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EP2855610A1 - Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques - Google Patents

Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques

Info

Publication number
EP2855610A1
EP2855610A1 EP13726551.8A EP13726551A EP2855610A1 EP 2855610 A1 EP2855610 A1 EP 2855610A1 EP 13726551 A EP13726551 A EP 13726551A EP 2855610 A1 EP2855610 A1 EP 2855610A1
Authority
EP
European Patent Office
Prior art keywords
metal sheets
monomers
stage
acid
polymer dispersion
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.)
Withdrawn
Application number
EP13726551.8A
Other languages
German (de)
English (en)
Inventor
Ekkehard Jahns
Hans-Jürgen Denu
Sebastian Roller
Alexander Kurek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13726551.8A priority Critical patent/EP2855610A1/fr
Publication of EP2855610A1 publication Critical patent/EP2855610A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • B05D1/14—Flocking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D1/12—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface
    • E04D1/18—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface of metal
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D1/12—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface
    • E04D1/22—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface of specified materials not covered by any one of groups E04D1/14 - E04D1/205, or of combinations of materials, where at least one is not covered by any one of groups E04D1/14 - E04D1/205
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D13/00—Special arrangements or devices in connection with roof coverings; Protection against birds; Roof drainage ; Sky-lights
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D2001/005—Roof covering by making use of tiles, slates, shingles, or other small roofing elements the roofing elements having a granulated surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • the present invention relates to the use of aqueous multi-stage polymer dispersions obtainable by free-radically initiated aqueous emulsion polymerization, having a soft and a hard phase and a step ratio of hard to soft from 25 to 95 wt .-% to 75 to 5 wt .-%, wherein the Glass transition temperature (Tg) of the soft phase as the first stage is -30 to 0 ° C and that of the hard phase as a second stage 20 to 60 ° C, containing at least one monomer of the general formula I.
  • Tg Glass transition temperature
  • n 0 to 2
  • R1, R2, R3 independently of one another hydrogen or methyl group
  • the present invention relates to metal sheets containing the polymer dispersion according to the invention, and to processes for producing the coated metal sheets.
  • Aqueous polymer dispersions of the prior art are used as binders in coating compositions, in particular also for coating metal sheets for roofing and as wall cladding.
  • These metal sheets as building materials consist for example of aluminum, zinc, copper or steel sheet with a corrosion protection primer of organic binders and anti-corrosive pigments, such as zinc phosphate, aluminum triphosphate, Zinkorthophosphathydrat, zinc aluminum orthophosphate hydrate, zinc molybdenum orthophosphate hydrate , Zinc-aluminum-molybdenum-orthophosphate hydrate, zinc-calcium-strontium-aluminum-orthophosphate-silicate hydrate. Often, these sheets are produced in the so-called coil coating process.
  • the metal sheets are provided from one roll with the anticorrosion primer, dried or hardened and then rolled up again almost endlessly. From these coated coils, metal sheets for roof and wall structures are formed by cutting and bending machines. These metal sheets can then be provided once more with a weatherproof final coating.
  • the sheets can also be formed and coated from precut metal plates.
  • the shaped metal sheets can also be used with a granulated surface for a different visual appearance. In addition to the other visual impression, this surface also serves to dampen noise in the rain. Furthermore, the slipping of snow is avoided.
  • prepared coil sheet (with and without primer) is cold formed into the corresponding roof elements. Subsequently, the surface is coated with a colored layer of the thickness of 100-800 ⁇ m. Granules are sprinkled directly into this still wet color coating. Non-adherent material is blown off with a stream of air. This granulate layer is fixed directly in connection with a second color layer or a transparent clearcoat. Subsequently, a final drying process takes place at elevated temperature.
  • processing requirements at the construction site are also important for the coating. This includes the adhesion of the coating to the metal sheet in dry as well as wet conditions. Adjustments to the elements when laying on the construction site are tested, among other things, with the testing of bending properties. Here, the elements are bent dry at -10 ° C up to 180 °. Also, the processing is simulated by a nail test and further mechanical stress.
  • a disadvantage is an increased stickiness of the coating at higher temperatures by the addition of the plasticizer. This leads to increased pollution in the outdoor area and as a result to increased growth of algae and mosses. Also, the water sensitivity of the coating is increased. Another problem can be the leaching of ingredients.
  • aqueous coating systems are generally used today which contain an aqueous polymer dispersion as the film-forming constituent.
  • binders usually single-stage binders based on aqueous polymer dispersions for facade paints of styrene acrylates, homo- and copolymers of vinyl acetate or pure acrylates in color formulations for the fixation of the granules used (see, for example, DE 21 64 256).
  • the coatings available with it were unable to avoid the disadvantage of low adhesion and elasticity during bending by up to 180 ° and at low temperatures.
  • These binders with a glass transition temperature (Tg) in the range of 10-35 ° C are therefore filmed by the addition of film-forming aids and plasticizers in the formulations.
  • the plasticizers increase flexibility at low temperatures, e.g. At -10 ° C and thus allow a bending of the sheets by up to 180 ° without cracking or detachment from the substrate.
