EP2456837A1 - Verwendung filmbildender polymere und organischer hohlteilchen für beschichtungsmittel - Google Patents

Verwendung filmbildender polymere und organischer hohlteilchen für beschichtungsmittel

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Publication number
EP2456837A1
EP2456837A1 EP10735269A EP10735269A EP2456837A1 EP 2456837 A1 EP2456837 A1 EP 2456837A1 EP 10735269 A EP10735269 A EP 10735269A EP 10735269 A EP10735269 A EP 10735269A EP 2456837 A1 EP2456837 A1 EP 2456837A1
Authority
EP
European Patent Office
Prior art keywords
acid
aqueous dispersion
acrylate
use according
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP10735269A
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German (de)
English (en)
French (fr)
Inventor
Arno Tuchbreiter
Oliver Wagner
Chris Titmarsh
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BASF SE
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BASF SE
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Priority to EP10735269A priority Critical patent/EP2456837A1/de
Publication of EP2456837A1 publication Critical patent/EP2456837A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C08L2205/20—Hollow spheres

Definitions

  • 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.
  • 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.
  • 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).
  • 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
  • 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
  • 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
  • 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
  • the invention further provides coating compositions in the form of an aqueous composition comprising:
  • At least one inorganic filler and / or inorganic pigment is optionally at least one inorganic filler and / or inorganic pigment
  • 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.
  • 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.
  • PD film-forming polymer
  • 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.
  • PD film-forming polymer
  • 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.
  • 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-C ⁇ -alkyl and particularly preferred
  • Ci-C4 alkyl groups 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-ethy
  • 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.
  • alkyl includes unsubstituted and substituted alkyl radicals.
  • 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.
  • 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.
  • 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.
  • aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • 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.
  • 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,
  • 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,
  • 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
  • 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, ⁇ -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 ⁇ ff listed monomers.
  • the plasticizer monomer used is preferably ⁇ -methylstyrene.
  • the neutralization listed under (vi) is carried out with a base to swell the core and thus formation of the hollow particle.
  • 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,
  • 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,
  • 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.
  • 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.
  • the pigments used can be completely or partially replaced by the polymer dispersion described here.
  • 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.
  • the usual equipment e.g. Stirred tank, stirred tank cascades, autoclaves, tube reactors and kneaders.
  • the polymerization may be carried out in solvents or diluents, e.g.
  • 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.
  • 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.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxydisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • organic SH groups such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-
  • 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.
  • 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.
  • 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.
  • diacrylates or dimethacrylates of at least dihydric saturated alcohols for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-prop
  • 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.
  • 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.
  • 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.
  • emulsifiers or protective colloids are used for this purpose.
  • 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.
  • 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.
  • 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.
  • 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.
  • primary, secondary and tertiary amines such as ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dime
  • 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.
  • ammonia, triethanolamine and diethanolamine are used for the partial or complete neutralization of ethylenically unsaturated carboxylic acids before or during the polymerization.
  • 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.
  • 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.
  • ⁇ 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 ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols, amides ⁇ , ß-ethylenically unsaturated Mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, primary amides of ⁇ , ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-viny
  • N-vinylamide compounds esters of allyl alcohol with C 1 -C 30 -monocarboxylic acids, esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, amides of ⁇ , ⁇ -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.
  • C 1 -C 20 -alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate,
  • 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, ⁇ -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.
  • 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.
  • vinylphosphonic and allylphosphonic are also suitable.
  • 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
  • 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.
  • 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.
  • C 2 -C 30 -alkanediols are e.g. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
  • Suitable primary amides of ⁇ , ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are acrylic acid amide, methacrylamide,
  • N-vinyl lactams and derivatives thereof are, for. B. N-vinylpyrrolidone,
  • 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 ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N, N-dimethylaminomethyl (meth) acrylate,
  • N, N-dimethylaminocyclohexyl (meth) acrylate N, N-dimethylaminocyclohexyl (meth) acrylate.
  • Suitable amides of ⁇ , ⁇ -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,
  • 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 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).
  • Such 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 Methacrylklam. All of the monomer combinations mentioned may additionally contain small amounts of further monomers, preferably acrylic acid, methacrylic acid, acrylamide and / or methacrylamide.
  • PVK pigment volume concentration
  • 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,
  • a coating composition comprising:
  • the proportion of (PD) to the above coating agent refers to solid, i. H. Emulsion polymer, without water.
  • 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.
  • 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.
  • 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 ischen Chemie, 4th Edition, Volume 15, p. 667.
  • 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.
  • the emulsion paints of the invention may also organic color pigments, for.
  • Suitable fillers are for.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Tg 3 and Tgb glass transition temperature of polymer "a" and "b"
  • Wa and Wb weight fraction of polymer "a” and "b"
  • 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).
  • 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.
  • 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 ⁇ m.
  • 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.
  • 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 ⁇ m by linear extrapolation 30-60 ⁇ m Production of the color paste
  • 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.
  • Dispersion B1 (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-.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 15.8 g of ⁇ -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.
  • 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.
  • 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.
  • pre-emulsion 2 consisting of 16 g of water, 0.6 g of arylsulfonate (15% strength) and 13.5 g of ⁇ -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.
  • 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
  • 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%
  • 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.
  • 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.
  • 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 ⁇ -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.
  • 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.
  • 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
  • the internal temperature was raised to 92 ° C and the sodium persulfate feed stopped.
  • pre-emulsion 2 consisting of 14 g of water, 0.5 g of arylsulfonate (15% strength) and 13.6 g of ⁇ -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.
  • the original consisting of 458 g of water and 154.5 g of dispersion B5
  • 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.
  • 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 ⁇ -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%
  • 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.
  • 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.
  • 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 ⁇ -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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 ⁇ -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.
  • 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.
  • an inline mixing element a or b
  • 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-
  • volume solids content (%) 38.2 38.1 38.2 38.2
  • the dispersion 3 was chosen as the aqueous polymer dispersion.
  • nine parts by weight of dispersion 3 were replaced by nine parts by weight of dispersion C7. The volume solid was not adjusted.
  • 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.
  • 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.
  • Example 4 has the same volume solids content as Example 1.
  • 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%.
  • the hiding power could be increased by 0.9 at a contrast ratio of 98% and the wet abrasion resistance by 6 ⁇ m.

