further, known in the art preparation steps are necessary, such. As drying, calcination, shaping and activation. For shaping optionally other auxiliaries such. B. Gra phit or magnesium stearate.

The Catalytic hydrogenation can be carried out in the melt, in solution a suitable solvent or the hydrogenation product itself as "solvent" used solvent, if desired, after be terminated reaction. The separated solvent can be traced back to the process whereby additional depending on the solvent used Purification steps for complete or partial removal of lighter or less volatile by-products, such as z. As methanol and water, may be necessary. suitable Solvents are those in which both the educt as well as dissolve the product in sufficient quantity, and which are inert under the chosen hydrogenation conditions. These are z. As alcohols, preferably n- and i-butanol, cyclic Ethers, preferably tetrahydrofuran and dioxane, alkyl ethers, aromatics, such as As xylene and esters, such as. For example, ethyl and butyl acetate. It also mixtures of these solvents are possible. The concentration of the resin in the solvent can be between 1 and 99% are varied, preferably between 10 and 50%.

Around high conversions with the lowest possible residence times to achieve in the reactor, relatively high pressures are advantageous. The total pressure in the reactor is between 50 and 350 bar, preferably 100 to 300 bar. The optimum hydrogenation temperature is of the used Hydrogenation catalyst dependent. So are rhodium catalysts already temperatures of 40 to 75 ° C, preferably 40 to 60 ° C sufficient, whereas with Cu or Cu / Cr catalysts Higher temperatures are necessary, typically between 100 and 140 ° C lie.

The Hydrogenation to the resins of the invention can be carried out in discontinuous or continuous driving. It is also a semi-continuous driving possible, in which in a batch reactor continuously resin and / or solvent is fed, and / or continuously one or more reaction products and / or solvents are removed.

The Catalyst load is 0.05 to 4 t of resin per cubic meter Catalyst and hour, preferably 0.1 to 2 t of resin per cubic meter Catalyst and hour.

to Control of the temperature profile in the reactor and in particular for Limit the maximum temperature are different, the expert known methods, suitable. So z. B. at sufficiently small Resin concentrations completely without additional Reactor cooling to be worked, the reaction medium completely absorbs the released energy and thereby convective out of the reactor. Suitable are still for example, tray reactors with intercooling, the use of hydrogen cycles with gas cooling, the Return of a part of the cooled Product (cycle reactor) and the use of external coolant circuits, especially in tube bundle reactors.

Preferred embodiment for Preparation of the invention essential, carbonyl-hydrogenated ketone-aldehyde resins A)

to Hydrogenation (process step II.) Of the prepared carbonyl group-containing Resin from process step I. is in continuous fixed bed reactors worked. Particularly suitable for the production of the inventive Resins are shaft furnaces and tube bundles which are preferred be operated in trickle bed mode. This will be hydrogen and the resin to be hydrogenated, optionally in a solvent dissolved, at the head of the reactor on the catalyst bed where. Alternatively, the hydrogen can also be in countercurrent of be guided down to the top. The optionally contained Solvent can - if desired - subsequently be separated.

to The drying speed can be improved Ketone-aldehyde resins (component A) also with di- and / or polyisocyanates be implemented. The urethanized products thus obtained have an improved drying and water resistance.

Suitable isocyanates are aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanates. Examples of diisocyanates are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI). , Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate, such as 4-isocyanatomethyl-1,8- octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecane diisocyanate and triisocyanate, dodecane diisocyanates and triisocyanates, isophorone diisocyanate (IPDI), 2,2'- and 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) alone or in mixtures, preferably the H ₁₂ MDI consists of at least 80 wt .-% of 4.4 '-H ₁₂ MDI, preferably 85-95% by weight, 2,5 (2,6) -bis (isocyanato-methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in admixture. Preference is given to H ₁₂ MDI, IPDI, HDI, TMDI, very particularly preferably H ₁₂ MDI, IPDI.

Another preferred class of polyisocyanates as component B) are the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such. As IPDI, TMDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (eg, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines. Also preferred are the isocyanurates obtainable by trimerization of the simple diisocyanates such as IPDI, HDI and H ₁₂ MDI. Very particular preference is given to isocyanurates of IPDI and to reaction products of IPDI, TMDI, HDI and / or H ₁₂ MDI with trimethylolpropane and / or pentaerythritol.

Component B)

The Inventive binders B) are used in amounts of from 20 to 90 wt .-%, preferably from 30 to 75 wt .-% used.

Prefers be binders, from the group of polyurethanes, polyacrylates, Polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyamides, casein, polyureas, Derivatives of cellulose such. B. cellulose nitrate, cellulose ethers and / or cellulose acetobutyrates, 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 (eg melamine, benzoguanamine resins), Polyolefins, acrylated polyesters, acrylated polyethers, acrylated Epoxy resins, urethane acrylates, epoxy resins, resoles, rosin resins, Resinates, silicic acid esters and alkali silicates (eg water glass), Silicone resins, chlorine and / or fluorine-containing polymers such. B. polyvinyl chloride and its derivatives, chlorinated rubbers, chlorinated polyesters, PVDF used. It can also be used mixtures. The binders can be foreign and / or self-crosslinking be air-drying (physically drying) and / or oxidative curing be. Preference is given to polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, Polyureas, derivatives of cellulose such as cellulose nitrate, cellulose ethers and / or Cellulose acetobutyrates, polyvinyl alcohols and derivatives, polyvinyl acetates, Polyvinylpyrolidones, natural resins, hydrocarbon resins such as coumarone, Indene, cyclopentadiene resins, terpene resins, maleate resins, phenolic resins, Phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, ketone resins, Aminoplasts such as melamine, benzoguanamine resins, resols, rosin resins, Resinates, used alone or in mixtures, binders can in organic solvents but also in Reactive diluents be soluble and / or in water soluble, mixed or dispersible.

in principle suitable are all binders used in the paint industry.

