WO2009047102A1

WO2009047102A1 - Coating material compositions

Info

Publication number: WO2009047102A1
Application number: PCT/EP2008/062499
Authority: WO
Inventors: Patrick GLÖCKNER; Andreas Wenning
Original assignee: Evonik Degussa Gmbh
Priority date: 2007-10-05
Filing date: 2008-09-19
Publication date: 2009-04-16
Also published as: DE102007047586A1; CN101423723A

Abstract

The invention relates to coating material compositions consisting of at least one binder, a formaldehyde-free, carbonyl-hydrogenated ketone-aldehyde resin based on formaldehyde of low viscosity, very low colour number and very high heat and light resistance, a colorant and optionally auxiliary and additive materials, their preparation and their use.

Description

Beschichtunqsstoffzusammensetzunqen

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

The coating compositions are used for coating various substrates, e.g. Metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic materials such. As ceramics, stone, concrete, plaster and / or glass, textiles, fibers, fabric materials, leather and synthetic materials, such as. As artificial leather, wood, films made of plastics and composites such. As aluminum-laminated films, wherein the coating is largely free of formaldehyde.

After the application of coating materials, rapid drying is desirable in order to ensure rapid further processing and to avoid defects caused by e.g. Avoid soiling such as dust and dirt, etc. In addition, high scratch resistance is important in order to obtain a coating that is insensitive to mechanical stress.

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. As 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.

For preparation, ketones and formaldehyde are normally reacted with each other in the presence of bases.

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

The carbonyl groups of the ketone-aldehyde resins are subject to z. B. irradiation with e.g. Sunlight classic degradation reactions such as. From the Norrish type I or Il [Laue, Piagens, name and keyword responses, 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 described in DE 33 34 631. As comprehensive own findings prove, all these hydrogenated products have a relatively high content of free formaldehyde in common. Although the proportion of free formaldehyde over the non-hydrogenated ketone-formaldehyde resins is reduced by the hydrogenation processes described by the prior art, significant amounts of free formaldehyde remain in the hydrogenation products. Higher temperatures during the hydrogenation can lead to a further reduced formaldehyde content, but this can be detrimental to other resin properties such. As color, melting ranges, OH numbers, etc. impact.

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.

A method of lowering the formaldehyde content of non-hydrogenated acetone-formaldehyde resins without reducing the carbonyl groups is described in US 5,247,066. 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 processes mentioned in the patents DE 826 974, DE 870 022, JP 11012338, US Pat. No. 6,222,009 and DE 33 34 631 lead to products which have improved properties with regard to color, heat and light resistance compared with the starting materials. From today's point of view these products are no longer sufficient despite their improvement.

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 resins have always been used to increase the content of non-volatile constituents in coating materials. Under the pressure of new guidelines such. For example, Council Directive 1999/13 / EC on the limitation of emissions of volatile organic compounds, these characteristics need to be further improved.

The object of the present invention was to find coating compositions for the coating of different substrates that are free from free formaldehyde. The coating compositions should have a high drying rate, water resistance and scratch resistance and a low solution viscosity at high solids content. In addition, the films should have a good adhesion to the substrate, a low gloss, high color stability and a high heat and light resistance.

The object underlying the invention has surprisingly been achieved by the use of special coating compositions, which are described in more detail below.

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 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,

I = 0 to 2, where the sum of k + I + 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 have CH ₂ groups linear and / or branching via CH groups are linked,

and B) 20 to 90 wt .-% of at least one binder, and

C) O 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 has been found that the combination of the coating composition described below from components A) to D) fulfill all the required criteria.

Component A)

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

I = 0 to 2, where the sum of k + I + 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 have CH ₂ groups linear and / or branching via CH groups are linked.

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,

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 5,000 and 12,000 mPa.s, more preferably between 6,000 and 10,000 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%.

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 then

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 ⁰ C, preferably between 50 and 140 ⁰ C.

In this way, the content of harmful formaldehyde can be greatly reduced. Formaldehyde-free means that the carbonyl-hydrogenated ketone-aldehyde resins essential to the invention have a content of free formaldehyde below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm. It has been found that a low color number and a high thermal stability is the result of a low carbonyl number (I <2 of 1c). The carbonyl number of the carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention 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 Gardner color number (50% in ethyl acetate) after thermal stress (24 h, 150 ° C) 2.0, preferably less than 1, 5, more preferably less than 1, 0.

