JPH04501737A - Method for producing multilayer coatings, water-dilutable paints, water-dilutable emulsion polymers, and water-dilutable emulsion polymers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for producing multilayer coatings, water-dilutable paints, water-dilutable emulsion polymers - and method for producing emulsion polymer dilutable with water The present invention (1) An emulsion polyester that can be diluted with water as a film-forming substance as an undercoat. A colored water-based paint containing mer is applied to the surface of the object to be coated, (2) forming a polymer coating film from the paint applied in step (1); (3) Apply a suitable transparent top coat on the undercoat layer thus obtained and Continuation (4) By baking the undercoat film together with the topcoat film, there is no damage to the surface of the object to be coated. The present invention relates to a method for producing multilayer protective and/or decorative coatings.

The invention also relates to water-dilutable coatings, water-dilutable emulsion polymers and The present invention relates to a method for producing a water-dilutable emulsion polymer.

The method for producing said multilayer protective and/or decorative coatings is known and is particularly applicable to motor vehicles. Used for metallic body painting (e.g. European Patent Publication No. 89497, West German Patent Application No. 3628124 and European Patent Application No. 38127 (See specification).

According to said method, the water-based basecoat used is coated, in particular using an automatic coating device. A relatively thin, fast-drying layer can be applied to the object and the step (3) And after carrying out (4), metal pigment particles are arranged parallel to the surface of the object to be coated. Metallic paint with a good metallic effect should only be applied when The undercoat film of the effect paint adheres well to the object to be coated, and the transparent topcoat film adheres well to the base coat. The composition should be such that it adheres well to the membrane. Furthermore, water-based undercoat paints are The applied metallic effect coating constantly condenses under load in air-conditioned rooms. The composition should be such that it does not exhibit clouding, peeling phenomena or even bubbles.

Finally, it is desirable that the water-based basecoat exhibit high storage stability.

West German Patent Application No. 3628124 discloses that the film-forming substance is dilutable with water. containing a mixture of a water-dilutable emulsion polymer and a water-dilutable polyurethane resin. A water-based undercoat paint is disclosed. This primer paint meets the above requirements to the utmost. Not quite satisfied.

The problem on which the invention is based is to provide a suitable method for the method, which optimally satisfies the above-mentioned requirements. Our objective is to provide a suitable water-based undercoat paint.

This challenge is surprisingly (a) In the first step, the ethylenically unsaturated monomer or ethylenically unsaturated monomer 10 to 90 parts by weight of the mixture in the aqueous phase with one or more emulsifiers and one or more radical forms. Polymerization is carried out in the presence of a formation initiator, during which ethylenically unsaturated monomers or ethylene In the first step, the mixture of unsaturated monomers is heated to a glass transition temperature (Ta+) of +30 to + selected to obtain a polymer having a temperature of 110°C, and (b) Ethylenically unsaturated monomer or monomer mixture used in the first step After at least 80% by weight has been converted, the ethylenically unsaturated monomer is converted in a second step. or 90 to 10% by weight of the mixture of ethylenically unsaturated monomers obtained in the first kneading process. The monomer used in the second step or the second step is polymerized in the presence of a polymer. The mixture of ethylene-based monomers used in the process is mixed with the ethylene-based monomer used in the second process. Unsaturated monomer or mixture of ethylenically unsaturated monomers used in the second step The single polymerization of and at that time, the reaction conditions are adjusted such that the number average fraction of the obtained emulsion polymer is selected to have a molecular weight of 200,000 to 2,000,000, and Ethylenically unsaturated monomer or monomer mixture used in the first step and the second step type and amount of ethylenically unsaturated monomer or monomer mixture used in the process. , the emulsion polymer obtained has a hydroxyl value of 2 to 100, And the deviation To, -Ti is selected so that it is 10 to 170°C. A water-based basecoat containing a water-dilutable emulsion polymer obtained by This problem can be solved by using paint.

The water-dilutable emulsion polymer used in the present invention can be prepared using known equipment, e.g. Two-stage emulsion in aqueous medium in a stirred vessel with heating and cooling devices It can be produced by polymerization. Addition of monomers consists of all water, emulsifier and some Charge the solution consisting of the initiator and add the monomer or monomer mixture and Separately but in parallel to them, gradually add the remaining initiator at the polymerization temperature. It can be done in a format. However, if some of the water and emulsifier are charged first and Prepare the pre-emulsion from the monomer or monomer mixture with the remaining water and emulsifier. It is also possible to prepare the emulsion and gradually add the emulsion at the polymerization temperature, in which case Add the emulsifier separately.

In the first step, the monomer or monomer mixture is added in the form of a pre-emulsion and In the second step, the monomer or monomer mixture is processed in bulk, i.e. with water and emulsifier. It is advantageous to add the emulsifier separately, but in parallel to them. . A portion of the pre-emulsion to be used in the first step (generally the entire emulsion to be used) (approximately 30% by weight of the polymer) and then used in the first step. It is particularly advantageous to add the remainder of the pre-emulsion. Polymerization temperature is generally 20 The monomer to water ratio in the range from ~100°C, advantageously from 40 to 90°C, is The dispersion has a solids content of 30-60% by weight, preferably 35-50% by weight. You can choose as follows.

As emulsifiers, anionic emulsifiers can be used alone or as a mixture. It's advantageous.

Examples of anionic emulsifiers are sulfuric acid half esters of alkylphenols or alcohols alkali metal salts of Sulfuric acid half ester of chilled alcohol, preferably ethylene oxide per mole Sulfuric acid half ester of nonylphenol reacted with 4 to 6 moles of hydroxide, alkyl- or is an alkali metal salt of aryl sulfonate, sodium lauryl sulfate, Sodium lauryl ethoxylate-sulfate, and carbon chains of 8 to 20 It is a sodium sulfonate having a carbon atom. anionic emulsification 1 of the agents in an amount of 0.1 to 50% by weight, preferably 0.5 to 3.0% by weight, based on the monomers. %. Furthermore, it can be additionally ethoxylated to increase the stability of the aqueous dispersion. nonionic emulsifiers of the alkylphenol or fatty acid type, such as nonylphenol The addition product of 1 mole of ethylene oxide and 4 to 30 moles of ethylene oxide is mixed with an anionic emulsifier. Can be used together.

Peroxide compounds are preferably used as radical formers. Initiator is water soluble or soluble in the monomer. Preference is given to using water-soluble initiators.

Initiators may include partially reducing agents such as sodium disulfite, hydrazine, hydrazine, etc. Droxylamine and catalytic amounts of promoters such as iron salts, cobalt salts, cerium salts and Common inorganic peracid compounds, such as ammonium persulfate, in combination with vanadyl salts potassium persulfate, ammonium and alkali metal peroxydiphosphonates and organic peroxides, such as benzoyl peroxide, organic peresters, Isobivalates, especially alkali metal or ammonium peroxydisulfates is appropriate. In addition, the record disclosed in European Patent Publication No. 107300 Dox initiators can also be used.

In the first step, an ethylenically unsaturated monomer or an ethyl-nonsaturated monomer, - from 10 to 90, preferably from 35 to 65% by weight of the mixture are emulsion polymerized.

