WO2011069891A1 - Procédé de fabrication de revêtements structurés au niveau de la charge - Google Patents

Procédé de fabrication de revêtements structurés au niveau de la charge Download PDF

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WO2011069891A1
WO2011069891A1 PCT/EP2010/068787 EP2010068787W WO2011069891A1 WO 2011069891 A1 WO2011069891 A1 WO 2011069891A1 EP 2010068787 W EP2010068787 W EP 2010068787W WO 2011069891 A1 WO2011069891 A1 WO 2011069891A1
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component
weight
average particle
polymer
particle diameter
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PCT/EP2010/068787
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German (de)
English (en)
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Uwe Hartnagel
Albert Budiman Sugiharto
Frank Wilco Bartels
Thomas Servay
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Basf Se
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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
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate

Definitions

  • the invention relates to coatings having a periodic structure of the surface potential on the basis of polymer latices and to a process for producing coatings having a periodic structure of the surface potential, comprising the following steps:
  • step (b) mixing the polymer dispersions of step (a) and optionally other components wherein the weight ratio of component A to component B in the mixture is 95 to 5 to 60 to 40 based on solids content; (c) applying the mixture of step (b) on a surface, preferably a substrate,
  • step (d) solidifying the mixture of step (c) to form a coating
  • the invention relates to the coatings thus obtainable and the use of coatings having a periodic structure of the surface potential on the basis of polymer latexes to reduce deposit formation.
  • Coatings or films which are obtained starting from dispersion mixtures having different particle sizes are known per se.
  • EP 1 685 859 A2 discloses film-forming compositions containing polymer particles of different sizes and glass transition temperatures. The resulting films are particularly suitable as a wound dressing. However, the resulting films are not patterned.
  • EP 0 612 805 A2 discloses film-forming compositions which are obtained starting from mixtures of polymer dispersions. The respective polymer dispersions differ with respect to the glass transition temperature and particle size of the polymer particles. However, the polymer films or polymer layers obtained therefrom have no surfaces which are periodically structured with respect to the surface potential.
  • deposits are understood to mean the formation or adhesion of deposits (deposits) on the surface of the coating. These are in particular lime deposits to be understood, which arise by evaporation of water. Agents which inhibit the formation of the abovementioned deposits are known to the person skilled in the art as "antiscalants”.
  • the corresponding film-forming compositions should have a wide range of applications and can be used, for example, in paints.
  • the resulting coatings should have a low tendency to scale adhesion, especially with regard to limescale adhesion. Once formed, especially limescale, it should be easy to detach from the surface, e.g. by rinsing.
  • the present invention relates to coatings having a periodic structure of the surface potential based on polymer latices and to a process for producing coatings having a periodic structure of the surface potential, comprising the following steps in the order of abcde:
  • step (b) mixing the polymer dispersions of step (a) and optionally other components wherein the weight ratio of component A to component B in the mixture is 95 to 5 to 60 to 40 based on solids content; (c) applying the mixture of step (b) on a surface, preferably a substrate,
  • step (d) solidifying the mixture of step (c) to form a coating
  • surface potential in the context of the present invention has the meaning according to IUPAC Compendium of Chemical Technology, 2nd Edition (1997), according to which surface potential is to be understood as the drop in the electrical potential at the surface of the coating
  • the surface potential of the coatings according to the invention is periodic Therefore, the surface potential has a local value (for a given location on the surface of the coating) and results in its local spatial dimension from the dispersion particles used.
  • the term "periodic structure of the surface potential” denotes a substantially recurring spatial sequence of regions of different surface potential .
  • the spatial dimension of the periodically repeating structure is preferably in the range from 1 to 1000 nm (hereinafter referred to as "nanostructured") .
  • the spatial dimension of the periodically recurring structure is characterized in particular by the size of the particles of components A and B.
  • periodic structure of the surface potential is used in the context of the present invention synonymously with the term “charge structure” or “charge-structured.”
  • the charge structure is based on local and periodically recurring different charge states (positive, neutral, negative) or on different states of charge states
  • a charge structure in the sense of the present invention is present when the difference of the surface potentials of the periodically recurring regions and thus of the components A and B is at least 20 mV
  • the difference of the surface potentials is at least 40 mV, in particular at least 60 mV, particularly preferably at least 80 mV, very particularly preferably at least 100 mV.
  • the charge structure is based on a spatially recurring sequence of positive and negative surface potentials or on a spatially recurring sequence of positive and substantially neutral surface potentials or on a spatially recurring sequence of negative and substantially neutral surface potentials based. It is particularly preferred if the charge structure is based on a spatially recurring sequence of positive and negative surface potentials.
  • the surface potentials are determined spatially resolved in the context of the present invention by means of Kelvin probe force microscopy (Kelvin probe force microscopy). The method is known to the person skilled in the art and is explained, for example, in Advanced Materials, 2006, 18, 145-164. Using Kelvin probe force microscopy, the local potential of the sample surface can be imaged with high resolution.
  • a conductive cantilever tip is used as a metallic probe to determine the potential difference between the tip and the sample surface.
  • the reference material is a gold substrate.
  • the electrostatic forces acting on the tip are used as a control signal during the scanning of the sample. h., one
  • Control circuit minimizes the interaction between a conductive AFM tip and the Sample surface by compensating the potential difference with an external DC voltage.
  • polymer dispersion denotes polymer particles dispersed in a liquid phase, which is preferably water
  • the polymer dispersions of components A and B used are stable, i.e. invariable over a period of at least 24 hours, in particular no coagulation occurs.