The lowest possible solution viscosity is desired so that the proportion of organic solvents which is necessary, inter alia, to lower the solution viscosity into the desired processing range is as low as possible due to the economy and due to environmental considerations. The solution viscosity of the carbonyl-hydrogenated ketone-aldehyde resins essential to the invention is 40% in phenoxyethanol, between 5000 and 12000 rnPa-s, more preferably between 6000 and 1000o mPa-S.

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

The highest possible melting range of the invention essential carbonyl-hydrogenated ketone-aldehyde A) is desirable so that z. B. the drying rate of the coating materials and the hardness of the coatings are as high as possible.

A high melting point / range can firstly be obtained via a high molecular weight (sum of k + I + m in formula I). However, the higher the molecular weight, the higher the solution viscosity. That's why it was desired to raise the melting point / range without increasing the molecular weight. This could be achieved, in which k always predominates in formula I and is preferably chosen as high as possible. The value of k is from 2 to 15, preferably from 3 to 12, particularly preferably from 4 to 12. The carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention have melting points of between 50 and 150.degree. C., preferably between 75 and 140.degree. C., more preferably between 100 and 130 ° C.

A high k according to formula I also has a positive effect on the solubility of the invention essential carbonyl-hydrogenated ketone-aldehyde A) in polar solvents such. As alcohols, which is especially important in coating materials, since often alcohols such. Ethanol can be used. Also, compatibility with polar binders, e.g. Nitrocellulose positively influenced thereby. Therefore, k is chosen such that k is greater than m and that 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 solubility properties can be adjusted by the ratio of k, I and m. The higher, for example, k and the lower m and I, the better the invention carbonyl-hydrogenated ketone-aldehyde resins A) are soluble in polar solvents such as alcohols and the better the compatibility with polar binders such. Nitrocellulose. On the other hand, the ratio of k, I and m must be chosen so that other properties such. B. the water resistance can not be adversely affected.

The values for k, I and m as well as the sum of the values can be integers, e.g. B. 2, but also intermediate values, such. B. 2.4 assume.

Components for the preparation of the carbonyl-containing base resins, process step I. Ketones and aldehydes Suitable ketones for the preparation of the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde are all ketones, in particular all α-methyl ketones which have no possibility of reacting in the α'-position to the carbonyl group or have only a low reactivity in the α'-position, such as As acetophenone, derivatives of acetophenone such. As hydroxyacetophenone, al kylsu bstitu ized 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 contained in the resins of the invention from 70 to 100 mol%, based on the ketone component. Carbonyl-hydrogenated ketone-aldehyde resins A) based on the ketones acetophenone, 3,3-dimethylbutanone and methyl isobutyl ketone are preferred, alone or in a mixture.

In addition, further CH-acidic ketones can be used in a subordinate scale in mixture with the abovementioned ketones up to 30 mol%, preferably up to 15 mol%, based on the ketone component, 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 having one or more alkyl radicals, having a total of 1 to 8 carbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones there may be mentioned 4-tert.-amylcyclohexanone, 2-sec.-butylcyclohexanone, 2-tert.-butylcyclohexanone, 4-tert.-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone. Preference is given to cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone.

In addition to formaldehyde are suitable as additional aldehyde components of the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde in principle, unbranched or branched aldehydes, such as. As acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used become. Preferably, however, formaldehyde is used alone. The further aldehydes can be used in proportions between 0 and 75 mol%, preferably 0 and 50 mol%, particularly preferably between 0 and 25 mol%, based on the aldehyde component. Aromatic aldehydes, such as. As benzaldehyde, may be included in a mixture with formaldehyde up to 10 mol% also.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other forms of formaldehyde are formaldehyde donating compounds such. Para- formaldehyde and / or trioxane.

Very particular preference is given as starting compounds for the carbonyl-hydrogenated ketone-aldehyde resins acetophenone, 3,3-dimethylbutanone and also 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 mixture and formaldehyde. It is also possible to use mixtures of 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-containing base resins, process step I.

