EP2456837A1 - Use of film-forming polymers and organic hollow particles for coating agents - Google Patents

Abstract

The present invention relates to the use of a mixture made of film-forming polymers and organic hollow particles for coating agents, particularly in coating compositions, and to coating agents comprising such blends.

Description

 The present invention relates to the use of a mixture of film-forming polymers and organic hollow particles for coating compositions, in particular in paints, and to coating compositions containing such mixtures.

Organic hollow particles are a special type of core-shell particles, consisting in dried form of an air-filled cavity surrounded by a hard shell. Because of this construction, they have the special property of scattering light, whereby their use as white pigment in paints, paper coatings and in cosmetic products, such as sun creams is due. Here they partially replace the inorganic white pigment titanium dioxide and additionally enhance the effect of the remaining OO2.

CJ McDonald and MJ Devon describe in Advances in Colloid and Interface Science 2002, 99, 181-213 a number of possibilities for the production of these hollow particles, such as inter alia swelling with organic solvents or blowing agents, encapsulation of hydrocarbons or approaches based on W / O / W emulsions. However, the preferred method for ecological as well as economic reasons is the osmotic swelling of special core-shell particles.

EP 1 904 544 discloses the preparation of organic hollow particles.

Film forming polymers are known in the art and are disclosed, for example, in EP 939,774.

WO 94/04603 discloses the use of organic hollow particles in combination with a binder wherein the preparation of the hollow particles with an acid-free core and the final dispersion in an ecologically as well as economically less preferred method takes place at a significantly higher temperature. The resulting hollow particles have an average particle diameter of 800 nm and larger. Such hollow particles are preferably used for paper coatings, where in addition to the opacity of the coating and their gloss after calendering plays a primary role.

JP60223873 also discloses blends of a water-based microvoid coating composition prepared by blending a film-forming polymer dispersion with a non-film-forming polymer dispersion consisting of a multilayered particle. The manufacturing process of the microvoided polymer particles is fundamentally different from the process published in this invention.

On the one hand, the compositions of the prior art have the disadvantage that they are less favorable both economically and ecologically, and on the other hand they fulfill them not the desired requirements in terms of hiding power and wet abrasion resistance:

The object of the present invention was therefore to develop a water-based dispersion as a coating agent for increasing the yield and the wet abrasion resistance of exterior and interior paints by mixing organic hollow particles, obtainable by a process which avoids the disadvantages of the processes of the prior art at least one aqueous dispersion of a film-forming polymer (PD). According to the invention, the object was achieved by the use of a blend of an aqueous dispersion of organic hollow particles with at least one aqueous dispersion of a film-forming polymer (PD), characterized in that the organic hollow particles by a process for the preparation of emulsion polymer by preparing a

Multi-stage emulsion polymer by sequential polymerization, i) one seed, followed by reaction with

ii) a seed seed containing 0 to 100% by weight of at least one nonionic-ethylenically unsaturated monomer and 0 to 40% by weight of at least one monoethylenically unsaturated hydrophilic monomer, based in each case on the total weight of the core-stage polymer containing both seed as well as swell seed, followed by polymerization with

iii) a first shell containing 85 to 99.9 wt .-% of at least one non-ionic ethylenically unsaturated monomer and 0.1 to 15 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer, followed by polymerization

iv) a second shell containing 85 to 99.9 wt .-% of at least one non-ionic ethylenically unsaturated monomer and 0.1 to 15 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer, then adding v) at least one plasticizer monomer with a Ceiling Temperature smaller

181 ⁰ C preferably less than 95 ° C.

vi) neutralization to a pH of at least 7.5 or greater, preferably greater than 8, of the particles thus formed with a base, subsequent polymerization vii) a third shell containing 90 to 99.9 wt .-% of at least one non-ionic ethylenically unsaturated monomer and 0.1 to 10% by weight of at least one hydrophilic monoethylenically unsaturated monomer,

viii) and optionally polymerization of further shells containing at least one nonionically ethylenically unsaturated monomer and at least one hydrophilic monoethylenically unsaturated monomer, are obtained as coating agents. The invention further provides coating compositions in the form of an aqueous composition comprising:

^■ a blend of at least one aqueous dispersion of organic Hohlteil- Chen, as defined below and at least one aqueous dispersion of a film-forming polymer (PD), as defined below,

^Optionally at least one inorganic filler and / or inorganic pigment,

^■ usual aids and

■ Water to 100 wt .-%.

Another object of the invention is the use of a blend of an aqueous dispersion of organic hollow particles according to the invention with at least one aqueous dispersion of a film-forming polymer (PD) as an additive for an aqueous coating agent to increase the hiding power and / or the wet abrasion resistance.

Another object of the invention is the use of a blend of an aqueous dispersion of organic hollow particles according to the invention with an aqueous dispersion of a film-forming polymer (PD) as an additive for paints.

Another object of the invention is the use of a blend of an aqueous dispersion of organic hollow particles according to the invention with an aqueous dispersion of a film-forming polymer (PD) as an additive for interior or exterior paints.

The mixing ratio of the aqueous dispersion containing the film-forming polymer with the aqueous dispersion containing the organic hollow particle is 30:70, preferably 20:80 or 5:95, more preferably 10:90. An advantage of the invention is that in the preparation the organic hollow particles in step (iv) when using monomers whose Ceiling temperature (Frieder Viebeg & Sohn Verlagsgesellschaft mbH, Braunschweig / Wiesbaden, 1997) below the source temperature or - as an extreme case thereof - which is not a homopolymer for thermodynamic reasons can form the disadvantages of the prior art can be bypassed and swelling without the addition of polymerization inhibitors or reducing agents is possible even in the presence of residual amounts of initiator, and also the preferred source temperature is less than 100 ⁰ C.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-C7-alkyl, preferably Ci-Cβ-alkyl and particularly preferred

Ci-C4 alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethyl-propyl, n-hexyl, 2-hexyl, 2- Methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, etc.

Suitable longer-chain Cs-Cso-alkyl groups are straight-chain and branched alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include z. N-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, etc The term alkyl includes unsubstituted and substituted alkyl radicals.

The above comments on alkyl also apply to the alkyl moieties in arylalkyl. Preferred arylalkyl radicals are benzyl and phenylethyl.

C 8 -C 32 -alkenyl in the context of the present invention represents straight-chain and branched alkenyl groups which may be mono-, di- or polyunsaturated. Preferably, it is Cio-C2o-alkenyl. The term alkenyl includes unsubstituted and substituted alkenyl radicals. Specifically, these are predominantly linear alkenyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include in particular octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, linolyl, linolenyl, eleostearyl and oleyl (9-octadecenyl). The term alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 7 carbon atoms, eg. As methylene, 1, 2-ethylene, 1, 3-propylene, etc.

Cycloalkyl is preferably C4-C8-cycloalkyl, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. The term aryl preferably represents phenyl, ToIyI, XyIyI, mesityl, duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, these aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.

The process according to the invention for producing the organic hollow particles is multi-stage sequential emulsion polymerization. Sequential refers to the implementation of the individual stages, whereby each individual stage can also be made up of several sequential steps. The term "seed" refers to an aqueous polymer dispersion used at the beginning of multistage polymerization which is the product of emulsion polymerization, or may refer to an aqueous polymer dispersion which is at the end of one of the polymerization stages for the preparation of the hollow particle dispersion, except the last one Stage, is present.

The seed used at the beginning of the first-stage polymerization may also be prepared in situ, and preferably consists of acrylic acid, methacrylic acid, esters of acrylic acid and methacrylic acid, or mixtures thereof. Particularly preferred are mixtures of n-butyl acrylate, methyl methacrylate and methacrylic acid.

The mean particle size of the seed polymer in the unswollen state is 40 to 100 nm, preferably 60 to 90 nm. The seed seed contains 0 to 100% by weight, preferably 55 to 80% by weight, of a nonionic ethylenically unsaturated monomer and 0 to 45 wt .-%, preferably 20 to 35 wt .-% of a monoethylenically unsaturated hydrophilic monomer.

The weight ratio of the seed seed (ii) to the seed polymer (i) is 2: 1 to 50: 1, preferably 2: 1 to 30: 1. The mean particle size in the unswollen state of the core-stage polymer consisting of seed (i) and seed seed (ii ) is 100 to 400 nm, preferably 100 to 250 nm.

The glass transition temperature determined by the Fox equation (John Wiley & Sons Ltd., Baffin Lane, Chichester, England, 1997) of the core stage polymer is between -20 ⁰ C and 150 ⁰ C.