The monomer or monomer mixture to be used in the first step is the same as that used in the first kneading. Upon complete starting polymerization of monomers or monomer mixtures, the glass transition temperature ('l "C1) A polymer having a temperature of +30°C to +110°C, preferably 60 to 95°C is obtained. Select as shown below. The glass transition temperature of emulsion polymers is determined by the equation n=1 [In the formula, T, = glass transition temperature of copolymer (0K) W, = weight proportion of nth monomer To, = glass transition temperature of homopolymer consisting of nth monomer X = number of different types of monomers can be calculated approximately based on The monomer or monomer mixture to be used in one step was used in the first mixture. Upon complete polymerization of the monomer or monomer mixture, the glass transition temperature (Ta+) In order to obtain a polymer having a temperature between +30°C and +110°C, preferably between 60 and 95°C. There is no problem in choosing.

Examples of monomers that can be used in the first step include: : vinyl aromatic hydrocarbons, such as styrene, α-alkylstyrene and vinyl Toluene, esters of acrylic acid or methacrylic acid, especially 20% in the alcohol group aliphatic or cycloaliphatic acrylates or methacrylates having up to 3 carbon atoms; For example, methyl, ethyl, propyl, butyl, hexyl, ethylhexy -, atearyl, lauryl and cyclohexyl acrylate or -methacrylate rylate, acrylic and/or methacrylic acid, acrylic and 2/or methacrylic acid lylic acid amide, N-methylol acrylamide and/or N-methylol methane lamamide, acrylic acid, methacrylic acid or other α, β-ethylene carboxylic acid Hydroxyl alkyl esters of acids, such as 2-hydroxylethyl acrylate 2-hydroxylpropyl acrylate, 3-hydroxybropylacrylate 2-hydroxybrobyl methacrylate, 3-hydroxybrobyl methacrylate .

rate, 2-hydroxyethyl methacrylate, 4-hydrodoquine butyl acrylate ester, 4-hydroxybutyl methacrylate, etc.

In the first step, ethylene containing substantially no hydroxyl groups and carboxyl groups is used. It is advantageous to use a mixture of ethylenically unsaturated monomers or ethylenically unsaturated monomers. It is advantageous. “Substantially free” means that it does not contain hydroxyl or carboxyl groups. It is advantageous to use monomers or monomer mixtures that are not The monomers or monomer mixtures used may contain small amounts of hydrogen (e.g. due to impurities). It is understood to mean that it may contain a roxyl group and/or a carboxyl group. It should be. The content of hydroxyl and carboxyl groups is preferably at most However, if the polymer is made from the monomer or monomer mixture used in the first step, It should be such that the remer has an OH number of up to 5 and an acid number of up to 3.

In the first step, it is particularly advantageous to (a), alicyclic or aliphatic ester of methacrylic acid or acrylic acid or The mixture of such esters contains 100 to 60% by weight, advantageously 99.5 to 75% by weight. Amount% and (a2) A monomer copolymerizable with (a1) or a mixture of such monomers using a mixture of 0 to 40% by weight, preferably 0.5 to 25% by weight of In this case, the sum of the weight percentages of (al) and (a2) is always 100 weight percent.

As the component (al), for example, the following can be used. Syl acrylate, cyclohexyl methacrylate, up to 20 alkyl groups Alkyl acrylates and alkyl methacrylates having carbon atoms of, e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, Stearyl- and lauryl acrylate and -methacrylate or monomers thereof mixture of ma.

Component (a2) includes, for example, vinyl aromatic hydrocarbons, such as styrene, α-alpha alkylstyrene and vinyltolulene, acrylic and methacrylamide, and Using crylic and methacrylnitrile or mixtures of these monomers be able to.

Less of the ethylenically unsaturated monomer or monomer mixture used in the first step After 80% by weight, preferably at least 95% by weight of both have reacted, in a second step the 90-1 of a thyrenically unsaturated monomer or a mixture of ethylenically unsaturated monomers 0 parts by weight, advantageously 65 to 35 parts by weight, in the presence of the polymer obtained in the first step. Monomer or monomer used in the second step during emulsion polymerization The mixture is a single polymerization of the monomer or monomer mixture used in the second step. has a glass transition temperature (Ta+) of -60 to +20°C, preferably -50 to 0°C. Select to produce a polymer. This selection is difficult for those skilled in the art. No, because the glass transition temperature of emulsion polymers has already been mentioned. This is because it can be easily calculated as an approximate value.

Another important thing for the present invention is the monomer used in the first step or The monomer mixture and the monomer or monomer mixture used in the second step are In terms of type and amount, the obtained emulsion polymer has a hydroxyl number of 2 to 10. 0, preferably between 10 and 50 and the deviation TOI To! =10-170, advantageous is selected to be 80 to 150°C.

Examples of monomers that can be used in the second step include: Vinyl aromatic hydrocarbons such as styrene, α-alkylstyrene and and vinyltolulene, esters of acrylic acid or methacrylic acid, especially alcohol groups. Aliphatic and cycloaliphatic acrylates or methacrylates having up to 20 carbon atoms in eg methyl-, ethyl-, propyl-.

Butyl, hexyl, ethylhexyl, stearyl, lauryl and cyclo lohexyl acrylate and -methacrylate, acrylic - and/or methacrylate acid, acrylic and/or methacrylamide, N-methylolacrylamide and/or N-methylol methacrylamide, acrylic acid, methacrylic acid or Hydroxyalkyl esters of other α,β-ethylenically unsaturated carboxylic acids, e.g. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate , 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate 4-hydroxybutyl acrylate, 4-human roxybutyl methacrylate et al.

In the second step, advantageously (bl) Alicyclic or aliphatic ester of methacrylic acid or acrylic acid or its (b2 )(bl), (b3) and (b4). 1 to 20% by weight of a monomer having a sil group or a mixture of such monomers, 5-15% by weight for profit; (b3) at least one polymer copolymerizable with (bl), (b2) and (b4); Monomers with ruboxy or sulfonic acid groups or mixtures of such monomers 0-8% by weight, preferably 2-6% by weight, (b4) (bl), (b2) and (b 3) Another monomer copolymerizable with 0-25 or a mixture of such monomers % by weight, preferably from 2 to 15% by weight, (bl), ( The sum of b2), (b3) and (b4) always amounts to 100% by weight.

As the component (bl), for example, the following can be used. Syl acrylate, cyclohexyl methacrylate, up to 20 alkyl groups Alkyl acrylates and alkyl methacrylates having carbon atoms of, e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, Stearyl- and lauryl acrylate and -methacrylate or these A mixture of monomers.

As component (b2), the following can be used, for example: nialic acid , methacrylic acid or another α,β-ethylenically unsaturated carboxylic acid. kill ester. These esters are alkylene glycols esterified with acids. or these can be reacted with acids and alkylene oxides. It can be obtained by Component (b2) is a hydroxyalkyl group Preferred hydroxyl acids of acrylic acid and methacrylic acid contain up to 4 carbon atoms. Using sialkyl esters or mixtures of these hydroxyalkyl esters do. Such hydroxyalkyl esters include 2-hydroxyethyl Acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl Acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutylene acrylate or 4-hydroxybutyl methacrylate. another failure Saturated acids such as ethacrylic acid, crotonic acid and the like with up to about 6 carbon atoms per molecule Corresponding esters of acids containing elementary atoms can also be used.