For the preparation of the carbonyl group-containing base resins I. the respective ketone or a mixture of different ketones is reacted with formaldehyde or a mixture of formaldehyde and additional aldehydes in the presence of at least one basic catalyst. In particular, when using formaldehyde as an aqueous solution and ketones whose water solubility is limited, water-soluble organic solvents can be used advantageously. Because of the Among other related better phase mixing, the reaction conversion is faster and more complete. In addition, optionally at least one phase transfer catalyst can additionally be used, whereby z. B. is possible to reduce the amount of alkali compound. After completion of the reaction, the aqueous phase is separated from the resin phase. The crude product is washed with acidic water until a melt sample of the resin appears clear. Then, the resin is 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 producing the base resins of ketone and aldehyde can be carried out by using an auxiliary solvent. As suitable, alcohols such. As methanol or ethanol proved. It is also possible to use water-soluble ketones as auxiliary solvents, which then react with the resin.

For purification of the base resins I. the basic catalyst used must be removed. This can be done easily by washing with water using acids for neutralization. In general, for neutralization all acids such. As all organic and / or inorganic acids suitable. Preferred are organic acids having 1 to 6 carbon atoms, more preferably organic acids having 1 to 4 carbon atoms.

In the polycondensation mixture for preparing the base resins from ketone and aldehyde, phase transfer catalysts may optionally be additionally used. 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,

Ri, R2, R3, R _4: may be the same or different and are an alkyl radical having 1 to 22 carbon atoms in the carbon chain and / or a phenyl and / or benzyl and

Y: the anion of an organic acid or a hydroxide ion.

In the case of quaternary ammonium salts, alkyl radicals (Ri _-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. , Cl ^", ^Br" J ^", and also hydroxides, methoxide or acetates. Examples of quaternary ammonium salts are cetyldimethylbenzylammonium, tributylbenzyl, trimethylbenzylammonium, Trimethylbenzylammoniumjodid, ammonium chloride Triethylbenzyl- or Thethylbenzylammoniumjodid, tetramethylammonium chloride, tetraethylammonium, tetrabutylammonium. Preferably benzyltributylammonium, cetyldimethylbenzylammonium is and / or thethylbenzylammonium chloride 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.

As quaternary phosphonium salts come z. B. Triphenylbenzylphosphoniumchlorid or Triphenylbenzylphosphoniumjodid in question. However, mixtures can also be used.

The optionally contained phase transfer catalyst is used in amounts of 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, in the polycondensation mixture used.

Particularly preferred embodiment

In a particularly preferred embodiment, the carbonyl group-containing base resin I. is first prepared. 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 ketone-aldehyde resins essential to the invention 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:

As catalysts, in principle all compounds can be used which catalyze the hydrogenation of carbonyl groups and the hydrogenation of free formaldehyde to methanol with hydrogen. It is possible to use homogeneous or heterogeneous catalysts; heterogeneous catalysts are particularly preferred.

In order to obtain the formaldehyde-free products according to the invention, in particular metal catalysts selected from nickel, copper, copper-chromium, palladium, platinum, ruthenium and rhodium alone or in mixture have been suitable proven, particularly 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. As graphite or magnesium stearate.

The catalytic hydrogenation may be carried out in the melt, in solution of a suitable solvent or the hydrogenation product itself as a "solvent." The optional solvent may, if desired, be separated after completion of the reaction after the solvent used, additional purification steps may be necessary to completely or partially remove minor or less volatile by-products, such as methanol and water Suitable solvents are those in which both the starting material and the product are present in the product dissolve sufficiently and behave inert under the selected hydrogenation. These are z. As alcohols, preferably n- and i-butanol, cyclic ethers, preferably tetrahydrofuran and dioxane, alkyl ethers, aromatics, such as. B. XyIoI and esters, such as. For example, ethyl and butyl acetate. There are also mixtures of these solvents possible. The concentration of the resin in the solvent can be varied between 1 and 99%, preferably between 10 and 50%.

In order to achieve high conversions with the lowest possible residence times 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 depends on the hydrogenation catalyst used. Thus, for rhodium catalysts already temperatures of 40 to 75 ° C, preferably from 40 to 60 ° C is sufficient, whereas with Cu or Cu / Cr catalysts higher temperatures are necessary, which are typically between 100 and 140 ° C.