Non-ionically ethylenically unsaturated monomers are understood as meaning styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, (C 1 -C 20) alkyl or (C 3 -C 20) alkenyl esters of acrylic or methacrylic acid,

Methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ricinoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, Erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid. The monoethylenically unsaturated hydrophilic monomers are acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, monomethylitaconate, maleic anhydride, fumaric acid, monomethylfumarate, itaconic anhydride, itaconic acid monomethyl ester. The first shell (iii) contains from 85 to 99.9% by weight of at least one nonionically ethylenically unsaturated monomer, preferably from 90 to 99.9% by weight, and from 0.1 to 15% by weight, preferably 0, 1 to 10 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer.

Non-ionically ethylenically unsaturated monomers are understood as meaning styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, (C 1 -C 20) alkyl or (C 3 -C 20) alkenyl esters of acrylic or Methacrylic acid, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyl groups containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ricinoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid , Erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid, preferably styrene, Ac nitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. The monoethylenically unsaturated hydrophilic monomers are acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, monomethylitaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid - methyl ester.

This first shell (iii) encloses the core-stage polymer. The weight ratio of the core-stage polymer to the first shell (iii) is 20: 1 to 1: 1, preferably 10: 1 to 1: 1, and the shell polymer has a glass transition temperature determined by the Fox equation between -60 ⁰ C to 120 ⁰ C. ,

The particle size of this step in the unswollen state is 120 nm to 500 nm, preferably 150 to 270 nm. The second shell (iv) contains 85 to 99.9, preferably 90 to 99.9 wt .-% of at least one non-ionic ethylenically unsaturated monomer and 0.1 to 15% by weight, preferably 0, 1 to 10% by weight of at least one hydrophilic monoethylenically unsaturated monomer.

Non-ionically ethylenically unsaturated monomers are understood as meaning styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, (C 1 -C 20) alkyl or (C 3 -C 20) alkenyl esters of acrylic or Methacrylic acid, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl methacrylate rylate, stearyl acrylate, stearyl methacrylate, hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ricinoleic acid, palmitoleic acid, oleic acid, elaidin acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid, preferably styrene, acrylonitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2 ethylhexyl methacrylate.

The monoethylenically unsaturated hydrophilic monomers are acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, monomethyllitaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid mono - methyl ester.

The first shell is enveloped by the second shell and the weight ratio of the first shell (iii) to the second shell (iv) is 1:30 to 1: 1, preferably 1:20 to 1: 1, and the shell polymer has a gas Fox transition temperature of 50 to 120 ^° C. The mean particle size of this step is 200 to 1500 nm, preferably 250 to 600 nm.

The plasticizer monomer listed under (v) is understood as meaning, for example, α-methylstyrene, esters of 2-phenylacrylic acid / atropic acid (for example methyl, ethyl, n-propyl, n-butyl), 2-methyl-2-butene, 2,3-dimethyl 2-butene, 1, 1-diphenylethene or methyl-2-tert-butyl acrylate and others in J. Brandrup, EH Immergut, Polymer Handbook 3rd Edition, 11/31 θff listed monomers. The plasticizer monomer used is preferably α-methylstyrene.

The neutralization listed under (vi) is carried out with a base to swell the core and thus formation of the hollow particle. As bases, for example, alkali or alkaline earth compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; Ammonia; primary, secondary and tertiary amines, such as ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, Diisopropanolamine, morpholine,

Ethylenediamine, 2-diethylaminethylamine, 2,3-diaminopropane, 1,2-propylenediamine, dimethylaminopropylamine, neopentanediamine, hexamethylenediamine, 4,9-dioxadodecane-1,12-diamine, polyethyleneimine or polyvinylamine. The third shell (vii) contains 90 to 99.9, preferably 95 to 99.9 wt .-% of at least one non-ionically ethylenically unsaturated monomer and 0.1 to 10, preferably 0.1 to 5 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer. Non-ionically ethylenically unsaturated monomers are understood as meaning styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, (C 1 -C 20) alkyl or (C 3 -C 20) alkenyl esters of acrylic or Methacrylic acid, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyl groups containing monomers, in particular Ci-Cio-Hydroxyaklkyl (meth) acrylates, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ricinoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid , Erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid, preferably styrene, A crylnitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. The monoethylenically unsaturated hydrophilic monomers are acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, monomethyllitaconate, maleic anhydride, fumaric acid, monomethylfurmarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid mono - methyl ester.

Also, the third shell envelopes the second shell and the weight ratio of the third to the second shell is 5: 1 to 1: 2, preferably 3: 1 to 1: 1, and the shell polymer has a Fox glass transition temperature of 50 to 120 ^° C.

The average final particle size is 300 to 800 nm.

In the paint, the pigments used, especially TiO 2, can be completely or partially replaced by the polymer dispersion described here. Typically, such paints include i.a. Water, thickener, caustic soda, pigment disperser, associative thickener, defoamer, biocide, binder, and film-forming aids.

The polymers can be prepared by customary polymerization processes of emulsion polymerization. It is preferably carried out with the exclusion of oxygen, preferably in a stream of nitrogen. For the polymerization method, the usual equipment is used, e.g. Stirred tank, stirred tank cascades, autoclaves, tube reactors and kneaders. The polymerization may be carried out in solvents or diluents, e.g. Toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkylaromatics, cyclohexane, technical Aliphatenmischungen, acetone, cyclohexanone, tetrahydrofuran, dioxane, glycols and glycol derivatives, polyalkylene glycols and their

Derivatives, diethyl ether, tert-butyl methyl ether, methyl acetate, isopropanol, ethanol, water or mixtures such as iso-propanol / water mixtures are performed. The polymerization can be carried out from 50 to 200 ⁰ C at temperatures of 20 to 300, preferably.

The polymerization is preferably carried out in the presence of free-radical-forming compounds. Of these compounds, up to 30, preferably 0.05 to 15, particularly preferably 0.2 to 8,% by weight, based on the monomers used in the polymerization, are required. For multicomponent initiator systems (e.g., redox initiator systems), the foregoing weights refer to the sum of the components. Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxydisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds. Examples of initiators which may be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl pemeodecanoate, tert. -Amylperpivalate, tert-butyl perpivalate, tert-butylpemeohexanoate, tert-butylper-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxydisulphate, azodiisobutyronitrile, 2,2'-azobis (2 - amidinopropane) dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid).

The initiators may be used alone or mixed together, e.g. Mixtures of hydrogen peroxide and sodium peroxydisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium. The known redox initiator systems can also be used as polymerization initiators. Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator, e.g. reducing sulfur compounds, for example bisulfites, sulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds. Thus, one can use combinations of peroxodisulfates with alkali metal or ammonium bisulfites, e.g. Ammonium peroxydisulfate and ammonium bisulfite. The amount of the peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.

In combination with the initiators or the redox initiator systems, transition metal catalysts may additionally be used, e.g. Salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are e.g. Ferrous sulfate, cobalt II chloride, nickel acetate sulfate, copper I chloride. Based on monomers, the reducing transition metal salt is used in a concentration of 0.1 ppm to 1 000 ppm. So you can use combinations of hydrogen peroxide with iron-Il salts, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.

Also in the polymerization in organic solvents can be used in combination with the abovementioned initiators redox coinitiators and / or transition metal catalysts, for example, benzoin, dimethylaniline, ascorbic acid and organically soluble Complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium. The amounts of redox coinitiators or transition metal catalysts usually used here are usually about 0.1 to 1000 ppm, based on the amounts of monomers used.

If the reaction mixture is polymerized at the lower limit of the temperature range for the polymerization and then polymerized at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that a sufficient concentration in each temperature interval is available to radicals.

The initiator can also be added in stages, or the rate of initiator addition can be varied over time. In order to prepare polymers of low average molecular weight, it is often convenient to carry out the copolymerization in the presence of regulators. Conventional regulators may be used for this purpose, for example compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptan, C 1 to C 4 Aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts, such as hydroxylammonium sulfate, formic acid, sodium bisulfite, hypophosphorous acid or salts thereof or isopropanol. The polymerization regulators are generally used in amounts of from 0.1 to 20% by weight, based on the monomers. The choice of the appropriate solvent can also influence the average molecular weight. Thus, the polymerization in the presence of diluents with benzylic H atoms, or in the presence of secondary alcohols such. B. isopropanol to a reduction of the average molecular weight by chain transfer.

Low or low molecular weight polymers are also obtained by: varying the temperature and / or the initiator concentration and / or the feed rate of the monomers.

To produce relatively high molecular weight copolymers, it is often useful to work in the polymerization in the presence of crosslinkers. Such crosslinkers are compounds having two or more ethylenically unsaturated groups, such as, for example, diacrylates or dimethacrylates of at least dihydric saturated alcohols, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate , Butanediol-1,4-dimethacrylate, hexanedioldiacrylate, hexanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate. The acrylic acid and methacrylic acid esters of alcohols having more than 2 OH groups can also be used as crosslinkers, for example trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Another class of crosslinking agents are diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols with molecular weights of from 200 to 9,000. Lyethylene glycols or polypropylene glycols which are used for the preparation of the diacrylates or dimethacrylates preferably have a molecular weight of from 400 to 2,000. In addition to the homopolymers of ethylene oxide or propylene oxide, it is also possible to use block copolymers of ethylene oxide and propylene oxide or copolymers of ethylene oxide and propylene oxide are used, which contain the ethylene oxide and propylene oxide units randomly distributed. The oligomers of ethylene oxide or propylene oxide are also suitable for the preparation of the crosslinking agents, for example diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.

