EP2029657A2

EP2029657A2 - Powder coating materials with high-functionality, highly branched or hyperbranched polycarbonates

Info

Publication number: EP2029657A2
Application number: EP07725130A
Authority: EP
Inventors: Andreas Joch; Werner-Alfons Jung; Werner BLÖMER; Bernd Bruchmann; Ria Kress; Norbert Wagner; Mirco Bassi
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2006-05-19
Filing date: 2007-05-11
Publication date: 2009-03-04
Also published as: WO2007134736A3; US20100028582A1; BRPI0712597A2; RU2008150054A; JP2009537673A; WO2007134736A2; MX2008014205A; CN101448870A; CA2652453A1

Abstract

Powder coating materials which comprise high-functionality, highly branched or hyperbranched polycarbonates based on dialkyl carbonates or diaryl carbonates or phosgene, diphosgene or triphosgene and on aliphatic, aliphatic/aromatic or aromatic diols or polyols.

Description

Powder coatings with highly functional, highly branched or hyperbranched polycarbonates

description

The present invention relates to powder coatings containing highly functional, highly branched or hyperbranched polycarbonates based on dialkyl or diaryl carbonates or phosgene, diphosgene or triphosgene and aliphatic, aliphatic / aromatic or aromatic diols or polyols.

Polycarbonates are usually obtained from the reaction of alcohols or phenols with phosgene or from the transesterification of alcohols or phenols with dialkyl or diaryl carbonates. Technically significant are aromatic polycarbonates, for example, prepared from bisphenols; Aliphatic polycarbonates have so far played a subordinate role in terms of market volume. See also Becker / Braun, Kunststoff-Handbuch Bd. 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag, Munich 1992, pages 118-119, and "Ulimann ^'s Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, Publisher Wiley-VCH.

The aromatic or aliphatic polycarbonates described in the literature are usually constructed linearly or with only a slight degree of branching.

Thus, US Pat. No. 3,305,605 describes the use of solid linear aliphatic polycarbonates with a molar mass above 15,000 Da as plasticizer for polyvinyl polymers.

US Pat. No. 4,255,301 describes linear cycloaliphatic polycarbonates as light stabilizers for polyesters. Linear aliphatic polycarbonates are furthermore preferably used for the production of thermoplastics, for example for polyesters or for polyurethane or polyurea urethane elastomers, see also EP 364052, EP 292772, EP 1018504 or DE 10130882. Characteristic of these linear polycarbonates is generally their high intrinsic viscosity.

EP-A 896 013 discloses crosslinked polycarbonates which are obtainable by reacting mixtures of diols and polyols having at least 3 OH groups with organic carbonates, phosgene or derivatives thereof. Preferably, at least 40% of the diol is used. The document contains no indications as to how, starting from the abovementioned starting materials, it would also be possible to prepare uncrosslinked, hyperbranched polycarbonates.

Defined, highly functional polycarbonates have only been known for a short time.

WO 2006/089940 describes hyperbranched, highly branched or hyperbranched polycarbonates and, more generally, their use in powder coatings.

However, special powder coatings are not described there.

S.P. Rannard and N.J. Davis, J. Am. Chem. Soc. 2000, 122, 11729, describe the preparation of perfectly branched dendrimeric polycarbonates by reaction of carbonylbisimidazole as a phosgene analogue compound with bis-hydroxyethylamino-2-propanol.

Syntheses to perfect dendrimers are multi-step, therefore costly and therefore unsuitable for transfer to an industrial scale. DH Bolton and KL Wooley, Macromolecules 1997, 30, 1890, describe the preparation of high molecular weight, very rigid hyperbranched aromatic polycarbonates by reacting 1,1,1-tris (4'-hydroxyphenyl) ethane with carbonylbisimidazole.

Hyperbranched polycarbonates can also be prepared according to WO 98/50453. According to the process described there, triols are in turn reacted with carbonylbisimidazole. Initially, imidazolides are formed, which then react further intermolecularly with the polycarbonates. According to the method mentioned, the polycarbonates are obtained as colorless or pale yellow rubbery products.

Scheel and co-workers, Macromol. Symp. 2004, 120, 101, describe the preparation of polycarbonates based on triethanolamine and carbonylbisimidazole, which, however, leads to thermolabile products.

The above-mentioned syntheses of highly branched or hyperbranched polycarbonates have the following disadvantages:

a) the hyperbranched products are either high-melting, rubbery or thermally labile, thereby significantly limiting later processability. b) liberated imidazole during the reaction must be removed from the reaction mixture consuming. c) the reaction products always contain terminal imidazolide groups. These groups are labile and must be followed by a sequential step, e.g. d) Carbonyldiimidazole is a relatively expensive chemical that greatly increases the cost of starting materials.

It is an object of the present invention to produce powder coatings which have improved flow properties and / or improved appearance. The problem could be solved by powder coatings containing at least one highly functional, highly branched or hyperbranched, uncrosslinked polycarbonate.

The high-functionality, highly branched or hyperbranched polycarbonates used for this purpose are liquid at room temperature (23 ⁰ C) or solid generally have a glass transition temperature of -70 to 50 ⁰ C, preferably from -70 to 20 ⁰ C and particularly preferably from -50 to +10 ⁰ C on.

The glass transition temperature T ₉ is determined by the DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82, the heating rate is preferably 10 ° C./min.

The OH number according to DIN 53240, Part 2 is usually 100 mg KOH / g or more, preferably 150 mg KOH / g or more.

The viscosity according to ISO 3219 of the polycarbonates in melt at 175 ° C is between 0 and 20,000 mPas, preferably 0-15,000 mPas.

The weight average molecular weight M _w is usually between 1,000 and 150,000, preferably from 2000 to 120,000 g / mol, the number average molecular weight M _n between 500 and 50,000, preferably between 500 and 40,000 g / mol.

The polycarbonates show an advantage in the powder coatings according to the invention, in particular as flow aids for improving the rheology.

Hyperbranched polycarbonates in the context of this invention are understood as meaning uncrosslinked macromolecules having hydroxyl and carbonate or carbamoyl chloride groups which are structurally as well as molecularly nonuniform. They can be on the one hand, starting from a central molecule analogous to dendrimers, but with be built uneven chain length of the branches. On the other hand, they can also be constructed linearly, with functional, branched side groups, or, as a combination of the two extremes, have linear and branched molecular parts. For the definition of dendrimeric and hyperbranched polymers see also PJ. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

By "high" and "hyperbranched" in the context of the present invention is meant that the degree of branching

(Degree of Branching, DB), that is, the mean number of dendritic

Joins plus average number of end groups per molecule, divided by the sum of the mean number of dendritic ones

Joins, the average number of linear joins and the average number of endgroups multiplied by 100, 10 to 99.9

%, preferably 20 to 99%, particularly preferably 20-95%.

In the context of the present invention, "dendrimer" is understood to mean that the degree of branching is 99.9-100%. For the definition of the degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.

It is an important feature of polycarbonates that they are uncrosslinked. "Uncrosslinked" in the context of this document means that a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, determined via the insoluble fraction of the polymer, is present.

The insoluble portion of the polymer was determined by extraction for four hours with the same solvent as used for gel permeation chromatography, that is selected from the group consisting of tetrahydrofuran, dimethylacetamide and hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble Soxhlet apparatus and after Dry the residue to constant weight Weigh the remaining residue.

The highly functional, highly branched or hyperbranched, uncrosslinked polycarbonates are preferably obtained by a process comprising the steps:

a) Preparation of one or more condensation products (K) either by

a1) reaction of at least one organic carbonate (A) of the general formula! RO [(CO) O] _n R with at least one aliphatic, aliphatic / aromatic or aromatic alcohol (B1) having at least 3 OH groups, with elimination of alcohols ROH, wherein each R is independently a straight or branched aliphatic, aromatic / aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms, and wherein the radicals R may also be joined together to form a ring, preferably a five- to six-membered ring, and n is an integer from 1 to 5 represents

or

a2) reaction of phosgene, diphosgene or triphosgene with said aliphatic, aliphatic / aromatic or aromatic alcohol (B1) to release hydrogen chloride,

and

b) intermolecular conversion of the condensation products (K) to a highly functional, highly branched or hyperbranched polycarbonate, wherein the quantitative ratio of the OH groups to the phosgene or the carbonates in the reaction mixture is chosen so that the condensation products (K) on average either a carbonate or carbamoyl chloride group and more than one OH group or one OH group and more than one carbonate have - or carbamoyl chloride group.

Specifically, for the procedure, the following is to be done:

Phosgene, diphosgene or triphosgene, among these preferably phosgene, can be used as starting material, but organic carbonates (A) are preferably used.

The radicals R used as starting material organic carbonates (A) of the general formula RO [(CO) O] _n R are each independently a straight-chain or branched aliphatic, aromatic / aliphatic (araliphatic) or aromatic hydrocarbon radical having 1 to 20 C atoms. The two radicals R can also be linked together to form a ring. The two radicals R may be the same or different, preferably they are the same. It is preferably an aliphatic hydrocarbon radical and particularly preferably a straight-chain or branched alkyl radical having 1 to 5 C atoms, or a substituted or unsubstituted phenyl radical.

R is a straight-chain or branched, preferably straight-chain, (cyclo) aliphatic, aromatic / aliphatic or aromatic, preferably (cyclo) aliphatic or aromatic, particularly preferably aliphatic, hydrocarbon radical having 1 to 20 C atoms, preferably 1 to 12, particularly preferably 1 to 6 and very particularly preferably 1 to 4 carbon atoms.