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

The catalyst loading is 0.05 to 4 t of resin per cubic meter of catalyst per hour, preferably 0.1 to 2 t of resin per cubic meter of catalyst per hour.

Various methods known to the person skilled in the art are suitable for controlling the temperature profile in the reactor and in particular for limiting the maximum temperature. So z. B. are working at sufficiently low resin concentrations completely without additional reactor cooling, wherein the reaction medium completely absorbs the released energy and thereby convectively leads out of the reactor out. Also suitable are, for example, tray reactors with intermediate Cooling, the use of hydrogen circuits with gas cooling, the recycling of a part of the cooled product (circulation reactor) and the use of external coolant circuits, especially in tube-bundle reactors.

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

For the hydrogenation (process step II.) Of the produced carbonyl-containing resin from process step I. is carried out in continuous fixed bed reactors. Particularly suitable for the preparation of the resins according to the invention are shaft furnaces and tube bundles, which are preferably operated in trickle bed mode. In this case, hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent, are added to the catalyst bed at the top of the reactor. Alternatively, the hydrogen can also be passed in countercurrent from bottom to top. The optionally contained solvent can - if desired - then be separated.

To improve the rate of drying, the ketone-aldehyde resins (component A) can also be reacted with di- and / or polyisocyanates. The urethanized products thus obtained have improved drying speed 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-thmethylhexane or 1,6-diisocyanato-2,2,4-thmethylhexane (TMDI), nonanetriisocyanate, such as 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 from 85 to 95 wt .-%, 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 binders B) essential to the invention are used in amounts of from 20 to 90% by weight, preferably from 30 to 75% by weight.

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, rosins , Resinate, silicic acid esters and alkali metal silicates (eg., Water glass), silicone resins, chlorine and / or fluorine-containing polymers such. As polyvinyl chloride and its derivatives, chlorinated rubber, chlorinated polyester, PVDF used. It can also be used mixtures. The binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing. 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, resoles, rosin resins, resinates, used alone or in mixtures

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 that are used in the paint industry are suitable.

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 Colohstischen aspects and requirements such as color tone, color intensity, brightness, saturation, transparency, hiding power, light fastness, bleeding, compatibility, etc., as well as mechanical aspects and requirements such. 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-shaped iron oxide, multilayer effect pigments from PVD films or produced by the CVD process (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 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 ".

Component D)

The component D) essential to the invention is used in amounts of from 5 to 75% by weight, preferably from 5 to 45% by weight.

In principle, all auxiliaries and additives (additives) that are used in the paint industry are suitable.

Particularly suitable as component D) 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 D) are those which are used in the paint 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.

Preparation of the Coating Compositions from Components A) to D):

The preparation of the coating compositions is carried out 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 may be first dissolved in suitable solvents or water prior to mixing, then the remaining components are added with stirring. In the case of, for example, pigments and / or fillers, dispersion takes place using suitable aggregates such as, for example, dissolvers, three-rolls, bead mills, ball mills or the like The formaldehyde content of the coating compositions is below 100 ppm, preferably below 50 ppm and more preferably below 10 ppm.

The claimed coating compositions are used for coating various substrates, e.g. Metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic materials such. As ceramics, stone, concrete, gypsum, glass, textiles, fibers, Gewebematehalien, leather, synthetic materials, such as. As artificial leather, wood, films made of plastics, or composites such. B. aluminum-laminated films.

The coating compositions are used both indoors and outdoors such. B. as BautenschutzfarbenAlacke, road marking paints, automotive coatings (OEM, Refinish), coil coatings, can coatings, textile finishing, wood coatings, plastic coatings, and for decorative applications, etc. Also 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 according to the invention are distinguished by a particularly high rate of drying, scratch and water resistance.

The films have a high gloss and a low gloss, high color stability and a very high heat and light resistance. The dried, cured or crosslinked films have good adhesion properties on underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.

The claimed coating compositions have a good flow on the substrates used and are free of surface defects, such as craters and wetting disorders.

Depending on the application method, the viscosities of the coating material compositions are adjusted. For a given solution viscosity, the claimed coating compositions have a non-volatile content of from 10% to 100% by weight, preferably from 25% to 100%.

