EP3083844A1 - Procédé de production de formulations contenant un pigment et une substance de charge - Google Patents

Procédé de production de formulations contenant un pigment et une substance de charge

Info

Publication number
EP3083844A1
EP3083844A1 EP13815500.7A EP13815500A EP3083844A1 EP 3083844 A1 EP3083844 A1 EP 3083844A1 EP 13815500 A EP13815500 A EP 13815500A EP 3083844 A1 EP3083844 A1 EP 3083844A1
Authority
EP
European Patent Office
Prior art keywords
group
groups
acid
primary
monomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13815500.7A
Other languages
German (de)
English (en)
Inventor
Konstantinos Markou
Andreas NIEGEMEIER
Sabine Holtschulte
Jerome MOEBIUS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
BASF Coatings GmbH
Original Assignee
Henkel AG and Co KGaA
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA, BASF Coatings GmbH filed Critical Henkel AG and Co KGaA
Publication of EP3083844A1 publication Critical patent/EP3083844A1/fr
Withdrawn legal-status Critical Current

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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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/005—Carbon black
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/006—Metal
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/007—Metal oxide
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/007—Metal oxide
    • C09D17/008—Titanium dioxide
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C25D13/06—Electrophoretic coating characterised by the process with organic material with polymers

Definitions

  • the present invention relates to a process for the preparation of pigment and / or filler-containing formulations using aqueous cationically stabilized primary dispersions containing polymer particles having an average particle diameter of 5 to 500 nm (so-called polymerized "miniemulsions”) the
  • pigment pastes or filler pastes which contain pigments in high concentration in predispersed form.
  • Predispersion is generally carried out using polymeric binders which, on the one hand, are intended to wet the pigment surfaces and, on the other hand, have good compatibility with the coating systems in which the pastes are used later.
  • the binders used to prepare the pigment and / or filler preparation correspond to the principal binders of the paint systems in which they are used.
  • the principal binders of the pigmented and / or filler-containing paint systems are unsuitable for effectively disaggregating the pigments and / or fillers and preventing reagglomeration.
  • the use of so-called special friction resins in the preparation of the pigment and / or filler preparations is recommended.
  • the amine-modified aromatic epoxy resins frequently used as main binders in the production of electrodeposition paints are less suitable in terms of their wetting properties to wet pigment and / or filler surfaces.
  • Reibharze be used.
  • Electrocoating lacquers are aqueous coating agent systems which are applied cathodically or anodically, preferably cathodically, by the process of electrocoating.
  • the main binders used in cathodically depositable electrodeposition paints are generally aqueous dispersions based on epoxy-amine resins. In some cases, however, amine-functionalized acrylate resins are also used
  • WO 82/00148 discloses the preparation of cathodically depositable primary dispersions using cationically adjustable emulsifiers.
  • the emulsifiers can carry reactive groups, by means of which they can be incorporated into the polymeric resin system during the crosslinking reaction.
  • Explicit examples of emulsifiers are the acetic acid salts of fatty mono- and diamines such as primary tallow and oleylamines or the acetic acid salts of tallow and oleyl diamines. Tallow and oleylamines contain hydrocarbon chains having at least one carbon-carbon double bond. Also polymers
  • Emulsifiers can be used, such as an epoxy-phenol adduct which has been reacted with diethanolamine and cationically adjusted with acetic acid.
  • Ethoduomeen TM T13 is used, which is a tertiary amine with unsaturated
  • Mini-emulsions are dispersions of water, an oil phase and one or more surface-active substances, wherein the dispersed particles present have an average particle diameter of 5 to 500, preferably 25 to 500 and particularly preferably 50 to 500 nm. Mini-emulsions are considered to be metastable (See Emulsion Polymerization and Emulsion Polymers, Editors, PA Lovell and Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pp. 700ff, Mohamed S.
  • compositions such as electrodeposition paints.
  • aqueous primary dispersions by means of miniemulsion polymerization is known, for example, from international patent applications WO 82/00148 and WO 98/02466 or German patent applications DE 196 28 143 A1 and DE 196 28 142 A2.
  • the monomers can be copolymerized in the presence of different low molecular weight, oligomeric or polymeric hydrophobic substances or co-stabilizers (cf DE 196 28 142 A 2).
  • hydrophobic, sparingly soluble in water, organic aids such as plasticizers, film-forming aids such as coalescing agents, or other organic additives can be incorporated into the monomer droplets of the miniemulsion (see DE 196 28 143 A1).
  • WO 82/00148 describes the use of emulsifiers for stabilizing the emulsions disclosed therein.
  • Aminoethylmethacrylat monomers wear a positive surface charge and thereby stabilized in the dispersion.
  • the saturated cetyl methylammonium bromide can be used, which has a quaternary nitrogen atom and therefore carries a permanent positive charge. The positive charge is compensated in both cases by halide anions.
  • An object of the present invention is to provide a process for preparing a pigment and / or filler-containing formulation.
  • the formulations containing the pigment and / or filler obtainable by the process should be usable in aqueous coating compositions and give them improved long-term stability.
  • the aqueous coating compositions prepared therefrom should also have better film-forming properties than those known hitherto, so that they can be used more broadly than was hitherto possible.
  • an object of the present invention to provide an aqueous preparation which contains the pigment and / or filler-containing formulation of the present invention, and which can be used in particular in the field of electrocoating as a coating agent to improve the film formation of the electrodeposition coatings and to achieve increased corrosion protection of metallic substrates, in particular of aluminum substrates.
  • One of the objects of the present invention has been achieved by providing a process for preparing a pigment and / or filler-containing formulation, wherein one or more solids selected from the group of pigments and fillers with an aqueous, cationically stabilized
  • (I) dispersed polymer particles the have a Z-average particle diameter of 5 to 500, preferably 25 to 500 and particularly preferably 50 to 500 nm, and which are obtainable by emulsion polymerization of at least one olefinically unsaturated monomer (A), wherein the
  • R 1 is at least one aromatic group and at least one aliphatic group-containing radical having 15 to 40 carbon atoms, the at least one functional group selected from hydroxyl groups, thiol groups and primary or secondary
  • R 2 , R 3 and R 4 are independently identical or different, aliphatic radicals having 1 to 14 carbon atoms, and X® is the acid anion of an organic or inorganic acid HX,
  • the pigments and / or solids are mechanically comminuted.
  • primary dispersion is understood to mean polymer dispersions having a disperse disperse phase and having a clear phase boundary between disperse phase (polymer) and dispersant (water) produced by emulsion polymerization in emulsion polymerization therefore be stabilized electrostatically or sterically, that is brought into a thermodynamically metastable state (see, for example: B. Müller, U. Poth, paint formulation and paint formulation, Vincentz Network, Hannover, 2nd edition 2005). "Watery” in connection with the primary dispersion to be used according to the invention, but also those described below
  • Electrodeposition coating compositions herein means that the volatile portion, i. the volatile fraction of the primary dispersion or of the coating composition which preferably comprises more than 50% by weight of water when dried at a temperature of 180 ° C. for 30 minutes, more preferably more than 70% by weight and very particularly preferably more as 90 wt .-% consists of water.
  • miniemulsion is understood herein to mean those primary dispersions whose primary dispersion particles have an intensity-based Z-average particle diameter of 5 to 500, preferably 25 to 500 and particularly preferably 50 to 500 nm
  • Z-average particle diameter can be determined according to the principle of dynamic light scattering according to ISO 13321 and ISO 22412. For this example, a
  • Particle size determination is carried out at 25 ° C on a primary dispersion according to the invention diluted with demineralized water (0.1 to 0.5 ml of primary dispersion per 100 ml of demineralized water). The measurement takes place
  • Disposable cuvette The evaluation of the measurement is carried out by means of the standard software of the above-mentioned measuring device.
  • the emulsifiers (E) or (EQ) to be used according to the invention do not interfere with the course of (co) polymerization and do not lead to coagulation of the primary dispersions of the invention, but rather to the improved properties of the primary dispersions and of them prepared pigment and / or filler containing formulation and the aqueous preparations are significantly responsible.
