EP2545115A1

EP2545115A1 - Heat-curable powder coating compositions, which after the coating has cured result in a matt surface and simple method for producing same

Info

Publication number: EP2545115A1
Application number: EP11707677A
Authority: EP
Inventors: Werner Grenda; Emmanouil Spyrou; Thomas Weihrauch; Christoph Lammers; Holger Loesch; Klaus Behrendt
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2010-03-11
Filing date: 2011-03-10
Publication date: 2013-01-16
Also published as: HK1177945A1; MX2012010450A; BR112012022874A2; US20140316056A1; US9096774B2; US20110288202A1; KR20130039715A; CN102782032A; US20130041103A1; AU2011226101B2; RU2012143306A; JP5730336B2; DE102011005369A1; JP2013522383A; US8524837B2; US20110224378A1; AU2011226101A1; US8476376B2; WO2011110640A1; CN102782032B

Abstract

The invention relates to heat-curable powder coating compositions, which after the coating has cured result in a matt surface and to a simple method for producing same.

Description

The invention relates to heat-curing powder coating compositions which have a matte surface after curing of the coating and to a simple process for their preparation.

Thermosetting powder coatings do not give organic when applied

Solvent and therefore have clear environmental benefits compared to liquid coatings. The crosslinking in the heat takes place via polyaddition or polycondensation reactions between the functional groups contained in the binders. Typical binder systems are epoxy resins with hardeners based on amines, amidines, acids, anhydrides; Carboxyl polyesters or polyacrylates with epoxy-based curing agents; Hydroxyl polyesters or polyacrylates with crosslinkers based on blocked isocyanates; Epoxy-containing polyacrylates with dicarboxylic acids as crosslinkers, carboxyl polyesters or - polyacrylates with crosslinkers based on ß-hydroxyalkylamides u. a. The different binder systems differ in addition to the coating properties, especially in the resistance to outdoor weathering. The pure binder systems usually lead to high-gloss surfaces, with a gloss level of> 80 scale divisions (DIN 67530 / ISO 2813, angle of incidence 60 °) when in a so-called one-shot process with only one reactant, e.g. Crosslinker and resin, processed and cured. Coating systems that give a substrate a uniform flat and matte finish are of considerable interest. The reason for this is mainly practical. Glossy surfaces require a much higher degree of cleaning than dull surfaces. In addition, it may look

safety reasons, be desirable to avoid highly reflective surfaces. In wide applications of the powder coating industry, such as

Architecture, automotive and metal furniture sector etc., the demand for matt (10 - 30 units) and semi-matt (30 - 50 units) surfaces measured measured as reflectometer values according to DIN 67530 / ISO 2813 at a Einstrahlwinkel of 60 °. The simplest principle to obtain a matte surface is to give the powder coating depending on the extent of the desired matte effect, smaller or larger amounts of fillers such. As chalk, finely divided silica or barium sulfate to mix. However, these additives cause deterioration of the paint film properties, such as adhesion, flexibility, impact resistance and chemical resistance.

The addition of substances that are incompatible with the paint, such as. As waxes or cellulose derivatives, indeed cause a significant matting, but slight changes during the extrusion lead to fluctuations in surface gloss and a so-called. "Fade-out" in dark shades The reproducibility of the matte effect is not guaranteed.

In EP 0698645, the preparation of matt powder coatings by means of dry blending of at least two separately manufactured

Hydroxyalkylamidepulververlacken described.

It is therefore proposed in US 3,842,035, matt powder coating by so-called drybending of finished powder coatings with sufficiently different reactivity, d. H. of powder coatings with very short and very long gel times to produce. The binders used are acrylic resins, alkyd resins, and preferably epoxy resins.

WO-A-89/06674 describes the production of satin-glossy or matt surfaces by drybending, ie physical mixtures of finished powder coatings, which are composed of different binder systems.

DE 2 324 696 discloses a process for producing matt coatings

Use of an epoxide-reactive specialty hardener, the salt of cyclic amidines with certain polycarboxylic acids, proposed. The crosslinking of the powder coating is carried out according to this method with different reactivity at different temperatures, which form microstructures on the surface, which identify a matte surface. However, the application of this method is limited to epoxy and carboxyl polyester / epoxy powder coatings, which is why no coatings with sufficient weather resistance can be produced by this method. EP 366 608 also proposes a process for producing powder coatings with matte surfaces. It relates to powder coatings based on

Epoxy resins or epoxy compounds, such as. B. triglycidyl isocyanurate (TGIC) with carboxyl-terminated polyester resins and mixtures of di-, tri- or tetrakis- (ß-carboxyethyl) cyclohexanones or cyclopentanones. The matte effect is attributed here to the different reactivity between the aliphatic carboxylate groups of the crosslinker and the aromatic carboxylate groups of the carboxyl-terminated polyester resin.

Another patent, DE 3 232 463, describes powder coatings with matte surfaces by co-extrusion of hydroxyl-terminated

Polyester resins, epoxy compounds, such as. As TGIC and special reversibly blocked polyisocyanates with free carboxylate groups.

US Pat. No. 4,801,680 (EP 322 834) describes a thermosetting powder coating which consists of a particle mixture of a carboxylate-containing polyester and a β-hydroxyalkylamide. This powder coating leads after application on a support to shiny lacquer surfaces. According to Example 2 of US Pat. No. 4,801,680, the lacquer surfaces obtained after carrying out an accelerated weathering test and using UV irradiation show no impairment of the lacquer surface.

EP 520429 describes a resin composition of polyesters with

different hydroxyl numbers. The described resin composition necessarily comprises an essentially ungelled polyester A, an im

Substantially ungelled polyester B, tetramethoxymethylglycoluril as

Curing agent and an organic sulfonic acid as a catalyst.

On the possibilities for matting Hydroxyalkylamidpulverlacken numerous other publications have appeared, for. BR Franiau, "Advances in β-hydroxyalkylamide crosslinking chemistry" ECJ, (2002) 10, p 409ff; D. Fink, U. Kubilius, "Optimizing the Matting of Powder Coatings", Powder Coatings Europe 2002 and R. Guida, "A Novel Approach to Produce Reduced Gloss ß-hydroxyl

Alkylamide Powder Coatings "Powder Coating 2002 PCI Conference; D. Beccaria et al." Modeling Gloss Control in Polyester / β-Hydroxyalkylamides Powder Coatings Based on SPM Structure-Property Relationship "Waterborne, High-Solids and Powder Coatings Symposium, Feb. 26- 28,2003, New Orleans, LA, USA. Laid-Open Specification KR 10-2009-01 1 1720 (application number 10-2008-0037454), translated title "CYCLOALKANIC DICARBOXAMIDE COMPOUNDS, THEIR PREPARATION AND APPLICATION" (See also J. Korean Ind. Eng. Chem., Vol. 20, no. 2, April 2009, 195-200) discloses, in particular in Example 1, the compound N ¹ , N ¹ , N ⁴ , N ⁴ -tetrakis (2-hydroxyethyl) cyclohexane-1, 4-dicarboxamide (formula 3) mentioned there 2 has only one peak according to DSC analysis with a maximum peak at about 190 ° C. A cis / trans content of the compound is not mentioned Further, carboxyl group-containing polyesters which are not well defined but only by wide ranges of some Can be specified (polyester not clearly characterized and unknown on the market with this viscosity), crosslinked with this compound and with the known ß-hydroxyalkylamides, here in Example 3 called as [N ¹ , N ¹ , N ⁶ , N ⁶ - tetrakis ( 2-hydroxyethyl) adipamide] (obtain commonly known as VESTAGON HAA 320 or PRIMID XL 552), ie with prior art curatives and long established market products, and which are known to result in glossy surfaces of the coatings produced. In Fig. 3 and 4, the sheets are shown. It is not described that it is dull coatings. This is also not possible because glossy coatings are obtained with the conventional hardener.

For matt and semi-matt (<50 units gloss) powder coating compositions with

Hydroxyalkylamides are well known in the art so-called dry blends, d. H. it requires the separate production of two Hydroxyalkylamidpullegacke based on ß-hydroxyalkylamides plus resins (polymers) with different acid numbers, which are then fed as a dry blend of the grinding. This requires a considerable additional effort and leads to a deviation

Binder component to gloss deviations whose correction means considerable additional effort. Furthermore, these dry blends also separate the final customer with the resulting gloss shift, if the powder coating is to be recycled as usual. The object of the invention was to find a heat-curing powder coating composition which have a matte surface after curing of the coating and to find a simple process for their preparation.