Also suitable as crosslinking agents are vinyl acrylate, vinyl methacrylate, vinyl itaconate, adipate redivinyl ester, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, pentaallyl sucrose, pentaallyl sucrose, methylenebis (meth) acrylamide, divinylethyleneurea, divinylpropyleneurea, divinylbenzene, divinyldioxane, triallylcyanurate , Tetraallylsilan, tetravinylsilane and bis- or polyacrylic siloxanes (eg Tegomere® Th. Goldschmidt AG).

The crosslinkers are preferably used in amounts of 0.1 to 30 wt .-%, based on the monomers to be polymerized or on the monomers of a stage to be polymerized. The crosslinkers can be added at any stage.

Furthermore, it may be advantageous to stabilize the polymer droplets or polymer particles by surface-active auxiliaries. Typically, emulsifiers or protective colloids are used for this purpose. There are anionic, nonionic, cationic and amphoteric emulsifiers into consideration. Anionic emulsifiers are, for example, alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. Examples of nonionic emulsifiers which can be used are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides. Examples of cationic or amphoteric emulsifiers are: quaternized aminal alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines.

Typical protective colloids are, for example, cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ethers, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, Polyvinyl-1, 3-oxazolidone-2, polyvinyl-2-methylimidazoline and maleic acid or maleic anhydride containing copolymers, as for example in DE 2 501 123 are described.

The emulsifiers or protective colloids are usually used in concentrations of 0.05 to 20 wt .-%, based on the monomers. If polymerization is carried out in aqueous solution or dilution, the monomers can be completely or partially neutralized by bases before or during the polymerization. As bases, for example, alkali or alkaline earth compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; Ammonia; primary, secondary and tertiary amines, such as ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, Diisopropanolamine or morpholine in question. Furthermore, it is also possible to use polybasic amines for neutralization, for example ethylenediamine, 2-diethylaminethylamine, 2,3-diaminopropane, 1,2-propylenediamine, dimethylaminopropylamine, neopentanediamine, hexamethylenediamine, 4,9-dioxado-decane-1, 12- diamine, polyethyleneimine or polyvinylamine. Preferably, for the partial or complete neutralization of ethylenically unsaturated carboxylic acids before or during the polymerization, ammonia, triethanolamine and diethanolamine are used.

Particularly preferably, the ethylenically unsaturated carboxylic acids are not neutralized before and during the polymerization. The polymerization can be carried out continuously or batchwise in a variety of variants. Usually, a portion of the monomers are optionally in an appropriate diluent or solvent and optionally in the presence of an emulsifier, a protective colloid or other auxiliaries before, rendered inert, and the temperature is raised until reaching the desired polymerization temperature. However, it may also be submitted only a suitable diluent. Within a defined period of time, the radical initiator, other monomers and other auxiliaries, such as e.g. Regulators or crosslinking agents optionally added in a diluent. The feed times can be chosen to be different. For example, you can choose a longer feed time for the Initiatorzulauf than for the monomer feed.

If the polymer is prepared in a steam-volatile solvent or solvent mixture, the solvent can be separated off by introducing steam, so as to obtain an aqueous solution or dispersion. The polymerizate can also be separated from the organic diluent by a drying process.

At least one α, β-ethylenically unsaturated monomer (M), which is preferably selected from esters, is used to prepare the polymer dispersion (PD)

α, ß-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C2o-alkanols, vinyl aromatics, esters of vinyl alcohol with Ci-C3o monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, monoethylenically unsaturated carboxylic and sulfonic acids, phosphorus-containing monomers, esters α, ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols, amides α, ß-ethylenically unsaturated Mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyl lactams, open-chain

N-vinylamide compounds, esters of allyl alcohol with C 1 -C 30 -monocarboxylic acids, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which contain at least one primary or secondary amino group N, N-diallylamines, N, N-diallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C 2 -C 8 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, polyether (meth) acrylates, urea group-containing monomers and mixtures thereof.

Suitable esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with

C 1 -C 20 -alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate,

Ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-hexyl ( meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate,

Myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate,

 Heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate,

Behenyl (meth) acrylate, lignoceryl (meth) acrylate, cerotinyl (meth) acrylate,

Melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate,

Linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate,

Lauryl (meth) acrylate and mixtures thereof.

Preferred vinyl aromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene and particularly preferably styrene. Suitable esters of vinyl alcohol with Ci-C3o-monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.

Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.

Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof. Suitable ethylenically unsaturated carboxylic acids, sulfonic acids and phosphonic acids or their derivatives are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the half esters of monoethylenically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6 C atoms, for. B. maleic acid methyl ester, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acids and 2-acrylamido-2-methylpropanesulfonic acid. Suitable styrenesulfonic acids and derivatives thereof are styrene-4-sulfonic acid and styrene-3-sulfonic acid and the alkaline earth or alkali metal salts thereof, e.g. For example, sodium styrene-3-sulfonate and sodium styrene-4-sulfonate. Particularly preferred are acrylic acid, methacrylic acid and mixtures thereof.

Examples of phosphorus-containing monomers are, for. For example, vinylphosphonic and allylphosphonic. Also suitable are the mono- and diesters of phosphonic acid and phosphoric acid with hydroxyalkyl (meth) acrylates, especially the monoesters. Also suitable are diesters of phosphonic acid and phosphoric acid which are simply acrylate with a hydroxyalkyl (meth) and additionally simply with a different alcohol, for. As an alkanol, are esterified. Suitable hydroxyalkyl (meth) acrylates for these esters are those mentioned below as separate monomers, in particular

2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Corresponding dihydrogen phosphate ester monomers include phosphoalkyl (meth) acrylates such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl ( meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are the esters of phosphonic acid and phosphoric acid with alkoxylated hydroxyalkyl (meth) acrylates, eg. B. the ethylene oxide condensates of (meth) acrylates, such as H ₂ C = C (CH ₃ ) COO (CH ₂ CH ₂ O) _n P (OH) ₂ and

H ₂ C = C (CH ₃ ) COO (CH ₂ CH ₂ O) _n P (= O) (OH) ₂ where n is 1 to 50. Also suitable are phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth) acrylates, phosphodialkyl crotonates and allyl phosphates. Other suitable phosphorus group-containing monomers are described in WO 99/25780 and US 4,733,005, which is incorporated herein by reference.

Suitable esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with

C ₂ -C 30 -alkanediols are e.g. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,

2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,

3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate,

3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,

6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate,

3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.

Suitable primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are acrylic acid amide, methacrylamide,

N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide,

N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide,

N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arachynyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignoceryl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide,

 N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide,

N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide,

Morpholinyl (meth) acrylamide.

Suitable N-vinyl lactams and derivatives thereof are, for. B. N-vinylpyrrolidone,

N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6- ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc.

Suitable open-chain N-vinylamide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N, N-dimethylaminomethyl (meth) acrylate,

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate,

N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and

N, N-dimethylaminocyclohexyl (meth) acrylate.

Suitable amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide,

 N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide,

N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide,

N- [4- (dimethylamino) cyclohexyl] methacrylamide etc.

Suitable monomers M) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products. Alkyl is preferably Ci-C24-alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.

Suitable monomers M) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts from that. Suitable C 2 -C 8 monoolefins and nonaromatic hydrocarbons having at least two conjugated double bonds are e.g. For example, ethylene, propylene, isobutylene, isoprene, butadiene, etc. Suitable urea group-containing monomers are, for. B. N-vinyl or

N-allylurea or derivatives of imidazolidin-2-one. These include N-vinyl and

N-Allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N- (2- (meth) acrylamidoethyl) imidazolidin-2-one, N- (2- (meth) acryloxyethyl) imidazolidin-2-one (= 2-ureido (meth) acrylate), N- [2 - ((meth) acryloxyacetamido) ethyl] imidazolidin-2-one, etc.

Preferred urea group-containing monomers are N- (2-acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one. Particularly preferred is N- (2-methacryloxyethyl) imidazolidin-2-one (2-ureidomethacrylate, UMA).

Further suitable monomers M) are alkyd resins, epoxy resins, polyester resins, polyurethanes or polyvinyl chlorides.

The aforementioned monomers (M) can be used individually, in the form of mixtures within a monomer class or in the form of mixtures of different monomer classes.

