Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Definitions

• the present invention relates to new aqueous primary dispersions and coating materials which contain dispersed and / or emulsified, solid and / or liquid polymer particles and / or dispersed solid core-shell particles with a particle diameter> 00 nm.
• the present invention relates to a new process for the preparation of the new aqueous primary dispersions and coating materials by controlled radical micro- and mini-emulsion polymerization.
• the present invention relates to the use of the new aqueous primary dispersions and coating materials for the production of single- or multi-layer clearcoats and single- or multi-layer color and / or effect coatings in automotive initial and refinishing, industrial painting, including container coating, coil Coating and coating of electrical components, and furniture painting.
• Micro and mini emulsions are dispersions of water, an oil phase and one or more surface-active substances which have droplet sizes of 5 to 50 nm (microemulsions) or of 50 to 500 nm. Microemulsions are considered to be thermodynamically stable, whereas the mini emulsions are considered to be metastable (cf. Emulsion Polymerization and Emulsion Polymers, editors. PA Lovell and Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pages 700 and following; Mohamed S.
• aqueous primary dispersions with the aid of radical mini-emulsion polymerization
• the monomers can be copolymerized in the presence of various low-molecular, oligomeric or polymeric hydrophobic substances, which are also referred to as costabilizers.
• hydrophobic, water-insoluble organic auxiliaries such as plasticizers, improvers of the stickiness of the resulting film, film-forming aids or other unspecified organic additives can be incorporated into the monomer droplets of the mini-emulsion.
• the use of the known aqueous primary dispersions for the production of coating materials is not apparent from the patents.
• Aqueous coating materials based on aqueous primary dispersions which contain solid core-shell particles and have been prepared by mini-emulsion 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.
• the known coating materials already have numerous advantageous properties, problems still arise which are associated with an inadequate distribution of the crosslinking agents in the aqueous dispersions. In particular, this means that a larger amount of crosslinking agents must be used than would be theoretically necessary. Unreacted crosslinking agents can then u. U. damage the application properties of the coatings made from the coating materials.
• Microencapsulation of hydrophobic organic solvents or of target materials such as biocides and herbicides in water-insoluble core-shell particles, produced by mini-emulsion polymerization, is known from the patents EP-A-0 203 724 or US-A-4,677,003.
• the (co) polymerization is not carried out in the presence of hydrophobic crosslinking agents for the (co) polymers formed from the monomers.
• the object of the present invention is to find new aqueous primary dispersions and coating materials containing dispersed and / or emulsified, solid and / or liquid polymer particles and / or dispersed solid core-shell particles of a particle diameter ⁇ 500 nm, which have the disadvantages of the prior art No longer have technology, but can be manufactured in a simple manner.
• the new aqueous primary dispersions and coating materials should contain crosslinking agents which are as finely divided as possible.
• the new aqueous primary dispersions and coating materials containing dispersed and or emulsified, solid and / or liquid polymer particles and / or dispersed solid core-shell particles of a particle diameter ⁇ 500 n have been found, which by radical micro- or miniemulsion polymerization of at least one olefinically unsaturated Monomer (A) can be prepared in the presence of at least one hydrophobic crosslinking agent for the (co) polymer resulting from the monomer or the monomers (A) and are referred to below for the sake of brevity as “primary dispersions or coating materials according to the invention”.
• aqueous primary dispersions and coating materials comprising dispersed and / or emulsified, solid and / or liquid polymer particles and / or dispersed solid core-shell particles of a particle diameter ⁇ 500 nm, was found, in which 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 the monomers (A) in a micro- or mini-emulsion, radically (co) polymerized and in the following for the sake of brevity as "inventive method" referred to as.
• the property hydrophilic means the constitutional property of a molecule or a functional group to penetrate into the aqueous phase or to remain therein.
• the property hydrophobic is understood to mean the constitutional property of a molecule or a functional group to be exophilic towards water, i.e. i.e. they show a tendency not to penetrate water or to leave the aqueous phase.
