CA2394029A1 - Aqueous primary dispersions and coating matters, a method for producing same and the use thereof - Google Patents

Abstract

The invention relates to aqueous primary dispersions and coating matters containing dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a particle diameter <= 500 nm. The inventive dispersions and coating matters can be produced by means of radical micro or miniemulsion polymerisation of at least one olefinically unsaturated monomer (A) in the presence of at least one hydrophobe cross-linking agent for the (co)polymer resulting from the monomer or the monomers (A). The invention also relates to a method for producing same and to the use thereof.

Description

AQUEOUS PRIMARY DISPERSIONS AND COATING MATTERS, A METHOD
FOR PRODUCING SAME AND THE USE THEREOF
The present invention relates to novel aqueous primary dispersions and coating materials which comprise dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter <_ 500 nm. The present invention further relates to a novel process for preparing the novel aqueous primary dispersions and coating materials by means of controlled free-radical microemulsion and miniemulsion polymerization. The present invention relates, furthermore, to the use of the novel aqueous primary dispersions and coating materials for producing single-coat or multicoat clearcoat systems and single-coat or multicoat color and/or effect paint systems in automotive OEM finishing and refinishing, industrial coating, including container coating, coil coating and the coating of electrical components, and furniture coating.
Microemulsions and miniemulsions are dispersions comprising water, an oil phase and one or more surface-active substances and having droplet sizes of from 5 to 50 nm (microemulsions) or from 50 to 500 nm.
Microemulsions are regarded as being thermodynamically stable, whereas the miniemulsions are regarded as being metastable (cf. Emulsion Polymerization and Emulsion .. ' CA 02394029 2002-06-10 Polymers, Editors: P.A. Lovell and Mohamed S. E1-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pages 700 et seq.; Mohamed S. E1-Aasser, Advances in Emulsion Polymerization and Latex Technology, 30th Annual Short Course, Volume 3, June 7-11, 1999, Emulsion Polymers Institute, Lehigh University, Bethlehem, Pennsylvania, USA). Both types of dispersions find broad application in the art: for example, in cleaning products, cosmetics or bodycare products. They may, however, also be used for polymerization reactions in place of the customary macroemulsions, in which droplet sizes >1000 nm are present.
The preparation of aqueous primary dispersions by means of free-radical miniemulsion polymerization is known, for example, from the international patent application WO 98/02466 or from German patents DE-A-196 28 143 and DE-A-196 28 142. In the case of these known processes, the monomers may be copolymerized in the presence of different low molecular mass, oligomeric or polymeric hydrophobic substances, which are also referred to as costabilizers. Furthermore, hydrophobic, organic auxiliaries of low solubility in water, such as plasticizers, enhancers of the tackiness of the resulting film, film-forming auxiliaries or other, unspecified organic additives, may be incorporated into the monomer droplets of the miniemulsion. The use of the known aqueous primary dispersions for preparing coating materials is not evident from the patents.
Aqueous coating materials based on aqueous primary dispersions which comprise solid core-shell particles and have been prepared by miniemulsion polymerization of monomers in the presence of hydrophobic polymers are known from the patents EP-A-0 401 565, WO 97/49739 or EP-A-0 755 946. Although the known coating materials already have numerous advantageous properties, problems associated with inadequate distribution of the crosslinking agents in the aqueous dispersions continue to arise. One particular consequence of this is the need to use a larger amount of crosslinking agents than would be necessary theoretically. Unreacted cross-linking agents may then, in certain circumstances, impair the performance properties of the coatings produced from the coating materials.
The microencapsulation of hydrophobic organic solvents or of target materials such as biocides and herbicides in water-insoluble core-shell particles, prepared by miniemulsion polymerization, is known from the patents EP-A-0 203 724 or US-A-4,&77,003. However, the (co)polymerization is not conducted in the presence of hydrophobic crosslinking agents for the (co)polymers formed from the monomers.

, - 4 -Patents EP-A-0 622 389 or DE-A-43 14 297 disclose the (co)polymerization of monomers in the presence of blocked polyisocyanates and epoxy resins. The technique used, however, is not that of miniemulsion polymerization. A comparable process is evident from patents EP-A-0 758 347 or WO 95/29944. The corresponding known (co)polymers and their primary dispersions are used to prepare coating materials. The known coating materials likewise possess the problems associated with inadequately fine distribution of the crosslinking agents in the coating materials.
It is an object of the present invention to find new aqueous primary dispersions and coating materials comprising dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter <_ 500 nm which no longer have the disadvantages of the prior art but instead can be prepared in a simple manner.
Furthermore, the new aqueous primary dispersions and coating materials ought to comprise very finely divided crosslinking agents.
A further object of the present invention was to find a new process for preparing aqueous primary dispersions and coating materials by free-radical microemulsion or miniemulsion polymerization which no longer has the disadvantages of the prior art.

. CA 02394029 2002-06-10 Accordingly, we have found the novel aqueous primary dispersions and coating materials comprising dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter <_ 500 nm, preparable by free-radical microemulsion or miniemulsion polymerization of at least one olefinically unsaturated monomer (A) in the presence of at least one hydrophobic crosslinking agent for the (co)polymer resulting from the monomer or monomers (A) , which are referred to below for short as "primary dispersions of the invention" and, respectively, "coating materials of the invention".
We have also found the novel process for preparing aqueous primary dispersions and coating materials comprising dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter < 500 nm which comprises subjecting at least one olefinically unsaturated monomer (A) to free-radical (co)polymer ization in a microemulsion or miniemulsion in the presence of at least one hydrophobic crosslinking agent for the (co)polymer resulting from the monomer or monomers (A), said process being referred to for short below as "process of the invention".
Further subjects of the invention will emerge from the following description.

