EP1948741A2 - Dispersions de poudre aqueuses durcissables par polymerisation radicalaire, procede pour leur production et leur utilisation - Google Patents

Dispersions de poudre aqueuses durcissables par polymerisation radicalaire, procede pour leur production et leur utilisation

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Publication number
EP1948741A2
EP1948741A2 EP06828966A EP06828966A EP1948741A2 EP 1948741 A2 EP1948741 A2 EP 1948741A2 EP 06828966 A EP06828966 A EP 06828966A EP 06828966 A EP06828966 A EP 06828966A EP 1948741 A2 EP1948741 A2 EP 1948741A2
Authority
EP
European Patent Office
Prior art keywords
free
particles
powder dispersions
acid
curable
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Withdrawn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
EP06828966A
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German (de)
English (en)
Inventor
Hubert Baumgart
Bertold Austrup
Bostjan Muhic
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1948741A2 publication Critical patent/EP1948741A2/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Withdrawn legal-status Critical Current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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/24—Treatment of polymer suspensions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated 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
    • C09D5/03—Powdery paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/20—Cross-linking

Definitions

  • the present invention relates to novel, by radical polymerization curable, aqueous powder dispersions.
  • the present invention relates to a novel process for the preparation of free-radically polymerizable, aqueous powder dispersions.
  • the present invention relates to the use of novel, curable by radical polymerization, aqueous powder dispersions and prepared by the new method, curable by free radical polymerization, aqueous powder dispersions as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals.
  • Aqueous powder dispersions in particular aqueous powder coating dispersions, are known to experts as “powder slurries” or “slurries” for short.
  • slurries here and below refers to powder slurries curable by free-radical polymerization.
  • radical polymerization is carried out with compounds containing olefinically unsaturated double bonds.
  • the radical polymerization can be initiated and maintained thermally or with actinic radiation.
  • electromagnetic radiation such as near infrared (NIR), visible light, UV radiation, X-rays or gamma rays, in particular UV radiation, or corpuscular radiation, such as electron radiation, proton radiation, beta radiation, alpha radiation or neutron radiation, in particular electron radiation , Understood.
  • NIR near infrared
  • UV radiation visible light
  • UV radiation X-rays or gamma rays
  • corpuscular radiation such as electron radiation, proton radiation, beta radiation, alpha radiation or neutron radiation, in particular electron radiation , Understood.
  • the known slurries can be cured after their application with near infrared and provide hard, solvent-resistant and yellowing-free coatings, especially clearcoats.
  • Structural viscous slurries are known from the German patent application DE 199 08 013 A1 whose solid, spherical particles have an average particle size of 0.8 to 20 ⁇ m measured using the laser diffraction method and a maximum particle size of 30 ⁇ m.
  • the curable with actinic radiation components of the known slurries have a content of ion-forming groups, in particular carboxyl groups, from 0.05 to 1 equ./kg and a content of neutralizing agents from 0.05 to 1 equ./kg.
  • the known slurries have at a shear rate of 1000 s "1 a viscosity of 50 to 1,000 mPas, at a shear rate of 10 s " 1 such from 150 to 8,000 mPas and 1 s ' 1 such from 180 to 12,000.
  • the known slurries can be cured after their application with UV radiation and provide coatings, especially clearcoats, which have an excellent appearance (Appearance), a high chemical resistance, a high hardness and a smooth surface. They also have no cookers in layer thicknesses of 40 to 50 ⁇ m and are free of cracking (mud cracking).
  • the coatings produced from the known slurries in particular clearcoats, with regard to chemical resistance, Rockfall resistance, scratch resistance and condensation resistance are further developed.
  • the new slurries should be particularly stable in storage, excluding actinic radiation, and should not tend to settle and / or agglomerate. If, after a relatively long time, there is still a slight sedimentation and / or agglomeration of particles, the sedimented particles should disperse again quickly by brief stirring and the agglomerated particles should be rapidly comminuted again.
  • the new slurries are said to provide coatings, in particular clearcoats, which have excellent appearance properties, in particular high gloss. It should be particularly resistant to chemicals, condensation and mechanical impact, especially by stone chipping. In addition, they should be highly scratch-resistant. In addition, they should effectively level out any unevenness in the surface, which can be felt up to the top coat of a multicoat paint system, and thus have a particularly smooth and trouble-free surface. Above all, they should still be free of digesters and mud cracking in particularly high layer thicknesses of more than 80 ⁇ m.