Examples thereof are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-butyl Dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, o- or p-tolyl or naphthyl. Preferred are methyl, ethyl, n-butyl and phenyl.

The radicals R may be the same or different, preferably they are the same.

The radicals R can also be linked together to form a ring. Examples of such divalent radicals R are 1, 2-ethylene, 1, 2-propylene and 1, 3-propylene.

In general, n is an integer from 1 to 5, preferably from 1 to 3, particularly preferably from 1 to 2.

The carbonates may preferably be simple carbonates of the general formula RO (CO) OR, i. in this case n stands for 1.

Dialkyl or diaryl carbonates can be prepared, for example, from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols with phosgene. Furthermore, they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO _x . For preparation methods of diaryl or dialkyl carbonates, see also "Ullmann's Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, Verlag Wiley-VCH.

According to the invention, it does not play any significant role in the manner in which the carbonate has been prepared.

Examples of suitable carbonates include aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, Ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate,

Ethyl phenyl carbonate, dibenzyl carbonate, dimethyl carbonate,

Diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate,

Diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate.

Examples of carbonates in which n is greater than 1 include dialkyl dicarbonates, such as di (tert-butyl) dicarbonate or dialkyl tricarbonates, such as di (tert-butyl) tricarbonate.

Aliphatic carbonates are preferably used, in particular those in which the radicals comprise 1 to 5 C atoms, for example dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-n-butyl carbonate or diisobutyl carbonate. A preferred aromatic carbonate is diphenyl carbonate.

The organic carbonates are reacted with at least one aliphatic or aromatic alcohol (B1) which has at least 3 OH groups or mixtures of two or more different alcohols.

The alcohol (B1) may be branched or unbranched, substituted or unsubstituted and have from 3 to 26 carbon atoms. It is preferably a (cyclo) aliphatic, particularly preferably an aliphatic alcohol.

Examples of compounds having at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 1, 2,4-butanetriol, tris (hydroxy-methyl) amine,

Tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol, polyglycerols, bis (tri-methylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate,

Phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, Phloroglucide, hexahydroxybenzene, 1,3,5-benzenetrimethanol, 1,1,1-tris (4'-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane,

Sugars, such as glucose, sugar derivatives, e.g. Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol, isomalt, trifunctional or higher polyethers based on trifunctional or higher alcohols and ethylene oxide, propylene oxide or butylene oxide or their mixtures, or polyesterols.

The abovementioned alcohols having at least three OH groups may optionally also be alkoxylated, i. with one to 30, preferably one to 20, more preferably one to 10 and most preferably one to five molecules of ethylene oxide and / or propylene oxide and / or iso-butylene oxide reacted per hydroxyl group.

Glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol and their polyetherols based on ethylene oxide and / or propylene oxide are particularly preferred.

These polyfunctional alcohols can also be used in a mixture with difunctional alcohols (B2), with the proviso that the average OH functionality of all the alcohols used together is greater than 2. Examples of suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 and 1, 3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2-, 1, 3- and 1,5-pentanediol, 1, 6-hexanediol, 1, 2- or 1, 3-cyclopentanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, 1 , 1-, 1, 2-, 1, 3- or 1, 4-cyclohexanedi-methanol, bis (4-hydroxycyclohexyl) methane, bis (4-

Hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1'-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl, bis- ( 4-hydroxyphenyl) sulfide, bis (4-

Hydroxyphenyl) sulfone, bis (hydroxymethyl) benzene, Bis (hydroxymethyl) toluene, bis (p-hydroxyphenyl) methane, bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) propane, 1,1-bis (p-hydroxyphenyl) cyclohexane, dihydroxybenzophenone, difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, polytetrahydrofuran having a molecular weight of 162 to 2000, polycaprolactone or polyesterols based on diols and dicarboxylic acids.

The diols serve to finely adjust the properties of the polycarbonate. If difunctional alcohols are used, the ratio of difunctional alcohols (B2) to the at least trifunctional alcohols (BI) will vary depending on the person skilled in the art

Properties of the polycarbonate set. As a rule, the

Amount of the alcohol or alcohols (B2) 0 to 39.9 mol% with respect to the total amount of all alcohols (B1) and (B2) together. The amount is preferably 0 to 35 mol%, particularly preferably 0 to 25 mol% and very particularly preferably 0 to 10 mol%.

The alcohols (B1) and (B2) are collectively referred to herein as (B).

The reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture is usually carried out with elimination of hydrogen chloride, the reaction of the carbonates with the alcohol or alcohol mixture to highly functional highly branched polycarbonate with elimination of the monofunctional alcohol or phenol from the carbonate molecule.

The highly functional highly branched polycarbonates formed by the process described are terminated after the reaction, ie without further modification, with hydroxyl groups and with carbonate groups or carbamoyl chloride groups. They dissolve well in various solvents. Examples of such solvents are aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters and ethers.

Preference is given to aromatic hydrocarbons, (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, ketones, alkoxylated alkanoic acid alkyl esters and mixtures thereof.

Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, ketones, Alkansäurealkylester and alkoxylated Alkansäurealkylester and mixtures thereof.

As the aromatic hydrocarbon mixtures, preferred are those which comprise predominantly aromatic C ₇ - to C include ₄ hydrocarbons and may comprise a boiling range from 110 to 300 ⁰ C, particularly preferably toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene, Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.

Examples include the Solvesso® brands of ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio-aromatics, boiling range about 154-178 ⁰ C), 150 (boiling range about 182 207 ⁰ C) and 200 (CAS No. 64742-94-5), as well as the shell oils (Shell) of the company Shell Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also under the names of crystal oil (for example, crystal oil 30, boiling range 158-198 ⁰ C or crystal oil 60:.. CAS No. 64742-82-1), petroleum spirit (for example likewise CAS No. 64742-82-1) or Solvent naphtha (light: boiling range about 155-180 ⁰ C, heavy: boiling range about 225 -. 300 ⁰ C) commercially available the aromatics content of such hydrocarbon mixtures is generally more than 90 wt%, preferably more than 95, more preferably more than 98 and most preferably more than 99 wt% can. be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.

The content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.

Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.

Examples of esters are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.

Examples of ketones are acetone, 2-butanone, 2-pentanone, 3-pentanone, hexanone, isobutyl methyl ketone, heptanone, cyclopentanone, cyclohexanone or cycloheptanone.

(Cyclo) aliphatic hydrocarbons are, for example, decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.

Preference is furthermore given to n-butyl acetate, ethyl acetate, 1-

Methoxypropylacetat-2, 2-methoxyethyl acetate, 2-butanone, iso-butyl methyl ketone and mixtures thereof, in particular with the above-listed aromatic hydrocarbon mixtures.

Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2 , Preferred solvents are butyl acetate, methoxypropyl acetate, iso-butyl methyl ketone, 2-butanone, Solvesso® brands and xylene.

Also suitable for the carbonates are, for example, water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene carbonate or propylene carbonate.

In the context of this invention, a high-functionality polycarbonate is to be understood as meaning a product which, in addition to the carbonate groups which form the polymer backbone, also has at least three, preferably at least six, more preferably at least ten functional groups. The functional groups are carbonate groups or carbamoyl chloride groups and / or OH groups. In principle, the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The high-functionality polycarbonates usually have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.

In the preparation of high-functionality polycarbonates, it is necessary to adjust the ratio of the compounds containing OH groups to phosgene or carbonate (A) so that the resulting simplest condensation product (hereinafter condensation product (K) called) on average either a carbonate or Carbamoylchloridgruppe and more than one OH group or an OH group and more than one carbonate or carbamoyl chloride group, preferably on average either a carbonate or carbamoyl chloride group and at least two OH groups or a OH group and at least two carbonate or carbamoyl chloride groups.

It may also be useful to use for fine adjustment of the properties of the polycarbonate at least one divalent carbonyl reactive compound (A1). These are understood to mean those compounds which have two carbonate and / or carboxyl groups.

Carboxyl groups may be carboxylic acids, carboxylic acid chlorides, carboxylic anhydrides or carboxylic acid esters, preferably carboxylic acid anhydrides or carboxylic acid esters and more preferably carboxylic acid esters.

If such divalent compounds (A1) are used, the ratio of (A1) to the carbonates or phosgene (A) of

Expert determined depending on the desired properties of the polycarbonate. As a rule, the amount of or the bivalent is

Compound (A1) 0 to 40 mol% with respect to the total amount of all

Carbonates / phosgene (A) and compounds (A1) together. The amount is preferably 0 to 35 mol%, particularly preferably 0 to 25 mol% and very particularly preferably 0 to 10 mol%.

Examples of compounds (A1) are dicarbonates or dicarbamoyl chlorides of diols, for example ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2-ethyl-1, 3-hexanediol , 2,4-diethyl-octane-1,3-diol,

Hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2 -, 1, 3 or 1, 4-cyclohexanediol. These can be prepared, for example, by reacting these diols with an excess of, for example, the above-mentioned carbonates RO (CO) OR or chloroformates, so that the resulting dicarbonates are substituted on both sides with groups RO (CO) -. Another possibility is to first react the diols with phosgene to form the corresponding chlorocarbonic acid esters of the diols and then to react with alcohols.

Further compounds (A1) are dicarboxylic acids, esters of dicarboxylic acids, preferably the methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sec / c-butyl or ferf Butyl esters, particularly preferably the methyl, ethyl or n-butyl esters.

Examples of such dicarboxylic acids are oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, azelaic, 1-cyclohexanedicarboxylic or

Tetrahydrophthalic, suberic, phthalic, tetrahydrophthalic, hexahydrophthalic,

tetrachlorophthalic

Endomethylenetetrahydrophthalic anhydride, glutaric anhydride, dimer fatty acids, their isomers and hydrogenation products.