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

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

Examples

Analytical Methods of Substantially Essential Component A)

Determination of free formaldehyde content

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 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 hydroxyl number

The OH number of component A) essential to the invention is determined on the basis of DIN 53240-2 "Determination of the Hydroxyl Number." Care must be taken to ensure that an acetylation time of 3 hours is exactly maintained.

Determination of carbonyl number

The determination of the carbonyl number of the invention essential component A) is carried out

FT-IR spectroscopy after calibration with 2-ethylhexanone in THF in a NaCl

Cuvette.

Determination of Gardner Color Number Before and After Thermal Exposure The Gardner 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 in this way the color number after thermal stress of the invention essential Component A) determined. 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 on the basis of DIN ISO 4630.

Determination of the solution viscosity of component A) The solution viscosity is determined according to DIN EN ISO 3219. The solid resin is dissolved in a suitable solvent such as phenoxyethanol, for example with a solids content of 40%. The viscosity is measured at 23 ° C by means of a plate / cone rotation viscometer (1/4 Os).

Determination of polydispersity

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

Determination of the melting range

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

Calculation of the copolymer distribution

To calculate the values for k, I and m of the component A) essential to the invention, the procedure is as follows.

Calculation example (for illustrative purposes, integers are used):

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

From a C = O-ZaN of 10 mg KOH / g result (10/56110 * 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 + I is thus 5.35 + 2.2 + 0.18 = 7.73

Analytical methods of the coating compositions of the invention

Determination of Yellowing, Light and Heat Resistance To determine resistance to yellowing, light and heat, the coating compositions were applied, freed from solvent and subjected to a Xenon 1200 test or stored at 100 ° C. for 24 hours. The CIE-Lab color differences before and after loading between the comparative films without the invention essential component A) and the film with the invention essential component A) were according to DIN 6174 / DIN 5033 with the meter x-rite 8200 spectrophotometer (measurement parameters: without gloss / aperture 12.7mm / illuminant D65 / 10 °).

Determination of the solution viscosity of the coating material

The determination of the solution viscosity of the coating material is carried out according to DIN

53211, 4 mm outlet cup.

Determination of substrate wetting and course

The determination of the substrate wetting and the course of the coating compositions takes place visually. Good wetting is achieved when the applied coating composition is a closed film without

Defects such. B. crater results. A good course is achieved when the applied, closed film has a low intrinsic structure (eg, orange peel, too deep penetration into the substrate in, for example, paper, or the like).

Determination of liability

The adhesion of the coatings was by means of cross-cut test before and after

Load tested (DIN EN ISO 2409).

Load tests / water resistance

Tropentest: Storage of the applied films at 40 ° C and 95% humidity Storage: DIN EN ISO 2812-2 (storage of the test panels at 40 ⁰ C in demineralised water)

Determination of the degree of gloss / luster The determination was carried out according to DIN EN ISO 2813.

Antrocknunqsqeschwindiqkeit

The coating materials are applied to the substrates to be examined. To

The fingernail test (see scratch resistance) is carried out for 5 min, 1 h and 24 h.

Scratch resistance (Finqernaqeltest)

The index finger is pulled over the coating and the degree of damage to the coating is assessed visually.

Determination of the content of nonvolatile matter (nfA)

The content of non-volatile components is given as the mean value of a duplicate determination. Approximately 2 g of the sample (coating material) are weighed (mass m _{2 of} the substance) into a cleaned aluminum dish (tare mass m.sub.2) on an analytical balance. The bowl 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:

φ = ™ iZ3 .. where [% by mass]

Determination of the content of free formaldehyde

The formaldehyde content is determined by the lutidine method by HPLC (Official

Components of the paint separated by centrifuging first.

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

Examples:

Non-inventive comparative examples

The document best describing the state of the art is DE 33 34 631 A1. The acetophenone / formaldehyde resin used here was obtained according to Example 2 of DE 892 974. Example A: Adjustment of Example 2 of DE 892 974

After addition of 240 g of 50% potassium hydroxide solution and 400 g of methanol, 1000 g of 30% strength formaldehyde solution are added to 1200 g of acetophenone over the course of 2 hours with vigorous stirring. The temperature increases to 90 ° C. This temperature is maintained for 10 h. It is acidified with sulfuric acid and the resulting condensation product is washed with hot water, melted and dehydrated in vacuo.