Component (b3) is preferably acrylic acid and/or methacrylic acid and/or acrylic acid. Acrylamidomethylpropanesulfonic acid is used. However, 6 in one molecule Other ethylenically unsaturated acids having up to carbon atoms can also be used. this Examples of such acids include ethacrylic acid, crotonic acid, maleic acid, fumaric acid and Itaconic acid is mentioned.

As component (b4) the following can be used, for example: vinyl aroma group hydrocarbons, such as styrene, α-alkylstyrenes and vinyltolulenes, lyl- and methacrylamide and acrylic- and methacrylnitrile or Mixtures of these monomers The emulsion polymers used in the present invention have number average molecular Amount (measurement: gel permeation chromatography using polystyrene as standard) 20 0.000 to 2,00°, ooo, advantageously 300,000 to 1,500°00 Should have 0.

Emulsion polyester having the above number average molecular weight? To be able to obtain - , it is well known to those skilled in the art how to choose the reaction conditions (eg F.

Hoescher, Chemie, Physik und Technol ogie derKunststoffe in Einzeldarstel Lungen, Dispersion Synthetischer Hochp olymer, Te1l, Springer Verlag, Berli water according to the invention (see Hejdelberg, New York, 1969) In addition to the above-mentioned emulsion polymers, the base coat can also be made of water-dilutable polyurethane. Tan resins can be included as film-forming substances.

The water-based basecoat according to the invention advantageously has a number average molecular weight (measurement: PO as standard). Gel permeation chromatography using Listyrene') 1000-60,000, Preferably it has a Ni of 1500 to 50,000 and an acid value of 5 to 70°, preferably 10 to 30. and a prepolymer having an isocyanate group and a polyamine and/or hydrazine The urea group, dilutable with water, can be prepared by reaction with, advantageously, chain lengthening. Contains polyurethane resin.

The isocyanate group-containing prepolymers have a hydroxyl number of 10 to 1800, preferably The polyalcohol having a molecular weight of 50-500 and excess polyisisanate at a temperature of 15 below 0°C, preferably between 50 and 130°C, and which cannot react with isocyanates. It can be produced by reacting in a clean organic solvent. NGO's OH group The equivalence ratio is 1.5-1.0:1.0, preferably 1.4-1.2: It is 1. The polyols used to make the prepolymers have low molecular weight and and/or high molecular weight, and these contain inactive anionic groups. can do.

To increase the hardness of polyurethane, low molecular weight polyols can be used. Ru. These have molecular weights from 60 to about 400 and are aliphatic, cycloaliphatic or aromatic. can contain groups. At that time, 30% by weight or less of the total polyol component, Advantageously, amounts of about 2 to 20% by weight are used. Preferably about 20 per molecule Low molecular weight polyols having up to 5 carbon atoms, such as ethylene glycol, di Ethylene glycol, triethylene glycol, 1,2-propanediol, 1 ．． 3-propanediol, 1,4-butanediol, 1,2-butylene glycol 1,6-hexanediol, trimethylolpropane, castor oil or hydrogenated Castor oil, di-trimethylolpropane ether, pentaerythritol, 1.2 -Cyclohexanediol, 1,4-cyclohexane dimetatool, bisphenol Alcohol A1 Bisphenol F1 Neopentyl glycol, hydroxypivalic acid- Neobentyl glycol esters, hydroxyethylated or hydroxyl glycol esters Lopylated bisphenol A1 Hydrogenated bisphenol A and these It is a mixture.

In order to obtain NCO prepolymers with high functionality, a high proportion of advantageous hydroxy A predominantly linear polyol with a molecular number of 130 to 150 should be added.

Up to 97% by weight of the total polyols have a molecular weight Mn of 400-5000 It may also consist of saturated and unsaturated polyesters and/or polyethers. high As a molecular weight polyol, the general formula: %formula%) [In the formula, R=a hydrogen atom or a lower alkyl group optionally having various substituents; for n = 2 to 6, preferably 3 to 4 and m = 2 to 100, preferably 5 to 50. Preference is given to aliphatic polyether diols having the following formula. Examples are linear or Branched polyether diols, such as poly(oxyethylene) glycol, poly(oxypropylene) glycol and/or poly(oxybutylene) glycol It is le. The polyether diol chosen should be one that introduces an excess amount of ether groups. This is not possible because otherwise the polymer formed would swell in water. be. Preferred polyether diols are in the molecular weight range Mn of 400 to 3000. Poly(oxypropylene) glycol. Polyester diol is an organic Manufactured by esterifying dicarboxylic acids or their anhydrides with organic diols. or derived from hydroxycarboxylic acids or lactones. branched chain poly To produce ester polyols, polyols with a small degree of high valence are used. or polycarboxylic acids can be used. Dicarboxylic acids and diols are linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or diols; It's fine.

The diols used to produce polyesters include, for example, alkylene glycosyl such as ethylene glycol, propylene glycol, butylene glycol , butanediol-1,4, hexanediol-1,6, neopentyl glycol and other diols such as dimethylcyclohexane. polyester The acid component of the formula preferably has 2 to 30, preferably 4 to 18 carbon atoms in the molecule. low molecular weight dicarboxylic acids or their anhydrides. Suitable acids include, for example, O- Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexa dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid Acid, fumaric acid, glutaric acid, hexachlorohebutanedicarboxylic acid, tetrachloro phthalic acid and/or dimerized fatty acids. Instead of these acids, it The anhydrides of these can be used as long as they are present. polyester polyester When forming riols, a small amount of carboxyl groups having three or more carboxyl groups is also used. Bonic acids, such as trimellitic anhydride or maleic anhydride, for unsaturated fatty acids Adducts can also be present.

According to the present invention, polyester diol obtained by reaction of lactone and diol also used. These are the presence of a terminal hydroxyl group and the formula:% formula%) Excellent repeating polyester component shown in

In this case, n is advantageously 4 to 6 and the substituent R is a hydrogen atom, an alkyl group, a It is a chloroalkyl group or an alkoxy group. the substituent has more than 12 carbon atoms Contains no. The total number of carbon atoms in the substituents is 12 per lactone ring. It cannot be surpassed. Examples of this are hydroxycaproic acid, hydroxybutyric acid, hydroxyde nicanoic acid and/or hydroxystearic acid.

The lactone used as a starting material has the following general formula [where n and R are already defined] can be expressed as: Production of polyester diol for a substituted compound in which n takes the value 4 and all R substituents are hydrogen atoms. Preference is given to ε-caprolactone, which does not contain ε-caprolactone. The reaction with lactones such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, Starting with ol, dimethylolcyclohexane. However, another anti- reactive components such as ethylenediamine, alkyl dialkanolamine or even urea can be reacted with caprolactone.

Examples of high molecular weight diols include ε-caprolactam and low molecular weight diols. Polylactam diols obtained by reaction are also suitable.

Typical polyfunctional isocyanates include at least two isocyanates per molecule per minute. Aliphatic, cycloaliphatic and/or aromatic polyisocyanates with isocyanate groups use. It is advantageous to use isomers or isomer mixtures of organic diisocyanates. It is advantageous. Examples of aromatic diisocyanates include phenylene diisocyanate, Louis diisocyanate, xylylene diisocyanate, biphenylene diisocyanate Cyanate, naphthylene diisocyanate and diphenylenemethane diisocyanate preferred.