• the primary dispersions and coating materials contain dispersed and / or emulsified solid and / or liquid polymer particles and / or dispersed solid core-shell particles.
• the size of the polymer particles or the dispersed core-shell particles results directly from the process according to the invention described below.
• the average particle diameter is less than 500 nm. It is preferably 10 to 500 nm, preferably 50 to 400 nm and very particularly preferably 100 to 350 nm
• Primary dispersions and coating materials according to the invention have an advantageously high solids content, for example of more than 20% by weight, preferably more than 30% by weight. Solids contents of over 40% by weight can even be achieved.
• the primary dispersions and coating materials according to the invention have a low viscosity even with a high solids content.
• the core-shell particles to be used according to the invention result from the graft copolymerization of organic solids and the monomers (A) to be used according to the invention described below.
• the 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, WO 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 can also be produced by the process according to the invention.
• the primary dispersions and coating materials according to the invention can also have a bimodal particle size distribution in which 0.1 to 80% by weight, in particular 1.0 to 50% by weight, of the (co) polymer resulting from the monomers (A) have a particle size, determined with an analytical ultracentrifuge, of 20 to 500 nm, in particular 50 to 300 nm, and 20 to 99.9% by weight, in particular 50 to 99% by weight of the (co) polymer, a particle size of Have 200 to 1,500 nm, in particular 300 to 900 nm, the particle sizes differing by at least 50 nm, in particular by at least 100 nm, very particularly preferably by at least 200 nm.
• the first starting compound essential to the invention for the primary dispersions or coating materials according to the invention or for the process according to the invention is at least one olefinically unsaturated monomer (A).
• At least one monomer (A) is preferably used here which contains reactive functional groups which can undergo crosslinking reactions with the complementary reactive functional groups of the crosslinking agents.
• suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview.
• the variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
• the selection of the respective complementary groups is based on the one hand on the fact that they do not undergo any undesired reactions when storing primary dispersions or coating materials according to the invention and / or, if appropriate, they must not interfere or inhibit curing with actinic radiation, and on the other hand in which temperature range the crosslinking to be held.
• Crosslinking temperatures of 100 ° C. to 180 ° C. are preferably used in the coating materials according to the invention.
• al) essentially acid-group-free (meth) acrylic acid esters such as (meth) acrylic acid alkyl or cycloalkyl esters with up to 20 carbon atoms in the alkyl residue, in particular methyl, ethyl, propyl, n-
• Mn molecular weight
• These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol,
• minor amounts of higher-functional monomers are understood to mean those amounts which do not lead to crosslinking or gelling of the copolymers (A), unless one wishes to produce crosslinked polymeric microparticles in a targeted manner.
• Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid which are derived from an alkylene glycol which is esterified with the acid or which can be obtained by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide, in particular hydroxyalkyl esters acrylic acid,
• a3) monomers which carry at least one acid group which can be converted into the corresponding acid anion group per molecule such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester,
• the monomers (a3) are not used as the sole monomers (A), but always in conjunction with other monomers (A) and only in such small amounts that the monomers (a3) do not fall outside the droplets polymerize the mini emulsion.
• 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 can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
• paraffinic hydrocarbons such as mineral oil fractions
• Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
• the vinyl esters (a4) can also be used in a manner known per se from the acids, for example by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom, but especially Vers atic® acids, are particularly preferably used.
• Methacrylic acid which is then reacted during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, which is branched in the alpha position.
• Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbones, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.
• (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl-, N, N-dimethyl-, N-ethyl-, N, N-diethyl-, N-propyl-, N, N-dipropyl-, N- Butyl, N, N-dibutyl, N-cyclohexyl, N, N-cyclohexyl-methyl and / or N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl ) -, N-ethoxymethyl and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide;
• Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid.
• vinylaromatic hydrocarbons such as styrene, alpha-alkylstyrenes, in particular alpha-methylstyrene, and or vinyltoluene; vinylbenzoic
• Methyl vinylbenzoic acid (all isomers), N, N-diethylamino-alpha-methylstyrene (all isomers) vmd / or p-vinylbenzenesulfonic acid.
