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WO2016000989A1 - Matériau de revêtement - Google Patents

Matériau de revêtement Download PDF

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Publication number
WO2016000989A1
WO2016000989A1 PCT/EP2015/063893 EP2015063893W WO2016000989A1 WO 2016000989 A1 WO2016000989 A1 WO 2016000989A1 EP 2015063893 W EP2015063893 W EP 2015063893W WO 2016000989 A1 WO2016000989 A1 WO 2016000989A1
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WO
WIPO (PCT)
Prior art keywords
optionally
meth
polymer
acrylate
carbon atoms
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PCT/EP2015/063893
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German (de)
English (en)
Inventor
Ulrich TROMSDORF
Manfred Dargatz
Sunitha Grandhee
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BASF SE
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BASF SE
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Classifications

    • 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
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to a one- and two-component coating composition
  • a one- and two-component coating composition comprising
  • At least one aqueous polymer dispersion obtainable by at least two-stage free-radically initiated aqueous emulsion polymerization of in a first stage reaction
  • (B1) optionally at least one vinylaromatic having up to 20 C atoms,
  • (D1) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms and vinyl ethers of 1 to 10 C-containing alcohols,
  • (E1) optionally at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid,
  • (F1) optionally at least one compound which has at least two non-conjugated ethylenically unsaturated groups
  • (B2) optionally at least one vinylaromatic having up to 20 C atoms,
  • (D2) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms and vinyl ethers of 1 to 10 C-containing alcohols,
  • (E2) optionally at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid,
  • (F2) optionally at least one compound which has at least two non-conjugated ethylenically unsaturated groups
  • (G2) optionally at least one compound selected from the group consisting of
  • the weight ratio of the sum of the monomers of the first stage (A1) to (11) to the sum of the monomers of the second stage (A2) to (12) is from 5:95 to 70:30,
  • the emulsion polymer obtained from the last stage has a particle size of 50 to 500 nm
  • crosslinker selected from the group consisting of polyisocyanates and melamine-formaldehyde resins
  • At least one corrosion inhibitor At least one corrosion inhibitor.
  • the present invention relates to processes for their preparation and their use in corrosion protection.
  • WO 201 1/073341 discloses an aqueous polymer dispersion of an at least two-stage dispersion polymer for coating applications, the first stage of which contains at least one hydroxy (meth) acrylate whose hydroxyl number is> 2 mg KOH / g polymer and whose acid number is not more than 10 mg KOH / g Polymer is.
  • WO 201 1/080067 describes an aqueous polymer dispersion of an at least two-stage dispersion polymer for one- or two-component coating applications whose first-stage polymer contains at least one hydroxy (meth) acrylate whose hydroxyl number is no more than 2 mg KOH / g polymer and whose acid number is 10 mg KOH / g polymer.
  • WO 2012/130712 two-stage emulsion polymer is disclosed, wherein the dispersed polymer of the first polymerization stage has a glass transition temperature of> 50 ° C and a weight average molecular weight of 5 to 100 kDa and contains at least one carboxylic acid and at least one other special monomer.
  • WO 2012/140042 describes two-stage emulsion polymers which are synthesized from a hydro-plastifiable, acid-rich first polymerization stage having a glass transition temperature in the range from 10 to 125 ° C. and a second, lower-acid polymerization stage having an acid number of not more than 23 mg KOH / g polymer.
  • two-stage emulsion polymers wherein the polymer of the first polymerization stage, a weight fraction of 10 to 30 wt .-% (based on the total polymer), a number average molecular weight in the range of 1000 to 4500 g / mol and an acid number of 5 to 100 mg KOH / g polymer.
  • the polymer of the second polymerization stage has an acid number which is at most half as large as the acid number of the polymer of the first polymerization stage.
  • the number average molecular weight of the second polymer should be> 20,000 g / mol.
  • EP-A 1978043 discloses a Mehrgenemulsionspolymerisat, which consists of an acid-rich first polymer having an acid number of 10 to 100 mg KOH / g polymer, wherein the acid groups are neutralized.
  • the polymer of the second polymerization stage has an acid number ⁇ 5 mg KOH / g polymer, a hydroxyl number ⁇ 5 mg KOH / g polymer and contains 0.5 to 5 wt .-% of a polyunsaturated monomer in copolymerized form.
  • ethylenically unsaturated monomers can be used:
  • This preferably comprises alkyl (meth) acrylates whose linear or branched alkyl radical has 1 to 20 carbon atoms, particularly preferably 1 to 10, very particularly preferably 1 to 8 and in particular 1 to 4 carbon atoms.
  • alkyl (meth) acrylates whose linear or branched alkyl radical has 1 to 20 carbon atoms, particularly preferably 1 to 10, very particularly preferably 1 to 8 and in particular 1 to 4 carbon atoms.
  • (Meth) acrylafriven generally include both the corresponding acrylic acid compounds as well as the corresponding methacrylic acid compounds.
  • Examples of (meth) acrylic acid alkyl esters are (meth) acrylic acid methyl ester, (meth) acrylic acid ethylester, (n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, (meth) butyl sec-butyl ester, (meth) acrylic acid n-pentyl ester, (meth) acrylic acid iso-pentyl ester, (meth) acrylic acid 2-methyl-butyl ester,
  • the monomers (A1) and (A2) are selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and 3-propylheptyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Such substituted vinylaromatics often have one or more, preferably 1 to 10 carbon atoms, often 1 to 6 and preferably 1 to 4 carbon atoms having linear or branched alkyl groups, which may be located on the aromatic or on the vinyl group.
  • the substituent When the substituent is at the aromatic, the substituent may preferably be in the ortho or para position, more preferably in the para position to the vinyl group.
  • Suitable vinylaromatic compounds are in particular vinyltoluene, vinylnaphthalene, o and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and / or styrene, although styrene and / or ⁇ -methylstyrene are particularly preferred.
  • the hydroxyalkyl (meth) acrylates are those (meth) acrylates whose alkylene group comprises one to 10, preferably 2 to 8, particularly preferably 2 to 6, very particularly preferably 2 to 4 and in particular 2 or 3 carbon atoms.
  • Preferred hydroxyalkyl (meth) acrylates are (meth) acrylic acid 2-hydroxyethyl ester,
  • hydroxyalkyl (meth) acrylates which have more than one hydroxyl group, for example two to five, preferably two to four, particularly preferably two to three.
  • examples of these are glycerol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and mono (meth) acrylates of sugar alcohols, such as, for example, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite) , Xylitol, dulcitol (galactitol), maltitol and isomalt.
  • sugar alcohols such as, for example, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabi
  • the compounds (D1) and (D2) are selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms and vinyl ethers of 1 alcohols containing up to 10 carbon atoms, preferably selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms and vinyl ethers of alcohols having from 1 to 10 carbon atoms, and particularly preferably ethylenically unsaturated nitriles having up to 20 C-atoms.
  • ethylenically unsaturated nitriles are fumaronitrile, acrylonitrile and methacrylonitrile, preferably acrylonitrile and methacrylonitrile and particularly preferably acrylonitrile.
  • Vinyl esters of carboxylic acids containing up to 20 carbon atoms Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate, vinyl butyrate and vinyl acetate, preferably vinyl acetate.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers there are e.g. Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether and n-octyl vinyl ether.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • (Meth) acrylic acid in this specification means methacrylic acid and acrylic acid.
  • Organic compounds which have at least two free-radically polymerizable double bonds preferably have 2 to 6, particularly preferably 2 to 4, very particularly preferably 2 to 3 and in particular exactly 2 free-radically polymerizable double bonds.
  • di- and poly (meth) acrylates 1, 2, 1, 3 and 1, 4-butanediol diacrylate, 1, 2 and 1, 3-propylene glycol (meth) acrylate, 1, 6-hexanediol di ( meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri and tetra (meth) acrylate.