There are obtained 1260 g of a yellow resin. 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. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol. The formaldehyde content is 255 ppm.

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

According to Example 3 of DE 33 34 631 A1, 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% strength solution of the resin in i-butanol were added, the pressure in the reactor being kept constant at 300 bar by adjusting the consumed hydrogen.

Inventive Examples

Inventive Example I)

Preparation of a base resin for further hydrogenation based on

Acetophenone and formaldehyde

1200 g of acetophenone, 220 g of methanol, 0.3 g of benzyltributylammonium chloride and 360 g of a 30% aqueous formaldehyde solution are initially charged and homogenized with stirring. Then, 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 stopped after 5 h stirring at reflux temperature and the aqueous phase separated from the resin phase. The crude product is washed with acetic acid water until a melt sample of the resin appears clear. Then, the resin is dried by distillation.

There are 1270 g of a slightly yellowish resin. The resin is clear and brittle and has a melting point of 72 ° C. The Gardner color number 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 catalyst basket, which is filled with 100 ml_ of a Raney-type nickel catalyst. 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%). Then, the hydrogenation is carried out at 260 bar and 120 ° C in an autoclave (Parr) with a catalyst basket, which is filled with 100 ml_ of a commercially available Ru catalyst (3% Ru on alumina). After 20 hours, the reaction mixture is drained from the reactor via a filter. Inventive Example 3:

The resin of Example I) was dissolved with 30% heating in i-butanol. The hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, silicon-supported copper-chromium contact. At 300 bar and 130 ° C 500 ml_ of the reaction mixture is driven hourly from top to bottom through the reactor (trickle). The pressure is kept constant by the addition of hydrogen.

Inventive Example 4:

The resin of Example I) was dissolved in 30% i-butanol with heating. The hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, Raney-type nickel catalyst. At 300 bar and 130 ° C., 400 ml of the reaction mixture are passed through the reactor from top to bottom every hour (trickle-flow method). The pressure is kept constant by the addition of hydrogen.

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

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 soluble in ethanol in any proportion. In contrast, the resin of Comparative Example B) is not perfectly soluble in ethanol at concentrations below 10% solids.

The resins 1 to 4 essential to the invention have a lower content of free formaldehyde compared to the noninventive resin of Example B. Corresponding to the lower carbonyl number, the color number and the color number after thermal stress are lower. Although these resins have up to 35% higher melting points than the noninventive resin of Example B, the viscosity is comparable to the resin of Example B. This may be explained by the higher polydispersity of the noninventive resin, if desired. Application Example 1: Plastic paint

The components shown in the table below were processed to a plastic paint. For this, 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.

Examples of sources of supply:

Substratbenetzunq / History

The coatings 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 coatings according to inventive examples A1 and A2

Antrocknunqsqeschwindiqkeit

To assess the rate of drying, the paints were on

Polystyrene substrates with a layer thickness of about 30 microns applied. After 5 minutes, 1 hour and 24 hours, the fingernail test was carried out and the film was checked for injuries.

1 very good, 6 insufficient

Without the addition of a hydrogenated ketone-aldehyde resin, the drying rate is poor (V1). The use of the comparative resin B in the formulation V2 leads to better results; However, a good adhesion is reached only after 24 h, which may be due to the low melting point of the resin of V2 is due. In contrast, the paints according to inventive examples A1 and A2 have very good values already after 5 minutes. It is thus shown that the resins according to the invention improve the drying rate.

Determination of liability

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.

0 very good, 5 insufficient

Overall, it should be noted that without the addition of a hydrogenated ketone aldehyde resin, the adhesion is always poor (V1). The use of the comparative resin B in the formulation V2 leads to better results. The best results are obtained by the lacquers with the resins of Examples A1 and A2 according to the invention. It is thus shown that the resins essential to the invention improve the adhesion even under critical conditions as well as the water resistance.

Determination of yellowing, light and heat resistance

To determine the yellowing, light and heat resistance, the paints were on

Polystyrene substrates with a layer thickness of about 30 microns applied. After 24 h were subjected the panels to a Xenon 1200 test for 24 h. For the determination of heat resistance, the samples were stored at 100 ° C for 24 hours.

