EP0447428B1 - 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 - Google Patents

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 Download PDF

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Publication number
EP0447428B1
EP0447428B1 EP90900099A EP90900099A EP0447428B1 EP 0447428 B1 EP0447428 B1 EP 0447428B1 EP 90900099 A EP90900099 A EP 90900099A EP 90900099 A EP90900099 A EP 90900099A EP 0447428 B1 EP0447428 B1 EP 0447428B1
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weight
mixture
stage
monomer
monomers
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German (de)
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EP0447428A1 (fr
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Stefan Wieditz
Jürgen Niemann
Arnold Dobbelstein
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BASF Farben und Fasern AG
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BASF Lacke und Farben AG
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    • 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
    • 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
    • B05D2451/00—Type of carrier, type of coating (Multilayers)

Definitions

  • the invention also relates to water-thinnable coating compositions, water-thinnable emulsion polymers and a process for the preparation of water-thinnable emulsion polymers.
  • aqueous base coating compositions used are composed such that they can be applied to the substrate in relatively thin, fast-drying layers, in particular with the aid of automatic painting systems, and after carrying out process steps (3) and (4), the metal pigment particles in parallel alignment to the substrate surface.
  • the aqueous base coating compositions must be composed in such a way that the base layer of the baked metal effect coating adheres well to the substrate and the transparent cover layer adheres well to the base layer. Furthermore, the aqueous base coating compositions must be composed in such a way that the baked-on metallic effect coating shows no matting, delamination phenomena or even bubbles after exposure to a constant temperature of condensed water.
  • aqueous basecoat compositions exhibit high storage stability.
  • DE-A-36 28 124 discloses aqueous base coating compositions which contain, as film-forming material, a mixture of a water-dilutable emulsification polymer and a water-dilutable polyurethane resin. These basecoat compositions do not optimally meet the requirements set out above.
  • the object on which the present invention is based is to provide aqueous base coating compositions which are suitable for the process in question and which optimally meet the requirements set out above.
  • aqueous coating compositions which can be used as wood lacquers and which contain a water-thinnable emulsion polymer which is free of hydroxyl groups and can be obtained via a two-stage emulsion polymerization process.
  • U.S. Patent 4,150,005 discloses aqueous coating compositions containing a water-thinnable emulsion polymer which can be obtained by preparing a highly hydrophilic polymer with a low glass transition temperature in a first emulsion polymerization stage and in its presence in a second emulsion polymerization stage a hydrophobic polymer with a high glass transition temperature is produced.
  • Multi-layer protective and / or decorative coatings of the type described above and the problems encountered in the manufacture of these coatings are not addressed in U.S. Patent No. 4,150,005.
  • GB-A-2,034,334 describes aqueous coating compositions which contain a water-thinnable emulsion polymer which can be obtained via a two-stage emulsion polymerisation process and which must have N-methylol groups.
  • GB-A-2,034,334 is not indicative of the fact that the two polymer stages have to differ in their glass transition temperatures in the manner according to the invention.
  • Multilayer protective and / or decorative coatings of the type described above and the problems encountered in the manufacture of these coatings are not addressed in GB-A-2,034,334.
  • EP-A-287 144 describes a process for producing a multilayer coating of the type described above, in which aqueous base coating compositions are used which contain a water-dilutable emulsification polymer which can be obtained via a two-stage emulsion polymerization process and which in the second stage ("shell" ) has a very high proportion of acid groups and in which the first and second polymer stages differ in their glass transition temperatures in such a way that the first stage has a lower glass transition temperature than the second stage.
  • aqueous base coating compositions which contain a water-dilutable emulsification polymer which can be obtained via a two-stage emulsion polymerization process and which in the second stage (“shell" ) has a very high proportion of acid groups and in which the first and second polymer stages differ in their glass transition temperatures in such a way that the first stage has a lower glass transition temperature than the second stage.
  • the water-dilutable emulsion polymers used according to the invention are, in a known manner, for example in a stirred tank, by a two-stage emulsion polymerization in an aqueous medium with heating and cooling device, producible.
  • 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 water and the emulsifier it is also possible to introduce some of the water and the emulsifier and to prepare a pre-emulsion from the rest of the water and the emulsifier and from the monomer or monomer mixture, which is added slowly at the polymerization temperature, the initiator again being added separately. It is preferred in the first stage to add the monomer or monomer mixture in the form of a pre-emulsion and in the second stage to add the monomer or monomer mixture in bulk, ie without water and emulsifier, and to add the initiator separately but in parallel.