The simplest structure of the condensation product (K), illustrated by the example of the reaction of a carbonate (A) with a di- or polyalcohol (B) gives the arrangement XY _m or Y _m X, where X is a carbonate or carbamoyl group, Y is a hydroxyl Group and m is usually an integer greater than 1 to 6, preferably greater than 1 to 4, particularly preferably greater than 1 to 3 represents. The reactive group, which results as a single group, is referred to hereinafter generally "focal group". If, for example, in the preparation of the simplest condensation product (K) from a carbonate and a dihydric alcohol, the molar conversion ratio is 1: 1, the average results in a molecule of the type XY ₁ illustrated by the general formula (I).

In the preparation of the condensation product (K) from a carbonate and a trihydric alcohol at a molar conversion ratio of 1: 1 results in the average molecule of the type XY2, illustrated by the general formula (II). Focal group here is a carbonate group.

In the preparation of the condensation product (K) from a carbonate and a tetrahydric alcohol also with the molar conversion ratio 1: 1 results in the average molecule of the type XY ₃ , illustrated by the general formula (III). Focal group here is a carbonate group.

In the formulas (I) to (III) R has the meaning defined above and R ¹ is an aliphatic or aromatic radical.

Furthermore, the preparation of the condensation product (K) for

Example of a carbonate and a trihydric alcohol, illustrated by the general formula (IV), take place, wherein the Reaction ratio at molar 2: 1 is. This results in the average molecule of type X ₂ Y, focal group here is an OH group. In the formula (IV), R and R ^{1 have} the same meaning as in the formulas (I) to (III) above.

If difunctional compounds, for example a dicarbonate or a dioi, are additionally added to the components, this causes an extension of the chains, as illustrated, for example, in the general formula (V). The result is again on average a molecule of the type XY ₂ , focal group is a carbonate group.

In formula (V), R ^{2 is} an aliphatic or aromatic radical, R and R ¹ are defined as described above.

It is also possible to use a plurality of condensation products (K) for the synthesis. In this case, on the one hand, several alcohols or more carbonates can be used. Furthermore, mixtures of different condensation products of different structure can be obtained by selecting the ratio of the alcohols used and the carbonates or phosgene. This is exemplified by the example of the reaction of a carbonate with a trihydric alcohol. If the starting materials are used in the ratio 1: 1, as shown in (II), one molecule XY2 is obtained. If the starting materials are used in a ratio of 2: 1, as in (IV) This results in a molecule X ₂ Y. At a ratio between 1: 1 and 2: 1, a mixture of molecules XY ₂ and X ₂ Y is obtained.

Typical reaction conditions of the reaction of (A) with (B) to the condensation product (K) are shown below:

The stoichiometry of components (A) and (B) is generally chosen so that the resulting condensation product (K) has on average either a carbonate or carbamoyl chloride group and more than one OH group or one OH group and more than one carbonate or Has carbamoyl chloride group. This is achieved in the first case by a stoichiometry of 1 mol carbonate groups:> 2 mol OH groups, for example a stoichiometry of 1: 2.1 to 8, preferably 1: 2.2 to 6, particularly preferably 1: 2.5 to 4 and most preferably 1: 2.8 to 3.5.

In the second case, this is achieved by a stoichiometry of more than 1 mol of carbonate groups: <1 mol of OH groups, for example a stoichiometry of 1: 0.1 to 0.48, preferably 1: 0.15 to 0.45, more preferably 1: 0.25 to 0.4 and most preferably 1: 0.28 to 0.35.

The temperature should be sufficient for the reaction of the alcohol with the corresponding carbonyl component. In general, for the

Reaction with a phosgene at a temperature of -20 ⁰ C to 120 ⁰ C, preferably 0 to 100 and particularly preferably 20 to 80 ⁰ C. When using a carbonate, the temperature should be 60 to 180 ⁰ C, preferably 80 to

160 ⁰ C, more preferably 100 to 160 and most preferably 120 to 140 ⁰ C.

Suitable solvents are the solvents already mentioned above. It is a preferred embodiment to carry out the reaction without solvent. The order of addition of the individual components usually plays a minor role. In general, it is useful to submit the excess component of the two reactants and add the sub-component. Alternatively, it is also possible to mix the two components before starting the reaction and then heat this mixture to the required reaction temperature.

The simple condensation products (K) described by way of example in the formulas (I) to (V) preferably react intermolecularly to form highly functional polycondensate products, referred to below as polycondensation products (P). The conversion to the condensation product (K) and the polycondensation product (P) is usually carried out at a temperature of 0 to 300 ⁰ C, preferably 0 to 250 ⁰ C, more preferably at 60 to 200 ⁰ C and most preferably at 60 to 160 ⁰ C. in substance or in solution. In general, all solvents can be used which are inert to the respective starting materials. Preferably used organic solvents, such as the above, and more preferably decane, dodecane, benzene, toluene, chlorobenzene, xylene ₁ dimethylformamide, dimethylacetamide or solvent naphtha.

In a preferred embodiment, the condensation reaction is carried out in bulk. The monofunctional alcohol or phenol ROH liberated in the reaction can be removed from the reaction equilibrium to accelerate the reaction, for example by distillation, if appropriate under reduced pressure.

The separation of the alcohol or phenol can also be carried out by passing a stripping under the reaction conditions substantially inert gas stream, such as nitrogen, water vapor, Carbon dioxide or an oxygen-containing gas, such as air or lean air, are supported.

If distilling off is intended, it is regularly recommendable to use those carbonates which, in the reaction, release alcohols or phenols ROH with a boiling point of less than 140 ^° C. at the present pressure.

To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze esterification or transesterification reactions, for example! Alkaühydroxide, alkali metal carbonates, alkali metal bicarbonates, preferably of sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, zirconium or bismuth organic compounds, also called double metal cyanide (DMC) catalysts as described, for example, in DE 10138216 or in DE 10147712.

Preferably, potassium hydroxide, potassium carbonate,

Potassium bicarbonate, diazabicyclooctane (DABCO),

Diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles such as imidazole, 1-methylimidazole or 1,2-dimethylimidazole, titanium tetrabutylate, titanium tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate or mixtures thereof.

The addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight, based on the amount of the alcohol or alcohol mixture used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, can be found on the composition of the starting components and over the residence time adjust the average molecular weight of the polymer (P).

The condensation products (K) or the polycondensation products (P) which have been prepared at elevated temperature are usually stable over a longer period of time, for example over at least 6 weeks, without turbidity, precipitations and / or an increase in viscosity.

Due to the nature of the condensation products (K), it is possible that from the condensation reaction

Polycondensation products (P) can result with different structures that have branches, but no crosslinks. Further, the polycondensation products (P) ideally have either a carbonate or carbamoyl chloride group as a focal group and more than two OH groups or an OH group as a focal group and more than two carbonate or carbamoyl chloride groups. The number of reactive groups results from the nature of the condensation products used (K) and the degree of polycondensation.

For example, a condensation product (K) according to the general formula (II) can react by three-fold intermolecular condensation to give two different polycondensation products (P) represented by the general formulas (VI) and (VII).

In formulas (VI) and (VII), R and R ^{1 are} as defined above.

There are various possibilities for stopping the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the product (K) or the polycondensation product (P) is storage stable. This is usually below 60 ° C, preferably below

50 ⁰ C, more preferably below 40 ⁰ C and most preferably at room temperature the case.

Furthermore, one can deactivate the catalyst, for basic catalysts, for example by adding an acidic component, for example a Lewis acid or an organic or inorganic protic acid.

Further, it is possible to stop the reaction by dilution with a pre-cooled solvent. This is particularly preferred if you have to adjust the viscosity of the reaction mixture by the addition of solvent. In a further embodiment, as soon as a polycondensation product (P) having the desired degree of polycondensation is present due to the intermolecular reaction of the condensation product (K), the product (P) is added to terminate the reaction with a product having groups which are reactive towards the focal group of (P) ,

Thus, in the case of a carbonate group or carbamoyl group, for example, a mono-, di- or polyamine can be added as the focal group.

In the case of a hydroxyl group as the focal group, the product (P) may be added with, for example, a mono-, di- or polyisocyanate, an epoxy group-containing compound or an OH derivative-reactive acid derivative.

The preparation of the highly functional polycarbonates is usually carried out in a pressure range of 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades, which are operated in batch mode, semi-continuous or continuous.

By the aforementioned adjustment of the reaction conditions and optionally by the choice of the appropriate solvent, the products can be further processed after preparation without further purification.

If necessary, the reaction mixture of a decolorization, for example by treatment with activated carbon or metal oxides, such as alumina, silica, magnesia, zirconia, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50 wt%, preferably 0.5 to 25 wt %, more preferably 1-10% by weight at temperatures of for example 10 to 100 ⁰ C, preferably 20 to 80 ⁰ C and particularly preferably 30 to 60 ⁰ C are subjected. Optionally, the reaction mixture may also be filtered to remove any precipitates that may be present.

In a further preferred embodiment, the product is stripped, that is freed from low molecular weight, volatile compounds. This can after reaching the desired degree of conversion of the

Catalyst optionally deactivated and the low molecular weight volatile

Ingredients, for example, monoalcohols, phenols, carbonates,

Hydrogen chloride or volatile oligomeric or cyclic compounds by distillation, optionally with the introduction of a gas, preferably nitrogen, carbon dioxide or air, optionally at reduced pressure, are removed.