  • the determination of the weight-average particle diameter is basically carried out by means of analytical ultracentrifuge. Corresponding methods are known to the person skilled in the art. By weight-average particle diameter is within the scope of the present invention as determined by the method of the analytical ultracentrifuge weight-average D W 5o value understood (see. This SE Har- ding 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. Switzerland Switzerland 1992, Chapter 10, Analysis of Polymer Dispersions with Eight Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Switzerland Switzerland 1992, Chapter 10, Analysis of Polymer Dispersions with Eight Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Switzerland Switzerland pp. 147-175).
  • narrow particle size distribution is to be understood as meaning the ratio of the weight-average particle diameter D w determined by the method of the analytical ultracentrifuge and the number-average particle diameter DN 50 [D W 5O / DN 50] ⁇ 2.0, preferably ⁇ 1.5 , particularly preferably ⁇ 1, 2 and in particular ⁇ 1, 1.
  • the mixture of components A and B resulting from step (b) is a film-forming composition in the context of the present invention.
  • film-forming composition is meant such a composition which forms a (polymer) film under suitable conditions upon removal of the liquid phase, preferably with crosslinking of the polymer particles.
  • film and the term “coating” is used interchangeably in the context of the present invention.
  • step (a) the provision of at least one first polymer dispersion as component A and at least one second polymer dispersion as component B takes place, wherein the components A and B are used in their chemical compositions. and wherein the ratio of the weight average particle diameter of the component A to that of the component B in the mixture of 3 to 1 to 15 to 1, the weight average particle diameter of the component A of 75 to 1000 nm and the weight average particle diameter of the component B of 10 to 200 nm.
  • the ratio of the weight average particle diameter of component A to that of component B is from 4: 1 to 10: 1, and more preferably from 4.5: 1 to 7: 1.
  • step (b) of the method according to the invention is carried out in the context of step (b) of the method according to the invention while avoiding coagulation.
  • the person skilled in the art thus selects the polymer dispersions of components A and B in such a way that coagulation is avoided.
  • the components A and B have no opposite surface charges in the inserted state. This avoids coagulation in step (b).
  • the surface charges of components A and B can be controlled by charges in the polymer itself, optionally by varying the pH via protonation or proton elimination, or by using corresponding charged or uncharged emulsifiers.
  • the weight-average particle diameter of component B is preferably from 25 to 150 nm, in particular from 35 to 90 nm.
  • the weight-average particle diameter of component A is preferably from 100 to 900 nm, in particular from 150 to 500 nm.
  • weight-average particle diameters of components A and B within the size and quantity ratios according to the invention, good properties with respect to the inhibition of the formation on limescale deposits are achieved, while at the same time good processability of the film-forming compositions. For example, use in paints becomes possible.
  • the favorable structure is in particular by more or less isolated and relatively large dispersion particles of the component A, which are nevertheless only slightly separated from each other, characterized.
  • the relatively large dispersion particles of component A are separated from each other in the polymer film by the filmed small particles.
  • the particle size distribution of the dispersions used in the present invention is narrow. This results in a particularly uniform and effective structure.
  • the polymer dispersions of components A and B are preferably obtainable by free-radically initiated emulsion polymerization, in particular emulsion polymerization in the aqueous phase.
  • the preparation of the dispersions of components A and B used according to the invention can be carried out in each case by a single-stage or by an at least two-stage aqueous radical emulsion polymerization.
  • a first polymer is first prepared in at least one step and a second polymer is prepared in at least one further step in the presence of the first polymer dispersion.
  • a polymer dispersion is often referred to as a polymer dispersion.
  • the terms "polymer dispersions" and “polymer latexes” are also synonymous.
  • the resulting polymer dispersion preferably has a core-shell structure in which the core of the first polymer is formed and the shell of the second polymer. Corresponding methods are known to the person skilled in the art.
  • the components A and B differ with respect to the weight-average particle diameter and in their chemical composition.
  • the resulting local surface potential of the coatings according to the invention is significantly influenced by the charge state of the monomers incorporated in the polymer dispersion. It is obvious to a person skilled in the art that the surface charges of a polymer dispersion and thus the resulting local surface potential in the corresponding coating in the case of polymer particles having a core-shell structure are controlled by the surface charge of the outer layer.
  • Permanently uncharged monomers (hereinafter referred to as type pu) which do not have a charged functional group in the pH range from 1 to 14.
  • a positively charged functional group such as a quaternary N atom
  • step (e) the charge of an acidic or basic group will depend on the pH.
  • the chemical reaction according to step (e) goes beyond the mere variation of the pH.
  • at least two monomers are copolymerized in each polymer dispersion in components A and B (hereinafter referred to as "comonomers").
  • the monomers in the polymer dispersions and in the coatings are in substantially reacted (polymeric) form
  • reference to monomers is therefore to be understood as referring to the corresponding monomer building blocks.
  • Preferred monomers of the pu type are those based on acrylates.
  • Monomers of the pu type are in particular esters based on
  • a 3 to 6 C-atoms in particular a 3 or 4 C-containing ⁇ , ⁇ -monoethylenically unsaturated mono- or dicarboxylic acid, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid and
  • an alkanol having 1 to 18 C atoms preferably an alkanol having 1 to 8 C atoms and particularly preferably an alkanol having 1 to 4 C atoms, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol , 2-methylpropanol-1, tert-butanol, n-pentanol, 3-methylbutanol-1, n-hexanol, 4-methylpentanol-1, n-heptanol, 5-methylhexanol-1, n-octanol, 6-methyl-heptanol -1, n-nonanol, 7-methyloctanol-1, n-decanol, 8-methylnonanol-1, n-dodecanol, 9-methyldecanol-1 or 2-ethylhexanol-1.
  • esters can be used.
