EP2324084A1 - Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques - Google Patents

Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques

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Publication number
EP2324084A1
EP2324084A1 EP09782463A EP09782463A EP2324084A1 EP 2324084 A1 EP2324084 A1 EP 2324084A1 EP 09782463 A EP09782463 A EP 09782463A EP 09782463 A EP09782463 A EP 09782463A EP 2324084 A1 EP2324084 A1 EP 2324084A1
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EP
European Patent Office
Prior art keywords
aqueous
monomers
particle dispersion
weight
aqueous composite
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Withdrawn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
EP09782463A
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German (de)
English (en)
Inventor
Bas Lohmeijer
Harm Wiese
Roland Baumstark
Luis Carlos Santos Esteves
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BASF SE
Original Assignee
BASF SE
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Priority to EP09782463A priority Critical patent/EP2324084A1/fr
Publication of EP2324084A1 publication Critical patent/EP2324084A1/fr
Withdrawn legal-status Critical Current

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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the quantitative determination of the initial solids concentration and the solids concentration after one hour and the determination of the mean particle diameter is carried out by the method of analytical ultracentrifuge (see also 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. Gurchtle, pages 147-175).
  • the values given for the particle diameter correspond to the so-called dso values.
  • an electrophoretic mobility with a negative sign 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight and particularly preferably 0.1 to 3 parts by weight of at least one cationic dispersant, 0.01 to 100 Parts by weight, preferably 0.05 to 50 parts by weight and more preferably 0.1 to 20 parts by weight of at least one nonionic dispersant and at least one anionic dispersant are used, the amount of which is such that the equivalent ratio of anionic to cationic dispersant is greater than 1, or
  • Finely divided inorganic solids are particularly suitable, the solubility speed in water at 20 0 C and atmospheric pressure ⁇ 1 g / l, preferably ⁇ 0.1 g / l and in particular ⁇ 0.01 g / l.
  • Particular preference is given to compounds selected from the group consisting of silicon dioxide, aluminum oxide, tin (IV) oxide, yttrium (III) oxide, cerium (IV) oxide, hydroxyaluminum oxide, calcium carbonate, magnesium carbonate, calcium methophosphate, magnesium orthophosphate, calcium metaphosphate , Magnesium metaphosphate, calcium pyrophosphate, magnesium pyrophosphate, orthosilicates such as lithiorthosilicate, calcium / magnesium orthosilicate, aluminum orthosilicate, iron (II) orthosilicate, iron (III) orthosilicate, magnesium orthosilicate, zinc orthosilicate, zirconium (III) orthosilicate , zirconium (IV) orthosilicate, metasi
  • the at least one finely divided inorganic solid is selected from the group comprising silicon dioxide, aluminum oxide, hydroxyaluminum oxide, calcium carbonate, magnesium carbonate, calcium orthophosphate, magnesium orthophosphate, iron (II) oxide, iron (III) oxide, iron (II / III) oxide, tin (IV) oxide, cerium (IV) oxide, yttrium (III) oxide, titanium dioxide, hydroxyapatite, zinc oxide and zinc sulfide.
  • LE Vasil ® - - advantageously also the commercially available compounds of the Aerosil ® may Ludox ® -, Nyacol ® - grades and Bindzil ® (silicon dioxide), Disperal ® brands
  • protective colloids whose dispersing component has at least one negative electrical charge include, for example, polyacrylic acids and polymethacrylic acids and their alkali metal salts, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid and / or maleic anhydride-containing copolymers and their alkali metal salts and alkali metal salts of sulfonic acids high molecular weight compounds such as polystyrene, into consideration.
  • Suitable cationic protective colloids are, for example, the nitrogen protonated and / or alkylated derivatives of N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine-containing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • mixtures of emulsifiers and / or protective colloids can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1500.
  • the individual components must be compatible with one another, which can be checked in case of doubt by means of fewer preliminary tests.
  • An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.
  • Nonionic emulsifiers are z.
  • B ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36).