  • the crosslinkers are particularly preferably selected from the group consisting of divinylbenzene, 1,4-butanediol diacrylate and allyl methacrylate.
  • Compounds (G1) and (G2) are selected from the group consisting of (meth) acrylic acid 2- (2-oxo-imidazolidin-1-yl) ethyl ester (ureidoethyl (meth) acrylate), N- [2- (2 oxo-oxazolidin-3-yl) ethyl] methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, diacetoneacrylamide (DAAM) and disaccharone methacrylamide.
  • DAAM diacetoneacrylamide
  • (meth) acrylic acid 2- (2-oxo-imidazolidin-1-yl) ethyl ester, (acetoacetoxy) ethyl methacrylate, diacetone acrylamide and / or diacetone methacrylamide preference is given to (meth) acrylic acid 2- (2 oxo-imidazolidin-1-yl) ethyl ester and (acetoacetoxy) ethyl methacrylate and very particularly preferred is diacetone acrylamide and / or diacetone methacrylamide.
  • Particularly preferred monomer (G1) is diacetone acrylamide and / or diacetone methacrylamide.
  • These compounds are at least one compound with one
  • These compounds are at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide, preferably an amide of the carboxylic acids mentioned under (C1) and (C2). Particularly preferred are (meth) acrylic acid amide, crotonic acid amide or amides of dicarboxylic acids, e.g. Itaconic acid diamide, maleic acid diamide or fumaric diamide, more preferably methacrylamide and acrylamide, most preferably acrylamide.
  • the monomer composition of the first stage is usually as follows:
  • (A1) 30 to 99.5% by weight, preferably 40 to 99% by weight, particularly preferably 50 to 97% by weight of at least one (meth) acrylic acid alkyl ester
  • the acid number is determined in this document, unless otherwise stated, according to DIN EN ISO 3682 (potentiometric). Unless stated otherwise, the hydroxyl number in this document is determined according to DIN 53240-2 (potentiometrically at an acetylation time of 20 minutes).
  • the free-radically initiated aqueous emulsion polymerization is conducted in such a way that after the first stage the monomers used have reacted to at least 95% by weight, preferably at least 98% by weight and more preferably at least 99% by weight.
  • the particle size of the polymer 1 obtained from the first stage is generally from 20 to 300 nm.
  • the particle size is 40 to 200 nm and often 60 to 150 nm
  • the particle size may be 20 to 300 nm, preferably 40 to 250 nm, particularly preferably 80 to 200 nm.
  • the particle size in this document is the weight-average diameter of the polymer particles in the dispersion (determined in accordance with IS013321 with a High Performance Particle Sizer from Malvern at 22 ° C. and a wavelength of 633 nm).
  • the weight-average molecular weight Mw of the polymer 1 obtained from the first step is from 5,000 to 100,000 g / mol, preferably from 7,000 to 50,000 g / mol, and more preferably from 10,000 to 35,000 g / mol.
  • the weight average molecular weight Mw is determined by size exclusion chromatography (SEC) with tetrahydrofuran containing 0.1% by weight of trifluoroacetic acid as eluent at a flow rate of 1 ml / min. And 35 ° ° C column temperature.
  • SEC size exclusion chromatography
  • the sample is diluted in the eluent to a concentration of 2 mg / ml and injected with 100 ⁇ of it after the sample solution has been filtered through a 0.2 ⁇ filter (Sartorius Minisart SRP 25) to remove any gel fraction.
  • any gel portion of the polymer is removed, so that the stated values relate to the sol fraction.
  • the insoluble portion of the polymer can be determined by extraction with tetrahydrofuran for four hours in a Soxhlet apparatus and, after drying the residue to constant weight, weighing the remaining residue.
  • the monomers (A1) to (11) are chosen so that the glass transition temperature Tg 1 advantageously in the range of 40 to 150 ° C, particularly advantageously in the range of 50 to 100 ° C and with particular advantage in Range 60 to 90 ° C.
  • the second stage monomer feed to prepare the polymer 2 is typically as follows:
  • the free-radically initiated aqueous emulsion polymerization is conducted in such a way that even after the second stage the monomers used have reacted to at least 95% by weight, preferably at least 98% by weight and more preferably at least 99% by weight.
  • the weight ratio of the sum of the monomers of the first stage (A1) to (11) to the sum of the monomers of the second (A2) to (12) according to the invention is in the range of 5:95 to 70:30, preferably in the range of 10:90 to 70:30, more preferably in the range of 15:85 to 65:35, most preferably in the range of 20:80 to 60:40 and particularly preferably in the range of 25:75 to 60:40.
  • the monomers (A2) to (12) are chosen such that a glass transition temperature Tg 2 results.
  • the monomer mixtures of the first and the second polymerization stage are chosen according to the invention such that the glass transition temperature Tg 1 of the polymer 1 is at least 40 ° C above the glass transition temperature Tg 2 of the polymer 2, the difference Tg 1 - Tg 2 So> 40 ° C is.
  • the difference Tg 1 - Tg 2 > 60 ° C and with particular advantage> 70 ° C.
  • the glass transition temperature Tg 2 is in the range from -30 to 10 ° C., particularly advantageously in the range from -25 to 5 ° C. and with particular advantage in the range from -20 to 0 ° C.
  • the polymer 2 has a glass transition temperature Tg 2 of not more than 0 ° C.
  • This second step may optionally be followed by one or more stages of radical polymerization with one or more of the monomers (A2) to (12).
  • the product obtained from the last stage generally has a particle size of 50 to 500 nm. If the reaction is carried out in the presence of at least one emulsifier, the particle size is 50 to 200 nm and often 60 to 150 nm. If, on the other hand, no emulsifier is present, the particle size can be 50 to 300 nm, preferably 60 to 250 nm, particularly preferably 80 to 200 nm be.
  • the increase in the diameter of the particles from the first to the second stage is dependent on the polymerized monomer amounts of the first and second stages.
  • the increase in the diameter of the particles from the first to the second stage will be from 5 to 50%, preferably from 10 to 40%, particularly preferably from 20 to 35%.
  • the product obtained from the last stage generally has a weight-average molecular weight Mw based on the sol fraction of 50,000 to 300,000 g / mol.
  • the more emulsifier and the more product from the first stage is present the smaller the particles of the product obtained from the last stage.
  • the polymer dispersions can be prepared in a conventional manner by the well-known methods of emulsion polymerization from the monomers using the usual emulsifiers.
  • the emulsifiers optionally used in amounts of at most 1 wt .-%, preferably from 0.1 to 1 wt .-%, more preferably from 0.1 to 0.9 wt .-%, most preferably from 0.2 to 0.8 wt .-% and in particular 0.3 to 0.7 wt .-%, based on the total amount of ethylenically unsaturated monomers used in all stages of the free-radical aqueous emulsion polymerization.
  • at least one emulsifier is present.
  • Emulsifiers for the purposes of the present specification are those compounds which are capable of stabilizing a dispersion of these phases by reducing the interfacial tension between an organic and an aqueous phase.
  • Common emulsifiers include ammonium or alkali metal salts of Cs to C20 alkyl sulfonates, sulfates, phosphonates, phosphates and carboxylates, such as higher fatty alcohol sulfates such as Na-n-lauryl sulfate, or from Cs to C2o alkylbenzenesulfonates, sulfates, phosphonates, phosphates and carboxylates, alkoxylated, preferably ethoxylated Cs to C12-alkylphenols having a degree of ethoxylation of 3 to 30 and alkoxylated, preferably ethoxylated Cs to C25 fatty alcohols having a degree of ethoxylation of 5 to 50.