  • suitable pu type monomers have at least two nonconjugated ethylenically unsaturated double bonds.
  • monomers containing two vinyl radicals, two vinylidene radical-containing monomers and two alkenyl radicals having monomers are particularly advantageous.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-Butylenglykoldiacrylat, 1, 4- Butylene glycol diacrylates and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol di-methacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide, Cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacryl
  • Suitable monomers of the pu type are in particular 3 to 6 carbon atoms having ⁇ , ⁇ -monoethylenically unsaturated amides of mono- or dicarboxylic acids such as in particular amides of acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid or acrylamide or methacrylamide or their mixtures.
  • ⁇ , ⁇ -ethylenically unsaturated compounds as monomers of the pu type: vinylaromatic monomers, preferably styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, vinyl halides, such as vinyl chloride or vinylidene chloride, esters of vinyl alcohol and 1 to Monocarboxylic acids having 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl steate, nitriles of ⁇ , ⁇ -mono- or diethylenically unsaturated carboxylic acids, such as acrylonitrile, methacrylonitrile, fumaronitrile, maleic acid dinitrile and 4-8 C atoms having conjugated dienes, such as 1, 3-butadiene and isoprene, moreover, N-vinylpyrrolidone, 2-vinyl-pyridine, 4-vin
  • Suitable monomers of the pu type have at least one hydroxyl, N-methylol or carbonyl group.
  • methacrylic acid and acrylic acid C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate , Of course, mixtures of the aforementioned monomers can be used.
  • Suitable monomers of the type pa are, in particular, ⁇ , ⁇ -monoethylenically unsaturated mono- or dicarboxylic acids having 3 to 6 C atoms, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid.
  • Suitable monomers of the type pa are also in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid and their water-soluble salts. Of course, mixtures of the aforementioned monomers can be used. It is known to the person skilled in the art that the acid groups are in equilibrium with the deprotonated anionic form. The higher the pH, the higher the proportion of the deprotonated anionic form.
  • polymer dispersions used in the process according to the invention in the context of component A or in the context of component B have such functional groups which are converted in step (e) such that a charge-structured surface is formed.
  • Preferred monomers of the type inter alia are in particular ⁇ , ⁇ -ethylenically unsaturated compounds having a carboxy group which is esterified with a tert-butyl group, in particular tert-butyl acrylate and tert-butyl methacrylate.
  • Preferred monomers of the type uk are ⁇ , ⁇ -ethylenically unsaturated compounds which contain an epoxide group as functional group, in particular acrylates with epoxide groups, more preferably glycidyl acrylate and / or glycidyl methacrylate.
  • Preferred polymer dispersions of components A and B each comprise at least two comonomers. It is preferred if at least one comonomer is of the pu type. At least one further comonomer is preferably selected such that either component A or component B is permanently charged, ie at least one comonomer of the polymer dispersions A or B is of the type pk or pa.
  • one of the components A or B is permanently charged, in particular comprises comonomers of the type pu and pa or pu and pk
  • the in each case other component B or A comprises the comonomers pu and uk or pu and others, so that a charge-structured coating is formed after the chemical conversion of the monomers of the type ua or uk, but on the other hand during the mixing of the two components A and B no opposite surface charges are present.
  • either component A or component B comprises comonomers of the type pu and pk and at the same time the respective other component B or A comprises comonomers of the type pu and ao.
  • either component A or component B comprises comonomers of the type pu and pa and at the same time the respective other component B or A comprises comonomers of the type pu and uk.
  • the aforementioned monomers of the type ua and uk have in common their property that functional groups charged in the coating by the subsequent reaction in the context of step (e) are produced in the coating.
  • a surface charge is generated in the respective spatial area, which is preferably opposite to the charge in the region of the respective other component.
  • the corresponding functional groups be present either in component A or in component B, but not simultaneously in A and B in equal or similar amounts.
  • the monomers are added to the aqueous reaction medium in the form of a mixture.
  • the addition of the monomers takes place in the form of an aqueous monomer emulsion.
  • the further monomers are advantageously added to the aqueous reaction medium continuously in one or more portions with constant or varying flow rates.
  • the monomers are added to the aqueous reaction medium in the form of a mixture.
  • the addition of the monomers takes place in the form of an aqueous monomer emulsion.
  • dispersants are also used which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus ensure the stability of the aqueous polymer dispersion produced.
  • Suitable dispersants are both the protective colloids commonly used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylpyrrolidone, Vinylcaprolactam, N-vinylcarbazole, 1 - vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, acrylates containing amine groups, methacrylates, acrylamides and / or methacrylamides containing homopolymers and copolymers.
  • protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 41 1 to 420.
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
  • the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • cationic emulsifiers while anionic and cationic emulsifiers are usually incompatible with each other.
  • An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.
  • Nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36).
  • Lutensol ® A grades C 2 C 4 fatty alcohol EO units: 3 to 8
  • Lutensol ® AO-marks C13C15-oxo-alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT CieCis ethoxylate fatty alcohol, EO: 1 1 to 80
  • Lutensol ON ® brands Cao-oxo alcohol ethoxylates, EO degree: 3 to 1: 1
  • ® Lutensol tO brands ds-oxo alcohol ethoxylates, EO grade: 3 to 20
  • Typical anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 to C 12), of alkyl sulfonic acids (alkyl radical: C 12 to C 18) and of alkylaryl sulfonic acids (alkyl radical: C 9 to C 18).
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Particularly advantageous are compounds (I) in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ® 2A1 (trademark of the Dow Chemical Company).
  • the compounds (I) are well known, for example, from US-A 4,269,749, and commercially available.