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 according to DIN 6174 / DIN 5033 with the meter x-rite 8200 spectrophotometer (measurement parameters: without gloss / aperture 12.7mm / illuminant D65 / 10 ⁰ ).

The use of the comparative resin B in formulation V2 leads to strong color deviations, possibly due to the high carbonyl number. In contrast, the coatings according to inventive examples A1 and A2 have a very good stability.

Determination of glossy grade / 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.

Without the addition of a hydrogenated ketone-aldehyde resin (V1), the gloss is relatively low and the haze is high. This may be due to poor pigment wetting / stabilization due to the lack of a hard resin. The use of the comparative resin B in the formulation V2 leads to better results. However, the Haze is also high here. The best results are obtained by the paints of Examples A1 and A2 according to the invention. This shows that the resins essential to the invention improve gloss and haze.

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, Examples 2 and 3) and the other components in the solvent mixture were dissolved with stirring.

Examples of sources of supply:

SubstratbenetzunqA / erlauf

The paints were applied to pine wood with a layer thickness of approx. 50 μm. In the paint of the blank V3, the paint penetrated strongly into the substrate (no sagging). The best topcoat and the best wetting reach the coatings with the addition of a hydrogenated ketone-aldehyde resin

Determination of glossy grade / glossy haze

To determine the gloss, the lacquers were applied to pine wood with a layer thickness of about 50 μm. After storage under normal conditions for 24 h, the

Measurement.

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

Application example 3: UV-curing lacquer

The components listed in the table are processed with stirring to form a UV varnish.

Determination of liability 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.

0 very good, 5 insufficient

Without the addition of a hydrogenated ketone-aldehyde resin, the adhesion is 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 varnishes with the resins of Examples A5 and A6 according to the invention. It is thus shown that the resins essential to the invention improve the adhesion even in UV lacquers.

Claims

claims:

1. Coating compositions containing free formaldehyde below 100 ppm, essentially containing

With

R = aromatic with 6-14 carbon atoms, (cyclo-) aliphatic with 1-12

Carbon atoms,

I = 0 to 2, where the sum of k + I + 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 linear and / or via CH Groups are linked branching,

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

2. coating material compositions according to claim 1, characterized in that the carbonyl-hydrogenated ketone-aldehyde resins A),

which essentially contain the structural elements according to formula I.

With

R = aromatic with 6-14 carbon atoms, (cyclo-) aliphatic with 1-12

Carbon atoms,

I = 0 to 2, where the sum of k + I + 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 have CH ₂ groups are 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,

and subsequently

II. Continuous, semi- or discontinuous hydrogenation of the carbonyl groups of the ketone-aldehyde resins (A) 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, more preferably between 150 and 300 bar and temperatures from 40 to 140 0C, preferably between 50 and 140 ⁰ C.

3. coating material compositions according to claim 1 or 2, wherein the carbonyl-hydrogenated ketone-aldehyde resins are characterized in that

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 5,000 and 12,000 nnPa-s, more preferably between 6,000 and 10,000 rnPa-s,

The melting point / range is between 50 and 150 ° C., preferably between 75 and 140 ° C., particularly preferably between 100 and 130 ° C.,

• The content of non-volatile constituents after tempering for 24 h at 150 ⁰ C over 97.0%, preferably above 97.5%.

4. 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 which have no possibility of reaction in α'-position to the carbonyl group or have only a low reactivity in α'-position become.

5. 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. As hydroxyacetophenone, alkyl-substituted Acetophenondehvate having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone, 3,3-dimethylbutanone, methyl isobuty I ketone, or propiophenone, used alone or in mixtures, in amounts of 70 to 100 mol%, based on the ketone component.

6. coating compositions according to at least one of the preceding claims, characterized in that as starting bonds for the preparation of the ketone-aldehyde A) up to 30 mol%, preferably up to 15 mol% based on the ketone component, CH-acidic ketones selected from acetone , Methyl ethyl ketone, heptanone-2, pentanone-3, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, cyclohexanone, all alkyl-substituted cyclohexanones having one or more alkyl radicals, the total 1 to 8 carbon atoms, used alone or in mixtures.