  • the polymerization temperature is generally in the range from 20 to 100 ° C., preferably 40 to 90 ° C.
  • the quantitative ratio between the monomers and the water can be selected so that the resulting dispersion has a solids content of 30 to 60% by weight, preferably 35 to 50% by weight.
  • An anionic emulsifier is preferably used alone or in a mixture as the 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 with 4-5 moles of ethylene oxide per mole Aryl sulfonate, sodium lauryl sulfate, sodium lauryl ethoxylate sulfate and 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 an addition product of 1 mol of nonylphenol and 4-30 mol of ethylene oxide, can be used in a mixture with the anionic emulsifier.
  • a peroxide compound is preferably used as the radical-forming initiator.
  • the initiator is water-soluble or monomer-soluble.
  • a water-soluble initiator is preferably used.
  • Suitable initiators are the customary inorganic 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, preferably alkali metal or ammonium peroxydisulfates.
  • reducing agents such as sodium disulfite, hydrazine, hydroxylamine
  • accelerators such as iron, cobalt, cerium and vanadyl salts, preferably alkali metal or ammonium peroxydisulfates.
  • the redox initiator systems disclosed in EP-A-107300 can also be used.
  • the first stage 10 to 90, preferably 35 to 65 parts by weight of an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers are emulsion polymerized.
  • the monomer or monomer mixture used in the first stage is selected so that when the monomer or monomer mixture used in the first stage is completely polymerized out, a polymer with a glass transition temperature (T G1 ) of + 30 ° C. to + 110 ° C, preferably 60 to 95 ° C is obtained. Since the glass transition temperature of emulsion polymers according to the equation
  • Examples of monomers which can be used in the first stage are: vinylaromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyltoluene, esters of acrylic acid or methacrylic acid, in particular aliphatic and cycloaliphatic acrylates or methacrylates with up to 20 carbon atoms in the alcohol radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl, lauryl and cyclohexyl acrylate or methacrylate, acrylic and / or methacrylic acid, acrylic and / or methacrylamide, N-methylolacrylamide and / or N-methylol methacrylamide, hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl
  • ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers which are essentially free of hydroxyl and carboxyl groups preference is given to using ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers which are essentially free of hydroxyl and carboxyl groups.
  • substantially free is intended to mean that it is preferred to use monomers or monomer mixtures which are free from hydroxyl and carboxyl groups, but that the monomers or monomer mixtures used also contain small amounts (for example as a result of impurities) of hydroxyl and / or may contain carboxyl groups.
  • the content of hydroxyl and carboxyl groups should preferably be at most so high that a polymer prepared from the monomer or monomer mixture used in the first stage has an OH number of at most 5 and an acid number of at most 3.
  • component (a1) can be used, for example: cyclohexyl acrylate, cyclohexyl methacrylate, alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
  • alkyl radical such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
  • component (a2) e.g. vinylaromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyltoluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers are used.
  • vinylaromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyltoluene, acrylic and methacrylamide and acrylonitrile and methacrylonitrile or mixtures of these monomers are used.
  • the monomer or monomer mixture used in the first stage and the monomer or monomer mixture used in the second stage are selected in such a way that the emulsion polymer obtained has a hydroxyl number of 2 to 100, preferably 10 to 50 and the difference T G1 - T G2 is 10 to 170, preferably 80 to 150 ° C.
  • Examples of monomers which can be used in the second stage are: vinylaromatic hydrocarbons, such as styrene, ⁇ -alkylstyrene and vinyltoluene, Esters of acrylic acid or methacrylic acid, in particular aliphatic and cycloaliphatic acrylates or methacrylates with up to 20 carbon atoms in the alcohol radical, such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl, lauryl and cyclohexyl acrylate or - methacrylate, acrylic and / or methacrylic acid, acrylic and / or methacrylamide, N-methylolacrylamide and / or N-methylolmethacrylamide, hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropy
  • component (b1) e.g. are used: cyclohexyl acrylate, cyclohexyl methacrylate, alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, such as e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
  • alkyl radical such as e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate or mixtures of these monomers.
  • hydroxyalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can be derived from an alkylene glycol esterified with the acid, or can be obtained by reacting the acid with an alkylene oxide.
  • 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 are preferably used as component (b2).
  • hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate.
  • 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.
  • Acrylic acid and / or methacrylic acid and / or acrylamidomethylpropanesulfonic acid are preferably used as component (b3).
  • 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 (b4) 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.