  • These alkoxylated Alcohols may also be esterified as sulfate, sulfonate, phosphate, polyphosphate or phosphonate with ammonium or alkali metal ions as
  • the emulsifiers used according to the invention are advantageously nonionic and / or anionic emulsifiers or combinations thereof, although anionic emulsifiers are preferred.
  • emulsifiers those which are incorporated in the free radical emulsion polymerization in the polymer. These are generally compounds which carry at least one free-radically polymerizable group, preferably selected from the group consisting of allyl, acrylate, methacrylate and vinyl ether, and at least one emulsifying group, preferably selected from the group indicated above.
  • Examples of these are incorporable emulsifiers brands bisomer ® MPEG 350 MA Laporte, Hitenol ® BC-20 (APEO), Hitenol ® BC-2020 Hitenol ® KH-10 or Noigen ® RN-50 (APEO) Dai-Ichi Kogyo Seiyaku Co., Ltd., MAXEMUL ® 6106, MAXEMUL ® 61 12,
  • Suitable polymerization initiators according to the invention are all inorganic peroxydisulfate compounds which are capable of initiating a free-radical emulsion polymerization in aqueous media, in particular ammonium, sodium and / or potassium peroxydisulfate ([NH 4 ] 2-, Na 2 - and or K2S2O8), with ammonium and / or sodium peroxodisulfate being preferred. With particular advantage, sodium peroxodisulfate is used.
  • the inorganic peroxidisulfate compounds are used according to the invention in amounts of from 0.1 to 10% by weight, preferably in amounts of from 0.1 to 2.0% by weight and more preferably in amounts of from 0.1 to 1.0% by weight. , each referring to the total amount of radical in all stages Emulsion polymerization used ethylenically unsaturated monomers (A1) to (12) used.
  • inorganic peroxidisulfate compounds it is also possible to use other conventional free-radical initiators, such as organic peroxides such as dibenzoyl peroxide or tert-butyl hydroperoxide, azo compounds such as azoisobutyrodinitrile and so-called redox systems such as combinations of peroxy compounds and a reducing co-initiator such as the sodium salt of hydroxymethanesulfinic acid, Ascorbic acid or ferrous salts.
  • organic peroxides such as dibenzoyl peroxide or tert-butyl hydroperoxide
  • azo compounds such as azoisobutyrodinitrile
  • so-called redox systems such as combinations of peroxy compounds and a reducing co-initiator such as the sodium salt of hydroxymethanesulfinic acid, Ascorbic acid or ferrous salts.
  • the total amount of the polymerization initiator in the aqueous reaction medium can be initially introduced before the initiation of the polymerization reaction.
  • Initiation of the polymerization reaction is understood to mean the start of the polymerization reaction of the monomers present in the polymerization vessel after radical formation of the radical initiator.
  • the initiation of the polymerization reaction by adding radical initiator to the aqueous polymerization mixture in the polymerization vessel can be carried out under polymerization conditions.
  • a partial or total amount of the radical initiator is added to the aqueous polymerization mixture containing the monomers in the polymerization vessel under conditions which are not suitable for initiating a polymerization reaction, for example at low temperature, and polymerization conditions are then set in the aqueous polymerization mixture .
  • Polymerization conditions are to be understood as meaning in general those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at a sufficient rate of polymerization. They are dependent, in particular, on the radical initiator used.
  • the type and amount of the radical initiator, the polymerization temperature and the polymerization pressure are advantageously selected so that the free-radical initiator has a half-life of ⁇ 3 hours, particularly advantageously ⁇ 1 hour, and there are always sufficient start-up radicals available to initiate and maintain the polymerization reaction.
  • the reaction temperature for the free-radically initiated aqueous emulsion polymerization is the entire range from 0 to 170 ° C into consideration. In this case, temperatures of 50 to 120 ° C, preferably 60 to 1 10 ° C and particularly preferably 70 to 100 ° C are used in the rule.
  • the free-radically initiated aqueous emulsion polymerization can be carried out at a pressure of less than, equal to or greater than 1 atm [1..013 bar (absolute), atmospheric pressure], so that the polymerization temperature can exceed 100 ° C. and can be up to 170 ° C. at In the presence of monomers (A1 + 2) to (11 + 2) having a low boiling point, the emulsion polymerization is preferably carried out under elevated pressure.
  • the pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar (absolute) or even higher values. If the emulsion polymerization is carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free-radical aqueous emulsion polymerization is carried out at 1 atm under exclusion of oxygen, in particular under an inert gas atmosphere, such as, for example, under nitrogen or argon.
  • a process for the preparation of an aqueous polymer dispersion by an at least two-stage free-radically initiated aqueous emulsion polymerization is involved, which is characterized in that in an aqueous medium in a first polymerization
  • (B1) optionally at least one vinyl aromatic having up to 20 C atoms,
  • (D1) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms and vinyl ethers of 1 to 10 C-containing alcohols,
  • (E1) optionally at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid,
  • (F1) optionally at least one compound which has at least two nonconjugated ethylenically unsaturated groups
  • (B2) optionally at least one vinyl aromatic having up to 20 carbon atoms,
  • (D2) optionally at least one free-radically polymerizable compound selected from the group consisting of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms and vinyl ethers of 1 to 10 C-containing alcohols,
  • (E2) optionally at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid,
  • (G2) optionally at least one compound selected from the group consisting of
  • the weight ratio of the sum of the monomers of the first stage (A1) to (11) to the sum of the monomers of the second stage (A2) to (12) is from 5:95 to 70:30,
  • the emulsion polymer obtained from the last step has a particle size of 50 to 500 nm.
  • the process according to the invention advantageously takes place in such a way that 95 95% by weight and particularly advantageously> 98% by weight of all monomers (A1) to (12) are fed to the aqueous medium under polymerization conditions.
  • the amount of inorganic peroxodisulfate compound is from 0.1 to 10% by weight, advantageously from 0.1 to 2.0% by weight and with particular advantage from 0.1 to 1.0% by weight, in each case based on the sum of all monomers used for the emulsion polymerization (A1) to (12).
  • aqueous polymer dispersions obtainable by the process according to the invention are also included according to the invention.
  • a feed process has proven useful in which one starts from a template consisting of a small portion (25% by weight) of the monomers, generally up to 20
  • the monomers can be distributed over several feeds and provided with variable metering rate and / or variable content of one or more monomers.
  • the polymerization of the monomers (A1) to (11) of the first polymerization stage takes place in the presence of a so-called free-radical chain regulator (also called chain transfer agent or chain transfer agent).
  • a so-called free-radical chain regulator also called chain transfer agent or chain transfer agent.
  • the amount and the type of metering of the radical chain regulator is selected so that the polymer 1 always in the claimed weight average molecular weight range of 5,000 to 100,000 g / mol, preferably from 7,000 to 50,000 g / mol and most preferably from 10,000 to 35,000 g / mol lies.
  • radical chain regulators are familiar to the person skilled in the art. Examples which may be mentioned are aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as, for example, ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentan
  • Octanethiol and its isomeric compounds n-nonanethiol and its isomeric compounds, n-decanethiol and its isomeric compounds, n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, such as for example, 2-hydroxyethanethiol, iso-octylmercaptopropionic acid, mercaptopropionic acid, 2-ethylhexyl-thioglycolic acid ester, 3-mercaptopropyltrimethoxysilane (MTMO), aromatic thiols such as benzenethiol, ortho-, meta-, or para-methylbenzenethiol, as well as all others in Polymerhandbook 3rd edtition , 1989, J.
  • substituted thiols such as for example, 2-
  • the amount of radical chain regulator used in the first polymerization stage is generally ⁇ 0.1 and ⁇ 12% by weight, often 0,2 0.25 and 55 , 0 wt .-% and often> 0.6 and ⁇ 3.5 wt .-%. It is advantageous if a partial or total amount of the radical chain regulator is supplied to the aqueous reaction medium before the initiation of the free-radical polymerization reaction. With particular advantage, it is also possible according to the invention to add a part or all of the radical chain regulator to the aqueous reaction medium together with the monomers (A1) to (11) under polymerization conditions.