  • Suitable cationic emulsifiers are generally primary, secondary, tertiary or quaternary ammonium salts containing C 6 -C 18 -alkyl, -alkylaryl or heterocyclic radicals, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amines. noxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethyl ammonium) ethylparaffinklar, N-cetylpyridinium sulfate, N-laurylpyridinium and N-cetyl-N, N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini-surfactant N, N '- ( lauryl) ethylendiamindisulfat, ethoxylated tallow alkyl-N-methyl ammonium sulfate and ethoxylated oleylamine
  • BASF AG about 12 ethylene oxide.
  • Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • anionic counterparts groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and Carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organo-sulfonic acids, such as methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, tetrafluoroborate, tetraphenylborate, tetrakis (pentafluoro-) phenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • nucleophilic such as perchlorate, sulfate, phosphate
  • the emulsifiers preferably used as dispersants are advantageously in a total amount of> 0.005 and ⁇ 10 wt .-%, preferably> 0.01 and ⁇ 5 wt .-%, in particular> 0.1 and ⁇ 3 wt .-%, respectively based on the total amount of monomers used.
  • the total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often> 0.1 and ⁇ 10% by weight and frequently> 0.2 and ⁇ 7% by weight, in each case based on the total amount of monomer.
  • anionic and / or nonionic emulsifiers and particularly preferably anionic emulsifiers as dispersants.
  • the release of the free-radically initiated aqueous emulsion polymerization takes place by means of a free-radical polymerization initiator (free-radical initiator).
  • free-radical initiator can be both peroxides and azo compounds.
  • redox initiator systems come into consideration.
  • peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, and also dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulphites, for example potassium and / or sodium sulphite, alkali hydrogen sulphites, for example potassium and / or sodium hydrogen sulphite, alkali metal bisulphites, for example potassium and / or sodium metabisulphite.
  • alkali metal sulphites for example potassium and / or sodium sulphite
  • alkali hydrogen sulphites for example potassium and / or sodium hydrogen sulphite
  • alkali metal bisulphites for example potassium and / or sodium metabisulphite.
  • the amount of the radical initiator used based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .
  • the total amount of the radical initiator is initially charged in the aqueous reaction medium.
  • the reaction temperature for the free-radical aqueous emulsion polymerization is the entire range from 0 to 170 ° C into consideration. As a rule, temperatures of 50 to 120 ° C, often 60 to 1 10 ° C and often 70 to 100 ° C are used.
  • the free-radical aqueous emulsion polymerization can be carried out at a pressure of less than or equal to 1 bar (absolute), so that the polymerization temperature can exceed 100 ° C. and can be up to 170 ° C.
  • volatile monomers such as 2-methyl-1-butene-1, 3-methylbutene-1, 2-methylbutene-2, butadiene, butene-2, 2-methylpropene, propene, ethylene or vinyl chloride are polymerized under elevated pressure.
  • the pressure may be 1, 2, 1, 5, 2, 5, 10, 15, 50, 100 bar or even higher values.
  • pressures 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free-radical aqueous emulsion polymerization is advantageously carried out at 1 atm (1:01 bar absolute) under an inert gas atmosphere, such as under nitrogen or argon.
  • the aqueous reaction medium may in principle also comprise, in minor amounts, water-soluble organic solvents, such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • water-soluble organic solvents such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • free-radical chain compounds in order to reduce or control the molecular weight of the polymers obtainable by the polymerization.
  • These are essentially aliphatic and / or araliphatic halogen compounds, such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylenedichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic Thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-
  • the total amount of radical chain transferring compounds optionally used in the preparation of the polymer dispersions, based on the total amount of monomers, is generally ⁇ 5% by weight, often ⁇ 3% by weight and frequently ⁇ 1% by weight. It is advantageous if a partial or total amount of the optionally used radical chain-transmitting compound is fed to the reaction medium before the initiation of the free-radical polymerization. In addition, a partial or total amount of the radical chain-transferring compound may advantageously also be added to the aqueous reaction medium together with the monomers during the polymerization.
  • the free-radically initiated aqueous emulsion polymerization in the presence of a polymer seed for example in the presence of 0.01 to 3 wt .-%, often from 0.02 to 2 wt .-% and often from 0.04 to 1, 5 wt. % of a polymer seed, in each case based on the total amount of monomers.
  • a polymer seed is used in particular when the particle size of the polymer particles to be prepared by free-radical aqueous emulsion polymerization is to be specifically adjusted (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).
  • a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters D w ⁇ 100 nm, frequently> 5 nm to ⁇ 50 nm and often> 15 nm to ⁇ 35 nm.
  • the polymer seed is used in the form of an aqueous polymer dispersion.
  • the aforementioned amounts are based on the polymer solids content of the aqueous Polymersaatdispersion; they are therefore given as parts by weight of polymer seed solids, based on the total amount of monomers. If a polymer seed is used, it is advantageous to use a foreign polymer seed.
  • a foreign polymer seed is understood to mean a polymer seed which in one Separate reaction step was prepared and their monomeric composition of the polymer prepared by the free-radically initiated aqueous emulsion polymerization is different, but this means nothing else than that used for the preparation of Fremdpolymersaat and for the preparation of the aqueous polymer dispersion different monomers or monomer mixtures of different composition become.
  • the production of a foreign polymer seed is subject to man and usually carried out such that a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel are introduced and at reaction temperature, a sufficient amount of polymerization initiator is added.
  • the total amount of foreign polymer seed may be presented in the reaction vessel prior to the beginning of the addition of the monomers used to prepare the polymer dispersions of components A and B. However, it is also possible to introduce only a subset of the foreign polymer seed prior to the beginning of the addition of the monomers in the reaction vessel and to add the remaining amount during the polymerization. If necessary, however, it is also possible to add the total amount of polymer seed in the course of the polymerization.