  • novel, free-radically polymerizable, aqueous, pseudoplastic, completely or substantially free of volatile organic compounds powder dispersions were found containing as disperse phase solid and / or highly viscous storage and application conditions dimensionally stable particles (A) with one with the photon correlation spectroscopy measured average particle size z
  • the particles (A) at least one free-radically crosslinkable binder (A1) having a glass transition temperature of -70 to + 50 ° C, a content of olefinically unsaturated double bonds of 2 to 10 equ./kg and a content at Acid groups of 0.05 to 15 equ./kg in an amount of, based on (A), 50 to 100 wt .-%.
  • the slurries according to the invention were particularly stable in storage, excluding actinic radiation, and did not tend to settle and / or agglomerate. If, after some time, the sedimentation and / or agglomeration of particles (A) were still slight, the sedimented particles (A) could be quickly dispersed again by brief stirring and the agglomerated particles (A) rapidly comminuted again.
  • the slurries according to the invention gave coatings according to the invention, in particular clearcoats according to the invention, which had outstanding optical properties (appearance), in particular high gloss. They were particularly stable against chemicals, condensation and mechanical impact, especially by stone chipping ,. In addition, they were highly scratch resistant. In addition, they leveled out unevenness in the substrate, which otherwise permeated the top coat of a multicoat paint system, and therefore had a particularly smooth and trouble-free surface. Above all, however, they were still free from digesters and mud cracking even in particularly high layer thicknesses of more than 80 ⁇ m.
  • the slurry according to the invention is completely or substantially free of organic solvents.
  • Substantially free means that the slurry according to the invention has a solvent content ⁇ 10% by weight, preferably in each case ⁇ 5% by weight and in particular ⁇ 2% by weight).
  • the slurry according to the invention is structurally viscous.
  • the viscosity behavior describes a state which, on the one hand, takes account of the requirements of storage and settling stability of the slurry according to the invention: in the agitated state, for example when pumping the slurry according to the invention in the ring line of a coating plant and when applied, the slurry of the invention assumes a low-viscosity state, which ensures good processability. Without shear stress, on the other hand, the viscosity increases and in this way ensures that the slurry according to the invention already present on the substrate to be coated has a reduced tendency to run off on vertical surfaces ("run formation").
  • the higher viscosity in the unmoved state prevents sedimentation of the solid particles (A) or ensures that the slurry of the invention which is only slightly deposited and / or agglomerated during the storage time is stirred up again.
  • the pseudoplastic behavior is preferably adjusted by means of suitable thickeners (A2), in particular nonionic and ionic thickeners (A2), which are preferably present in the aqueous phase (B).
  • the slurry according to the invention contains as disperse phase solid and / or highly viscous, dimensionally stable particles (A).
  • Dispossionally stable means that under the usual and known conditions of storage and application of pseudoplastic aqueous powder dispersions, the particles (A) only slightly agglomerate, if at all, and / or disintegrate into smaller particles, but also under the influence of shear forces preserve the original form completely or substantially.
  • the particles (A) have an average particle size z-mean of 80 to 750 nm, preferably 80 to 600 nm and in particular 80 to 400 nm, measured by photon correlation spectroscopy.
  • Photon correlation spectroscopy is a common and known method for measuring dispersed particles with particle sizes ⁇ 1 ⁇ m.
  • the measurement can be performed using the Malvern® Zetasizer 1000.
  • the particle size distribution can be adjusted in any way.
  • the particle size distribution results from the use of suitable wetting agents (A2).
  • the content of the slurry of particles (A) according to the invention can vary very widely and depends on the requirements of the individual case.
  • the content is preferably from 5 to 70, preferably from 10 to 60, more preferably from 15 to 50 and in particular from 15 to 40,% by weight, based on the inventive slurry.
  • the particles (A) contain at least one, in particular a, radically crosslinkable binder (A1) a glass transition temperature of -70 to +50 0 C, preferably -60 to + 20 0 C and in particular -60 to +10 0 C,
  • a content of acid groups of 0.05 to 15 equ./kg, preferably 0.08 to 10 equ./kg, preferably 0.1 to 8 equ./kg, more preferably 0.15 to 5 equ./kg, most preferably 0.18 to 3 equ./kg and in particular 0.2 to 2 equ./kg of the binder (A1).
  • the content of acid groups is preferably determined by the acid number according to DIN EN ISO 3682.