  • the primary dispersions used according to the invention contain dispersed
  • Polymer particles The size of the polymer particles results directly from the
  • the primary dispersions preferably have a high solids content, for example of more than 20% by weight, preferably more than 30% by weight. It can even be achieved solids contents of over 40 wt .-% up to 45 wt .-%.
  • the solids content is usually not more than 60% by weight.
  • the solids content is determined by drying 2.0 ⁇ 0.2 g of the primary dispersion for 30 minutes at 180 ° C. The remaining residue is weighed and set in relation to the weight, which results in the solids content.
  • Primary dispersions usually have a low viscosity, even at a high solids content, which represents a further particular advantage of the primary dispersions and of the formulations and pigments and / or fillers prepared therefrom.
  • An essential starting compound for the preparation of the primary dispersions to be used according to the invention is the at least one olefinically unsaturated monomer (A).
  • A olefinically unsaturated monomer
  • Suitable olefinically unsaturated monomers (A) are: a1) substantially acid group-free (meth) acrylic esters, such as
  • Carbon atoms in the alkyl or cycloalkyl in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and Lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indenemethanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid alkyl esters or oxacycloalkyl esters such as ethyltriglycol (meth) acrylate and
  • Methoxyoligoglycol (meth) acrylate having a number average molecular weight M n (determined by gel permeation chromatography using a polystyrene standard) of preferably about 300 to 800 g / mol or other ethoxylated and / or propoxylated hydroxyl-free (meth) acrylic acid derivatives.
  • M n number average molecular weight
  • minor amounts of higher-functional monomers are quantities which do not lead to crosslinking or gelation of the copolymers (A); a2) monomers which carry at least one hydroxyl group, one primary, secondary, tertiary or quaternized amino group, one alkoxymethylamino group or imino group per molecule and are essentially free from acid groups, such as hydroxyalkyl esters of acrylic acid, of methacrylic acid or of another alpha, beta-olefinically unsaturated carboxylic acid, derived from an alkylene glycol esterified with the acid, or obtainable by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethy
  • the emulsifiers (E) which can be used according to the invention are not included in the monomers a2), although some emulsifiers (E) fulfill the formal definition of the monomers a2); 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
  • the monomers a3) are not used as the sole monomers (A), but always in conjunction with other monomers (A) and even in such small amounts that the monomers a3) not outside the sole monomers (A), but always in conjunction with other monomers (A) and even in such small amounts that the monomers a3) not outside the sole monomers (A), but always in conjunction with other monomers (A) and even in such small amounts that the monomers a3) not outside the sole monomers (A), but always in conjunction with other monomers (A) and even in such small amounts that the monomers a3) not outside the
  • 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 cracked products of paraffinic hydrocarbons, such as
  • Mineral oil fractions may contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • the reaction of such olefins with formic acid or with carbon monoxide and water produces a mixture of carboxylic acids in which the carboxyl groups are predominantly on a quaternary carbon atom.
  • Other olefinic starting materials are, for.
  • the vinyl esters a4) can also be prepared in known manner from the acids, for. B. by adding the acid Acetylene reacts.
  • Vinylbenzoic acid (all isomers), ⁇ , ⁇ -diethylaminostyrene (all isomers), alpha-methylvinylbenzoic acid (all isomers), ⁇ , ⁇ -diethylamino-alpha-methylstyrene (all isomers) and / or p-vinylbenzenesulfonic acid; a10) nitriles, such as acrylonitrile and / or methacrylonitrile; a1 1) 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-vinylpyrrolidone; Vinyl ethers, such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
  • M n 1000 to 40,000 and on average from 0.5 to 2.5 ethylenically unsaturated
  • polysiloxane macromonomers which have a number-average molecular weight M n of 2,000 to 20,000, more preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1, 5, ethylenically unsaturated double bonds per molecule , as described in DE 38 07 571 A 1 on pages 5 to 7, DE 3706095 A1 in columns 3 to 7, EP 0358153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 4421823 A1 or in the
  • any of the above-mentioned monomers a1) to a14) except the monomer (a3) may be polymerized by itself.
  • the monomers (A) are selected so that
  • (Meth) acrylate copolymers whose property profile is determined primarily by the (meth) acrylates described above.
  • comonomer (A) preference is given to using vinylaromatic hydrocarbons a9), in particular styrene.
  • the emulsifiers (E) and / or (EQ) used according to the invention can also be incorporated as polymerizable monomers in copolymerization with the monomers (A) in the preparation of the primary dispersion in the polymer, provided that the aliphatic group in the radical R 1 at least one alkenic or alkinisch
  • the emulsifier (E) used is the emulsifier E1 described and used in the examples
  • the emulsifier (EQ) of the general formula R 1 -N ⁇ (R 2 ) (R 3 ) (R 4 ) X® in the radical R 1 contains 1, 2 or 3 carbon-carbon double bonds which correspond to a
  • Copolymerization with the monomers (A) are available.
  • monomers (A) it is preferred to use monomers from the above groups a1), a2) and a9). From the group a1) are very particularly preferred alkyl esters of (meth) acrylic acid such as dC 4 alkyl esters of
  • hydroxy-C 2 -C 4 -alkyl esters of (meth) acrylic acid and / or aminoalkyl esters of (meth) acrylic acid including in particular N, N-dialkylaminoalkyl esters of (meth) acrylic acid, very particularly preferably N, N-di-d-C 4 alkylamino-C2-C4-acrylic acid alkyl ester of (meth).
  • Aminoalkyl esters of (meth) acrylic acid including in particular the N, N-dialkylaminoalkyl esters of (meth) acrylic acid, most preferably N, N-di-d-C4-alkylamino-C2-C acrylic acid 4 alkyl esters of (meth) takes place particularly preferred when the emulsifier (E) or (EQ) has no polymerizable carbon-carbon double bonds, that is not capable of copolymerizing with the monomers (A) and / or if the primary emulsion no further cathodic
  • Suitable comonomers a9) are preferably vinylaromatic hydrocarbons, in particular styrene and / or 1,1-diphenylethylene.
  • At least one monomer (A) which contains reactive functional groups (a) which can undergo thermally initiated crosslinking reactions with groups (a) of their own kind or with complementary reactive functional groups (b).
  • reactive functional groups (a) which can undergo thermally initiated crosslinking reactions with groups (a) of their own kind or with complementary reactive functional groups (b).
  • the particular primary dispersions used according to the invention and the coating materials prepared therefrom according to the invention are self-crosslinking.
  • complementary reactive functional groups (b) may also be present in the crosslinking agents (V) described below which contain the
  • Primary dispersions can be added before, during and / or after their preparation.
  • the relevant primary dispersions and those produced therefrom can be added before, during and / or after their preparation.
  • Formulations and preparations are externally crosslinking in this case.
  • Hydroxyl groups on the one hand, and crosslinking agents with anhydride, carboxy, epoxy, blocked isocyanate, urethane, methylol, methylol ether, N-methylol-N-alkoxymethylamino, siloxane, amino, hydroxy and / or beta Hydroxyalkylamid- groups, but especially blocked isocyanate, urethane or
  • Methylolether fraction on the other hand applied.
  • Self-crosslinking primary dispersions are preferably methylol
  • Methylol ethers N-methylol-N-alkoxymethylamino groups used.
  • Isocyanate groups are used, the constituents containing them,
  • the crosslinking agents until shortly before the use of
  • the constituents containing them are preferably added to the primary dispersions prior to preparation or during preparation, so that they contain from the outset in the primary dispersions prepared therefrom and thus also in the formulations and preparations according to the invention are.
  • These formulations and preparations according to the invention are also known by experts as
  • Electrocoating paints are, for example, usually such one-component systems.
  • the (co) polymer formed from the monomers (A) and optionally emulsifier (E) or (EQ) is none
  • the (co) polymerization is conducted so that a molecular weight distribution M w / M n measured with
  • the emulsifiers (E) and / or (EQ) used to prepare the primary dispersions have the general formulas:
  • R 1 is a radical containing at least one aromatic group and at least one aliphatic group having 15 to 40 carbon atoms, which contains at least one functional group selected from hydroxyl groups, thiol groups and primary or secondary amino groups and / or has at least one carbon-carbon multiple bond,
  • R 2 , R 3 and R 4 are independently identical or different, aliphatic radicals having 1 to 14 carbon atoms, and
  • X® stands for the acid anion of an organic or inorganic acid HX.