  • the polymerization can be carried out as described in EP 853 636 or in US 3804881.
  • the disclosure of these two documents is hereby expressly incorporated by reference.
  • the aqueous polymer dispersions thus obtained preferably have a solids content of from 35 to 65% by weight, particularly preferably from 40 to 55% by weight.
  • the glass transition temperatures Tg are generally determined in this document according to DIN EN ISO 1 1357-2 (2013-09) by differential scanning calorimetry (DSC) with a heating rate of 20 K / min.
  • the minimum film-forming temperature (MFT) of such polymer dispersions used for coating compositions according to the invention is advantageously not more than 15 ° C., preferably not more than 10 ° C. and particularly preferably not more than 5 ° C. Nevertheless, the resulting films are not sticky.
  • the minimum film-forming temperature is determined in such a way that the aqueous polymer dispersion is applied to a plate which is heated at one end and cooled at the other end (DIN ISO 21 15: 2001 -04).
  • the minimum film-forming temperature can be determined by visual assessment and temperature sensors at close intervals along the plate.
  • aqueous polymer dispersions prepared by the at least two-stage aqueous emulsion polymerization comprise polymers which contain ethylenically unsaturated monomers having keto-, aldehyde- and / or acetoacetoxy-carbonyl groups in copolymerized form, it may be advantageous if the aqueous polymer dispersion or the additionally prepared, a crosslinking agent is added to the aqueous coating composition prepared.
  • the crosslinking agent may be an organic compound having two or more primary amino groups such as isophoronediamine or 4,7-dioxadecane-1,10-diamine or an organic compound having two or more hydrazide groups such as IQ adipic dihydrazide (ADDH), oxalic dihydrazide, phthalic dihydrazide , Terephthalic acid dihydrazide.
  • IQ adipic dihydrazide ADDH
  • oxalic dihydrazide oxalic dihydrazide
  • phthalic dihydrazide Terephthalic acid dihydrazide.
  • the present polymer dispersions are characterized by a high stability and there are hardly coagulum formations. With the same hydroxyl number, the same solids content and the same molecular weight, the polymer dispersions according to the invention have a lower viscosity than comparable polymer dispersions which have not been obtained according to the invention.
  • the aqueous polymer dispersions can be used as binders for one-component and two-component coating compositions, e.g. for paints, protective coatings, road markings, decorative coatings, paints, coatings.
  • auxiliaries may be added, such as leveling agents, thickeners, defoamers, fillers, pigments, dispersing agents for pigments, etc.
  • the coatings can be obtained by applying the coating compositions to suitable substrates, such as wood, concrete, metal, glass, plastic, ceramics, plasters, stone, asphalt, textiles, painted, primed or weathered substrates.
  • suitable substrates such as wood, concrete, metal, glass, plastic, ceramics, plasters, stone, asphalt, textiles, painted, primed or weathered substrates.
  • Coating materials for coating metals and metal alloys, in particular in light, medium or heavy corrosion protection.
  • a crosslinker is required as further component, which is, for example, polyisocyanates known to the person skilled in the art for these purposes.
  • the monomeric isocyanates used for the preparation of the polyisocyanates may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which is referred to in this document briefly as (cyclo) aliphatic, particularly preferred are aliphatic isocyanates.
  • Aromatic isocyanates are those which contain at least one aromatic ring system, ie both purely aromatic and also araliphatic compounds. The former is understood as meaning isocyanates in which the isocyanato groups are attached directly to aromatic ring systems whereas in the latter case the isocyanato groups are bonded to alkylene groups, but the compounds also contain aromatic ring systems, as is the case with TMXDI, for example.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.
  • Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • the monomeric isocyanates are preferably diisocyanates which carry exactly two isocyanate groups. In principle, however, it may also be monoisocyanates with an isocyanate group. In principle, higher isocyanates having an average of more than 2 isocyanate groups are also considered.
  • Triisocyanates such as triisocyanatononane, 2'-isocyanatoethyl- (2,6-diisocyanatohexanoate), 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, tri- and higher polyisocyanates which are obtained, for example, by phosgenation of corresponding aniline / formaldehyde condensates and represent methylene bridged polyphenyl polyisocyanates.
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 carbon atoms.
  • customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, (for example methyl or ethyl-2, 6-diisocyanatohexanoate), trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyan
  • Isophorone diisocyanate is usually present as a mixture, namely of the cis and trans isomers, generally in the ratio of about 60:40 to 90:10 (w / w), preferably from 70:30 to 90:10.
  • Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.
  • diisocyanates it is possible to use both those diisocyanates obtained by phosgenation of the corresponding amines and those obtained without the use of phosgene, i. after phosgene-free process, are produced.
  • EP-A-126,299 US 4,596,678)
  • EP-A-126,300 US 4,596,679
  • EP-A-355,443 US 5,087,739
  • HDI 1,6-hexamethylene diisocyanate
  • isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-3-isocyanato-methyl-3,5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to give (cyclo) aliphatic biscarbamic acid esters and their thermal cleavage into the corresponding diisocyanates and alcohols.
  • HDI 1,6-hexamethylene diisocyanate
  • isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-3-is
  • diisocyanates generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
  • the isocyanates used have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, in particular less than 15 ppm and specifically less than 10 ppm. This can be measured, for example, by ASTM D4663-98. Of course, it is also possible to use monomeric isocyanates having a higher chlorine content, for example up to 500 ppm.
  • mixtures of such monomeric isocyanates which have been obtained by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the obtained (cyclo) aliphatic biscarbamic, with such diisocyanates obtained by phosgenation of the corresponding amines are used.
  • the average NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably 2 to 5 and particularly preferably 2.4 to 4.
  • the content of isocyanate groups after the oligomerization, calculated as NCO 42 g / mol, unless otherwise stated, is usually from 5 to 25% by weight.
  • the polyisocyanates are preferably the following compounds:
  • isocyanurates are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • the isocyanatoisocyanurates generally have an NCO content of from 10 to 30% by weight, in particular from 15 to 25% by weight, and an average NCO functionality of from 2.6 to 8.
  • the polyisocyanates containing isocyanurate groups can also contain urethane to a lesser extent. and / or allophanate groups, preferably with a content of bound alcohol of less than 2% by weight, based on the polyisocyanate.
  • polyisocyanates containing uretdione groups with aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the polyisocyanates containing uretdione groups are frequently obtained in a mixture with other polyisocyanates, in particular those mentioned under point 1).
  • Uretdione group-containing polyisocyanates usually have functionalities of 2 to 3.
  • the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or the uretdione groups are first formed and then added to the other polyisocyanates. Cyanates are reacted or the diisocyanates first to the other polyisocyanates and then these are converted to uretdione-containing products
  • Biuret group-containing polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs.
  • These biuret polyisocyanates generally have an NCO content of 18 to 24 wt .-% and an average NCO functionality of 2.8 to 6 on.
  • diisocyanate for example hexamethylene diisocyanate or isophorone diisocyanate
  • monohydric or polyhydric alcohols monohydric or polyhydric alcohols.
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.0 to 4.5.
  • Such polyisocyanates containing urethane and / or allophanate groups may be uncoked or, preferably, in the presence of catalysts such as ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Bismuth, cobalt, cesium, Zn (II) or Zr (IV) compounds, each in the presence of mono-, di- or polyvalent, preferably monohydric alcohols.
  • catalysts such as ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Bismuth, cobalt, cesium, Zn (II) or Zr (IV) compounds, each in the presence of mono-, di- or polyvalent, preferably monohydric alcohols.
  • Oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
  • Iminooxadiazindion phenomenon containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.
  • Hyperbranched polyisocyanates as known, for example, from DE-A 10013186 or DE-A 10013187.
  • Polyurethane / polyisocyanate prepolymers of di- and / or polyisocyanates with alcohols.
  • the polyisocyanates 1) -1 1), preferably 1), 3), 4) and 6) described under the abovementioned points can, after their preparation, be polyisocyanates containing biuret groups or urethane / allophanate groups with aromatic, cycloaliphatic or aliphatic bonded, preferably (cyclo) aliphatically bonded isocyanate groups, transferred.
  • the formation of biuret groups is carried out, for example, by adding water or
  • urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts.
  • These biuret or urethane / allophanate groups containing polyisocyanates generally have an NCO content of 10 to 25 wt .-% and an average NCO functionality of 3 to 8.
  • Hydrophilic modified polyisocyanates i. Polyisocyanates which contain, in addition to the groups described under 1) to 12), those which formally arise by adding molecules having NCO-reactive groups and hydrophilizing groups to the isocyanate groups of the above molecules.
  • the latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.
  • Modified Polyisocyanates for Dual Cure Applications i. Polyisocyanates which contain, in addition to the groups described under 1) to 13), those which are formally formed by addition of molecules with NCO-reactive groups and groups which can be crosslinked by UV or actinic radiation to the isocyanate groups of the above molecules. These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxy-vinyl compounds.
  • the polyisocyanates are hydrophilic modified polyisocyanates.
  • the polyisocyanate is polyisocyanates based on 1,6-hexamethylene diisocyanate.
  • the polyisocyanate is a mixture of polyisocyanates, most preferably of 1, 6-hexamethylene diisocyanate and of isophorone diisocyanate.
  • the polyisocyanate is a mixture containing low-viscosity polyisocyanates, preferably containing isocyanurate groups Polyisocyanates having a viscosity of 600 to 1500 mPa * s, in particular less than 1200 mPa * s, low viscosity urethanes and / or allophanates having a viscosity of 200 to 1600 mPa * s, in particular 600 to 1500 mPa * s, and / or iminooxadiazinedione groups polyisocyanates.
  • the viscosity values given in this document are determined according to DIN EN ISO 3219 / A.3 at 23 ° C with a cone-plate system with a velocity gradient of 1000 s _1 , unless otherwise stated.
  • the process for preparing the polyisocyanates can be carried out as described in WO 2008/68198, there especially from page 20, line 21 to page 27, line 15, which is hereby incorporated by reference in the present application.
  • reaction can be stopped, for example, as described there from page 31, line 19 to page 31, line 31 and the workup carried out as described there from page 31, line 33 to page 32, line 40, which is hereby incorporated by reference the present application.
  • reaction can also be stopped, as described in WO 2005/087828 from page 11, line 12 to page 12, line 5, which is hereby incorporated by reference in the present application.
  • thermally labile catalysts it is also possible to stop the reaction by heating the reaction mixture to a temperature above at least 80 ° C, preferably at least 100 ° C, more preferably at least 120 ° C. This usually already warming of the reaction mixture, as required for the separation of the unreacted isocyanate by distillation in the workup.
  • deactivators are, for example, hydrogen chloride, phosphoric acid, organic phosphates, such as dibutyl phosphate or diethylhexyl phosphate, carbamates, such as hydroxyalkyl carbamate or organic carboxylic acids. These compounds are added neat or diluted at the appropriate concentration necessary for reaction termination.
  • Melamine-formaldehyde resins can be classified according to fields of application (molding compounds, glues, impregnating resins, lacquers), alkylating agents (etherification with butanol, methanol, mixed etherification) or as here listed by the ratio of triazine: formaldehyde: etherification alcohol characterize:
  • the completely etherified melamine-formaldehyde resins are used in practice preferably in laminations of cans (can-coating) and metal strips (coil coatings) worldwide and in NAFTA also for all layers of automotive finishing.
  • the second large group of partially etherified melamine-formaldehyde resins which in practice usually have a built-in molar ratio of melamine: formaldehyde: alcohol of 1: 3 to 5.4: 2 to 4.3, are markedly increased compared to the first group thermal reactivity without acid catalysis.
  • a self-condensation takes place, which leads to a higher viscosity (lower high-solids behavior) and thus makes it more difficult to remove the free formaldehyde during the distillation.
  • the high-imino types differ from the methylol types in that they have a high degree of alkylation, ie the proportion of the etherified methylol groups on the incorporated formaldehyde equivalents, usually up to 80% by weight, whereas the methylol types in the rule ⁇ 70 wt .-% have.
  • Fields of application for the partially methylolated melamine-formaldehyde resins extend over all areas of application, also in combination with HMMM types for reactivity adjustment, where curing temperatures of 100 to 150 ° C are required. Additional catalysis using weak acids is possible and common practice.
  • Another group of aminoplast resins which are very similar in structure and properties to the melamine-formaldehyde resins, are the benzoguanamine resins (benzoguanamine / formaldehyde resins). Free OH groups can also be at least partially etherified with lower alcohols, especially C 1 -C 4 -alcohols, more preferably methanol or n-butanol.
  • aminoplast resins examples include urea resins, ie polycondensation products of urea and formaldehyde (abbreviation UF, according to DIN EN ISO
  • Free OH groups can also be at least partially etherified with lower alcohols, especially C 1 -C 4 -alcohols, more preferably methanol or n-butanol.
  • the aminoplast resins may preferably be melamine-formaldehyde resins, benzoganamine / formaldehyde resins and urea / formaldehyde resins, each of which may optionally be at least partially etherified and are preferably at least partially etherified.
  • Melamine-formaldehyde resins which can be used according to the invention as amino resins are, for example, constructed as follows:
  • melamine-formaldehyde resins are frequently characterized by the incorporation ratio melamine: formaldehyde: alcohol.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • Melamine-formaldehyde resins which can be used according to the invention can have a built-in oil ratio of 1: 2 to 6: 1 to 6, and in some cases a formaldehyde incorporation ratio of up to 8 can be conceivable by formation of oligoformalcohols.
  • Prefabricated bath ratios of 1: 3 to 6: 1, 5 to 6 are preferred.
  • built-in molar ratios of 1: 3.6 to 5.7: 2.1 to 4.7 are particularly preferred, very particularly preferred Einbaumoldung of 1: 5 to 6: 3.5 to 6, in particular 1: 5 to 6: 4 to 5.
  • the melamine-formaldehyde resins that can be used have not only one melamine group per polycondensate, but also quite a few, preferably up to six, particularly preferably up to four, very particularly preferably up to three and in particular up to two.
  • Benzoguanamine / formaldehyde resins which can be used according to the invention as amino resins are, for example, constructed as follows. Benzoguanamine-formaldehyde resins are also frequently characterized by the incorporation ratio of benzoguanamine: formaldehyde: alcohol.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • Benzoguanamine-formaldehyde resins which can be used according to the invention can have a built-in oil ratio of 1: 1, 5 to 4: 1 to 4, and in some cases a formaldehyde incorporation ratio of up to 6 can also be conceivable by formation of oligoformalcohols.
  • Einbauteoldung of 1: 2 to 4: 1, 5 to 4 are preferred.
  • built-in molar ratios of 1: 2.2 to 3.7: 2.1 to 3.0 are particularly preferred, very particularly preferred incorporation ratios of from 1: 3 to 4: 1, 5 to 4, in particular 1 : 3 to 4: 2.0 to 3.0.
  • n-butyl-etherified benzoguanamine-formaldehyde resins Einbaumolixie of 1: 2.2 to 3.7: 1, 3 to 2 are particularly preferred, very particularly preferred Einbaumolixie of 1: 3 to 4: 1, 5 to 4, in particular 1 : 3 to 4: 1, 5 to 2.5.