  • the particles (A) contain the binders (A1) in an amount of 50 to 100 wt.%, Preferably 55 to 100 wt.%, Preferably 60 to 99 wt.%, Particularly preferably 70 to 99 wt. and in particular 80 to 99 wt .-%, each based on (A).
  • the particles (A) may consist of the binder (A1).
  • the particles (A) preferably also comprise at least one of the additives (A2) described below.
  • the olefinically unsaturated double bonds of the binder (A1) lie in groups selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornyl, isoprenyl , Isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, preferably (meth) acrylate groups.
  • the olefinically unsaturated double bonds are present in acrylate groups.
  • the binders (A1) are oligomeric or polymeric.
  • Oletymer means that the relevant binder (A1) is composed of 3 to 12 monomeric structural units.
  • Polymer means that the relevant binder (A1) is composed of more than 8 monomeric structural units.
  • binder (A1) composed of 8 to 12 monomeric units is considered to be an oligomer or a polymer depends primarily on its number average molecular weight.
  • the number average molecular weight of the binder (A1) can vary very widely and depends on the requirements of the individual case, in particular the viscosity, which is advantageous for the processing and the use of the binder (A1).
  • the viscosity of the binder (A1) is usually adjusted so that a smooth and easy filming of the particles (A) is achieved after the application of the slurry according to the invention and the drying of the resulting wet layer.
  • the number-average molecular weight is preferably from 1000 to 50,000 daltons, preferably from 1,500 to 40,000 daltons and in particular from 2,000 to 20,000.
  • the nonuniformity of the molecular weight may likewise vary widely and is preferably from 1 to 10, in particular from 1.5 to 8.
  • Suitable binders (A1) are all oligomers and polymers which have the property profile described above.
  • the binder (A1) is selected from the group consisting of oligomeric and polymeric epoxy (meth) acrylates, urethane (meth) acrylates and carbonate (meth) acrylates.
  • urethane (meth) acrylates are used.
  • the urethane (meth) acrylates (A1) can be prepared by reacting
  • (a1) at least one compound containing at least two isocyanate groups, selected from the group consisting of aliphatic, aromatic or cycloaliphatic di- and polyisocyanates, with
  • (a3) at least one compound having at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, acid group, preferably selected from the group consisting of carboxylic, phosphonic, phosphinic, sulfonic, and sulfinic, preferably carboxylic acid - And sulfonic acid groups, in particular carboxylic acid groups, and
  • Suitable compounds (a1) are customary and known di- and polyisocyanates having an isocyanate functionality of on average 2 to 6, preferably 2 to 5 and in particular 2 to 4.
  • Aliphatic means that the isocyanate group in question is linked to an aliphatic carbon atom.
  • Cycloaliphatic means that the isocyanate group in question is linked to a cycloaliphatic carbon atom.
  • Aromatic means that the isocyanate group in question is linked to an aromatic carbon atom.
  • Suitable aliphatic diisocyanates (a1) are aliphatic diisocyanates, such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate,
  • Suitable cycloaliphatic diisocyanates (a1) are 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, tetramethylcyclohexane diisocyanate, bis (4'- isocyanatocyclohexyl) methane, (4'-isocyanatocyclohexyl) - (2'-isocyanatocyclohexyl) methane, 2,2-bis (isocyanatocyclohexyl) propane, 2,2- (4'-isocyanatocyclohexyl) - (2'-isocyanatocyclohexyl) propane, 1- isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 2,4- or 2,6-diisocyanato-1-methylcyclohexane or diisocyanates derived from dimer fatty acids, such as those sold under the trade name DD
  • aromatic diisocyanates (a1) are 2,4- or 2,6-toluylene diisocyanate or mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-
  • Phenylene diisocyanate 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate,
  • aliphatic and cycloaliphatic diisocyanates (a1) especially hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and / or di (isocyanatocyclohexyl) methane used.
  • suitable polyisocyanates (a1) are triisocyanates such as nonane triisocyanate (NTI) and polyisocyanates (a1) based on the above-described diisocyanates and triisocyanates (a1), especially oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, Carbodiimide, urea, uretonimine and / or uretdione groups.
  • suitable polyisocyanates (a1) of this type and processes for their preparation are described, for example, in patents and patent applications CA 2,163,591 A 1, US Pat. No. 4,419,513 A, US Pat. No.
  • the oligomers (a1) of hexamethylene diisocyanate and isophorone diisocyanate are used.