In a further preferred embodiment, the polycarbonates, in addition to the functional groups already obtained by the reaction, can be given further functional groups. The functionalization can during the molecular weight build-up or even subsequently, i. take place after completion of the actual polycondensation.

If components are added before or during the molecular weight build-up which have other functional groups or functional elements in addition to hydroxyl or carbonate groups, a polycarbonate polymer having randomly distributed functionalities different from the carbonate or carbamoyl chloride and hydroxyl groups is obtained.

Such effects can be achieved, for example, by addition of compounds during the polycondensation which, in addition to hydroxyl groups, carbonate groups or carbamoyl chloride groups further functional groups or functional elements, such as mercapto, primary, secondary or tertiary amino groups, ether groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or derivatives thereof , Phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl radicals or long-chain alkyl radicals.

For modification by means of carbamate groups, for example, ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2-

(Cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2'-aminoethoxy) ethanol or higher alkoxylation products of ammonia, 4-

Hydroxy-piperidine, 1-hydroxyethylpiperazine, diethanolamine,

Dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane,

Use ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.

Mercaptoethanol can be used for the modification with mercapto groups, for example. Tertiary amino groups can be used for

Example by incorporation of triethanolamine, tripropanolamine, N-

Methyldiethanolamine, N-methyldipropanolamine or N ₁ N-

Produce dimethylethanolamine. Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols. By addition of dicarboxylic acids, tricarboxylic acids,

Dicarboxylic esters, such as dimethyl terephthalate or Tricarbonsäureestem can produce ester groups. By

Reaction with long-chain alkanols or alkanediols can introduce long-chain alkyl radicals. The reaction with alkyl or aryl diisocyanates generates alkyl, aryl and urethane group-containing polycarbonates, the addition of primary or secondary

Amines leads to the introduction of urethane or urea groups.

Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polycarbonate in an additional process step (step c) with a suitable functionalizing reagent which can react with the OH and / or carbonate or carbamoyl chloride groups of the polycarbonate. implements. Hydroxyl-containing high-functionality, highly branched or hyperbranched polycarbonates can be modified, for example, by addition of molecules containing acid groups or isocyanate groups. For example, polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.

Furthermore, hydroxyl-containing high-functionality polycarbonates can also be converted into highly functional polycarbonate-polyether polyols by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or butylene oxide.

This may be useful, for example, to increase the solubility in water or to induce water emulsifiability. These are the hydroxy groups with at least one alkylene oxide, for example

Ethylene oxide, propylene oxide, iso-butylene oxide and / or styrene oxide, preferably ethylene oxide and / or propylene oxide, and particularly preferably

Implemented ethylene oxide. For each hydroxy group, it is used for from 1 to 200, preferably 2 to 200, more preferably 5 to 100, most preferably 10 to 100 and in particular 20 to 50

Alkylene oxides.

A preferred embodiment of the present invention provides at least partially reacting the polycarbonates with at least one monofunctional polyalkylene oxide polyether alcohol. As a result, an improved Wasseremulgierbarkeit is effected.

Monofunctional polyalkylene oxide polyether alcohols are reaction products of suitable starter molecules with polyalkylene oxides.

Suitable starter molecules for preparing monohydric polyalkylene oxide polyether alcohols are thiol compounds, Monohydroxy compounds of the general formula

R ⁵ -OH

or secondary monoamines of the general formula

R ⁶ R ⁷ NH,

in which R ⁵ , R ⁶ and R ⁷ independently of one another independently of one another are each of C 1-6 -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted nano-groups

C ₂ - Ciβ alkyl, _C6 - _Ci2 aryl, C ₅ - C ₂ denote cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle or R ⁶ and R ⁷ together form an unsaturated , saturated or aromatic and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups

Form ring, wherein said radicals are each represented by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or

Heterocycles may be substituted.

R ⁵ , R ⁶ and R ⁷ are each independently of the other Ci to Cj-alkyl, ie methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, se / c-butyl or te / f-butyl, more preferably R ⁵ , R ⁶ and R ^{7 are} methyl.

Examples of suitable monohydric starter molecules may be saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, cyclopentanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxy-methyloxetane, or tetrahydrofurfuryl alcohol; unsaturated alcohols such as allyl alcohol, 1, 1-dimethyl-allyl alcohol or Oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol; secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, bis (2-ethylhexyl) amine, N-methyl and

N-ethylcyclohexylamine or dicyclohexylamine, heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1 H-pyrazole, and amino alcohols such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-diisopropylaminoethanol, 2-dibutylaminoethanol, 3- (dimethylamino) -1-propanol or 1- (dimethylamino) -2-propanol.

Examples of the amine-started polyethers are the so-called Jeffamine® M series, which are methyl-capped polyalkylene oxides having an amino function, such as M-600 (XTJ-505), having a propylene oxide (PO) / ethylene oxide (EO) ratio of ca. 9: 1 and a molecular weight of about 600, M-1000 (XTJ-506): PO / EO ratio 3:19, molecular weight about 1000, M-2005 (XTJ-507): PO / EO ratio 29: 6, molecular weight about 2000 or M-2070: PO / EO ratio 10:31, molecular weight about 2000.

Suitable for the alkoxylation reaction alkylene oxides are ethylene oxide, propylene oxide, / so-butylene oxide, vinyloxirane and / or styrene oxide, which can be used in any order or in a mixture in the alkoxylation reaction.

Preferred alkylene oxides are ethylene oxide, propylene oxide and mixtures thereof, particularly preferred is ethylene oxide.

Preferred polyether alcohols are those based on polyalkylene oxide polyether alcohols, in the preparation of which saturated aliphatic or cycloaliphatic alcohols of the abovementioned type were used as starter molecules. Very particularly preferred are those based on polyalkylene oxide polyether alcohols which have been prepared using saturated aliphatic alcohols having 1 to 4 carbon atoms in the alkyl radical. Especially Preference is given to methanol-initiated polyalkylene oxide polyether alcohols.

The monohydric polyalkylene oxide polyether alcohols generally have on average at least 2 alkylene oxide units, preferably 5 ethylene oxide units, per molecule, more preferably at least 7, very preferably at least 10 and in particular at least 15.

The monohydric polyalkylene oxide polyether alcohols generally have on statistical average up to 50 alkylene oxide units, preferably ethylene oxide units, per molecule, preferably up to 45, more preferably up to 40 and most preferably up to 30.

The molecular weight of the monohydric polyalkylene oxide polyether alcohols is preferably up to 4000, particularly preferably not more than 2000 g / mol, very particularly preferably not less than 500 and in particular 1000 ± 200 g / mol.

Preferred polyether alcohols are thus compounds of the formula

wherein

R ^{5 has} the abovementioned meanings, k is an integer from 5 to 40, preferably 7 to 45 and particularly preferably 10 to 40 and each X j for i = 1 to k can be selected independently of one another from the group -CH ₂ - CH ₂ -O-, -CH ₂ -CH (CH ₃ ) O-, -CH (CHa) -CH ₂ -O-, -CH ₂ -C (CHa) ₂ -O-,

-C (CHa) ₂ -CH ₂ -O-, -CH ₂ -CHVJn-O-, -CHVm-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, are preferred from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) O- and -CH (CH ₃ ) -CH ₂ -O-, and particularly preferred -CH ₂ -CH ₂ -O-, where Ph is phenyl and Vin is vinyl.

To carry out the reaction of the polycarbonates, the polycarbonates (K) and / or (P) at temperatures of 40 to 180 ⁰ C, preferably 50 to 150 ° C, while maintaining a carbonate or carbamoyl chloride / OH equivalent ratio of 1: 1 to 100: 1, preferably from 1: 1 to 50: 1, more preferably 1, 5: 1 to 20: 1 reacted together.

A big advantage of the method lies in its economy. Both the conversion to a condensation product (K) or polycondensation product (P) and the reaction of (K) or (P) to polycarbonates with other functional groups or elements can be carried out in a reaction apparatus, which is technically and economically advantageous.

The highly functional highly branched polycarbonates formed by the process are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with carbonate or carbamoyl chloride groups. They dissolve well in various solvents, for example in water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, ethylene carbonate or propylene carbonate.

The powder coatings according to the invention contain, in addition to the hyperbranched polycarbonates, at least one binder (O) and at least one crosslinker (V). Optionally, the powder coatings may also contain other additives (F), such as in particular pigments.

As binder component (O), for example, optionally together with other hydroxyl or amino groups having Binders, in question hydroxy (meth) acrylates,

Hydroxystyryl (meth) acrylates, linear or branched polyesters, polyethers, polycarbonates, melamine resins or urea-formaldehyde resins, together with carboxy and / or hydroxy functional reactive crosslinking compounds, for example with isocyanates, capped isocyanates, epoxides and / or aminoplasts, preferably isocyanates , Epoxides or aminoplasts, more preferably with isocyanates or epoxides, and most preferably with isocyanates.

The present invention further relates to the use of the curable powder coatings for automotive finishing, the painting of buildings indoors and outdoors, the painting of doors, windows and furniture, industrial painting, including coil coating, container coating and impregnation and / or coating electrotechnical components, as well as the painting of white goods, including household appliances, boilers and radiators.

For the sake of brevity, the curable powder coatings are referred to below as "powder coatings".

The powder coatings are curable precursors of thermoplastic or duromeric plastics, which are applied in powder form to preferably metallic substrates. Usually this powder coating systems are used, as described in the above-listed company documents. This shows the two fundamental advantages of powder coatings, the complete or extensive freedom from organic solvents and the easy recycling of the powder coating overspray in the coating process.

