WO1990006187A1 - Proceder pour obtenir un vernis multicouches, vernis soluble dans l'eau, procede pour obtenir des microparticules de polymeres reticulees et microparticules de polymeres reticulees - Google Patents

Proceder pour obtenir un vernis multicouches, vernis soluble dans l'eau, procede pour obtenir des microparticules de polymeres reticulees et microparticules de polymeres reticulees Download PDF

Info

Publication number
WO1990006187A1
WO1990006187A1 PCT/EP1989/001435 EP8901435W WO9006187A1 WO 1990006187 A1 WO1990006187 A1 WO 1990006187A1 EP 8901435 W EP8901435 W EP 8901435W WO 9006187 A1 WO9006187 A1 WO 9006187A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
ethylenically unsaturated
component
mixture
meth
Prior art date
Application number
PCT/EP1989/001435
Other languages
German (de)
English (en)
Inventor
Stefan Wieditz
Jürgen Niemann
Arnold Dobbelstein
Original Assignee
Basf Lacke + Farben Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Lacke + Farben Aktiengesellschaft filed Critical Basf Lacke + Farben Aktiengesellschaft
Publication of WO1990006187A1 publication Critical patent/WO1990006187A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • 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

Definitions

  • the invention relates to a method for producing a multilayer coating on a substrate surface, in which
  • the invention also relates to a water-dilutable lacquer which is obtained by emulsion polymerization of
  • the invention further relates to a method for producing crosslinked polymer microparticles and to crosslinked polymer microparticles produced by this method.
  • aqueous basecoat materials are used in the process in question which contain crosslinked polymer microparticles obtainable by emulsion polymerization of ethylenically unsaturated monomers (cf. EP-B-38 127, column 4, lines 51 to 60, column 20, line 40 to column 25, Line 50), then coatings are obtained which need improvement with regard to gloss and adhesion properties.
  • the object on which the present invention is based consists in the provision of pigmented aqueous basecoats which are obtained by emulsion polymerization of
  • basecoats which contain crosslinked polymer microparticles which can be obtained by using 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5% by weight as component (B).
  • the crosslinked polymer microparticles used according to the invention can be prepared by emulsion polymerization of components (A) and (B) in an aqueous medium in the known apparatus, for example in a stirred kettle with a heating and cooling device.
  • the monomers can be added in such a way that a solution of all of the water, the emulsifier and part of the initiator is introduced and the monomer or monomer mixture and separately therefrom, but in parallel the rest of the initiator is slowly added at the polymerization temperature .
  • the emulsion polymerization process is a process that has been known for a long time (cf. e.g. chemistry, physics and technology of plastics in individual representations, dispersions of synthetic high polymers, Part I by F. Hölscher,
  • emulsion polymerization to be carried out to produce the crosslinked polymer microparticles to be used according to the invention is initiated with a redox initiator system consisting of H 2 O 2 and a nonionic, water-soluble reducing agent (as described in EP-A-107 300), basecoat materials are obtained , which can be used to produce multi-layer coatings with high resilience in a condensed water constant climate.
  • a redox initiator system consisting of H 2 O 2 and a nonionic, water-soluble reducing agent (as described in EP-A-107 300)
  • nonionic, water-soluble reducing agents which can be used are: ascorbic acid, sulfur compounds, such as thiourea and mercaptans, amines, such as hydroxylamine, triethylamine and ethanolamine, reducing acids, such as glycolic acid, tartaric acid and diphenylglycolic acid and benzyl alcohol.
  • Ascorbic acid is preferably used.
  • the emulsion polymerization in question can also be carried out by conventional initiators, e.g. Per compounds such as ammonium persulfate, potassium persulfate, ammonium or alkali metal peroxydiphosphate and organic peroxides such as e.g. Benzoyl peroxide, organic peresters such as perisopivalate, partly in combination with reducing agents such as sodium disulfite, hydrazine, hydroxylamine and catalytic amounts of accelerators such as iron, cobalt, cerium and vanadyl salts are initiated.
  • Per compounds such as ammonium persulfate, potassium persulfate, ammonium or alkali metal peroxydiphosphate and organic peroxides such as e.g. Benzoyl peroxide, organic peresters such as perisopivalate, partly in combination with reducing agents such as sodium disulfite, hydrazine, hydroxylamine and catalytic amounts of accelerators such as iron,
  • An anionic emulsifier can be used alone or as a mixture as an emulsifier.
  • anionic emulsifiers are the alkali metal salts of sulfuric acid half-esters of alkylphenols or alcohols, furthermore the sulfuric acid half-esters of oxethylated alkylphenols or oxethylated alcohols, preferably the alkali metal salts of sulfuric acid half-esters of a nonylphenol, alkyl or sodium lauryl sulfonate, alkyl or arylsulfurate, and sodium lauryl sulfonate, with 4-5 moles of ethylene oxide per mole secondary sodium alkane sulfonates, the carbon chain of which contains 8-20 carbon atoms.