  • suitable compounds (a2) are the monoesters of (a21) Diols and polyols which preferably contain 2 to 20 carbon atoms and at least 2 hydroxyl groups in the molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2 ethanediol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol,
  • (a22) alpha, beta-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid,
  • Methacrylamidoglycolic acid especially acrylic acid.
  • suitable compounds (a2) are the monovinyl ethers of the above-described diols and polyols (a21).
  • suitable compounds (a2) are the monoesters or monoamides of the above-described alpha, beta-unsaturated carboxylic acids (a22) with
  • (a23) amino alcohols such as 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol,
  • polyamines such as ethylenediamine or diethylenetriamine.
  • hydroxycarboxylic acids such as hydroxyacetic acid (glycolic acid), 2- or 3-hydroxypropionic acid, 3- or 4-hydroxybutyric acid, hydroxypivalic acid, 6-hydroxycaproic acid, citric acid, malic acid, tartaric acid, 2,3- Dihydroxypropionic acid (glyceric acid), dimethylolpropionic acid,
  • amino acids such as 6-aminocaproic acid, aminoacetic acid (glycine), 2-aminopropionic acid (alanine), 3-aminopropionic acid (beta-alanine) or the other essential amino acids; N, N-bis (2-hydroxyethyl) glycine, N- [bis (hydroxymethyl) methyl] glycine or imidodiacetic acid,
  • sugar acids such as gluconic acid, glucaric acid, glucuronic acid, galacturonic acid or mucic acid (galactaric acid),
  • sulfonic acids such as 2-aminoethanesulfonic acid (taurine), aminomethanesulfonic acid,
  • hydroxyacetic acid (glycolic acid) (a31) is used.
  • the acid groups can be ionized.
  • Suitable counterions are lithium, sodium, potassium, rubidium, cesium, magnesium, strontium, barium or ammonium ions and primary, secondary, tertiary or quaternary ammonium ions, which are derived from customary and known organic amines.
  • Suitable compounds (a4) are the above-described compounds diols and polyols (a21), amino alcohols (a23), thioalcohols (a24) or polyamines (a25).
  • the compounds (a1), (a2) and (a3) and optionally (a4) are reacted in a molar ratio with each other to 3 equ.
  • Isocyanate groups from the compound (a1) 0.5 to 3, preferably 0.8 to 2.5, particularly preferably 1, 0 to 2.2 and in particular 1, 4 to 1, 8 equ. isocyanate-reactive functional groups from the compound (a2) and
  • the preparation of the urethane (meth) acrylates (A1) has no special features, but takes place under the customary and known conditions of the reaction of polyisocyanates with the exclusion of water at temperatures of 5 to 100 ° C.
  • To a polymerization of the olefinically unsaturated To inhibit double bonds is preferably carried out under an oxygen-containing gas, in particular under air or air-nitrogen mixtures.
  • the slurry of the invention consists of at least one disperse phase (A) and a continuous aqueous phase (B).
  • the disperse phase (A) consists of the binder (A1) and the continuous phase (B) of water.
  • the slurry according to the invention also contains at least one customary and known additive (A2) in customary and known amounts.
  • an additive (A2) may be present in the disperse phase (A), ie the dimensionally stable particles (A); but it can also form a separate disperse phase (A2), such as a pigment. In addition, it may be exclusively in the aqueous phase (B), such as a water-soluble salt, or may accumulate in the interface between aqueous phase (B) and disperse phase (A), such as a wetting agent. Last but not least, the additive (A2) can be distributed between the disperse phase (A) and the aqueous phase (B), such as, for example, a molecularly dispersed organic dye.
  • the additive (A2) from the group consisting of residue-free or substantially residue-free thermally decomposable salts; binders which are physically, thermally and / or actinically radiation-curable with respect to the binders (B); Neutralizing agents; thermally curable reactive diluents; curable with actinic radiation reactive diluents; opaque and transparent, color and / or effect pigments; molecularly soluble dyes; opaque and transparent fillers; nanoparticles; Light stabilizers; antioxidants; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Initiators of radical polymerization, especially photoinitiators; thermolabile radical initiators; Adhesion promoters; Leveling agents; film-forming aids; Rheology auxiliaries, such as thickeners and pseudoplastic Sag control agents, SCA; Flame retardants
  • the slurry according to the invention preferably contains residue-free or essentially residue-free, thermally decomposable salts, light stabilizers, wetting agents, emulsifiers, leveling agents, photoinitiators and rheological aids as additives (A2).
  • the slurry according to the invention if it is to be used as a clearcoat slurry, contains no opaque constituents, in particular no opaque pigments and fillers.