Particularly suitable monomer combinations for the aqueous dispersion of the film-forming polymer (PD) are, for example, n-butyl acrylate with vinyl acetate; n-butyl acrylate with styrene; n-butyl acrylate with ethylhexyl acrylate; Butadiene with styrene; Butadiene with acrylonitrile and / or methacrylonitrile; Butadiene and isoprene with acrylonitrile and / or methacrylonitrile; Butadiene with acrylic esters; Butadiene with Methacrylsäureestem. All of the monomer combinations mentioned may additionally contain small amounts of further monomers, preferably acrylic acid, methacrylic acid, acrylamide and / or methacrylamide.

A preferred preparation process for the dispersion of the film-forming polymer (PD) according to the invention is described in EP 939 774, to the contents of which reference is made in its entirety. The blends according to the invention are preferably used in aqueous paints. These paints are for example in the form of an unpigmented system (clearcoat) or a pigmented system. The proportion of pigments can be described by the pigment volume concentration (PVK). PVK describes the ratio of the volume of pigments (Vp) and fillers (V _F ) to the total volume, consisting of the volumes of binder (VB), pigments and fillers of a dried coating film in percent: PVK = (VP + VF) x 100 / (VP + VF + VB). For example, paints can be classified using the PVK as follows: high filled interior paint, washable, white / matt approx. 85

 Interior paint, abrasion resistant, white / matt approx. 80

 Semi-gloss paint, semi-gloss approx. 35

 Semi-gloss color, silky-gloss approx. 25

 High gloss color approx. 15-25

 Exterior facade color, white approx. 45-55

 Clearcoat 0

The invention further provides a coating composition in the form of an aqueous composition, comprising: a blend of at least one aqueous dispersion of organic hollow particles according to the invention, and at least one aqueous dispersion of a film-forming polymer (PD) according to the invention,

if appropriate at least one inorganic filler and / or inorganic pigment,

 usual aids and

 - Water to 100 wt .-%.

Preference is given to a coating composition comprising:

3 to 60 wt .-%, based on the solids content of a blend of at least one aqueous dispersion of organic hollow particles according to the invention, and at least one aqueous dispersion of a film-forming polymer (PD) according to the invention as defined above,

 From 10 to 70% by weight of inorganic fillers and / or inorganic pigments,

 0.1 to 20 wt .-% of conventional adjuvants, and

 - Water to 100 wt .-%.

The proportion of (PD) to the above coating agent refers to solid, i. H. Emulsion polymer, without water.

The novel coating compositions in the form of an aqueous composition are preferably used as paints. One embodiment is paint in the form of a clearcoat. Another embodiment is paints in the form of an emulsion paint.

In the following, the composition of a conventional emulsion paint will be explained. Dispersion paints generally contain from 30 to 75% by weight, and preferably from 40 to 65% by weight, of nonvolatile constituents. This is to be understood as meaning all constituents of the preparation which are not water, but at least the total amount of binder, filler, pigment, low-volatile solvents (boiling point above 220 ^° C.), eg. As plasticizers, and polymeric adjuvants. This accounts for about a) from 3 to 90% by weight, in particular from 10 to 60% by weight, of the blending of at least one aqueous dispersion of organic hollow particles according to the invention and at least one aqueous dispersion of a film-forming polymer (PD) according to the invention as defined above,

b) 0 to 85% by weight, preferably 5 to 60% by weight, in particular 10 to 50% by weight, of at least one inorganic pigment,

c) 0 to 85 wt .-%, in particular 5 to 60 wt .-%, of inorganic fillers and d) 0.1 to 40 wt .-%, in particular 0.5 to 20 wt .-%, of conventional auxiliaries.

The polymer dispersions according to the invention are particularly preferably suitable for the production of interior and exterior paints. These are typically characterized by a pigment volume concentration PVK in the range of 30 to 65 for facade paints and with a PVK in the range of 65 to 80 for interior paints.

The pigment volume concentration PVK is understood to mean the quotient, multiplied by 100, of the total volume of pigments plus fillers divided by the total volume of pigments, fillers and binder polymers; see. Ullmann's Enzyklopadie der technischen Chemie, 4th Edition, Volume 15, p. 667.

In the context of this invention, all pigments and fillers, eg. As color pigments, white pigments and inorganic fillers. These include inorganic white pigments, such as titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, Antimony black, manganese violet, Paris blue or Schweinfurter green. In addition to the inorganic pigments, the emulsion paints of the invention may also organic color pigments, for. As sepia, gum, Kasseler brown, Toluidin red, Para red, Hansa yellow, indigo, azo dyes, anthraquinoid and indiogide dyes and dioxazine, quinacridone, phthalocyanine, isoindolinone and metal complex pigments. Also suitable are synthetic white pigments with air inclusions to increase the light scattering, such as the Rhopaque © dispersions.

Suitable fillers are for. As aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates, such as calcium sulfate, silicon dioxide, etc. In paints naturally finely divided Fillers preferred. The fillers can be used as individual components. In practice, however, filler mixtures have proven particularly useful, for. As calcium carbonate / kaolin, Caldumcar- carbonate / talc. Glossy paints generally have only small amounts of very finely divided fillers or contain no fillers.

Finely divided fillers can also be used to increase the hiding power and / or to save on white pigments. To adjust the opacity of the hue and the color depth are preferably used blends of color pigments and fillers.

The usual auxiliaries include, in addition to the emulsifiers used in the polymerization, wetting agents or dispersants, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1 diphosphonic acid sodium and naphthalenesulfonic acid salts, in particular their sodium salts. Further suitable auxiliaries are leveling agents, defoamers, biocides and thickeners. Suitable thickeners are z. B. Associative thickener, such as polyurethane thickener. The amount of thickener is preferably less than 1 wt .-%, more preferably less than 0.6 wt .-% thickener, based on solids content of the paint. The preparation of the paint according to the invention is carried out in a known manner by mixing the components in mixing devices customary for this purpose. It has proven useful to prepare an aqueous paste or dispersion from the pigments, water and optionally the adjuvants, and then first the polymeric binder, d. H. as a rule, to mix the aqueous dispersion of the polymer with the pigment paste or pigment dispersion.

The paints according to the invention generally contain from 30 to 75% by weight and preferably from 40 to 65% by weight of nonvolatile constituents. These are to be understood as meaning all constituents of the preparation which are not water, but at least the total amount of binder, pigment and auxiliary agent, based on the solids content of the paint. The volatile constituents are predominantly water.

The paint of the invention can be applied in a conventional manner to substrates, for. B. by brushing, spraying, dipping, rolling, knife coating, etc.

It is preferably used as a decorative paint, i. H. used for coating buildings or parts of buildings. It may be mineral substrates such as plasters, gypsum or plasterboard, masonry or concrete, wood, wood materials, metal or paper, z. B. wallpaper or plastic, z. As PVC, act.

Preferably, the paint is used for building interior parts or facades.

The paints according to the invention are characterized by simple handling and good processing properties, such as high resistance to wet abrasion and high coverability. The paints are low in emissions. They have good performance properties, eg. B. a good water resistance, good wet adhesion, especially on alkyd paints, good blocking resistance, good paintability and they show a good course when applied. The tool used can be easily cleaned with water. The invention will be further illustrated by the following non-limiting examples.

Experimental methods

Determination of the glass transition temperature

The glass transition temperatures were determined by theoretical calculation by Fox equation (John Wiley & Sons Ltd., Baffins Lane, Chichester, England, 1997). 1 / Tg = Wa / T _g a + Wb / T _g b, where

Tg ₃ and Tgb = glass transition temperature of polymer "a" and "b"

Wa and Wb = weight fraction of polymer "a" and "b"

Measurement of particle size

The particle sizes were determined by means of a Coulter M4 + (particle analyzer) or, with the aid of photon correlation spectroscopy, also known as quasi-elastic light scattering or dynamic light control (ISO 13321 standard) using an HPPS (High Performance Particle Sizer) from Malvern or by means of the hydro-dynamic fractionation with a PSDA (Particle Size Distribution Analyzer) from the company Polymer Labs or by means of AUZ (Analytical Ultracentrifuge).

Wet abrasion resistance

To test the wet abrasion resistance, the paint to be tested was coated on a film with a film applicator of a defined thickness. After seven days of drying at room temperature and two days at 50 ⁰ C, the coated film was subjected to an abrasion tester 200 abrasion cycles and the loss of layer calculated in microns. The test was carried out in accordance with DIN EN ISO 1 1998.

fertility

A film with a standardized surface with black and white fields was weighed. The paint was applied to the weighed films by means of a film applicator in wet thicknesses of 150, 200 and 240 μm. The freshly coated films were weighed again and then dried at 23 ° C and 50% humidity for 24 hours. After that, the contrast ratio of all lifts was with a Byk Gardner

Spectrophotometer with so-called gloss trap measured. For this purpose, measurements were made at five measuring points for each of three black (Ys values) and three white fields (Yw values). The contrast ratio was determined by quotient Ys / Yw ^* 100 [%] of the average values Yw and Ys. The yield was then determined in m2 / L at a contrast ratio of 98%, taking into account the specific density of the paint and the quantity of paint applied in each case.