This object is achieved by the novel β-hydroxyalkylamides according to the invention as crosslinkers (hardeners) and the process according to the invention.

The invention relates to a powder coating composition, essentially containing

A) at least one carboxylate group-containing polymer having an acid number of 5 to 350 mg KOH / g, and a glass transition temperature T _g of greater than 40 ° C, and

B) at least one .beta.-hydroxyalkylamide having two or three or four .beta.-hydroxyalkylamide groups per molecule of the formula I.

R ¹ R ¹ OOR ¹ R ¹

HO- -N - -OH

RRR ² R ² RR with

R ¹ , R ² independently of one another are identical or different radicals selected from the alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals may also contain heteroatoms and / or functional groups,

and wherein R ^{1 may} also be hydrogen, and where R ^{2 is} also can be; and

with R ³ : independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more

Substituents R ³ may be linked together to form rings; wherein the β-hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the

Carboxylate groups between 0.5: 1 to 1, 5: 1. Surprisingly, it has been found that the use of the novel β-hydroxyalkylamides of the formula I according to the invention as crosslinkers

Coatings with matte (10 - 30 units) and semi matte (30 - 50 units) surfaces measured as reflectometer values according to DIN 67530 / ISO 2813 at an angle of incidence of 60 ° can be obtained.

Surprisingly, it has been found that by the inventive method, in a so-called one-shot operation, that is, by common extrusion of all components, the inventive Powder coating composition can be obtained on the basis of carboxylate-containing polymers and β-hydroxyalkylamides according to the invention as crosslinking agents.

In the context of this invention, the terms crosslinker and hardener are used equally important.

There is no elaborate dry blend (dry blend) of at least two powder coatings, which differ in the reactivity, based on ß-hydroxyalkylamides needed as a crosslinker. Furthermore, no

Polyester blend or polyacrylate mixture of at least two resins with different reactivity required.

As reactants for the β-hydroxyalkylamide compounds used according to the invention for the preparation of the powder coating composition

Carboxylate group-containing polymers A) in question. As polymers it is possible to use polymers, polycondensates and polyaddition compounds. In principle, any polymer can be used which contains at least two carboxylate groups and glass transition temperature T _g greater than 40 ° C. Poloxylate-containing polymers are suitable for the powder coatings according to the invention those having acid numbers of 5 - 350 mg KOH / g, preferably 15 - 150 mg KOH / g, with OH numbers <15 mg KOH / g. Preferably, these polymers have at least two terminal carboxylate groups.

Particular preference is given in the context of the invention to carboxylate-containing polyesters and / or polyacrylates.

The carboxylates containing polyesters A) are preferably polyester polycarboxylic acids which are prepared from polyols and polycarboxylic acids or derivatives thereof. The glass transition temperature T _{g of} these acidic polyesters is in a range of 40 to 80 ° C, preferably 40 to 70 ° C; their acid value varies from 5 to 250 mg KOH / g, preferably from 10 to 150 mg KOH / g, preferably from 12 to 120 mg KOH / g. The OH numbers are below 15 mg KOH / g. They have an average molecular weight M _{w of} from 1000 to 10000 g / mol, preferably from 1 500 to 9000 g / mol, particularly preferably from 2000 to 8000 g / mol. For the preparation of the invention to be used carboxylate groups containing polycarboxylic acids such. Oxalic, succinic, adipic, 2,2,4 (2,4,4) -trimethyladipine, azelaic, sebacic, decanedicarboxylic,

Dodecanedicarboxylic, fumaric, phthalic, isophthalic, terephthalic, trimellitic,

Pyromellitic acid used. For the acidic polyesters, the following are used as examples of the following: ethylene glycol, 1,2,3- and 1,3-propanediol, 1,2-, 1,3-, 1,4- and 2,3-butanediol, 1,5-pentanediol , 3-methyl-1,5-pentanediol, neopentyl glycol, 1,12-dodecanediol, 2,2,4 (2,4,4) -trimethyl-1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, 1, 4- Bishydroxymethylcyclohexane, cyclohexane-1, 4-diol,

Diethylene glycol, triethylene glycol and dipropylene glycol. Of course, hydroxyl-containing polyesters prepared by known methods from polycarboxylic acids and polyols can be reacted with polycarboxylic acids and / or polycarboxylic anhydrides to the polyester polycarboxylic acids.

The preparation of the carboxylate-containing polyester resins is carried out by known processes by esterification or transesterification of di- and / or polyvalent linear or branched, aliphatic or cycloaliphatic polyols with polybasic, preferably di- or polyhydric aliphatic, cycloaliphatic or aromatic carboxylic acids or their anhydrides or their esters in Presence of an esterification or transesterification catalyst at temperatures up to about 250 ° C and towards the end under reduced pressure.

Preferred polyols are 2,2-dimethyl-1,3-propanediol (neopentyl glycol),

Ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-dimethylolcyclohexane, 2,2- [bis (4-hydroxycyclohexyl)] propane, diethylene glycol, dipropylene glycol, glycerol,

Pentaerythritol, etc. Preferably, the polyol component contains a high proportion of neopentyl glycol to obtain the highest possible glass transition temperatures.

Preferred polybasic carboxylic acids are terephthalic acid, isophthalic acid, trimellitic acid, adipic acid, and / or 1, 4-cyclohandicarboxylic acid. The

Functionality of the preferred carboxylate group-containing polyester resins is adjusted via the ratio of di- and more than dibasic carboxylic acids.

Suitable carboxylate group-containing acrylate polymers have an acid number of 10 to 350 mg KOH / g, preferably 20 to 300 mg KOH / g and a

Glass transition temperature T _g of greater than 40 ° C, preferably from 45 to 100 ° C, prepared by homopolymerization or copolymerization of a monomer mixture.

The polyacrylate contains carboxylic acid groups and may be a homopolymer or a copolymer.

Monomers which can be used are acrylic acid and / or methacrylic acid, C 1 -C ₄₀ -alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid,

Hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1, 2-epoxybutyl acrylate, 1, 2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate and the analogous amides, wherein also styrene and / or its derivatives may be present.

Preference is given to using butyl acrylate and / or butyl methacrylate, 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate, methyl methacrylate, styrene, (meth) acrylic acid and optionally further unsaturated monomers, where at least one carboxylate group-containing monomer is used.

Other suitable monomers are (cyclo) alkyl esters of acrylic or

Methacrylic acid having 2 to 18 carbon atoms in the (cyclo) alkyl radical. Examples of suitable or preferably suitable monomers are ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,

isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,

Cyclohexyl methacrylate, neopentyl methacrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate and stearyl methacrylate.

As monomers come z. As styrene, vinyl toluene and ethyl styrene into consideration. Examples of these are acrylic and methacrylic acid, which are also preferably used, as well as crotonic acid, itaconic acid, fumaric acid, maleic acid and citaconic acid.

The polyacrylate preferably has an OH number of less than 10 mg KOH / g, an acid number of 5 to 350 mg KOH / g, preferably 20 to 300 mg KOH / g, particularly preferably from 30 to 250 mg KOH / g, a Tg of 40 to 1 10 ° C, preferably 45 to 100 ° C, an M _w of 500 to 50 000 g / mol, preferably 1 000 to 30 000 g / mol, particularly preferably from 1 500 to 20 000 g / mol.

As a co-crosslinker and epoxy resins can be used. In question come here z. As glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates. Examples of such epoxides are triglycidyl isocyanurate (TGIC trade names, e.g., ARALDIT PT 810, Huntsman, TEPIC G, Nissan, Taida TGIC, Anhui Taida), mixtures of

Terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade names eg ARALDIT PT 910 and PT 912, Huntsman), glycidyl ester of versatic acid (trade name eg CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC) Diglycidyl ether based on bisphenol A

(Trade name eg EPIKOTE 828, Shell) ethylhexyl glycidyl ether,

Butylglycidyl ether, pentaerythritol tetraglycidyl ether (trade name eg POLYPOX R 16, UPPC AG) as well as other polypoctypes with free epoxy groups. It can also be used mixtures. Preference is given to using TEPIC G or ARALDIT PT 910 and 912. Such co-crosslinkers can be used up to 50 wt .-% of the hardener mixture used from the invention ß-hydroxyalkylamide (Matthärter) and co-crosslinker. Surprisingly, it has been found that β-hydroxyalkylamides having a

Cyclohexane ring in the backbone and wherein the ß-hydroxyalkylamides are below 150 ° C in solid form, as crosslinkers for carboxyl-containing polymers in powder coatings after curing lead to dull surfaces. The β-hydroxyalkylamides B) can be prepared from various starting materials. The reaction of β-hydroxyalkylamines with esters of carboxylic acids is known, the latter producing the skeleton (A). Depending on the choice of the starting materials, the β-hydroxyalkylamides according to the invention can be produced in this way.