  • inventive slurry contains thermally curable constituents, they are preferably present in the dimensionally stable particles (A) in an amount of ⁇ 40% by weight, preferably ⁇ 30% by weight and in particular ⁇ 20% by weight.
  • the slurry according to the invention is preferably prepared by the secondary dispersion process known from German Patent Application DE 199 08 013 A1, German Patent DE 198 41 842 C2 or German Patent Application DE 100 55 464 A1.
  • the ionically stabilizable binders (A1) and optionally the additives (A2) are dissolved in organic solvents, in particular readily volatile, water-miscible solvents.
  • the resulting solutions are dispersed in water with the aid of neutralizing agents (A2).
  • it is diluted with water while stirring. It initially forms a water-in-oil emulsion, which turns on further dilution in an oil-in-water emulsion. This point is generally reached at solids contents of ⁇ 50% by weight, based on the emulsion, and is externally evident from a greater decrease in viscosity during dilution.
  • the oil-in-water emulsion can also be prepared directly by the melt emulsification of the binders (A1) and optionally the additives (A2) in water.
  • wetting agents (A2) are added to the organic solution and / or the water before or during the emulsification. Preferably, they are added to the organic solution.
  • the solvent-containing emulsion thus obtained is subsequently freed of solvents by azeotropic distillation.
  • the removal-solvent at a distillation temperature below 70 ° C, preferably below 50 0 C and are distilled in particular below 40 0C.
  • the distillation pressure is chosen so that this temperature range is maintained at higher boiling solvents.
  • the azeotropic distillation can be accomplished by stirring the emulsion at room temperature in an open vessel for several days.
  • the solvent-containing emulsion is freed from the solvents by vacuum distillation.
  • the evaporated or distilled off amount of water and solvents are replaced by water to avoid high viscosities.
  • the addition of the water can before, after or during the evaporation or distillation by adding in portions.
  • the glass transition temperature of the dispersed dimensionally stable particles increases, and instead of the previous solvent-containing emulsion, the pseudoplastic aqueous dispersion (B) is formed, i. the inventive slurry (A), from.
  • the dimensionally stable particles are mechanically comminuted in the wet state, which is also referred to as wet milling.
  • wet milling Preferably conditions 60 and in particular 5O 0 C in this case be applied so that the temperature of the ground material 70 preferably does not exceed.
  • the specific energy input during the milling process is preferably 10 to 1000, preferably 15 to 750 and in particular 20 to 500 Wh / g.
  • suitable devices which produce low shear fields are customary and known stirred tanks, gap homogenizers, microfluidizers or dissolvers.
  • Examples of suitable devices which produce high shear fields are conventional and known stirred mills or inline dissolvers.
  • the devices that produce high shear fields are used.
  • the agitator mills according to the invention are particularly advantageous and are therefore used with very particular preference.
  • the slurry according to the invention is fed by means of suitable devices, such as pumps, in particular gear pumps, to the devices described above and driven in a circle over this until the desired particle size is reached.
  • suitable devices such as pumps, in particular gear pumps
  • the slurry of the invention is filtered before use.
  • the usual and known filtration devices and filters are used.
  • Mesh size of the filter can vary widely and depends primarily on the
  • filters are monofilament surface filters or bag filters. These are available on the market under the brands Pong® or Cuno®.
  • the slurry according to the invention can be prepared in an outstanding manner by means of the customary and known methods of applying liquid coating materials, such as e.g. Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling, apply.
  • liquid coating materials such as e.g. Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling, apply.
  • spray application methods are used.
  • actinic radiation is excluded.
  • the slurry according to the invention dries without problems and shows filming at the processing temperature, generally at room temperature.
  • the slurry of the invention applied as a wet layer releases at room temperature or slightly elevated temperatures with release of water, the particles contained therein changing their original shape, flowing together and forming a homogeneous film (A).
  • the applied slurry according to the invention can also dry in powder form.
  • the drying may be accelerated by the use of a gaseous, liquid and / or solid hot medium such as hot air, heated oil or heated rolls, or microwave, infrared and / or near infrared (NIR) light.
  • a gaseous, liquid and / or solid hot medium such as hot air, heated oil or heated rolls, or microwave, infrared and / or near infrared (NIR) light.
  • NIR near infrared
  • the wet layer is dried in a circulating air oven at 23 to 150 ° C, preferably 30 to 120 0 C and in particular 50 to 100 0 C dried.
  • the dried layer (A) according to the invention is cured by free-radical polymerization.