Execution of the whiteness measurement

6g of the color paste described below and 1 g of the approximately 30% hollow particle dispersion are weighed into a vessel and the mixture is homogenized without stirring. Using a 200 μm doctor blade, a film of this mixture is drawn out onto a black plastic film (matt finish, article No. 13.41 EG 870934001, Bernd Schwegmann GmbH & Co. KG, D) at a speed of 0.9 cm / sec. The samples are dried at 23 ° C and a relative humidity of 40-50% for 24 h. Subsequently, the whiteness is measured at three different points using a "Minolta CM-508i" spectrophotometer, and the measuring points are marked in order to subsequently determine the respective layer thicknesses of the color film with a micrometer screw by measuring the difference relative to the uncoated plastic film After calculating an average layer thickness and an average brightness of the three individual measurements, the resulting whiteness is finally normalized to a dry layer thickness of 50 μm by linear extrapolation 30-60 μm Production of the color paste

 A) 240 g of water are placed in a vessel and then the following starting materials are added in the order given under a dissolver at about 1000 rpm and stirred for a total of about 15 minutes until homogeneous:

2.5 g Natrosol ^® 250 HR (hydroxyethyl cellulose thickener from Hercules GmbH), 1 g of 10% sodium hydroxide solution, 6 g of Pigmentverteiler® ^® MD 20 (copolymer of maleic acid and diisobutylene from BASF AG), 10 g of Collacral ^® LR 8990 (polyurethane associative thickener BASF AG), 3g Agitan ^® e 255 (siloxane defoamer from Münzing Chemie GmbH), 2g Proxel BD ^® 20 (biocide from Avecia Inc.), 370g Acronal ^® A 684 (binder, 50% dispersion from BASF AG), 20 g of Texanol ^® (film-forming assistant from Eastman Chemical company), 2g Agitan ^® e 255 (siloxane defoamer Munzing Chemie GmbH), 10g 5% strength Collacral® LR 8989 (polyurethane associative thickener from BASF AG).

B) 250 g of water are placed in a vessel and then the following feedstocks are added in the order given under a dissolver at about 1000 rpm and stirred for a total of about 15 minutes until homogeneous:

2.5 g Natrosol ^® 250 HR (hydroxyethyl cellulose thickener from Hercules GmbH), 1 g of 10% sodium hydroxide solution, 6g Pigmentverteiler MD 20 ^® (copolymer of maleic acid and diisobutylene from BASF AG), 10 g of Collacral ^® LR 8990 (Polyu- rethan- associative thickener from BASF AG), 3g Agitan ^® e 255 (siloxane

Defoamer from Münzing Chemie GmbH), 2g Proxel ^® BD 20 (biocide from Avecia Inc.), 203g Kronos 2300, 370g Acronal ^® A 684 (binder, 50% dispersion of BASF AG), 20 g of Texanol ^® (film-forming auxiliaries of Eastman Chemical company), 2g Agitan ^® e 255 (siloxane defoamer Munzing Chemie GmbH), 10g 5% strength Collacral® LR 8989 (polyurethane associative thickener

BASF AG), 116g hollow particle dispersion. Examples

Preparation of the dispersion of the organic hollow particles

 The production process according to the invention for the aqueous dispersion of the organic hollow particles is disclosed by the sequential sequence of several individual steps. First, the preparation of the dispersion A, then the reaction of dispersion A, in which dispersion B is obtained and then the reaction of this dispersion B, which leads to dispersion C. Dispersion A (seed)

A pre-emulsion was prepared from 230 g of water, 2.17 g of arylsulfonate (15%), 338 g of n-butyl acrylate, 303.6 g of methyl methacrylate and 8.45 g of methacrylic acid. The template, consisting of 2356 g of water, 32.0 g of aryl sulfonate (15%) and 41, 2 g of the pre-emulsion was in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature heated from 80 ⁰ C and grafted after addition of 14 g of a 22.4% strength ammonium persulfate solution for 15 min. Then the rest of the pre-emulsion was added within 60 min at 80 ⁰ C. The mixture was subsequently polymerized for a further 15 minutes and cooled to 55 ° C. within 20 minutes. To deplete the residual monomers then 6.5 g of a 10% tert-butyl hydroperoxide solution and 8.1 g of a 5% Rongalit C solution were added to the reaction mixture, after cooling to 30 ⁰ C by addition of 8.1 g 25% ammonia solution adjusted the pH of the dispersion. Solids content: 19.7%

pH: 2.6

Particle size (AUZ, D50): 47 nm

Dispersion B1 (source core)

The original, consisting of 1455 g of water and 63.2 g of dispersion A, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 79 ° C and after addition of 10 g of a 2.5% strength sodium persulfate solution for 5 min anpolyme-. Then, pre-emulsion 1 consisting of 262 g of water, 3.33 g of arylsulfonate

(15%), 20.75 g Lutensit A-EP (acid form, 20%), 186.6 g of methyl methacrylate and 124.4 g of methacrylic acid, added within 113 min at 79 ° C. Subsequently, pre-emulsion 2, consisting of 254 g of water, 2.67 g of arylsulfonate (15%), 187 g of methyl methacrylate and 2.05 g of methacrylic acid, together with 22 g of a 2.5% sodium persulfate solution within of 67 min at 79 ° C added. Finally, polymerization was continued for a further 30 minutes. Solids content: 19.9%

pH: 2.5

 Particle size (Autosizer): 195 nm Dispersion B2 (source core)

The original, consisting of 1455 g of water and 42.0 g of dispersion A, was heated in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels to a temperature of 79 ° C. in a nitrogen atmosphere and after addition of 10 g of a 2.5% sodium persulfate solution for 5 min anpolyme-. Then Voremulsion 1, consisting of 262 g of water, 3.33 g of aryl sulfonate (15%), 20.75 g Lutensit A-EP (acid form, 20%), 211, 8 g of methyl methacrylate and 104.3 g of methacrylic acid, added at 79 ° C within 113 min. Subsequently, preemulsion 2, consisting of 254 g of water, 2.67 g of arylsulfonate (15%), 186 g of methyl methacrylate and 2.05 g of methacrylic acid, together with 22 g of a 2.5% sodium persulfate solution within of 67 min at 79 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.7%

pH: 2.9

 Particle size (Autosizer): 211 nm

Dispersion B3 (swelling core) The initial charge, consisting of 1009 g of water and 28.7 g of Acronal A 508, was heated to 82 ° C. in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere heated and after addition of 20.2 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then Voremulsion 1, consisting of 163 g of water, 2.24 g of aryl sulfonate (15%), 13.95 g Lutensit A-EPA (partially neutralized, 20%), 124.9 g of methyl methacrylate, 83.6 g of methacrylic acid and 0.50 g allyl methacrylate, dosed within 70 min at 82 ° C. After the end of the feed, 3.0 g of a 2.5% sodium persulfate solution were added and stirred for 5 min. This was followed by pre-emulsion 2, consisting of 171 g of water, 1.79 g of arylsulfonate (15%), 112 g of methyl methacrylate, 13.8 g of n-butyl acrylate and 1.38 g of methacrylic acid, together with 12 g of a 2.5 Percent sodium persulfate solution within 70 min at 82 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.8%

pH value: 4.4

Particle size (Autosizer): 207 nm Dispersion B4 (source core)

The original, consisting of 1542 g of water and 44.2 g of dispersion A, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature of 82 ° C. and after addition of 10.6 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then Voremulsion 1, consisting of 277 g of water, 3.53 g of aryl sulfonate (15%), 22.00 g Lutensit A-EP (acid form, 20%), 222.6 g of methyl methacrylate and 109.7 g of methacrylic acid, metered within 113 min, while the polymerization temperature was continuously lowered from 82 ° C to 80 ⁰ C. Following this, preemulsion 2, consisting of 269 g of water, 2.83 g of 15% arylsulfonate, 196 g of methyl methacrylate, and 2.17 g of methacrylic acid, was added along with 23 g of a 2.5% sodium persulfate solution within the range of 67 min at 80 ⁰ C added. Finally, polymerization was continued for a further 30 minutes. Solids content: 19.7%

pH value: 2.7

Particle size (Autosizer): 215 nm

Dispersion B5 (source core)