• alO nitriles such as acrylonitrile and / or methacrylonitrile.
• vinyl compounds in particular vinyl 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-vinylimidazole or N-vinylpyrrohdon; 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 the 2-
• allyl compounds in particular allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
• polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and on average 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular
• Polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular
• each of the above-mentioned monomers (A), with the exception of the monomer (a3), can be polymerized on its own, which results in polymers. According to the invention, however, it is advantageous to use at least two monomers (A) because this allows the profile of properties of the resulting copolymers to vary very widely in a particularly advantageous manner and can be adapted to the particular intended use of the primary dispersions according to the invention or of the coating materials according to the invention.
• the monomers (A) are preferably selected so that (meth) acrylate (co) polymers result whose profile of properties is primarily determined by the (meth) acrylates described above. Vinylaromatic hydrocarbons (a9), in particular styrene, are then preferably used as comonomers (A).
• the monomers (A) to be used according to the invention are reacted with one another to form (co) polymers in the presence of at least one water- and / or oil-soluble initiator which forms free radicals.
• 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; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; KaHum, sodium or ammonium peroxodisulfate; Azo initiators, for example azo dinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide. Combinations of the initiators described above can also be used.
• Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (A) and the initiator, particularly preferably 0.2 to 20% by weight, very particularly preferably 0.5 is up to 15 wt .-% and in particular 1.0 to 10 wt .-%.
• the monomers (A) are copolymerized in the presence of at least one hydrophobic crosslinking agent.
• the hydrophobic crosslinking agents preferably contain the reactive functional groups described above, the complementary reactive functional groups present in the resulting (co) polymers
• crosslinking reactions examples include blocked polyisocyanates, tris (alkoxycarbonylamino) triazines or completely etherified aminoplast resins.
• blocking agents for the preparation of the blocked polyisocyanates are the blocking agents known from US Pat. No. 4,444,954:
• phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol,
• lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam or ß-propiolactam
• active methylenic compounds such as diethyl malonate, dimethyalononate, ethyl or methyl acetoacetate or acetylacetone;
• alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
• mercaptans such as butyl mercaptan, hexyl mercaptan, t-buryl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
• acid amides such as acetoanilide, acetoanisidinamide, acrylamide, mexhacrylamide, acetic acid amide, stearic acid amide or benzamide;
• imides such as succinimide, phthalimide or maleimide
• amines such as diphenylamine, phenylnaphxhylamine, xylidine, N-phenylxyhdin, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
• imidazoles such as imidazole or 2-ethylimidazole
• ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
• xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone
• imines such as ethyleneimine
• xiii) oxides such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oxime;
• xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite
• xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate
• suitable organic polyisocyanates to be blocked are in particular the so-called lacquer polyisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups.
• polyisocyanates to be blocked are found in "Methods of Organic Chemistry", 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.
• the isocyanate group-containing polyurethane prepolymers are suitable, which can be prepared by reacting polyols with an excess of polyisocyanates and which are preferably low-viscosity.
• suitable polyisocyanates to be blocked are polyisocyanates having isocyanurate, biuret, AUophanat, iminooxadiazmdione, urethane, urea and / or uretdione groups.
• Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, such as, for example, trimethylolpropane and glycerol.
• Aliphatic or cycloaliphatic polyisocyanates in particular hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, diisocyanates derived from dimer fatty acids, such as those sold under the trade name DDI 1410 by the Henkel company, and in the patent specifications from Henkel DO 97/49745 and WO 97/49747 describe in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -l-pentylcyclohexane; or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoexh-1 -yl) cyclohe
• aminoplast resins examples include melamine resins, guanamine resins or urea resins. Any aminoplast resin suitable for clearcoats or a mixture of such aminoplast resins can be used here.
• the particularly suitable tris (alkoxycarbonylam_mo) triazines had the following formula:
• tris (alkoxycarbonylamino) xriazines examples include butoxycarbonylamino) xriazines, and azines.