  • Lutensol brands ® A C 2 Ci4-fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C13C15- Oxoalkoholethoxilate, EO units: 3 to 30
  • Lutensol ® AT-marks Ci 6 Ci 8 - fatty alcohol ethoxylates, EO grade: 1 1 to 80
  • Lutensol ® ON grades C10-
  • Usual anionic emulsifiers are z.
  • alkali metal and ammonium salts of Al kylsulfaten (alkyl radical: Cs to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and of ethoxylated alkylphenols (EO units: 3 to 50, Alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to Cis) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and A and B may be alkali metal ions and / or ammonium ions, proved.
  • 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 -H, wherein R 1 and R 2 are not both simultaneously H atoms are.
  • a and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous are compounds I in which A and B are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • Suitable cationic emulsifiers are generally a C 1 -C 6 -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine. oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklareester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N-octyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini-surfactant N, N'- (lauryldimethyl) ethylenediamine dibromide.
  • aqueous composite-particle dispersions between 0.1 to 10 wt .-%, often 0.5 to 7.0 wt .-% and often 1, 0 to 5.0 wt .-% of dispersant, respectively to the total amount of aqueous composite particle dispersion used.
  • emulsifiers in particular nonionic and / or anionic emulsifiers.
  • anionic, cationic and nonionic emulsifiers are used as dispersants.
  • the monomers mentioned usually form the main monomers which, based on the total amount of monomers A to be polymerized by the process according to the invention, normally have a proportion of> 50% by weight, 80% by weight or 90% by weight .-% to unite. As a rule, these monomers in water ser under standard conditions (20 0 C, atmospheric pressure), only a moderate to low solubility.
  • Other monomers A which usually increase the internal strength of the films of the polymer matrix, usually have at least one hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
  • Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers.
  • Particularly advantageous are the diesters of dihydric alcohols with .alpha.,. Beta.-monoethylenically unsaturated monocarboxylic acids, of which the acrylic and methacrylic acids are preferred.
  • the abovementioned monomers based on the total amount of the monomers A to be polymerized, in amounts of up to 5 wt .-%, in particular 0.1 to 3 wt .-% and preferably 0.5 to 2 wt .-% for the polymerization used.
  • Examples of such monomers AS are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid, as well as phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, such as, for example, phosphoric acid monoesters of hydroxyethyl acrylate, n- Hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxypropyl methacrylate or n-hydroxybutyl methacrylate.
  • the monomers AN used are ethylenically unsaturated monomers which contain at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated ammonium derivatives.
  • Arkema 2- (N, N-dimethylamino) ethyl acrylate (for example, commercially available as Norsocryl ® ADAME from Arkema), 2- (N, N-dimethylamino) ethyl methacrylate (for example, commercially available as Norsocryl ® MADAME Fa Arkema), 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N, N-di-n-propylamino) ethyl acrylate, 2- (N, N-di- n propylamino) ethyl methacrylate, 2- (N, N-diisopropylamino) ethyl acrylate, 2- (N, N-diisopropylamino) ethyl methacrylate, 3- (N-methylamino) propy
  • Examples of monomers AN, a ureido group containing at least 1 N N '- divinylethyleneurea and 2- (1-imidazolin-2-onyl) ethyl methacrylate for example commercially available as NORSOCRYL 100 from Arkema ®.
  • the monomers employed are the following compounds: 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N 1 N-dimethylamino) ethyl methacrylate, 2- (N, N- diethylamino) ethyl acrylate, ethyl methacrylate, 2- (N 1 N-diethylamino), 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N' - methacrylamide dimethylaminopropyl) and 2- (1-imidazolin-2 -onyl) ethyl methacrylate.
  • some or all of the aforementioned nitrogen-containing monomers AN may be present in the nitrogen-protonated quaternary ammonium form.