In the light of the prior art it was surprising and unforeseeable for the skilled worker that the object on which the present invention was based could be achieved through the primary dispersions of the invention and the coating materials of the invention and also through the process of the invention. In particular it was surprising that the (co)polymers present in the primary dispersions of the invention have properties which make them highly suitable for use in coating materials. It was also surprising that the primary dispersions of the invention can be used directly as coating materials, requiring even less crosslinking agent than conventional coating materials. Not least was it surprising that the process of the invention yields, as intended, the primary dispersions and coating materials of the invention in a particularly simple manner without the occurrence of the above-described problems known from the prior art.
For the purposes of the present invention, the property of being hydrophilic is understood as the constitutional property of a molecule or functional group to penetrate into the aqueous phase or to remain therein. Accordingly, for the purposes of the present invention, the property of being hydrophobic is understood as the constitutional property of a molecule or functional group to exhibit exophilic behavior with respect to water; i.e., they display the tendency not to penetrate into water, or to depart the aqueous _ 7 _ phase. For further details refer to Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hydrophilicity", "Hydrophobicity", pages 294 and 295.
In accordance with the invention, the primary dispersions and coating materials comprise dispersed and/or emulsified solid and/or liquid polymer particles and/or dispersed solid core-shell particles. The size of the polymer particles or of the dispersed core-shell particles is a direct result of the process of the invention described below. In this case the average particle diameter is less than 500 nm. It is preferably from 10 to 500 nm, more preferably from 50 to 400 nm, and with very particular preference from 100 to 350 nm.
The primary dispersions and coating materials of the invention have an advantageously high solids content of, for example, more than 20~ by weight, preferably more than 30~ by weight . It is , even possible to obtain solids contents of more than 40~ by weight. The primary dispersions and coating materials of the invention have a low viscosity even at high solids content.
The core-shell particles for use in accordance with the invention result from the graft copolymerization of organic solids and the monomers (A) for use in accordance with the invention, described below. Said organic solids are preferably hydrophobic polymers, as described, for example, in the patents EP-A-0 401 565, page 3, lines 5 to page 4, line 50, W0. 97/49739, page 4, lines 19 to page 5, line 3, or EP-A-0 755 946, page 3, line 26 to page 5, line 38. These hydrophobic polymers may also be prepared by the process of the invention.
The primary dispersions and coating materials of the invention may also have a bimodal particle size distribution in which from 0.1 to 80~ by weight, in particular from 1.0 to 50~ by weight, of the (co) polymer resulting from the monomer or monomers (A) have a particle size, determined using an analytical ultracentrifuge, of from 20 to 500 nm, in particular from 50 to 300 nm, and from 20 to 99.9 by weight, in particular from 50 to 99~ by weight, of the (co)polymer have a particle size of from 200 to 1500 nm, in particular from 300 to 900 nm, said particle sizes differing by at least 50 nm, in particular by at least 100 nm, with very particular preference by at least 200 nm. Concerning the measurement method, reference is made for further details to lines 5 to 9 of page 6 of German patent application DE-A-196 28 142.
The first starting compound essential to the invention for the primary dispersions or coating materials of the invention, and for the process of the invention, is at least one olefinically unsaturated monomer (A).

._ g ._ In this context it is preferred to use at least one monomer (A) comprising reactive functional groups which are able to enter into crosslinking reactions with the complementary reactive functional groups of the crosslinking agents. Examples of suitable complementary reactive functional groups for use in accordance with the invention are collated in the overview below. In the overview, the variable R is an acyclic or cyclic aliphatic radical, an aromatic radical and/or an aromatic-aliphatic (araliphatic) radical; the variables R' and R" are identical or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
Overview: Examples of complementary functional groups Monomer (A) and crosslinking agent (C) or Crosslinking agent (C) and monomer (A) -SH -C(O)-OH
-NH2 -C (0) -O-C (O) --OH -NCO
-O- (CO) -NH- (CO) -NHZ -NH-C (O) -OR
-0- (CO) -NH2 -CH2-OH

~

>NH -CHZ -O-CH3 -NH-C (O) -CH (-C (O) OR) 2 -NH-C (O) -CH (-C (O) OR) (-C (O) -R) -NH-C (O) -NR' R"
15 -C (O) -OH
=Si (OR) 2 -CH-CHI
-CH-CHI
The selection of the respective complementary groups is guided on the one hand by the consideration that, during the storage of primary dispersions or coating materials of the invention, these groups do not enter into any unwanted reactions and/or, if appropriate, do not inhibit or disrupt curing with actinic radiation, and on the other hand by the temperature range within which crosslinking is to take place.