  • the total amount of Fremdpolymersaat is submitted before the beginning of the addition of the monomers in the reaction vessel.
  • Aqueous polymer dispersions preferred for components A and B usually have a polymer solids content of> 10 and ⁇ 80% by weight, preferably> 15 and ⁇ 70% by weight and often> 20 and ⁇ 50% by weight, in each case based on the aqueous Polymer dispersion, on.
  • the polymer solids contents of components A and B are particularly preferably from 15 to 40% by weight.
  • the polymer dispersions from step (a) and optionally further components are mixed according to step (b), the weight ratio of component A to component B being 95: 5 to 60: 40, based on the solids content.
  • the weight Ratio of the components A to B in the mixture thus obtained from 90 to 10 to 70 to 30 (each based on the solids content).
  • topcoat Corresponding formulations for coatings (topcoat) are known to the person skilled in the art, for example, from R. Schwalm: “UV Coatings: basics, recent developments and new applications", Elsevier (2007), in particular pages 140 to 145.
  • Formulations for paints are One skilled in the art, for example, from R. Baumstark, M. Schwartz: “Dispersions for architectural paints: acrylate systems in theory and practice", Curt R. Vincentz Verlag (2001), in particular pages 52 to 54 and 217 to 218, known.
  • step (c) of the process according to the invention the mixture of step (b) is applied to a surface, preferably a substrate.
  • Suitable substrates are in particular plastics, steel, ceramics, glass and concrete.
  • the term surface includes any suitable surface-having base for the coating.
  • the application is carried out on a substrate.
  • the application takes place on a surface in the construction sector, in particular a wall, wherein the application takes place within the scope of a formulation, in particular as a facade paint.
  • the application can be carried out by customary application and / or coating methods known to the person skilled in the art. Suitable methods are, for example, doctoring, brushing, dip-coating or spray-coating. Criteria for the choice of a suitable application method and the determination of the specific parameters of the application are known per se to the person skilled in the art and depend in a known manner on the type and shape of the surface and the specific properties of the mixture to be applied.
  • step (d) of the process according to the invention the solidification of the mixture from step (c) takes place to form a coating.
  • the term "solidification” In this case, the formation of a solid, ie coherent structure, which is already to be regarded as a coating, is not to be understood as meaning that liquid residual components in the coating are excluded.
  • the solidification of the mixture takes place in the presence of the substrate with at least partial removal, especially extensive removal of the liquid phase (“drying").
  • drying extensive removal of the liquid phase
  • the filming of the particles of component B with one another is preferred. Corresponding methods are known to the person skilled in the art.
  • the solidification of the mixture according to step (d) can be carried out in particular at room temperature or at elevated temperature, for example at 25 ° C to 100 ° C.
  • the drying is at room temperature.
  • the pressure applied during drying can vary over a wide range and correlates in a known manner with the rate of drying.
  • the water content of the ambient air can vary. Usually it is dried in air.
  • the duration of the drying may vary over a wide period of time depending on the aforementioned parameters, for example from 10 minutes to 24 hours. The duration of the drying also depends on the layer thickness.
  • Step (d) may proceed smoothly in step (e), i. H. Step (d) may not necessarily have resulted in complete drying before step (e) is performed. By definition, however, the coating resulting from step (d) must have at least one coherent solid structure.
  • step (e) the further chemical conversion of the coating takes place within the scope of step (e), with the result that a periodic structure of the surface potential is obtained.
  • step (e) in the context of step (e), the change in the surface charge of one of the components A or B from neutral to positive or from neutral to negative.
  • the type and conditions of the chemical reaction according to step (e) are dependent on the type of monomers used, in particular of which was used under the conditions of step (e) reactive type monomer (ua or uk).
  • the further chemical reaction according to step (e) takes place under the action of an elevated temperature and elimination of a molecule. The prerequisite for this is the use of a corresponding monomer of the type ua or uk (in particular type ua), which is thermally convertible into a charged monomer unit.
  • one of the dispersions A or B comprises tert-butyl acrylate as comonomer.
  • the removal of isobutene by applying an elevated temperature of 150 to 300 ° C, in particular from 180 ° C to 250 ° C. The time varies with the temperature and is from 10 minutes to 24 hours. If other monomers than tert-butyl acrylate are used as monomer of the type ua or uk, which can be converted thermally into a monomer unit with charged functional group, the skilled person adjusts the temperature ranges and time periods suitable for the cleavage by appropriate preliminary experiments.
  • the further chemical reaction according to step (e) takes place under the action of a chemical compound, in particular a nucleophilic compound, wherein the further chemical reaction particularly preferably comprises the opening of epoxide groups.
  • a chemical compound in particular a nucleophilic compound
  • the further chemical reaction particularly preferably comprises the opening of epoxide groups.
  • the prerequisite for this is the use of a corresponding type of monomer ua or uk as described above (in particular type uk).
  • the further reaction by the action of a chemical compound can in principle be carried out by means of any form of contacting with the chemical compound.
  • the further chemical reaction is carried out by spraying the solidified coating with the chemical compound.
  • the appropriate substrate or polymer film is preferably (preferably sprayed) at room temperature with a suitable nucleophile during step (e).
  • a suitable nucleophile for example, the reaction between amines and epoxide groups takes place very rapidly and quantitatively even at room temperature.
  • the epoxide ring is opened by the amine and an amine noalcohol formed.
  • the resulting tertiary amine is protonated and thus cationically charged.