  • EP 623 659 discloses multistage polymer dispersions and their use in coating compositions. However, the dispersions disclosed therein contain no monomer of the general formula I and do not describe the coating of metal sheets.
  • None of the multistage polymers disclosed in the prior art contains a monomer of the general formula I and is used for coating metal sheets.
  • the single-stage binders in coatings of the prior art have the disadvantage that they are often too hard to achieve good blocking resistance and therefore can not be formulated without solvents or film-forming aids. These coatings can be easily cracked and dull when weathered outdoors, so have no very good weather resistance.
  • the two-stage binders of the prior art e.g. Although described in EP 623 659 give a satisfactory blocking resistance by their proportion of hard phase, their weather resistance does not meet the requirements. It is an object of the present invention to provide binders and coating compositions, in particular for coating granulated and ungranulated metal sheets, such as aluminum or steel sheets, which exhibit increased weather resistance and, moreover, excellent blocking resistance and excellent adhesion and elasticity distinguished.
  • multistage polymer dispersions obtainable by free-radically initiated aqueous emulsion polymerization with a soft phase and a hard phase and a step ratio of hard to soft phase of from 25 to 95% by weight to 75 to 5% by weight (based on polymer mass ), the glass covers ,
  • transition temperature of the soft phase as the first stage is -30 to 0 ° C and that of the hard phase as the second stage 20 to 60 ° C, containing at least one monomer of the general formula I.
  • n 0 to 2
  • R1, R2, R3 independently of one another hydrogen or methyl group
  • Y H, alkali metal, NH 4 ,
  • binders according to the invention makes possible optimally improved adhesion under all test conditions without the additional use of plasticizers and the associated disadvantages.
  • the coatings using the binders of the invention adhere better and are less susceptible to mechanical stress at higher temperatures. Tests at low temperatures and under wet conditions show advantages in terms of adhesion. Also, weather resistance and durability are improved.
  • Suitable substrates include metal sheets of aluminum, zinc, copper or steel as well as industrially pretreated "coils” or their derivatives in the form of flat or preformed metal sheets or cut sheet metal strips.
  • the improved weather resistance can be based on a very good filming (low MFT) at the same time high film hardness and is reflected for example by increased gloss retention after UV / water exposure (eg Sun- / Xenotest or outdoor weathering) for clearcoats or low pigmented coatings or a good color retention for higher pigmented coatings - Durability, the systems show excellent blocking resistance and excellent adhesion and elasticity.
  • the metal sheets can be granulated or "ungranulated” used. ._
  • the coating according to the invention can be applied by dipping, spraying, rolling or brushing or by a curtain curtain or curtain coater.
  • prepared coil sheet (with and without primer) is cold-formed into the corresponding roof elements the surface is coated with a color layer of the thickness 100-800 ⁇ containing the polymer dispersion according to the invention
  • fillers calcium carbonates, silicates, etc.
  • pigments iron oxides, chromium oxides, carbon black etc.
  • additives such as wetting agents, defoamers, thickeners can be added to the color layer.
  • granules can be sprinkled directly into this still wet color coating.Non-adhesive material is blown off with a stream of air.
  • the granules are usually a silicate material which, depending on the application, is coated with a pigment.
  • This granulate layer is fixed directly in connection with a second color layer containing the binder according to the invention or a transparent clearcoat (150-180 g / m 2 ).
  • the clearcoat may contain both the inventive polymer dispersion or else be a pure acrylate with high UV resistance.
  • the sheets After coating and drying, the sheets are usually stacked on each other while still warm.
  • the polymer dispersion according to the invention can therefore be used both in the so-called basecoat, ie the first color coat on the primed metal which binds the granules, or in a second color coat or in a UV stable topcoat (clear coat).
  • the aqueous multistage polymer dispersion used according to the invention is preferably understood as meaning an aqueous polymer dispersion whose soft phase as the first stage has a Tg of -30 to 0 ° C., preferably -20 to 0 ° C. and whose hard phase second stage is a Tg of 20 to 60 ° C, preferably from 30 to 50 ° C and a step ratio of hard to soft of 25-95: 75-5.
  • the granulated or non-granulated metal sheets according to the invention are understood to be sheets of aluminum, zinc, copper or steel.
  • the metal sheets can be formed into roof moldings and coated in the process described above.
  • the present invention relates to a method for producing the metal sheets coated according to the invention.
  • Another object of the invention are granulated or non-granulated metal sheets, which are coated with the aqueous polymer dispersion of the invention.
  • the polymer dispersions used according to the invention are obtainable by free-radical emulsion polymerization of ethylenically unsaturated compounds (monomers).
  • a polymer is prepared from monomers which contain at least one monomer I and optionally a monomer having at least one acid group in an amount of 0.1 part by weight, preferably from 0.5 to 2.5% by weight. Parts based on the total amount of monomers of the first and second stage include.
  • the acid monomers used in the first stage can be copolymerized with monomers without an acid group.
  • the first stage polymer is preferably formed from at least 40% by weight of the major nonionic monomers defined below and from a second type of monomer selected from ethylenically unsaturated acid monomers.