  • the emulsion polymer used according to the invention should have a number average molar mass (determination: gel permeation chromatography using polystyrene as the standard) of 200,000 to 2,000,000, preferably 300,000 to 1,500,000.
  • aqueous base coating compositions according to the invention contain, in addition to the emulsion polymer described above, a water-dilutable polyurethane resin as the film-forming material.
  • the base coating compositions according to the invention preferably contain water-thinnable, urea-containing polyurethane resins which have a number average molecular weight (determination: gel permeation chromatography using polystyrene as the standard) of 1000 to 60,000, preferably 1500 to 50,000 and an acid number of 5 to 70, preferably 10 to 30 and by reaction, preferably chain extension of prepolymers containing isocyanate groups with polyamines and / or hydrazine can be produced.
  • a number average molecular weight determination: gel permeation chromatography using polystyrene as the standard
  • 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, succeed.
  • 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, 1,2-butylene glycol, 1,6-hexanediol, are advantageous , Trimethylolpropane, castor oil or hydrogenated castor oil, di-trimethylolpropane ether, pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentylglycol, hydroxypivalic acid-neopentylglycol ester, hydroxyethylated or hydroxypropylated bisphenol A, bisphenol A, mixtures thereof .
  • 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 exist from 400 to 5000.
  • 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 molecular weight 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 hydroxycarboxylic 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 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.
  • 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 molecule.
  • 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, glutaric acid, hexachlorheptanedicarboxylic acid, tetrachlorophthalic acid and / or.
  • their anhydrides if they exist, can also be used.
  • polyester polyols smaller ones can also be used Amounts of 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 content of the formula - (- CO- (CHR) n -CH2-0 -) -.
  • 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 has the value 4 and all R substituents are hydrogen, is preferred for the preparation of the polyester diols.
  • the reaction with lactone is started by low molecular weight polyols, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, dimethylolcyclohexane.
  • other reaction components such as ethylenediamine, alkyldiacanolamines or urea, can also be reacted with caprolactone.
  • polylactam diols which are produced by reacting, for example, ⁇ -caprolactam with low molecular weight diols.
  • Aliphatic, cycloaliphatic and / or aromatic poly are used as typical multifunctional isocyanates isocyanates with at least two isocyanate groups per molecule.
  • 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. 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.
  • aromatic diisocyanates such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylmethane diisocyanate.
  • aliphatic diisocyanates 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 been found to be suitable as triisocyanates are those which are formed by trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with compounds containing polyfunctional OH or NH groups.
  • 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 Lich, if special components are not incorporated in 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 which are capable of forming anions are carboxyl, sulfonic acid and / or phosphonic acid groups.
  • Carboxylic acid or carboxylate groups are preferably used. They should be so inert that 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, dihydroxysuccinic acid and dihydroxybenzoic acid.
  • 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-diaminodiphenyl ether sulfonic acid.
  • the polyol containing carboxyl groups can be 3 to Make up 100% by weight, preferably 5 to 50% by weight, of the total polyol component in the NCO prepolymer.
  • the amount of ionizable carboxyl groups available through 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 in stages in the prescribed order. Examples are described in DE 26 24 442 and DE 32 10 051.
  • the reaction temperature is up to 150 ° C, with a temperature in the range of 50 to 130 ° C being preferred. The reaction continues until practically all of the hydroxyl functions have been converted.
  • 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.
  • a catalyst such as organotin compounds and / or tertiary amines.
  • organic that do not contain Zerewitinoff active hydrogen are possible.
  • 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 vary within wide limits and should be sufficient to form a prepolymer solution with a suitable viscosity.
  • Suitable tertiary amines are, for example, trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, N-methylmorpholine.
  • the NCO prepolymer is diluted with water and then results in a finely divided dispersion.
  • the isocyanate groups still present are included Di- and / or polyamines reacted with primary and / or secondary amino groups as chain extenders. This reaction leads to a further linkage and increase in the molecular weight.
  • the competitive reaction between amine and water with the isocyanate must be well coordinated (time, temperature, concentration) in order to obtain optimum properties and well monitored for reproducible production.
  • Water-soluble compounds are preferred as chain extenders because they increase the dispersibility of the polymeric end product in water.
  • Hydrazine and organic diamines are preferred because they usually build up the highest molecular weight without gelling the resin.
  • the prerequisite for this is that 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.
  • the diamines 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 that has at least three amine groups with a reactive hydrogen.