(cyclo)fats with low gelling tendency based on good stability against UV radiation Group diisocyane-1 products result. An example for this is isophorone diisocyanate ate, cyclopentylene diisocyanate and aromatic diisocyanate water oxidation products, e.g. cyclohexylene diisocyanate, methylcyclobexylene diisocyanate and dicyclohexylmethane diisocyanate. fat Examples of group diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, Diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate Soocyanate, propylene diisocyanate, ethyl ethylene diisocyanate , dimethylethylene diisocyanate, methyltrimethylene diisocyanate and and trimethylbexane diisocyanate-1. As diisocyanate isophorone diisocyanate and dicyclohexyl-methane diisocyanate. is particularly advantageous. Polyisocyanate used to form prepolymers The polyisocyanate component can replace the more expensive polyisocyanate component without causing gel formation. It can be contained under the prerequisite that As triisocyanate, di By trimerization or oligomerization of isocyanates or with diisocyanates. Preference is given to products formed by the reaction of compounds containing functional OH or N H groups. It turned out that it was. These include, for example, hexamethylene diisocyanate and Biuret of water, isocyanurate of hexamethylene diisocyanate or tri It belongs to the adduct of inphorone diisocyanate to methylolpropane.

The average functionality is optionally lowered by adding monoisocyanates be able to. An example of such a chain-interrupting monoisocyanate is phenylene isocyanate. With cyanate, cyclohexylene isocyanate and stearyl isocyanate be.

Polyurethane can be produced without introducing special constituents during its synthesis and/or without special preparation. They are generally not compatible with water unless a manufacturing process is carried out. At that time, neutralized raw The acid value is introduced to the extent that the composition can be stably dispersed in water. For this, isosia at least two H active groups that react with the nate groups and are capable of forming anions. Also useful are compounds containing one group. Suitable groups that react with isocyanate groups are , especially hydroxyl groups and primary and/or secondary amino groups. shaped anion The groups that can be formed include carboxyl groups, sulfonic acid groups and/or phosphonic acid groups. It is the basis. Preference is given to using carboxylic acid or carboxylate groups.

These are compounds in which the isocyanate group of the diisocyanate preferentially converts to isocyanate in the molecule. It should be inactive to the extent that it will react with another group that is reactive towards the t group.

For this purpose, an alkanoic acid having two substituents on the carbon atom is used.

The substituents may be hydroxyl, alkyl or alkylol groups. child These polyols contain at least 1, generally 1 to 3 carboxyl groups in the molecule. It has a group. These have from 2 to about 25, preferably from 3 to 10 carbon atoms.

Examples of such compounds are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. Particularly advantageous groups of dihydroxyalkanoic acids are Form: %formula% [wherein R represents a hydrogen atom or an alkyl group having up to about 20 carbon atoms] α,α~dimethylolalkanoic acid represented by of such compounds Examples are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2.2-dimethylolpropionic acid, -dimethylolbutyric acid and 2,2-dimethylolpentanoic acid. favorable dihydres Roxyalkanoic acid is 2,2-dimethylolpropionic acid. Contains amino group Compounds include, for example, -diaminovaleric acid, 3,4-diaminobenzoic acid, 2 ．． 4-Diaminotoluenesulfonic acid and 2,4-diamino-diphenylene ether It is rusulfonic acid. Polyols containing carboxyl groups are NGO prepolyols. from 3 to 100% by weight, advantageously from 5 to 50% by weight of the total polyol component in the polymer. can become.

Amounts of ionizable carboxylic acid available in salt form by carboxyl group neutralization The group generally contains at least 0.4% by weight, based on the solids, preferably at least 0° It is 7% by weight. The upper limit is about 6% by weight. in the unneutralized prepolymer. The amount of dihydroxyalkanoic acid has an acid number of at least 5, advantageously at least 10. arise. The upper limit for the acid number is 70, preferably 40, based on solids.

This dihydroxyalkanoic acid is used to avoid reaction with isocyanate. Before reacting with the socyanate, it is preferably neutralized batchwise with a tertiary amine.

The NGO prepolymer used in the present invention can be used in combination with a polyol or polyol mixture. It can be produced by simultaneous reaction with excess diisocyanate. On the other hand, the reaction can be carried out step by step in the above order.

Examples include West German Patent No. 2,624,442 and West German Patent No. 3,210,051. It is stated in the detailed description.

The reaction temperature is below 1.50°C, with temperatures in the range from 50 to 130°C being preferred. It is. The reaction continues until virtually all hydroxyl groups have reacted.

The NGO prepolymer contains at least about 0.5 weight isocyanate groups on solids. %, preferably less than 1% by weight, with an upper limit of about 15% by weight, preferably 1% by weight. 0% by weight, particularly preferably 5% by weight. The reaction is optionally carried out using a catalyst, e.g. It can be carried out in the presence of a Luganotin compound and/or a tertiary amine. Reaction formation In order to keep the components in liquid state and allow good temperature control during the reaction, It is also possible to add organic solvents that do not contain active hydrogen based on Uchinov.

Solvents that can be used are, for example, dimethylformamide, esters, ethers, e.g. Diethylene glycol-dimethyl ether, ketoester, ketone, e.g. ethyl ketone and acetone, ketones substituted with methoxy groups, e.g. methoxy -Hexanones, glycol ether esters, chlorinated hydrocarbons, aliphatics.

and alicyclic hydrocarbon pyrrolidones, such as N-methylpyrrolidone, hydrogenated pyrrolidone, ran, aromatic hydrocarbons and/or mixtures thereof. The amount of solvent can vary widely To form a prepolymer solution with a suitable viscosity that can be varied within should be sufficient for The solvent is at least 0.01. ~15 % by weight, advantageously from 0.02 to 8% by weight, is sufficient. In some cases, water-insoluble solvents If the solvent boils at a lower temperature than water, the solvent After production, it can be gently distilled off by vacuum distillation or thin film evaporation. High boiling point solution The agent should be water-soluble and facilitate flow of the polymer particles during film formation. remains in the aqueous polyurethane dispersion. Particularly advantageous as a solvent is optionally mixed with a ketone, e.g. methyl ethyl ketone. It is pyrrolidone.

The anionic groups of the NGO prepolymer are at least partially neutralized with a tertiary amine. Ru. The resulting improved dispersibility in water is sufficient for infinite dilutability. It's a minute. This also ensures stable dispersion of neutralized urea-containing polyurethane. is also sufficient. Suitable tertiary amines include, for example, trimethylamine, triethylamine, amine, dimethylethylamine, diethylmethylamine, N-methylmorpholine be. After neutralization, the NCO prepolymer is diluted with water and then formed into a fine dispersion. Jiru. Immediately thereafter, the isocyanate groups still present are added to the chain extender. and/or di- and/or polyamines having secondary amino groups. This anti The reaction results in further binding and/or increase in molecular weight. Amine and water and isocarbon Competitive reactions with anates should be well matched (with time) to achieve optimal properties. , temperature, concentration) and should be adequately monitored for reproducible products. chain spread As preservatives, water-soluble compounds are advantageous, since they absorb water's pores. This is because it improves the dispersibility of the remer target product. hydrazine and/or organic dia Mines are advantageous since they generally constitute the largest molecular weight and only This is because the resin does not gel. However, the prerequisite for this is that The ratio of mino groups to isocyanate groups is selected depending on the purpose.