Alternative but less preferred methods are based on others

Carboxylic acid derivatives such. As carboxylic acids, carboxylic acid chlorides,

Carboxylic anhydrides or other activated carboxylic acid derivatives as

Starting materials which are reacted with β-hydroxyalkylamines. Suitable β-hydroxyalkylamines are those which have alkyl groups with at least 2 to 10 carbon atoms in the hydrocarbon skeleton. The alkyl groups may be linear, branched or cyclic. Likewise, the

Alkyl groups with heteroatoms, preferably oxygen, nitrogen substituted. Furthermore, these alkyl groups may also contain functional groups, preferably carbonyl groups, carboxyl groups, amino groups, amide groups, urethane groups and may carry an additional alkyl radical on the nitrogen.

Preferably in this invention, the β-hydroxyalkylamides are prepared from N-alkyl-1,2-alkanolamines and / or from N, N-bis-2-hydroxyalkylamines and esters of cyclohexanedicarboxylic acids.

Particular preference is given to using β-hydroxyalkylamines of the formulas II and / or III:

Formulas II

With

R ¹ is hydrogen, methyl, ethyl, propyl,

R is methyl;

Formulas III

R ¹ HHR ¹ H

or DH- ^■ CCNCC OH

HHHH with R ^1, simultaneously or independently of one another, is hydrogen, methyl, ethyl, propyl.

Particularly preferred according to the invention, the following compounds are used as starting materials for the preparation of ß-hydroxyalkylamides: diethanolamine (DEA), di-isopropanolamine (DIPA), di-sec-butanolamine, N-methylethanolamine, N-methyl-isopropanolamine.

Suitable starting compounds for the substituent A in the β-hydroxyalkylamides according to the invention are 1, 2, 1, 3 and 1, 4-cyclohexanedicarboxylic acid derivatives, in particular

Cyclohexanedicarboxylic. The starting compounds may have any desired cis / trans content.

Preference is given to using compounds of the formula IV

A ⁴ A ⁵ A ⁶ with R ⁴ simultaneously or independently of one another methyl, ethyl, propyl, butyl. Particular preference is given to using 1,4-substituted cyclohexanedicarboxylic acid esters, very particularly preferably dimethyl-1,4-cyclohexyldicarboxylate.

The present invention particularly preferred β-hydroxyalkylamides of dialkyl-1, 4-cyclohexyldicarboxylaten, preferably from dimethyl-1, 4-cyclohexyldicarboxylat, have a trans content, based on the position of the carboxyl groups on the cyclohexyl of greater than or equal to 70 mol%, preferably greater 80 mol%, and more preferably greater than 85 mol%. In this case, dialkyl-1, 4-cyclohexyldicarboxylate can be used for the preparation of the preferred ß-hydroxyalkylamides having any trans content.

The β-hydroxyalkylamides (I) according to the invention are present in solid form below 150 ° C., preferably below 170 ° C., particularly preferably below 180 ° C.

Particularly preferred β-hydroxyalkylamides according to the invention have the following formulas:

HHOOHH Formula V

CH ₃ HOOH CH Formula VI

H CH OO CH ₃ H Formula VII H3C-CH2 HOOH CH2-CH3 Formula VII I

Formula IX

CH ₃ HOO CH ₃ H Formula X

H ₃ C CH ₂ HOOH ₃ C CH ₂ H Formula XI with

R ² : methyl, or

is hydrogen, and R ^{1 B is} methyl, ethyl, propyl, or

R ^{1A is} methyl, ethyl, propyl and R ^1B is hydrogen; and

A: 1,4-disubstituted cyclohexane ring of the formula

wherein the trans content of A is> 70 mol%; and wherein the β-hydroxyalkylamides are below 150 ° C in solid form.

The present invention particularly preferred β-hydroxyalkylamide of dimethyl-1, 4-cyclohexyldicarboxylate and diethanolamine with four ß-hydroxyalkylamide groups per molecule

of formula XII,

has a trans content at the cyclohexyl ring of greater than or equal to 70 mol%, preferably greater than 80 mol% and particularly preferably greater than 85 mol%. To achieve good coating properties of the

Powder coating composition is the ratio of ß-hydroxyalkylamide groups to the carboxylate groups of the polymers containing carboxylate groups preferably from 0.5 to 1.5: 1, more preferably from 0.8 to 1.2: 1.

The powder coating composition, the customary in powder coating technology auxiliaries and additives C), such as leveling agents, for. As polysilicone or acrylates, light stabilizers z. Sterically hindered amines and / or absorbers,

Degassing agents (for example benzophenone), modified phenolic resins, catalysts and / or other auxiliaries, such as. As described in EP 669 353, are added in a total amount of 0.1 to 10 wt .-%. Fillers and pigments such. Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.

The powder coating compositions are quantitatively composed as follows:

Wt .-%

Inventive β-0.5 to 20

Hydroxylalkylamide (Matthärter) B)

preferably 1 to 15

Optional HAA Hardener 0 to 10

preferably 0 to 8

Carboxylate groups containing 35 to 96

Polymers A)

preferably 50 to 80

Optional co-crosslinker 0 to 5

preferably 0 to 3

Additives, fillers, pigments, etc. 0.1 to 50

C)

preferably 5 to 40 The powder coating compositions according to the invention have good storage stability at temperatures of 30 ± 1 or 40 ± 1 ° C. in the storage test according to DIN EN ISO 8130-8 customary for powder coatings, and are storable for> 30 days.

In the particularly preferred embodiment of the invention, the powder coating compositions according to the invention contain:

At least one carboxylate-containing polyester having an acid number of 15 to 150 mg / KOH / g and a glass transition temperature of at least 40 ° C,

At least one β-hydroxyalkylamide according to the invention having at least two or more, preferably four β-hydroxyalkylamide groups, or else mixtures thereof having the same and / or different functionality,

• and optionally further, customary for powder coatings additional and

Adjuvants, e.g. Wetting, leveling or degassing agents, heat or UV stabilizers, pigments, dyes, fillers, co-crosslinkers.

The invention relates to a process for the preparation of a

Powder coating composition, substantially containing

A) at least one carboxylate group-containing polymer having an acid number of 5 to 250 mg KOH / g, and a glass transition temperature T _g of greater than 40 ° C, and

R 'R' O O R 'R'

HO- N- ^■ N- OH

R 'R' R ^ R ² RR '

With

R ¹ , R ² : independently of one another are identical or different radicals selected from the alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where R ^{1 is} also hydrogen can and where R ^{2 is} also

can be; and

Substituents R ³ may be linked together to form rings;

wherein the β-hydroxyalkylamides are below 150 ° C in solid form;

C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1;

in the melt by co-extrusion of all components at temperatures between 80 to 150 ° C.

The invention also provides a process for the preparation of a

Powder coating composition, wherein as component B) N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XI IA is contained,

where it has the following parameters:

1 . a trans content on the cyclohexyl ring of greater than or equal to 70 mol%,

based on the total amount of all present isomers of

N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1,4-diamide,

and

2. has two endothermic peaks according to differential scanning calorimetry (DSC) analysis, where peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C, and peak 2 in the range of 170-210 ° C lies with a maximum of 175 - 207 ° C,

and

3. the ratio of enthalphies from endothermic peak 1 to

endothermic peak 2 is 1: 1 to 1: 5,

and

4. the XRPD spectrum of the powdered sample in the X-ray diffractometer measured with Cu Ka radiation (1, 541 Å) has the following peaks:

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1 26.00 3.43

The invention also provides a process for the preparation of a

Powder coating composition, wherein as component B) N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included

where it has the following parameters:

1 . a trans content on the cyclohexyl ring of greater than or equal to 70 mol%,

based on the total amount of all present isomers of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1,4-diamide,

and

3. the ratio of enthalphies from endothermic peak 1 to

endothermic peak 2 is 1: 1 to 1: 5,

and

4. the XRPD spectrum of the powdered sample in the X-ray diffractometer measured with Cu Ka radiation (1, 541 Å) has the following peaks: Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 5. and wherein this has the following parameters according to X-ray structural analysis of a single crystal:

Crystal System: Orthorhombic

Room group: Pbca

Dimensions Unit cell: a = 10.06350 (10) Ap = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °. c = 14.6275 (2) λγ = 90 °.