  • This type of polyamine can be used in such an amount that unreacted amine nitrogen atoms with 1 or 2 reactive hydrogen atoms are present after the polymer has been extended.
  • useful polyamines are diethylenetriamine, triethylenetetraamine, dipropylenetriamine and dibutylenetriamine.
  • Preferred polyamines are the alkyl or cycloalkyl triamines, such as diethylenetriamine.
  • monoamines such as ethylhexylamine, can also be added.
  • the mixture of emulsion polymer and polyurethane resin contained in the preferred aqueous base coating compositions as a film-forming material consists of 95 to 40% by weight of emulsion polymer and 5 to 60% by weight of polyurethane resin, the proportions each referring to the solids content and their total always 100% by weight .-%.
  • the aqueous base coating compositions according to the invention advantageously also contain further compatible water-dilutable synthetic resins, such as, for example, aminoplast resins, polyesters and polyethers, which generally serve as grind resins for the pigments.
  • the aqueous base coating compositions according to the invention preferably contain 5 to 20, particularly preferably 10 to 16% by weight, based on the total solids content of the base coating compositions, 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 and 5 to 20, preferably 8 to 15% by weight
  • a water-dilutable polyether eg polypropylene glycol with a number average molecular weight of 400 to 900.
  • the base coating compositions according to the invention can contain coloring pigments on an inorganic basis, such as e.g. Titanium dioxide, iron oxide, soot, etc., coloring pigments on an organic basis as well as common metal pigments (e.g. commercially available aluminum bronzes, stainless steel bronzes ...) and non-metallic effect pigments (e.g. pearlescent or interference pigments).
  • the base coating compositions according to the invention preferably contain metal pigments and / or effect pigments.
  • the pigmentation level is in the usual ranges.
  • crosslinked polymeric microparticles such as are disclosed in EP-A-38 127 and / or customary rheological inorganic or organic additives, can be added to the base coating compositions according to the invention.
  • water-soluble cellulose ethers such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl cellulose
  • synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride, act as thickeners Copolymers and their derivatives or also hydrophobically modified ethoxylated urethanes or polyacrylates.
  • Carboxyl group-containing polyacrylate copolymers are particularly preferred with an acid number of 60 to 780, preferably 200 to 500.
  • the base coating compositions according to the invention generally have a solids content of about 15 to 50% by weight.
  • the solids content varies with the intended use of the coating compositions.
  • 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 coating compositions according to 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 base coating compositions according to the invention are generally adjusted to a pH between 6.5 and 9.0.
  • the pH can be adjusted with conventional amines, e.g. Ammonia, triethylamine, dimethylaminoethanol and N-methylmorpholine can be adjusted.
  • the task explained at the outset is solved.
  • the base coating compositions according to the invention high-quality coatings can be produced even without overcoating with a transparent top coating composition.
  • the coating compositions according to the invention can be applied to any substrates, such as metal, wood, plastic or paper.
  • Emulsion polymer dispersion 1 Emulsion polymer dispersion 1
  • Emulsion polymer dispersion 2 Emulsion polymer dispersion 2
  • An emulsion is prepared in the stirrable feed vessel from 720 g deionized water, 24 g emulsifier 1, 10.8 g acrylamide, 518 g methyl methacrylate, 292 g n-butyl methacrylate and 205 g styrene. 30% by weight of this emulsion are added for presentation. A solution of 0.9 g of ammonium peroxodisulfate APS in 55 g of deionized water is then added dropwise in the course of 5 minutes. An exothermic reaction occurs. The reaction temperature is kept between 80 and 85 ° C.
  • a mixture of 700 g of n-butyl acrylate, 89.8 g of hydroxypropyl methacrylate, 35.9 g of methyl methacrylate, 35.9 g of methacrylic acid, 26.9 g of acrylamide and 4.5 g is then added within 2 hours Eikosa (ethylene glycol) nonylphenyl ether (Antarox®CO 850 from GAF Corp., emulsifier 2) was added. After the addition has ended, the reaction mixture is kept at 82 ° C. for a further 1.5 hours. It is then cooled and the dispersion is spread over a fabric 30 ⁇ m mesh size given. A finely divided dispersion with a non-volatile content of 45% by weight, a pH of 2.5, an acid number of 14 and an OH number of 20 is obtained.