In the case of the coating materials of the invention, it is preferred to use crosslinking temperatures of from 100 to 180°C. For this reason it is preferred to use monomers (A) containing thio, hydroxyl, alkoxymethylamino, imino, carbamate, allophanate and/or carboxyl groups, but in particular amino, alkoxymethylamino or hydroxyl groups, especially hydroxyl groups, on the one hand, and crosslinking agents containing anhydride, carboxyl, epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, hydroxyl and/or beta-hydroxyalkylamide groups, but especially blocked isocyanate, urethane or methylol ether groups, on the other.
Examples of suitable monomers (A) are al) substantially acid-group-free (meth)acrylic esters such as (meth)acrylic alkyl or cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, especially methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth)acrylic esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indenemethanol acrylate or tert-butylcyclohexyl (meth)acrylate; (meth)acrylic oxaalkyl esters or oxacycloalkyl esters such as ethyltriglycol (meth)acrylate and methoxy-oligoglycol (meth)acrylate having a molecular weight Mn of preferably 550, or other ethoxylated and/or propoxylated hydroxyl-free (meth)acrylic acid derivatives. These may contain minor amounts of (meth)acrylic alkyl or cycloalkyl esters of higher functionality, such as the di(meth)acrylates of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, octahydro-4,7-methano-1H-indenedimethanol or 1,2-, 1,3- or 1,4-cyclohexanediol; trimethylolpropane di- or tri(meth)acrylate; or pentaerythritol di-, tri- or tetra(meth)acrylate. For the purposes of the present invention, minor amounts of monomers of higher functionality in this case are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers (A) unless the specific intention is to prepare crosslinked polymeric microparticles.
a2) Monomers which carry per molecule at least one hydroxyl, thio, amino, alkoxymethylamino, carbamate, allophanate or imino group, in particular a hydroxyl, amino or alkoxymethylamino group, and are substantially free from acid groups, such as hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha,beta-olefinically unsaturated carboxylic acid, which derive from an alkylene glycol esterified with the acid, or which are obtainable by reacting the ~
. CA 02394029 2002-06-10 - 1~ _ alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide, especially hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, malefic acid, fumaric acid or itaconic acid in which the hydroxyalkyl group contains 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 hydroxycyclo-alkyl esters such as 1,4-bis(hydroxymethyl)-cyclohexane, octahydro-4,7-methano-1H-indene-dimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleate, monofurriarate or monoitaconate; or reaction products of cyclic esters, such as epsilon-caprolactone, for example, and these hydroxyalkyl or hydroxycycloalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol or polyols such as trimethylolpropane monoallyl or diallyl ether or pentaerythritol monoallyl, diallyl or triallyl ether (as far as these monomers (a2) of higher functionality are concerned, the comments made above relating to the monomers (al) of higher functionality apply analogously); N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate or N,N-di(methoxymethyl)aminoethyl acrylate and - ~4 -methacrylate or N,N-di(butoxymethyl)aminopropyl acrylate and methacrylate;
a3) monomers which carry per molecule at least one acid group which can be converted into the corresponding acid anion group, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, malefic acid, fumaric acid or itaconic acid;
olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or mono(meth)acryloyloxyethyl maleate, succinate or phthalate. For the purposes of the present invention the monomers (a3) are not used as the sole monomers (A) but are always used in conjunction with other monomers (A) and, moreover, in amounts so small that the monomers (a3) do not polymerize outside the droplets of the miniemulsion.
a4) Vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule.
The branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins may be cracking products of paraffinic hydrocarbons, such as mineral oil fractions, and may comprise both branched and straight-chain acyclic and/or cycloaliphatic olefins. The reaction of such olefins with formic acid or, respectively, with carbon monoxide and water produces a mixture of carboxylic acids in which the carboxyl groups are located predominantly on a quaternary carbon atom, Examples of other olefinic starting materials are propylene trimer, propylene tetramer and diisobutylene. Alternatively, the vinyl esters (a4) may be prepared in a conventional manner from the acids, by reacting, for example, the acid with acetylene. Particular preference, owing to their ready availability, is given to using vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms that are branched on the alpha carbon atom, especially Versatic~ acids.
a5) 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 is then reacted during or after the polymerization reaction with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, especially a Versatic~ acid.
a6) Cyclic and/or acyclic olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, cyclo-hexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and/or dicyclo-pentadiene.
a7) (Meth)acrylamides such as (meth)acrylamide, N-methyl-, N,N-dimethyl-, N-ethyl-, N,N-diethyl-, N-propyl-, N,N-dipropyl-, N-butyl-, N,N-dibutyl-, N-cyclohexyl-, N,N-cyclohexylmethyl-~ and/or N-methylol-, N,N-dimethylol-, N-methoxymethyl-, N,N-di(methoxymethyl)-, N-ethoxymethyl- and/or N,N-di(ethoxyethyl)-(meth)acrylamide;
a8) monomers containing epoxide groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, malefic acid, fumaric acid and/or itaconic acid.
a9) Vinylaromatic hydrocarbons such as styrene, alpha-alkylstyrenes, especially alpha-methylstyrene, and/or vinyltoluene; vinylbenzoic acid (all isomers), N,N-diethylaminostyrene (all isomers), alpha-methylvinylbenzoic acid (all isomers), N,N-diethylamino-alpha-methylstyrene (all isomers) and/or p-vinylbenzenesulfonic acid.
a10) nitrites such as acrylonitrile and/or methacrylo-nitrite.

_ 17 -all) Vinyl compounds, especially vinyl halides and/or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam, 1-vinyl-imidazole or N-vinylpyrrolidone; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and/or vinyl cyclohexyl ether; and/or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and/or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
a12) Allyl compounds, especially allyl ethers and allyl esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
a13) Polysiloxane macromonomers having a number-average molecular weight Mn o~ from 1000 to 40,000 and having on average from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; especially polysiloxane macromonomers having a number-average molecular weight Mn of from 2000 to 20,000, with particular preference from 2500 to 10, 000 and, in particular, from 3000 to 7000 and having on average from 0.5 to 2.5, preferably from 0.5 to 1.5, ethylenically unsaturated double bonds per ~