Component C)

Component C) is used in amounts of from 0 to 50% by weight, preferably from 10 to 40% by weight. In principle, all colorants and / or fillers which are used in the paint industry are suitable. They are selected according to coloristic aspects and requirements such. B. hue, color intensity, brightness, saturation, transparency, hiding power, light fastness, bleeding fastness, compatibility, etc., as well as mechanical aspects and requirements such. As hardness, elasticity, etc .. There are inorganic pigments and fillers such. B. Milori blue, 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, silicas, 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, quinacridone, perylene, dioxazine, phthalocyanine pigments used. In addition, metallic effect pigments such. As 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 iron oxide, multilayer effect pigments from PVD films or by the CVD method Herge (Chemical Vapor Deposition) and liquid crystal (polymer) pigments are used. In addition, dyes are used. A list of pigments, fillers and / or dyes used is given in " Römpp Lexikon, paints and printing inks, publisher Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 "or" Pigment and Filler Tables, publisher Olaf Lückert, Vincentz Verlag, Hannover, 2002 "given.

Component D)

The Invention essential component D) is used in amounts of 5 to 75 Wt .-%, preferably from 5 to 45 wt .-% used.

in principle suitable are all auxiliaries and additives (additives), which in the Paint industry can be used.

When Component D) are particularly suitable auxiliaries and additives such for example, inhibitors, organic solvents, water, surfactants, oxygen and / or radical scavengers, Catalysts, light stabilizers, color lighteners, photosensitizers and initiators, additives for influencing rheological properties such as B. thixotropic and / or thickening agents, leveling agents, Anti-skinning agents, defoamers and deaerators, Antistatic agents, lubricants, wetting and dispersing agents, crosslinkers such as 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.

When Solvents D) are suitable in the paint industry be used. For example, z. As alcohols, acetates, ketones, Ethers, glycol ethers, aliphatics, aromatics, alone or in mixture. But there may also be so-called reactive diluents which are commonly used in radiation-curing coating materials Find application such. B. mono-or higher functional Acrylate monomers, which may also be alkoxylated, and / or Vinyl ethers.

Preparation of coating compositions from the components A) to D):

The preparation of the coating material compositions is carried out by intensive mixing of the components at temperatures of 20 to 80 ° C ( "Textbook of Paint Technology", Th. Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, page 229 ff. ).

Not liquid components may be used first before mixing in suitable solvents or water in solution brought, then the remaining components added with stirring. In the case of z. B. pigments and / or fillers are dispersed using suitable aggregates such. B. dissolvers, three-rolls, bead mills, Ball mills o. Ä.

Of the Formaldehyde content of the coating compositions below 100 ppm, preferably below 50 ppm and more preferably below of 10 ppm.

The claimed coating compositions are used for the coating of different substrates, such. Metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic substances such. Ceramic, stone, concrete, gypsum, glass, Textiles, fibers, fabric materials, leather, synthetic materials, such as As artificial leather, wood, films made of plastics, or composites such as B. aluminum-laminated films.

The Coating compositions are used both internally and as well as outdoors, such. B. as Bautenschutzfarben / -lacke, Road marking paints, Automotive paints (OEM, Refinish), Coil coatings, Can-Coatings, textile finishing, wood coatings, plastic coatings, as well as for decorative applications, etc. Also for the Use in adhesives, such. B. for the bonding of Textiles, leather, paper, plastics, metals and the like Materials, such compositions are 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 coating composition according to the invention is characterized by a particularly high drying speed, scratch and water resistance.

The Films have high gloss and low haze, a high color stability and a very high heat and Light resistance.

The have dried, cured or crosslinked films good adhesion properties on underlying coatings; also the intercoat adhesion is to overlying Positively influenced layers.

The claimed coating compositions have the used substrates have a perfect course and are free of surface defects, such as Craters and wetting disorders.

ever After application, the viscosities of the Coating composition set. For given solution viscosity For example, the claimed coating compositions have one non-volatile content of 10% to 100% by weight, preferably from 25% to 100%.

object The invention also includes those with the coating compositions coated objects.

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

Examples

Analytical methods of the invention essential Component A)

Determination of the content of free formaldehyde

• Gerät: HPLC-System mit zwei isokratischen Pumpen, thermostatisiertem Reaktor, variablem UV/VIS-Detektor und Auswerteeinheit, z. B. Hewlett-Packard HP 1100 mit PC-gestützter Auswertesoftware ChemStation.
• Stationäre Phase C18-reversed-Phase, 5 μm, 250 × 4,0 mm
• Mobile Phase Milli-Q-Wasser
• Injektionsvolumen 20 μl
• Nachsäulenderivatisierung Acetylaceton-Lösung
• Fluss 1,0 ml/min
• Detektion UV-Detektion bei 420 nm
• Probenvorbereitung 250 mg in 3 ml THF lösen und mit Wasser auf 25 ml auffüllen
• Kalibrierlösung 100 mg Formaldehyd-Lösung/100 ml Wasser 1:1000 Verdünnung in Wasser
• Auswertung gegen externen Standard

The formaldehyde content is determined by the lutidine method by HPLC ( Official collection of test methods according to § 64 LFGB K 84.00 7 (EG): "Detection and quantitative determination of free formaldehyde" )

• Device: HPLC 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 hydroxyl number

The determination of the OH number of the invention essential component A) is based on the DIN 53240-2 "Determination of the hydroxyl number" , It should be ensured that an acetylation time of 3 h is exactly maintained.