  • a carbon-carbon multiple bond herein is meant a carbon-carbon double bond or a carbon-carbon triple bond.
  • the carbon-carbon multiple bond is a carbon-carbon double bond.
  • the radical R 1 contains an aromatic group Gr ar om and two bound to Gr ar om aliphatic groups Gr Gr and a ni a ii2- Particularly preferably, the radical R 1 has - the structure of Gr A III-Gr Gr ar0 m-ii2 a -.
  • the radical R 1 contains at least one carbon-carbon multiple bond in the at least one aliphatic group Gr a ni, more preferably at least one carbon-carbon double bond.
  • the presence of carbon-carbon multiple bonds, in particular carbon-carbon double bonds has a positive effect on the shear stability of the dispersions and coating compositions prepared using the emulsifiers. In particular, an undesirable migration of the emulsifiers in the dispersions and Coating composition prevented or reduced.
  • the radical R 1 contains from one to three carbon-carbon double bonds in the at least one aliphatic group Gr a ni.
  • the radical R 1 contains at least one aliphatic group Gr a ni least one carbon-carbon multiple bond
  • the second aliphatic group Gr a i i2 at least one functional group selected from
  • blocked or unblocked polyisocyanates aminoplast resins such as melamine-formaldehyde resins, tris (alkoxycarbonylamino) triazines, which are different from the aforementioned crosslinkers or even
  • Epoxy group-containing resins Epoxy group-containing resins.
  • Primary dispersions containing such emulsifiers which carry hydroxyl groups, thiol groups and / or primary or secondary amino groups can thus be incorporated in the curing process of a coating agent prepared by means of the primary dispersions
  • the at least one aliphatic group Gr a ni in the radical R 1, which carries at least one carbon-carbon double bond may be linear or branched and is preferably linear. It may also be substituted or unsubstituted and is preferably unsubstituted. In addition, this aliphatic group
  • This aliphatic group in the radical R 1 is therefore particularly preferably linear, unsubstituted, heteroatom-free and contains one to three double bonds.
  • the group Gr a ni contains from 8 to 30, particularly preferably 10 to 22 and most preferably 12 to 18 carbon atoms, for example 15 carbon atoms.
  • the at least one aliphatic group Gr a N 2 in the radical R 1 which carries at least one functional group selected from hydroxyl groups, thiol groups and primary or secondary amino groups, among which OH groups are particularly preferred, and which is different from Gr a iM, can be linear or be branched and is
  • this aliphatic group preferably linear. It may also be substituted or unsubstituted and is preferably unsubstituted. In addition, this aliphatic group
  • the aliphatic group Gr a N 2 is preferably bonded directly to the nitrogen atom listed in the above general formula of the emulsifier (E) or (EQ). If the "nitrogen atom in the general formula of
  • Emulsifier (E) or (EQ) "of the invention is meant herein, then it is meant to the radicals R 1 , R 2 , R 3 and R 4 bound positively charged nitrogen.
  • the at least one functional group is selected from hydroxyl groups, thiol groups and primary or secondary amino groups in beta position to the nitrogen atom of the above general formula of the emulsifier (E) or (EQ). If one of the abovementioned groups is in the beta position relative to the nitrogen atom of the general formula of the emulsifier (E), then tertiary can be formed
  • a particular advantage of the present emulators (EQ) is the permanent positive charge of the nitrogen atom in the general formula of the emulsifier of the invention. As a result, the permanent positive charge can further increase the dispersion and storage stability of such primary dispersions of the invention or of coating compositions prepared therefrom and prevent an amine-catalyzed reaction.
  • Hydroxyl group, thiol group, or a primary or secondary amino group in beta position to the nitrogen atom of the emulsifier of the general formula (E) or (EQ), lies in the ability to form chelates with metal ions, which is advantageous is when targeted the formulations of the invention containing pigments and / or fillers are used in coating compositions, from which metal ions are to be deposited.
  • Correspondingly chelated metal ions present provide improved deposition and may increase the anti-corrosive effect of such coatings.
  • a hydroxyl group is in beta position to said nitrogen atom.
  • the group Gr a i i2 contains 2 to 10, particularly preferably 2 to 8 and most preferably 2 to 6 carbon atoms such as 2 or 3 carbon atoms.
  • the aromatic group Gr ar om in the radical R 1 is preferably a phenylene or naphthylene group, preferably a phenylene group.
  • the aromatic group Gr ar om may be substituted or unsubstituted and is preferably unsubstituted.
  • the aromatic group Gr ar om may contain heteroatoms selected from the group consisting of O, S and N, but is preferably heteroatom-free.
  • the group Gr ar om contains 6 to 15, particularly preferably 6 to 12 and most preferably 6 to 10 carbon atoms such as 6
  • Gr is a ni linear, unsubstituted, and heteroatom-free and one to three, preferably one or two double bonds,
  • Gr arom is a phenylene or naphthylene group
  • Gr a i i2 is linear, carries a hydroxyl group, preferably in beta position to
  • Nitrogen atom of the general formula of the emulsifier (E) or (EQ) and additionally as the hetero atom O contains, in the form of an ether group, wherein preferably, in the case where Gr arom a phenylene group which groups Gr a ni and Gr a i i2 are bonded in meta position to each other to the phenylene group.
  • the radicals R 2 , R 3 and R 4 independently of one another are identical or different, aliphatic radicals having 1 to 14, preferably 2 to 10, particularly preferably 2 to 8 carbon atoms.
  • R 1 contains no functional group selected from hydroxyl groups, thiol groups and primary or secondary amino groups
  • at least one of the radicals R 2 , R 3 and R 4 bears such a functional group.
  • at least two of the radicals R 2 , R 3 and R 4 carry a functional group selected from hydroxyl groups, thiol groups and primary or secondary amino groups.
  • hydroxyl groups Particularly preferred is said functional group in the radicals R 2 , R 3 and R 4 terminal, while it is non-terminal in the radical R 1 .
  • R 2 , R 3 and R 4 may be linear or branched, preferably they are linear.
  • R 2 , R 3 and R 4 may carry carbon-carbon multiple bonds, but are preferably saturated.
  • the aliphatic radicals R 2 , R 3 and / or R 4 preferably contain, in addition to the abovementioned hydroxyl, thiol and primary and secondary amino groups
  • the anion X® in the emulsifiers (EQ) is the acid anion of an organic or inorganic acid HX, preferably excluding halides. Particularly preferred is the anion of a monocarboxylic acid such as those used in the neutralization of cathodic electrodeposition resins
  • Monocarboxylic acids Suitable anions of monocarboxylic acids are preferably those having 1 to 10 carbon atoms such as formates, acetates or lactates.
  • X® particularly preferably represents anions of hydroxycarboxylic acids, in particular of lactate.
  • the emulsifier (E) is a cardanolaminopolyol as described in the Chinese patent applications CN 102633661 A and CN 102875394 A and has the following formula:
  • This compound is the neutral form of the emulsifier E1 as described in the example part of the present invention.
  • This compound is obtainable, for example, by reacting diethanolamine with a cardanol glycidyl ether of the formula
  • Cardanolglycidyl ethers of this type are known, for example, as Cardolite® NC 513 from Cardolite Europe N.V. (Ghent, Belgium) available.
  • Emulsifiers by addition of an amine of the general formula HN (R 2 ) (R 3 ) to the Produce oxirane ring.
  • R 2 and R 3 have the meanings already given above.
  • the emulsifier (EQ) is one as represented in the following formula:
  • This compound is obtainable, for example, by adding N, N-dimethylethanolamine lactate to a
  • Cardanolglycidylether can be, for example, a variety of preferred, inventive emulsifiers by addition of a
  • Cardanol is such a mixture in which the individual components differ by the number of double bonds in the R chain.