  • step (e) outweigh the few opposing charges which originate from superficially adsorbed charged emulsifiers or protective colloids or copolymerized charged groups from the initiator.
  • a further subject of the present invention are the coatings obtainable according to the process according to the invention and the use of the coatings according to the invention for the reduction of deposit formation, in particular for the reduction of quench deposits on surfaces which come into contact with water.
  • the present invention relates to the use of coatings having a periodic structure of surface potential to reduce deposit formation.
  • the coatings are obtained by a process comprising the steps of:
  • step (b) mixing the polymer dispersions from step (a) and optionally further components, wherein the weight ratio of component A to component B relative to the solids content is from 95: 5 to 60: 40,
  • step (c) applying the mixture from step (b) to a surface, preferably a substrate,
  • step (d) solidifying the mixture of step (c) to obtain a coating
  • Feed 1 was metered in evenly over 2 hours. Feed 3 was metered in evenly over 4 hours. Feed 1 was an aqueous emulsion prepared from 448.50 g of deionized water, 0.75 g of Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative), 238.50 g of n-hexane.
  • Feed 3 was a solution of 90.00 g deionized water and 3.00 g Azostarter V-50 (2-2 ' azobis (2-methylpropionamidine) dihydrochloride, from Wako). After the end of feed 1, feed 2 was started after 30 minutes and metered in uniformly over one hour. Feed 2 was an aqueous emulsion prepared from 225.00 g of deionized water, 0.75 g of Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative, trademark of BASF SE) and 60.00 g of tert-butyl acrylate.
  • Azostarter V-50 2-2 ' azobis (2-methylpropionamidine) dihydrochloride
  • the aqueous polymer dispersion obtained had a solids content of 19.1% by weight (weight-average particle diameter 380 nm).
  • a mixture of 450.0 g deionized water and 60.00 g Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative) was heated to 85 ° C under a nitrogen atmosphere under heating / cooling. For this purpose, the partial amount of 106.20 g of feed 1 was added. For this purpose, the portion of 9.30 g of feed 2 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 2 were started. Feed 1 was added uniformly over 3 hours. Feed 2 was metered in evenly over 4 hours.
  • Feed 1 was an aqueous emulsion prepared from 747.00 g deionized water, 15.00 g Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative), 149.25 g styrene, 149.25 g, n-butyl acrylate and 1, 50 g of allyl methacrylate.
  • Feed 2 was a solution of 90.00 g deionized water and 3.00 g azo starter V-50. After the end of feed 2, the mixture was stirred at 85 ° C. for a further 60 minutes and the reaction mixture was then cooled to room temperature. cools. The aqueous polymer dispersion obtained had a solids content of 19.5% by weight (weight-average particle diameter 53 nm).
  • a mixture of 450.0 g deionized water and 60.00 g Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative) was heated to 85 ° C under a nitrogen atmosphere under heating / cooling.
  • 78.07 g of feed 1 was added at a predetermined temperature.
  • 28.88 g of feed 3 were added.
  • feed 1 and feed 3 were started.
  • Feed 1 was metered in evenly over 2 hours.
  • Feed 3 was metered in evenly over 4 hours.
  • Feed 1 was an aqueous emulsion prepared from 525.75 g of deionized water, 15.00 g of Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative), 238.50 g of n-butyl acrylate and 1.50 g of allyl methacrylate.
  • Feed 3 was a solution of 90.00 g deionized water and 3.00 g Azostarter V-50. After the end of feed 1, feed 2 was started after 30 minutes and metered in uniformly over one hour.
  • Feed 2 was an aqueous emulsion prepared from 225.00 g of deionized water, 3.75 g of Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative, trademark of BASF SE) and 60.00 g of tert-butyl acrylate. After the end of feeds 2 and 3, the mixture was stirred at 85 ° C. for a further 60 minutes and the reaction mixture was subsequently cooled to room temperature. The aqueous polymer dispersion obtained had a solids content of 19.6% by weight (weight-average particle diameter 44 nm).
  • Example 4 Example 4:
  • Heating / cooling device was heated to 85 ° C 450.0 g of deionized water under a nitrogen atmosphere. For this purpose, the partial amount of 24.35 g of feed 1 was added. For this purpose, after stirring for 5 minutes at a given temperature, the partial amount of 9.30 g of feed 2 was added. After 15 minutes, feed 1 and feed 2 were started. Feed 1 was added uniformly over 3 hours. Feed 2 was metered in evenly over 4 hours.
  • Feed 1 was an aqueous emulsion prepared from 672.75 g of deionized water, 1.13 g of Lipamin® OK (a 37% solution of an o-methylated fatty amine derivative), 149.25 g of styrene, 149.25 g of n-butyl acrylate and 1.50 g of allyl methacrylate.
  • Feed 2 was a solution of 90.00 g deionized water and 3.00 g Azostarter V-50. After the end of the feed 2 was stirred for a further 60 minutes at 85 ° C and the reaction mixture was then cooled to room temperature.
  • the aqueous polymer dispersion obtained had a solids content of 19.1% by weight (weight-average particle diameter 395 nm).
  • a mixture of 450.0 g deionized water and 60.00 g Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative) was heated to 85 ° C under a nitrogen atmosphere under heating / cooling. For this purpose, the partial amount of 107.70 g of feed 1 was added. For this purpose, the portion of 9.30 g of feed 2 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 2 were started. Feed 1 was added uniformly over 3 hours. Feed 2 was metered in evenly over 4 hours.
  • Feed 1 was an aqueous emulsion prepared from 747.00 g deionized water, 15.00 g Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative), 238.50 g styrene, 75.00 g quaternized.