  • the polymer of the first stage may optionally be formed from further, preferably nonionic monomers.
  • the polymer of the first stage is preferably at least 40% by weight, in particular from 60 to 99% by weight or from 80 to 98% by weight, based on all monomers of the first stage, of main monomers which are selected from the group consisting of C 1 - to C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds and mixtures of these monomers.
  • Main monomers for the polymer of the first stage are z.
  • Ethylhexyl acrylate In particular, mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Vinylaromatic compounds include vinyltoluene, alpha- and para-methylstyrene, alpha-butyl ⁇
  • styrene 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Preference is given to using vinyl ethers of alcohols containing from 1 to 4 carbon atoms.
  • hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene.
  • Preferred main monomers for the polymer of the first stage are C 1 - to C 10 -alkyl acrylates, C 1 - to C 10 -alkyl methacrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms and mixtures of these monomers, in particular C 1 - to C 8 -alkyl acrylates and cis-bis Cs-alkyl methacrylates and vinyl esters.
  • Very particular preference is given to 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate and styrene.
  • the polymer of the first stage further contains optionally 0.1 wt .-%, in particular from 0.5 to 2.5 wt .-%, based on all monomers of the first stage, of ethylenically unsaturated acid monomers.
  • Ethylenically unsaturated acid monomers are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid.
  • the ethylenically unsaturated carboxylic acids used are preferably alpha, beta-monoethylenically unsaturated mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule.
  • acrylic acid methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinyllactic acid and 2-carboxyethyl acrylate.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid or styrenesulfonic acid. Preference is given to acrylic acid and methacrylic acid or their mixture.
  • the amides and the hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated C 3 -C 6 -carboxylic acids particularly preferably acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate or 1, 4-butanediol monoacrylate can be used.
  • the monomers may be used alone or in combinations of e.g. Acids and amides are used.
  • monomers of the general formula I are used as monomers of the first stage.
  • the sodium, ammonium and potassium metal salts are particularly suitable.
  • the polymer of the first stage is a copolymer which
  • (ii) is made up of at least 80% by weight and up to 99% by weight of main monomers which are selected from the group consisting of C 1 - to C 10 -alkyl (meth) acrylates, amides and hydroxyalkyl esters of ⁇ , ⁇ - unsaturated C 3 -C 6 -carboxylic acids, particularly preferably acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate or 1,4-butanediol monoacrylate and mixtures of these monomers, in particular n-butyl acrylate, methyl methacrylate and acrylamide, and
  • seed latex is an aqueous dispersion of fine-particle polymer particles having an average particle diameter of preferably 20 to 40 nm. Seed latex is used in an amount of preferably 0.05 to 5% by weight, particularly preferably 0.1 to 3% by weight. based on the total amount of monomers of the first and second stages. It is suitable, e.g. a latex based on polystyrene or based on polymethylmethacrylate. A preferred seed latex is polystyrene seed.
  • the monomers used for the polymerization of the second stage are preferably at least 60% by weight, preferably at least 80% by weight, for example from 80 to 100% by weight, particularly preferably at least 95% by weight, based on the total amount of second stage monomers, of one or more of the major monomers described below.
  • the main monomers are selected from the group consisting of C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of 1 up to 10 C atoms are contained _
  • alcohols aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester having a Ci-Cio-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, n-butyl methacrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, alpha- and para-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether.
  • vinyl ethers will be from 1 to 4 carbon atoms-containing alcohols.
  • hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene.
  • Preferred main monomers for the second-stage polymerization are the C 1 -C 10 -alkyl acrylates and C 1 -C 10 -alkyl methacrylates, in particular C 1 -C -alkyl acrylates and C 1 -C 10 -alkyl methacrylates and vinylaromatics, in particular styrene and mixtures thereof.
  • methyl acrylate methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, styrene, vinyl acetate and mixtures of these monomers.
  • the monomers for the second stage polymerization may comprise other monomers, e.g. Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Other monomers are z. As well as hydroxyl-containing monomers, in particular C1-C10 hydroxyalkyl (meth) acrylates and (meth) acrylamide.
  • Phenyloxyethylglycol mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may also be mentioned as further monomers.
  • Other monomers which may also be mentioned are crosslinking monomers.
  • the polymer of the second stage further contains optionally 0.1% by weight, in particular from 0.5 to 2.5% by weight, based on all monomers of the second stage, of ethylenically unsaturated acid monomers.
  • Ethylenically unsaturated acid monomers are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated "_
  • the ethylenically unsaturated carboxylic acids used are preferably alpha, beta-monoethylenically unsaturated mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule. Examples thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinyllactic acid and 2-carboxyethyl acrylate.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid or styrenesulfonic acid. Preference is given to acrylic acid and methacrylic acid and their mixture.
  • the amides and the hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated C 3 -C 6 -carboxylic acids more preferably acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate or 1, 4-butanediol monoacrylate can be used.
  • the monomers may be used alone or in combinations of e.g. Acids and amides are used.