Volume: 1744.79 (3) Ä ³

The preparation of the powder coating composition of the invention is preferably carried out in the melt by coextrusion of all

Components A) to C) at temperatures between 80 to 150 ° C. The extrudate is then cooled, ground and screened or classified to a particle size of <120 μηη preferably <100 μηη. The thermosetting and toxicologically flawlessly produced according to the invention

Powder coating compositions thus consist of the matrix obtained by coextrusion of all the components.

To achieve the effect of the invention, namely the formation of matte surfaces with a degree of gloss according to DIN 67530 / ISO 2813 of <50 at an angle of incidence of 60 °, numerous carboxylate group-containing polymers, in particular carboxylate terminated polyester or polyacrylates, which be different in functionality and reactivity. The desired gloss can thus over the selected binder partner (polyester) in conjunction with the Hydroxylalkylamiden invention in a

considerable bandwidth (examples: 1 -7), otherwise the wording is the same. Example (8) with the polyacrylate differs therefrom, since more crosslinker is needed for the increased acid number and a lower pigmentation was chosen due to the expected higher brittleness.

The use and the application of powder coatings for the production of

Coatings are carried out by conventional methods for powder coatings, preferably by means of an electrostatic powder coating spray device by the triboelectric or corona process or by the fluidized bed process.

At normal ambient temperatures, the powder coating compositions according to the invention have a good storage stability and show after crosslinking between 150 to 220 ° C good paint properties, optically good surfaces and the described low gloss levels.

In contrast to the prior art are with the inventive

Powder coating compositions, coatings with optically very good running (PCI rating table 8-10), but matte (10-30 units) and / or semi-matte (30-50 units) surfaces measured as reflectometer values according to DIN 67530 / ISO 2813 at a Einstrahlwinkel of 60 °, where neither a dry blend (dry blend) nor polyester blend yet

Polyacrylate mixture (one-shot blend) are needed.

In addition to this variation, it is also possible to shift the measured reflectometer value, in accordance with DIN 67530 / ISO 2813 at an angle of incidence of 60 °, to higher values up to regaining the high gloss> 80 scale parts in the 60 ° angle. This is done by partial replacement of the invention Matthew B) with a commercially available ß-hydroxyalkylamide having two or more than two ß-Hydroxylalkylamidgruppen or mixtures thereof with different functionality. The invention relates to the use of a powder coating composition, essentially containing

A) at least one carboxylate group-containing polymer having an acid number of 5 to 350 mg KOH / g, and a glass transition temperature T _g of greater than 40 ° C,

and

B) at least one ß-hydroxyalkylamide having two or three or four

ß-hydroxyalkylamide groups per molecule of the formula I.

R R O O R R

HO- N- ^■ N- ^" OH

RRR ^ R ² RR '

With

independently of one another are identical or different radicals selected from the group consisting of alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals can also contain heteroatoms and / or functional groups, and where R ^{1 can} also be hydrogen, and where R ² also

R R

C C OH

R R

can be; and

Substituents R ³ may be linked together to form rings;

wherein the β-hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1;

for the production of coatings with matte surfaces, with a degree of gloss according to DIN 67530 / ISO 2813 of <50 at an angle of incidence of 60.

Very particularly preferred subject of the invention is a

A powder coating composition comprising the compound N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA as component B),

where it has the following parameters:

1 . a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, based on the total amount of all present isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide,

and

2. two endothermic peaks according to DSC analysis, (differential scanning

calorimetry), wherein peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C, and peak 2 in the range of 170-210 ° C has a maximum of 175-207 ° C,

and

3. the ratio of enthalphs from endothermic peak 1 to endothermic peak 2 is 1: 1 to 1: 5,

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 Description of the particularly preferred component B):

Particularly preferred subject of the invention is a

Powder coating composition, wherein as component B) the β-hydroxyalkylamide N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included, having a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, preferably greater than 80 mol% and particularly preferably greater than 85 mol%, based on the total amount of all the isomers of Ν, Ν, Ν ', Ν'-tetrakis (2-hydroxyethyl) cyclohexyl 1, 4-diamids. In addition, this β-hydroxyalkylamide according to the invention, used as component B), has N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XI IA, two endothermic peaks according to DSC analysis, ( differential scanning calorimetry): first a peak with a maximum (peak 1) of about 160 ° C and another second peak with a maximum (peak 2) at about 190 ° C, they are the illustrations for the examples. Preferably, the first peak is in the range of 140-170 ° C with a maximum of 155-165 ° C and the second peak is in the range of 170-210 ° C with a maximum of 175-207 ° C. More preferably, the first peak is in the range of 155-170 ° C with a maximum of 158-165 ° C and the second peak is in the range of 170-210 ° C with a maximum of 180-205 ° C.

The ratio of enthalphies from endothermic peak 1 (-160 ° C.) to endothermic peak 2 (-190 ° C.) can be 1: 1 to 1: 5, preferably 1: 1 to 1: 3.

The DSC measurements were carried out in accordance with DIN EN ISO 1 1357-1 of March 2010. A heat flow differential calorimeter manufactured by Mettler-Toledo model DSC 821 was used. The samples are run once from -30 ° C to 250 ° C at 10K / min.

The XRPD measurements of powdered samples were in one

X-ray diffractometer with Cu Ka radiation (1, 541 Ä) performed. According to FIG. 9, the following significant and characteristic 6 peaks of the β-hydroxyalkylamide N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA were found:

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 The most preferred component B) is the β-hydroxyalkylamide

N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA having a trans content at the cyclohexyl ring of greater than or equal to 92 mol%, preferably greater than 94 mol% and particularly preferably greater than 96 mol%, and very particularly preferably greater than 98 mol%, based on the total amount of all present isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1 , 4 diamids.

The β-hydroxyalkylamide of the formula XIIA used as component B) according to the invention is below 175 ° C., preferably below 180 ° C. and more preferably below 185 ° C., in solid form. The β-hydroxyalkylamide of the formula XIIA according to the invention used as component B) with the features 1. to 4. was investigated by an X-ray structure analysis of a single crystal. Detailed information on the measurement is available in the

Appendix 1 summarized. The X-ray structure analysis of a single crystal gave the following result for the structure:

Crystal System: Orthorhombic

Space group: Pbca

Unit cell dimensions: a = 10.06350 (10) A α = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °. c = 14.6275 (2) λγ = 90 °. Volume: 1744.79 (3) Ä ³

The values in the bracket indicate the measurement accuracy in plus and minus for the corresponding last digit and last two digits, respectively.

Very particularly preferred subject of the invention is a

Powder coating composition containing the compound Ν, Ν, Ν ', Ν'-tetrakis (2) hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA as component B),

where it has the following parameters:

and

2. two endothermic peaks according to DSC analysis, (differential scanning

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1 26.00 3.43

5. and wherein this has the following parameters according to X-ray structure analysis of a single crystal:

Crystal System: Orthorhombic

Space group: Pbca Dimensions Unit cell: a = 10.06350 (10) Ap = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °. c = 14.6275 (2) λγ = 90 °.

Volume: 1744.79 (3) Ä ³

manufacturing

The particularly preferred N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide used as component B) according to the formula XIIA can be obtained by various processes:

First, as described in detail above, the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA in an extruder, intensive kneader, intensive mixer or static Mixer, preferably in an extruder, preferably solvent-free, prepared. Temperatures of 100 to 180 ° C are used. This is followed by recrystallization in a suitable solvent, preferably water. After dissolving at

Temperatures of 20 - 100 ° C and the crystallization is the Ν, Ν, Ν ', Ν'-

Tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA obtained with the parameters mentioned above. This can then be subsequently washed with alcohols, preferably methanol and dried. Preferably, the drying takes place at temperatures of 20-90 ° C, and can also be carried out at a vacuum. A further variant of the preparation is carried out as described in more detail above, characterized in that the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA in an extruder, intensive Kneader, intensive mixer or static mixer, preferably in an extruder, preferably solvent-free, is produced. Temperatures of 100 to 180 ° C are used. Subsequently, a heat treatment at temperatures of 50 - 100 ° C, preferably at temperatures of 70 - 85 ° C. The period is more than 6 hours, preferably more than 12 hours. The heat treatment can be carried out in vacuo.

The particularly preferred N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide used as component B) according to the formula XIIA can also

discontinuously in the solvent, ie in a batch process.

The reaction is carried out in conventional reactors. It can be used without pressure, using a reflux condenser, or under pressure with the reactor closed.