The amount of chain length depends on its functionality, the NGO content in the prepolymer and the duration of the reaction. Depends on it. The ratio of active hydrogens in the chain extender to NCO groups in the prepolymer is , generally from 2 to less than 1, advantageously 1. o: to 1.75:1. Especially the first The presence of an excess of active hydrogen, in the form of monoamino groups, can lead to undesirable low molecular weight polymers. may cause the formation of

Polyamines contain substantially 1 to 40 carbon atoms, advantageously about 2 to 15 carbon atoms. It is an alkylene-polyamide with a polyamide. These react with isocyanate groups can have a substituent that does not contain a hydrogen atom. Examples are linear or branched having a chain aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups; It is a polyamine that Diamines include ethylene diamine and propylene diamine. amine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethy Ruamine, hexamethylenediamine-1,6, trimethylhexamethylenediamine methane diamine, isophorone diamine, 4,4'-diaminodicyclohexyl silmethane and amineonithylethanolamine. Advantageous diamines are Lugyl- or cycloalkyl diamines, such as propylene diamine and 1-amino Nor-3-amino-methyl-3,5,5-trimethylcyclohexane.

Chain extension consists, at least in part, of at least three atoms having reactive hydrogen atoms. This can be carried out using a polyamine having a mino group. This polyamine tie The polymer has 1 to 2 reactive hydrogen atoms after chain extension. It can be used in such an amount that additional amine nitrogen atoms are present. Use like this Possible polyamines include diethylenetriamine, triethylenetetraamine, dipropylene diamino and diethylenetriamine. Advantageous polyamines are an alkyl- or cycloalkyltriamine, such as diethylenetriamine . A small amount of monomer, e.g. ethylhexyl, is added to prevent gelation during chain extension. Silamines can also be added.

The water-dilutable polyurethane resin to be used in the present invention and its production are disclosed in the European Patent Also described in Publication No. 89479 and US Pat. No. 4,719,132 ing.

Emulsion polysaccharides included as film-forming substances in preferred water-based basecoats. The mixture of emulsion polymer and polyurethane resin contains 95 to 40% by weight of emulsion polymer. % by weight of polyurethane and/or polyurethane, the proportions being in each case relative to the solid components. And the sum is always 100% by weight.

The water-based basecoat according to the present invention is an emulsion polymer or an emulsion polymer. In addition to the mixture of remer and polyurethane resin, I11 may also be diluted with another compatible water. aminoblast, which can be used as a grinding resin for pigments; Contains polyester and polyether.

The water-based basecoat according to the invention is dilutable with water based on the total solids content of the basecoat. aminoplast resins, preferably melamine resins, preferably 5 to 20% by weight, in particular Advantageously 10 to 16% by weight and water dilutable polyethers (e.g. number average molecular weight) polysilopylene glycol having an amount of 400 to 900) 5 to 20% by weight, advantageously contains 8-15% by weight.

The water-based undercoating paint according to the present invention uses a colored pigment based on an inorganic substance as a pigment, For example, materials based on organic substances such as titanium dioxide, iron oxide, carbon black, etc. Color pigments as well as conventional metal pigments (e.g. commercially available aluminum bronze, stainless steel) bronze, etc.) and non-metallic effect pigments (e.g. pearlescent or interference pigments) can contain. The basecoat according to the invention advantageously contains metallic pigments and/or or contain effect pigments. The degree of pigmentation is within normal ranges.

Furthermore, the primer coating according to the present invention may be used as described in, for example, European Patent Publication No. 38127. cross-linked polymer microparticles and/or conventional rheological inorganics as disclosed in Or organic additives can be added. Thickeners such as water Soluble cellulose ethers, such as hydroxyethylcellulose, methylcellulose cellulose or carboxymethylcellulose and ionic and/or associative acting synthetic polymers with groups, e.g. polyvinyl alcohol, poly(meth)acrylic Amide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-malein Acid anhydride or ethylene medic acid anhydride copolymer and derivatives thereof or In addition, hydrophobically modified ethoxylated urethanes or polyacrylates do. Particularly advantageous are those having an acid number of 60 to 780, preferably 200 to 500. It is a carboxyl group-containing polyacrylate copolymer.

The basecoat according to the invention generally has a solids content of about 15 to 50% by weight. solid The content varies depending on the intended use of the paint. For metallic lacquers, the inclusion The amount is, for example, advantageously from 17 to 25% by weight. For single color lacquers, the content is higher (e.g. 30-45% by weight).

The basecoat according to the invention can additionally contain customary organic solvents.

The proportion should be as small as possible. For example, less than 15% by weight.

The basecoat according to the invention is generally adjusted to a pH value of 6.5 to 9.0. pH value is the usual amine, e.g. ammonia, triethylamine, dimethylaminoethanol and N-methylmorpholine.

The preparation of the base coating according to the invention solves the problem mentioned at the beginning.

By using the undercoat paint according to the present invention, quality can be achieved without the need for topcoating with a transparent topcoat paint. It is possible to produce relatively expensive coatings.

The base coat according to the invention can be applied to any coated material, such as metal, wood, plastic or can be painted on paper.

Next, the present invention will be explained in detail with reference to Examples.

Cylinder with stirrer, reflux condenser, stirrable feed vessel, dropping funnel and thermometer In a double-walled glass container, add 1344 g of deionized water and penta(ethylene glycol). Ammonium salt of nonylphenyl ether sulfate (GAF Ca rp, Fenopon EP 110, emulsifier 1) 30% aqueous solution 1 Charge 2 g and heat to 82°C. Deionized in a stirrable supply vessel. 720 g of water, 24 g of emulsifier (1), 10.8 g of acrylamide, 1 methyl methacrylate Manufacture emulsion from 846g of Lyreite and 216g of n-butyl methacrylate do. Add 30% by weight of this emulsion to the previous charge. Then deionized A solution of 3.1 g of ammonium peroxydisulfate (APS) in 188 g of diluted water 28% by weight is added dropwise within 5 minutes. An exothermic reaction occurs. The reaction temperature is 82-8 Keep at 8℃. 15 minutes after the addition of ammonium peroxydisulfate was completed, The remaining 70% by weight of the emulsion was combined with the remaining 70% by weight of the ammonium peroxydisulfate solution. 2% by weight within 1 hour, maintaining the temperature at 85°C. Then 8 842 g of n-butyl acrylate was cooled to 2°C and within 2 hours. Lopyl methacrylate 108g, methyl methacrylate 43g 1 methacrylic acid 4 3゜2g1 Acrylamide 32.4g and Eicosa (ethylene glycol) Nylphenyl ether (GAF Corp.