molecule, as are described in DE-A-38 07 571 on pages 5 to 7, in DE-A-37 06 095 in columns 3 to 7, in EP-B-0 358 153 on pages 3 to 6, in US-A-4, 754, 014 in columns 5 to 9, in DE-A-44 21 823 or in the international patent application WO
92/22615 on page 12, line 18 to page 18, line 10.
and/or a14) Acryloyloxysilane-containing vinyl monomers, preparable by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth)acrylic acid and/or hydroxyalkyl and/or hydroxycycloalkyl esters of (meth)acrylic acid (cf. monomers a2).
Further examples of suitable monomers (A) are disclosed in German patent application DE-A-196 28 142, page 2, line 50 to page 3, line 7.
Each of the abovementioned monomers (A), with the exception of the monomer (a3), can be polymerized alone to give polymers. In accordance with the invention, however, it is advantageous to use at least two monomers (A), since by this means it is possible to vary the profile of properties of the resulting copolymers very widely, in a particularly advantageous manner, and to tailor said profile of properties to the particular intended use of the primary dispersions of the invention or of the coating materials of the invention.
Preferably, the monomers (A) are selected so as to give (meth)acrylate (co)polymers whose profile of properties is determined primarily by the (meth)acrylates described above. In that case it is preferred as comonomers (A) to use vinylaromatic hydrocarbons (a9), especially styrene.
The monomers (A) to be used in accordance with the invention are reacted with one another to form (co)polymers in the presence of at least one water-soluble and/or oil-soluble initiator which forms free radicals. Examples of initiators which can be used are:
dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; per esters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; peroxodicarbonates; potassium, sodium or ammonium peroxodisulfate; azo initiators, examples being azodinitriles such as azobisisobutyro-nitrile; C-C-cleaving initiators such as benzpinacol silyl ethers; or a combination of a nonoxidizing initiator with hydrogen peroxide. Combinations of the initiators described above may also be used.

Further examples of suitable initiators are described in German patent application DE-A-196 28 142, page 3, line 49 to page 4, line 6.
It is preferred to add comparatively large amounts of free-radical initiator, the proportion of the initiator in the reaction mixture being, based in each case on the overall amount of the monomers (A) and of the initiator, with particular preference from 0.2 to 20~
by weight, with very particular preference from 0.5 to 15~ by weight, and in particular from 1.0 to 10~s by weight.
In accordance with the invention, the monomers (A) are copolyme-rized in the presence of at least one hydrophobic crosslinking agent. The hydrophobic crosslinking agents preferably contain the above-described reactive functional groups which enter into crosslinking reactions with the complementary reactive functional groups present in the resulting (co) polymers .
Examples of particularly suitable crosslinking agents are blocked polyisocyanates, tris(alkoxycarbonyl amino)triazines or fully etherified amino resins.
Examples of suitable blocking agents for preparing the blocked polyisocyanates are the blocking agents known from the patent US-A-4,444,954:

i) phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butyl-phenol, hydroxybenzoic acid, esters of these acids, or 2,5-di-tert-butyl-4-hydroxytoluene;
ii) lactams, such as E-caprolactam, 8-valerolactam, y-butyrolactam or (3-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-butanoJ., isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic esters, lactic acid, lactic esters, methylolurea, methylolmelamine, diacetone alcohol, ethylenechlorohydrin, ethylenebromohydrin, 1,3 dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanohydrin;
v) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthio-phenol or ethylthiophenol;
vi) acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetamide, stearamide 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, ethylenethiourea or 1,3-diphenylurea;
xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone;
xii) imines such as ethyleneimine;
xiii)oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzo-phenone oxime or chlorohexanone oximes;

~~

xiv) salts of sulfurous acid such as sodium bisulfate or potassium bisulfate;
xv) hydroxamic esters such as benzyl methacrylo hydroxamate (BMH) or allyl methacrylohydroxamate;
or xvi) substituted pyrazoles, especially dimethyl-pyrazole, or triazoles; and also to xvii)mixtures of these blocking agents, especially dimethylpyrazole and triazoles, malonic esters and acetoacetic esters or dimethylpyrazole and succinimide.
Examples of suitable organic polyisocyanates for blocking are in particular the so-called paint polyisocyanates having isocyanate groups attached to aliphatic, cycloaliphatic, araliphatic and/or aromatic structures. Preference is given to polyisocyanates having from 2 to 5 isocyanate groups per molecule and having viscosities of from 100 to 10,000, preferably from 100 to 5000.
Further examples of suitable polyisocyanates for blocking are described in "Methoden der organischen Chemie", Houben-Weyl, Volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136. Suitable examples are the polyurethane prepolymers which contain isocyanate groups, can be prepared by reacting polyols with an excess of polyisocyanates and are preferably of low viscosity.
Further examples of suitable polyisocyanates for blocking are polyisocyanates containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea and/or uretdione groups. Polyisocyanates containing urethane groups, for example, are obtained by reacting some of the isocyanate groups with polyols, such as trimethylolpropane and glycerol, for example.
Preference is given to the use of aliphatic or cycloaliphatic polyisocyanates, especially hexa-methylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane 2,4'-diisocyanate, dicyclohexyl-methane 4,4'-diisocyanate, diisocyanates derived from dimeric fatty acids, as marketed under the commercial designation DDI 1410 by Henkel and described in patents DO 97/49745 and WO 97/49747, especially 2-heptyl-3,4-bis(9-isocyanatononyl)-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 or 1,2-, 1,4- or 1,3-bis(4-isocyanatobut-1-yl)cyclohexane, 1,8-diiso-cyanato-4-isocyanatomethyloctane, 1,7-diisocyanato-4-isocyanatomethylheptane or 1-isocyanato-2-(3-iso-' CA 02394029 2002-06-10 cyanatopropyl)cyclohexane, or mixtures of these polyisocyanates.
Very particular preference is given to the use of mixtures of polyisocyanates containing uretdione and/or isocyanurate groups and/or allophanate groups, which are based on hexamethylene diisocyanate, as formed by catalytic oligomerization of hexamethylene diisocyanate using appropriate catalysts.
Examples of particularly suitable amino resins are melamine resins, guanamine resins or urea resins. In this context it is possible to use any amino resin that is suitable for clearcoats, or a mixture of such amino resins. For further details reference is made to Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, page 29, "Amino resins", and the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff . , or to the book "Paints, Coatings and Solvents", second completely revised edition, editors: D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff. Also suitable are the customary and known amino resins some of whose methylol and/or methoxymethyl groups have been defunctionalized by means of carbamate or allophanate groups. Crosslinking agents of this kind are described in the patents US-A-4 710 542 and EP-B-0 245 700 and also in the article by B. Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for ~