  • monomers of the general formula I are also used as monomers of the second stage.
  • the sodium, ammonium and potassium metal salts are particularly suitable.
  • the monomers for the second stage polymerization are at least 60% by weight, more preferably at least 80% by weight, e.g. from 60 to 99% by weight, and very particularly preferably at least 95% by weight, selected from at least one C 1 to C 20 alkyl acrylate, at least one C 1 to C 20 alkyl methacrylate, their mixture or mixture thereof with at least one further monomer selected from Amides and the hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated C 3 -C 6 -carboxylic acids, more preferably acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate or 1,4-butanediol monoacrylate
  • the monomers of the first-stage polymerization are selected such that the glass transition temperature calculated for a polymer prepared from the monomers of the first stage is -30 ° C to 0 ° C, and that for one of the monomers of the second ""
  • polymer prepared at the stage is 20 ° C to 60 ° C.
  • x 1 , x 2 , .... x n are the mass fractions of the monomers 1, 2, .... n and T g 1 , T g 2 , .... T g n the glass transition temperatures of each of only one of Monomers 1, 2, .... n constructed polymers in degrees Kelvin.
  • the T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; Further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York 1966, 2 nd Ed. J. Wiley, New York 1975, and 3 rd Ed. J. Wiley, New York 1989.
  • ethyl acrylate a value of -13 ° C is used.
  • the actual glass transition temperature can be determined by differential scanning calorimetry (ASTM D 3418-08, so-called "midpoint temperature").
  • the weight ratio of the amount of monomers used in the first stage to the amount of monomers used in the second stage is 25-95: 75-5, preferably 5:95 to 50:50.
  • At least one crosslinker may be used in addition to the aforementioned monomers.
  • Monomers having a crosslinking function are compounds having at least two polymerizable, ethylenically unsaturated, non-conjugated double bonds in the molecule.
  • a networking can also z.
  • the complementary groups may both be bound to the emulsion polymer, but for crosslinking it is also possible to use a crosslinker which is capable of undergoing a chemical crosslinking reaction with functional groups of the emulsion polymer.
  • Suitable crosslinkers are z. As acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as
  • ethylene oxide or propylene oxide In addition to the homopolymers of ethylene oxide or propylene oxide, it is also possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which contain incorporated ethylene oxide and propylene oxide groups.
  • underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, cyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.
  • crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, 1-butene-3-ol, 5-hexene-1-ol, 1-octene-3-ol, 9-decene-1-ol, dicyclopentenyl alcohol, 10-undecene-1-ol, cinnamyl alcohol , Citronellol, crotyl alcohol or cis-9-octadecene-1-ol.
  • esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • a preferred crosslinker is allyl methacrylate.
  • crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • crosslinking agents are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene,
  • crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines. Such amines are for. B.
  • 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine are also suitable.
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least divalent carboxylic acids, as described above.
  • triallylamine and Triallylmonoalkylammoniumsalze z.
  • suitable as a crosslinker suitable as a crosslinker.
  • N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartaramide, for. B. ⁇ , ⁇ '-Divinylethylenharnstoff or N, N'-divinylpropyleneurea.
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • water-soluble crosslinkers are used.
  • the crosslinking monomers include those which in addition to an ethylenically unsaturated double bond, a reactive functional group, eg. Example, an aldehyde group, a keto group or an oxirane group, which can react with an added crosslinker.
  • a reactive functional group eg. Example, an aldehyde group, a keto group or an oxirane group, which can react with an added crosslinker.
  • the functional groups are keto or aldehyde groups.
  • the keto or aldehyde groups are preferably bonded to the polymer by copolymerization of copolymerizable, ethylenically unsaturated compounds with keto or aldehyde groups.
  • Suitable such compounds are acrolein, methacrolein, vinyl alkyl ketones having 1 to 20, preferably 1 to 10 carbon atoms in the alkyl radical, formylstyrene, (meth) acrylic acid alkyl esters having one or two keto or aldehyde, or an aldehyde and a keto group in Alkyl radical, wherein the alkyl radical preferably has a total of 3 to 10 carbon atoms ".
  • the crosslinkers are preferably a compound having at least 2 functional groups, in particular 2 to 5 functional groups, which can undergo a crosslinking reaction with the functional groups of the polymer, especially the keto or aldehyde groups. These include z.
  • hydrazide hydroxylamine or oxime ether or amino groups as functional groups for the crosslinking of the keto or aldehyde groups.
  • Suitable compounds with hydrazide groups are, for. B. Polycarbonsaurehydrazide having a molecular weight of up to 500 g / mol.
  • Particularly preferred hydrazide compounds are dicarboxylic acid dihydrazides having preferably 2 to 10 C atoms. These include z.
  • oxalic acid dihydrazide malonic acid dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic acid dihydrazide and / or isophthalic dihydrazide.
  • adipic dihydrazide sebacic dihydrazide and isophthalic dihydrazide.
  • Suitable compounds with hydroxylamine or oxime ether groups are, for. As mentioned in WO 93/25588.