The synthesis is carried out in a solvent, preferably in alcohols, preferably methanol. The added amount of solvent is greater than 10 wt .-%, preferably greater than 15 wt .-%, based on the total amount of all starting materials used (starting materials). In this case, under reflux, or even at lower temperatures, and higher temperatures, under pressure, can be used.

The preparation is carried out at temperatures of 20 to 120 ° C, preferably at 60 to 90 ° C, particularly preferably at 70 to 85 ° C.

After crystallization, the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is obtained with the parameters mentioned above.

In addition, the preparation of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA in closed apparatus under pressure at temperatures of 60 to 140 ° C without the addition of solvents respectively.

The thus prepared in a batch process N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA can be in suitable Solvents, preferably in water or alcohols, preferably in methanol, are recrystallized.

In addition, the preparation of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA can also be carried out batchwise without solvent. The reaction is carried out in conventional reactors. It can under

Using a reflux condenser, to be worked. Preferably, the preparation is carried out at temperatures of 20 to 140 ° C, preferably 60 to 90 ° C, more preferably at 70 to 85 ° C. The β-hydroxyalkylamide thus obtained in a batch process is then recrystallized in suitable solvents, preferably in water or alcohols, preferably in methanol. You get after the

Crystallize the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA with the parameters mentioned above.

The concentration of all isomers of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide in the final product after its preparation is 75% by mass, preferably 80% by mass and more preferably 85% by mass -%.

This as described and characterized herein β-hydroxyalkylamide Ν, Ν, Ν ', Ν'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide of the formula XIIA gives

thorough matting in powder coatings with a gloss of less than 50

Scale parts at 60 ° angle, as shown in the examples. This product of the formula XIIA thus differs clearly from the disclosed β-hydroxyalkylamide according to the laid-open specification KR 10-2009-01 1 1720 (and that from β-hydroxyalkylamide Korean Ind. Eng. Chem., Vol. 20, No. 2, April 2009, 195-200), as evidenced in Fig. 2 on page 15, which has only one peak according to DSC analysis at about 190 ° C, and as Comparative Example 4c shows, does not lead to coatings with matte surfaces.

The invention is also the use of a

Powder coating composition as described above, wherein as component

Ν, Ν, Ν ', Ν'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included,

where it has the following parameters:

1 . a trans content on the cyclohexyl ring of greater than or equal to 70 mol%,

and

3. the ratio of enthalphies from endothermic peak 1 to

endothermic peak 2 is 1: 1 to 1: 5,

and

4. the XRPD spectrum of the powdered sample in the X-ray diffractometer measured with Cu Ka radiation (1. 541 Å) has the following peaks: peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 for the production of coatings with matte surfaces, with <50 units of gloss, measured as reflectometer values according to DIN 67530 / ISO 2813 at an irradiation angle of 60 °.

The invention is also the use of a

Powder coating composition as described above, wherein as component B) Ν, Ν, Ν ', Ν'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included,

where it has the following parameters:

and

2. two endothermic peaks according to DSC analysis, (differential scanning

and

4. the XRPD spectrum of the powdered sample in the X-ray diffractometer

measured with Cu Ka radiation (1.541 Å) has the following peaks: Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 5. and wherein this according to X-ray structure analysis of a single crystal

has the following parameters:

Crystal System: Orthorhombic

Room group: Pbca

Dimensions Unit cell a = 10.06350 (10) Ap = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °. c = 14.6275 (2) λγ = 90 °.

Volume (Volumen): 1744.79 (3) Ä ³ for the production of coatings with matte surfaces with <50 units of gloss, measured as reactometer values according to DIN 67530 / ISO 2813 at an irradiation angle of 60 °. Examples

The following examples and Tables 1, 2 and 3 characterize the

Composition of the coating system and the properties of the respective coating after its application and curing. Starting materials:

1) β-hydroxyalkylamide a) β-hydroxyalkylamide (matte hardener) based on 1 .4-cyclohexanedicarboxylic acid and diethanolamine with four β-hydroxyalkylamide groups per molecule of the formula XII, has a trans content on the cyclohexyl ring of> 90% (Evonik

Degussa GmbH, D).

Analytical values by GC

OH number: DIN 53240

Base number: DIN 53176

Melting range: DIN EN ISO 3146 b) VESTAGON® HA 320, OH number: 660-740 mg KOH / g, Mb: 1 15-130 ° C., (Evonik Degussa GmbH, D)) Carboxylate group-containing polymers - resins a) Amorphous polyester :

Crylcoat® 2617-3, SZ number: 33 mg KOH / g, Tg: 61 ° C, (Cytec Inc., USA)

Crylcoat® 2618-3, SZ number: 35 mg KOH / g, Tg: 61 ° C, (Cytec Inc., USA)

Crylcoat® E 36988, SZ number: 30 mg KOH / g, Tg: 54 ° C, (Cytec Inc., USA) Uralac® P 800, SZ Number: 28 mg KOH / g, Tg: 61 ° C, (DSM Resins BV, NL)

Uralac® P 865, SZ number: 35 mg KOH / g, Tg: 56 ° C., (DSM Resins B.V., NL)

Pulverol® 8120, SZ number: 33 mg KOH / g, Tg: 60 ° C, (Neochimiki LV s.a., GR)

Pulverol® 8123, SZ number: 33 mg KOH / g, Tg: 60 ° C, (Neochimiki LV s.a., GR) b) Polyarclate

Joncryl® 819, SZ number: 75 mg KOH / g, Tg: 57 ° C, (BASF AG.,

D)

3) co-crosslinker

a) Triglycidyl isocyanurate:

TEPIC ^® G, epoxy equiv .: <1 10 g / Eq, Smb: 90-125 ° C (Nissan

Chemical Ind. Ltd., J)

4) Further formulation ingredients:

Titanium dioxide Kronos® 2160, (Kronos Titan GmbH, D),

Resiflow® PV 88, (Worlee-Chemie GmbH, D),

Benzoin, (Merck-Schuchard, D).

Powder coating and coating

The preparation of the powder coating was firstly by mixing all components according to Table 1 and 2 at room temperature in a MIT mixer at 500 rpm for 120 seconds and then secondly by

common extrusion in the melt at a temperature (housing) of 90 ° C (about 130 ° C melt temperature). The stoichiometric ratio of acid groups of the polyester or polyacrylate to OH groups of the β-hydroxyalkylamides (hardeners) was about 1: 1. When co-crosslinkers were used, they became stoichiometric considered in the amount of hardener.

The extrudate was then cooled, ground and screened to a particle size of <100 μηη. The powder coating thus prepared was with a

electrostatic powder spray system at 60 KV on degreased steel sheets (deep-drawing St Fa Crüppel 210 x 70 x 0.8 mm) and / or aluminum sheets (Q-panel AL-36 5005 H 14/08 0.8 mm) applied and in a convection oven baked between 160 to 220 ° C. The cured lacquer films had a layer thickness of about 55-65 μm. The example data refer to a burn-in duration of 20 min. at 200 ° C.

Table 1

Testing according to the behavior with various polyesters and polyacrylate Formulation examples with inventive β-hydroxyalkylamide 1 a (Matthärter) and various resins

By replacing the β-hydroxyalkylamide according to the invention 1 a) with a commercial ß-hydroxyalkylamide such. B. the VESTAGON HA 320 1 b), or also mixtures with other commercial products of equal and / or different functionality, the gloss can be maintained in low admixtures or, if desired, be shifted to higher values with increased addition or exchange. Shown here in Examples 9 to 13 using a polyester.

Formulation examples with inventive β-hydroxyalkylamide 1 a (Matthärter) and various resins and with commercially available β-hydroxyalkylamide 1 b) Table 2

As a co-crosslinker and epoxy resins can be used. In question come here z. As glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates. Examples of such epoxides are triglycidyl isocyanurate (TGIC trade names, eg ARALDIT PT 810, Huntsman, TEPIC G, Nissan, Taida TGIC, Anhui Taida), mixtures of

Terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade names, eg, ARALDIT PT 910 and PT 912, Huntsman), glycidyl ester of versatic acid (Trade name eg CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A

(Trade name eg EPIKOTE 828, Shell) ethylhexyl glycidyl ether,

Butylglycidyl ether, pentaerythritol tetraglycidyl ether (trade name, e.g., POLYPOX R 16, UPPC AG) and other epoxy-type polypots. It can also be used mixtures. Preference is given to using TEPIC G or ARALDIT PT 910 and 912.