' - 26 -the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207.
The particularly suitable tris(alkoxycarbonylamino)-triazines had the following formula:
H
N N I
R 0 C J / ~C OR
II N ~N
0 .
N
H ~ ~'C OR

Examples of particularly suitable tris(alkoxy carbonylamino)triazines are described in the patents US-A-4,939,213, US-A-5,084,541 or EP-A-0 624 577. Use is made in particular of the tris(methoxy-, tris (butoxy- and/or tris(2-ethylhexoxycarbonylamino) triazines (R = methyl, butyl or ethylhexyl).
The methyl butyl mixed esters, the butyl 2-ethylhexyl mixed esters and the butyl esters are of advantage.
They have the advantage over the simple methyl ester of better solubility in polymer melts and also have less of a tendency to crystallize out.

Of the crosslinking agents described above, the blocked polyisocyanates offer particular advantages and are therefore used with very particular preference in accordance with the invention.
In the process of the invention, the ratio of the monomers (A) comprising complementary reactive functional groups to the crosslinking agents may vary very widely. In accordance with the invention it is of advantage if the molar ratio of complementary reactive functional groups in (A) to complementary reactive functional groups in the crosslinking agents is from 5.0 . 1.0 to 1.0 . 5.0, preferably from 4.0 . 1.0 to 1.0 . 4.0, with particular preference from 3.0 . 1.0 to 1.0 . 3.0, and in particular from 2.0 . 1 to 1 . 2Ø
Particular advantages result if the molar ratio is approximately or precisely 1.0 . 1Ø
The monomers (A) for use in accordance with the invention are preferably copolymerized in the presence of emulsifiers and/or protective colloids. Examples of suitable emulsifiers and/or protective colloids, and the amounts in which they are advantageously used, are disclosed in German patent application DE-A-196 28 142, page 3, lines 8 to 48.
In addition to the hydrophobic crosslinking agents described above for use in accordance with the invention, the (co)polymerization of the monomers (A) ~

- 2$ -to be used in accordance with the invention may also be accompanied by hydrophobic compounds which differ materially from the crosslinking agents. These hydrophobic compounds are also referred to by those in the art as costabilizers.
The hydrophobic compounds comprise water-insoluble low molecular mass, oligomeric or polymeric substances.
Examples of suitable hydrophobic compounds are esters of alpha, beta-monoolefinically unsaturated carboxylic acids, having 3 to 6 carbon atoms, with alcohols having 12 to 30 carbon atoms in the alkyl radical; esters of vinyl alcohol and/or allyl alcohol with alkanemono-carboxylic, -sulfonic and/or -phosphonic acids having 12 to 30 carbon atoms in the molecule; amides of alpha, beta-monoolefinically unsaturated carboxylic acids having 3 to 6 carbon atoms with alkylamines having 12 to 30 carbon atoms in the alkyl radical;
macromonomers based on olefinically unsaturated compounds having on average at least one olefinically unsaturated group, in particular at least one terminal olefinically unsaturated group, in the molecule;
polysiloxane macromonomers having on average at least one olefinically unsaturated group, in particular at least one terminal olefinical'ly unsaturated group, in the molecule; oligomeric and/or polymeric products of addition polymerization, polycondensation and/or polyaddition; water.-insoluble molecular weight regulators, especially mercaptans; aliphatic, cycloaliphatic and/or aromatic halogenated and/or nonhalogenated hydrocarbons; alkanols and/or alkylamines having at least 12 carbon atoms in the alkyl radical; organosilanes and/or organosiloxanes;
vegetable, animal, semisynthetic and/or synthetic oils;
hydrophobic dyes. Further examples of suitable hydrophobic compounds, or costabilizers, and the amounts in which they are advantageously used, are disclosed in German patent application DE-A-196 28 142, page 4, lines 37 to 59.
In terms of molecular weight and the molecular weight distribution, the (co)polymers formed from the monomers (A) are not subject to ar_y restrictions whatsoever.
Advantageously, however, the (co)polymerization is conducted so as to result in a molecular weight distribution Mw/Mn, measured by gel permeation chromatography using polystyrene as standard, of 5 12, with particular preference <_ 10, and in particular <_ 7.
Suitable reactors for the (co)polymerization processes are the customary and known stirred tanks, stirred tank cascades, tube reactors, loop reactors or Taylor reactors, as described, for example, in the patents DE-B-1 071 241 or EP-A-0 498 583 or in the article by K.
Kataoka in Chemical Engineering Science, Volume 50, No.
9, 1995, pages 1409 to 1416. The free-radical (co)polymerization is preferably conducted in stirred tanks or Taylor reactors, the Taylor reactors being ~