  • crosslinkers which can be used both in the first-stage and second-stage polymerization and subsequently are, for example, acetoacetoxyalkyl (meth) acrylates, N-vinylpyrolidone, N- (2-methacryloyloxyethyl) ethyleneurea, N - (2-acryloyloxyethyl) ethyleneurea, 2-acetoacetoxyethyl acrylate,
  • the crosslinking component is preferably in an amount of 0.0005 to
  • crosslinkers can be used both only in the first, as well as only in the second stage or in both stages.
  • the radical polymerization of the monomer mixture M) can be carried out in the presence of at least one regulator.
  • Regulators are preferably used in an amount of 0.0005 to 5 wt .-%, particularly preferably from 0.001 to 2.5 wt .-% and in particular from 0.01 to 1, 5 wt .-%, based on the total weight of the Polymerization used monomers used. ", _
  • Regulators are generally compounds with high transfer constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate. In the case of the regulators, one can distinguish between mono-, bi- or polyfunctional regulators depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions. Suitable regulators are described in detail, for example, by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11-81-11 / 141.
  • Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionic aldehyde, n-butyraldehyde, isobutyraldehyde.
  • regulators formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.
  • halogen compounds for example, alkyl halides, such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide and benzyl compounds, such as benzyl chloride or benzyl bromide.
  • alkyl halides such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide
  • benzyl compounds such as benzyl chloride or benzyl bromide.
  • Suitable regulators are allyl compounds, such as. Allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ethers. Preference is given to using compounds which contain sulfur in bound form as regulators.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, Dialkyl sulfide, dialkyl disulfide and / or diaryl sulfide.
  • thiols compounds which contain sulfur in the form of SH groups, also referred to as mercaptans.
  • Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids. Examples of these compounds are allyl thioglycolates,
  • 3-mercaptopropionic acid mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan or tert. or n-dodecylmercaptan.
  • bifunctional regulators containing two sulfur atoms in bonded form are bifunctional thiols such as. As dimercaptopropanesulfonic acid (sodium salt), di-mercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol-bis-thioglycolate.
  • polyfunctional regulators are compounds containing more than two sulfur atoms in bonded form. Examples of these are trifunctional and / or tetrafunctional mercaptans.
  • a specific embodiment relates to polymer dispersions prepared by free-radical emulsion polymerization without addition of a regulator.
  • the monomers can be polymerized by means of free-radical initiators.
  • the peroxo and / or azo compounds customary for this purpose can be used, for example alkali metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide,
  • the Red / Ox initiator systems consist of at least one usually inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is z. B. to the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as.
  • sodium sulfite, sodium hydrogen sulfite, alkali metal salts of the desulfurous acid such as sodium disulfite, bisulfite tadditionsorganiz aliphatic aldehydes and ketones such as acetone bisulfite or Re- "_,
  • red / ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
  • Usual Red / Ox initiator systems are z.
  • the individual components eg. As the reduction component, mixtures may also be z.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on all monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • the preparation of the polymer dispersion is usually carried out in the presence of at least one surface-active compound.
  • a detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry,
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers. Emulsifiers whose relative molecular weights are usually below those of protective colloids are preferably used as surface-active substances.
  • nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C -Cio), ethoxylates of long-chain alcohols (EO degree: 3 to 100, alkyl radical: C8 -C36) and polyethylene oxide / polypropylene oxide homo- and copolymers.
  • alkylene oxide units may contain randomly distributed alkylene oxide units or polymerized in the form of blocks.
  • Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8-C22), of sulfuric monoesters of ethoxylated alkanols "_
  • alkyl radical: C 12 -C 18 alkyl radical: C 12 -C 18
  • alkylarylsulfonic acids alkyl radical: C9-C18
  • emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, p 192-208).
  • anionic emulsifiers are bis (phenylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C 4 -C 24 -alkyl group on one or both of the aromatic rings. These compounds are well known, for. From US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).
  • Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • quaternary ammonium halides e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • the amount of emulsifier is generally about 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the amount of monomers to be polymerized.
  • the neutralization of acid groups of the first polymer is carried out by at least partial addition of a neutralizing agent during the polymerization of the second stage, wherein the feed of neutralizing agent is preferably carried out in parallel to the monomer feed.
  • the neutralizing agent can be added in a common feed with the monomers to be polymerized or in a separate feed. After all monomers have been fed in, the amount of neutralizing agent required for the neutralization of at least 10%, preferably 30 to 100% or 30 to 90% acid equivalents, is preferably contained in the polymerization vessel.
  • the emulsion polymerization is generally carried out at 30 to 130 ° C, preferably at 50 to 95 ° C.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization of the first stage can be carried out either as a batch process or in the form of a feed process, including a stepwise or gradient procedure. In the polymerization, a polymer seed is preferably introduced for better adjustment of the particle size.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%, particularly preferably greater than or equal to 50 wt .-%.
  • solids contents 15 to 75 wt .-%, preferably from 40 to 75 wt .-%, particularly preferably greater than or equal to 50 wt .-%.
  • dispersions having the highest possible solids content are preferred.