  • the radical polymerization can be thermally initiated and maintained.
  • the devices and methods described above are used.
  • the crosslinking temperature is preferably between 120 and 160 ° C.
  • the corresponding burn-in time is between 10 and 60 minutes.
  • the free-radical polymerization is preferably initiated and maintained with actinic radiation, preferably electron radiation or UV radiation, preferably UV radiation, in particular UV irradiation.
  • actinic radiation preferably electron radiation or UV radiation, preferably UV radiation, in particular UV irradiation.
  • the curing with actinic radiation has no special features, but can with the help of the usual and known devices and methods, as described for example in German Patent Application DE 198 18 735 A 1, column 10, lines 31 to 61, the German patent application DE 102 02 565 A1, page 9, paragraph [0092], to page 10, paragraph [0106], German patent application DE 103 16 890 A1, page 17, paragraphs [0128] to [0130], in the international patent application WO 94 / 11123, page 2, lines 35, to page 3, line 6, page 3, lines 10 to 15, and page 8, lines 1 to 14, or US Pat. No. 6,743,466 B2, column 6, line 53, to column 7 , Line 14, are described.
  • the cure is combined with actinic radiation with the thermal cure.
  • the slurry according to the invention and the materials according to the invention can be used extremely widely.
  • they are used as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals according to the invention.
  • the coatings, adhesive layers and seals according to the invention can be used for coating, bonding and sealing a wide variety of coated and uncoated substrates.
  • the substrates are um
  • Hollow glass body industrial small parts such as screws, nut, hubcaps or rims,
  • Containers such as coils, containers or packaging, electrotechnical components, such as electronic winding goods, for example coils, optical components, mechanical components and white goods, such as domestic appliances, boilers and radiators.
  • the substrates are car bodies and parts thereof.
  • the slurry according to the invention is preferably used for the production of the coatings according to the invention.
  • the slurry according to the invention can be used with particular advantage as a primer, primer, filler, basecoat, solid-color topcoat and clearcoat to produce one-coat or multi-coat primer finishes, anticorrosion coatings, antistonechip primers, surfacer finishes, basecoats, solid-color topcoats and clearcoats.
  • the slurry according to the invention is used for the production of clearcoats in the context of multicoat color and / or effect paint systems, in particular by the customary and known wet-on-wet processes (cf., German Patent Application DE 100 27 292 A1 , Page 13, paragraph [0109], to page 14, paragraph [0118]) are prepared from basecoats and the slurry according to the invention.
  • the inventive slurry and the clearcoats of the invention prepared therefrom are outstandingly suitable for the original coating of passenger cars (OEM) and for the repair of car paint finishes, in particular finishes of passenger cars of the upper class.
  • the repair small area, for example, as a spot repair, or large area both the car manufacturer in the line, for example, as an end-of-line repair, as well as in the paint shop done.
  • the damaged surfaces can be pretreated in the area of the areas to be repaired. This can be done for example by dissolving the surface with an organic solvent, heads, grinding, corona treatment or flame treatment. It is a particular advantage of the slurry according to the invention that in many cases such pretreatments can be dispensed with.
  • the multicoat color and / or effect coating systems according to the invention which comprise at least one clearcoat according to the invention fulfill all the requirements which are imposed on automotive finishes (see European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40) ) and fully conform to the appearance of a Class A surface. In particular, they are particularly smooth, even in high layer thicknesses free from paint defects such as craters or cracks, weather-resistant, chemical-resistant, resistant to condensation, resistant to stone chips, and scratch-resistant.
  • Isopropenylidenedicyclohexanol was coarsely dispersed in hydroxyethyl acrylate at 60 ° C. with stirring.
  • the polyisocyanates pentaerythritol tri / tetra-acrylate, hydroquinone monomethyl ether, 1,6-di-tert-butyl-p-cresol and methyl ethyl ketone.
  • dibutyltin dilaurate the reaction mixture warmed. The mixture was stirred at 75 ° C for several hours until the content of free isocyanate groups was constant. Then glycolic acid and methanol were added and stirred until no more free isocyanate groups were detectable.
  • Methyl ethyl ketone corresponding to a solids content of 70 wt .-% in
  • the resulting binder (A1) had a glass transition temperature of 2.5 ° C, a viscosity at 23 ° C of 2.0 Pas, a content of olefinically unsaturated double bonds of 3.12 equiv. / kg solids and an acid number of 11, 41 mg KOH / g solids on. It was excellently suited for the production of clearcoat slurries.