  • the most common single components contain 0 to 3
  • Primary dispersions apply that not only an emulsifier (E) or (EQ), but also a mixture of several emulsifiers (E) and / or (EQ) can be used. Preferred among these are those mixtures in which a part of the emulsifiers in the radical R 1 carries carbon-carbon multiple bonds and another part in the radical R 1 contains no carbon-carbon multiple bonds.
  • emulsifier mixtures of a plurality of emulsifiers (E) and / or (EQ) are used, preferably more than 50 mol%, particularly preferably more than 70 mol%, of the radicals R 1 contain carbon-carbon multiple bonds, with carbon-carbon double bonds being particularly preferred are.
  • the emulsifiers (E) and (EQ) are preferably used in the primary dispersion according to the invention in an amount of 1 to 10 wt .-%, particularly preferably an amount of 2 to 8 wt .-% and most preferably in an amount of 3 to 6 wt .-%, each based on the weight of one liter of the dispersion used.
  • pigments and fillers can be used as pigments and fillers.
  • the pigments and fillers are usually selected in relation to the purpose of the pigment and / or filler-containing formulation. If the formulation, for example, the pigmentation of cathodic electrodeposition paints serve, which are known to have a pH in the acid, so come for example for the
  • Formulations no chalk pigments or chalk fillers (calcium carbonate) in question, as they would dissolve completely in an acidic medium. However, partial dissolution of pigments in the later coating agent may even be desirable if, for example, catalytically active metal ions are thereby released slowly and successively.
  • Typical inorganic pigments are oxide and oxide hydroxide pigments such as titanium dioxide, zinc oxide, iron oxide and chromium oxide, oxide mixed phase pigments such as bismuth-molybdenum-vanadium oxide yellow, chromium titanium yellow, spinel blue, iron manganese brown, zinc iron brown, iron manganese black and spinel black, sulfide and sulfide selenide pigments such as zinc sulfide, lithopone, cadmium yellow and cadmium red,
  • Carbonate pigments such as calcium carbonate (with the above
  • chromate and chromate-molybdenum mixed-phase pigments such as, for example, chrome yellow and molybdate orange and red
  • complex salt pigments such as, for example, iron blue
  • silica clays such as
  • pigments of chemical elements such as aluminum, copper-zinc alloys and carbon black
  • other pigments such as barium sulfate
  • Typical organic pigments are monoazo pigments, disazo pigments and polycyclic pigments such as perylene pigments and
  • Phthalocyanine pigments are derived from Phthalocyanine pigments.
  • Typical inorganic fillers are silicates such as talc and kaolin, silicas such as precipitated or fumed silicas, oxides such as aluminum hydroxide or magnesium hydroxide, sulfates such as
  • blanc fixe and calcium sulfates as well as various carbonates.
  • the pigments and fillers are also counted herein as those sparingly soluble compounds which, for example, can also perform catalytic tasks in addition to the typical tasks of pigments and fillers.
  • Preparations obtained using pigment and / or filler-containing formulations comprising poorly soluble bismuth compounds may be added with complexing agents such as EDTA, bicin or others to produce successively soluble bismuth.
  • pigments For the present invention, a sharp distinction between pigments and fillers is not necessary.
  • the refractive index is often used to distinguish. If this is above 1, 7 is usually referred to as pigments, it is below this value of fillers.
  • the primary dispersions can still network and / or
  • crosslinking agents can also be present with the primary dispersions or the pigment and / or filler
  • the substantially water-insoluble crosslinking agents contain the above-described reactive functional groups (a) or (b) which are complementary to the reactive (c) polymers and / or emulsifier (s) and / or (EQ) functional groups (a) or (b) undergo crosslinking reactions.
  • the resulting primary dispersions contain the crosslinking agents in a particularly good distribution, which is why the
  • hydrophobic, that is substantially water-insoluble, crosslinking agents are blocked polyisocyanates
  • Tris (alkoxycarbonylamino) triazines or completely etherified amino resins, blocked polyisocyanates are particularly suitable.
  • suitable organic polyisocyanates to be blocked are, in particular, the so-called lacquer polyisocyanates having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups. To be favoured
  • Polyisocyanates having an average of 2 to 5, more preferably 2.5 to 5 isocyanate groups per molecule used.
  • Particular suitable polyisocyanates to be blocked are isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea and / or
  • Urethane-containing polyisocyanates are, for example, by
  • the polyisocyanates to be blocked aliphatic or cycloaliphatic diisocyanates in particular
  • the diisocyanates may also be blocked for production
  • Diisocyanates are used. Preferably, however, they are not alone, but in admixture with the polyisocyanates, which have on average more than two
  • Isocyanurate and / or allophanate-containing polyisocyanates based on diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, toluene 2,4- diisocyanate and / or toluene-2,6-diisocyanate and the adducts of the above diisocyanates to polyols, in particular triols such as trimethylolpropane and glycerol.
  • blocking agents for the preparation of the blocked di- or polyisocyanates are the blocking agents known from US Pat. No. 4,444,954, such as, for example: b1) phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol,
  • lactams such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactone or beta-propiolactam
  • active methylenic compounds such as diethyl malonate, dimethyl malonate, 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, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, butyl diglycol, propylene glycol, Diethylene glycol monomethyl ether
  • allyl methacrylohydroxamate or b16) substituted pyrazoles, in particular dimethylpyrazole, or triazoles; and b17) mixtures of the abovementioned blocking agents.
  • Suitable completely etherified amino resins are melamine resins, guanamine resins or urea resins. Furthermore, the customary and known amino resins, their methylol and / or
  • Methoxymethyl groups are defunctionalized in part by means of carbamate or allophanate.
  • Crosslinking agents of this type are described in the patents US 4,710,542 A 1 and EP 0 245 700 B 1 as well as in the article by B.
  • Singh et al. “Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry” in Advanced Organic Coatings Science and Technology Series, 1991, Vol. 13, pages 193 to 207.
  • Suitable tris (alkoxycarbonylamino) triazines are for example in the
  • the blocked polyisocyanates offer particular advantages and are therefore used with very particular preference according to the invention.
  • the ratio of monomers (A) containing complementary reactive functional groups (a) or (b) to the crosslinking agents can vary widely.
  • the molar ratio of complementary reactive functional groups (a) or (b) in (A) to complementary reactive functional groups (a) or (b) in the crosslinking agents at 5: 1 to 1: 5, preferably 4: 1 to 1: 4, more preferably 3: 1 to 1: 3 and especially 2: 1 to 1: 2.
  • Particular advantages result when the molar ratio is about or exactly 1: 1.
  • the other constituents of the primary dispersions to be used according to the invention can be divided into those which serve to control and carry out the preparation process of the primary dispersions, for example initiators for free-radical emulsion polymerization or compounds which are capable of controlling the molecular weight of the polymers, such as mercaptans, in particular Dodecylmercaptan and, on the other hand, those having the property profile of
  • the monomers (A) to be used according to the invention and optionally emulsifiable emulsifiers (E) or (EQ) are usually reacted with one another in the presence of at least one water-soluble and / or oil-soluble, radical-forming initiator to give copolymers.
  • Suitable initiators 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-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; Peroxodicarbonates such as bis (4-tert-butylcyclohexyl) peroxydicarbonate; Potassium, sodium or ammonium peroxodisulfate; Azo initiators, for example, azodinitriles such as azobisisobutyronitrile; Initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide.
  • the proportion of the initiator in the reaction mixture in each case based on the total amount of the monomers (A) and the initiator from 0.1 to 1, 5 wt .-%, particularly preferably 0.2 to 1, 0 wt .-% and very particularly preferably 0.3 to 0.7 wt .-%.
  • molecular weight regulators are preferably water-insoluble
  • molecular weight regulator Particularly suitable are mercaptans such as tert. Dodecyl.
  • mercaptans such as tert. Dodecyl.
  • the property profile of the primary dispersions determining further constituents
  • oligomeric or polymeric substances water-insoluble low molecular weight, oligomeric or polymeric substances are used.