  • 2- (dimethylaminoethyl acrylate Feed 2 was a solution of 90.00 g of deionized water and 3.00 g of Azostarter V-50 After the end of feed 2, the mixture was stirred at 85 ° C. for a further 60 minutes and the reaction mixture was then taken up in vacuo
  • the aqueous polymer dispersion obtained had a solids content of 20.4% by weight (weight-average particle diameter 65 nm).
  • Heating / cooling device a mixture of 450.0 g of deionized water and 60.00 g of Lipamin® OK (a 37% solution of an oxyethylated fatty amine derivative) was heated under nitrogen atmosphere to 85 ° C. For this purpose, the partial amount of 106.20 g of feed 1 was added. For this purpose, the portion of 9.30 g of feed 2 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 2 were started. Feed 1 was added uniformly over 3 hours. Feed 2 was metered in evenly over 4 hours.
  • Lipamin® OK a 37% solution of an oxyethylated fatty amine derivative
  • Feed 1 was an aqueous emulsion prepared from 739.50 g of deionized water, 15.00 g of Lipamin® OK, 132.75 g of n-butyl acrylate, 132.75 g of styrene, and 37.50 g of quaternized 2- (dimethylaminoethyl acrylate). Methyl chloride and 4.50 g of allyl methacrylate.
  • Feed 2 was a solution of 90.00 g deionized water and 3.00 g Azostarter V-50. After the end of the feed 2 was stirred for a further 60 minutes at 85 ° C and the reaction mixture was then cooled to room temperature.
  • the aqueous polymer dispersion obtained had a solids content of 19% by weight (weight-average particle diameter 46 nm).
  • Heating / cooling device was heated to 80 ° C 375.00 g of deionized water under nitrogen atmosphere. For this purpose, the partial amount of 21, 09 g of feed 1 was added. For this purpose, the portion of 3.75 g of feed 2 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 2 were started. Feed 1 and feed 2 were metered in evenly over 3 hours.
  • Feed 1 was an aqueous emulsion prepared from 592.64 g deionized water, 1, 1 1 g of a 45 wt .-% aqueous solution of the sodium salt of a Ci2-substituted Biphenylethersulfonates (Dowfax ® 2A1, trademark of Dow Chemical Company), 1 1 1, 88 g of n-butyl acrylate, 1 1 1, 88 g of styrene, 25.00 g of acrylic acid and 1, 25 g of allyl methacrylate.
  • Feed 2 was 37.50 g of a 2% strength by weight aqueous solution of sodium peroxidisulfate.
  • Heating / cooling device a mixture of 375.00 g of deionized water and 16.67 g Dowfax® 2A1 was heated to 80 ° C under a nitrogen atmosphere. For this purpose, the partial amount of 75.53 g of feed 1 was added. For this purpose, the portion of 3.75 g of feed 3 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 3 were started. Feed 1 was metered in evenly over 2 hours. Feed 2 was added uniformly over 3 hours.
  • Feed 1 was an aqueous emulsion prepared from 520.44 g deionized water, 4.89 g of a 45 wt .-% aqueous solution of the sodium salt of a Ci2-substituted Biphenylethersulfonates (Dowfax ® 2A1), 199.00 g of n-butyl acrylate and 1 , 00 g of allyl methacrylate.
  • Feed 3 was 37.50 g of a 2% strength by weight aqueous solution of sodium peroxidisulfate. After the end of the feed 1 was stirred for a further 30 minutes at 80 ° C and then feed 2 was added evenly in 30 minutes.
  • Feed 2 was an aqueous emulsion prepared from 99.28 g of deionized water, 1, 22 g of a 45 wt .-% aqueous solution of the sodium salt of a Ci2-substituted Biphenylethersulfonates (Dowfax ® 2A1), 25.00 g of methyl methacrylate and 25.00 g glycidyl methacrylate. After the end of feeds 2 and 3, the mixture was stirred at 80 ° C. for a further 30 minutes and the reaction mixture was subsequently cooled to room temperature. The aqueous polymer dispersion obtained had a solids content of 20.0% by weight (weight average particle diameter 80 nm).
  • Heating / cooling device was heated to 80 ° C 375.00 g of deionized water under nitrogen atmosphere. For this purpose, the partial amount of 16.95 g of feed 1 was added. For this purpose, the portion of 3.75 g of feed 3 was added after stirring for 5 minutes at a given temperature. After 15 minutes, feed 1 and feed 3 were started. Feed 1 was metered in evenly over 2 hours. Feed 2 was metered in uniformly over 3 hours. Feed 1 was an aqueous emulsion prepared from 475.83 g of deionized water,
  • Feed 3 was 37.50 g of a 2% by weight aqueous solution of sodium peroxydisulfate. After the end of feed 1, an additional 30 minutes were added
  • Feed 2 was an aqueous emulsion prepared from 1 18.54 g of deionized water, 0.28 g of a 45 wt .-% aqueous solution of the sodium salt of a Ci2-substituted Biphenylethersulfonates (Dowfax ® 2A), 25.00 g of methyl methacrylate and 25, 00 g of glycidyl methacrylate. After the end of feeds 2 and 3, the mixture was stirred at 80 ° C. for a further 30 minutes and the reaction mixture was subsequently cooled to room temperature.
  • a Ci2-substituted Biphenylethersulfonates Dowfax ® 2A
  • Example 10 A mixture of 375.00 g of deionized water and 16.67 g of a 45% strength by weight aqueous solution of the sodium salt of a C 12 -substituted biphenyl ether sulfonate (Dowfax® 2A1) under a nitrogen atmosphere was placed in a 2 liter reactor with paddle stirrer and heating / cooling device heated to 80 ° C. For this purpose, the partial amount of 87.58 g of feed 1 was added. For this purpose, the portion of 3.75 g of feed 2 was added after stirring for 5 minutes at a given temperature.