  • Emulsion polymer dispersion 5 Emulsion polymer dispersion 5
  • stirrable feed vessel 720 g of deionized water 24 g of emulsifier 1, 43.2 g of acrylamide, 907 g of methyl methacrylate and 216 g of n-butyl methacrylate, 842 g of n-butyl acrylate, 108 g of hydroxypropyl methacrylate, 43.2 g of methacrylic acid and 5.4 g emulsifier 2 an emulsion is prepared. 10% by weight of this emulsion are added for presentation. A solution of 0.87 g of ammonium peroxodisulfate in 53 g of deionized water is then added dropwise in the course of 5 minutes. An exothermic reaction occurs.
  • reaction temperature is kept between 82 and 88 ° C. 15 minutes after the addition of the APS solution has ended, the remaining 90% by weight of the emulsion are added within 3 hours and a solution of 2.23 g of APS in 478 g of deionized water is added within 3.5 hours, the temperature being at Is held at 82 ° C.
  • reaction mixture is kept at 82 ° C. for a further 1.5 hours. It is then cooled and the dispersion is passed over a 30 ⁇ m mesh. A finely divided dispersion with a non-volatile content of 45% by weight, a pH of 5.8, an acid number of 13 and an OH number of 20 is obtained.
  • the mass obtained is poured into 1840 g of cold deionized water with vigorous stirring. 86 g of a 15% hydrazine solution are added to the dispersion obtained within 20 minutes, with vigorous stirring. The resulting, very finely divided dispersion has a solids content of 35% and a run-out time of 27 seconds in the DIN cup 4.
  • the mixture is adjusted to a pH value of 7.7 with a 5% aqueous dimethylethanolamine solution and with 9.4 g of a 3.5% solution of a commercially available polyacrylic acid thickener (Viscalex®HV 30 from Allied Colloids, pH value: 8 , 0) offset.
  • Mixture 2 is obtained.
  • Mixtures 1 and 2 are produced at 800-1000 rpm for 30 minutes to produce the basecoats of the invention. mixed and then adjusted to a pH of 7.7 with a 5% aqueous solution of dimethylethanolamine. The viscosity is then adjusted to an outflow time of 25 seconds in a DIN 4 cup by adding deionized water.
  • the base coating compositions BB1, BB2, BB3 and BB4 according to the invention are obtained.
  • the base coating composition BB5 is obtained by incorporating 36.2 g of the emulsion polymer dispersion 1 into the mixture 2. BB5 does not contain a polyurethane resin dispersion.
  • the base coating compositions thus obtained show excellent storage stability.
  • the base coating compositions are sprayed onto well-known methods onto phosphated steel sheets (Bonder 132) coated with a commercially available electrodeposition coating and a commercially available filler, overcoated with a commercially available clearcoat after a flash-off time of 10 minutes and baked at 140 ° C. for 20 minutes.
  • the metallic effect coatings obtained in this way show a good metallic effect, good adhesion to the filler, good adhesion between the basecoat and topcoat, good gloss and good resistance in a condensed water constant climate according to DIN 50 017.
  • BB1, BB2, BB3 and BB4 show a better metallic effect than BB5.
  • a part of the painted sheets is coated again with the base coating compositions BB1, BB2, BB3, BB4 and BB5 and overcoated with a commercially available clear coat.
  • the coatings obtained in this way are baked at 80 ° C. for 40 minutes.
  • the coatings baked at 80 ° C adhere well to the coatings baked at 140 ° C.
  • a basecoat composition prepared as described above using the emulsion polymer dispersion 5 shows insufficient storage stability.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Procédé pour obtenir un revêtement multicouches à partir d'un composé de revêtement de base aqueux et pigmentaire qui contient un polymère d'émulsion soluble dans l'eau en tant que matière filmogène. Le polymère d'émulsion soluble dans l'eau est obtenu par polymérisation d'émulsion en deux phases. Dans une première phase, on obtient un polymère à température de transition vitreuse (TG1) comprise entre +30 et +110°C. Dans une seconde phase, on polymérise, en présence du polymère obtenu lors de la première phase, un mélange de monomères qui, s'il était polymérisé seul, produirait un polymère à température de transition vitreuse (TG2) comprise entre -60 et +20°C. L'indice d'hydroxyle du polymère d'émulsion est compris entre 2 et 100.