  • Suitable monomers AN which sen a quaternary Alkylammonium gleichtechnikwei- on the nitrogen, may be mentioned by way of example, 2- (N, N, N-trimethyl ammonium) (commercially available for example as NORSOCRYL ® ADAMQUAT MC 80 from. Arkema) ethylacrylatchlorid, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride (e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
  • Arkema 2- (N-methyl-N, N-diethylammonium) ethylacrylatchlorid, 2- (N-methyl-N, N-diethylammonium ) Ethyl methacrylate chloride, 2- (N-methyl-N, N-dipropylammonium) ethyl acrylate chloride, 2- (N-methyl-N, N-dipropylammonium) ethyl methacrylate, 2- (N-benzyl-N, N-dimethylammonium) ethyl acrylate chloride (for example, commercially available as NORSOCRYL ® ADAMQUAT BZ 80 from.
  • NORSOCRYL ® ADAMQUAT BZ 80 for example, commercially available as NORSOCRYL ® ADAMQUAT BZ 80 from.
  • Arkema 2- (N-benzyl-N, N-dimethylammonium) ethyl methacrylate chloride (e.g., commercially available as NORSOCRYL ® MADQUAT BZ 75 from. Elf Atochem), 2- (N-benzyl -N, N-diethylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-diethylammonium) ethyl methacrylate atchloride, 2- (N-benzyl-N, N-dipropylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-dipropylammonium) ethyl methacrylate chloride, 3- (N, N, N-trimethylammonium) propyl acrylate chloride, 3- (N, N).
  • mixtures of the abovementioned ethylenically unsaturated monomers AS or AN can also be used. It is important that in the case of WO 03/000760 in the presence of dispersed solid particles having an electrophoretic mobility with a negative sign, a partial or total amount of at least one anionic dispersant by the equivalent amount of at least one monomer AS and in the case of may be replaced by the equivalent amount of at least one monomer AN of dispersed solid particles having an electrophoretic mobility with a positive sign, a partial or the total amount of the at least one cationic dispersant.
  • the amount of epoxy monomer is optionally 0 to 5 10 wt .-%. Frequently the total amount of epoxy monomer is> 0.01% by weight,> 0.1% by weight or> 0.5% by weight, often> 0.8% by weight,> 1% by weight or > 1, 5 wt .-%, or ⁇ 8 wt .-%, ⁇ 7 wt .-% or ⁇ 6 wt .-% and often ⁇ 5 wt%, ⁇ _ 4 wt .-% or ⁇ _ 3 wt .-%, each based on the total amount of monomers.
  • the amount of epoxide monomers is preferably ⁇ 0.1 and ⁇ 5% by weight and in particular preferably ⁇ 0.5 and ⁇ 3% by weight, in each case based on the total monomer amount.
  • the monomer mixture to be polymerized preferably consists of> 95 and ⁇ 99.9% by weight and particularly preferably> 97 and ⁇ 99.5% by weight of monomers A and> 0.1 and ⁇ 5% by weight and particularly preferably> 0.5 and ⁇ 3 wt .-% of epoxy monomers.
  • the epoxide monomers according to the invention are used in the monomer mixture with the monomers A.
  • the epoxide monomers may be added to the polymerization medium batchwise in one or more portions or continuously with equal amounts. be added metering or changing flow rates. In general, however, the epoxide monomers are fed to the polymerization medium together with the monomers A in the monomer mixture.
  • the monomer mixture to be polymerized is selected so that the resulting polymer has a glass transition temperature ⁇ 100 0 C, preferably ⁇ 60 0 C or ⁇ 40 0 C, in particular ⁇ 30 0 C or ⁇ 20 0 C and often> -60 0 C. or> -40 0 C and often> -30 0 C and thus the aqueous composite particle dispersions - optionally in the presence of conventional film-forming aid - in a simple manner in which the finely divided inorganic solids-containing polymer films (composite films) can be transferred.
  • aqueous composite-particle dispersion which can be used according to the invention by free-radical polymerization
  • free-radical polymerization initiators which are capable of initiating a free-radical aqueous emulsion polymerization are suitable.
  • these can be both peroxides and azo compounds.
  • redoxini- tiatorsysteme come into consideration.