configured such that the conditions of Taylor flow are met over the entire length of the reactor, even if the kinematic viscosity of the reaction medium alters greatly - in particular, increases - as a result of the (co)polymerization.
In accordance with the invention, the (co)polymerization is conducted in an aqueous medium.
The aqueous medium comprises essentially water. In addition to the above-detailed crosslinking agents, emulsifiers and/or protective colloids and/or hydrophobic compounds, the aqueous medium may also comprise customary and known additives and/or other dissolved, solid, liquid or gaseous, organic and/or inorganic, low and/or high molecular mass substances, provided the latter do not adversely affect or even inhibit the (co)polymerization. For the purposes of the present invention, the term "minor amount" means an amount which does not destroy the aqueous character of the aqueous medium.
Alternatively, the aqueous medium may also comprise straight water.
The (co)polymerization is advantageously conducted at temperatures above room temperature, preference being given to the choice of a temperature range of from 30 ' CA 02394029 2002-06-10 to 95°C, with very particular preference from 5U to 90°C.
When using particularly volatile monomers (A) the (co)polymerization may also be conducted under pressure, preferably under from 1.5 to 3000 bar, with particular preference from 5 to 1500 and, in particular, from 10 to 1000 bar. In specific cases, temperatures higher than 95°C may be used here. Use may be made in this context of the regimes described in German patent application DE-A-196 28 142, page 4, lines 6 to 36.
In accordance with the invention, the (co)polymer-ization is conducted in a microemulsion or miniemulsion, in particular a miniemulsion. In this case the average particle diameter of the emulsified monomer droplets is below 500 nm. It is preferably from 10 to 500 nm, more preferably from 50 to 400 nm, and with very particular preference from 100 to 300 nm.
Said particle diameter is the so-called z-average particle diameter, which is determined by means of photon correlation spectroscopy in accordance with the principle of dynamic, quasielastic light scattering.
For this purpose use may be made, for example, of a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments or a PCS Malvern Zetasizer 1000.
The measurement is normally made on an aqueous emulsion containing 0.01% by weight of the emulsified monomer droplets. The aqueous emulsion further comprises, in the aqueous phase, the corresponding monomers in dissolved form (up to saturation), so that the emulsified monomer droplets do not break up.
The process of the invention may be performed so as to give the bimodal particle size distribution described above. Methods of producing bimodal particle size distributions are customary and known in the technological field in question here. It is preferred to use the seed method described in German patent application DE-A-196 28 142, page 5, lines 31 to 49.
The preparation of the miniemulsion as part of the process of the invention has no particular features as regards method, but instead takes place in accordance with the customary and known methods of dispersing or emulsifying in a high shear field. Examples of suitable methods are described in the patents DE-A-196 28 142, page 5, lines 1 to 30, DE-A-196 28 143, page 7, lines to 58, or EP-A-0 401 565, lines 27 to 51.
An essential advantage of the primary dispersions of the invention is that they can be used per se as 25 coating materials of the invention, preferably surfacers, solid-color topcoat, aqueous basecoat and clearcoat materials, in particular as clearcoat materials. For these end uses, at least one conventional and known additive in effective amounts ' CA 02394029 2002-06-10 may be added to the primary dispersions of the invention before, during and/or after their preparation. Before or during the preparation of the primary dispersions of the invention, the only additives added are those which do not disrupt, or even totally inhibit, the miniemulsion polymerization. The general technical knowledge of the skilled worker allows him or her to identify such additives.
Preferably, said additives are added after the preparation of the primary dispersions of the invention.
Examples of suitable additives are pigments, as described in Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, pages 176, "Effect pigments";
pages 380 and 381 "Metal oxide-mica pigments" to "Metal pigments"; pages 180 and 181, "Iron blue pigments" to "Black iron oxide"; pages 451 to 453, "Pigments" to "Pigment volume concentration"; page 563, "Thioindigo pigments"; and page 567, "Titanium dioxide pigments".
Pigments are used when the coating materials of the invention are used as surfacers, solid-color topcoat or aqueous basecoat materials, but in particular as aqueous basecoat materials in the context of the so-called wet-on-wet technique (cf., for example, European patent 0 089 497), to produce multicoat color and/or effect paint systems.