Such co-crosslinkers can be up to 50 wt .-% of the used

Hardener mix from Matthärter and co-crosslinker can be used.

Formulation examples with inventive β-hydroxyalkylamide 1 a (Matthärter) and co-crosslinker

Table 3

Examples 3a, b; 4a, b, c, d

The DSC measurements The DSC measurements were carried out in accordance with DIN EN ISO 1 1357-1 of March 2010.

A heat flow differential calorimeter manufactured by Mettler-Toledo Model: DSC 821 with serial no .: 51 16131417 was used. The samples are run once from -30 ° C to 250 ° C at 10K / min.

Detailed description of the measuring method:

1 . Type (heat flow difference calorimeter or power compensated

Calorimeter), model and manufacturer of the DSC device used;

2. Material, type and type and, if necessary, mass of used

Crucible;

3. Type, purity and flow rate of the purge gas used;

4. Type of calibration procedure and details of the ones used

Calibrant substances, including source, mass and other properties of importance for calibration;

5. Details of sampling, specimen preparation and conditioning

Heat-flow differential calorimeter

Manufacturer: Mettler-Toledo

Model: DSC 821

Serial No .: 51 16131417

2: crucible material: pure aluminum

Size: 40μΙ, without pin,

Mettler Order No .: ME-26763

Mass incl. Lid: approx. 48 mg

Purge gas: nitrogen

Purity: 5.0 (> 99.999 vol.%)

Flow rate: 40 ml / min

4: Calibration method: easy

Material 1: indium Mettler Calibration Set ME-51 1 19991

Mass: approx. 6 mg per weight

Calibration of temperature (onset) and heat flow

Material 2: RE water

Removal from the house system

Mass: approx. 1 mg per weight

Calibration of the temperature (Onset)

5: Sampling: from delivered sample vial

Sample weight: 8 to 10 mg

Sample preparation: pressed on the bottom of the crucible with a stamp Crucible lid: perforated

Measurement program: -30 to 250 ° C 10K / min 1 x Description of the XRPD measurement:

The powdered sample is pressed into a powder holder and in

Philips PW1800 X-ray diffractometer with Cu Ka radiation (1. 541 A) under the following conditions:

Excitation: 40 kV, 45 mA

Measuring range: 3 ° <2Θ <40 °

Step size: 0.1 ° (2Theta)

Time per step: 20 s

Rotation: 1/4 revolution / sec

Receivingslit: coarse

Divergence slot: automatic Examples 3a, b; 4a, b, c, d

Example 3a

In a three-necked flask with reflux condenser and glass stirrer, 92.24 g of dimethyl 1, 4-cyclohexyldicarboxylate with 96.91 g of diethanolamine, 10.84 g of 30% pure

Sodium methylate in methanol and 52 g of methanol submitted. It creates a homogeneous solution.

The mixture is refluxed in the oil heating bath with stirring for six hours (bath temperature 80 ° C.). It starts to precipitate after about 0.5 hours of product.

The reaction mixture is allowed to cool, with further product crystallizing out. Subsequently, the precipitated product is separated by filtration from the methanol and then dried. The yield is over 80% of theory. Table 3a

An N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to formula XI IA having two endothermic peaks (1. At about 160 ° C. and 2. At about 190) is thus obtained ° C) in the DSC according to Figure 1 and the XRPD spectrum according to Figure 5 and Table 5. This product produced in this way results in thorough matting in powder coatings with a gloss of less than 50 scale units at a 60 ° angle, Table 3a.

Example 3b The product prepared in 3a is dissolved in boiling water, then slowly cooled again and after crystallization briefly washed with methanol. Table 3a This product shows the two endothermic peaks, see Figure 2, with existing matting effect in the resulting powder coatings of 29 divisions at 60 degrees, Table 3a.

-.UU3UU ---- 0

TABLE 3a Final products from discontinuous preparation Examples 3a-3b and their characterization according to GC analysis ¹

'Analytical values by GC

GC after silylation with silyl 991 (BSTFA-TMCS 99: 1) from Macherey and Nagel Best. No. 701,490,150. Silylation: 1 ml silyl 991, 1 pyridine, 35 mg reaction product, 35 mg C-18 hydrocarbon as internal standard, heat for 30 minutes at 80 ° C in a sealed ampoule.

-.UU3UU ---- 0

46

Continuation Table 3a

Powder coating data

OH number: DIN 53240

-.UU3UU ---- 0

47

Base number: DIN 53176

Production Example A

Preparation of a β-hydroxyalkylamide of formula XIIA from dimethyl-1 .4-cyclohexyldicarboxylate and diethanolamine in the extruder

It was worked with three streams: stream 1 consisted of DMCD

Stream 2 was DEA

Stream 3 consisted of the catalyst, the methanolic sodium methylate solution.

The material flows were metered so that the molar ratio between dimethyl-1, 4-cyclohexyldicarboxylate and diethanolamine 1: 1, 95.

The total amount of catalyst (only sodium methylate, calculated solvent-free) based on the total formulation was 0.50 to 3.0%.

Stream 1 was added to the first housing at a rate of 10.0 kg / hr

Twin-screw extruder (ZSK 30, 32 d) fed (temperature of the stream 80 to 130 ° C).

Stream 2 was fed at a rate of 9.9 kg / h (temperature of the

Material flow 65 to 145 ° C).

Stream 3 was injected from inlet to the extruder into Stream 2 (0.5 to 2.0 kg / hr). The extruder used consisted of 8 housings which could be heated and cooled separately. Housing 1 - 5: 160 ° C, housing 6 - 8: 120 - 160 ° C. The housings 3, 5 and 8 were provided with a vacuum dome (100 to 600 mbar).

The extruder screws were equipped with conveying elements. Before

Vacuum domes were kneading blocks installed.

All temperatures represented nominal temperatures. The regulation took place via electric heating or water cooling. The extruder head was also electrically heated (100 - 160 ° C). The screw speed was 300 rpm. The reaction product was conveyed out of the extruder via a gear pump. The total throughput was 20 kg / h.

The end product was cooled down a pipe section or via an extruder and passed to a cooling belt and cooled further.

Example 4a and 4b 4a

It is an N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide with the

Product data 4a prepared analogously to Example A in the extruder (Werner and Pfleiderer ZSK 30, 32 d). Table 4

4b

This product as described and prepared in Example 4a becomes

recrystallized. For this purpose, the product from Example 4a is dissolved in demineralized water under boiling and then slowly cooled and crystallized, so as to be converted back into the solid form. The following is washed with methanol and dried at about 20 mbar and 50 ° C in a vacuum oven. Table 4 Thus, an N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide having two endothermic peaks (1st at about 160 ° C and 2nd at about 190 ° C) is obtained DSC.

This product, with the two peaks in the DSC as shown in Figure 3 and the XRPD spectrum as shown in Figure 7, provides deep matting in powder coatings with a gloss of 30 divisions at a 60 ° angle. Table 4

Comparative Example 4c

An N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide not according to the invention was prepared by the DSC according to FIG. 4.

This product shows in the DSC only an endothermic peak at about 190 ° C as shown in Figure 4 and an XRPD spectrum as shown in Figure 6 and Table 6. The resulting powder coating does not show any significant matting, but a gloss of 95 divisions at 60 degrees. Table 4

Example 4d

It is an N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide of the formula XIIA with the product data 4d analogously as described in Example 1 in the extruder (Werner and Pfleiderer ZSK 30, 32 d). Table 4

This product thus prepared is run on a cooling belt and collected. This material is then annealed in a drying oven at 80 ° C for 24 h under vacuum and then comminuted the product thus obtained.

This product gives thorough matting in powder coatings with a gloss of 40 divisions at a 60 ° angle. Table 4

-.UU3UU ---- 0

51

Table 4: End-products from continuous production Examples 4a-4b and their characterization according to GC analysis

^' Analytical values by GC. GC after silylation with silyl 991 (BSTFA-TMCS 99: 1) from Macherey and Nagel Best. No. 701,490,150. Silylation: 1 ml silyl 991, 1 ml pyridine, 35 mg reaction product, 35 mg C-18 hydrocarbon as internal standard, heat for 30 minutes at 80 ° C 5 in a sealed ampoule.

-.UU3UU ---- 0

52

Continuation Table 4

Powder coating data

OH number: DIN 53240

Base number: DIN 53176

Table 4 Continuation: end products from the preparation of Comparative Example 4c and characterization according to GC analysis ¹⁾ and powder coating

Powder coating data

Example 5

A β-hydroxyalkylamide of the formula XIIA was prepared as in Example 3a. From this, a single crystal was grown. The formula XIIA according to the invention was investigated by an X-ray structure analysis of a single crystal. Detailed information on the measurement is summarized in Appendix 1.