Regardless of which powder coating equipment and methods are used, the powder coatings are applied in a thin layer on the substrate and melted, so that a forms closed powder coating layer, after which the resulting coating is cooled. The curing takes place during or after the melting of the powder coating layer. Preferably, the minimum curing temperature is above the melting range of the powder coating so that reflow and cure are separate. This has the advantage that the powder coating melt runs well due to their relatively low viscosity before curing sets.

The curable powder coatings contain, in addition to the polycarbonates, at least one functional constituent (F) of a powder coating. In addition, the powder coating contains at least one oiigorneren and / or polymeric component (O) as a binder and at least one crosslinker (V).

Suitable functional constituents (F) are all powder coating components, with the exception of the substances mentioned under (0) or (V) and the hyperbranched polycarbonates.

Examples of suitable powder coating components (F) are color and / or effect pigments, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powders, soluble organic dyes, organic and inorganic, transparent or opaque fillers and / or nanoparticles and / or auxiliary and / or additives such as UV absorbers, light stabilizers, radical scavengers, deaerating agents, slip additives, polymerization inhibitors, crosslinking catalysts, thermolabile radical initiators, photoinitiators, thermally curable reactive diluents, actinic radiation-curable reactive diluents, adhesion promoters, leveling agents, film-forming auxiliaries, flame retardants, corrosion inhibitors, Flow aids, waxes and / or matting agents. The components (F) can be used individually or as mixtures. In the context of the present invention, actinic radiation is electromagnetic radiation such as near infrared, visible light, UV radiation or X-radiation, in particular UV radiation, or corpuscular radiation such as electron beams.

Examples of suitable effect pigments are metal flake pigments such as commercial aluminum bronzes, aluminum chromates chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and nonmetallic effect pigments such as pearlescent or interference pigments, platelet-shaped iron oxide-based effect pigments having a hue from pink to brownish red or liquid-crystalline effect pigments. In addition, Rornpp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 176, "effect pigments" and pages 380 and 381 "metal oxide mica pigments" to "metal pigments", and the patent applications and patents DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311 A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417 567 A1, US 4,828,826 A or US 5,244,649 A.

Examples of suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.

Examples of suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments,

Benzimidazole pigments, quinacridone pigments, quinophthalone pigments, Diketopyrrolopyrrolpigmente, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments,

Thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.

In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", pages 451 to 453, "Pigments" to "Pigment Volume Concentration," page 563, "Thioindigo Pigments," Page 567 "Titanium Dioxide Pigments," pp. 400 and 467, "Naturally Occurring Pigments," page 459, "Polycyclic Pigments," p. 52, "AzoiTiethin Pigrnente," "Azopigrnente," and p. 379, "Metal Complex Pigments." ,

Examples of fluorescent pigments (daylight pigments) are bis (azomethine) pigments.

Examples of suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.

Examples of magnetically shielding pigments are pigments based on iron oxides or chromium dioxide.

Examples of suitable metal powders are powders of metals and metal alloys aluminum, zinc, copper, bronze or brass.

Suitable soluble organic dyes are non-fading organic dyes with little or no tendency to migrate from the powder coating and the coatings made therefrom. The migration tendency can be estimated by the person skilled in the art on the basis of his general expert knowledge and / or determined by means of simple orienting preliminary tests, for example in the context of tinting experiments. Examples of suitable organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular of polyamide or polyacrylonitrile. In addition, reference is made to Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., »Fillers«.

Preferably, mica and talc are used when the scratch resistance of the coatings prepared from the powder coatings is to be improved.

In addition, it is advantageous to use mixtures of platelet-shaped inorganic fillers such as talc or mica and non-platelet inorganic fillers such as chalk, dolomite calcium sulfates, or barium sulfate, because this makes it possible to adjust the viscosity and flow behavior very well.

Examples of suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide, but in particular nanoparticles based thereon.

As constituents (F) are also auxiliaries and / or additives such as UV absorbers, light stabilizers, radical scavengers, deaerating agents, slip additives, polymerization inhibitors, catalysts for crosslinking, thermolabile radical initiators, photoinitiators, thermally curable reactive diluents, curable with actinic radiation reactive diluents, adhesion promoters , Leveling agents, film-forming aids, flame retardants, corrosion inhibitors, flow aids, waxes and / or matting agents, which can be used individually or as mixtures into consideration.

Examples of suitable thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl groups hyperbranched compounds or dendrimers, as described in the patent applications DE 198 09 643 A1, DE 198 40 605 A1 or DE 198 05 421 A1.

Examples of suitable reactive curatives curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the heading "reactive diluents".

Examples of suitable thermolabile radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxycarboxylic acids,

Peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.

Examples of suitable crosslinking catalysts are bismuth lactate, citrate, ethyl hexanoate or dimethylol propionate dibutyltin dilaurate, lithium decanoate or zinc octoate, amine-blocked organic sulfonic acids, quaternary ammonium compounds, amines, imidazole and imidazole derivatives such as 2-styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylimidazole, as described in Belgian Patent No. 756,693, or phosphonium catalysts such as ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium thiocyanate, ethyltriphenylphosphonium acetate

Acetic acid complex, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and tetrabutylphosphonium acetate-acetic acid complex, as described, for example, in US Pat. Nos. 3,447,990 A or 3,341,580 A.

Examples of suitable photoinitiators are described in Rompp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, or in Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446. Examples of suitable antioxidants are hydrazines and phosphorus compounds.

Examples of suitable light stabilizers are HALS compounds, benzotriazoles or oxalanilides.

Examples of suitable radical scavengers and polymerization inhibitors are organic phosphites or 2,6-di-tert-butylphenol derivatives.

Examples of suitable deaerating agents are diazadicycloundecane or benzoin;

Further examples of the above-listed and other functional ingredients (F) are described in detail in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.

Preferred suitable crosslinking agents (V) are polyisocyanates.

The polyisocyanates contain on statistical average at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule. The number of isocyanate groups is basically not limited to the top; According to the invention, it is advantageous if the number does not exceed 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0.

Examples of suitable polyisocyanates are isocyanate-group-containing polyurethane prepolymers which can be prepared by reaction of polyols with an excess of diisocyanates and are preferably of low viscosity.

Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5- isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethylcyclohexane _I 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethylcyclohexane, 5-isocyanato (4-isocyanatobut-1-yl) -1,3,3-trimethylcyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) -cyclohexane, 1-isocyanato-2- (3 - isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) -cyclohexane, 1, 2-diisocyanate-ocyclobutane, 1, 3-diisocyanatocyclobutane, 1, 2-diisocyanatocyclopentane, I .S Diiso-cyanatocyclopentane, 1, 2-diisocyanatocyclohexane, 1, 3-diisocyanatocyclohexane, 1, 4-

Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI),

Ethyl ethylenediisocyanate, trimethylhexa-diisocyanate,

Heptamethylene diisocyanate or diisocyanates derived from dimer fatty acids, as sold under the trade name DDI 1410 by Henkel and described in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanato -onyl) -1-pentylcyclohexane, or 1, 2, 1, 4 or 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 2, 1, 4 or 1, 3-bis (2-isocyanatoeth 1 -yl) cyclohexane, 1, 3-bis (3-isocyanatoprop-1-yl) cyclohexane, 1, 2, 1, 4- or 1, 3-bis (4-isocyanatobut-1-yl) cyclohexane or liquid Bis (4-isocyanatocyclohexyl) methane of a trans / trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as disclosed in patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1, preferably isophorone diisocyanate, 5-isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1 - ( 3-isocyanatoprop-1-yl) -1,3,3-trimethylcyclohexane, 5-isocyanato (4-isocyanato-butyl) 1 -yl) -1,3,3-trimethylcyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) -cyclohexane or HDI, in particular HDI.

It is also possible to use isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea carbodiimide and / or uretdione groups containing polyisocyanates are prepared which are prepared in a conventional manner from the diisocyanates described above. Examples of suitable preparation processes and polyisocyanates are described, for example, in patents CA 2,163,591 A, US Pat. No. 4,419,513, US Pat. No. 4,454,317 A, EP 0 646 608 A, US Pat. No. 4,801,675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US Pat. No. 5,258,482 A1, US Pat. No. 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1.

Further examples of suitable crosslinking agents are blocked polyisocyanates.

Examples of suitable blocking agents for the preparation of the blocked polyisocyanates are the blocking agents known from US Pat. No. 4,444,954 A or US Pat. No. 5,972,189 A, such as US Pat

i) phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;

ii) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;

iii) active methylenic compounds, such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;

iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol,

Lauryl alcohol, ethylene glycol monomethyl ether,

Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether

Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diethylene glycol monobutyl ether propylene glycol monomethyl ether, methoxymethanol, 2- (hydroxy-ethoxy) phenol, 2-

(Hydroxypropoxy) phenol, glycolic acid, glycolic esters,

Lactic acid, lactic acid ester, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1, 3

Dichloro-2-propanol, 1, 4-cyclohexyldimethanol or

acetone cyanohydrin;

v) mercaptans such as butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole,

Thiophenol, methylthiophenol or ethylthiophenol;

vi) acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;

vii) imides such as succinimide, phthalimide or maleimide;

viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine,

Dibutylamine or butylphenylamine;

ix) imidazoles such as imidazole or 2-ethylimidazole;

x) ureas such as urea, thiourea, ethyleneurea, ethylene thiourea or 1,3-diphenylurea;

xi) carbamates such as N-phenylcarbamic acid phenyl ester or 2-oxazolidone;

xii) imines such as ethyleneimine; xiii) oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes;

xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;

xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or

xvi) substituted pyrazoles, ketoximes, imidazoles or triazoles; such as

Mixtures of these blocking agents, in particular dimethylpyrazole and triazoles, malonic esters and acetoacetic acid esters, dimethylpyrazole and succinimide or butyldiglycol and trimethylolpropane.