  • suitable hydrophobic compounds are oligomeric and / or polymeric polymerization, polycondensation and / or polyaddition products.
  • polymers can already be used which are tailored to the subsequent use of the pigment and / or filler-containing formulation in a particular type of coating agent.
  • epoxy-amine adducts can be incorporated before or during the polymerization, as are commonly used in coating compositions, in particular electrodeposition paints. Preference is given in particular to those epoxy-amine adducts which contain quaternary nitrogen atoms, these can be obtained by reacting
  • Epoxy groups of the epoxy-amine resin with ammonium salts of the general formula HN ⁇ (R 2 ) (R 3 ) (R 4 ) (X®) - analogous to the preparation of (EQ) - can be obtained.
  • the definitions of the radicals R 2 , R 3 , R 4 and X® correspond to the definitions for the formula (EQ).
  • This mixture is optionally at least partially neutralized with an acid, preferably carboxylic acid such as formic acid or lactic acid and stirred vigorously until a coarse emulsion is formed.
  • a highly homogeneous, not yet polymerized miniemulsion is produced by introducing high shear forces, optionally under pressure, by means of a homogenizer, preferably high-pressure homogenizer.
  • reactors for the (co) polymerization the usual and known stirred tank, stirred tank cascades, tubular reactors, loop reactors or
  • the free-radical copolymerization is carried out in stirred tanks or Taylor reactors, wherein the Taylor reactors are designed so that the conditions of the Taylor flow are satisfied over the entire reactor length, even if the kinematic viscosity of the reaction medium due to the copolymerization greatly changes, in particular increases.
  • the copolymerization is carried out in an aqueous medium.
  • the aqueous medium may, in addition to the emulsifiers described above in detail, optionally crosslinking agents and optionally hydrophobic
  • the term "minor amount” is to be understood as meaning an amount which does not abolish the aqueous character of the aqueous medium. however, the aqueous medium may also be pure water
  • the (co) polymerization is advantageously carried out at temperatures above the Room temperature (25 ° C), preferably a temperature range of 25 to 95 ° C, most preferably 30 to 90 ° C, is selected. Preferably, it is polymerized under a protective gas atmosphere, in particular a nitrogen atmosphere.
  • (Co) polymerization under pressure preferably below 1, 5 to 3000 bar, more preferably 5 to 1500 bar and in particular 10 to 1000 bar are performed. In some cases higher temperatures than 95 ° C can be used.
  • the activation and initiation of the polymerization is usually carried out by water-soluble initiators.
  • Suitable initiators are, for example, sodium, potassium and ammonium persulfate or tert-butyl hydroperoxide. Particular preference is given to using tert-butyl hydroperoxide, which is obtained, for example, by
  • iron (III) ions formed can be reduced again by reducing agents to iron (II) ions.
  • reducing agent for example, sodium formaldehyde sulfoxilate is suitable.
  • the pigments and / or fillers are mixed with the primary dispersion.
  • the mixing is accompanied by a dispersion of the pigments and / or fillers and has the object dispersions to obtain that contain the highest possible proportion of pigment and / or filler primary particles.
  • the mixing thus serves as far as possible a homogeneous dispersion of the pigments and / or fillers in the primary dispersion.
  • conglomerates that is loose
  • Aggregates in turn, which consist of surface forces by firmly adhering pigment primary particles are usually crushed only by strong shear forces.
  • the aim of the dispersing process is to disperse the pigments and / or fillers used to such an extent that the highest possible proportion of primary particles, that is to say individual pigment particles, is produced.
  • An illustrative comparison of primary particles, aggregates and agglomerates, for example, the DIN 53206, sheet 1 can be removed.
  • the term "comminution” as used herein means disruption of conglomerates, agglomerates and / or aggregates, not further comminution of the primary particles.
  • auxiliaries in particular wetting agents and / or dispersants, and organic solvents may be added to the primary dispersion before or while stirring.
  • solvents that favor dispersion, including, in particular, monoalcohols and glycols. Wetting agents are used successfully in particular with some poorly wettable organic pigments.
  • predispersion is then carried out by means of a so-called dissolver, these being high-speed stirring disc aggregates.
  • the Predispersion usually serves to achieve high throughput rates for the downstream Schodispergieraggregate.
  • pigments such as titanium dioxide pigments can also be completely dispensed with predispersion.
  • the predispersion already makes so-called colloidally disperse systems, which are characterized in that the solid particles do not sediment under the action of gravity due to their small size.
  • colloidally disperse systems which are characterized in that the solid particles do not sediment under the action of gravity due to their small size.
  • wetting and / or dispersing agents in predispersion also stabilizes the smaller particles in comparison with reagglomeration.
  • Dissolvers can be used not only for predispersion, but also for the incorporation of matting agents at lower shear rates, or in some cases for
  • the circumferential speed is calculated from the disk circumference of the stirring disks and the number of revolutions per unit of time.
  • Predispersing conventional peripheral speeds are about 5 m / s higher, at 15 to 25 m / s, such as 21 m / s, with dispersing times of 10 to 20 min and temperatures in the range of 35 to 50 ° C.
  • the peripheral velocities are again about 5 m / s higher than in the predispersion, for example in a range of 20 to 30 m / s, for example 25 m / s, for dispersion times in the range from 20 to 40 min and temperatures in the range of 50 to 70 ° C.
  • the above values can be regarded as general indications, preferably the ranges apply to batch sizes from 500 to 1000 kg.
  • Various dissolver types are described in detail with their corresponding typical operating data in Kittel, "Textbook of coatings and coatings", Vol. 8, 2004, pp. 47-50.
  • the main dispersion is then, for example, in so-called three-roll, ball mills or
  • Agitator mills performed. Among these, ball mills and especially agitator mills are particularly suitable. All three aforementioned types of mill are described in detail with their corresponding typical operating data in Kittel, "Textbook of coatings and coatings", Vol. 8, 2004, p 53ff.
  • containing formulations can be determined by determining the grindometer value. This is a simple determination of
  • the measuring and assessment method is explained in more detail in the example section and corresponds to DIN 53203.
  • Another object of the invention are those according to the invention.
  • Formulations These are often referred to in the literature as pigment preparations, pigment pastes or regrind.
  • Silicas such as certain Aerosils up to 900 g of binder per 100 g Aerosil. Relevant information can also be found in the Römpp Lexikon Lacke und Druckmaschine, 1998, page 369, keyword "regrind”.
  • the formulations containing pigment and / or filler according to the invention serve to prepare aqueous preparations, in particular the preparation of coating materials. Further subject of the present invention are thus aqueous preparations, in particular coating compositions, which contain the pigment and / or filler-containing formulations according to the invention.
  • the aqueous formulations of the invention are preferably pigmented coating compositions, very particularly preferably cathodically depositable electrodeposition coatings.
  • at least one conventional coating additive may be added in effective amounts to the primary dispersions to be used according to the invention before, during and / or after their preparation.
  • paint additives are added after the preparation of the primary dispersions.
  • suitable additives are thermally curable reactive diluents, low-boiling and / or high-boiling organic solvents, UV absorbers,
  • Light stabilizers radical scavengers, thermolabile radical initiators, catalysts for crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, leveling agents, film-forming aids, rheology control additives or flame retardants.
  • suitable paint additives are described in the textbook Coat Additives by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.
  • Coating materials also be curable with actinic radiation (dual cure), preferably contain additives that are curable with actinic radiation.
  • the actinic radiation may be electromagnetic radiation such as near-infrared (NIR), visible light, ultraviolet light, or X-radiation, or
  • Corpuscular radiation act like electron radiation.
  • suitable actinic radiation-curable additives are known from German Patent DE 197 09 467 C1.
  • the application of the aqueous preparations according to the invention, in particular of the coating materials has no special features, but can by all the usual application methods, such as spraying, knife coating, brushing, dipping, eaves or rollers or by means of electrocoating,
  • Suitable substrates are all surfaces to be painted, which are not damaged by curing of the coatings thereon using heat and, if appropriate, actinic radiation, into consideration; these are
  • the coating material according to the invention is also suitable for applications outside the automotive finishing. He comes in particular for the painting of furniture and industrial painting, including coil coating, container coating and the impregnation or coating of electrical components into consideration. In the context of industrial coatings, it is suitable for painting virtually all parts for private or industrial use such as radiators, household appliances, small metal parts such as nuts and bolts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.