Determination of carbonyl number

The Determination of carbonyl number of the invention essential component A) is FT-IR spectroscopy after calibration with 2-ethylhexanone in THF in a NaCl cuvette.

Determination of color number according to Gardner and after thermal stress

Gardner's color number of component A) essential to the invention is determined in 50% strength solution of the resin in ethyl acetate on the basis of DIN ISO 4630 ,

Also, the color number after thermal stress of the invention essential component A) is determined in this way. For this purpose, 5 g of the resin A) are first stored for 24 h at 150 ° C in an air atmosphere. The Gardner color number is then determined in 50% strength solution of the thermally loaded resin in ethyl acetate in accordance with DIN ISO 4630 ,

Determination of the solution viscosity component A)

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

Determination of polydispersity

It the measurement of the molecular weight distribution of the invention is essential Component A) by means of gel permeation chromatography in tetrahydrofuran against polystyrene as standard. The polydispersity (Mw / Mn) is calculated from the ratio of the weight average (Mw) to the number average (Mn).

Determination of the melting range

The determination of the melting point / melting range of the invention essential component A) is carried out with a Kapillarschmelzpunkt-measuring device (Büchi B-545) based on the DIN 53181 ,

Calculation of the copolymer distribution

mit R = PhenylThe following procedure is used to calculate the values for k, l and m of component A) essential to the invention. Calculation example (for illustrative purposes, integers are used):

with R = phenyl

assumptions:

The Molecular weight (Mn) is 1000 g / mol, the OH number is 300 mg KOH / g, the carbonyl number is 10 mg KOH / g.

Out an OH number of 300 mg KOH / g (300/56110 · 1000) 5.35 OH groups per 1000 g / mol. This means that k = 5.35.

• Berechnung von m: (1000 g/mol – (5,35 mol·134 g/mol) – (0,18 mol·132 g/mol))/118 g/mol = 259/118 = 2,2
• Die Summe aus k + m + l ist somit 5,35 + 2,2 + 0,18 = 7,73

From a C = O number of 10 mg KOH / g result (10/56110 x 1000) 0.18 C = O groups per 1000 g / mol. This means that I = 0.18.

• Calculation of m: (1000 g / mol - (5.35 mol · 134 g / mol) - (0.18 mol · 132 g / mol)) / 118 g / mol = 259/118 = 2.2
• The sum of k + m + l is thus 5.35 + 2.2 + 0.18 = 7.73

Analytical methods of the invention Coating compositions

Determination of yellowing, light and heat resistance

To determine the yellowness, light and heat resistance, the coating compositions were applied, freed from solvent and subjected to a Xenon 1200 test or they were stored at 100 ° C for 24 h. The CIE-Lab color differences before and after exposure between the comparative films without the invention essential component A) and the film with the invention essential component A) 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 the solution viscosity of the coating material

The determination of the solution viscosity of the coating material takes place after the DIN 53211 , 4 mm flow cup.

Determination of substrate wetting and of course

The Determination of the substrate wetting and the course of the coating material compositions done visually. Good wetting is achieved when the applied Coating composition a closed film without Defects such. B. crater results. A good course has been achieved if the applied, closed film has a low intrinsic structure (For example, orange peel, too deep penetration into the substrate at z. B. paper, o. Ä.) Has.

Determination of liability

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

Stress testing / water resistance

• Tropentest: storage of the applied films 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 gloss level / glossy haze

The determination was made according to DIN EN ISO 2813 ,

initial drying

The Coating materials are applied to the substrates to be examined. After 5 min, 1 h and 24 h, the fingernail test (see scratch resistance) carried out.

Scratch resistance (fingernail test)

Of the Forefinger is pulled over the coating and the Degree of damage of the coating is visually evaluated.

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

The content of non-volatile components is given as the mean value of a duplicate determination. Approx. 2 g of the sample (coating substance) are weighed into a cleaned aluminum dish (tare mass m ₁ ) on an analytical balance (mass m _{2 of} the substance). Then you give the aluminum bowl over 2 h at 150 ° 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 the content of free formaldehyde

• Gerät: HPLC-System mit zwei isokratischen Pumpen, thermostatisiertem Reaktor, variablem UV/VIS-Detektor und Auswerteeinheit, z. B. Hewlett-Packard HP 1100 mit PC-gestützter Auswertesoftware ChemStation.
• Stationäre Phase C18-reversed-Phase, 5 μm, 250 × 4,0 mm
• Mobile Phase Milli-Q-Wasser
• Injektionsvolumen 20 μl
• Nachsäulenderivatisierung Acetylaceton-Lösung
• Fluss 1,0 ml/min
• Detektion UV-Detektion bei 420 nm.
• Probenvorbereitung 250 mg in 3 ml THF lösen und mit Wasser auf 25 ml auffüllen
• Kalibrierlösung 100 mg Formaldehyd-Lösung/100 ml Wasser 1:1000 Verdünnung in Wasser
• Auswertung gegen externen Standard

The formaldehyde content is determined by the lutidine method by HPLC ( Official collection of test methods according to § 64 LFGB K 84.00 7 (EG): "Detection and quantitative determination of free formaldehyde" ). For this purpose, the solid components of the paint are first separated by centrifuging.

• Device: HPLC 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

Examples:

Not according to the invention Comparative Examples

The document which best describes the state of the art is DE 33 34 631 A1 ,

The acetophenone / formaldehyde resin used here was according to Example 2 of DE 892 974 receive.