As polyfunctional isocyanates, preference is given to using mixtures of aliphatic polyisocyanates having an average functionality of from 3 to 6, preferably from 3.5 to 5, isocyanate groups per mole. The amount of isocyanate is preferably selected so that 1, 2 to 3, in particular 1, 5 to 2.5, isocyanate groups per hydroxyl group of the (co) polymer to react, the remaining isocyanate groups are converted by reaction with amines in urea groups.

As an example of particularly suitable isocyanate mixtures are mixtures of 0.1 to 10 wt .-%, especially 0.3 to 8 wt .-% of a diisocyanate (eg hexamethylene diisocyanate), 30 to 80 wt .-%, especially 42 to 79 Wt .-%, of a triisocyanate (eg trifunctional biuret of hexamethylene diisocyanate) and 20 to 60 wt .-%, especially 22 to 50 wt .-%, of an isocyanate having a functionality of 4 to 10 (eg, a corresponding higher-functionality biuret of

Hexamethylene diisocyanate). Further examples of suitable crosslinking agents are all known aliphatic and / or cycloaliphatic and / or aromatic, low molecular weight, oligomeric and polymeric polyepoxides, for example based on bisphenol-A or bisphenol-F. Also suitable as polyepoxides are, for example, the polyepoxides commercially available under the names Epikote® from Shell, Denacol® from Nagase Chemicals Ltd., Japan, such as Denacol EX-411 (pentaerythritol polyglycidyl ether), Denacol EX-321

(Trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether), or the glycidyl ester of trimellitic acid or trigylcidyl isocyanurate (TGIC).

As crosslinking agents it is also possible to use tris (alkoxycarbonylamino) triazines (TACT) in which the alkyl radicals contain from 1 to 10 carbon atoms.

Examples of suitable tris (alkoxycarbonylamino) triazines are described in the patents US 4,939,213 A, US 5,084,541 A or EP 0 624 577 A1. In particular, the tris (methoxy, tris (n-butoxy and / or tris (2-ethylhexyloxycarbonylamino) triazines are used.

Of advantage are the methyl-butyl mixed esters, the butyl-2-ethylhexyl mi- esters and the butyl esters. These have the advantage over the pure methyl ester the advantage of better solubility in polymer melts and also less prone to crystallization.

Furthermore, aminoplast resins, for example melamine resins, are useful as crosslinking agents. Any aminoplast resin suitable for transparent topcoats or clearcoats or a mixture of such aminoplast resins may be used here. Particularly suitable are the customary and known amino resins whose methylol and / or methoxymethyl z. T. are defunctionalized by means of carbamate or allophanate. Crosslinking agents of this type are described in US Pat. Nos. 4,710,542 and EP 0 245 700 B1 and in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13 , Pages 193 to 207. The aminoplast resins can also be used as binders (O).

Further examples of suitable crosslinking agents are beta-hydroxyalkylamides such as N, N, N ^l, N ^I-tetrakis (2-hydroxyethyl) adipamide or N, N, N ^l, N ^l tetrakis (2-hydroxypropyl) adipamide.

Furthermore, carboxylic acids, in particular saturated, straight-chain, aliphatic dicarboxylic acids having 3 to 20 carbon atoms in the molecule, in particular dodecanedioic acid, can be used.

Further examples of suitable crosslinking agents are siloxanes, in particular siloxanes having at least one trialkoxy or dialkoxysilane group.

Which crosslinking agents are used in detail depends on the complementary reactive functional groups contained in the binders of the powder coatings.

Examples of suitable complementary reactive functional groups of binder and crosslinker to be used according to the invention are summarized in the following overview. In the overview, the variable R ^{8 is} an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R ⁹ and R ¹⁰ stand for identical or different aliphatic radicals or are linked together to form an aliphatic or heteroaliphatic ring. Overview: Examples of complementary reactive functional groups

Binders and crosslinking agents or crosslinking agents and binders

-SH -C (O) -OH

-NH ₂ -C (O) -OC (O) -

-OH -NCO

-O- (CO) -NH- (CO) -NH ₂ -NH-C (O) -OR

-O- (CO) -NH ₂ -CH ₂ -OH

-NH-CH ₂ -OR ⁸

-NH-CH ₂ -OH

-N (-CH ₂ -OR ⁸ ) ₂

-NH-C (O) -CH (-C (O) OR ⁸ ) ₂

-NH-C (O) -CH (-C (O) OR ⁸ ) (-C (O) -R ⁸ )

-NH-C (O) -NR ⁹ R ¹⁰

-Si (OR ⁸ ) ₂

epoxy

ethylene

Binder and crosslinking agent or

Crosslinking agent and binder

O / \

/ ^

-C (O) -OH epoxy

-C (O) -N (CH ₂ -CH ₂ -OH) ₂

Complementary reactive functional groups which are particularly well suited for use in the powder coatings of the invention are

- Carboxyl groups on the one hand and epoxy groups and / or beta hydroxyalkylamide groups on the other hand and

Hydroxyl groups on the one hand and blocked and unblocked isocyanate groups or urethane or alkoxymethylamino groups on the other.

As the binder (O), any of oligomeric or polymeric resins can be used.

Oligomers are understood as meaning resins which contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood as meaning resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms on Römpp lexicon Paints and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, Oligomers, page 425, referenced.

Examples of suitable constituents (O) are random, alternating and / or block-structured linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or

Polycondensation. These terms are supplemented by Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (polyadducts)", and pages 463 and 464, "polycondensates", "Polykondensatioπ" and

"Polykondensationsharze", and pages 73 and 74, "binder", referenced.

Examples of suitable (co) polymers are

(Meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers, especially with vinylaromatics.

Examples of suitable polyaddition resins and / or

Polycondensation resins are polyesters, alkyds, aminoplasts, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, especially polyester-polyurethanes.

The constituents (O) may be non-crosslinking or physically crosslinking thermoplastic, thermally self-crosslinking or externally crosslinking. In addition, they may be thermally and / or curable with actinic radiation. The combined use of thermal curing and curing with actinic radiation is also referred to in the art as dual-cure. The self-crosslinking binders (O) of the thermally curable powder coatings and the dual-cure powder coatings contain reactive functional groups which can enter into crosslinking reactions with groups of their type or with complementary reactive functional groups. The externally crosslinking binders contain reactive functional groups that can undergo crosslinking reactions with complementary reactive functional groups present in crosslinking agents. Examples of suitable complementary reactive functional groups to be used according to the invention are those described above. In this case, the components (O) and (V) are united in a union.

The functionality of the self- and / or foreign-crosslinking constituents (O) with respect to the reactive functional groups described above can vary very widely and depends in particular on the crosslinking density which is to be achieved and / or on the functionality of the particular crosslinking agent used. For example, in the case of carboxyl group-containing constituents (O), the acid number is preferably from 10 to 100, preferably from 15 to 80, particularly preferably from 20 to 75, very particularly preferably from 25 to 70 and in particular from 30 to 65 mg KOH / g. Or in the case of hydroxyl-containing constituents (O), the OH number is preferably 15 to 300, preferably 20 to 250, particularly preferably 25 to 200, very particularly preferably 30 to 150 and in particular 35 to 120 mg KOH / g. Or in the case of epoxide group-containing components (O) is the

Epoxy equivalent weight preferably at 400 to 2,500, preferably 420 to 2,200, more preferably 430 to 2,100, most preferably 440 to 2,000 and especially 440 to 1,900.

The complementary functional groups described above can be incorporated into the binders by the usual and known methods of polymer chemistry. This can be done, for example the incorporation of monomers which carry the corresponding reactive functional groups, and / or by means of polymer-analogous reactions.

Examples of suitable olefinically unsaturated monomers having reactive functional groups are

d) monomers which carry at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule

Hydroxyalkyl esters of acrylic acid, methacryic acid or other alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol esterified with the acid, or obtained by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide in particular hydroxyalkyl esters of acrylic acid, methacryic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the

Hydroxyalkyl group containing up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1, 4-

Bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomalate, monofumarate or monoitaconate; Reaction products of cyclic esters, e.g. epsilon-caprolactone and these hydroxyalkyl or cycloalkyl esters;

olefinically unsaturated alcohols such as allyl alcohol; Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;

Reaction products of acrylic acid and / or

Methacrylic acid with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, or instead of the reaction product an equivalent amount of acrylic and / or methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;

Aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate;

N, N-di (methoxymethyl) aminoethyl acrylate or methacrylate or N, N-di (butoxymethyl) aminopropyl acrylate or

methacrylate;

(Meth) acrylic acid amides such as (meth) acrylamide, N-methyl, N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl) -, N-ethoxymethyl and / or N ₁ N

Di (ethoxyethyl) - (meth) acrylamide;

Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; other examples of suitable monomers containing carbamate groups are described in US-A-3,479,328, US 3,674,838 A, US 4,126,747 A, US 4,279,833 A or US 4,340,497 A; c2) monomers which carry at least one acid group per molecule, such as

Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;

olefinically unsaturated sulfonic or phosphonic acids or their partial esters;

Maleic acid, mono (meth) acryloyloxyethyl ester,

Succinic acid mono (meth) acryloyloxyethyl ester or

Phtha acid mono (metri) acrylic oyloxyethylester!; or

Vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or

Vinylbenzenesulfonic acid (all isomers).

c3) monomers containing epoxide groups, such as the glycidyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid or

Allyl.