  • solids contents> 60 wt .-% you should set a bimodal or polymodal particle size, otherwise the viscosity is too high, and the dispersion is no longer manageable.
  • the generation of a new generation of particles can be carried out, for example, by adding seed (EP 81083), by adding excess quantities of emulsifier or by adding miniemulsions. Another benefit associated with low viscosity at high solids content is improved coating behavior at high solids levels.
  • the generation of a new / new particle generation (s) can take place at any time. It depends on the particle size distribution desired for a low viscosity.
  • the aqueous polymer dispersion obtained after completion of the polymerization stages is subjected to an after-treatment to reduce the residual monomer content.
  • the aftertreatment is carried out either chemically, for example by completing the polymerization reaction by using a more effective radical initiator system (so-called postpolymerization) and / or physically, for example by stripping the aqueous polymer dispersion with steam or inert gas.
  • a more effective radical initiator system so-called postpolymerization
  • postpolymerization a more effective radical initiator system
  • stripping the aqueous polymer dispersion with steam or inert gas.
  • Corresponding chemical and / or physical methods are familiar to the person skilled in the art [see, for example, EP-A 771 328, DE-A 196 24 299, DE-A 196 21 027, DE-A 197 41 184, DE-A 197 41 187, DE-A.
  • VOCs volatile organic compounds
  • a silane monomer is used in both stages, such as Vinyltrialkoxisilane, z. Vinyltrimethoxysilane, alkylvinyldialkoxisilanes, e.g.
  • Methylvinyldialkoxysilane or (meth) acryloxyalkyltrialkoxisilanes, e.g. B. (meth) acryloxypropyltrimethoxysilane and (meth) acryloxypropyltriethoxysilane.
  • These silane monomers can be used in amounts of up to 2 wt .-%, preferably 0.05 to 1 wt .-%, based on the total weight of the monomers.
  • the aqueous polymer dispersions obtainable by the process according to the invention have polymerizate particles which have a weight-average particle diameter Dw in the range> 50 and ⁇ 500 nm, preferably> 70 and ⁇ 300 nm and particularly preferably> 80 nm to ⁇ 200 nm.
  • the determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge.
  • Weight-average particle diameter in this document is understood to mean the weight-average Dwso value determined by the method of the analytical ultracentrifuge (cf., for this purpose, SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with Eight-Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Gurchtie, pp. 147-175).
  • the corresponding polymer powders are accessible from the novel aqueous polymer dispersions in a simple manner (for example freeze drying or spray drying). These polymer powders obtainable according to the invention can likewise be used as a component in the production of coating materials for metal sheets.
  • the aqueous polymer dispersion usually has a solids content of from 20 to 70% by weight, preferably from 40 to 65% by weight.
  • the dispersion according to the invention is used both for itself and with additives for coating metal sheets which serve for roofing or wall cladding.
  • additives may be: an aromatic ketone such as benzophenone according to DE-A 38 27 975 as a photoinitiator for the purpose of crosslinking under the action of electromagnetic radiation, or a water-soluble dihydric azide, according to DE-A 39 01 073, if the polymer have carbonyl groups - Monopolymers copolymerized
  • aqueous preparations used according to the invention may also contain crosslinking additives.
  • Such additives may be: aromatic see ketones, z.
  • alkyl phenyl ketones which optionally have one or more substituents on the phenyl ring, or benzophenone and substituted benzophenones as photoinitiators.
  • suitable photoinitiators are, for. B. from DE-A 38 27 975 and EP-A 417 568.
  • Suitable crosslinking compounds are also water-soluble compounds having at least two amino groups, for example dihydrazides of aliphatic dicarboxylic acids according to DE-A 39 01 073, when the copolymer contains copolymerized monomers containing carbonyl groups.
  • the aqueous preparations are used in the form of pigment and / or filler-containing preparations.
  • the total content of copolymer in the aqueous preparation is in the range of 10 to 60 wt .-%, preferably in the range of 20 to 50 wt .-%, the content of adjuvants in the range of 0.1 to 30 wt .-% and preferably in the range of 0.5 to 10 wt .-% and the content of fillers and / or pigments in the range of 0.1 to 60 wt .-% and in particular 0.2 to 50 wt .-%.
  • the amount of pigments and / or fillers is generally between 0.5 and 150 parts by weight, based on 100 parts by weight of copolymer in the aqueous preparation.
  • pigment-containing preparations in addition to the film-forming aids and the defoamers are preferably also a dispersant or wetting agent.
  • the aqueous dispersion of the polymer is used in pigmented form for the coating of metal sheets, which are used for roofing and wall cladding.
  • Typical white pigments are, for example, titanium dioxide, preferably in the rutile form, barium sulfate, zinc oxide or lithopone (zinc sulfide + barium sulfate).
  • the formulations may also contain colored pigments, for example yellow, red, brown and black iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurter green.
  • pigments are, for example, barium sulfate, talc, kaolin, feldspar, nepheline synenite, mica, calcium carbonate, dolomite, quartz powder and mixtures thereof. ⁇
  • the clearcoats and pigmented paints used according to the invention may contain further customary auxiliaries, such as, for example, As wetting agents, pot and film preservatives, Ver-thicker, defoamers, fungicides, algicides, flow promoters and cryoprotectants in the usual amounts.