Example A: Reconstitution of Example 2 of DE 892 974

To 1200 g of acetophenone are added after addition of 240 g of 50% potassium hydroxide solution and 400 g of methanol 1000 g of 30% formaldehyde solution in Over a period of 2 h with vigorous stirring. It increases the temperature is at 90 ° C. This temperature will be 10 h kept. It is acidified with sulfuric acid and the resulting condensation product with hot water washed, melted and dehydrated in vacuo.

It 1260 g of a yellow resin are obtained. The resin is clear and brittle and has a melting point of 67 ° C. The Gardner color number is 3.8 (50% in ethyl acetate). It is Z. B. in acetates such. As butyl and ethyl acetate, in aromatics such as toluene and xylene soluble. It is insoluble in ethanol. The formaldehyde content is 255 ppm.

Example B: Reconstitution of Example 3 of DE 33 34 631 A1

Example 3 of the DE 33 34 631 A1 Accordingly, the resin obtained from Example A was continuously hydrogenated at 300 bar and 180 ° C in a trickle bed reactor. The reactor was filled with 100 ml of Harshaw Ni-5124 contact (available from Engelhard Corp.). Every hour, 50 ml of a 30% solution of the resin in i-butanol were fed in, wherein the pressure in the reactor was kept constant by tracking the consumed hydrogen at 300 bar.

Examples according to the invention

Inventive example I)

Preparation of a base resin for the further hydrogenation based on acetophenone and formaldehyde

1200 g acetophenone, 220 g methanol, 0.3 g benzyltributylammonium chloride and 360 g of a 30% aqueous formaldehyde solution are presented and homogenized with stirring. thereupon with stirring, the addition of 32 g of a 25%, aqueous sodium hydroxide solution. At 80 to 85 ° C is then added with stirring, the addition of 655 g of a 30%, aqueous formaldehyde solution over 90 min. The stirrer is after 5 h stirring at reflux temperature turned off and the aqueous phase separated from the resin phase. The crude product is washed with acetic acid water until a melt sample the resin appears clear. Then the resin becomes by distillation dried.

It 1270 g of a slightly yellowish resin are obtained. The resin is clear and brittle and has a melting point of 72 ° C. The color number according to Gardner is 0.8 (50% in ethyl acetate). It is Z. B. in acetates such. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol. The formaldehyde content is 35 ppm.

Hydrogenation of the resin based on acetophenone and formaldehyde from Example I)

Inventive example 1:

300 g of the resin from Example I) are dissolved with heating in 700 g of i-butanol. Then, the hydrogenation is carried out at 260 bar and 120 ° C in an autoclave (Parr) with a catalyst basket containing 100 mL of a Raney-type nickel catalyst is filled. After 8 h, the reaction mixture is drained from the reactor via a filter.

Inventive example 2:

300 g of the resin from Example I) are dissolved in 700 g of tetrahydrofuran (water content about 7%) solved. Then the hydrogenation is carried out at 260 bar and 120 ° C in an autoclave (Parr) with catalyst basket, with 100 mL of a commercial Ru catalyst (3% Ru on alumina) is filled. After 20 h, the reaction mixture is over a filter is drained from the reactor.

Inventive example 3:

The Resin from Example I) was heated to 30% in i-butanol solved. The hydrogenation takes place in a continuous manner operated fixed bed reactor containing 400 mL of a commercial, filled with silica-supported copper-chromium contact is. At 300 bar and 130 ° C every hour 500 mL of the reaction mixture passed through the reactor from top to bottom (Downflow). The pressure is achieved by tracking hydrogen kept constant.

Inventive example 4:

The Resin from Example I) was heated to 30% in i-butanol solved. The hydrogenation takes place in a continuous manner operated fixed bed reactor containing 400 mL of a commercial, Raney-type nickel catalyst is filled. At 300 bar and 130 ° C per hour 400 mL of the reaction mixture driven from top to bottom through the reactor (trickle down). The pressure is constant by tracking hydrogen held.

The resin solutions of Examples 1 to 4 and Comparative Example B are freed from the solvent in vacuo. The properties of the resulting resins are listed in Table 1. Table 1: Properties of the hydrogenated resins of Examples 1 to 4 Comp. B Resin 1 Resin 2 Resin 3 Harz 4 Free formaldehyde content [ppm] 6.0 1.2 1.1 <1 1.3 Carbonyl number [mg KOH / g] 24.3 14.9 5.8 2.5 5.2 Hydroxyl number [mg KOH / g] 210 295 315 335 317 Melting point [° C] 92 109 114 124 118 Gardner color number (50% in ethyl acetate) 2.2 0.4 0.2 0.1 0.1 Color number according to Gardner (after thermal exposure for 24 h at 150 ° C, 50% in ethyl acetate) 3.1 0.6 0.3 0.2 0.2 Viscosity (40% in phenoxyethanol) 6800 6600 7300 8600 7900 Mn (GPC vs PS) 910 980 1000 1070 1040 Mw (GPC vs PS) 1570 1490 1430 1550 1530 polydispersity 1.73 1.52 1.43 1.45 1.47 k 3.4 5.2 5.6 6.4 5.9 l 0.4 0.3 0.1 0.1 0.1 m 3.4 2.2 1.2 1.8 2.0 k + l + m 7.2 7.6 7.7 8.2 8.0

All resins are soluble in common paint solvents. In contrast to the base resin of Example I), the resins are now soluble in polar solvents such as alcohols. For example, the resins are soluble in Dichloromethane, ethyl acetate, butyl acetate, isopropanol, acetone and diethyl ether.