  • 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 sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or Sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II ) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides
  • the reaction temperature for the radical aqueous polymerization reaction in the presence of the finely divided inorganic solid the entire range of 0 to 170 0 C into consideration. In this case, temperatures of 50 to 120 0 C, often 60 to 110 0 C and often> 70 to 100 0 C are usually applied.
  • the free-radical aqueous emulsion polymerization can be carried out at a pressure of less than or equal to 1 bar (absolute), the polymerization temperature exceeding 100 ° C. and up to 170 ° C.
  • volatile monomers such as ethylene, butadiene or vinyl chloride are polymerized under elevated pressure. The pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar or even higher values.
  • emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free-radical aqueous polymerization is advantageously carried out at 1 atm (absolute) under an inert gas atmosphere, such as under nitrogen or argon.
  • radical-chain-transferring compounds can optionally also be used in the processes for preparing the aqueous composite-particle dispersion in order to reduce or control the molecular weight of the polymers obtainable by the polymerization.
  • aliphatic thiols such as, for example, ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3 Pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl 2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethi
  • the aqueous composite-particle dispersions obtainable by the process according to the invention usually have a total solids content of from 1 to 70% by weight, frequently from 5 to 65% by weight and often from 10 to 60% by weight.
  • the average composite particle diameter is also determined by the analytical ultracentrifuge method (see, for example, SE Harding et al., Analytical Ultra-centrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W.
  • Suitable for use in elastic coatings are advantageously composite particle dispersions whose composite particles have an average particle diameter of> 50 nm and ⁇ 300 nm, preferably ⁇ 200 nm and in particular 5 150 nm.
  • the composite particles obtainable by the various methods can have different structures.
  • the composite particles may contain one or more of the finely divided solid particles.
  • the finely divided solid particles may be completely enveloped by the polymer matrix.
  • part of the finely divided solid particles is enveloped by the polymer matrix, while another part is arranged on the surface of the polymer matrix.
  • a large part of the finely divided solid particles is bound to the surface of the polymer matrix.
  • the composite particles obtainable by the various methods have a finely divided inorganic solid content of> 10% by weight, preferably> 15% by weight and particularly preferably> 20% by weight,> 25% by weight or> 30% by weight .-%, in each case based on the composite particles (corresponding to the sum of the amount of polymer and amount of particulate matter).
  • Advantageously used in accordance with the invention are those aqueous composite-particle dispersions whose composite particles have a content of finely divided inorganic solid in the range of 10 to 60% by weight and more preferably 25 to 50% by weight.
  • the abovementioned aqueous composite-particle dispersions are advantageously suitable as binders in elastic coating compositions.
  • elastic coating compositions according to the invention contain an aqueous composite-particle dispersion, wherein in the preparation of the aqueous composite-particle dispersion ethylenically unsaturated monomers are dispersed in an aqueous medium and by means of at least one free-radical polymerization initiator in the presence of at least one finely divided, finely divided inorganic solid having an average particle diameter ⁇ _ 100 nm and at least one dispersant are polymerized by the method of free-radically aqueous emulsion polymerization, and wherein ethylenically unsaturated monomers, a monomer mixture is used which ethylenically unsaturated monomers A and optionally 0 to ⁇ 10 wt .-% of at least one, having an epoxide group ethylenically unsaturated monomer B (epoxide monomer).
  • elastic coating compositions are understood as meaning all water-based formulations which contain the composite particle dispersion as binder.
  • Elastic coating compounds are intended to protect buildings reliably against moisture and other weather conditions. They are accordingly used in paints, such as facade paints.
  • the present invention therefore also paints or facade paints containing the elastic coating compositions of the invention.
  • the preparation of the paint according to the invention is carried out in a known manner by mixing the components in mixing devices customary for this purpose. It has proven useful to prepare an aqueous paste or dispersion from the pigments, water and optionally the adjuvants, and then first the polymeric binder, i. as a rule, to mix the aqueous dispersion of the polymer with the pigment paste or pigment dispersion.