• methyl-butyl mixed esters the butyl-2-ethylhexyl mixed esters and the butyl esters are advantageous. Compared to the pure methyl ester, these have the advantage of better solubility in polymer melts and also have less tendency to crystallize out.
• the blocked polyisocyanates offer particular advantages and are therefore used with very particular preference in accordance with the invention.
• the ratio of the monomers (A) which contain complementary reactive functional groups to the crosslinking agents can vary very widely. According to the invention, it is advantageous if the molar ratio of complementary reactive functional groups in (A) to complementary reactive functional groups in the crosslinking agents is 5.0: 1.0 to 1.0: 5.0, preferably 4.0: 1 , 0 to 1.0: 4.0, particularly preferably 3.0: 1.0 to 1.0: 3.0 and in particular 2.0: 1 to 1: 2.0. Particular advantages result if the molar ratio is approximately or exactly 1.0: 1.0.
• the monomers (A) to be used according to the invention are preferably copolymerized in the presence of emulsifiers and / or protective colloids.
• emulsifiers and / or protective colloids examples of suitable emulsifiers and / or protective colloids and the amounts in which they are advantageously used can be found in German patent application DE-A-196 28 142, page 3, pages 8 to 48.
• the (co) polymerization of the monomers (A) to be used according to the invention may also include hydrophobic compounds which differ materially from the crosslinking agents. These hydrophobic compounds are also called costabilizers by experts.
• hydrophobic compounds were water-insoluble, low molecular weight, oligomeric or polymeric substances.
• suitable Hydrophobic compounds are esters of 3 to 6 carbon atoms containing alpha, beta-monoolefinically unsaturated carboxylic acids with alcohols with 12 to 30 carbon atoms in the alkyl radical; Esters of vinyl and / or allyl alcohol with 12 to 30 carbon atoms in the molecule having alkane monocarboxylic, sulfonic and or phosphonic acids; Amides of 3 to 6 carbon atoms containing alpha, beta-monoolefinically unsaturated carboxylic acids with alkylamines with 12 to 30 carbon atoms in the alkyl radical; Macromomers based on olefinically unsaturated compounds with an average of at least one, in particular terminal, olefinically unsaturated group in the molecule; Polysiloxane macromonomers with an average of at least one, in particular terminal, olefinically unsatur
• the (co) polymers formed from the monomers (A) are not subject to any restrictions.
• the (co) polymerization is advantageously carried out in such a way that a molecular weight distribution Mw / Mn measured with
• the reactors for the (co) polymerization processes are the customary and known stirred tanks, stirred tank cascades, tubular 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 carried out in stirred tanks or Taylor reactors, the Taylor reactors being designed in such a way that the conditions of the Taylor flow are met over the entire length of the reactor, even if the kinematic viscosity of the reaction medium changes greatly as a result of the (co) polymerization , especially increases.
• the (co) polymerization is carried out in an aqueous medium.
• the aqueous medium essentially contains water.
• the aqueous medium can comprise customary and known additives and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or high molecular weight substances included, provided that these do not negatively influence or even inhibit the (co) polymerization.
• the term “minor amount” is understood to mean an amount which does not cancel out the aqueous character of the aqueous medium.
• the aqueous medium can also be pure water.
• the (co) polymerization is advantageously carried out at temperatures above room temperature, a temperature range from 30 to 95 ° C., very particularly preferably 50 to 90 ° C., being selected. If particularly volatile monomers (A) are used, the (co) polymerization can also be carried out under pressure, preferably under 1.5 to 3,000 bar, particularly preferably 5 to 1,500 and in particular 10 to 1,000 bar. In individual cases, temperatures higher than 95 ° C can be used.
• the procedures described in German patent application DE-A-196 28 142, page 4, lines 6 to 36 can be used here.
• the (co) polymerization is carried out in a micro- or mini-emulsion, in particular a mini-emulsion.
• a micro- or mini-emulsion in particular a mini-emulsion.
• Particle diameter of the emulsified monomer droplets below 500 nm.