  • the amount of the anionic emulsifier is 0.1-5.0% by weight, based on the monomers, preferably 0.5-3.0% by weight.
  • a nonionic emulsifier of the ethoxylated alkylphenol or fatty alcohol type for example a Addition product of 1 mol nonylphenol and 4 - 30 mol
  • Ethylene oxide can be used in a mixture with the anionic emulsifier.
  • the emulsion polymerization is generally carried out at temperatures from 20 to 100 ° C., preferably 40 to 90 ° C.
  • a mixture of is preferably used as component (A)
  • (a4) 0 to 30, preferably 5 to 20% by weight of a further, ethylenically unsaturated monomer or a mixture of such monomers which can be copolymerized with (a1), (a2) and (a3), used, the sum of the proportions by weight of (a1), (a2), (a3) and (a4) always giving 100% by weight.
  • component (a1) e.g. are used: cyclohexyl acrylate, cyclohexyl methacrylate, alkyl acrylates and
  • Alkyl methacrylates with up to 20 carbon atoms in the alkyl radical e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
  • Acrylic acid and / or methacrylic acid are preferably used as component (a2).
  • other ethylenically unsaturated acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • component (a3) hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid. These esters can be derived from an alkylene glycol esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide.
  • component (a3) preference is given to using hydroxyalkyl esters of acrylic acid and methacrylic acid in which the hydroxyalkyl group contains up to 4 carbon atoms, or mixtures of these hydroxyalkyl esters.
  • hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroproxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl acrylate or 4-hydroxybutyl called (meth) acrylate.
  • esters of other unsaturated acids such as ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule, can also be used.
  • component (a4) e.g. are used: vinyl aromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyl toluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers.
  • vinyl aromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyl toluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers.
  • component (B) 0.5 to 2.4, preferably 1.0 to 2.0, particularly preferably 1.5
  • the crosslinked polymer microparticles used according to the invention must have a diameter of 0.01 to 10 ⁇ m.
  • Basecoats which in addition to the crosslinked polymer microparticles described above also contain a water-dilutable polyurethane resin, also provide multi-layer coatings particularly good effect and are preferred.
  • the preferred basecoats preferably contain, as polyurethane resins, water-dilutable polyurethane resins containing urea groups and having a number average molecular weight of 1000 to 60,000, preferably 1,500 to 50,000 (determination:
  • Such polyurethane resins can be prepared by reacting prepolymers containing isocyanate groups with organic polyamines and / or hydrazine.
  • the prepolymer containing isocyanate groups can be prepared by reacting polyalcohols having a hydroxyl number from 10 to 1800, preferably 50 to 500, with excess polyisocyanates at temperatures up to 150 ° C., preferably 50 to 130 ° C., in organic solvents which do not react with isocyanates can be done.
  • the equivalence ratio of NCO to OH groups is between 1.5 and 1.0 to 1.0, preferably between 1.4 and 1.2 to 1.
  • the polyols used to prepare the prepolymer can be low molecular weight and / or high molecular weight and they can contain inert anionic groups.
  • Low molecular weight polyols can be used to increase the hardness of the polyurethane. They have a molecular weight from 60 to about 400 and can contain aliphatic, alicyclic or aromatic groups. Amounts of up to 30% by weight of the total polyol constituents, preferably about 2 to 20% by weight, are used. The low molecular weight polyols with up to about 20 carbon atoms per molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, are advantageous.
  • a high proportion of a predominantly linear polyol with a preferred hydroxyl number of 30 to 150 should be added.
  • Up to 97% by weight of the total polyol can consist of saturated and unsaturated polyesters and / or polyethers with a molecular weight Mn of 400 to 5000.
  • Suitable high molecular weight polyols are aliphatic polyether diols of the general formula H - (- O - (- CHR-) n -) m -OH in the
  • Examples are linear or branched polyether diols, such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and / or poly (oxybutylene) glycols.
  • the selected polyether diols should not introduce excessive amounts of ether groups, otherwise the polymers formed will swell in water.
  • the preferred polyether diols are poly (oxypropylene) glycols in the molar mass range Mn from 400 to 3000.
  • Polyester diols are produced by esterification of organic dicarboxylic acids or their anhydrides with organic diols or are derived from a hydroxy carboxylic acid or a lactone.
  • polyols or polycarboxylic acids with a higher valency can be used to a small extent.
  • the dicarboxylic acids and diols can be linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or be diols.
  • the diols used to prepare the polyesters consist, for example, of alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and other diols, such as dimethylcyclohexane.
  • alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and other diols, such as dimethylcyclohexane.
  • the acid component of the polyester consists primarily of low molecular weight dicarboxylic acids or their anhydrides with 2 to 30, preferably 4 to 18 carbon atoms in the
  • Suitable acids are, for example, o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid,
  • Cyclohexanedicarboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid,
  • Tetrachlorophthalic acid and / or dimerized fatty acids Tetrachlorophthalic acid and / or dimerized fatty acids.
  • polyester polyols can also be used. Smaller amounts of can also form in the formation of polyester polyols
  • Carboxylic acids with 3 or more carboxyl groups for example trimellitic anhydride or the adduct of maleic anhydride with unsaturated fatty acids, are present.
  • polyester diols are also used which are obtained by reacting a lactone with a diol. They are characterized by the presence of a terminal hydroxyl group and recurring polyester components of the formula - (CO- (CHR) n -CH 2 -O-).
  • n is preferably 4 to 6 and the substituent R is hydrogen, an alkyl,
  • Cycloalkyl or alkoxy radical No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.
  • the lactone used as a raw material can be represented by the following general formula in which n and R have the meaning already given.
  • Unsubstituted ⁇ -caprolactone in which n is 4 and all R substituents are hydrogen, is preferred for the preparation of the polyester diols.
  • the reaction with lactone is carried out by low molecular weight polyols, such as
  • Alkyldialkanolamines or urea can be reacted with caprolactone.
  • polylactam diols which are produced by reacting, for example, ⁇ -caprolactam with low molecular weight diols.
  • Aliphatic, cycloaliphatic and / or aromatic polyisocyanates with at least two isocyanate groups per molecule are used as typical multifunctional isocyanates.
  • the isomers or isomer mixtures of organic diisocyanates are preferred.
  • Suitable aromatic diisocyanates are phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate and diphenylmethane diisocyanate.
  • (cyclo) aliphatic diisocyanates Due to their good resistance to ultraviolet light, (cyclo) aliphatic diisocyanates produce products with a low tendency to yellowing. Examples include isophorone diisocyanate, cyclopentylene diisocyanate and the hydrogenation products of aromatic diisocyanates, such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylmethane diisocyanate.
  • aliphatic di Isocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, dimethylethylene diisocyanate, methyltrimethylene diisocyanate and trimethylhexane diisocyanate.
  • Isophorone diisocyanate and dicyclohexyl methane diisocyanate are particularly preferred as diisocyanates.
  • the polyisocyanate component used to form the prepolymer can also contain a proportion of higher-quality polyisocyanates, provided that this does not cause gel formation. Products which have proven useful as triisocyanates are those which contain trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with polyfunctional OH or NH groups
  • Connections are created. These include, for example, the biuret of hexamethylene diisocyanate and water, the
  • Isocyanurate of hexamethylene diisocyanate or the adduct of isophorone diisocyanate with trimethylolpropane isocyanurate of hexamethylene diisocyanate or the adduct of isophorone diisocyanate with trimethylolpropane.
  • the average functionality can optionally be reduced by adding monoisocyanates.
  • chain terminating monoisocyanates are phenyl isocyanate, cyclohexyl isocyanate and stearyl isocyanate.
  • Polyurethanes are generally not compatible with water unless special components are incorporated into their synthesis and / or special manufacturing steps are carried out. So large an acid number is built in that the neutralized product can be dispersed stably in water.
  • compounds which contain two H-active groups reacting with isocyanate groups and at least one group capable of forming anions. Suitable groups which react with isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups. Groups that are capable of forming anions are carboxyl, sulfonic acid and / or phosphonic acid groups. Carboxylic acid or carboxylate groups are preferably used.
  • the isocyanate groups of the diisocyanate preferably react with the other groups of the molecule that are reactive toward isocyanate groups.
  • alkanoic acids with two substituents on the ⁇ -carbon atom are used.
  • the substituent can be a hydroxyl group, an alkyl group or an alkylol group.
  • These polyols have at least one, generally 1 to 3 carboxyl groups in the molecule. They have two to about 25, preferably 3 to 10, carbon atoms. Examples of such compounds are dihydroxypropionic acid,
  • R hydrogen or an alkyl group having up to about 20 carbon atoms.
  • Examples of such compounds are 2,2-dimethylol acetic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid and 2,2-dimethylol pentanoic acid.
  • the preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid.
  • Compounds containing amino groups are, for example, ⁇ , ⁇ -diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diamino-diphenyl ether sulfonic acid.
  • the polyol containing carboxyl groups can be 3 to