They are preferably used for the preparation of the preferred (meth) acrylate copolymers, especially those containing glycidyl groups.

Higher functional monomers of the type described above are generally employed in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, in particular the (meth) acrylate copolymers, unless it is intended to selectively produce crosslinked polymeric microparticles. Examples of suitable monomer units for introducing reactive functional groups into polyesters or polyester-polyurethanes are 2,2-dimethylolethyl- or -propylamine blocked with a ketone, the resulting ketoxime group being rehydrated after incorporation; or compounds which contain two hydroxyl groups or two primary and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or at least one sulfonic acid group, such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-

Dimethylolpropionic acid, 2,2-dimethylol butyric acid, 2,2-

Dirnenthicylpentanoic acid, Diarninovaleric acid, 3,4-

Diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid or 2,4-diamino-diphenyl ether sulfonic acid.

An example of the introduction of reactive functional groups via polymer-analogous reactions is the reaction of hydroxyl-containing resins with phosgene resulting in chloroformate group-containing resins, and the polymer-analogous reaction of chloroformate group-containing resins with ammonia and / or primary and / or secondary amines to resins containing carbamate groups. Further examples of suitable methods of this type are known from the patents US 4,758,632 A, US 4,301, 257 A or US 2,979,514 A.

The constituents (O) which can be crosslinked with actinic radiation or with dual-cure, contain on statistical average at least one, preferably at least two, group (s) having at least one bond (s) activatable with actinic radiation per molecule.

In the context of the present invention, a bond which can be activated with actinic radiation is understood as meaning a bond which becomes reactive upon irradiation with actinic radiation and with other activated bonds of its kind polymerization reactions and / or Crosslinking reactions occur, which proceed by radical and / or ionic mechanisms. Examples of suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous and are therefore most preferably used. For the sake of brevity, they will be referred to as "double bonds" in the following.

Thus, the preferred group contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds may be conjugated. It is advantageous if the double bonds are present in isolation, in particular each terminally, in the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.

If more than one actinic radiation activatable group per molecule is used on a statistical average, the groups are structurally different or of the same structure.

If they are structurally different from each other, this means in the context of the present invention that two, three, four or more, but in particular two, actinic radiation activatable groups are used, which are of two, three, four or more, but especially two, Derive monomer classes.

Examples of suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups. The groups are preferably bound to the respective basic structures of the constituents (O) via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups. This is usually done by conventional and known polymer-analogous reactions such as the reaction of pendant glycidyl groups with the above-described olefinically unsaturated monomers containing an acid group of pendant hydroxyl groups with the halides of these monomers, isocyanates containing hydroxyl groups with double bonds such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-methyl-3-nato-1 = methylethyl) -3- (1-methylethyl) benzo! (TM! ® from CYTEC) or from isocyanate groups with the hydroxyl-containing monomers described above.

However, it is also possible to use mixtures of purely thermally curable and actinic-radiation-curable constituents (O).

As ingredients or binders (O) come

All these are described in US Pat. No. 4,268,542 A1 or US Pat. No. 5,379,947 A1 and patent applications DE 27 10 421 A1, DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE 196 13 547 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086

A1, DE 198 14 471 A1, DE 198 41 842 A1 or DE 198 41 408 A1, DE 199 08 018 or DE 199 08 013 or European Patent EP 0 652 264 A1, for use in thermal and / or actinic Radiation curable powder clearcoat slurries provided binder,

all the binders described in patent applications DE 198 35 296 A1, DE 197 36 083 A1 or DE 198 41 842 A1, intended for use in dual-cure clearcoats, all those in the German patent application DE 42 22 194 A1, the product information of BASF Lacke + Farben AG, "powder coatings", 1990, or the company brochure of BASF Coatings AG "powder coatings, powder coatings for industrial applications",

January, 2000, intended for use in thermally curable powder clearcoats or binders

all those in European patent applications EP 0 928 800 A1, 0 636 669 A1, 0 410 242 A1, 0 783 534 A1, 0 650 978

A1, 0 650 979 A1, 0 650 985 A1, 0 540 884 A1, 0 568 967 A1, 0

054 505 AI or 0 002 866 AI, the German

Patent applications DE 197 09 467 A1, 42 03 278 A1, 33 16 593

A1, 38 36 370 A1, 24 36 186 A1 or 20 03 579 B1, International Patent Applications WO 97/46549 or 99/14254 or US Pat. Nos. 5,824,373 A,

4,675,234 A, 4,634,602 A, 4,424,252 A, 4,208,313 A, 4,163,810

A, 4,129,488 A, 4,064,161 A or 3,974,303 A, for use in UV-curable clearcoats and powder clearcoats provided binder

into consideration.

The preparation of the constituents (O) has no methodical particularities, but takes place with the aid of the customary and known methods of polymer chemistry, as described in detail, for example, in the abovementioned patents.

Further examples of suitable manufacturing methods for

(Meth) acrylate copolymers (O) are described in European patent applications or EP 0 767 185 A1, German patents DE 22 14 650 B1 or DE 27 49 576 B1 and US Pat. Nos. 4,091,048 A1, 3,781,379 A, US Pat 5,480,493 A, US 5,475,073 A or US 5,534,598 A or in the standard work Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255, 1961 described. Suitable reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tube reactors, loop reactors or Taylor reactors, as described, for example, in the patent specifications and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Vol. 50, No. 9, 1995, pp. 1409-1416.

The production of polyesters and alkyd resins (O), for example, in the standard work Uürnanns Encyclopedia of Industrial Chemistry, 3rd Edition, Volume 14, Urban & Schwarzenberg, Munich, Berlin, 1963, pages 80 to 89 and pages 99 to 105, and in Books: "Resines Alkydes-Polyester" by J. Bourry, Paris, Dunod, 1952, "Alkyd Resins" by CR Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology" by TC Patton, Intersience Publishers , 1962, described.

The preparation of polyurethanes and / or acrylated polyurethanes (O) is described for example in the patent applications EP 0 708 788 A1, DE 44 01 544 A1 or DE 195 34 361 A1.

Examples of particularly suitable constituents (O) are the epoxy group-containing (meth) acrylate copolymers having an epoxide equivalent weight preferably at 400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, very particularly preferably 440 to 2,000 and in particular 440 to 1,900, a number average Molecular weight (determined by gel permeation chromatography using a polystyrene standard) of preferably 2,000 to 20,000 and especially 3,000 to 10,000, and a glass transition temperature (TQ) of preferably 30 to 80, preferably 40 to 70 and in particular 40 to 60 ⁰ C (measured by means of differential scanning calometry (DSC), as described in the patents and patent applications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A or US 3,781,379 A.

The paints in which the polycarbonates can be used as binders or rheology modifiers are essentially solvent-free and water-free solid basecoats (powder coatings and pigmented powder coatings) or substantially solvent-free, possibly pigmented powder coating dispersions (powder slurry basecoats). They can be thermal, radiation or DuaICure-curable, and self-crosslinking or externally crosslinking. The powder coatings may be basecoats, clearcoats or topcoats.

The powder coatings are often prepared either by the dry-blend process with subsequent screening or by melt homogenization of the starting materials with subsequent grinding and screening. Both methods involve many process steps. So first, the thermoplastics must be roughly ground. Subsequently, additives such as pigments or powverlackeypische additives are mixed together and extruded on Spezialextrudem. The extrudate is discharged and cooled, for example, on a cooling belt. The extrudates are pre-crushed, finely ground and sieved (with the oversize re-fed to the fine mill), after which the resulting thermoplastic powder coating is weighed and packaged. The composition of the thermoplastic powder coatings produced by this process is solely dependent on the original weight; a subsequent correction of the composition is not possible.

In a preferred embodiment, the powder coatings according to the invention are prepared as follows: The individual components are mixed in a receiving vessel and, for example, physically intensively premixed and pre-crushed in tumbling, plowshare, Henschel or overhead mills.

The pre-mix thus obtained is preferably melted in an extruder at elevated temperature, for example 80-120 ⁰ C and its components then pass through the mixing and kneading elements intimately contact each other. In this process, intensive mixing of the raw materials takes place: Fillers are coated with binders, pigments are dispersed and finely distributed, binders and hardeners are brought into close contact. Especially this contact is necessary to achieve a good filming later when baking the powder coating.

The melt homogenized mixture leaves the extruder generally at about 100 ⁰ C and must be cooled as soon as possible to room temperature in order to prevent a pre-reaction of the now thermo-reactive material as much as possible. For this purpose, the extrudate is often rolled out on cooling rolls to a thin strip of material, transferred to cooling belts and cooled there within less than one minute to room temperature. The material is then broken down into chips to ensure optimum dosing for the next process step.

The powder coating chips are then ground in classifier mills to the finished powder coating according to the principle of impact crushing. The desired grain size according to DIN 55990-2 is between 10 and 150 microns, preferably between 30 and 70 microns. Optionally, a sieving step for separating coarse and / or fine grain is still required.

The powder coatings of the invention are particularly suitable for coating substrates such as plastic surfaces, glass, ceramics, leather, mineral building materials, such as cement blocks and Fiber cement boards and especially for wood and MDF, and in particular for metals and coated metals.

In particular, the powder coatings of the production of coatings on pipes (pipelines), all kinds of wire products, flanges and fittings in indoor and outdoor areas, coat racks and

Bedsteads, fence posts, garden furniture, crash barriers,

Laboratory equipment, Wire grates, Dishwasher inserts,

Shopping baskets, machine parts, electric machines, rotors, stators, electric coils, insulation boxes, boilers, brake cylinders,

Chemical plants or street signs.