Antarox Co 850, emulsifier 2) 5.4g and deionized Add a mixture consisting of 343 g of water. After the addition is complete, the reaction mixture is Keep at ℃ for 1.5 hours. Thereafter, the dispersion was cooled and the mesh width was 30 μm. Pour onto a filter cloth. Non-volatile components 45% by weight, pH value 3.4, acid value 13 and OHH A fine dispersion with 2O2 is obtained.

Emulsion polymer dispersion 2 Cylinder with stirrer, reflux condenser, stirrable feed vessel, dropping funnel and thermometer In a double-walled glass container, add 1344 g of deionized water and penta(ethylene glycol). Ammonium salt of nonylphenyl ether sulfate (GAF Co RP, Fenopon EP 110, emulsifier 1) 40% aqueous solution 1 Charge 2 g and heat to 80°C. Deionized in a stirrable supply vessel. 720g of water, emulsifier (1 north side 4g, acrylamide 10.8g1 methyl methacrylate) From 518g of Reito, 292g of n-butyl methacrylate and 205g of styrene. Manufacture emulsion. Add 30% by weight of this emulsion to the previous charge.

Then ammonium peroxydisulfate (APS) in 55 g of deionized water 0.9 g of solution is added dropwise within 5 minutes. An exothermic reaction occurs. The reaction temperature is 80 Keep at ~85°C. 15 minutes after the addition of ΔPS was completed, A in 480 g of water was added. PS 2.2 g of the solution within 3 hours and the remaining 70 weight of the emulsion % within 1 hour, keeping the temperature at 80°C. End of emulsion addition After that, it was cooled to 77°C and within 2 hours, 745 g of n-butyl acrylate-I, 119 g of tyl methacrylate, 108 g of hydroxypropyl methacrylate, 54 g of styrene 42.7 g of ethylhexyl acrylate, 42 g of methacrylic acid ．． 7 g, acrylamide 21.6 g and emulsifier (2) 2.2 g. add things After the addition has ended, the reaction mixture is still kept at 80° C. for 1.5 hours.

Thereafter, it is cooled and the dispersion is poured onto a filter cloth with a mesh width of 30 μm. nonvolatile Fine fraction with 45% by weight of active components, pH value 3.8, acid value 13 and OH value J9 A dispersion is obtained.

Emulsion Poly7-Dispersion 3 Cylinder with stirrer, reflux condenser, stirrable feed vessel, dropping funnel and thermometer In a double-walled glass container, add 1109 g of deionized water and penta(ethylene glycol). Recall) Ammonium salt of nonylphenyl ether sulfate (GAF C orp, Fenopon EP] 10, 30% aqueous solution of emulsifier 1) Charge 10 g of liquid and heat to 82°C. Deionization in a stirrable supply vessel 748.2 g of water, 20.3 g of emulsifier (1), 9.0 g of acrylamide. Og, me methyl methacrylate) 718.1 g and n-butyl methacrylate 179.5 g Prepare an emulsion from g. Add 30% by weight of this emulsion to the previous charge. I can do it. Then ammonium peroxydisulfate 7 in 305 g of deionized water ．． 2 g of a solution 10% by weight are added dropwise within 5 minutes. An exothermic reaction occurs. reaction temperature The temperature is maintained at 82-88°C. Addition of the above ammonium chloroxonisulfate solution is completed. After 15 minutes, the remaining 70% by weight of the emulsion was diluted with ammonium beroxonisulfate. of the remaining 90% by weight of the Ni solution within 1 hour, at a temperature of 82°C. Keep at ℃. Then, within 2 hours, 700g of n-butyl acrylate, hydroxyl 89.8 g of propyl methacrylate, 35.9 g of methyl methacrylate, Tacrylic acid 35.9 g.

Acrylamide 26.9 g and eicosa (ethylene glycol) nonylphenyl ether (GAF Carp, Antarox”’ Co 850, emulsifier 2) Add a mixture consisting of 4.5 g. After the addition is complete, the reaction mixture is kept at 82°C. Keep it for 1.5 hours. Thereafter, the dispersion was cooled and the mesh width was 30 μm. Pour onto filter cloth. Non-volatile components 45% by weight, pH value 2.5, acid value 14 and OHH2 A fine dispersion with O2 is obtained.

Emulsion polymer dispersion 4 Cylinder with stirrer, reflux condenser, stirrable feed vessel, dropping funnel and thermometer In a double-walled glass container, add 1344 g of deionized water and penta(ethylene glycol). Ammonium salt of nonylphenyl ether sulfate (GAF Co rp, Fenopon EP 110, emulsifier 1) 30% aqueous solution 1 Charge 2 g and heat to 82°C. Deionized in a stirrable supply vessel. 477g of water, 66.7g of emulsifier (1), 10.8g of acrylamide, methylmethane Emulsion from 864 g of Takuri L/-t and 216 g of n-butyl methacrylate Manufacture John. Add 30% by weight of this emulsion to the previous charge. then , a solution of 8.6 g of ammonium peroxydisulfate in 183 g of deionized water. 3.6% by weight is added dropwise within 5 minutes. An exothermic reaction occurs. The reaction temperature is 82~ Keep at 88℃. 15 minutes after the end of the addition of the Belogisonisulfate solution Add the remaining 70% by weight of the emulsion to the remaining ammonium peroxodisulfate solution. 96.4 wt.

After that, within 2 hours, 842 g of n-butyl acrylate, hydroxypropyl 108 g of methacrylate, 43.2 g of methyl methacrylate, acrylamide Propanesulfonic acid 43.2 g, acrylamide 32, 4 g% emulsifier ( 1) 66.7g and eicosa (ethylene glycol) nonylphenyl ether ( GAF Corp, Antarox 'Shishi' Cog50, Emulsifier 2) 5.4g Add a mixture consisting of. After the addition was complete, the reaction mixture was kept at 82°C for 1.5 hours. keep. Thereafter, the dispersion is cooled and poured onto a filter cloth having a mesh width of 30 μm. . Fine with non-volatile content 46% by weight, pH value 2.5, acid number 6 and OH number 19 A dispersion liquid is obtained.

Emulsion polymer dispersion 5 Cylinder with stirrer, reflux condenser, stirrable feed vessel, dropping funnel and thermometer In a double-walled glass container, add 1344 g of deionized water and penta(ethylene glycol). Ammonium salt of nonylphenyl ether sulfate (GAF Co rp, Fenopon EP 110, emulsifier 1) 30% aqueous solution 1 Charge 2 g and heat to 82°C. Deionized in a stirrable supply vessel. 720 g of water, 24 g of emulsifier (1), 43.2 g of acrylamide, 1 methyl methacrylate 907 g of relite and 216 g of n-butyl methacrylate, n-butyl acrylate 842 g hydroxypropyl methacrylate 108 g 1 methacrylic acid 4 An emulsion is prepared from 3.2 g and 5.4 g of emulsifier (2). This emulsion Add 10% by weight of water to the previous charge. The base in 53 g of deionized water was then A solution of 0.87 g of ammonium fluorodisulfate is added dropwise within 5 minutes. anti fever response occurs. The reaction temperature is maintained at 82-88°C. 1 after the addition of APS solution is completed. After 5 minutes, the remaining 90% by weight of the emulsion is deionized within 3 hours. A solution of 2.23 g APS in 478 g water was added within 3.5 hours, with the temperature The temperature is kept at 82℃.