  • the aqueous formulations according to the invention or the coating compositions according to the invention can preferably be applied by means of electrocoating, more preferably cathodic electrocoating.
  • Another object of the present invention is therefore a
  • Electrocoating composition (also referred to as electrocoating for short) containing the pigment and / or filler according to the invention
  • Such an electrodeposition coating composition is particularly suitable for cathodic electrodeposition (KTL).
  • KTL cathodic electrodeposition
  • another object of the present invention is the use of
  • formulations containing pigment and / or filler according to the invention in electrodeposition coating compositions in particular cathodically depositable electrodeposition coating compositions.
  • the electrodeposition paints according to the invention preferably have one
  • Solid content of 5 to 50, preferably 5 to 35% by mass.
  • solids is to be understood as meaning the proportion of an electrodeposition paint which remains after drying at 180 ° C. for 30 minutes.
  • the electrocoating compositions according to the invention contain as binder at least the dispersed polymer particles contained in the formulations containing the pigment and / or filler according to the invention and those used for the production of
  • Coating means such as an electrocoating minus the fillers and pigments contained understood.
  • the dispersed polymer particles contained in the formulations containing pigment and / or filler according to the invention preferably already comprise reactive functional groups which, with complementary reactive functional groups present in the abovementioned crosslinking agents, comprise thermal
  • Suitable reactive functional groups already mentioned above are hydroxyl groups, thiol groups and primary and secondary amino groups, in particular hydroxyl groups. Particularly preferably, those used in the invention
  • Primary dispersions containing polymer particles at least one type of cationic and / or potentially cationic groups which can be copolymerized, for example, by using the monomers a2) or carbon-carbon multiple bonds carrying emulsifiers (E) or (EQ).
  • Potentially cationic groups are, for example, initially uncharged primary, secondary or tertiary amino groups, which can be converted by protonation with inorganic or preferably organic acids into ammonium groups. Since cathodic electrodeposition paints usually have a pH of 4.5 to 6.5, which is usually adjusted by the addition of acids, the pH of the electrodeposition coatings is usually sufficient to convert potentially cationic groups into cationic groups.
  • suitable acids for the potentially cationic groups are inorganic and organic acids such as sulfuric acid, phosphoric acid, formic acid, acetic acid, lactic acid,
  • Propionic acid alpha-methylolpropionic acid, dimethylolpropionic acid, gamma-hydroxypropionic acid, glycolic acid, tartaric acid, malic acid, citric acid,
  • Sugar acids such as amidosulfonic acids and alkanesulfonic acids, such as methanesulfonic acid, in particular formic acid, acetic acid or lactic acid.
  • Suitable cationic groups are quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or tertiary sulfonium groups, but in particular quaternary ammonium groups, as occur in particular in the emulsifiers (EQ).
  • binders typical for electrodeposition paints may be present in the electrodeposition paint according to the invention.
  • Further binders for electrodeposition paints are disclosed in the publications EP 0 082 291 A1, EP 0 234 395 A1, EP 0 227 975 A1, EP 0 178 531 A1, EP 0 333 327, EP 0 310 971 A1, EP 0 456 270 A1, US 3,922,253 A, EP 0 261 385 A1, EP 0 245 786 A1, EP 0 414 199 A1, EP 0 476 514 A1, EP 0 817 684 A1, EP 0 639 660 A1, EP 0 595 186 A1, DE 41 26 476 A1 , WO 98/33835, DE 33 00 570 A1, DE 37 38 220 A1, DE 35 18 732 A1 or DE 196 18 379 A1. These are preferably primary, secondary, tertiary or
  • Quaternary amino or ammonium groups and / or tertiary sulfonium-containing resins having amine numbers preferably between 20 and 250 mg KOH / g and a weight average molecular weight of 300 to 10,000 daltons.
  • amino (meth) acrylate resins aminoepoxide resins,
  • Very particularly preferred epoxy-amine resins are the resins known from WO-A-2004/007443 and also used in the experimental part of the present invention.
  • Suitable crosslinking agents are all customary and known crosslinking agents which contain suitable complementary reactive functional groups.
  • the crosslinking agents are selected from the group of crosslinking agents already described above.
  • Electrocoating paints preferably contain metal compounds in which the metal is in the form of a cation, most preferably bismuth compounds.
  • Emulsifiers (E) and (EQ) in beta position to the nitrogen atom in the general formula of the emulsifiers (E) or (EQ) carry a hydroxyl group, thiol group or primary or secondary amino group.
  • the abovementioned groups in the beta position favor the crosslinking density of the coating.
  • the aqueous preparations in particular the cathodic electrodeposition coating materials, preferably contain at least 30 ppm, more preferably at least 100 ppm, most preferably at least 200 ppm and in particular at least 250 ppm of bismuth in dissolved form, based on the total weight of the aqueous preparation.
  • the content of dissolved bismuth should preferably not exceed 20000 ppm, more preferably 10000 ppm.
  • the above-mentioned bismuth pigment can of course be used.
  • aqueous formulations according to the invention may contain at least one customary and known additive, selected from the group of additives generally already described above, in effective amounts.
  • Electrocoating paints are prepared by mixing the aforementioned ingredients.
  • the ingredients can be homogenized.
  • the electrodeposition paints according to the invention by means of conventional and well-known
  • Micromixers, Zahnkranzdispergatoren, pressure relief nozzles and / or Microfluidizern be prepared.
  • Electrocoating paints are used in particular for cathodic dip painting.
  • the aqueous preparations according to the invention, in particular the electrodeposition paints can usually be cathodically deposited on electrically conductive, for example electrically conductive or conductive, made for example by metallization electrically conductive plastic substrates or in particular metallic substrates.
  • the invention therefore also relates to a process for the cathodic deposition of the aqueous preparations according to the invention, in particular the electrodeposition paints on such substrates.
  • the method has no special features.
  • the electrodeposition coating materials according to the invention can be used for the production of primer layers by cathodic dip-coating of substrates with electrically conductive surfaces.
  • metallic substrates parts of all common metals,
  • the electrodeposition paints of the invention can also be used in the painting of motor vehicles or parts thereof.
  • Very particularly preferred substrates are aluminum substrates.
  • the substrates can be applied by applying a
  • Conversion layer pretreated for example, be phosphated or chromated.
  • the substrates are neither phosphated nor chromated.
  • the substrate is dipped in the aqueous composition and switched as a cathode.
  • the deposition from the aqueous composition is at least two stages, wherein in a first stage, a voltage in the range of 1 to 50 V and in the second stage, a voltage of 50 to 400 V is applied, provided that in the second stage, the voltage at least 10 V above the voltage of the first stage.
  • the voltage is maintained in each stage preferably at least 10 seconds to a maximum of 300 seconds.
  • Substrates are preferably used aluminum substrates.
  • the cathodic deposition can be followed by further treatment stages prior to curing of the coating, for example rinsing with water and / or ultrafiltrate or, in a particularly preferred embodiment of the process, a so-called sol-gel rinsing with a sol-gel composition.
  • sol-gel composition compositions and sol-gels
  • An aqueous "sol-gel composition” in the context of the present invention is preferably understood to mean an aqueous composition to which Preparation of at least one starting compound which has at least one metal atom and / or semimetal atom such as M 1 and / or M 2 and at least two hydrolyzable groups such as two hydrolyzable groups X 1 , and which optionally further comprises at least one non-hydrolyzable organic radical such as R 1 is reacted with water with hydrolysis and condensation.
  • the at least two hydrolyzable groups are preferably in each case bonded directly to the at least one metal atom contained in the at least one starting compound and / or at least one semimetal atom in each case by means of a single bond. Due to the presence of the non-hydrolyzable organic radical such as R 1 , such a sol-gel composition used according to the invention may also be referred to as a "sol-gel hybrid composition".