The template, consisting of 1009 g of water and 28.7 g of Acronal A 508, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature of 82 ° C and after addition of 20.2 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then Voremulsion 1, consisting of 163 g of water, 2.24 g of aryl sulfonate (15%), 13.95 g Lutensit A-EPA (partially neutralized, 20%), 125.0 g of methyl methacrylate, 83.6 g of methacrylic acid and 0.34 g of allyl methacrylate, dosed within 70 min at 82 ° C. After the end of the feed, 3.0 g of a 2.5% sodium persulfate solution were added and stirred for 5 min. This was followed by pre-emulsion 2, consisting of 171 g of water, 1.79 g of arylsulfonate (15%), 112 g of methyl methacrylate, 13.8 g of n-butyl acrylate and 1.38 g of methacrylic acid, together with 12 g of a 2 , 5% sodium persulfate solution within 70 min at 82 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.8%

pH value: 4.4

 Particle size (Autosizer): 220 nm

Dispersion B6 (swelling core) The original, consisting of 1613 g of water and 45.2 g of Acronal A 508, was heated in a nitrogen atmosphere to a temperature of 82 ° C. in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels heated and after addition of 10.6 g of a 2.5% strength sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 127 g of water, 1.77 g of arylsulfonate (15%), 11, 13 g Lutensit A-EPA (partially neutralized, 20%), 99.1 g of methyl methacrylate and 65.7 g of methacrylic acid, dosed within 70 min at 82 ° C. At the same time Voremulsion 2, consisting of 127 g of water, 1, 77 g of aryl sulfonate (15%), 11, 13 g Lutensit A EPA (partially neutralized, 20%), 110.1 g of methyl methacrylate, 54.2 g of methacrylic acid and 0.53 g of allyl methacrylate, dosed within 70 min in preemulsion 1 (power feed procedure). After the feeds had ended, 4.7 g of a 2.5% strength sodium persulfate solution were added and the mixture was stirred for 5 minutes. This was followed by pre-emulsion 3, consisting of 269 g of water, 2.83 g of arylsulfonate (15%), 176 g of methyl methacrylate, 21, 7 g of n-butyl acrylate and 2.17 g of methacrylic acid, together with 19 g of a 2.5 Percent sodium persulfate solution within 70 min at 82 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.8%

pH value: 4.3

 Particle size (Autosizer): 210 nm

Dispersion B7 (source core)

The original, consisting of 1589 g of water and 45.2 g of Acronal A 508, was heated in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and after Addition of 10.6 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then Voremulsion 1, consisting of 277 g of water, 3.53 g of aryl sulfonate (15%), 22.00 g Lutensit A-EPA (partially neutralized, 20%), 222.1 g of methyl methacrylate, 0.53 g of allyl methacrylate and 109.7 g of methacrylic acid, dosed within 70 min at 82 ° C. After the end of the feed, 4.7 g of a 2.5% strength sodium persulfate solution were added and the mixture was stirred for 5 minutes. Following this, preemulsion 2, consisting of 269 g of water, 2.83 g of arylsulfonate (15%), 196 g of methyl methacrylate and 2.17 g of methacrylic acid, together with 23 g of a 2.5% sodium persulfate solution within 70 min at 82 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.7%

pH value: 4.8

 Particle size (Autosizer): 209 nm Dispersion B8 (source core)

The initial charge, consisting of 986 g of water and 28.2 g of Acronal A 508, was heated to a temperature of 82 ° C. in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere and after Addition of 20.9 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then Voremulsion 1, consisting of 161 g of water, 2.20 g of aryl sulfonate (15%), 13.70 g Lutensit A-EPA (partially neutralized, 20%), 0.07 g of tert-dodecyl mercaptan, 136.3 g Methyl methacrylate, 0.66 g of allyl methacrylate and 68.3 g of methacrylic acid, dosed within 70 min at 82 ° C. At the end of the feed 2.9 g of a 2.5% sodium Umpersulfat solution was added and stirred for 5 min. This was followed by pre-emulsion 2 consisting of 167 g of water, 1.76 g of arylsulfonate (15%), 110 g of methyl methacrylate, 13.5 g of n-butyl acrylate and 1.35 g of methacrylic acid, together with 12 g of a 2.5 Percent sodium persulfate solution within 70 min at 82 ° C added. Finally, polymerization was continued for a further 30 minutes.

Solids content: 19.7%

pH value: 4.3

 Particle size (Autosizer): 213 nm

Dispersion C1:

The initial charge consisting of 513 g of water and 158.3 g of dispersion B1, was heated in a polymerization vessel, which was equipped Faessen with an anchor stirrer, reflux condenser and two Zulaufge- in a nitrogen atmosphere to a temperature of 80 ⁰ C and after the addition of 14.4 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 158 g of water, 6.6 g of arylsulfonate (15%), 11.3 g of methacrylic acid and 180 g of styrene, together with 18.3 g of a 2.5% sodium persulfate solution within 80 Starting at 80 ⁰ C starting dosed, towards the end of the feed, the internal temperature was raised to 92 ° C and the sodium persulfate feed stopped. After the end of the emulsion feed, pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 15.8 g of α-methylstyrene was added and stirred for 5 minutes, then 30 g of 10% were added ammonia; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 210 g of water, 7.5 g of aryl sulfonate (15%), 22.5 g of methyl methacrylate and 221 g of styrene, along with 27.4 g of a 2.5% sodium persulfate solution within 100 min at 92 ° C added. Finally, polymerization was continued for a further 30 minutes. To reduce the residual monomers, a final chemical deodorization was carried out. For this purpose, 13.5 g of a 10% strength tert-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree.

Solids content: 29.9%

pH value: 7.6

Further hollow particle dispersions according to the invention:

Dispersion C2a:

The template, consisting of 501 g of water and 152.0 g of dispersion B2, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 80 ⁰ C and after addition of 14 , 4 g of a 2.5% sodium persulfate solution for 5 minutes anpoly- merized. Then, pre-emulsion 1 consisting of 158 g of water, 6.6 g of arylsulfonate (15%), 9.7 g of methacrylic acid and 155 g of styrene, together with 16.7 g of a 2.5% sodium persulfate solution within 80 Starting at 80 ⁰ C starting dosed, towards the end of the feed, the internal temperature was raised to 92 ° C and the sodium persulfate feed stopped. After the end of the emulsion feed, pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 13.5 g of α-methylstyrene was added and stirred for 5 minutes, then 26 g of 10% were added ammonia; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 229 g of water, 7.5 g of arylsulfonate (15%), 25.2 g of methyl methacrylate and 247 g of styrene, together with 29.0 g of a 2.5% sodium persulfate solution within 100 min dosed at 92 ° C. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 13.5 g of a 10% strength tert-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree.

Solids content: 28.5%

pH value: 8.7

Particle size (Autosizer): 731 nm (0.13 polydispersity)

Whiteness: 74

Dispersion C2b: The template, consisting of 486 g of water and 174.7 g of dispersion B2, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 80 ⁰ C and after Addition of 14.4 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 179 g of water, 7.5 g of arylsulfonate (15%), 11.0 g of methacrylic acid and 176 g of styrene, together with 18.9 g of a 2.5% strength

Sodium persulfate solution added within 90 min starting at 80 ⁰ C, towards the end of the feed, the internal temperature was raised to 92 ° C and the sodium persulfate feed stopped. After the end of the emulsion feed, pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 15.3 g of α-methylstyrene was added and stirred for 5 minutes, then 29 g of 10 were added % ammonia water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 207 g of water, 6.6 g of aryl sulfonate (15%), 22.7 g of methyl methacrylate and 225 g of styrene, along with 26.7 g of a 2.5% sodium persulfate solution within 90 min at 92 ° C added. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 13.5 g of a 10% strength tert-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree. Solids content: 29.3%

pH value: 8.7

 Particle size (Autosizer): 719 nm (0.18 PD)

Whiteness: 70

Dispersion C3:

The original, consisting of 486 g of water and 181.2 g of dispersion B3, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 82 ° C and after addition of 14 , 4 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1, consisting of 179 g of water, 7.5 g of arylsulfonate (15%), 11.0 g of methacrylic acid and 176 g of styrene, together with 18.9 g of a 2.5% sodium persulfate solution within 90 min at 82 ° C added. After the end of both feeds, the internal temperature was raised to 92 ° C. within 30 minutes and then pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 15.3 g of α-methylstyrene was added and the mixture was stirred for 5 minutes , then added 29 g of 10% ammonia water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Thereafter, 4.0 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 177 g of water, 6.6 g of arylsulfonate (15%), 22.7 g of methyl methacrylate and 223 g of styrene, together with 26.7 g of a 2.5% sodium persulfate solution within 115 min dosed at 92 ° C. After a feed time of 55 minutes, 32.1 g of 7% itaconic acid were added to the pre-emulsion 3. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 13.5 g of a 10% strength tert-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree. Solids content: 29.1%

pH value: 7.0

 Particle size (Autosizer): 519 nm (0.09 PD)

Whiteness: 73 Dispersion C4:

The initial charge consisting of 431 g of water and 155.3 g of dispersion B4, was heated in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 80 ⁰ C charged and, after adding of 12.8 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 159 g of water, 6.7 g of arylsulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene, together with 16.8 g of a 2.5% sodium persulfate solution within 90 Starting at 80 ⁰ C starting dosed, towards the end of the feed, the internal temperature was raised to 92 ° C and the sodium persulfate feed stopped. After the end of the emulsion feed, pre-emulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of α-methylstyrene was added and stirred for 5 minutes, then 26 g of 10% were added ammonia; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 158 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene, together with 23.7 g of a 2.5% sodium persulfate solution within 90 min at 92 ° C added. After a running time of 45 minutes, 28.6 g of 7% itaconic acid were added to the pre-emulsion 3. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 12.0 g of a 10% strength tert-butyl hydroperoxide solution and 12.0 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree. Solids content: 28.8%

pH value: 8.0

 Particle size (Autosizer): not measurable

Whiteness: 72 Dispersion C5:

The original, consisting of 458 g of water and 154.5 g of dispersion B5, was heated in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels in a nitrogen atmosphere to a temperature of 82 ° C. and after addition of 12.8 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 159 g of water, 6.7 g of arylsulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene, together with 16.8 g of a 2.5% sodium persulfate solution within 90 min at 82 ° C added. After the end of both feeds, the internal temperature was raised to 92 ° C. within 30 minutes and then pre-emulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of α-methylstyrene was added, and stirred, then the addition of 26 g of 10% ammonia water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 157 g of water, 5.9 g of arylsulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene, together with 23.7 g of a 2.5% sodium persulfate solution within 100 min dosed at 92 ° C. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 12.0 g of a 10% strength tert-butyl hydroperoxide solution and 12.0 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree. Solids content: 28.9%

pH value: 8.3

 Particle size (Autosizer): 571 nm (0.06 PD)

Whiteness: 78

Dispersion C6:

The original, consisting of 458 g of water and 154.5 g of dispersion B6, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature of 82 ° C. and after addition of 12.8 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 159 g of water, 6.7 g of arylsulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene, together with 16.8 g of a 2.5% sodium persulfate solution within 90 min at 82 ° C added. At the end of both feeds, the internal temperature was raised to 92 ° C. over the course of 30 minutes and then preemulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of α-methylstyrene was added, and stirred, then the addition of 26 g of 10% ammonia water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 157 g of water, 5.9 g of arylsulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene, together with 23.7 g of a 2.5% sodium persulfate solution within 100 min dosed at 92 ° C. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 12.0 g of a 10% strength tert-butyl hydroperoxide solution and 12.0 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree.

Solids content: 29.4%

pH value: 8.8

Particle size (Autosizer): 560 nm (0.11 PD)

Whiteness: 77

Dispersion C7: The template, consisting of 458 g of water and 155.3 g of dispersion B7, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature of 82 ° C and after Addition of 12.8 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 159 g of water, 6.7 g of arylsulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene, together with 16.8 g of a 2.5% strength

Sodium persulfate solution within 90 min at 82 ° C added. After the end of both feeds, the internal temperature was raised to 92 ° C. within 30 minutes and then pre-emulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of α-methylstyrene was added and the mixture was stirred for 5 minutes , then the addition of 26 g of 10% ammonia Water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 157 g of water, 5.9 g of arylsulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene, together with 23.7 g of a 2.5% sodium persulfate solution within 100 min dosed at 92 ° C. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 12.0 g of a 10% strength tert-butyl hydroperoxide solution and 12.0 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree.

Solids content: 29.4%

pH value: 8.8

 Particle size (Autosizer): 578 nm (0.08 PD)

 Whiteness: 77

Dispersion C8:

The original, consisting of 458 g of water and 154.5 g of dispersion B8, was heated in a polymerization vessel, which was equipped with an anchor stirrer, reflux condenser and two feed vessels, in a nitrogen atmosphere to a temperature of 82 ° C. and after addition of 12.8 g of a 2.5% sodium persulfate solution polymerized for 5 min. Then, pre-emulsion 1 consisting of 159 g of water, 6.7 g of arylsulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene, together with 16.8 g of a 2.5% sodium persulfate solution within 90 min at 82 ° C added. At the end of both feeds, the internal temperature was raised to 92 ° C. over the course of 30 minutes and then pre-emulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of α-methylstyrene was added, and stirred, then the addition of 26 g of 10% ammonia water; the reaction mixture was stirred at 92 ° C for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution were added within 3 min. Pre-emulsion 3, consisting of 157 g of water, 5.9 g of arylsulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene, together with 23.7 g of a 2.5% sodium persulfate solution within 100 min dosed at 92 ° C. Finally, polymerization was continued for a further 30 minutes. Finally, a chemical deodorization was carried out to reduce the residual monomers. For this purpose, 12.0 g of a 10% strength tert-butyl hydroperoxide solution and 12.0 g of a 10% ascorbic acid solution were added in parallel to the reaction mixture over the course of 60 minutes at 92.degree.

Solids content: 29.3%

pH value: 8.6

Particle size (Autosizer): 544 nm (0.13 PD)

Whiteness: 76 Preparation of the aqueous dispersion of the film-forming polymer (PD):

Feed 1A and 2 were combined in one piece of pipe. This mixture of feed 1A and 2, feed 1B was then added. The mixture of feed 1A, 1B and 2 was then emulsified by means of an inline mixing element (a or b), which was mounted directly in front of the stirred tank in the feed line, and then passed into the stirred tank.

As inline mixing elements were:

a) a static mixer of the type SMX-S, DN 3.2, consisting of 10 mixing elements from Sulzer Chemtech,

b) a Zahnrranzdispergiermaschine Megatron MT 5000 from. Kinematica used. Dispersion 1:

In a stirred tank 13 kg of water were placed and heated to 9O ⁰ C. Subsequently, 5% of feed 1 and 9% of feed 2 were added and polymerized for 5 min. Thereafter, the residual amounts of feed 1A and B and feed 2 were metered in while maintaining the polymerization temperature within 3 h after one of the metering processes described above. Thereafter, the reaction was postpolymerized for 1 h to complete the conversion.

Feed 1:

 A: 24.94 kg of water

 4.33 kg emulsifier I

 1, 25 kg of acrylic acid

 1, 50 kg 50 wt .-% aqueous solution of acrylamide

 B: 25.00 kg of n-butyl acrylate

 23.00 kg vinyl acetate

Feed 2:

 Solution from:

 0.375 kg sodium peroxodisulfate

 4.98 kg of water

Solids content: 52.0% Dispersion 2:

In a stirred tank 15 kg of water were introduced and heated to 85 ⁰ C. Subsequently, 6% of feed 1 and 10% of feed 2 were added and polymerized for 10 min. Thereafter, the residual amounts of feed 1A and B and feed 2 while maintaining the polymerization temperature within 3.5 h after each one of the above-described dosed metering process. Thereafter, the reaction was postpolymerized for 1 h to complete the conversion.

Feed 1:

 A: 19.01 kg of water

 2,00 kg Emulsifier Il

 B: 30.00 kg of n-butyl acrylate

 20.00 kg styrene inlet 2:

 Solution from:

 0.30 kg of sodium peroxodisulfate

 4.70 kg of water Solids content: 55.6%

Dispersion 3:

4.33 kg of water were placed in a stirred tank and heated to 85 ^° C. Subsequently, 5% of feed 1 and 8% of feed 2 were added and polymerized for 5 min. Thereafter, the residual amounts of feed 1A and B and feed 2 were metered in while maintaining the polymerization temperature within 3.5 h after each of the metering methods described above. Thereafter, the reaction was postpolymerized for 1 h to complete the conversion.

Feed 1:

 A: 10.25 kg of water

 1, 33 kg emulsifier II

 1, 50 kg emulsifier III

 1, 00 kg of acrylic acid

 1, 40 kg 25 wt .-% aqueous solution of

 sodium hydroxide

 B: 15.00 kg of ethylhexyl acrylate

 34.00 kg n-butyl acrylate

Feed 2:

 Solution from:

 0.35 kg of sodium peroxodisulfate

 5.48 kg of water

Solids content: 68.6% Dispersion 4:

In a pressure-resistant stirred vessel, a mixture of 16.7 kg water and 0.3 kg of itaconic acid was charged and heated to 85 ⁰ C. Then 4.8% of feed 1 and 9% of feed 2 were added and polymerized for 10 min. After that, the

Residues feed 1 A and B and feed 2 while maintaining the polymerization temperature within 4.5 h after each metered one of the dosing methods described above. Subsequently, to complete the conversion for 1, 5 h polymerized.