~

_ 3g _ Further examples of suitable additives which can be used both in the pigmented coating materials and in the unpigmented coating materials are additional binders such as oligomeric and polymeric, thermally curable, linear and/or branched poly(meth)acrylates or acrylate copolymers of block, comb and/or random structure, especially those described in the patent DE-A-197 36 535, polyesters, especially those described in the patents DE-A-40 09 858 or DE-A-44 37 535, alkyds, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth)acrylate diols, partially hydrolyzed polyvinyl esters, poly-urethanes and acrylated polyurethanes, as described in the patents EP-A-0 521 928, EP-A-0 522 420, EP-A-0 522 419, EP-A-0 730 613 or DE-A-44 37 535, or polyureas.
Further examples of suitable additives are customary and known coating additives such as organic and inorganic fillers, thermally curable reactive diluents, low-boiling and/or high-boiling organic solvents ("long solvents"), UV absorbers, light stabilizers, free-radical scavengers, thermally labile free-radical initiators, crosslinking catalysts, devolatilizers, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, leveling agents, film-forming auxiliaries, rheology control additives, or flame retardants. Further examples of suitable paint additives are described in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.
If the coating materials of the invention are to be curable with actinic radiation as well (dual cure), they comprise additives curable with actinic radiation.
Said actinic radiation may comprise electromagnetic radiation such as near infrared (NIR), visible light, W light or X-rays, or corpuscular radiation such as electron beams. Examples of suitable additives curable with actinic radiation are known from German patent DE-C-197 09 467.
In terms of method, the application of the coating materials of the invention has no special features, but instead can be carried out by all customary application methods, such as spraying, knife coating, brushing, flow coating, dipping, trickle coating or roller coating, for example. It is preferred to use spray application methods, such as for example compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot air spraying, for example.
Suitable substrates are all surfaces to be coated which are not damaged by curing of the coatings present on them with application of heat; examples include metals, plastics, wood, ceramic, stone, textile, fiber " CA 02394029 2002-06-10 composites, leather, glass, glass fibers, glasswool and rockwool, mineral-bound and resin-bound building materials, such as plasterboard and cement slabs or roof shingles, and also assemblies of these materials.
Accordingly, the coating material of the invention is also suitable for applications outside of automotive ..
finishing, especially for the coating of furniture and for industrial coating, including coil coating, container coating and the impregnation or coating of electrical components. In the context of industrial coatings, it is suitable for coating virtually- all parts for private or industrial use, such as radiators, domestic appliances, small metal parts such as nuts and bolts, hub caps, wheel rims, packaging, or electrical components such as motor windings or transformer windings.
In the case of electrically conductive substrates it is possible to use primers produced in a customary and known manner from electrodeposition (ED) coating materials. Suitable for this purpose are both anodic (AED) and cathodic (CED) electrodeposition coating materials, but especially CED. Unfunctionalized and/or apolar plastic surfaces can be subjected to conventional pretreatment before coating, such as with a plasma or by flaming, or may be provided with an aqueous primer.

The method of curing the applied coating materials of the invention also has no special features, but instead takes place in accordance with the customary and known thermal methods such as heating in a forced air oven or irradiation with IR lamps, which in the case of dual cure may be supplemented by exposure to actinic radiation. In this context it is possible to use radiation sources such as high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open up a radiation window up to 405 nm; or electron beam sources.
The resultant coatings of the invention, especially the single-coat or multicoat color and/or effect paint systems and clearcoats of the invention, are easy to produce and have outstanding optical properties and very high chemical resistance and weathering stability.
Accordingly, the substrates of the invention, comprising at least one coating of the invention, are of particularly high service value and have a particularly long service life, which makes them particularly attractive, economically and technically, for producers and users.
Example 1 The preparation of a primary dispersion of the invention and of a coating material of the invention by the process of the invention ~

' - 38 -For the implementation of example 1 an emulsifier was first dissolved in water. Thereafter, the olefinically unsaturated monomers (A), the blocked polyisocyanate, and an oil-soluble initiator were mixed with one another. The resulting organic solution and the solution of the emulsifier were converted into a milky emulsion over the course of 40 seconds using an Ultraturrax, at room temperature. The resultant preemulsion was stable for several minutes, i.e., did not exhibit phase separation and could therefore be processed further without problems to give the fine miniemulsion, using a high-pressure homogenizer. To prepare the miniemulsion the preemulsion was introduced into the supply vessel of a pressure release homogenizer and an emulsification was carried out in circulation mode for 10 minutes under maximum pressure, with cooling. Following emulsification, the miniemulsion had particle sizes in the range from 100 nm to 500 nm and contained 40% by weight of monomer mixture and polyisocyanate (in 100% form), based on the total amount of the respective miniemulsion, and was stable on storage for several weeks.
Table 1 gives an overview of the starting materials used for the miniemulsions. of the amounts in which they were used, and of the z-average particle diameter of the monomer droplets, which was determined by means of photon correlation spectroscopy in accordance with _ 30 _ the principle of dynamic, qudsielastic light scattering, using a PCS Malvern Zetasizer 1000.
The miniemulsion was transferred to a suitable steel reactor and heated slowly to 80°C with stirring. At this temperature the miniemulsion was stirred until the solids content of the resultant primary dispersion of the invention showed no further increase. The primary dispersion of the invention was stable to sedimentation over several weeks.
Table 1 gives an overview of the polymerization time, the theoretical glass transition temperature Tg, calculated by the method of Fox, of the (co)polymer present in the primary dispersion of the invention, its hydroxyl number, its molecular weight, and the polydispersity of its molecular weight distribution, and also the z-average particle diameter (measured using a PCS Malvern Zetasizer 1000), the solids content, and the pH of the primary dispersion of the invention.
The primary dispersion of the invention was knife coated onto glass plates, in a wet film thickness of 150 ~.m, and baked for 30 minutes at 145°C, 160°C and 180°C. The results set out in Table 1 for the methyl ethyl ketone test demonstrate that the resultant coating of the invention had a particularly high solvent stability.