Claims (11)

  1. Procédé de fabrication d'un revêtement à plusieurs couches, protecteur et/ou décoratif, sur une surface de substrat, suivant lequel :
    (1) on applique, sur la surface de substrat, comme composition de revêtement de base, une composition de revêtement aqueuse, pigmentée, qui contient, comme matière filmogène, un polymère en émulsion diluable dans l'eau ;
    (2) à partir de la composition appliquée à l'étape (1), on forme un film de polymère ;
    (3) sur la couche de base ainsi obtenue, on applique une composition de couche de revêtement transparente, appropriée, puis
    (4) on soumet la couche de base à une cuisson conjointement avec la couche de recouvrement,
    caractérisé par le fait que la composition de revêtement de base contient un polymère en émulsion diluable dans l'eau, qui peut être obtenu
    (a) en polymérisant, dans une première étape, 10 à 90 parties en poids d'un mélange de
    (a1) 100 à 60% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ; et
    (a2) 0 à 40% en poids d'un monomère copolymérisable avec (a1) ou d'un mélange de tels monomères, en phase aqueuse, en présence d'un ou plusieurs émulsifiants et d'un ou plusieurs initiateurs formant des radicaux libres, la somme des parties en poids de (a1) et (a2) donnant toujours 100% en poids, et (a1) et (a2) étant choisis de telle sorte que, dans la première étape, il soit obtenu un polymère présentant une température de transition vitreuse (TG1) de +30 à +110°C ; et
    (b) après qu'au moins 80% en poids du monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, aient réagi, en polymérisant, dans une deuxième étape, 90 à 10 parties en poids d'un mélange de
    (b1) 47 à 99% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ;
    (b2) 1 à 20% en poids d'un monomère copolymérisable avec (b1), (b3) et (b4), portant au moins un groupe hydroxyle, ou d'un mélange de tels monomères ;
    (b3) 0 à 8% en poids d'un monomère copolymérisable avec (b1), (b2) et (b4), portant au moins un groupe acide carboxylique ou acide sulfonique, ou d'un mélange de tels monomères ; et
    (b4) 0 à 25% en poids d'un autre monomère copolymérisable avec (b1), (b2) et (b3), ou d'un mélange de tels monomères,
    en présence du polymère obtenu dans la première étape, la somme des parties en poids de (b1), (b2), (b3) et (b4) donnant toujours 100% en poids, et (b1), (b2), (b3) et (b4) étant choisis de telle sorte qu'une polymérisation exclusive du mélange de monomères utilisé dans la deuxième étape conduirait à un polymère présentant une température de transition vitreuse (TG2) de -60 à +20°C, et les conditions de réaction étant choisies de telle sorte que le polymère en émulsion obtenu présente une masse moléculaire moyenne en nombre de 200 000 à 2 000 000, et le monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, et le mélange de monomères utilisé dans la deuxième étape étant choisis dans leur type et dans leur quantité, de telle sorte que le polymère en émulsion obtenu présente un indice d'hydroxyle de 2 à 100 et que la différence TG1 - TG2 s'élève à 10 à 170°C.
  2. Procédé selon la revendication 1, caractérisé par le fait que la composition de revêtement de base contient un pigment métallique, de préférence, un pigment d'aluminium.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé par le fait que 99,5 à 75% en poids du composant (a1) et/ou 0,5 à 25% en poids du composant (a2) et/ou 75 à 90% en poids du composant (b1) et/ou 5 à 15% en poids du composant (b2) et/ou 2 à 6% en poids du composant (b3) et/ou 2 à 15% en poids du composant (b4) sont polymérisés.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que la matière filmogène se compose de 95 à 40% en poids du polymère en émulsion et de 5 à 60% en poids d'une résine de polyuréthanne diluable dans l'eau, les parties en poids se rapportant à chaque fois à la fraction de matières solides et leur somme s'élevant toujours à 100% en poids.