Feed 1:

 A: 19.21 kg of water

 3,00 kg Emulsifier Il

 0.69 kg of acrylic acid

 0.40 kg 25 wt .-% aqueous solution of

 sodium hydroxide

 B: 31, 00 kg of styrene

 18.00 kg butadiene

 0.44 kg of tert-dodecylmercaptan

Feed 2:

 Solution from:

 0.35 kg of sodium peroxodisulfate

 5.50 kg of water

Solids content: 53.7%

Emulsifiers used here were:

 Emulsifier I: 30% strength by weight aqueous solution of the sulfuric acid half ester of ethoxylated isononylphenol, EO degree: 25

 Emulsifier II: 15% strength by weight aqueous solution of sodium lauryl sulfate

 Emulsifier III: 20% strength by weight aqueous solution of ethoxylated isooctylphenol, EO-

Grade: 25

Example formulations and tests

There were color formulations for interior colors consisting of

Formulation Example 1 Example 2 Example 3 Example 4

Water 326 326 326 326

Natrosol 250 HR (Hercules Aqualon) 6 6 6 6

TPCP, 50% (Ronas Chemicals) 2 2 2 2

Pigment Distributor S (BASF SE) 4 4 4 4 Parmetol A 26 (Schülke & Mayr) 3 3 3 3

Agitan 280 (Münzing) 2 2 2 2

(Test gasoline (180-210 ⁰ C) DHC Solvent 12 12 12 12

Chemistry)

 Texanol (Eastman) 13 13 13 13

Tronox CR-828 (Tronox) 115 115 109 104

Omyacarb 2 GU (Omya) 205 205 210 215

Plustalc C 700 AW (Mondominerals) 60 60 60 60

Omyacarb 5 GU (Omya) 160 160 160 160

Agitan 280 (Münzing) 2 2 2 2

Dispersion 3 90

 Dispersion 3 / Dispersion C7 (9: 1) 90 90 90

Water 0 0 1 1

Total 1000 1000 1000 1000

Solids 59.4 59.2 59.1 59.1

Volume solids content (%) 38.2 38.1 38.2 38.2

PVC (%) 81, 6% 81, 6% 81, 7% 81, 7%

Density of formulation (calculated) 1, 553 1, 552 1, 549 1, 547

ICI 2.5 2.5 2.5 2.4

KU after 24 h 132 128 127 129

KU after 14 d 50 ⁰ C 126 124 120 125

Density 1, 556 1, 553 1, 549 1, 548

Contrast ratio (KV,%) 97.24 97.25 97.14 97.67

 98.19 98.42 98.46 98.42

98.91 99.22 98.98 99.09

Brightness (%) 90.96 91, 37 91, 12 91, 07

 91, 67 91, 76 91, 83 91, 69

92.02 92.26 92.23 92.22

Hiding power at 98% KV 7.9 8.1 8.0 8.8

Rub resistance after 7 days and

 another 2 days at 50 ° C drying

 ISO 13300 22 25 25 28

Gloss after 24 h, 240μm film lift

 60 ° 2.1 2.1 2.1 2.1

85 ° 3.9 4.1 4.2 4.1. The dispersion 3 was chosen as the aqueous polymer dispersion. In Example 2, nine parts by weight of dispersion 3 were replaced by nine parts by weight of dispersion C7. The volume solid was not adjusted. In Example 3, nine parts by weight of dispersion 3 were replaced by nine parts by weight of dispersion C7. Tronox CR-828 has been reduced by six parts by weight. Omyacarb 2 GU has been increased by five parts by weight. Example 3 has the same volume solids content as Example 1. In Example 4, nine parts by weight of dispersion 3 were replaced by nine parts by weight of dispersion C7. Tronox CR-828 has been reduced by eleven parts by weight. Omyacarb 2 GU has been increased by ten parts by weight. Example 4 has the same volume solids content as Example 1. In Example 3, the opacity could be increased by 0.1 and the wet abrasion resistance by 3 microns compared to Example 1 at a contrast ratio of 98%. In Example 4, in comparison to Example 1, the hiding power could be increased by 0.9 at a contrast ratio of 98% and the wet abrasion resistance by 6 μm.

Claims

claims

Use of a blending of an aqueous dispersion of organic hollow particles with at least one aqueous dispersion of a film-forming polymer (PD), characterized in that the organic hollow particles are produced by a process for the preparation of emulsion polymer particles by preparing a multi-stage emulsion polymer by sequential polymerization Sowing, subsequent implementation with

 ii) a seed seed containing 0 to 100% by weight of at least one nonionic ethylenically unsaturated monomer and 0 to 40% by weight of at least one monoethylenically unsaturated hydrophilic monomer, each based on the total weight of the core stage polymer comprising both seed and seed seed , followed by polymerization with

 iii) a first shell containing 85 to 99.9 wt .-% of at least one nonionic ethylenically unsaturated monomer and 0.1 to 15 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer, followed by polymerization

 iv) a second shell containing 85 to 99.9 wt .-% of at least one nonionic ethylenically unsaturated monomer and 0.1 to 15 wt .-% of at least one hydrophilic monoethylenically unsaturated monomer, followed by addition

v) at least one plasticizer monomer having a Ceiling temperature less than 181 ⁰ C preferably less than 95 ° C.

 vi) Neutralization to a pH of at least 7.5 or greater, preferably greater than 8, of the particles thus formed with a base, followed by polymerization

 vii) a third shell containing from 90 to 99.9% by weight of at least one nonionically ethylenically unsaturated monomer and from 0.1 to 10% by weight of at least one hydrophilic monoethylenically unsaturated monomer, viii) and optionally polymerizing further shells containing at least one nonionic ethylenically unsaturated monomer and at least one hydrophilic monoethylenically unsaturated monomer are obtained as coating agents.

2. Use according to claim 1, characterized in that the weight ratio of the seed seed (ii) to the seed polymer (i) is 2: 1 to 50: 1.

3. Use according to any one of claims 1 or 2, characterized in that the average particle size in the unswollen state of the core-stage polymer, consisting of seed (i) and seed seed (ii), 100 to 400 nm.

Use according to any one of claims 1 to 3, characterized in that the weight ratio of the core-stage polymer to the first shell (iii) is 20: 1 to 1: 1.

5. Use according to any one of claims 1 to 4, characterized in that the weight ratio of the first shell (iii) to the second shell (iv) is 1: 30 to 1: 1.

6. Use according to one of claims 1 to 5, characterized in that the listed under (v) plasticizer monomer is selected from the group α-

Methylstyrene, esters of 2-phenylacrylic acid / atropic acid (eg methyl, ethyl, n-propyl, n-butyl), 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1, 1-diphenylethene or methyl 2-tert-butyl acrylate.

7. Use according to any one of claims 1 to 6 as an additive for an aqueous coating agent for increasing the hiding power and / or the wet abrasion resistance.

8. Use according to one of claims 1 to 6, characterized in that the coating agent is a paint.

9. Use according to claim 8, characterized in that the paint is an interior or an exterior paint.

10. Use according to one of claims 1 to 9, characterized in that the monomers for the aqueous dispersion of the film-forming polymer (PD) are selected from the group n-butyl acrylate with vinyl acetate; n-butyl acrylate with styrene; n-butyl acrylate with ethylhexyl acrylate; Butadiene with styrene; Butadiene with acrylonitrile and / or methacrylonitrile; Butadiene and isoprene with acrylonitrile and / or methacrylonitrile; Butadiene with acrylic esters; Butadiene with Methacrylsäureestem.

11. Use according to any one of claims 1 to 10, characterized in that the monomers for the aqueous dispersion of the film-forming polymer (PD) contain small amounts of further monomers, preferably acrylic acid, methacrylic acid, acrylamide and / or methacrylamide.

12. Use according to any one of claims 1 to 11, characterized in that the mixing ratio of the aqueous dispersion containing the film-forming polymer with the aqueous dispersion containing the organic hollow particle is 30: 70.

13. Use according to one of claims 1 to 11, characterized in that the mixing ratio of the aqueous dispersion containing the film-forming polymer with the aqueous dispersion containing the organic hollow particle is 20: 80.

14. Use according to any one of claims 1 to 11, characterized in that the mixing ratio of the aqueous dispersion containing the film-forming polymer with the aqueous dispersion containing the organic hollow particle is 5: 95.

15. Use according to any one of claims 1 to 11, characterized in that the mixing ratio of the aqueous dispersion containing the film-forming polymer with the aqueous dispersion containing the organic hollow particle is 10: 90.

16. A coating composition in the form of an aqueous composition comprising: a blend of at least one aqueous dispersion of organic hollow particles as in claims 1 to 15 and at least one aqueous dispersion of a film-forming polymer (PD) as defined in claims 1 to 15,

 if appropriate at least one inorganic filler and / or inorganic pigment,

 usual aids and

 - Water to 100 wt .-%.

17. Coating composition containing:

3 to 60 wt .-%, based on the solids content of a blend of at least one aqueous dispersion of organic hollow particles according to the invention, and at least one aqueous dispersion of a film-forming polymer (PD) according to the invention as defined in claims 1 to 15,

 From 10 to 70% by weight of inorganic fillers and / or inorganic pigments,

0.1 to 20% by weight of conventional auxiliaries, and

 - Water to 100 wt .-%.