  • the resulting mixture was dispersed in 1004 parts by weight of deionized water. To this dispersion was added 0.171 parts by weight of ammonium acetate. The degree of neutralization of the binder (B1) was 75%. Subsequently, dispersion was filtered through a filter 1 ⁇ m Cuno® white.
  • the filtered dispersion was stirred for 24 hours at room temperature in an open vessel to evaporate the methyl ethyl ketone.
  • the solvent-free dispersion was completed with 0.788 parts by weight of Baysilone® AI 3468 (leveling agent from Borchers) and 15.776 parts by weight of Acrysol® RM-8W (nonionic associative thickener from Rohm & Haas).
  • the mean particle size z-mean of the resulting clearcoat slurry was measured by means of photon correlation spectroscopy (Malvern Zetasizer® 1000); it was 140 nm.
  • the clearcoat slurry had a solids content of 36.2% by weight. It was outstandingly suitable for the production of color and / or effect multicoat paint systems for passenger cars.
  • the clearcoat slurry of Example 1 was applied to the dried basecoat film in wedge form, so that after drying the resulting clearcoat film and the joint curing of the surfacer coat, the basecoat film and the clearcoat film resulted in a wedge-shaped clearcoat a layer thickness of 10 to 100 microns.
  • the curing itself was carried out thermally for 15 minutes at 155 ° C and with UV radiation of a dose of 1, 5 J / cm 2 (iron-doped mercury vapor lamp from the company IST) under an oxygen-depleted atmosphere (1 vol .-% oxygen).
  • the clearcoat was free of craters, mud cracking and micro-disturbances (starry sky) even with a layer thickness> 80 ⁇ m.
  • Example 1 the clearcoat slurry of Example 1 was applied to the dried basecoat film in a uniform layer thickness, so that after drying the resulting clearcoat film and the joint curing of the surfacer coat, the basecoat film and the clearcoat film resulted in a clearcoat of a film thickness of 40 microns.
  • the curing itself was also carried out here thermally for 15 minutes at 155 ° C in a convection oven and with UV radiation of a dose of 1, 5 J / cm 2 (iron-doped mercury vapor lamp from the company IST) under an oxygen-depleted atmosphere (1 vol .-% oxygen) ,
  • the resulting black multicoat paint systems were particularly brilliant, glossy, chemical-resistant, impact-resistant, hard, flexible, scratch-resistant and resistant to condensation, which could be substantiated by the following test results:
  • Tree resin > 75 ° C
  • Residual gloss without cleaning 65 units
  • Residual gloss after cleaning 71 units
  • Residual gloss 81%

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des dispersions de poudre aqueuses à viscosité intrinsèque, durcissables par polymérisation radicalaire et intégralement ou pratiquement exemptes de composés organiques volatils. Ces dispersions de poudre contiennent, en tant que phase dispersée, des particules solides et/ou très visqueuses (A) présentant une stabilité dimensionnelle dans des conditions de stockage et d'utilisation et ayant une taille moyenne z-Mean mesurée par spectroscopie de corrélation photonique comprise entre 80 et 750 nm. Les particules (A) contiennent au moins un agent liant réticulable radicalairement (A1) ayant une température de transition vitreuse comprise entre -70 et +50 °C, une teneur en liaisons doubles oléfiniquement insaturées comprise entre 2 et 10 eq/kg et une teneur en groupes d'acide comprise entre 0,05 et 15 eq/kg, dans une quantité de 50 à 100 % en poids par rapport à (A). L'invention concerne également un procédé pour la production de telles dispersions de poudre, ainsi que leur utilisation.