  • the amount of ionizable carboxyl groups available as a result of the carboxyl group neutralization in salt form is generally at least 0.4% by weight, preferably at least 0.7% by weight, based on the solid.
  • the upper limit is about 6% by weight.
  • the amount of dihydroxyalkanoic acids in the unneutralized prepolymer gives an acid number of at least 5, preferably at least 10.
  • the upper limit of the acid number is 70, preferably 40, based on the solids.
  • this dihydroxyalkanoic acid is advantageously at least partially neutralized with a tertiary amine in order to avoid a reaction with the isocyanates.
  • the NCO prepolymers used according to the invention can be prepared by simultaneously reacting the polyol or polyol mixture with an excess of diisocyanate.
  • the implementation can also be carried out step by step in the prescribed order.
  • the reaction temperature is up to 150 ° C, with a temperature in the range of 50 to 130 ° C
  • the NCO prepolymer contains at least about 0.5% by weight of isocyanate groups, preferably at least 1% by weight of NCO, based on the solid.
  • the upper limit is approximately 15% by weight, preferably 10% by weight, particularly preferably 5% by weight.
  • the reaction can optionally be carried out in the presence of a catalyst such as organotin compounds and / or tertiary amines. In order to keep the reactants in a liquid state and to enable better temperature control during the reaction, it is possible to add organic solvents which do not contain any active hydrogen according to Zerewitinoff.
  • Usable solvents are, for example, dimethylformamide, esters, ethers, such as diethylene glycol dimethyl ether, keto esters, ketones, such as methyl ethyl ketone and acetone, ketones substituted with methoxy groups, such as methoxy hexanone, glycol ether esters, chlorinated hydrocarbons, aliphatic and alicyclic hydrocarbon pyrrolidones, such as N-methylpyrrolidone Furans, aromatic hydrocarbons and their mixtures.
  • the amount of solvent can and should vary within wide limits sufficient to form a prepolymer solution with a suitable viscosity.
  • water-insoluble solvents boil lower than water, they can be gently distilled off after the polyurethane dispersion containing urea groups has been prepared by vacuum distillation or thin-layer evaporation.
  • High-boiling solvents should be water-soluble and remain in the aqueous polyurethane dispersion in order to
  • Particularly preferred solvents are N-methylpyrrolidone, optionally in a mixture with ketones, such as methyl ethyl ketone.
  • the anionic groups of the NCO prepolymer are at least partially neutralized with a tertiary amine.
  • the resulting increase in dispersibility in water is sufficient for infinite dilutability. It is also sufficient to consistently disperse the neutralized polyurethane containing urea groups.
  • Suitable tertiary amines are, for example, trimethylamine, triethylamine,
  • N-methylmorpholine After neutralization, the NCO prepolymer is diluted with water and then results in a finely divided dispersion. Shortly thereafter, the isocyanate groups still present are reacted with di- and / or polyamines with primary and / or secondary amino groups as chain extenders. This reaction leads to a further linkage and an increase in the molecular weight.
  • the competitive reaction between amine and water with the isocyanate must be well coordinated (time, temperature, concentration) and well monitored for reproducible production in order to obtain optimal properties.
  • Water-soluble compounds are preferred as chain extenders because they improve the dispersibility of the polymeric end product in water increase. Hydrazine and organic diamines are preferred because they generally build up the highest molar mass without gelling the resin.
  • the ratio of the amino groups to the isocyanate groups is selected appropriately.
  • the amount of chain extender is determined by its functionality, the NCO content of the prepolymer and the duration of the reaction.
  • the ratio of the active hydrogen atoms in the chain extender to the NCO groups in the prepolymer should generally be less than 2: 1 and preferably in the range from 1.0: 1 to 1.75: 1.
  • the presence of excess active hydrogen, especially in the form of primary amino groups, can result in polymers with undesirably low molecular weights.
  • Polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that have no hydrogen atoms that are reactive with isocyanate groups. Examples are polyamines with a linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.
  • diamines examples include ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, 1,6-hexamethylenediamine, trimethylhexamethylenediamine, methanediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane and aminoethylethanolamine.
  • Preferred diamines are alkyl or cycloalkyl diamines, such as propylenediamine and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.
  • the chain can be extended at least partially with a polyamine which has at least three amine groups with a reactive hydrogen.
  • This type of polyamine can be used in an amount such that unreacted amine nitrogen atoms with 1 or 2 reactive hydrogen atoms are present after the polymer has been extended lie.
  • Such useful polyamines are diethylenetriamine, triethylenetetraamine, dipropylenetriamine and dibutylenetriamine.