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Families Citing this family (20)

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EP2754692B1 (en) * 2011-08-31 2018-02-21 Sekisui Plastics Co., Ltd. Resin particle aggregate, method for manufacturing same and application of same
KR102013251B1 (ko) * 2012-06-05 2019-08-22 다우 글로벌 테크놀로지스 엘엘씨 안정성이 개선된 수성 코팅 조성물
DE102012213978A1 (de) * 2012-08-07 2014-02-13 Evonik Degussa Gmbh Unterkritisch formulierte Beschichtungen
JP2014070078A (ja) * 2012-09-27 2014-04-21 Nippon Zeon Co Ltd 中空重合体粒子、水性分散液、塗被組成物、および塗被紙
CN104704068B (zh) 2012-10-12 2018-11-02 陶氏环球技术有限公司 具有改进粘度稳定性的水性涂料组合物
CN104277649B (zh) * 2013-07-08 2019-09-27 罗门哈斯公司 双峰吸附胶乳
RU2717795C2 (ru) 2013-08-22 2020-03-25 Басф Се Способ получения эмульсионных полимеров
JP6856377B2 (ja) * 2013-08-22 2021-04-07 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ エマルションポリマーの製造法
WO2015080132A1 (ja) * 2013-11-28 2015-06-04 日本ゼオン株式会社 顔料分散液、塗被紙用組成物および塗被紙
CN104211858B (zh) * 2014-09-17 2015-12-30 珠海金鸡化工有限公司 羧基丁苯胶乳及其制备方法
CN104231173B (zh) * 2014-09-17 2018-08-14 珠海金鸡化工有限公司 羧基丁苯胶乳制备系统及其制备方法
US10577505B2 (en) * 2015-01-21 2020-03-03 Basf Coatings Gmbh Aqueous dispersions containing multistage produced polymers and coating agent compositions containing the same
CN105175614B (zh) * 2015-08-17 2017-11-17 清华大学 彩色中空聚合物乳液及其制备方法
WO2017191167A1 (en) * 2016-05-04 2017-11-09 Basf Se Process for preparing an aqueous polymer latex
WO2017206162A1 (en) * 2016-06-03 2017-12-07 Dow Global Technologies Llc Aqueous polymer dispersion and aqueous coating composition comprising the same
PL3523382T3 (pl) 2016-10-07 2021-05-31 Basf Se Sposób wytwarzania wodnych dyspersji
CN106583884B (zh) * 2016-11-18 2020-02-04 中车齐齐哈尔车辆有限公司 补焊方法
CN110872367B (zh) * 2018-09-04 2023-10-03 罗门哈斯公司 多级聚合物颗粒的水分散体
US20230203317A1 (en) * 2020-05-25 2023-06-29 Dow Global Technologies Llc Aqueous coating composition and process for preparing the same
CN115521407A (zh) * 2022-09-27 2022-12-27 佛山罗斯夫科技有限公司 一种提高耐擦洗的聚丙烯酸铵盐分散剂的制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2501123C2 (de) 1975-01-14 1984-02-09 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Suspensions-Copolymerisaten
JPS60223873A (ja) 1984-04-20 1985-11-08 Dainippon Ink & Chem Inc 水性塗料組成物
US4733005A (en) 1986-04-21 1988-03-22 The Dow Chemical Company Phosphinyl-containing ethylenically unsaturated compounds
EP0656033B1 (en) 1992-08-19 1997-05-21 The Dow Chemical Company Hollow polymer latex particles
DE19648744A1 (de) 1996-11-25 1998-05-28 Basf Ag Verfahren zur Herstellung einer Polymerdispersion durch radikalische wäßrige Emulsionspolymerisation mit einer kontinuierlich hergestellten wäßrigen Monomerenemulsion
DE19750618A1 (de) 1997-11-14 1999-05-20 Basf Ag Pigmenthaltige Zubereitungen auf der Basis wässriger Polymerisatdispersionen
US6624272B2 (en) * 1999-12-20 2003-09-23 Jsr Corporation Hollow crosslinked cationic polymer particles, method of producing said particles, and paint composition, cationic electrodeposition paint composition, resin composition, filled paper, paper coating composition, and coated paper
AU2001249257A1 (en) * 2000-03-16 2001-09-24 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
CN1324059C (zh) * 2002-08-21 2007-07-04 Jsr株式会社 中空聚合物颗粒及制法,纸涂布组合物、涂布纸及制法
DE102005033516A1 (de) * 2005-07-14 2007-01-18 Basf Ag Verfahren zur Herstellung von Emulsionspolymerisaten
CN100427510C (zh) * 2006-06-27 2008-10-22 上海东升新材料有限公司 一种中空聚合物乳胶粒及其制备方法
JP2008223188A (ja) * 2007-03-14 2008-09-25 Jsr Corp 塗工用組成物、及び塗工体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011009875A1 *

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