  5. Compositions de revêtement diluables dans l'eau, caractérisées par le fait qu'elles contiennent, comme matière filmogène, un polymère en émulsion diluable dans l'eau, qui peut être obtenu
    (a) en polymérisant, dans une première étape, 10 à 90 parties en poids d'un mélange de
    (a1) 100 à 60% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ; et
    (a2) 0 à 40% en poids d'un monomère copolymérisable avec (a1) ou d'un mélange de tels monomères,
    en phase aqueuse, en présence d'un ou plusieurs émulsifiants et d'un ou plusieurs initiateurs formant des radicaux libres, la somme des parties en poids de (a1) et (a2) donnant toujours 100% en poids, et (a1) et (a2) étant choisis de telle sorte que, dans la première étape, il soit obtenu un polymère présentant une température de transition vitreuse (TG1) de +30 à +110°C ; et
    (b) après qu'au moins 80% en poids du monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, aient réagi, en polymérisant, dans une deuxième étape, 90 à 10 parties en poids d'un mélange de
    (b1) 47 à 99% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ;
    (b2) 1 à 20 % en poids d'un monomère copolymérisable avec (b1), (b3) et (b4), portant au moins un groupe hydroxyle, ou d'un mélange de tels monomères ;
    (b3) 0 à 8% en poids d'un monomère copolymérisable avec (b1), (b2) et (b4), portant au moins un groupe acide carboxylique ou acide sulfonique, ou d'un mélange de tels monomères ; et
    (b4) 0 à 25% en poids d'un autre monomère copolymérisable avec (b1), (b2) et (b3), ou d'un mélange de tels monomères,
    en présence du polymère obtenu dans la première étape, la somme des parties en poids de (b1), (b2), (b3) et (b4) donnant toujours 100% en poids, et (b1), (b2), (b3) et (b4) étant choisis de telle sorte qu'une polymérisation exclusive du mélange de monomères utilisé dans la deuxième étape conduirait à un polymère présentant une température de transition vitreuse (TG2) de -60 à +20°C, et les conditions de réaction étant choisies de telle sorte que le polymère en émulsion obtenu présente une masse moléculaire moyenne en nombre de 200 000 à 2 000 000, et le monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape et le mélange de monomères utilisé dans la deuxième étape, étant choisis dans leur type et dans leur quantité, de telle sorte que le polymère en émulsion obtenu présente un indice d'hydroxyle de 2 à 100 et que la différence TG1 - TG2 s'élève à 10 à 170°C.
  6. Compositions de revêtement selon la revendication 5, caractérisées par le fait qu'elles contiennent un pigment métallique, de préférence, un pigment d'aluminium.
  7. Compositions de revêtement selon l'une des revendications 5 ou 6, caractérisées par le fait que 99,5 à 75% en poids du composant (a1) et/ou 0,5 à 25% en poids du composant (a2) et/ou 75 à 90% en poids du composant (b1) et/ou 5 à 15% en poids du composant (b2) et/ou 2 à 6% en poids du composant (b3) et/ou 2 à 15% en poids du composant (b4) sont polymérisés.
  8. Polymères en émulsions, diluables dans l'eau, caractérisés par le fait qu'ils sont obtenus :
    (a) en polymérisant, dans une première étape, 10 à 90 parties en poids d'un mélange de
    (a1) 100 à 60% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ; et
    (a2) 0 à 40% en poids d'un monomère copolymérisable avec (a1) ou d'un mélange de tels monomères,
    en phase aqueuse, en présence d'un ou plusieurs émulsifiants et d'un ou plusieurs initiateurs formant des radicaux libres, la somme des parties en poids de (a1) et (a2) donnant toujours 100% en poids, et (a1) et (a2) étant choisis de telle sorte que, dans la première étape, il soit obtenu un polymère présentant une température de transition vitreuse (TG1) de +30 à +110°C ; et
    (b) après qu'au moins 80% en poids du monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, aient réagi, en polymérisant, dans une deuxième étape, 90 à 10 parties en poids d'un mélange de
    (b1) 47 à 99% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ;
    (b2) 1 à 20% en poids d'un monomère copolymérisable avec (b1), (b3) et (b4), portant au moins un groupe hydroxyle, ou d'un mélange de tels monomères ;
    (b3) 0 à 8% en poids d'un monomère copolymérisable avec (b1), (b2) et (b4), portant au moins un groupe acide carboxylique ou acide sulfonique, ou d'un mélange de tels monomères ; et
    (b4) 0 à 25% en poids d'un autre monomère copolymérisable avec (b1), (b2) et (b3), ou d'un mélange de tels monomères,
    en présence du polymère obtenu dans la première étape, la somme des parties en poids de (b1), (b2), (b3) et (b4) donnant toujours 100% en poids, et (b1), (b2), (b3) et (b4) étant choisis de telle sorte qu'une polymérisation exclusive du mélange de monomères utilisé dans la deuxième étape conduirait à un polymère présentant une température de transition vitreuse (TG2) de -60 à +20°C, et les conditions de réaction étant choisies de telle sorte que le polymère en émulsion obtenu présente une masse moléculaire moyenne en nombre de 200 000 à 2 000 000, et le monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, et le mélange de monomères utilisé dans la deuxième étape étant choisis dans leur type et dans leur quantité, de telle sorte que le polymère en émulsion obtenu présente un indice d'hydroxyle de 2 à 100 et que la différence TG1 - TG2 s'élève à 10 à 170°C.