  • the useable benzoguanamine-formaldehyde resins can not only have one benzoguanamine group per polycondensate, but also quite a few, preferably up to five, particularly preferably up to four, very particularly preferably up to three and in particular up to two.
  • Urea / formaldehyde resins that can be used according to the invention as amino resins are, for example, structured as follows
  • Urea-formaldehyde resins which can be used according to the invention can have a built-in molar ratio of urea: formaldehyde: alcohol of 1: 1 to 4: 0.3 to 3, preferably 1: 1 to 3: 0.4 to 2, particularly preferably 1: 1, 5 to 2.5: 0.5 to 1, 5, most preferably from 1: 1, 6 to 2.1: 0, 6 to 1, 3 have.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • the urea / formaldehyde resins also include so-called glycoluril resins formed by reacting glycoluril, the reaction product of glyoxal with two equivalents of urea, with formaldehyde, optionally etherified with one or more alcohols.
  • the application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done.
  • the coating thickness is generally in a range of about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 . Subsequently, the volatile constituents of the dispersions are removed. If desired, this process can be repeated one or more times.
  • the aqueous polymer dispersion is dried after application to the substrate, for example in a tunnel kiln or by vent th.
  • the drying can also be done by NIR radiation, where as NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 ⁇ , preferably from 900 to 1500 nm is designated.
  • the drying can be carried out at a temperature of ambient temperature to 100 ° C over a period of a few minutes to several days.
  • the polymer dispersion of the invention is suitable in a particular embodiment as a binder for paints and as a binder for paints.
  • anticorrosive agents such as corrosion inhibitors or active anticorrosive pigments may be used in the anticorrosive coatings application.
  • corrosion inhibitors examples include hexamine, benzotriazole, phenylenediamine, dimethylethanolamine, polyaniline, sodium nitrite, cinnamaldehyde, condensation products of aldehydes and amines (imines), chromates, nitrites, phosphates, hydrazine and ascorbic acid.
  • anticorrosive pigments examples include modified zinc orthophosphate (eg HEUCOPHOS ® ZPA, ZPO and ZMP), polyphosphates (for example HEUCOPHOS ® ZAPP, SAPP, SRPP and CAPP), WSA - Wide Spectrum Anticorrosives (eg HEUCOPHOS ® ZAMPLUS and ZCPPLUS) and modified silicate pigments (for example HAY COSIL ® CTF, Halox ® 750), for example those from Heubach GmbH, as well as Bariumborphosphat (for example, Halox ® 400), Bariumphosphosilikate (for example, Halox ® BW-1 1 1, Halox ® BW-191), Calciumborosilikate (for example, Halox ® CW 291, CW-22/221 CW-2230), Calciumphosphosilikat (for example, Halox ® CW-491), Strontiumphosphosilikat
  • the type of metal can in principle be any metals. In particular, however, are such metals or alloys, which are commonly used as metallic construction materials, and must be protected from corrosion.
  • the surfaces of iron, steel, Zn, Zn alloys, Al or Al alloys are treated as substrates for corrosion protection.
  • the surface may be uncoated, coated with zinc, aluminum or their alloys, hot dip galvanized, electrogalvanised, sherardised or precoated with primers.
  • these are the surfaces of iron, steel, zinc, zinc alloys, aluminum or aluminum alloys.
  • Steel may contain the usual alloying components known to those skilled in the art. These may be the surfaces of bodies made entirely of said metals or alloys. However, they can also be the surfaces of bodies coated with Zn, Zn alloys, Al or Al alloys, where the bodies can be made of other materials, for example of other metals, alloys, polymers or composite materials.
  • Zinc or aluminum alloys are known in the art. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd.
  • typical constituents of aluminum alloys include Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.
  • the term "zinc alloy” is also meant to include Al / Zn alloys in which Al and Zn are present in approximately the same amount , Depending on the desired application, the skilled person will select the type and amount of alloying components.
  • Zn or aluminum coatings can be applied to steel, for example by hot dip processes, eg hot dip galvanizing, or by sherardizing. If the component is immobile or the component geometry does not permit it, corresponding layers can also be applied by means of thermal spraying (spray-galvanizing, spray-aluminizing).
  • polymer dispersions according to the invention it is possible, in particular, to protect metallic surfaces against corrosion which are in contact with atmospheric air during use, but they can also be surfaces which are in contact with water, soil or other corrosive media during use ,
  • the metallic surfaces which are to be protected against corrosion by means of the polymer dispersions according to the invention and the coating compositions may in principle be any desired surfaces. However, it is preferably the surfaces of metallic structures or metal structures or the components required therefor.
  • Metal structures are usually made of structural steel, such as steel beams, steel pipes or steel sheets by riveting, welding or screws to appropriate constructions.
  • the coated articles may be immobile metallic structures such as buildings, bridges, power pylons, containers, pipelines, power plants, chemical plants, ships, cranes, piles, sheet piles, fittings, pipes, tanks, fittings, flanges , Clutches, halls, roofs and structural steel act.
  • anti-corrosive coatings are usually brushed or sprayed in place. This can be either a first protection or a repair.
  • the drying and curing of such anti-corrosion coatings is carried out under atmospheric conditions, ie at ambient temperature and in the presence of air and usual humidity.
  • the relative humidity can be arbitrary, preferably it is between 10 and 80% and more preferably between 30 and 70%.
  • the anticorrosion agent of surfaces is also referred to as corrosion protection coatings as light, medium and heavy corrosion protection.
  • the polymer dispersions and coating compositions according to the invention can be used as or in preparations for the treatment of metallic surfaces. This can be done in light, medium or heavy corrosion protection, for example by spraying or brushing, the paint then cures under atmospheric conditions. It is of course also possible to apply a plurality of paints or coatings of the same or different composition one after the other. The total thickness (dry) of such anticorrosive coatings is determined by the skilled person depending on the desired properties of the anticorrosion layer.
  • the upper limit for the total layer thickness ie the thickness of all applied anticorrosive layers together, is 2 mm, preferably less than 1.5 mm, more preferably less than 1 mm, very particularly preferably less than 800 ⁇ m and in particular less than 500 ⁇ m.
  • the application of the paints of the invention can in any way, for. B. done by brushing or spraying.
  • the curing method depends on the nature of the crosslinker and is usually carried out under atmospheric conditions.
  • the temperature required for curing depends in particular on the crosslinker used. Very reactive crosslinkers can be cured at lower temperatures than less reactive crosslinkers.
  • atmospheric corrosion protection in the context of this invention means that the coating containing at least one inventive polymer dispersion, a layer thickness after drying of at least 40 ⁇ , preferably at least 50 ⁇ , more preferably at least 60 ⁇ and most preferably at least 80 ⁇ and a layer thickness of up to 2 mm, preferably less than 1.5 mm, more preferably less than 1 mm, very particularly preferably less than 800 ⁇ m and in particular less than 500 ⁇ m, the coating composition being applied to the surface under usual ambient conditions, ie at ambient or room temperature, in the presence of air and conventional humidity without the use of additional equipment or facilities cure.
  • typical curing temperatures are more than 0 to 40 ° C., preferably 5 to 35 ° C., particularly preferably 10 to 30 ° C. and very particularly preferably 15 to 25 ° C. in the presence of air and customary atmospheric humidity.
  • the relative humidity can be arbitrary, preferably it is between 10 and 80% and more preferably between 30 and 70%. It will be apparent to those skilled in the art that the time to complete cure of one and the same binder system may vary depending on the actual environmental conditions.
  • the polymer dispersions and coating compositions according to the invention can be used in clearcoats and direct-to-metal coatings.
  • the former are characterized by a lack of any pigments, the latter have no anti-corrosive pigments, are applied to the metal in a single layer and are used in particular when, in addition to a corrosion protection effect, chemical resistance or gloss is required.