  • the present invention can be used in the optional sol-gel rinsing aqueous sol-gel composition is obtainable by reacting at least one compound Si (X 1) 3 (R 1), wherein R 1 therein is a non-hydrolyzable organic radical which at least one reactive functional group selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, and groups which have an ethylenically unsaturated double bond, in particular at least one compound Si (X 1 ) 3 (R 1 ), wherein R 1 therein is a non-hydrolyzable organic group having at least one epoxy group as a reactive functional group, and wherein X 1 is a hydrolyzable group such as an O-C 1-6 alkyl group, and further optionally at least one further compound Si (X 1 ) 3 (R 1 ), wherein R 1 therein is a non-hydrolyzable organic radical which at least e ine reactive functional group selected from the group consisting of primary amino groups and secondary Amino groups,
  • the curing of the applied coating materials or electrodeposition paints 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 convection oven or irradiation with IR lamps which can be supplemented in the case of dual cure by the irradiation with actinic radiation.
  • radiation sources such as high or low pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window of up to 405 nm, or electron beam sources may be used.
  • the electroconductive substrates coated with a cathodic electrodeposition coating layer which are likewise the subject of the present invention, can be coated with one or more further coating layers, such as, for example, one or more surfacer layers, one or more basecoat films and / or one or more clearcoat films.
  • one or more further coating layers such as, for example, one or more surfacer layers, one or more basecoat films and / or one or more clearcoat films.
  • Paint structures are known in particular from automotive painting. In other However, even the application of an electrodeposition coating layer according to the invention may already be sufficient.
  • the determination of filiform corrosion serves to determine the
  • Corrosion resistance of a coating on a substrate is carried out in accordance with DIN EN 3665 (date 1 .8.1997) for the electrically conductive substrate aluminum (ALU) coated with a coating composition according to the invention or with a comparative coating composition over a period of 1008 hours.
  • the respective coating starting from a line-shaped violation of the coating, is infiltrated in the form of a line or thread-like undercorrosion.
  • the mean and maximum thread length in [mm] can be measured in accordance with DIN EN 3665 (method 3) and are a measure of the resistance of the coating to corrosion.
  • the infiltration in [mm] according to PAPP WT 3102 (Daimler) (date 21.12.2006) is determined.
  • Grindometer block and scraper are visually checked for integrity.
  • the grindometer block is placed on a level non-slip surface and wiped clean immediately before the test. Then the sample, which must be free of air bubbles, applied to the lowest point of the measuring channel and with the scraper in about one second with light pressure to the flat end of the gutter pulled out. The reading must be done within 3 seconds; The grindometer block is held to the light so that the surface structure of the coated paint film is clearly visible. You can mark the reading point on the film with the Finder nail; individual specks or grooves are ignored. Of the
  • Reading point is where the particles protruding from the paint film begin to pile up.
  • the viscosity of the sample to be measured is about
  • Freshly dispersed regrind must be allowed to cool to room temperature (25 ° C) before measurement If the cold specimen is too viscous it is thinned with the binder contained in the millbase
  • Measurement suitably stirred with one part of non-thixotropic binder and one part of solvent. Are air bubbles present in the millbase, the sample is filtered through a 100 ⁇ sieve. For grain sizes of 10 to 20 ⁇ a "25 Grindometer”, for 15 to 40 ⁇ a "50 Grindometer” and for grain sizes of 25 to 100 ⁇ a "100 Grindometer” used.
  • Cardolite NC 513 (EEW 532 g / eq) are heated to 70 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and dropping funnel. Then 282.9 parts
  • Cardolite NC 513 (EEW 532 g / eq) are mixed with 357.1 parts of the above-prepared adduct of diethylenetriamine and ⁇ -caprolactone in one
  • Reaction vessel equipped with stirrer, reflux condenser, temperature probe and nitrogen inlet heated to 80 ° C with stirring until all NH equivalents are reacted and an epoxy-amine value of 1, 12 mmol / g is reached, but at least for two hours. Then 93.4 parts of 90% lactic acid are added and stirred for 30 minutes at 80 ° C.
  • a dimethylethanolammonium lactate is produced.
  • 51 1 90 parts of dimethylethanolamine, 71 1, 9 parts of an 80% lactic acid, 644.2 parts of butyl glycol and 74.8 parts of demineralized water are stirred in a reaction vessel equipped with a stirrer and reflux condenser for 24 hours.
  • Cardolite NC 513 (EEW 532 g / eq) are heated to 60 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and dropping funnel. Subsequently, 1942.8 parts of the above dimethylethanolamine lactate are slowly added dropwise over 30 minutes.
  • the coarse emulsion is transferred to an apparatus for introducing high shear forces and then passages twice at 600 bar with a
  • High-pressure homogenizer (Model 1 10Y from Microfluidics equipped with a H230Z and H210Z homogenization chamber) homogenized.
  • the miniemulsion is then heated to 75 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and metering unit. At 75 ° C, 0.2 parts of a 1% solution of iron (II) sulfate are added and a solution of 1.0 parts
  • Coarse emulsion is then stirred for at least 5 minutes.
  • the coarse emulsion is transferred to an apparatus for introducing high shear forces and then passages twice at 600 bar with a
  • High-pressure homogenizer (Model 1 10Y from Microfluidics equipped with a H230Z and H210Z homogenization chamber) homogenized.
  • the miniemulsion is then heated to 75 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and metering unit. At 75 ° C, 0.2 parts of a 1% solution of iron (II) sulfate are added and a solution of 1.0 parts
  • EA1 To EA1 are added at room temperature 8.0 parts isobornyl methacrylate, 43.0 parts methyl methacrylate, 37.0 parts butyl acrylate, 5.1 parts hydroxyethyl methacrylate, 14.0 parts polyethylene glycol methyl ether methacrylate (number average molecular weight ⁇ 300 g / mol), 49.0 parts bisphenol A diglycidyl ether (EEW 186 g / eq) (Araldit GY 2600, commercial product from BASF SE), 17.44 parts Super Iso Stable (TDI trimethylolpropane adduct blocked with 3 equivalents of phenol, sales product of the company Super Urecoat Industries), 0.8 parts of tert-dodecylmercaptan and 51, 5 parts of the emulsifier E1 added and stirred until a solution is present. Thereafter, 7.0 parts of an 80% lactic acid are added and allowed to stand for 10 minutes
  • the coarse emulsion is transferred to an apparatus for introducing high shear forces and then passages twice at 600 bar with a
  • High-pressure homogenizer (Model 1 10Y from Microfluidics equipped with a H230Z and H210Z homogenization chamber) homogenized.
  • the miniemulsion is then heated to 75 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and metering unit. At 75 ° C, 0.2 parts of a 1% solution of iron (II) sulfate are added and a solution of 1.0 parts
  • Emulsifier EQ1 added and stirred until a solution is present. Then 1 191, 4 parts of demineralized water are slowly added with vigorous stirring. The resulting coarse emulsion is then stirred for at least 5 minutes.
  • the coarse emulsion is transferred to an apparatus for introducing high shear forces and then passages twice at 600 bar with a
  • High-pressure homogenizer (Model 1 10Y from Microfluidics equipped with a H230Z and H210Z homogenization chamber) homogenized.
  • the miniemulsion is then heated to 75 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and metering unit. At 75 ° C, 0.4 part of a 1% solution of ferrous sulfate is added and a solution of 2.2 parts
  • the coarse emulsion is transferred to an apparatus for introducing high shear forces and then passages twice at 600 bar with a
  • High-pressure homogenizer (Model 1 10Y from Microfluidics equipped with a H230Z and H210Z homogenization chamber) homogenized.