The Resins of Examples 1-4 are in ethanol in any ratio soluble. In contrast, the resin is from the comparative example B) not perfectly soluble in ethanol at concentrations below 10% solids.

The Inventive resins 1 to 4 have in comparison to the non-inventive resin according to Example B a lower content of free formaldehyde. Corresponding to the lower one Carbonyl number are the color number and color number after thermal Load less. Although these resins are up to 35% higher Melting points than non-inventive Resin according to Example B, the viscosity is comparable Magnitude to the resin of Example B. This may optionally with the higher polydispersity of the non-invention resin explained become.

Application Example 1: Plastic Paint

The components shown in the table below were processed to a plastic paint. For this purpose, the resins (according to Example B, Examples 2 and 3), the Degalan and the SER-AD were dissolved in the solvent mixture with stirring. After addition of the pigment, paints were prepared by dispersion, which were adjusted by addition of the solvent mixture methyl isobutyl ketone / n-butanol / isopropanol (2: 1: 1) to a viscosity at 23 ° C of 18 s in DIN 4 mm cup. component Zero sample V1 Comparative Example V2 Example A1 Example A2 DEGALAN ^® MB 319 362 362 362 362 BAYERTITAN ^® R-FD 1 271 271 271 271 SER-AD-FX 100 5 5 5 5 ethanol 140 181 181 181 methyl isobutyl ketone 250 319 319 319 n-butanol 125 160 160 160 isopropanol 125 160 160 160 Resin according to Comp. Example B 181 Resin according to Example 2 181 Resin according to Example 3 181 Examples of sources of supply: DEGALAN ^® MB 319 Evonik Degussa GmbH BAYERTITAN ^® R-FD 1 Bayer AG SER-AD-FX 100 Sasol Servo BV test method Zero sample V1 Comparative Example V2 Example A1 Example A2 Free formaldehyde content [ppm] <10 <10 <10 <10 Nonvolatile content [%] 42.2 44.1 45.6 46.0 Solution viscosity [s, DIN 4 mm cup] 16 17 17 18

Substrate wetting / History

The paints were applied to polystyrene substrates with a layer thickness of about 30 microns. The course of the blank is unsatisfactory. One recognizes a pronounced intrinsic structure (orange peel). Partially pinholes are visible. The use of the comparative resin B in the formulation V2 leads to better results. The best course and the best wetting reach the paints according to the invention Examples A1 and A2

initial drying

• 1 sehr gut, 6 ungenügend

To assess the drying rate, the paints were applied to polystyrene substrates with a layer thickness of about 30 microns. After 5 minutes, 1 hour and 24 hours, the fingernail test was carried out and the film was checked for injuries. Time Zero sample V1 Comparative Example V2 Example A1 Example A2 5 min 5 4 2 2 1 h 4 3 1-2 1-2 24 hours 3 1-2 1 1

• 1 very good, 6 insufficient

Without the addition of a hydrogenated ketone-aldehyde resin is the rate of drying bad (V1). The use of the comparative resin B in the formulation V2 leads to better results; however, it will be a good one Liability only after 24 h, which may be due to the low melting point of the resin from V2 is due. In contrast to have the paints according to the invention Examples A1 and A2 after 5 min very good values. This is have shown that the resins of the invention the Improve drying speed.

Determination of liability

• 0 sehr gut, 5 ungenügend

To assess the adhesion, the coatings were applied to polystyrene substrates with a layer thickness of about 30 microns. After 24 h, the panels were stored under standard climate, tropical climate and under water for 24 h, then the cross-cut was carried out and the adhesion checked. Load type Zero sample V1 Comparative Example V2 Example A1 Example A2 standard climate 5 1 0 0-1 tropical climate 5 1-2 0 0-1 water storage 5 2 0-1 1

• 0 very good, 5 insufficient

All in all It should be noted that without the addition of a hydrogenated ketone-aldehyde resin the liability is always bad (V1). The use of the comparative resin B in formulation V2 gives better results. The best results are obtained by the varnishes with the resins from the Inventive examples A1 and A2. This shows that the resins essential to the invention are the adhesion improve even under critical conditions as well as the water resistance.

Determination of yellowing, light and heat resistance

to Determination of yellowing, light and heat resistance the paints were on polystyrene substrates with a layer thickness of about 30 microns applied. After 24 h, the panels were for 24 h subjected to a Xenon 1200 test. For the determination the heat resistance, the samples were at 100 ° C for 24 h stored.

The CIE-Lab color differences before and after exposure between the comparative films without the invention essential component A) and the film with the invention essential component A) 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 °). Zero sample V1 Comparative Example V2 Example A1 Example A2 ΔE after 24 h xenon 1200 test 0.1 1.2 0.4 0.3 ΔE after thermal stress 0.2 1.5 0.3 0.4

The Use of the comparative resin B in Formulation V2 leads excessive color deviations, possibly due to the high carbonyl number. In contrast, the paints according to the inventive examples A1 and A2 a very good stability.

Determination of gloss level / glossy haze

To determine the gloss and the haze, the lacquers were applied to polystyrene substrates with a layer thickness of about 30 μm. After storage in normal atmosphere for 24 h, the measurement was carried out. Zero sample V1 Comparative Example V2 Example A1 Example A2 20 ° 72 83 93 92 60 ° 87 92 96 97 Haze 34 29 8th 13

Without the addition of a hydrogenated ketone-aldehyde resin (V1) is gloss relatively low and the Haze high. This may be a bad one Pigment wetting / stabilization due to the absence of a hard resin due. The use of the comparative resin B in formulation V2 gives better results. Indeed Haze is also high here. The best results will be through the paints of Examples A1 and A2 received. This shows that the invention essential Resins improve shine and shine.