  • Typical dry film thicknesses are from 15 to 200 ⁇ m, preferably from 20 to 100 ⁇ m, and particularly preferably from 20 to 80 ⁇ m.
  • the coating compositions of the invention in particular the mixtures of melamine-formaldehyde resins and the polymer dispersions or urea-formaldehyde resins and the polymer dispersions are at a temperature between room temperature and 200 ° C, preferably 100 to 150 ° C over a period of 1 minute to Stired for 40 minutes, preferably 10 to 25 minutes.
  • aqueous polymer dispersions and preparations according to the invention in corrosion inhibitors which are used in categories C2 (according to DIN EN ISO 12944) or higher, preferably in corrosivity categories C3 or higher, and more preferably in corrosivity categories C4 or higher.
  • the corrosivity categories according to DIN EN ISO 12944 are defined as follows for unalloyed steel or for zinc based on the area-related mass loss or on the thickness decrease after the first year of removal:
  • Zinc mass loss> 15-30 g / m 2
  • Zinc mass loss> 30 - 60 g / m 2
  • Emulsion paints also called emulsion paints, are one of the largest product groups in the paint and paint industry (see Ullmann's Encyclopedia of Industrial Chemistry, 4th ed., Volume 15, Verlag Chemie, Weinheim 1978, p 665).
  • Emulsion paints usually contain as binder a film-forming polymer and as a coloring component at least one inorganic pigment, further inorganic fillers and auxiliaries, such as defoamers, thickeners, wetting agents and optionally film-forming agents.
  • Another important property of the polymer dispersions is the good blocking resistance of the coatings, which is understood to mean a low adhesion of the paint film to itself under pressure and elevated temperature.
  • the paints according to the invention preferably contain pigments and fillers in amounts such that the pigment volume concentration (PVK) is from 10 to 85%, particularly preferably from 10 to 55% and very particularly preferably from 10 to 40%. It is also possible to use these as clearcoats without pigments.
  • PVK pigment volume concentration
  • the emulsion paints may also contain colored pigments such as iron oxides, carbon black, graphite, luminescent pigments, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurter green.
  • the emulsion paints according to the invention may also contain organic color pigments, e.g.
  • Suitable fillers include aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates, such as calcium sulfate, silica, etc.
  • the fillers can be used as individual components become. In practice, however, filler blends have proven particularly useful, e.g. Calcium carbonate / kaolin, calcium carbonate / talc.
  • finely divided fillers for example finely divided calcium carbonate or mixtures of different calcium carbonates with different particle sizes, are frequently used.
  • blends of color pigments and fillers are preferably used.
  • aqueous polymer dispersions according to the invention in a simple manner (for example freeze or spray drying) the corresponding polymer powders are accessible.
  • These polymer powders obtainable in accordance with the invention can also be used as components in the production of adhesives, sealants, plastic plasters, paper coating slips, fiber webs, paints and coating compositions for organic substrates and for the modification of mineral binders.
  • Another object of the present invention are one- and two-component coating compositions containing
  • At least one polymer dispersion according to the invention as binder at least one polymer dispersion according to the invention as binder,
  • crosslinker selected from the group consisting of polyisocyanates, melamine-formaldehyde resins and urea-formaldehyde resins,
  • At least one corrosion inhibitor is the use of such one- or two-component coating compositions for coating metals and metal alloys and thus for corrosion protection, preferably for light, medium or heavy corrosion protection, particularly preferably for medium or heavy corrosion protection.
  • the aqueous polymer dispersions according to the invention can be formulated together with a crosslinker as a two-component coating composition.
  • these two-component coating compositions may be composed as follows:
  • these one-component coating compositions may be composed as follows: From 20 to 100% by weight, preferably from 25 to 90% by weight and particularly preferably from 30 to 80% by weight, of the aqueous polymer dispersion according to the invention as binder (based on the solids content of the aqueous polymer dispersion),
  • the binders other than the aqueous polymer dispersions according to the invention may be, for example, water-based, water-dilutable, water-miscible polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea; Polyester polyacrylate polyols; polyester polyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers, graft polymers of the substance groups mentioned with e.g. different glass transition temperatures and mixtures of said binders act. Preference is given to polyacrylate polyols, polyester polyols and polyure
  • Preferred hydroxyl numbers of these other binders are 40 to 350 mg KOH / g and preferably 80 to 180 mg KOH / g solid resin for polyester polyols, and 15 to 250 mg KOH / g and preferably 80 to 160 mg KOH / g solid resin for polyacrylate polyols and 10 to 150 mg KOH / g and preferably 20 to 100 mg KOH / g solid resin for polyurethane polyols.
  • these other binders may have an acid number according to DIN EN ISO 3682 (potentiometric) of up to 200 mg KOH / g, preferably of up to 150 and more preferably of up to 100 mg KOH / g binder.
  • Particularly preferred other binders are polyacrylate polyols and polyesterols.
  • Polyacrylate polyols preferably have a number average molecular weight M n of at least 500 g / mol, more preferably at least 1200 g / mol.
  • the molecular weight M n may in principle be unlimited upwards, preferably up to 50,000 g / mol, more preferably up to 20,000 g / mol, very particularly preferably up to 10,000 g / mol and in particular up to 5,000 g / mol.
  • Further other binders are, for example, polyesterpolyols, such as are obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids, with polyols, in particular diols.
  • triols, tetrols, etc., as well as triacids, etc. are also used in some cases.
  • Polyesterpolyols are known, for example, from Ullmanns Enzyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated.
  • the one- or two-component coating compositions may contain at least one organic solvent which preferably acts as a film-forming assistant.
  • aromatics such as solvent naphtha, benzene, toluene, xylene, or mixtures of aromatic hydrocarbons, such as those sold as Solvesso ® 100, 150 or 200, chlorobenzene, esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol, methoxypropyl, 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol ® Eastman), dipropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethers such as butyl glycol, tetrahydrofuran, dioxane, ethyl glycol ether, diethylene glycol monoethyl ether, diethylene
  • glycol di-n-propyl ether dipropylene glycol dimethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-tert-butyl ether, dipropylene glycol di-tert-butyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monophenyl ether, propylene glycol mono-tert-butyl ether, Propylene glycol diphenyl ether, propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and poly (allyl glycidyl ether), ketones such as acetone, methyl ethyl ketone, halogen-containing organic solvents such as methylene chloride or trich
  • feed 1 was metered in continuously within 40 minutes at a constant flow rate. Thereafter, the polymerization mixture was allowed to react for a further 10 minutes at 80.degree. Following this, 19.3 g of a 2% strength by weight aqueous ammonia solution were added to the polymerization mixture. Thereafter, feed 2 was metered in continuously within 90 minutes at a constant flow rate. Subsequently, the polymerization mixture was left to react for a further 100 minutes at 80 ° C. and then 17.5 g of deionized water were added to the polymerization mixture.
  • aqueous polymer dispersion was cooled to room temperature and treated with 50.0 g of a 12 wt .-% adipamide dihydrazide and 7.5 g of deionized water and filtered through a 125 ⁇ filter.
  • Feed 1 (homogeneous mixture of):
  • the polymer dispersion obtained had a solids content of 40.9% by weight.
  • the weight-average particle diameter of the resulting dispersion particles was 104 nm.
  • a glass transition temperature at +85 ° C (step 1) and a glass transition temperature at -10 ° C (step 2) were determined.
  • the hydroxyl number of the dispersion polymer was determined to be 0 mg KOH / g.
  • a 0.5 ml sample was taken from the reaction mixture and the weight-average molecular weight of the polymer of the first polymerization stage was determined to be 26100 g / mol.