EP06828966A 2005-11-10 2006-11-09 Dispersions de poudre aqueuses durcissables par polymerisation radicalaire, procede pour leur production et leur utilisation Withdrawn EP1948741A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005053663A DE102005053663A1 (de) 2005-11-10 2005-11-10 Durch radikalische Polymerisation härtbare, wässrige Pulverdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2006/010718 WO2007054289A2 (fr) 2005-11-10 2006-11-09 Dispersions de poudre aqueuses durcissables par polymerisation radicalaire, procede pour leur production et leur utilisation

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EP1948741A2 true EP1948741A2 (fr) 2008-07-30

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US (1) US20090298997A1 (fr)
EP (1) EP1948741A2 (fr)
JP (1) JP2009515018A (fr)
KR (1) KR101003917B1 (fr)
CN (1) CN101305059A (fr)
DE (1) DE102005053663A1 (fr)
WO (1) WO2007054289A2 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
DE102006030059A1 (de) * 2006-06-29 2008-01-17 Basf Coatings Ag Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen
EP2143748A1 (fr) 2008-07-10 2010-01-13 Cytec Surface Specialties, S.A. Compositions aqueuses de polyuréthanes durcissables par irradiation
DE102008036685A1 (de) 2008-08-06 2010-02-11 Basf Coatings Ag Zweischicht-Beschichtungssysteme mit verbesserter Zwischenhaftung
US9404015B2 (en) * 2013-01-15 2016-08-02 Nd Industries, Inc. Multifunctional coatings for fasteners
WO2014202724A1 (fr) 2013-06-19 2014-12-24 Igp Pulvertechnik Ag Procédé de revêtement d'une surface d'un substrat électriquement non conducteur au moyen de peintures en poudre
WO2016052053A1 (fr) 2014-09-29 2016-04-07 富士フイルム株式会社 Particules de gel, composition d'encre, procédé de fabrication de cette composition d'encre, composition photosensible, et procédé de formation d'image
CN107083226B (zh) * 2017-06-13 2020-06-02 吉林大学珠海学院 一种利用聚氨酯预聚体反相悬浮聚合法制备聚氨酯粉末胶粘剂的工艺
CN107356497A (zh) * 2017-07-25 2017-11-17 哈尔滨工业大学 一种利用旋转流变仪测试环氧树脂上浆剂相反转点的方法
CN110845915A (zh) * 2019-11-04 2020-02-28 泰州清润环保科技有限公司 一种道路标识涂料及其去除、更改方法
CN117505205A (zh) * 2023-11-16 2024-02-06 广东西敦千江粉漆科学研究有限公司 一种水分散粉末涂料的微波加热固化方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2916201A1 (de) * 1979-04-21 1980-10-30 Huels Chemische Werke Ag Verfahren zur trimerisierung von diisocyanaten
DE3033860A1 (de) * 1980-09-09 1982-04-15 Bayer Ag, 5090 Leverkusen Neue isocyanato-isocyanurate, ein verfahren zu ihrer herstellung, sowie ihre verwendung als isocyanatkomponente in polyurethanlacken
DE3621706A1 (de) * 1986-06-28 1988-01-07 Bayer Ag Verfahren zur herstellung von isocyanatgruppen aufweisenden prepolymeren, die nach diesem verfahren erhaeltlichen prepolymeren und ihre verwendung als bindemittel in einkomponentenlacken
US5258482A (en) * 1992-06-12 1993-11-02 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from a mixture of diisocyanates and their use in two-component coating compositions
US5290902A (en) * 1993-06-22 1994-03-01 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from cyclic diisocyanates and their use in two-component coating compositions
DE19908013A1 (de) * 1999-02-25 2000-08-31 Basf Coatings Ag Mit aktinischer Strahlung und gegebenenfalls themisch härtbare Pulverslurrys, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19964282B4 (de) * 1999-12-06 2004-01-29 Basf Coatings Ag Verfahren zur Herstellung einer farb- und/oder effektgebenden Mehrschichtlackierung auf einem grundierten oder ungrundierten Substrat und mit Hilfe des Verfahrens herstellbare Mehrschichtlackierungen
DE10061726A1 (de) * 2000-12-12 2002-06-13 Basf Ag Verfahren zur Herstellung einer härtbaren wässrigen Polymerdispersion
US6432490B1 (en) * 2001-02-12 2002-08-13 E. I. Du Pont De Nemours And Company Process for coating substrates
DE10115505B4 (de) * 2001-03-29 2007-03-08 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbare wäßrige Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10126653A1 (de) * 2001-06-01 2002-12-12 Basf Coatings Ag Pigmentierte Pulverlacksuspersionen (pigmentierte Pulverslurries), Verfahren zu ihrer Herstellung und ihre Verwendung
US6743466B2 (en) * 2001-08-03 2004-06-01 E. I. Du Pont De Nemours And Company Process for repairing coated substrate surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007054289A2 *

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CN101305059A (zh) 2008-11-12
KR101003917B1 (ko) 2010-12-30
JP2009515018A (ja) 2009-04-09
DE102005053663A1 (de) 2007-05-16
WO2007054289A3 (fr) 2007-09-13
US20090298997A1 (en) 2009-12-03
KR20080080523A (ko) 2008-09-04
WO2007054289A2 (fr) 2007-05-18

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