ANNEX 1

single-crystal

Analysis Method: Single Crystal X-ray Structure Analysis "2012-0573602-06D"

Report: WHC 1 1/1 1 EKS

Sample receipt: 201 1 -02-22

Report Date: 201 1 -02-25

Research question: Determination of the single crystal structure.

Compound: N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1,4-diamide Formula XIIA

Crystallization: by the chemist.

Crystal dimensions: colorless block, 0.50 x 0.40 x 0.40 mm ³

Code: vesta

Comment: The asymmetric unit contains half a molecule. Figure 10: Ortep plot (50%) with numbering scheme.

Experimental

The determination of the single crystal structure was carried out with a device of the company Oxfor Diffraction, which equipped with a CCD detector (model Ruby), a conventional X-ray tube with Cu _Ka radiation, Osmic mirror as a monochromator and a cryogenic Cryojet (T = 100 K) was. The data collection was performed in phi and omega scans. Data collection and reduction were done with Crysalis (Oxford Diffraction 2007).

Structure solution and refinement took place with SHELXTL (V. 6.10, Sheldrick, University of Göttingen, 2000). All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were refined as riding groups.

tables

Table a: Crystal data and structural refinement data for vesta.

Identification code vesta

Summation formal C16 H30 N206

Formula weight 346.42

Temperature 100K

Wavelength 1.54178 Ä

Crystal System Orthorhombic

Room group Pbca

Unit cell a = 10.06350 (10) λ = 90 °.

b = 11.85290 (10) λ = 90 °. c = 14.6275 (2) λ = 90 °.

Volume 1744.79 (3) Ä ³

Z 4

Density (calculated) 1,319 Mg / m ³

Absorption coefficient 0.832 mm ^"1

F (000) 752

Crystal dimensions 0.50 x 0.40 x 0.40 mm ³

Theta area for data collection 6.05 to 65.68 °.

Index range -11 <h <10, -12 <k <14, -14 <l <17

Number of reflexes collected 9191

Symmetry independent reflexes 1482 [R (int) = 0.0345]

Completeness to theta = 65.68 ° 98.5%

Absorption correction Crysalis

Refinement of full-matrix least-squares on F ^

Data / restraints / Parameter 1482/0/111

Goodness-of-fit on 1,065

Final R values [l> 2sigma (l)] R1 = 0.0316, wR2 = 0.0792

R values (all data) R1 = 0.0358, wR2 = 0.0817

Largest difference peaks 0.199 and -0.189 eA ^"3 Table b: Bond lengths [Ä] and angles [°] for vesta.

0 (1) -C (4) 1.2478 (15) N (1) -C (7) 1.4727 (15) C (3) -C (1) # 1 1.5291 (17) 0 (2) -C (6) 1.4221 (15) C (1) -C (3) # 1 1.5291 (17) C (5) -C (6) 1.5182 (16) 0 (3) -C (8) 1.4205 (16) C (1) - C (2) 1.5398 (16) C (7) -C (8) 1.5159 (17) N (1) -C (4) 1.3479 (16) C (2) -C (4) 1.5189 (17)

N (1) -C (5) 1.4741 (15) C (2) -C (3) 1.5405 (16)

C (4) -N (1) -C (5) 124.59 (10) 0 (1) -C (4) -N (1) 119.97 (11)

C (4) -N (1) -C (7) 117.87 (10) 0 (1) -C (4) -C (2) 120.15 (10)

C (5) -N (1) -C (7) 117.54 (9) N (1) -C (4) -C (2) 119.84 (10)

C (3) # 1-C (1) -C (2) 110.62 (10) N (1) -C (5) -C (6) 113.66 (9)

C (4) -C (2) -C (1) 111.04 (10) 0 (2) -C (6) -C (5) 110.97 (10)

C (4) -C (2) -C (3) 108.67 (10) N (1) -C (7) -C (8) 113.52 (10)

C (1) -C (2) -C (3) 110.09 (10) 0 (3) -C (8) -C (7) 113.31 (10)

C (1) # 1-C (3) -C (2) 111.18 (10)

Symmetry operations to produce Equivalent atoms:

# 1 -x + 1, -y + 1, -z

Table c: Torsion angle [°] for vesta.

C (3) # 1-C (1) -C (2) -C (4) 177.11 (9) C (4) -N (1) -C (5) -C (6) 80.57 (13)

C (3) # 1-C (1) -C (2) -C (3) 56.72 (14) C (7) -N (1) -C (5) -C (6) -99.58 (12)

C (4) -C (2) -C (3) -C (1) # 1-178.85 (9) N (1) -C (5) -C (6) -O (2) 61.92 (13)

C (1) -C (2) -C (3) -C (1) # 1 -57.04 (14) C (4) -N (1) -C (7) -C (8) 86.25 (13)

C (5) -N (1) -C (4) -0 (1) 176.19 (10) C (5) -N (1) -C (7) -C (8) -93.60 (12)

C (7) -N (1) -C (4) -O (1) -3.65 (16) N (1) -C (7) -C (8) -O (3) 73.97 (13)

C (5) -N (1) -C (4) -C (2) -6.21 (16)

C (7) -N (1) -C (4) -C (2) 173.95 (10)

C (1) -C (2) -C (4) -O (1) -54.62 (14)

C (3) -C (2) -C (4) -O (1) 66.61 (14)

C (1) -C (2) -C (4) -N (1) 127.78 (11)

C (3) -C (2) -C (4) -N (1) -110.98 (12) Symmetry operations to produce Equivalent atoms:

# 1 -x + 1, -y + 1, -z

Figure 11:

Calculated powder diffraction pattern based on the single crystal structure of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide (sample vesta)

Claims

claims:

1 . Powder coating composition, substantially containing

R 'R' O O R 'R'

HO- N- ^■ N- OH

R 'R' R ^ R ² RR '

With

R ¹ , R ² independently of one another are identical or different radicals selected from the alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24

Carbon atoms, wherein the radicals can also contain heteroatoms and / or functional groups, and wherein R ^{1 can} also be hydrogen, and wherein R ² also

R R

C C OH

R R

can be; and

A ¹ A ² A ³ with R ³ : independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and wherein two or more substituents R ³ may be linked together to form rings; wherein the β-hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1.

2. powder coating composition according to claim 1,

characterized in that

ß-hydroxyalkylamines having alkyl groups having at least 2 to 10 carbon atoms in the hydrocarbon skeleton are used as starting compounds, wherein the alkyl groups may be linear, branched or cyclic, and wherein the

Alkyl groups with heteroatoms, preferably oxygen, nitrogen may be substituted, these alkyl groups also functional groups, preferably carbonyl groups,

Carboxyl groups, amino groups, amide groups, urethane groups may contain and may carry an additional alkyl radical on the nitrogen.

3. powder coating composition according to at least one of the preceding claims,

characterized in that

ß-hydroxyalkylamides of N-alkyl-1, 2-alkanolamines and / or from N, N-bis-2-hydroxyalkylamines and esters of cyclohexanedicarboxylic acids are included.

4. Powder coating composition according to at least one of the preceding claims, characterized in that

ß-hydroxyalkylamines of the formulas II and / or III are used as starting compounds:

Formulas II

With

R ¹ is hydrogen, methyl, ethyl, propyl,

R is methyl;

Formulas III

R ¹ HHR ¹ H

or OH-C C N C C OH

5. Powder coating composition according to at least one of the preceding claims,

characterized in that the following compounds are used as starting materials for the preparation of the .beta.-hydroxyalkylamides: diethanolamine (DEA), di-isopropanolamine (DIPA), di-sec-butanolamine, N-methylethanolamine, N-methyl-isopropanolamine.

6. Powder coating composition according to at least one of the preceding claims, characterized in that

as starting compounds for the substituent A for Herstellugn of

β-hydroxyalkylamides 1, 2-substituted, 1, 3-substituted and 1, 4-substituted

Cyclohexandicarbonsäurederivate, especially Cyclohexandicarbonsäuredialkylester be used.

7. Powder coating composition according to at least one of the preceding claims, characterized in that

Compounds for the preparation of ß-hydroxyalkylamides of the formula IV are used:

A ⁴ A ⁵ A ⁶

with R ⁴ simultaneously or independently of one another methyl, ethyl, propyl, butyl.