Example of use 2: Wood varnish

The components shown in the table below were processed to a wood finish. For this purpose, the resins (according to Example B, Example 2 and 3) and the other components in the solvent mixture were dissolved with stirring. component Zero sample V3 Comparative Example V4 Example A3 Example A4 Nitrocellulose, standard 27 E 65% in n-butanol 240 100 100 100 VESTINOL ^® 9 50 50 50 50 RESAMIN ^® HF 480 60 60 60 60 EDENOL D ^® 81 40 40 40 40 butyl 170 170 170 170 ethyl acetate 200. 200. 200. 200. xylene 80 80 80 80 n-butanol 90 90 90 90 methoxypropanol 50 50 50 50 butylglycol 20 20 20 20 Resin according to Comp. Example B 140 Resin according to Example 2 140 Resin according to Example 3 140 Examples of sources of supply: VESTINOL ^® Evonik Degussa GmbH RESAMIN ^® Cytec EDENOL ^® handle test method Zero sample V3 Comparative Example V4 Example A3 Example A4 Free formaldehyde content [ppm] <10 <10 <10 <10 Nonvolatile content [%] 23.4 29.8 30.1 30.3

Substrate wetting / History

The Paints were on pine wood with a layer thickness of about 50 microns applied. In the paint of the blank V3 the paint penetrated strongly the substrate (no stamina). The best topcoat and the best wetting reach the paints with addition of a hydrogenated Ketone-aldehyde

Determination of gloss level / glossy haze

To determine the gloss, the lacquers were applied to pine wood with a layer thickness of about 50 μm. After storage in normal atmosphere for 24 h, the measurement was carried out. Zero sample V3 Comparative Example V4 Example A3 Example A4 20 ° 15 48 65 61 60 ° 35 65 78 81

Without the addition of a hydrogenated ketone-aldehyde resin (V3) is gloss relatively low. The use of the comparative resin B in the formulation V4 leads to better results. The best results will be by the paints of the invention examples A3 and A4 received. This shows that the invention essential Resins improve the shine.

Application example 3: UV curing paint

The components listed in the table are processed with stirring to form a UV varnish. component Zero sample V5 Comparative Example V6 Example A5 Example A6 ACTILANE 170 ^® (Nuplex) 38.0 26.5 26.5 26.5 Adduct of 2 moles of hydroxyethyl acrylate and 1 mole of TMDI 12.0 12.0 12.0 12.0 TPGDA 20.5 7.4 7.4 7.4 TEGO ^® wheel 2300 0.5 0.4 0.4 0.4 Benzophenone (40% in TPGDA) 10.0 10.0 10.0 10.0 EBECRYL ^® P 115 (Cytec) 4.0 4.0 4.0 4.0 Resin according to Comp. Example B (35% in TPGDA) 24.6 Resin according to Example 2 (35% in TPGDA) 24.6 Resin according to Example 3 (35% in TPGDA) 24.6

Determination of liability

• 0 sehr gut, 5 ungenügend

The respective lacquer was applied to polyester plates with a 50 μm doctor blade. Then the adhesion of the paints was checked by cross-hatching. Zero sample V5 Comparative Example V6 Example A5 Example A6 3-4 2-3 1 1

• 0 very good, 5 insufficient

Without the addition of a hydrogenated ketone-aldehyde resin is the liability not optimal (V5). The use of the comparative resin B in the Formulation V6 leads to better results. The best Results are obtained by the paints with the resins of the invention Examples A5 and A6 obtained. This shows that the invention essential Resins improve the adhesion in UV coatings.

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 3324287 [0005]
• - US 2540885 [0005]
• - US 2540886 [0005]
• - DE 1155909 [0005]
• - DD 12433 [0005]
• - DE 1300256 [0005]
• - DE 1256898 [0005]
• DE 826974 [0009, 0015]
• - DE 870022 [0009, 0015]
• - JP 11012338 [0009, 0015]
• US 6222009 [0009, 0015]
• - DE 3334631 [0010, 0015]
• US 5247066 [0014]
• - DE 102006009079 [0016]
• - DE 3334631 A1 [0107, 0110, 0111]
• - DE 892974 [0108, 0108]

Cited non-patent literature

• - Ullmann Vol. 12, p. 551 [0004]
• - Römpp Lexikon, paints and printing inks, publisher Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 [0068]
• - Pigment and Filler Tables, Editor Olaf Lückert, Vincentz Verlag, Hannover, 2002 [0068]
• - "Lehrbuch der Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, page 229 et seq. [0073]
• - Official collection of test methods according to § 64 LFGB K 84.00 7 (EG): "Detection and quantitative determination of free formaldehyde" [0086]
• - DIN 53240-2 "Determination of the hydroxyl number" [0087]
• - DIN ISO 4630 [0089]
• - DIN ISO 4630 [0090]
• - DIN EN ISO 3219 [0091]
• - DIN 53181 [0093]
• - DIN 6174 [0098]
• - DIN 5033 [0098]
• - DIN 53211 [0099]
• - DIN EN ISO 2409 [0101]
• - DIN EN ISO 2812-2 [0101]
• - DIN EN ISO 2813 [0102]
• - Official Collection of Examination Procedures According to § 64 LFGB K 84.00 7 (EG): "Detection and Quantitative Determination of Free Formaldehyde" [0106]
• - DIN 6174 [0129]
• - DIN 5033 [0129]

Claims (29)

Coating composition compositions containing less than 100 ppm of free formaldehyde, substantially containing A) from 5 to 75% by weight of at least one carbonyl-hydrogenated ketaldehyde aldehyde resin based on formaldehyde, containing less than 3 ppm of free formaldehyde, which is substantially the same Contains structural elements according to formula I.