  • Preferred polyamines are the alkyl or cycloalkyl triamines, such as diethylenetriamine.
  • small amounts of monoamines such as ethylhexylamine, can also be added.
  • the water-dilutable polyurethane resins to be used according to the invention and their production are also used in the water-dilutable polyurethane resins to be used according to the invention and their production are also used in the water-dilutable polyurethane resins to be used according to the invention and their production are also used in the water-dilutable polyurethane resins to be used according to the invention and their production are also used in the water-dilutable polyurethane resins to be used according to the invention and their production are also used in the
  • the preferred basecoats contain a mixture of 90 to 40% by weight of the crosslinked polymer microparticles described above and 10 to 60% by weight of the water-dilutable polyurethane resin containing urea groups described above, the proportions each referring to the solids content and their total always 100% by weight .-%.
  • the aqueous basecoats of the invention advantageously contain further water-thinnable synthetic resins, such as Aminoplast resins, polyesters and polyethers, which generally serve as grinding resins for the pigments.
  • further water-thinnable synthetic resins such as Aminoplast resins, polyesters and polyethers, which generally serve as grinding resins for the pigments.
  • the aqueous basecoats of the invention preferably contain 5 to 20, particularly preferably 10 to 16% by weight, based on the total solids content of the basecoats, of a water-dilutable aminoplast resin, preferably melamine resin, and 5 to 20, preferably 8 to 15% by weight, of a water-dilutable polyether (eg polypropylene glycol with a number average molecular weight of 400 to 900).
  • a water-dilutable aminoplast resin preferably melamine resin
  • a water-dilutable polyether eg polypropylene glycol with a number average molecular weight of 400 to 900.
  • the basecoats of the invention can be color-imparting pigments based on inorganic, such as titanium dioxide, iron oxide, carbon black, etc., color-imparting pigments based on orga nical basis and common metal pigments (e.g. commercially available aluminum bronzes, stainless steel bronzes ).
  • the basecoats according to the invention preferably contain metal pigments and / or effect pigments.
  • the pigmentation level is in the usual ranges.
  • theological inorganic or organic additives can also be added to the basecoats of the invention. So act as a thickener, for example
  • water-soluble cellulose ethers such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose, and
  • Ethylene-maleic anhydride copolymers and their derivatives or also hydrophobically modified ethoxylated urethanes or polyacrylates are particularly preferred.
  • the basecoats of the invention generally have a solids content of about 15 to 50% by weight.
  • the solids content varies with the intended use of the basecoats.
  • metallic paints for example, it is preferably 17 to 25% by weight.
  • plain-colored paints it is higher, for example 30 to 45% by weight.
  • the basecoats of the invention can additionally contain customary organic solvents. Their share is kept as low as possible. For example, it is below 15% by weight.
  • the basecoats of the invention are generally adjusted to a pH between 6.5 and 9.0.
  • the pH can be adjusted with conventional amines, such as. B. ammonia, triethylamine, dimethylaminoethanol and N-methylmorpholine.
  • the water-dilutable lacquers according to the invention can be applied to any substrates, such as e.g. Metal, wood, plastic or paper can be applied. Essentially all known application methods, e.g. Syringes, squeegees, dipping etc. are used.
  • Polyurethane resin dispersion 2 830 g of a polyester made of neopentyl glycol, 1,6-hexanediol and adipic acid with a hydroxyl number of 135 and an acid number below 3 are dewatered in vacuo at 100 ° C. for 1 hour. 524 g of 4,4-dicyclohexylmethane diisocyanate are added at 80 ° C. and the mixture is stirred at 90 ° C. until the free isocyanate group content is 6.18% by weight, based on the total weight.
  • the mass obtained is poured into 2400 g of cold deionized water with vigorous stirring. You get a fine one partial dispersion. 80 g of a 30% strength aqueous solution of ethylenediamine are added to this dispersion with vigorous stirring within 20 minutes. The resulting, very fine-particle dispersion has a solids content of 35% and a run-out time of 23 seconds in the DIN cup 4.
  • the mixtures 1 and 2 are mixed at 800-1000 rpm for 30 minutes and then adjusted to a pH of 7.7 using a 5% strength aqueous dimethylethanolamine solution. The viscosity is then adjusted by adding deionized water to a run-out time of 25 seconds in a DIN 4 cup.
  • the basecoats are sprayed onto well-known methods onto phosphate-coated steel sheets (Bonder 132) coated with a commercially available electro-dip coating and a commercially available filler, after a flash-off time of 10 minutes they are overpainted with a commercially available clearcoat and baked at 140 ° C for 20 minutes. A part of the painted sheets is coated again with the basecoats and overcoated with a commercially available clearcoat. The paintwork thus obtained is baked at 80 ° C. for 40 minutes.