7. coating compositions according to at least one of the preceding claims, characterized in that as starting bonds for the preparation of the ketone-aldehyde A) up to 30 mol%, preferably up to 15 mol% based on the ketone component, C-H-acid

Ketone selected from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and / or 3,3,5-hexanediol.

Trimethylcyclohexanone.

8. coating composition 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 are used.

9. coating composition 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 para-formaldehyde and / or trioxane are used.

10. coating compositions according to at least one of the preceding claims, characterized in that as starting compounds for the preparation of the ketone-aldehyde A) in addition to formaldehyde aldehydes selected from acetaldehyde, n-butyraldehyde, iso-butyraldehyde, valeric aldehyde, dodecanal, alone or in mixtures in proportions up to 75 mol%, preferably up to 50 mol%, particularly preferably up to 25 mol%, based on the aldehyde component.

11. coating composition according to at least one of the preceding claims, characterized in that as starting compounds for the preparation of the ketone-aldehyde 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 are used.

12. coating composition 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 is.

13. coating composition according to at least one of the preceding claims, characterized in that the 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, resoles, rosin resins, resinates, silicic acid esters and alkali silicates, silicone resins, fluorine-containing polymers, chlorinated rubbers, chlorinated polyesters, PVDF, alone or in mixtures.

14. coating composition according to at least one of the preceding claims, characterized in 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 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, resoles, rosin resins, resinates, alone or in mixtures, are included.

15. Coating composition according to claim 1, characterized in that as component C) inorganic pigments and fillers selected from milori blue, titanium dioxide, iron oxides, metal pigments, carbon blacks, carbonates, sulfates, silicates, pyrophyllite, chlorite, mica, kaolin, slate meal, Field columns, precipitated Ca, Al, Ca / AL, Na / Al silicates, silicas, diatomaceous earth, precipitated and / or fumed silicas, glass powder, oxides, alone or in mixtures are included.

16. coating compositions according to at least one of the preceding claims, characterized in that as component C) organic pigments such. As isoindoline, azo, quinacridone, perylene, dioxazine, phthalocyanine pigments, alone or in mixtures.

17. coating compositions according to at least one of the preceding claims, characterized in that as component D) inhibitors, organic solvents, water, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, rheological additives, leveling agents, skin preventatives, defoamers, deaerators, antistatics, lubricants, 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, are included.

18. coating composition according to at least one of the preceding claims, characterized in that as the organic solvent of component D) alcohols, acetates, ketones,

Ethers, glycol ethers, aliphatic, aromatic, alone or in mixtures are included.

19. coating composition according to at least one of the preceding claims, characterized in that the component A) was additionally reacted with diisocyanates and / or polyisocyanates.

20. Coating composition according to claim 19, characterized in that as di- and / or polyisocyanates cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, toluene 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-thmethylhexane ( TMDI), nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate 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% by weight of the 4,4'-H ₁₂ MDI, preferably from 85 to 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) can be used.

21. A coating composition according to claim 19, characterized in that polyisocyanates prepared by Dimehsierung, trimerization, allophanatization, biuretization and / or urethanization simple diisocyanates, alone or in mixtures, for the preparation of component A) are used.

22. Coating composition according to claim 19, characterized in that isocyanates based on IPDI, TMDI, H ₁₂ MDI and / or HDI, alone or in mixtures, for the preparation of component A) are used

23. coating composition 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.

24. coating composition 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 in mixtures, for the preparation of component A) are used.

25. A process for the preparation of coating material compositions according to at least one of the preceding claims by intensive mixing of the components at temperatures of 20 to 80 ° C.

26. Use of the coating material compositions according to at least one of the preceding claims 1 - 25 for the coating of metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic materials such. As ceramics, stone, concrete, plaster, glass, textiles, fibers, fabric materials, leather, synthetic materials, such as. As artificial leather, wood, films made of plastics, or composites.

27. Use of the coating material compositions according to at least one of the preceding claims 1 to 25 as building protection paints / coatings, road marking paints, automotive coatings (OEM, Refinish), coil coatings, can coatings, textile finishing, wood coatings, plastic coatings.

28. Use of the coating material compositions according to at least one of the preceding claims 1 to 25 for the bonding of textiles, leather, paper, plastics, metals.

29. articles coated with the coating material compositions according to at least one of claims 1 to 25.