  • a C 12 -substituted biphenyl ether sulfonate Dowfax® 2A1
  • Feed 1 was an aqueous emulsion prepared from 619.72 g deionized water, 6.1 1 g of a 45 wt .-% aqueous solution of the sodium salt of a Ci2-substituted Biphenylethersulfonates (Dowfax ® 2A1), 1 1 1, 88 g of n- Butyl acrylate, 1 1 1, 88 g of styrene, 25.00 g of acrylic acid and 1, 25 g of allyl methacrylate.
  • a Ci2-substituted Biphenylethersulfonates Dowfax ® 2A1
  • 1 1 1, 88 g of n- Butyl acrylate 1 1 1, 88 g of styrene
  • 25.00 g of acrylic acid and 1, 25 g of allyl methacrylate.
  • Feed 2 was 37.50 g of a 2% by weight aqueous solution of sodium peroxodisulfate. After the end of feeds 1 and 2, the mixture was stirred at 80 ° C. for a further 30 minutes and the reaction mixture was subsequently cooled to room temperature. The aqueous polymer dispersion obtained had a solids content of 17.9% by weight (weight-average particle diameter 67 nm).
  • dispersion dispersions listed below were prepared from the dispersions of Examples 1 to 10.
  • the dispersion mixtures were prepared in the following mixing ratio (parts by weight) based on the solids content by intensive stirring.
  • Blend 1 Dispersion from Example 1 and dispersion from Example 2 in a weight ratio based on the solids content Example 1 / Example 2 of 75 wt .-% / 25 wt .-%.
  • Blend 2 90 wt.% Example 1/10 wt.%
  • Blend 3 90 wt.%
  • Blend 3 90 wt.%
  • Blend 3 90 wt.%
  • Example 4 90 wt.%
  • Blend 4 80 wt .-% Example 1/20 wt .-% Example 5 Blend 5: 90 wt .-% Example 1/10 wt .-% Example 6) Blend 6: 75 wt .-% Example 1/25 wt .-% Example 6 Blend 7: 90 wt .-% Example 7/10 wt .-% Example 8 Blend 8: 90 wt .-% Example 9/10 wt .-% Example 10 Blend 9: 75 wt .-% Example 9/25 wt. Example 10 Blend 10: 50 wt.% Example 9/50 wt.% Example 10 Blend 1 1: 25 wt.% Example 9/75 wt.% Example 10
  • Blend 12 95% by weight Example 1/5% by weight Example 6
  • Blend 13 50% by weight Example 1/50% by weight
  • Blend 14 25% by weight Example 1/75% by weight
  • the respective dispersion mixture was applied by knife coating to glass slides which had been cleaned beforehand with acetone and then dried. After the coating has been formed, aftertreatment was carried out as described below in step (e).
  • a paddle stirrer was modified by attaching 2 glass slides (slides) to it.
  • a 0.01 molar aqueous solution of CaC was used as a template.
  • the thus prepared glass slides were on the Affixed paddle stirrer, introduced into the 0.01 molar CaC template and carried out the antiscaling experiment in the manner described below.
  • the speed of rotation of the stirrer was set at 100 revolutions per second.
  • a 0.01 molar aqueous Na 2 CO 3 solution was added uniformly. Thereafter, stirring was continued for a further 23 minutes at a constant stirring speed. After a total of 30 minutes, the slides were removed from the measuring device and dried.
  • step (e) The assessment of the degree of calcification was based on a scale ++ / + / 07 - / - where ++ indicates the absence of deposits and - strong lime deposits.
  • step (e) in addition to the coatings resulting from the dispersion blends and subsequent chemical reaction of step (e), the corresponding coatings resulting from the individual components and from the dispersion blend without performing step (e) are also listed , The coatings resulting from step (e) are characterized as being "blended".
  • Example 1 Example 6 Blend 5 Blend 5 treated

Abstract

L'invention concerne des revêtements dotés d'une structure périodique du potentiel de surface à base de latex de polymères et un procédé de fabrication de revêtements dotés d'une structure périodique du potentiel de surface, comprenant les étapes suivantes : (a) préparation d'au moins une première dispersion de polymère comme composant A et d'au moins une seconde dispersion de polymère comme composant B, les composants A et B différant dans leur composition chimique, (b) mélange des dispersions de polymères provenant de l'étape (a) et d'autres composants facultatifs, le rapport pondéral du composant A au composant B dans le mélange par rapport à la teneur en matières solides allant de 95/5 à 60/40, (c) application du mélange provenant de l'étape (b) sur une surface, de préférence un substrat, (d) durcissement du mélange provenant de l'étape (c) avec formation d'un revêtement, et (e) nouvelle réaction chimique du revêtement avec obtention d'une structure périodique du potentiel de surface, le rapport du diamètre de particule moyen en poids du composant A à celui du composant B allant de 3/1 à 15/1, le diamètre de particule moyen en poids du composant A allant de 75 à 1 000 nm et le diamètre de particule moyen en poids du composant B allant de 10 à 200 nm. L'invention concerne également les revêtements ainsi obtenus et l'utilisation de revêtements dotés d'une structure périodique du potentiel de surface à base de latex de polymères pour réduire la formation de dépôt.
PCT/EP2010/068787 2009-12-08 2010-12-03 Procédé de fabrication de revêtements structurés au niveau de la charge WO2011069891A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN112762078A (zh) * 2021-01-11 2021-05-07 昆山联滔电子有限公司 一种紧固组件以及紧固组件的安装方法

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