  9. Polymères en émulsion selon la revendication 8, caractérisés par le fait que 99,5 à 75% en poids du composant (a1) et/ou 0,5 à 25% en poids du composant (a2) et/ou 75 à 90% en poids du composant (b1) et/ou 5 à 15% en poids du composant (b2) et/ou 2 à 6% en poids du composant (b3) et/ou 2 à 15% en poids du composant (b4) sont polymérisés.
  10. Procédé de fabrication de polymères en émulsion diluables dans l'eau, caractérisé par la fait que
    (a) dans une première étape, on polymérise 10 à 90 parties en poids d'un mélange de
    (a1) 100 à 60% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ; et
    (a2) 0 à 40% en poids d'un monomère copolymérisable avec (a1) ou d'un mélange de tels monomères,
    en phase aqueuse, en présence d'un ou plusieurs émulsifiants et d'un ou plusieurs initiateurs formant des radicaux libres, la somme des parties en poids de (a1) et (a2) donnant toujours 100% en poids, et (a1) et (a2) étant choisis de telle sorte que, dans la première étape, il soit obtenu un polymère présentant une température de transition vitreuse (TG1) de +30 à +110°C ; et
    (b) après qu'au moins 80% en poids du monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, aient réagi, on polymérise, dans une deuxième étape, 90 à 10 parties en poids d'un mélange de
    (b1) 47 à 99% en poids d'un ester cycloaliphatique ou aliphatique de l'acide méthacrylique ou de l'acide acrylique ou d'un mélange de tels esters ;
    (b2) 1 à 20% en poids d'un monomère copolymérisable avec (b1), (b3) et (b4), portant au moins un groupe hydroxyle, ou d'un mélange de tels monomères ;
    (b3) 0 à 8% en poids d'un monomère copolymérisable avec (b1), (b2) et (b4), portant au moins un groupe acide carboxylique ou acide sulfonique, ou d'un mélange de tels monomères ; et
    (b4) 0 à 25% en poids d'un autre monomère copolymérisable avec (b1), (b2) et (b3), ou d'un mélange de tels monomères,
    en présence du polymère obtenu dans la première étape, la somme des parties en poids de (b1), (b2), (b3) et (b4) donnant toujours 100% en poids, et (b1), (b2), (b3) et (b4) étant choisis de telle sorte qu'une polymérisation exclusive du mélange de monomères utilisé dans la deuxième étape conduirait à un polymère présentant une température de transition vitreuse (TG2) de -60 à +20°C, et les conditions de réaction étant choisies de telle sorte que le polymère en émulsion obtenu présente une masse moléculaire moyenne en nombre de 200 000 à 2 000 000, et le monomère ou mélange de monomères à insaturation éthylénique, utilisé dans la première étape, et le mélange de monomères utilisé dans la deuxième étape étant choisis dans leur type et dans leur quantité, de telle sorte que le polymère en émulsion obtenu présente un indice d'hydroxyle de 2 à 100 et que la différence TG1 - TG2 s'élève à 10 à 170°C.
  11. Procédé selon la revendication 10, caractérisé par le fait que 99,5 à 75% en poids du composant (a1) et/ou 0,5 à 25% en poids du composant (a2) et/ou 75 à 90% en poids du composant (b1) et/ou 5 à 15% en poids du composant (b2) et/ou 2 à 6% en poids du composant (b3) et/ou 2 à 15% en poids du composant (b4) sont polymérisés.
EP90900099A 1988-12-09 1989-11-27 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 Expired - Lifetime EP0447428B1 (fr)

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DE3841540A DE3841540A1 (de) 1988-12-09 1988-12-09 Verfahren zur herstellung eines mehrschichtigen ueberzuges, wasserverduennbare beschichtungszusammensetzungen, wasserverduennbare emulsionspolymere und verfahren zur herstellung von wasserverduennbaren emulsionspolymeren

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CA2004988A1 (fr) 1990-06-09
DE58905068D1 (de) 1993-09-02
AU4655089A (en) 1990-06-26
EP0447428A1 (fr) 1991-09-25
DE3841540A1 (de) 1990-06-13
BR8907816A (pt) 1991-10-22
JPH075860B2 (ja) 1995-01-25
WO1990006186A1 (fr) 1990-06-14
AU630645B2 (en) 1992-11-05
ES2060136T3 (es) 1994-11-16
ZA899023B (en) 1990-08-29
JPH04501737A (ja) 1992-03-26
CA2004988C (fr) 1999-08-24

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