with R = aromatic having 6-14 carbon atoms, (cyclo) aliphatic having 1-12 carbon atoms, R '= H, CH ₂ OH, k = 2 to 15, preferably 3 to 12, particularly preferably 4 to 12, m = 0 to 13, preferably 0 to 9, l = 0 to 2, wherein the sum of k + l + m is between 5 and 15 and k> m, preferably between 5 and 12, the three structural elements can be distributed alternately or statistically and wherein the structural elements via CH ₂ groups are linearly and / or branched via CH groups, and B) 20 to 90 wt .-% of at least one binder, and C) 0 to 50 wt .-% of at least one colorant and / or Filler and D) 5 to 75 wt .-% of at least one additive, wherein the sum of the weights of component A) to D) is 100 wt .-%. Coating material compositions according to claim 1, characterized in that the carbonyl-hydrogenated ketone-aldehyde resins A), which contain substantially the structural elements according to formula I.

with R = aromatic having 6-14 carbon atoms, (cyclo) aliphatic having 1-12 carbon atoms, R '= H, CH ₂ OH, k = 2 to 15, preferably 3 to 12, particularly preferably 4 to 12, m = 0 to 13, preferably 0 to 9, l = 0 to 2, wherein the sum of k + l + m is between 5 and 15 and k> m, preferably between 5 and 12, the three structural elements can be distributed alternately or statistically and wherein the structural elements via CH ₂ groups linearly and / or branched via CH groups are obtained by I. the preparation of the base resins by condensation of at least one ketone with at least one aldehyde in the presence of at least one basic catalyst and optionally at least one phase transfer catalyst , solvent-free or using a water-miscible organic solvent, followed by II. continuous, semi-batch or discontinuous hydrogenation of the carbonyl groups of the ketone-aldehyde resins (A) in the melt or r in solution of a suitable solvent with hydrogen in the presence of a catalyst at pressures between 50 and 350 bar, preferably between 100 and 300 bar, more preferably between 150 and 300 bar and temperatures between 40 and 140 ° C, preferably between 50 and 140 ° C. , Coating material compositions according to claim 1 or 2, wherein the carbonyl-hydrogenated ketone-aldehyde resins are characterized in that • the content of free formaldehyde is below 3 ppm, preferably below 2.5 ppm, more preferably below 2.0 ppm, • the carbonyl number is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g, • the hydroxyl number is between 50 and 450 mg KOH / g, preferably between 150 and 400 mg KOH / g, particularly preferably between 200 and 375 mg KOH / g, Gardner color number (50% in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75, Gardner color number (50%) in ethyl acetate) after thermal loading of the resin (24 h, 150 ° C) below 2.0, preferably below 1.5, more preferably below 1.0, • the polydispersity (Mw / Mn) of the resins between 1.35 and 1.6, more preferably between 1.4 and 1.58, • the solution viscosity, 40% in phen oxyethanol, between 5000 and 12000 mPa · s, more preferably between 6000 and 10000 mPa · s, • the melting point / range between 50 and 150 ° C, preferably between 75 and 140 ° C, particularly preferably between 100 and 130 ° C. lies, • The content of non-volatile constituents after tempering for 24 h at 150 ° C over 97.0%, preferably above 97.5%. Coating compositions according to at least one of the preceding claims, characterized in that for the preparation of the ketone-aldehyde resins A) α-methyl ketones, the α'-position to the carbonyl group no reaction possibility own or in α'-position only a low reactivity have to be used. Coating compositions according to at least one of the preceding claims, characterized in that as starting bonds for the preparation of the ketone-aldehyde resins A) Acetophenone, derivatives of acetophenone such. For example, hydroxyacetophenone, alkyl-substituted acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone, 3,3-dimethylbutanone, methyl isobutyl ketone, or propiophenone, used alone or in mixtures, in amounts of 70 to 100 mol%, based on the ketone component. Coating compositions according to at least one of the preceding claims, characterized that as starting bonds for the preparation of the ketone-aldehyde resins A) up to 30 mol%, preferably up to 15 mol%, based on the ketone component, C-H-acidic ketones selected from acetone, methyl ethyl ketone, Heptanone-2, pentanone-3, cyclopentanone, cyclododecanone, mixtures from 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, Cyclohexanone, all alkyl-substituted cyclohexanones with one or a plurality of alkyl radicals having a total of 1 to 8 hydrocarbon atoms may be used alone or in mixtures. Coating compositions according to at least one of the preceding claims, characterized that as starting bonds for the preparation of the ketone-aldehyde resins A) up to 30 mol%, preferably up to 15 mol%, based on the ketone component, C-H-acidic ketones are used, selected from cyclohexanone, Methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and / or 3,3,5-trimethylcyclohexanone. Coating compositions according to at least one of the preceding claims, characterized in that as starting compound for the preparation of the ketone-aldehyde resins A) Formaldehyde and / or formaldehyde donating compounds used become. Coating compositions according to at least one of the preceding claims, characterized that as a starting compound for the preparation of the ketone-aldehyde resins A) formaldehyde and / or para-formaldehyde and / or trioxane used become. Coating compositions according to at least one of the preceding claims, characterized that as starting compounds for the preparation of the ketone-aldehyde resins A) in addition to formaldehyde selected aldehydes from acetaldehyde, n-butyraldehyde, isobutyraldehyde, valeric aldehyde, Dodecanal, alone or in mixtures in proportions of up to 75 mol%, preferably up to 50 mol%, more preferably up to 25 mol% based to the aldehyde component used. Coating compositions according to at least one of the preceding claims, characterized that as starting compounds for the preparation of the ketone-aldehyde resins A) acetophenone, 3,3-dimethylbutanone and / or methyl isobutyl ketone and optionally CH-acidic ketones selected