  • auxiliaries such as, for example, As wetting agents, pot and film preservatives, Ver-thicker, defoamers, fungicides, algicides, flow promoters and cryoprotectants in the usual amounts.
  • the amount of dispersant used is 0.5 to 6, preferably 1 to 3 wt .-% based on the amount of monomers to be radically polymerized.
  • the application rate of the aqueous polymer preparation to be applied for preservation is 50 to 400 g / m 2 (calculated wet).
  • the order can be done in a conventional manner by spraying, filling, doctoring, rolling or pouring. It is essential that the method according to the invention can be used for single and double coating (wet-wet) of granulated or ungranulated metal sheets pre-primed with anti-corrosion coatings.
  • an emulsion was prepared from the following components:
  • Feed 1 and 3 started simultaneously. Feed 1 was metered in in the course of 1.5 h and then feed 2 in 1.5 h. Feed 3 was metered in over 3 hours. It was then 30 min. stirred and then within 1 h 1 1.7 g of a 10% wr. Solution of ieri-butyl hydroperoxide and 9.1 g of a 10% aq. Lsg. Of hydroxymethanesulfinic dosed. Subsequently, with 55.99 g of a 2% wr. NaOH neutralized, 10 min. stirred, the stirring speed reduced to 100 rpm and cooled. Thereafter, 2.6 g of a 5% aq. Hydrogen peroxide solution and 78.78 g of water was added. There were obtained 2674 g of a 49.9% dispersion.
  • an emulsion was prepared from the following components:
  • an emulsion was prepared from the following components:
  • Feed 1 and 3 started simultaneously. Feed 1 was metered in in the course of 1.5 h and then feed 2 in 1.5 h. Feed 3 was metered in over 3 hours. It was then 30 min. stirred and then within 1 h 1 1.7 g of a 10% wr. Solution of ieri-butyl hydroperoxide and 9.1 g of a 10% aq. Lsg. Of hydroxymethanesulfinic dosed. Subsequently, with 55.99 g of a 2% wr. NaOH neutralized, 10 min. stirred, the stirring speed reduced to 100 rpm and cooled. Thereafter, 2.6 g of a 5% aq. Hydrogen peroxide solution and 78.78 g of water. There were obtained 2674 g of a 49.9% dispersion.
  • Example dispersion (two-stage), according to the invention with monomers I, more hard phase In a polymerization vessel equipped with metering device and temperature control were charged:
  • an emulsion was prepared from the following components:
  • an emulsion was prepared from the following components:
  • Feed 1 and 3 started simultaneously. Feed 1 was metered in in 36 minutes and then feed 2 in 2 hours 24 minutes. Feed 3 was metered in over 3 hours. It was then 30 min. stirred and then within 1 h 1 1.7 g of a 10% wr. Solution of ieri-butyl hydroperoxide and 9.1 g of a 10% aq. Lsg. Of hydroxymethanesulfinic dosed. Subsequently, with 55.99 g of a 2% wr. NaOH neutralized, 10 min. stirred, the stirring speed reduced to 100 rpm and cooled. Thereafter, 2.6 g of a 5% aq. Hydrogen peroxide solution and 78.78 g of water was added. There were obtained 2674 g of a 49.7% dispersion. ⁇
  • an emulsion was prepared from the following components:
  • an emulsion was prepared from the following components:
  • an emulsion was prepared from the following components: Feed 1:
  • the initial charge was heated to 95 ° C. (external temperature, polymerization temperature 90 ° C., stirring speed 150 rpm). After 5 minutes, the feed was 1 and feed 2 started and both dosed in 2.5h. 30 min. stirred. With 54g 10% sodium hydroxide solution, the approach was neutralized.
  • the test is carried out with sheets only with the first color coat and with the complete set-up (paint coat, granules and final coat).
  • the steel sheet which is coated with an epoxy primer, is cured for at least 24 hours at room temperature (RT).
  • RT room temperature
  • the adhesion is tested at RT and after 24 hours of water storage.
  • the samples are frozen for 24 h at -20 ° C. Thereafter, a hammer test and the bending test with 180 ° bend takes place immediately.
  • Adhesion is rated on a scale of 1 - 5, where 1 represents optimum adhesion without irregularities and 5 a detachment without further mechanical influence.
  • cracking and flaking are also rated with a scale of 1-5.
  • the grade 1 here means practically no flaking and cracks and grade 5 a complete detachment at the test site.
  • the bending test takes place at -10 ° C.
  • the metal sheet is bent 180 ° C with the coating facing outwards. Thereafter, the adhesion of the coating to the substrate is evaluated, in particular in the region of the bend.
  • Hammer impact test (based on the impact test according to EN 1004b, but without notch and only manually with hammer)
  • a xenon test in accordance with DIN EN ISO 1 1341 (Cycle A) for paints is carried out and patterned off after every 500 hours.