Abstract

Procédé permettant d'obtenir un vernis multicouches à partir d'un vernis de base pigmentaire contenant des microparticules de polymère réticulées obtenues par polymérisation par dispersion. Le procédé est caractérisé en ce que les microparticules de polymère contenues dans le vernis de base s'obtiennent en utilisant entre 0,5 et 2,4 % en poids d'allylméthacrylate ou entre 1,5 et 8,0 % en poids d'éthylèneglycoldi(méth)acrylate ou entre 1,5 et 8,0 % en poids de butanedioldi(méth)acrylate ou entre 1,5 et 10,0 % en poids d'hexanedioldi(méth)acrylate ou entre 0,5 et 6,0 % en poids de divinylbenzène, les pourcentages en poids étant calculés par rapport à la quantité totale du monomère utilisé.
PCT/EP1989/001435 1988-12-09 1989-11-27 Proceder pour obtenir un vernis multicouches, vernis soluble dans l'eau, procede pour obtenir des microparticules de polymeres reticulees et microparticules de polymeres reticulees WO1990006187A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3841541A DE3841541A1 (de) 1988-12-09 1988-12-09 Verfahren zur herstellung einer mehrschichtigen lackierung, wasserverduennbarer lack, verfahren zur herstellung von vernetzten polymermikroteilchen und vernetzte polymermikroteilchen
DEP3841541.0 1988-12-09

Publications (1)

Publication Number Publication Date
WO1990006187A1 true WO1990006187A1 (fr) 1990-06-14

Family

ID=6368826

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1989/001435 WO1990006187A1 (fr) 1988-12-09 1989-11-27 Proceder pour obtenir un vernis multicouches, vernis soluble dans l'eau, procede pour obtenir des microparticules de polymeres reticulees et microparticules de polymeres reticulees

Country Status (5)