After the addition has ended, the reaction mixture is still kept at 82° C. for 1.5 hours. Then, only cooling The dispersion was poured onto a filter cloth having a mesh width of 30 μm. Non-volatile ingredients 45wt %, pH value 5.8, acid value 13 and OHH2O2 fine dispersion is obtained. .

Made from caprolactone and ethylene glycol, hydroxyl number 196 570 g of a commercially available polyester having the following properties are dehydrated in vacuo at 100° C. for 1 hour. 80 ℃, 4.4'-dicyclohexylmethanediol diisocyanate-1.524 g and at 90°C until the isocyanate content is 7.52% by weight of the total weight. Stir with After cooling to 60°C, dimethylene in 400 g of N-methylpyrrolidone Add 67 g of roll propionic acid and 50 g of triethylamine solution and heat at 90°C. Stir for 1 hour. Add 1 ml of cold deionized water to the resulting material while stirring vigorously. Add to 840g. The resulting dispersion was mixed with Add 86 g of 5% hydrazine solution. The resulting extremely fine dispersion contains solids. with a volume of 35% and an outflow time in DIN beaker 4 of 27 seconds.

Polyurethane resin dispersion liquid 2 Consisting of neopentyl glycol, hexanediol-1゜6 and adipic acid, 830 g of polyester having a hydroxyl number of 135 and an acid number of less than 3 are Dehydrate at 00°C for 18 hours. At 80°C, 4,4'-dicyclohexylmethanedio Add 524 g of diisocyanate and at 90°C, the total isocyanate content Stir until the volume is 6.18% by weight. After cooling to 60°C, N-methylpi 67g of dimethylolpropionic acid and 5g of triethylamine in 400g of lolidon Add 0g solution and stir at 90°C for 1 hour. Stir the resulting material vigorously. Add to 2400 g of cold deionized water. A fine dispersion is obtained. child 30% of ethylenediamine in water within 20 minutes with vigorous stirring. Add 80 g of solution. The resulting extremely fine dispersion had a solids content of 35% and a D.I. The outflow time in the N beaker 4 is 23 seconds.

Manufacture of C8 undercoat paint Butyl glycol 18.2 g, commercially available melamine-formaldehyde resin (Cy mel + Rゝ301) 3, 7 g, polypropylene glycol (average molecular weight =400) 3.1g and the aluminum of West German Patent Application No. 3636183 7.2 g of aluminum bronze (aluminum content 260% by weight) was mixed with a high-speed stirrer for 30 minutes. Stir for 15 minutes at 0-500 rpm. A mixture 1 is obtained.

1.2.3 or 427.2g of emulsion polymer dispersion as polyurethane resin Mix with 11.6 g of dispersion (1) and 19.6 g of deionized water. the mixture was adjusted to pHHI37 with a 5% dimethylethanolamine aqueous solution and a commercially available Lyacrylic Acid Thickener (ViscalexLI″ from Allied Colloids) 'HV 30. Add 9.4 g of a 3.5% solution of pH 8.0). mixture Product 2 is obtained.

To produce the basecoat according to the invention, mixtures 1 and 2 were mixed at 800 to 1000 Mix for 30 minutes at rpm and then add 5% dimethylethanolamine in water. Adjust the pH to 37 with liquid. Continue adding deionized water to reduce viscosity. Adjust the drain time in the beaker to DIN 4 - 25 seconds. Primer according to the invention Paint BB1. BB2. BB3 and BH3 are obtained.

Undercoat paint BB5 contains 36.2 g of emulsion polymer dispersion (1) in mixture 2. Obtained by blending. BH3 does not contain polyurethane resin dispersion .

The basecoat thus obtained exhibits excellent storage stability.

The primer coating is applied using commercially available electrocoating equipment and commercially available filaments using well-known methods. Spray onto a phosphated steel plate (Bonder 132) coated with After a ventilation period of 10 minutes, it was overcoated with a commercially available clear lacquer and heated at 140℃ for 20 minutes. Bake for a minute.

The metallic effect coating film thus obtained has a good metallic effect and is resistant to fillers. sufficient adhesion, according to DIN 50017 (condensation constant undercoating in air-conditioned rooms) Indicates sufficient adhesion between the paint and the topcoat. BBl, BH2, BH3 and BH 3 shows a better metallic effect than BH3.

Part of the painted thin plate is coated again with primer paints BBI, BH2, BH3, BH3 and BH. 3 and overcoat with a commercially available clear lacquer. The coating film thus obtained is 8 Bake at 0℃ for 40 minutes. The paint film baked at 80℃ was baked at 140℃. Adheres well to the paint film.

Comparative example Undercoat film produced using emulsion polymer dispersion 5 based on the above description shows poor storage stability.

Procedural amendments issued by Dian) July 5, 1991

Claims (1)