• the particle diameter is the so-called z-average particle diameter, which is determined by means of photon correlation spectroscopy according to the principle of dynamic, quasi-elastic light scattering becomes. For example, a
• PCS Malvem Zetasizer 1000 can be used. The measurement is usually carried out on an aqueous emulsion which contains 0.01% by weight of the emulsified monomer droplets. The aqueous emulsion also contains in the aqueous
• the process according to the invention can be carried out in such a way that the bimodal particle size distribution described above results.
• Methods for producing bimodal particle size distributions are customary and known in the technological field in question.
• the seed method described in German patent application DE-A-196 28 142, page 5, lines 31 to 49 is preferably used.
• the production of the mini emulsion in the process according to the invention has no special features in terms of method, but instead takes place in accordance with the customary and known processes of dispersion or emulsification in a high shear field. Examples of suitable processes are described in the patents DE-A-196 28 142, page 5, lines 1 to 30, DE-A-196 28 143, page 7, pages 30 to 58, or EP-A-0 401 565, lines 27 to 51.
• Solid-color top coats water-based lacquers and clear lacquers, in particular clear lacquers, can be used.
• the invention can be used.
• Suitable additives are pigments, such as those found in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, pages 176, "Effect Pigments”; Pages 380 and 381 "Metal oxide ghmer pigments” to “Metal pigments”; Pages 180 and 181, “Iron Blue Pigments” to “Iron Oxide Black”; Pages 451 to 453, “Pigments” to "Pigments Volume Concentration”; Page 563, “Thioindigo Pigments”; and page 567, "Titanium Dioxide Pigments”; to be discribed.
• Pigments are used when the coating materials according to the invention are used as fillers, solid-color topcoats or waterborne basecoats, but especially as waterborne basecoats within the scope of the so-called wet-on-wet process (see, for example, European Patent 0 089 497) can be used to produce multicoat paint and / or effect coatings.
• additives which can be used both in the pigmented lacquers and in the unpigmented ones are additional binders such as oligomeric and polymeric, thermally curable, linear and / or branched and / or block-like, comb-like and / or statistically constructed poly ( meth) acrylates or acrylate copolymers, in particular the polyesters described in the patent DE-A-197 36 535, in particular the alkyds, acrylated polyesters, polylactones described in the patents DE-A-40 09 858 or DE-A-44 37 535 , Polycarbonates, polyethers, epoxy resin-ainine adduct,
• additional binders such as oligomeric and polymeric, thermally curable, linear and / or branched and / or block-like, comb-like and / or statistically constructed poly ( meth) acrylates or acrylate copolymers, in particular the polyesters described in the patent DE-A-197 36 535, in particular the alkyds
• suitable additives are customary and known paint additives such as organic and inorganic fillers, thermally curable reactive thinners, low-boiling and / or high-boiling organic solvents (“long solvents”), UV absorbers, light stabilizers, radical scavengers, thermally labile radical initiators, and catalysts for crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, flow control agents, film-forming aids, rheology-controlling additives or flame retardants
• suitable paint additives are given in the textbook "Paint Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York , 1998.
• the coating materials of the invention are also to be curable with actinic radiation (dual cure), they contain additives which are curable with actinic radiation.
• Actinic radiation can be electromagnetic radiation such as near infrared (NIR), visible light, UV light or X-rays, or corpuscular radiation such as electron beam radiation. Examples of suitable additives curable with actinic radiation are known from German patent DE-C-197 09 467.
• the application of the coating materials according to the invention has no peculiarities, but can be carried out by all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
• Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as, for example, hot air hot spraying.
• Suitable substrates are all surfaces to be painted, which are not damaged by curing the paintwork thereon using heat; these are e.g. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as plaster and cement boards or roof tiles, as well as composites of these materials.
• the coating material of the invention is also suitable for applications outside of automotive painting. He is particularly suitable for painting furniture and industrial painting, including coil coating, container coating and the impregnation or coating of electrical components. As part of industrial painting, it is suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as Screws and nuts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.
• primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
• ETL electrocoat materials
• KTL cathodic
• these can be pretreated in a known manner, such as with a plasma or with flame, or provided with a hydro primer before coating.
• the curing of the applied coating materials according to the invention also has no special features in terms of method, but instead takes place according to 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 can also be supplemented by irradiation with actinic radiation , Radiation sources such as high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window up to 405 nm, or electron beam sources can be used.
• the resulting coatings according to the invention in particular the single- or multi-layer color and / or effect coatings and clearcoat quantities according to the invention are simple to produce and have excellent optical properties and very high resistance to chemicals and weathering. Accordingly, the substrates according to the invention which contain at least one coating according to the invention are of a particularly high utility value and a particularly long service life, which makes them economically and technically particularly attractive for manufacturers and users. example 1
• Example 1 To carry out Example 1, an emulsifier was first dissolved in the water. The olefinically unsaturated monomers (A), the blocked polyisocyanate and an oil-soluble initiator were then mixed together. The resulting organic solution and the emulsifier solution were converted into a milky emulsion using an Ultraturrax at room temperature within 40 seconds. The resulting pre-emulsion was stable for a few minutes, i.e. that is, they had no phase separation and could therefore be further processed without problems using a high-pressure homogenization unit to form the finely divided mini-emulsion.
• the pre-emulsion was placed in the reservoir of a pressure homogenizer and emulsified for 10 minutes at maximum pressure in a circular manner with cooling. After the emulsification, the miniemulsion had particle sizes in the range from 100 nm to 500 nm and a content of monomer mixture and polyisocyanate (100%) of 40% by weight, based on the total amount of the respective miniemulsion, and was stable in storage for several weeks.
• Table 1 provides an overview of the miniemulsion starting products used, the amounts in which they were used, and the z-average particle diameter of the monomer droplets, which is determined by means of photon correlation spectroscopy according to the principle of dynamic, quasi-elastic light scattering with a PCS Malvern Zetasizer 1000 has been.
• the miniemulsion was transferred to a suitable steel reactor and slowly heated to 80 ° C. with stirring.
• the mini emulsion was stirred at this temperature until the solids content of the resulting primary dispersion according to the invention no longer increased.
• the primary dispersion according to the invention was stable over several weeks.
• Table 1 gives an overview of the polymerization time, the theoretical glass transition temperature Tg of the (co) polymer contained in the primary dispersion according to the invention, its hydroxyl number, its molecular weight and its non-uniformity in the molecular weight distribution and the z-average particle diameter (measured using a PCS Malvem Zetasizer 1000), the solids content and the pH of the primary dispersion according to the invention.
• the primary dispersion according to the invention was knife-coated onto glass plates with a wet film thickness of 150 ⁇ and baked at 145 ° C., 160 ° C. and 180 ° C. for 30 minutes.
• the results of the methyl ethyl ketone test listed in Table 1 demonstrate that the resulting coating according to the invention had a particularly high solvent stability.
• Table 1 Material composition and properties of the miniemulsion according to the invention, polymerization conditions, material composition and properties of the primary dispersion according to the invention and the solvent stability of the coating according to the invention
• Initiator c) (parts by weight per 100 parts by weight of emulsifier, monomer mixture and blocked polyisocyanate) 3.26
• Solids content d) (% by weight) 39 particle diameter (nm) 157 pH 6.0
• Copolymer number average molecular weight

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• Chemical & Material Sciences (AREA)
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• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
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• Application Of Or Painting With Fluid Materials (AREA)
• Polymerisation Methods In General (AREA)
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• 1999
  • 1999-12-11 DE DE1999159928 patent/DE19959928A1/de not_active Withdrawn
• 2000
  • 2000-11-08 AU AU11463/01A patent/AU1146301A/en not_active Abandoned
  • 2000-11-08 WO PCT/EP2000/011028 patent/WO2001042379A1/de not_active Application Discontinuation
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  • 2000-11-08 CA CA002394029A patent/CA2394029A1/en not_active Abandoned
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