Table l: Material composition and properties of the miniemulsion of the invention, polymerization conditions, material composition and properties of the primary dispersion of the invention, and solvent stability of the coating of the invention Example 1 Miniemulsion:

Compositon (parts by weight):

Emulsifiera~ ~ 0.521 Methyl methacrylate 16.95 n-Butyl methacrylate 13.69 Styrene 16.29 Hydroxypropyl methacrylate 18.25 Blocked polyisocyanateb~ 34.29 OH NCO ratio 1:l Particle diameter (nm) 146 Polymerization:

Initiator~ (parts by weight per 100 parts by weight of emulsifier, monomer mixture and blocked polyisocyanate) 3.26 Polymerization time (h) 6.0 Primary dispersion:

Solids contentd~ (% by wt.) 39 Particle diameter (nm) 157 PH 6.0 Sediment, wet (g) 0 Copolymer:

Number-average molecular weight Mne~ (daltons) 102.700 Mass-average molecular weight Mwe~ (daltons) ' 557.400 Polydispersity Mw/Mn 5.43 Glass transition ' temperature (theoretical, acc. to Fox) (C) 74.55 Hydroxyl number (mg KOH/g) 109 Clearcoat:

MEK DSf~ (145/160/180C) 5/43/>200 a) Sodium lauryl sulfate, Texapon~ from Henkel;
b) dimethylpyrazole-blocked commercial polyiso-cyanate;
c) tert-butyl peroxyethylhexanoate;
d) 130°C, one hour;
e) measured by gel permeation chromatography with polystyrene as internal standard;
f) number of double strokes with a cotton pad soaked with methyl ethyl ketone;

Claims (15)

Claims

1. Aqueous primary dispersions and coating materials comprising dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter <= 500 nm, preparable by free-radical microemulsion or miniemulsion polymerization of at least one olefinically unsaturated monomer (A) in the presence of at least one hydrophobic crosslinking agent for the (co)polymer resulting from the monomer or monomers (A).

2. A process for preparing aqueous primary dispersions and coating materials comprising dispersed and/or emulsified, solid and/or liquid polymer particles and/or dispersed solid core-shell particles having a diameter <= 500 nm, in which at least one olefinically unsaturated monomer (A) is subjected to free-radical (co)polymerization in a microemulsion or miniemulsion in the presence of at least one hydrophobic crosslinking agent for the (co)polymer resulting from the monomer or monomers (A).

3. The aqueous primary dispersions and coating materials as claimed in claim 1 and the process as claimed in claim 2, characterized in that said monomer (A), or at least one of said monomers (A), comprises at least one reactive functional group which is able to enter into crosslinking reactions with the complementary reactive functional groups of said crosslinking agent.

4. The aqueous primary dispersions and coating materials as claimed in claim 1 or 3 and the process as claimed in claim 2 or 3, characterized in that monomers (A) used are a1) substantially acid-group-free (meth)acrylic esters;
a2) monomers which carry per molecule at least one hydroxyl, thio, amino, alkoxymethylamino, carbamate, allophanate or imino group, in particular a hydroxyl, amino or alkoxymethylamino group, and are substantially free from acid groups;
a3) monomers which carry per molecule at least one acid group which can be converted into the corresponding acid anion group;
a4) vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule;
a5) reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of an alpha-branched monocarboxyiic acid having 5 to 18 carbon atoms per molecule;
a6) cyclic and/or acyclic olefins;
a7) (meth)acrylamides;
a8) monomers containing epoxide groups;
a9) vinylaromatic hydrocarbons;
a10) nitriles;
all) vinyl compounds, especially vinyl halides and/or vinylidene dihalides, N-vinylpyrrolidone, N-vinylamides, vinyl ethers and/or vinyl esters;
a12) allyl compounds, especially allyl ethers and allyl esters;
a13) polysiloxane macromonomers having a number-average molecular weight Mn of from 1 000 to 40 000 and having on average from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; and/or a14) acryloyloxysilane-containing vinyl monomers, preparable by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with methacrylic acid and/or hydroxyalkyl esters of (meth)acrylic acid;
with the proviso that the monomers (a3) are not used as sole monomers (A).

5. The aqueous primary dispersions and coating materials as claimed in any of claims 1, 3 or 4 and the process as claimed in any of claims 2 to 4, characterized in that said crosslinking agents comprise blocked polyisocyanates, tris(alkoxycarbonylamino)-triazines and/or fully etherified amino resins.

6. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 5 and the process as claimed in any of claims 2 to 5, characterized in that said monomer or monomers (A) is or are copolymerized in the presence of emulsifiers and/or protective colloids.

7. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 6 and the process as claimed in any of claims 2 to 6, characterized in that said monomer or monomers (A) is or are copolymerized in the presence of at least one further hydrophobic compound other than the crosslinking agent.

8. The aqueous primary dispersions and coating materials and the process as claimed in claim 7, characterized in that the hydrophobic compounds comprise water-insoluble low molecular mass, oligomeric or polymeric substances.

9. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 8 and the process as claimed in any of claims 2 to 8, characterized in that the controlled free-radical microemulsion or miniemulsion polymerization is initiated by water-soluble and/or oil-soluble initiators which form free radicals.

10. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 9 and the process as claimed in any of claims 2 to 9, characterized in that the dispersed core-shell particles comprise cores of organic solids and shells of polymers containing at least one monomer (A) and at least one monomer (B) in copolymerized form.

11. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 10 and the process as claimed in any of claims 2 to 10, characterized in that the cores of the core-shell particles are prepared by free-radical microemulsion or miniemulsion polymerization.

12. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 11, characterized in that they comprise at least one additive.

13. The aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 12, characterized in that they comprise additives curable with actinic radiation.

14. The use of the aqueous primary dispersions and coating materials as claimed in any of claims 1 or 3 to 13 or of the aqueous primary dispersions and coating materials prepared by the process as claimed in any of claims 2 to 13 in automotive OEM finishing and refinishing, industrial coating, including coil coating, container coating and the coating of electrical components, and furniture coating.

15. Primed or unprimed substrates comprising at least one single-coat or multicoat clearcoat and/or at least one single-coat or multicoat color and/or effect paint system based on the aqueous primary dispersions and coating materials as claimed in any of claims l or 3 to 14 or on the aqueous primary dispersions and coating materials prepared by the process as claimed in any of claims 2 to 11.