[Claims] 1. (1) An emulsion that can be diluted with water as a film-forming substance and as an undercoat. A colored water-based paint containing a polymer is applied to the surface of the object to be coated, (2) forming a polymer coating film from the paint applied in step (1); (3) Apply a suitable transparent top coat on the undercoat layer thus obtained and Continuation (4) By baking the undercoat film together with the topcoat film, a large amount of In a method for producing a layer protective and/or decorative coating, (a) In the first step, the ethylenically unsaturated monomer or ethylenically unsaturated monomer 10 to 90 parts by weight of the mixture in the aqueous phase with one or more emulsifiers and one or more radical forms. Polymerization is carried out in the presence of a formation initiator, during which ethylenically unsaturated monomers or ethylene In the first step, the mixture of unsaturated monomers is heated to a glass transition temperature (Tc1) of +30 to + selected to obtain a polymer having a temperature of 110°C, and (b) Ethylenically unsaturated monomer or monomer mixture used in the first step After at least 80% by weight has been converted, the ethylenically unsaturated monomer is converted in a second step. or 90-10% by weight of the mixture of ethylenically unsaturated monomers obtained in the first step. The monomer used in the second step or the second step is polymerized in the presence of a polymer. The mixture of ethylene-based monomers used in the process is mixed with the ethylene-based monomer used in the second process. Unsaturated monomer or mixture of ethylenically unsaturated monomers used in the second step Single polymerization of produces a polymer with a glass transition temperature (Tc2) of -60 to +20°C. The reaction conditions selected to produce the resulting emulsion polymer is selected to have a number average molecular weight of 200,000 to 2,000,000, and Ethylenically unsaturated monomer or monomer mixture used in the first step and the ethylenically unsaturated monomer or monomer mixture used in the second step. In terms of type and amount, the resulting emulsion polymer has a hydroxyl number of 2 to 100. and the deviation Tc1 - Tc2 = 10 to 170°C. Features: A method for producing multilayer coatings. 2. In a paint that can be diluted with water, the paint serves as a film-forming substance, (a) In the first step, the ethylenically unsaturated monomer or ethylenically unsaturated monomer 10 to 90 parts by weight of the mixture in the aqueous phase with one or more emulsifiers and one or more radical forms. Polymerization is carried out in the presence of a formation initiator, during which ethylenically unsaturated monomers or ethylene In the first step, the mixture of unsaturated monomers is heated to a glass transition temperature (Tc1) of +30 to + selected to obtain a polymer having a temperature of 110°C, and (b) Ethylenically unsaturated monomer or monomer mixture used in the first step After at least 80% by weight has been converted, the ethylenically unsaturated monomer is converted in a second step. or a mixture of ethylenically unsaturated monomers 90-10% by weight etc. obtained in one step. The monomer used in the second step or the second step is polymerized in the presence of a polymer. The mixture of ethylene-based monomers used in the process is mixed with the ethylene-based monomer used in the second process. Unsaturated monomer or mixture of ethylenically unsaturated monomers used in the second step Single polymerization of produces a polymer with a glass transition temperature (Tc2) of -60 to +20°C. The reaction conditions selected to produce the resulting emulsion polymer is selected to have a number average molecular weight of 200,000 to 2,000,000, and Ethylenically unsaturated monomer or monomer mixture used in the first step and the ethylenically unsaturated monomer or monomer mixture used in the second step. In terms of type and amount, the resulting emulsion polymer has a hydroxyl number of 2 to 100. and the deviation Tc1 - Tc2 = 10 to 170°C. characterized by containing a water-dilutable emulsion polymer obtained by A water-dilutable primer paint. 3. The base coat or paint contains one or more metallic pigments, preferably aluminum pigments. The method according to claim 1, comprising: 4. The film-forming substance is dilutable with 95-40% by weight of emulsion polymer and water. Consists of 5 to 60% by weight of polyurethane resin, with the weight percentage depending on the solid component. 4. The method according to claim 1, wherein the sum is always 100% by weight. 5. In the first step, (a1) Alicyclic or aliphatic ester of methacrylic acid or acrylic acid or its 100 to 60, preferably 99.5 to 75% by weight of esters such as (a2) A monomer copolymerizable with (a1) or a mixture of such monomers 0- 40, preferably using a mixture consisting of 0.5 to 25% by weight, (a1) The method according to claim 1, 3 or 4, wherein the sum of the weight percentages of and (a2) is always 100 weight percent. Law. 6. In the second step, (b1) Alicyclic or aliphatic ester of methacrylic acid or acrylic acid or its 47 to 99, preferably 75 to 90% by weight, of esters such as (b2) (b 1), at least one hydroxyl group copolymerizable with (b3) and (b4) 1 to 20, preferably 5 to 1 monomers or mixtures of such monomers with 5% by weight, (b3) at least one polymer copolymerizable with (b1), (b2) and (b4); Monomers with ruboxy or sulfonic acid groups or mixtures of such monomers 0 to 8, preferably 2 to 6% by weight of (b4) (b1), (b2) and (b3) 0-25% by weight of other copolymerizable monomers or mixtures of such monomers , preferably a mixture consisting of 2 to 15% by weight, in which case (b1), (b2) , (b3) and (b4) is always 100% by weight. The method described in any one of the above. 7. (a) In the first step, an ethylenically unsaturated monomer or an ethylenically unsaturated monomer 10 to 90 parts by weight of a mixture of one or more emulsifiers and one or more radicals in an aqueous phase. Polymerization in the presence of an ethylenically unsaturated monomer or polymer-forming initiator. The mixture of tyrenic unsaturated monomers is heated to a glass transition temperature (Tc1) +30 in the first step. selected to obtain a polymer having a temperature of ~+110°C, and (b) Ethylenically unsaturated monomer or monomer mixture used in the first step After at least 80% by weight has been converted, the ethylenically unsaturated monomer is converted in a second step. or 90-10% by weight of the mixture of ethylenically unsaturated monomers obtained in the first step. The monomer used in the second step or the second step is polymerized in the presence of a polymer. The mixture of ethylene-based monomers used in the process is mixed with the ethylene-based monomer used in the second process. Unsaturated monomer or mixture of ethylenically unsaturated monomers used in the second step Single polymerization of produces a polymer with a glass transition temperature (Tc2) of -60 to +20°C. The reaction conditions selected to produce the resulting emulsion polymer is selected to have a number average molecular weight of 200,000 to 2,000,000, and Ethylenically unsaturated monomer or monomer mixture used in the first step and the ethylenically unsaturated monomer or monomer mixture used in the second step. In terms of type and amount, the resulting emulsion polymer has a hydroxyl number of 2 to 100. and the deviation Tc1 - Tc2 = 10 to 170°C. water-dilutable emulsion, characterized in that it is obtained by polymer. 8. In a method of producing a water-dilutable emulsion polymer, (a) In the first step, the ethylenically unsaturated monomer or ethylenically unsaturated monomer 10 to 90 parts by weight of the mixture in the aqueous phase with one or more emulsifiers and one or more radical forms. Polymerization is carried out in the presence of a formation initiator, during which ethylenically unsaturated monomers or ethylene In the first step, the mixture of unsaturated monomers is heated to a glass transition temperature (Tc1) of +30 to + selected to obtain a polymer having a temperature of 110°C, and (b) Ethylenically unsaturated monomer or monomer mixture used in the first step After at least 80% by weight has been converted, the ethylenically unsaturated monomer is converted in a second step. or 90-10% by weight of the mixture of ethylenically unsaturated monomers obtained in the first step. The monomer used in the second step or the second step is polymerized in the presence of a polymer. The mixture of ethylene-based monomers used in the process is mixed with the ethylene-based monomer used in the second process. Unsaturated monomer or mixture of ethylenically unsaturated monomers used in the second step Single polymerization of produces a polymer with a glass transition temperature (Tc2) of -60 to +20°C. The reaction conditions selected to produce the resulting emulsion polymer is selected to have a number average molecular weight of 200,000 to 2,000,000, and Ethylenically unsaturated monomer or monomer mixture used in the first step and the ethylenically unsaturated monomer or monomer mixture used in the second step. In terms of type and amount, the resulting emulsion polymer has a hydroxyl number of 2 to 100. and the deviation Tc1 - Tc2 = 10 to 170°C. A method for producing a dilutable emulsion polymer, characterized in that: 9. In the first step, (a1) Alicyclic or aliphatic ester of methacrylic acid or acrylic acid or its 100 to 60, preferably 99.5 to 75% by weight of esters such as (a2) A monomer copolymerizable with (a1) or a mixture of such monomers 0- A mixture of 40% by weight, preferably from 0.5 to 25% by weight, is used, with (a The method according to claim 7 or 8, wherein the sum of the weight percentages of 1) and (a2) is always 100 weight%. Mulsion polymer or method. 10. In the second step, (b1) Alicyclic or aliphatic ester of methacrylic acid or acrylic acid or its 47 to 99, preferably 75 to 90% by weight, of esters such as (b2) (b 1), at least one hydroxyl group copolymerizable with (b3) and (b4) 1 to 20, preferably 5 to 1 monomers or mixtures of such monomers with 5% by weight, (b3) at least one polymer copolymerizable with (b1), (b2) and (b4); Monomers with ruboxy or sulfonic acid groups or mixtures of such monomers 0 to 8, preferably 2 to 6% by weight of (b4) (b1), (b2) and (b3) 0-25% by weight of other copolymerizable monomers or mixtures of such monomers , preferably a mixture consisting of 2 to 15% by weight, in which case (b1), (b2) , (b3) and (b4) is always 100% by weight. An emulsion polymer or method according to any one of the above.