  • coated metal sheets of 5 * 13cm in size are alternately illuminated alternately for 102 minutes and illuminated for 18 minutes, while the plates are moistened with a fine mist of water.
  • the relative humidity is set to 50% and the black standard temperature is at 65 ° C.
  • the irradiance corresponds to 60 W UV light at 300 - 400 nm or 0.51 W / (m 2 nm) at 340 nm light wavelength.
  • color changes and loss of gloss are assessed.
  • the color gloss is measured with a Glossmeter at 60 ° gloss before and after the weathering test.
  • dyes were prepared according to the following recipe:
  • the paints were customrak- on primed metal sheets with 300 ⁇ wet layer thickness.
  • the sheets were primed with an epoxy coating. Some of the sheets are dried for 3 hours in an oven at 40 ° C and then for 3 days at room temperature and then tested. The second part of the sheets is processed directly. In the still wet color, the granules are interspersed and knocked off. It takes place abruptly, the coating with a clear lacquer (130-180 g / m 2) based on a networked Reinacrylats (Acronal ® 8974) is then also dried in the same manner.
  • the coating to be tested was knife-coated with an Erichsen film applicator (200 ⁇ wet) on a 38 ⁇ 7 cm glass plate. After drying for 1 d at room temperature or for 30 min at 60 ° C. and 1 d room temperature, three measured values were blotted on three places of the glass plate. The measurement was carried out according to König (DIN EN ISO 1522). Measurements were taken after 1d, 4d, 6d and 14d.

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  • Polymers & Plastics (AREA)
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  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne l'utilisation de dispersions aqueuses de produits de polymérisation en plusieurs étapes, pouvant être obtenues par une polymérisation initiée par voie radicalaire en émulsion aqueuse, comprenant une phase molle et une phase dure et un rapport de phase dure à phase molle de 25 à 95 % en poids à 75 à 5 % en poids. La température de transition vitreuse (Tg) de la phase molle est de -30 à 0 °C et celle de la phase dure, en tant que deuxième étape, entre 20 et 60 °C. Les dispersions contiennent au moins un monomère de formule générale (I), dans laquelle les variables ont la signification suivante : n = 0 à 2, R1, R2, R3 = indépendamment les uns des autres, hydrogène ou un groupe méthyle, X = O ou NH, Y = H, un métal alcalin, NH4, et elles sont utilisées pour le revêtement de tôles métalliques.
EP13726551.8A 2012-06-05 2013-06-04 Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques Withdrawn EP2855610A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13726551.8A EP2855610A1 (fr) 2012-06-05 2013-06-04 Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12170841 2012-06-05
PCT/EP2013/061504 WO2013182571A1 (fr) 2012-06-05 2013-06-04 Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques
EP13726551.8A EP2855610A1 (fr) 2012-06-05 2013-06-04 Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques

Publications (1)

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EP2855610A1 true EP2855610A1 (fr) 2015-04-08

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EP13726551.8A Withdrawn EP2855610A1 (fr) 2012-06-05 2013-06-04 Utilisation de dispersions de produit de polymérisation en plusieurs étapes pour le revêtement de tôles métalliques

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Country Link
US (1) US9617447B2 (fr)
EP (1) EP2855610A1 (fr)
JP (1) JP6238972B2 (fr)
KR (1) KR20150023549A (fr)
CN (1) CN104540906B (fr)
AU (1) AU2013273573B2 (fr)
BR (1) BR112014030294A2 (fr)
CA (1) CA2875440A1 (fr)
MX (1) MX2014014975A (fr)
MY (1) MY171387A (fr)
NZ (1) NZ702367A (fr)
PH (1) PH12014502719A1 (fr)
RU (1) RU2674410C2 (fr)
WO (1) WO2013182571A1 (fr)
ZA (1) ZA201409467B (fr)

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Publication number Priority date Publication date Assignee Title
KR20150023549A (ko) * 2012-06-05 2015-03-05 바스프 에스이 금속 시트를 코팅하기 위한 다-단 중합물 분산액의 용도
EP2685775B1 (fr) 2012-07-12 2020-05-13 Alcatel Lucent Acquisition de ressources communes

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PH12014502719B1 (en) 2015-02-02
MY171387A (en) 2019-10-10
AU2013273573A1 (en) 2015-01-15
BR112014030294A2 (pt) 2017-06-27
JP2015526536A (ja) 2015-09-10
JP6238972B2 (ja) 2017-11-29
RU2674410C2 (ru) 2018-12-07
CN104540906A (zh) 2015-04-22
RU2014153985A (ru) 2016-08-10
CN104540906B (zh) 2017-04-05
NZ702367A (en) 2016-09-30
WO2013182571A1 (fr) 2013-12-12
PH12014502719A1 (en) 2015-02-02
MX2014014975A (es) 2015-08-05
KR20150023549A (ko) 2015-03-05
US20150104658A1 (en) 2015-04-16
AU2013273573B2 (en) 2016-05-26
CA2875440A1 (fr) 2013-12-12
ZA201409467B (en) 2016-09-28
US9617447B2 (en) 2017-04-11

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