from cyclohexanone, Methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone, alone or in mixtures, and Formaldehyde be used. Coating compositions according to at least one of the preceding claims, characterized in that the molar ratio between the ketone and the aldehyde component between 1: 0.25 to 1 to 15, preferably between 1: 0.9 to 1: 5 and more preferably between 1: 0.95 to 1: 4. Coating material compositions according to at least one of the preceding claims, characterized in that binder B), from the group of polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyamides, casein, polyureas, derivatives of cellulose, polyvinyl alcohols and derivatives , Polyvinyl acetates, polyvinylpyrolidones, (cyclo) rubbers, natural resins, hydrocarbon resins, terpene resins, maleate resins, phenolic resins, phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, ketone resins, aminoplasts, polyolefins, acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, epoxy resins , Resols, Rosin Resin, Resinate, Silica and alkali metal silicates, silicone resins, fluorine-containing polymers, chlorinated rubber, chlorinated polyester, PVDF, alone or in mixtures are included. Coating compositions according to at least one of the preceding claims, characterized that as binder B) polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, Polyureas, derivatives of cellulose such as cellulose nitrate, cellulose ethers and / or cellulose acetobutyrates, polyvinyl alcohols and derivatives, Polyvinyl acetates, polyvinylpyrolidones, natural resins, hydrocarbon resins such as cumarone, indene, cyclopentadiene resins, terpene resins, maleate resins, Phenolic resins, phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, Ketone resins, aminoplasts such as melamine, benzoguanamine resins, resoles, Rosin resins, resinates, alone or in mixtures are. Coating compositions according to at least one of the preceding claims, characterized that as component C) inorganic pigments and fillers selected from milori blue, titanium dioxide, iron oxides, metal pigments, Carbon blacks, carbonates, sulphates, silicates, pyrophyllite, Chlorite, mica, kaolin, slate flour, field fissures, precipitated Ca, Al, Ca / AL, Na / Al silicates, silicas, kieselguhr, precipitated and / or pyrogenic silicas, glass flour, Oxides, alone or in mixtures, are included. Coating compositions according to at least one of the preceding claims, characterized that as component C) organic pigments such. B. isoindoline, Azo, quinacridone, perylene, dioxazine, phthalocyanine pigments, alone or in mixtures. Coating compositions according to at least one of the preceding claims, characterized that as component D) inhibitors, organic solvents, Water, surfactants, oxygen and / or Free radical scavengers, catalysts, light stabilizers, color lighteners, Photosensitizers and initiators, additives for influencing rheological properties, leveling agents, skin preventatives, Defoamer, deaerator, antistatic agent, lubricant, Wetting and dispersing agents, crosslinking agents, preservatives, fungicides, Biocides, thermoplastic additives, plasticizers, matting agents, Fire retardants, internal release agents, or propellants, alone or in mixtures. Coating compositions according to at least one of the preceding claims, characterized in that the organic solvents of component D) are alcohols, Acetates, ketones, ethers, glycol ethers, aliphatics, aromatics, alone or in mixtures. Coating compositions according to at least one of the preceding claims, characterized that component A) additionally with diisocyanates and / or Polyisocyanates was reacted. Coating material compositions according to claim 19, characterized in that as di- and / or polyisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI) , Nonanetriisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecanediisocyanate and triisocyanate, dodecane diisocyanate and triisocyanate, isophorone diisocyanate (IPDI), 2,2'- and 2,4 ' - And 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) alone or in mixtures, preferably the H ₁₂ MDI consists of at least 80 wt .-% of 4,4'-H ₁₂ MDI, preferably au s 85-95% by weight, 2.5 (2.6) bis (isocyanato-methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in mixtures, for the preparation of component A). Coating composition according to claim 19, characterized in that polyisocyanates prepared by Dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates, alone or in mixtures, for the preparation of component A) can be used. Coating material compositions according to claim 19, characterized in that the isocyanates based on IPDI, TMDI, H ₁₂ MDI and / or HDI, alone or in mixtures, for the preparation of component A) are used Coating material compositions according to claim 19, characterized in that isocyanurates of the diisocyanates IPDI, HDI and / or H ₁₂ MDI, alone or in mixtures, for the preparation of component A) are used. Coating material compositions according to claim 19, characterized in that reaction products of IPDI, TMDI, HDI and / or H ₁₂ MDI with trimethylolpropane and / or pentaerythritol, alone or mixtures, are used for the preparation of component A). Process for the preparation of coating compositions according to at least one of the preceding claims by intensive Mix the components at temperatures from 20 to 80 ° C. Use of coating compositions according to at least one of the preceding claims 1-25 for coating metals, plastics, paper, Paper laminates, cardboard, cardboard, inorganic materials such. Ceramic, Stone, concrete, plaster, glass, textiles, fibers, fabric materials, Leather, synthetic materials, such. As artificial leather, wood, films made of plastics, or composites. Use of coating compositions according to at least one of the preceding claims 1 to 25 as building protection paints / varnishes, road marking paints, Automotive Finishing (OEM, Refinish), Coil-Coatings, Can-Coatings, Textile Finishing, Wood coatings, plastic coatings. Use of coating compositions according to at least one of the preceding claims 1 to 25 for the bonding of textiles, leather, paper, plastics, Metals. Articles coated with the coating compositions according to at least one of claims 1 to 25.