For coating is usually coated with the powder coatings of the invention in a conventional manner, then dried to remove any solvent present and cured.

The substrates are coated by customary methods known to those skilled in the art, at least one powder coating being applied to the substrate to be coated in the desired thickness and the volatile constituents removed. If desired, this process can be repeated one or more times. The application to the substrate can in a known manner, for. Example by spraying, spraying, knife coating, brushing, rolling, rolling and in particular by electrostatic spraying. The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

Preferably, they are applied by the so-called vortex sintering process. For this purpose, the preheated workpieces are "dipped" for a few seconds in a coating tank which is filled with fluidized by air flow powder coating. After dewatering, the sintered powder melts within a few seconds to a closed film. A relatively uniform powder surface sintered on all sides now surrounds the workpiece. The Layer thicknesses can be 250 to 700 microns. The vortex sintered powders have a particle size between 50 and 300 μm. They are therefore coarser than electrostatic powder whose grain size is generally between 1 and 200 microns. In principle, however, each fluidized sinter powder can also be adjusted by finer grinding so that it becomes accessible to the electrostatic powder coating.

Another object of the present invention is a method for coating objects by applying a powder coating of the invention in any manner to an object and at an object temperature between 100 ⁰ C and 220 ⁰ C, preferably between 145 ° C and 175 ⁰ C over a Haitezeit between 3 s - 20 min, preferably between 10 - 15 min according to DIN 55990-4 burned. The object temperature should be at least 100, preferably 110, more preferably at least 120, and most preferably at least 125 ^° C.

The object temperature is the temperature that the painted article must reach in the baking oven for complete crosslinking of the binder in the paint film. The object temperature is reached only after a certain preheating time and is usually lower than the circulating air temperature. The object temperature is usually measured by thermocouples on specimens in the furnace flow.

The threshold temperature, ie the minimum temperature or light-off temperature at which the chemical crosslinking of the components begins, is generally about 10 to 20 ^° C. lower than the stoving temperature, ie the temperature which is necessary for complete curing of the powder coatings for a given stoving time. The powder coatings are generally insensitive to overburning.

The present invention will be explained in more detail with reference to the following examples. General procedure:

The polyfunctional alcohol, diethyl carbonate and 0.15 wt.% Potassium carbonate as catalyst (amount based on amount of alcohol) were initially charged according to the amounts shown in Table 1 in a three-necked flask equipped with stirrer, reflux condenser and internal thermometer, the mixture heated to 140 ⁰ C, and stirred for 2 h at this temperature. As the reaction progressed, the temperature of the reaction mixture was reduced due to the incipient boiling cooling of the released ethanol. Now, the reflux condenser was exchanged for a descending condenser, based on the equivalent amount of catalyst, one equivalent of phosphoric acid was added, ethanol was distilled off and the temperature of the reaction mixture was slowly increased to 160 ^° C. The alcohol distilled off was collected in a cooled round bottomed flask, weighed and the conversion percentage determined in relation to the theoretically possible full conversion (see Table 1). Dry nitrogen was then passed through the reaction mixture at 160 ^° C. over a period of 1 hour in order to remove remaining amounts of monomers. Thereafter, the reaction mixture was cooled to room temperature.

The products were added neat to the paint formulations.

Analysis of the polycarbonates according to the invention:

The polycarbonates were analyzed by gel permeation chromatography with a refractometer as detector. Dimethylacetamide was used as the mobile phase and polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.

The OH number was determined in accordance with DIN 53240, Part 2. Table 1: Starting materials and end products

TMP = trimethylolpropane EO = ethylene oxide PO = propylene oxide

The term "TMP x 1, 2 PO" describes therein a product which has been reacted per mole of trimethylolpropane with an average of 1.2 moles of propylene oxide, analogously, "TMP x 12 EO" is a product which contains on average per mole of trimethylolpropane 12 moles of ethylene oxide has been reacted.

Production of paints:

The components of the powder coating were mixed according to the amounts in Table 2 and placed in an extruder / kneader with a length: diameter ratio of 40. The extrusion conditions are summarized in Table 3. Table 2: Paint components

The pigments were mixed in the ratio as follows: Pigment titanium rutile 2310 from Kronos International

96% soot Flame - 101 powder from Degussa AG

2% Bayferrox® 180 Fa. Lanxess Deutschland GmbH 1, 25%

Bayferrox® 316 from Bayer AG

0.75%

Table 3: Extrusion conditions

Subsequently, the extruded material was ground in a mill to an average particle size of 50 microns.

The following measurement results of the obtained Huiverlacke were found:

OK: okay

Test Methods:

Gel time: Measured is an increase in viscosity during curing. The finished powder coating is applied with a defined amount of 200-500 mg placed a hot plate with a defined temperature: The powder is melted and the crosslinking begins. A solid object is immersed until the object gets stuck.

The test gives two pointers: 1. The identity of the material is easily checked, since same times are measured for the same material. 2. There is an indication for flow characteristics: the longer the gel time, the better the course.

Sagging test: The powder coating is heated to stoving temperature and the travel on a vertical surface determined. A higher value shows a better course.

Bending: The sheet is bent 90 ° at one edge, the paint film must not be damaged.

Gloss: Gloss measurement with a BYK-Gardener micro-tri-gloss. The shine is a visual perception. This is the more pronounced, the more directed the light is reflected. This means that the higher the measured gloss unit, the smoother the surface. In the medium gloss range is measured with a 60 ° geometry, in the high gloss range with a 20 ° geometry.

Wavescan DOI: Analysis with a BYK-Gardener Wavescan DOI: Statement about Long / Shortwave-Values and Haze. The smaller the value, the better the appearance.

DSC measurements: With a Q1000 from TA Instruments (in general: with a dynamic differential calorimeter). (Parameter: heating ramp at 10 ° C / min., Nitrogen atmosphere, evaluation of the second run). Statement about the glass transition temperatures of the uncrosslinked and the crosslinked powder. Statement of the exothermic crosslinking signal: temperature at which the crosslinking reaction takes place and the enthalpy of the crosslinking reaction. Viscosity-temperature measurements: With an MCR500 from Anton Paar (in general: with an air-bearing rheometer). (Parameters: heating rate 2 ° C / min, frequency 1Hz, deformation 1%). Statement: The lower the viscosity at the minimum of the curve and the higher the sol-gel temperature (G '= G "), the better the appearance.

In general, the use of high-functionality polycarbonates leads to an improvement in the flow properties and the appearance of the powder coating. The measurement differences are significant.

Claims

claims

1. Powder coatings containing at least one highly functional, highly branched or hyperbranched, uncrosslinked polycarbonate.

2. Powder coating according to claim 1, characterized in that the polycarbonate has a glass transition temperature according to ASTM 3418/82 of less than 50 ⁰ C.

3. Powder coating according to one of the preceding claims, characterized in that the polycarbonate has an OH number according to DIN 53240, Part 2 of 100 mg KOH / g drier more.

4. Powder coating according to one of the preceding claims, characterized in that the polycarbonate is a weight-average

Mol weight M _w between 1,000 and 150,000.

5. powder coating according to any one of the preceding claims, further comprising - at least one functional component (F), at least one oligomeric and / or polymeric component (O) as a binder and - at least one crosslinker (V).

6. Powder coating according to claim 5, characterized in that the functional constituent is selected from the group consisting of color and / or effect, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powder, soluble organic

Dyes, organic and inorganic, transparent or opaque fillers and / or nanoparticles, UV absorbers, light stabilizers, radical scavengers, deaerators, slip additives, polymerization inhibitors, catalysts for the Crosslinking, thermolabile radical initiators, photoinitiators, thermally curable reactive diluents, actinic radiation curable reactive diluents, adhesion promoters, leveling agents, film-forming auxiliaries, flame retardants, corrosion inhibitors, flow aids,

Waxing and matting agents.

7. Powder coating according to one of claims 1 to 6, characterized in that the binder (O) has an acid number of 10 to 100 mg KOH / g.

8. Powder coating according to one of claims 1 to 6, characterized in that the binder (O) has an OH number of 15 to 300 mg KOH / g.

9. Powder coating according to one of claims 1 to 6, characterized in that the binder (O) has an epoxide equivalent weight of 400 to 2,500.

10. Powder coating according to one of the preceding claims, characterized in that the crosslinker (V) is selected from the group consisting of isocyanates, blocked isocyanates, epoxides, tris (alkoxycarbonyl-amino) triazines and

aminoplasts

11. Use of powder coatings according to one of claims 1 to 10 for the coating of plastic surfaces, glass, ceramics, leather, mineral building materials, such as cement blocks and fiber cement boards, wood, MDF, metals and coated metals.

12. Use of powder coatings according to one of claims 1 to 10 for the coating of pipes (pipelines), wire goods of all kinds, flanges and fittings in indoor and Outdoor, wall-mounted and bed frames, fence posts, garden furniture, guardrails, laboratory equipment, wire shelves, dishwashers, shopping baskets, machine parts, electric machines, rotors, stators, electric coils, insulation boxes, boilers,

Brake cylinders, chemical plants or street signs.

13. A process for coating objects, in which one applies a powder coating according to any one of claims 1 to 10 in any manner on the object and in a

Object temperature between 100 ⁰ C and 220 ⁰ C over a holding time between 3 s - 20 min according to DIN 55390-4 burns.

14. An article coated with a powder coating according to any one of claims 1 to 10.