Country Link
AU (1) AU4644189A (fr)
CA (1) CA2004987A1 (fr)
DE (1) DE3841541A1 (fr)
WO (1) WO1990006187A1 (fr)
ZA (1) ZA899022B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110520C5 (de) * 1991-03-30 2005-10-20 Basf Coatings Ag Mischsystem zur Herstellung wasserverdünnbarer Überzugsmittel
DE4143688B4 (de) 1991-03-30 2007-03-29 Basf Coatings Ag Verwendung eines Mischsystems sowie Verfahren zur Herstellung von Wasserbasislacken und von wasserverdünnbaren Überzugsmitteln
NO922508L (no) * 1991-06-28 1992-12-29 Morton Coatings Inc Hurtigtoerkende vannbasert vegmerkingsmaling
DE4338265C1 (de) * 1993-11-10 1994-12-08 Herberts Gmbh Verfahren zur Beschichtung im Coil Coating Verfahren unter Verwendung von Überzugsmitteln auf der Basis organischer Lösemittel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089741A2 (fr) * 1982-03-18 1983-09-28 Basf Corporation Procédé pour produire un revêtement multicouche sur un substrat et substrat ainsi revêtu
EP0038127B1 (fr) * 1980-04-14 1984-10-17 Imperial Chemical Industries Plc Procédé pour enduire en plusieurs couches, comprenant l'utilisation d'une composition aqueuse à caractère thixotropique d'enduit de fond contenant des particules d'un polymère réticulé
EP0248612A2 (fr) * 1986-06-03 1987-12-09 Crown Berger Limited Epaississants pour peintures en émulsion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0038127B1 (fr) * 1980-04-14 1984-10-17 Imperial Chemical Industries Plc Procédé pour enduire en plusieurs couches, comprenant l'utilisation d'une composition aqueuse à caractère thixotropique d'enduit de fond contenant des particules d'un polymère réticulé
EP0089741A2 (fr) * 1982-03-18 1983-09-28 Basf Corporation Procédé pour produire un revêtement multicouche sur un substrat et substrat ainsi revêtu
EP0248612A2 (fr) * 1986-06-03 1987-12-09 Crown Berger Limited Epaississants pour peintures en émulsion

Also Published As

Publication number Publication date
AU4644189A (en) 1990-06-26
CA2004987A1 (fr) 1990-06-09
ZA899022B (en) 1990-08-29
DE3841541A1 (de) 1990-06-13

Similar Documents

Publication Publication Date Title
EP0507819B1 (fr) Utilisation d'un procédé pour la fabrication d'un revètement multicouche
EP0521040B1 (fr) Procede de production d'un enduit de laque multicouche de reparation
EP0730613B1 (fr) Procede permettant de realiser un revetement de peinture a deux couches, et peintures aqueuses
EP0521928B1 (fr) Procede de production d'enduits de laque a couches multiples et laque aqueuse
EP0447428B1 (fr) Procede pour obtenir un revetement multicouches, compose de revetement soluble dans l'eau, polymeres d'emulsion et procede de preparation de polymeres d'emulsion solubles dans l'eau
DE19722862C1 (de) Wäßriger Lack und dessen Verwendung zur Herstellung einer zweischichtigen Lackierung
EP0256540B1 (fr) Enduit aqueux, son procédé de préparation et son utilisation
EP0787159B1 (fr) Polyacrylate modifie a l'aide de polyurethane
EP0593454B1 (fr) Procede pour la fabrication d'un laquage multicouche et laques de base aqueuses se pretant a ce procede
EP0260447B1 (fr) Composition aqueuse de revêtement, son procédé de préparation et son application
EP0297576B1 (fr) Procédé pour produire un revêtement multicouche et agent de revêtement aqueux adapté
EP0521919B1 (fr) Procede pour la fabrication d'un laquage multicouche et laques de base aqueuses se pretant a ce procede
DE4115042A1 (de) Physikalisch trocknendes ueberzugsmittel auf waessriger basis und dessen verwendung
EP0662992B1 (fr) Systeme mixte pour la fabrication d'agents de revetement diluables a l'eau
WO1990006187A1 (fr) Proceder pour obtenir un vernis multicouches, vernis soluble dans l'eau, procede pour obtenir des microparticules de polymeres reticulees et microparticules de polymeres reticulees
EP0720637B1 (fr) Procede de production de couches de vernis de finition et vernis aqueux
WO1994012579A1 (fr) Procede permettant d'appliquer une couche de fond ou une seule couche de peinture sur des matieres plastiques a l'aide d'un agent de revetement aqueux
DE10128886B4 (de) Thermisch oder thermisch und mit aktinischer Strahlung härtbarer, wäßriger, farb- und/oder effektgebender Beschichtungsstoff und seine Verwendung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LU NL SE