  • the miniemulsion is then heated to 75 ° C. with stirring in a reaction vessel equipped with stirrer, reflux condenser, temperature probe, nitrogen inlet and metering unit. At 75 ° C, 0.6 part of a 1% solution of ferrous sulfate is added and a solution of 3.0 parts
  • Dissolver (company VME-Getzmann GmbH, model Dispermat® FM10-SIP) briefly premixed. Subsequently, one after the other with stirring 6.1 parts
  • Bismuth subnitrate 1.5 parts of Deuteron MK-F6 (thermosetting matting resin, sales product of Deuteron GmbH), 0.5 part of Carbon Black Monarch 120 (black pigment, commercial product of Cabot Corp.), 0.2 part of Lanco PEW 1555 (hard, hydrophilic low molecular weight polyethylene wax, sales product of Lubrizol Advanced Materials Inc.), 10.7 parts of aluminum silicate ASP 200 (at least 98% kaolin content, commercial product of BASF SE) and 30.95 parts of titanium dioxide R 900-28 ( Titanium dioxide of the rutile type; sales product of EI du Pont de Nemours and Company). Then the mixture for 10 minutes at about 800 rpm vorissolvert and then with grinding beads
  • Zirconia (Silibeads type ZY, diameter 1, 2 - 1, 4 mm) and a bead / regrind ratio of 1/1 (w / w) at 2500 rpm while milled with a Teflon disc adapted to the container size, to a fineness ⁇ 12 ⁇ , measured with a grindometer.
  • a stainless steel anode of size 30x70 mm was in the bath as an antipole.
  • a voltage of 5 volts was applied directly for 1 minute.
  • the voltage was raised to 200 to 300 volts within 30 seconds. This voltage was held for 2 minutes.
  • the test sheet was removed from the bath and the adhering non-coagulated paint was rinsed with demineralized water.
  • the sheet was recirculated for 30 minutes at 180 ° C in a commercial grade
  • Lacquer drying oven of the Heraeus brand networked With the selected voltage programs, a dry film thickness of approximately 20 ⁇ m is obtained on the test sheet after crosslinking. This was determined non-destructively with a device of the company Electrophysics under the trade name Minitest 720.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Paints Or Removers (AREA)
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Abstract

L'invention concerne des dispersions primaires aqueuses à stabilisation cationique, comprenant des particules de polymère dispersées qui présentent un diamètre moyen de particules Z de 5 à 500 nm, et qui peuvent être obtenues par polymérisation en émulsion d'au moins un monomère oléfiniquement insaturé (A). La polymérisation en émulsion s'effectue en présence d'un ou plusieurs émulsifiants (E) qui possèdent la formule générale suivante R1 -N(R2)(R3), dans laquelle R1 est un radical contenant au moins un groupe aromatique et au moins un groupe aliphatique et présentant 15 à 40 atomes de carbone, qui contient au moins un groupe fonctionnel choisi parmi des groupes hydroxyle, des groupes thiol et des groupes amino primaires ou secondaires et/ou présente au moins une liaison carbone-carbone multiple, et R2 et R3 sont, indépendamment l'un de l'autre, des radicaux aliphatiques identiques ou différents présentant 1 à 14 atomes de carbone. L'invention concerne en outre un procédé de production desdites dispersions primaires, des agents de revêtement qui comprennent lesdites dispersions primaires, l'utilisation desdites dispersions primaires pour la production de peintures électrophorétiques ainsi que des substrats conducteurs qui sont revêtus desdites compositions d'agents de revêtement.
EP13815500.7A 2013-12-20 2013-12-20 Procédé de production de formulations contenant un pigment et une substance de charge Withdrawn EP3083844A1 (fr)

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EP (1) EP3083844A1 (fr)
JP (1) JP6415594B2 (fr)
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WO (1) WO2015090443A1 (fr)

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KR20160102260A (ko) * 2013-12-20 2016-08-29 바스프 코팅스 게엠베하 수성 1 차 분산물, 그 제조 방법 및 용도
CN105899627A (zh) * 2013-12-20 2016-08-24 巴斯夫涂料有限公司 包含颜料和填料的配制物
WO2019072774A1 (fr) * 2017-10-09 2019-04-18 Basf Coatings Gmbh Peinture pour électrophorèse contenant au moins un composé triazine
CN109111563B (zh) * 2018-07-19 2021-06-15 浩力森化学科技（江苏）有限公司 用于底面合一阴极电泳涂料的颜料分散树脂及其制备方法
CN112251126A (zh) * 2020-10-29 2021-01-22 浩力森化学科技（江苏）有限公司 一种水性环保高性能低温涂料及制备方法
KR102442887B1 (ko) * 2022-04-12 2022-09-14 주식회사 한미 우레아 기반의 기능성 도료 및 이를 이용한 도장 및 방수공법

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225407A (en) * 1979-04-04 1980-09-30 The Dow Chemical Company Cathodic electrodeposition of polymers onto a conductive surface
DE3126522A1 (de) * 1981-07-04 1983-01-20 Basf Ag, 6700 Ludwigshafen Quaternaere ammoniumsalze und verfahren zu ihrer herstellung
JPS5928566B2 (ja) * 1982-01-14 1984-07-13 日本ペイント株式会社 α，β−不飽和化合物の重合体エマルジヨン、その製造法および用途
US4818435A (en) * 1987-03-12 1989-04-04 Hercules Incorporated Aqueous suspension of delaminated vermiculite
JPH04215830A (ja) * 1990-03-23 1992-08-06 Dainippon Ink & Chem Inc カチオン性界面活性剤、顔料分散剤および顔料分散液
JPH05117573A (ja) * 1991-10-24 1993-05-14 Toyo Ink Mfg Co Ltd 水性顔料分散体
JPH0925448A (ja) * 1995-07-10 1997-01-28 Sekisui Chem Co Ltd 水性着色ペースト及び水性カラーレジスト、並びにこれらの製造方法
JP2001323221A (ja) * 2000-05-19 2001-11-22 Nippon Paint Co Ltd ４級アンモニウム塩を含有するカチオン電着塗料組成物
DE10106574A1 (de) 2001-02-13 2002-08-22 Basf Coatings Ag Wäßriger Mehrkomponentenbeschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung
DE10153645A1 (de) 2001-10-31 2003-05-22 Basf Coatings Ag Härtbares Stoffgemisch, Verfahren zu seiner Herstellung und seine Verwendung
WO2004007443A2 (fr) * 2002-07-15 2004-01-22 Henkel Kommanditgesellschaft Auf Aktien Films resistant a la corrosion a base d'emulsions epoxy modifiees par monomere insature en ethylene
US20050173248A1 (en) * 2004-02-06 2005-08-11 Y.S. Fung Electrophoretic nano-coating
JP2007008998A (ja) * 2005-06-29 2007-01-18 Sanyo Chem Ind Ltd 有機酸塩の水分散体の製造法
JP2007154073A (ja) * 2005-12-06 2007-06-21 Dai Ichi Kogyo Seiyaku Co Ltd 乳化重合用乳化剤、ポリマーエマルションの製造方法及びポリマーエマルション
JP2007154075A (ja) * 2005-12-06 2007-06-21 Dai Ichi Kogyo Seiyaku Co Ltd 乳化重合用乳化剤、ポリマーエマルションの製造方法及びポリマーエマルション
WO2008156125A2 (fr) 2007-06-20 2008-12-24 Kansai Paint Co., Ltd. Procédé de production de film de revêtement multicouche
JP5513043B2 (ja) * 2009-09-10 2014-06-04 大日精化工業株式会社 水性顔料分散液および筆記具用またはインクジェット用水性顔料インク
JP5685465B2 (ja) * 2011-03-28 2015-03-18 株式会社Adeka 溶剤型塗料組成物
CN102382504B (zh) * 2011-10-18 2013-09-18 中国印刷科学技术研究所 一种利用蠕虫状胶束体系分散的水性uv油墨及其制备方法
DE102011089223A1 (de) * 2011-12-20 2013-06-20 Henkel Ag & Co. Kgaa Färbemittel mit direktziehenden Farbstoffen und zwitterionischen Tensiden

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015090443A1 *

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US9914840B2 (en) 2018-03-13
KR20160099709A (ko) 2016-08-22
CN105874017A (zh) 2016-08-17
JP6415594B2 (ja) 2018-10-31
CN105874017B (zh) 2018-08-28
US20170002213A1 (en) 2017-01-05
JP2017511834A (ja) 2017-04-27
WO2015090443A1 (fr) 2015-06-25

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