  • the hydroxyl numbers of the dispersion polymers were generally determined in accordance with DIN 53240-2 (potentometrically with an acetylation time of 20 minutes).
  • the glass transition temperatures were generally determined in accordance with DIN EN ISO 1 1357-2 (2013-09) by differential scanning calorimetry (DSC) at a heating rate of 20 K / min using a DSC Q2000 from TA Instruments. The midpoint temperatures were used for the determination.
  • the solids contents were generally determined by drying a defined amount of the aqueous polymer dispersion (about 0.8 g) with the aid of the moisture analyzer HR73 from Mettler Toledo at a temperature of 130 ° C. to constant weight. In each case, two measurements are carried out and the mean value of these two measurements is given.
  • the weight-average particle sizes were generally determined according to ISO 13321 using a High Performance Particle Sizer from Malvern at 22 ° C. and a wavelength of 633 nm.
  • Comparative Example 1 was completely analogous to the preparation of Example 1 with the difference that feed 1 had the following composition:
  • Feed 1 (homogeneous mixture of):
  • the polymer dispersion obtained had a solids content of 38.9% by weight.
  • the weight-average particle diameter of the resulting dispersion particles was 1 10 nm.
  • a glass transition temperature at +85 ° C (step 1) and a glass transition temperature at -10 ° C (step 2) were determined.
  • the weight-average molecular weight of the polymer of the first polymer stage was determined to be 26,700 g / mol.
  • the hydroxyl number of the dispersion polymer was determined to be 4.7 mg KOH / g. Comparative Example 2
  • Comparative Example 2 The preparation of Comparative Example 2 was carried out completely analogously to the preparation of Example 1 with the difference that 420.8 g of a 10 wt .-% aqueous solution of tert-butyl hydroperoxide together with 9.0 g of a 0.5 wt .-% pure aqueous potassium (ethylenediaminetetraacetato) ferrate (II) solution instead of the aqueous sodium peroxodisulfate solution.
  • II ethylenediaminetetraacetato
  • 1.3 g of ascorbic acid dissolved in 50.7 g of deionized water were metered in.
  • the production of the aqueous polymer dispersion had to be stopped due to strong coagulum formation during the second polymerization stage.
  • Example 1 410.6 g aqueous polymer dispersion from Example 1 was mixed with 1 .3 g BYK ® offset 022 (defoamer from Byk) and then a mixture consisting of 0.4 g Lutensit ® A-EP by a Dispermat (dispersant from BASF SE) , 6.6 g of 25 wt .-% aqueous ammonia solution and 35.2 g of deionized water was added.
  • BYK ® offset 022 defoamer from Byk
  • Bayferrox ® 51 were 130 m (iron oxide pigment from Bayer), 21, 6 g of talc 20 M 2 (filler), 38.3 g calcium carbonate and 76.7 g lithopone ® L (filler based on barium sulphate and Zinc sulfide from Sachtleben Chemie GmbH) was added. The entire mixture was dispersed for 30 minutes with glass beads (0 3 mm). Then, 1 g of BYK ® 022 and 2.2 g of a 1, with further stirring 1: 1 mixture of deionized water, and corrosion inhibitor were added L1 (Flash Rust Inhibitor of C. H) and then screened, the glass beads.
  • L1 Flash Rust Inhibitor of C. H
  • Circuit for disconnecting the aqueous formulation was prepared with a mixture of 2.2 g of Collacral ® pi 85 (thickener based on polyurethane from BASF SE), and 7.9 g of butyl glycol (solvent) comparable.
  • a corrosion primer with a pigment / volume concentration (PVC) of 23% was obtained.
  • Comparative Formulation The comparison formulation was prepared completely analogously to the preparation of Formulation 1, but with the difference that 431.7 g of aqueous polymer dispersion from Comparative Example 1 were used.
  • the formulations to be tested were mounted on a cleaned and fat-free deep-drawn sheet (200 ⁇ 80 ⁇ 0.9 mm) with a box doctor blade.
  • the gap size was chosen so that after drying, a dry layer thickness between 60 and 85 ⁇ results.
  • the drying took place over a period of one week at a temperature of 20 to 25 ° C (room temperature) and a relative humidity of 65%.
  • the rear side of the test panels was coated with a solvent-based varnish to protect against corrosion, and the edges were covered with a plastic film.
  • three sheets each each were coated with formulation 1 or the comparative formulation. Subsequently, the test panels were scratched on the side coated with the primer to be tested with a scoring sting to the metal.
  • the coated surfaces were subjected to a salt spray test with a 5 wt .-% aqueous sodium chloride brine according to DIN EN ISO 9227 at a temperature of 35 ° C for 1500 hours. It showed that the coating according to DIN EN ISO 4628-8 with Formulation 1 was up to 3.5 mm rusted, while the coating with the comparative formulation had an undercut of up to 6 mm.

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Abstract

Matériaux de revêtement à un et deux constituants, destinés à la protection contre la corrosion.
PCT/EP2015/063893 2014-07-02 2015-06-22 Matériau de revêtement Ceased WO2016000989A1 (fr)

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US10259967B2 (en) 2014-12-03 2019-04-16 Basf Se Binder system for high-gloss coatings
WO2020083755A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse
WO2020083754A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse à base de polyuréthanes fonctionnalisés
US11098147B2 (en) 2017-01-27 2021-08-24 Celanese International Corporation Aqueous polymer dispersions
CN119081200A (zh) * 2024-11-06 2024-12-06 四川大学 一种基于两步正交引发聚合反应的亲水润滑涂层及其制备方法和应用

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EP0710680A2 (fr) * 1994-11-04 1996-05-08 Basf Aktiengesellschaft Dispersion aqueuse de polymère
US6005042A (en) * 1996-03-11 1999-12-21 Clariant Gmbh Aqueous polymer dispersions as binders for elastic, nonblocking and scratch-resistant coatings
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WO2013087461A1 (fr) * 2011-12-15 2013-06-20 Basf Se Utilisation de dispersions polymères aqueuses pour améliorer la résistance aux agressions chimiques

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EP0710680A2 (fr) * 1994-11-04 1996-05-08 Basf Aktiengesellschaft Dispersion aqueuse de polymère
US5744540A (en) * 1994-11-04 1998-04-28 Basf Aktiengesellschaft Aqueous polymer emulsion
US6005042A (en) * 1996-03-11 1999-12-21 Clariant Gmbh Aqueous polymer dispersions as binders for elastic, nonblocking and scratch-resistant coatings
US20050107527A1 (en) * 2003-11-13 2005-05-19 Pavel Holub Aqueous dispersions containing multi-stage emulsion polymers
WO2009095569A1 (fr) * 2007-11-30 2009-08-06 Cray Valley Sa Dispersion aqueuse de polymere structuree en coeur/ecorce, son procede de preparation et son application dans les revetements
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WO2012130712A1 (fr) * 2011-03-30 2012-10-04 Basf Se Dispersion aqueuse multi-étape de polymérisat, son procédé de production et son utilisation comme liant pour le revêtement de fonds
WO2013087461A1 (fr) * 2011-12-15 2013-06-20 Basf Se Utilisation de dispersions polymères aqueuses pour améliorer la résistance aux agressions chimiques

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10259967B2 (en) 2014-12-03 2019-04-16 Basf Se Binder system for high-gloss coatings
US11098147B2 (en) 2017-01-27 2021-08-24 Celanese International Corporation Aqueous polymer dispersions
WO2020083755A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse
WO2020083754A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse à base de polyuréthanes fonctionnalisés
US12134695B2 (en) 2018-10-26 2024-11-05 Basf Se Aqueous binder formulation based on functionalized polyurethanes
CN119081200A (zh) * 2024-11-06 2024-12-06 四川大学 一种基于两步正交引发聚合反应的亲水润滑涂层及其制备方法和应用

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