8. Powder coating composition according to at least one of the preceding claims, characterized in that

1, 4-substituted cyclohexanedicarboxylic be used as starting compounds, preferably dimethyl-1, 4-cyclohexyldicarboxylate.

9. powder coating composition according to at least one of the preceding claims, characterized in that

the β-hydroxyalkylamides have the following formulas: HHOOHH

CH ₃ HOOH CH ₃

Formula VI

H CH ₃ OO CH ₃ H

Formula VII

H ₃ C-CH ₂ HOOH CH ₂ -CH ₃

Formula VIII Formula IX CH ₃ HOO CH ₃ H

H ₃ C CH ₂ HOOH ₃ C CH ₂ H With

R ² : methyl, or

_R 1A _R 1 B c- c- OH

HH is hydrogen, and R ^1B is methyl, ethyl, propyl, or

R ^{1A is} methyl, ethyl, propyl and R ^1B is hydrogen; and

A: 1,4-disubstituted cyclohexane ring of the formula

10. Powder coating composition according to at least one of the preceding claims,

where β-hydroxyalkylamides are prepared from dialkyl-1,4-cyclohexyldicarboxylates, preferably from dimethyl 1,4-cyclohexyldicarboxylate, having a trans content, based on the position of the carboxyl groups on the cyclohexyl ring, of greater than or equal to 70 mol%, preferably greater than 80 mol%. % and more preferably greater than 85 mol%.

1 1. Powder coating composition according to at least one of the preceding claims,

wherein the β-hydroxyalkylamide is prepared from dimethyl 1,4-cyclohexyldicarboxylate and diethanolamine having four β-hydroxyalkylamide groups per molecule of the formula XII,

consists, with a trans content at the cyclohexyl ring of greater than or equal to 70 mol%, preferably greater than 80 mol% and particularly preferably greater than 85 mol%;

12. Powder coating composition according to at least one of the preceding claims,

characterized in that

the ß-hydroxyalkylamides below 150 ° C, preferably below 170 ° C, more preferably below 180 ° C, in solid form.

13. Powder coating composition according to at least one of the preceding claims,

characterized in that

Carboxylate group-containing polyesters A) having a glass transition temperature T _g in a range from 40 to 80 ° C, preferably 40 to 70 ° C; having an acid value varies from 5 to 250 mg KOH / g, preferably from 10 to 150 mg KOH / g, preferably from 12 to 120 mg KOH / g;

with an OH number of less than 15 mg KOH / g;

having an average molecular weight M _{w of} from 1000 to 10000 g / mol, preferably from 1 500 to 9000 g / mol, particularly preferably from 2000 to 8000 g / mol;

are included.

14. Powder coating composition according to at least one of the preceding claims,

characterized in that

Carboxylate group-containing acrylate polymers A), which

an OH number of less than 10 mg KOH / g;

an acid number of 10 to 350 mg KOH / g, preferably 20 to 300 mg KOH / g, more preferably from 30 to 250 mg KOH / g;

a Tg of 40 to 1 10 ° C, preferably 45 to 100 ° C;

a Mw of 500 to 50,000 g / mol, preferably 1,000 to 30,000 g / mol, more preferably from 1,500 to 20,000 g / mol;

have included.

15. Powder coating composition according to at least one of the preceding claims,

characterized in that

Co-crosslinker based on epoxy resins and / or ß-hydroxyalkylamides different from B) are included.

16. A process for producing a powder coating composition, substantially containing

A) at least one carboxylate group-containing polymer having an acid number of 10 to 250 mg KOH / g, and a glass transition temperature t _g of greater than 40 ° C, and

B) at least one .beta.-hydroxyalkylamide having two or three or four .beta.-hydroxyalkylamide groups per molecule of the formula I. RROORR

HO- N- ^■ N- OH

RRR ^ R ² RR '

With

Carbon atoms, wherein the radicals can also contain heteroatoms and / or functional groups, and wherein Ri can also be hydrogen, and wherein R ² also

can be; and

A ¹ A ² A ³ with R ³ : independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals can also contain heteroatoms and / or functional groups, and wherein two or more substituents R ₃ may be linked together to form rings; wherein the β-hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1;

17. Use of a powder coating composition, substantially containing

R 'R' O O R 'R'

HO- -N- -N- -OH

R 'R' R ^ R ² R ¹ R ¹

With

Carbon atoms, wherein the radicals can also contain heteroatoms and / or functional groups, and wherein R ^{1 can} also be hydrogen, and wherein R also

R R

C C OH

R R

can be; and

with R ³ : independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24

Carbon atoms, wherein the radicals may also contain heteroatoms and / or functional groups, and wherein two or more substituents R ³ may be linked together to form rings; wherein the β-hydroxyalkylamides are below 150 ° C in solid form;

C) optional adjuvants and / or additives; wherein the ratio of β-hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1; for the production of coatings matte surfaces, with a degree of gloss according to DIN 67530 / ISO 2813 of <50 at an angle of incidence of 60.

18. Powder coating composition according to at least one of claims 1 to 15,

which comprises N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA as component B),

where it has the following parameters:

and

2. two endothermic peaks according to DSC analysis, (differential scanning calorimetry)

wherein peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C, and peak 2 in the range of 170-210 ° C has a maximum of 175-207 ° C,

and

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43

19. Powder coating composition according to claim 18,

with a trans content at the cyclohexyl ring of greater than or equal to 92 mol%, preferably greater than 94 mol% and more preferably greater than 96 mol%, and most preferably greater than 98 mol%, based on the total amount of all present Isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide.

20. Powder coating composition according to claim 18 or 19,

characterized,

the β-hydroxyalkylamide of the formula XIIA is present in solid form below 175 ° C., preferably below 180 ° C. and particularly preferably below 185 ° C.

21. Powder coating composition according to at least one of claims 18 to 20,

characterized,

the concentration of all isomers of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide in the end product after its preparation is 75% by mass, preferably 80% by mass and more preferably 85 Mass%, is.

22. Powder coating composition according to at least one of claims 18 to 21,

wherein the ratio of enthalphies from the endothermic peak 1 (-160 ° C,) to

endothermic peak 2 (-190 ° C) 1: 1 to 1: 3, is.

23. Powder coating composition according to at least one of claims 18 to 22, which N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA as component B)

where it has the following parameters:

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43

5. and wherein this according to X-ray diffraction analysis of a single crystal, the following

Parameter has:

Crystal System: Orthorhombic

Room group: Pbca

Dimensions Unit cell: a = 10.06350 (10) Ap = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °.

c = 14.6275 (2) λγ = 90 °.

Volume: 1744.79 (3) Ä ³

24. Use of a powder coating composition according to at least one of the preceding claims 1 to 23, wherein as component B) N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included .

where it has the following parameters:

and

2. has two endothermic peaks according to differential scanning calorimetry (DSC) analysis, where peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C, and peak 2 in the range of 170-210 ° C lies with a maximum of 175 -

207 ° C,

and

3. the ratio of enthalphs from endothermic peak 1 to endothermic peak 2 1:

1 to 1: 5,

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09 4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 for the production of coatings with matte surfaces with <50 units of gloss, measured as reflectometer values according to DIN 67530 / ISO 2813 at an irradiation angle of 60 °.

Use of a powder coating according to claim 24, wherein as component B) N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included

IA with the following parameters:

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 and this according to X-ray structure analysis of a single crystal having the following parameters:

Crystal System Orthorhombic

Room group: Pbca

Dimensions Unit cell a = 10.06350 (10) Ap = 90 °.

b = 1 1 .85290 (10) Ä ß = 90 °.

c = 14.6275 (2) λγ = 90 °.

Volume: 1744.79 (3) Ä ³

A process for the preparation of a powder coating composition according to claim 16, wherein as component B) N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XI IA is contained, where it has the following parameters:

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19

5 21, 60 4,1 1

6 26.00 3.43 A process for preparing a powder coating composition according to claim 16, wherein as component B) N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XI IA is included

where it has the following parameters:

and

Peak no. Grade 2theta

± 0.2 degrees 2theta d (A)

1 14.90 5.94

2 16.70 5.31

3 17,40 5,09

4 21, 20 4,19 5 21.60 4.11

6 26.00 3.43

Crystal System: Orthorhombic

Space group: Pbca Dimensions Unit cell: a = 10.06350 (10) Ä a = 90 °.

b = 11.85290 (10) Ä ß = 90 °.

c = 14.6275 (2) λγ = 90 °.

Volume: 1744.79 (3) Ä ³