  • An elastic coating composition according to the invention contains in the wet state
  • wt .-% preferably 1 to 3 wt .-%, particularly preferably 0 to 1 wt .-%, of one or more pigments and v. 0 to 20 wt .-%, preferably 0 to 10 wt .-%, particularly preferably 0 to 5 wt .-% depending on further auxiliaries, such as biocides, pigment distributors, film-forming aids and defoamers.
  • minerals such as silica, calcium sulfate (gypsum), which does not originate from flue gas desulphurisation systems in the form of anhydrite, hemihydrate or dihydrate, quartz powder, silica gel, precipitated or natural barium sulfate, titanium dioxide, zeolites, leucite, potassium feldspar, biotite, the group of , Cyclo, ino, phyllo and tectosilicates, the group of sparingly soluble sulfates, such as gypsum, anhydrite or barite, and calcium minerals, such as calcite or chalk (CaCO 3 ).
  • silica calcium sulfate
  • CaCO 3 calcium sulfate
  • the said inorganic materials can be used individually or in a mixture.
  • Other suitable materials are precipitated or natural kaolin, talc, magnesium or aluminum hydroxide (to set the fire class), zinc oxide and zirconium salts.
  • light fillers - ceramic hollow microspheres, glass hollow spheres, foam glass spheres or other lightweight fillers, such as those manufactured by Omega-Minerals parameters such as dimensional stability and density can be influenced.
  • thickeners iii. they are usually high-molecular substances that either absorb water and thereby swell or form intermolecular lattice structures.
  • the organic thickening agents eventually transform into a viscous true or colloidal solution.
  • thickeners based on acrylic acid and acrylamide for example Collacral® HP
  • carboxyl group-containing acrylic acid ester copolymers such as Latekoll® D
  • PU thickeners for example Collacral® PU 75
  • celluloses and ren derivatives and natural thickeners such as bentonites, alginates or starch.
  • the thickeners (iii.) are used in amounts of 0 to 5 wt .-%, preferably 0.1 to 2.5% by weight.
  • the pigments (iv.) serve to color the elastic coating compositions.
  • organic pigments and / or inorganic pigments such as iron oxides are used.
  • the pigments are used in amounts of 0 to 5 wt .-%, preferably 0 to 1 wt .-%.
  • the elastic coating composition is essentially an aqueous composite particle dispersion. Further auxiliaries v. can be added to the aqueous dispersion in a simple manner.
  • excipients include, for example, preservatives to prevent fungal and bacterial attack, solvents for influencing the open time and the mechanical properties, for example butylglycol, dispersing agents to improve the wetting behavior, for example Pigment Distributor NL (BASF Aktiengesellschaft, DE), emulsifiers (Emulphor® OPS 25, Lutensol® TO 89), antifreeze (ethylene glycol, propylene glycol).
  • Other auxiliaries may be crosslinkers, adhesion promoters (acrylic acid, silanes, aziridines) or defoamers (Lumiten® brands).
  • the feed 1 was a monomer mixture consisting of 93.7 g of methyl methacrylate (MMA), 218.8 g of n-butyl acrylate (n-BA), 6.5 g of glycidyl methacrylate (GMA) and 0.5 g of methacryloxypropyltrimethoxysilane ( MEMO) and as feed 2, an initiator solution consisting of 3.8 g of sodium peroxodisulfate, 1 1, 5 g of a 10 wt .-% solution of sodium hydroxide and 280 g of deionized water, forth.
  • MMA methyl methacrylate
  • n-BA n-butyl acrylate
  • GMA glycidyl methacrylate
  • MEMO methacryloxypropyltrimethoxysilane
  • reaction mixture stirred reaction mixture for 5 minutes via two separate feed lines 21, 1 g of feed 1 and 57.1 g of feed 2 was added. Thereafter, the reaction mixture was stirred for one hour at the reaction temperature. Subsequently were added 0.92 g of a 45 wt.% Aqueous solution of Dowfax ® 2A1 to the reaction mixture. Within 2 hours, the remainder of feed 1 and feed 2 were added continuously to the reaction mixture at the same time. Thereafter, the reaction mixture was stirred for a further hour at the reaction temperature and then cooled to room temperature.
  • the resulting aqueous composite-particle dispersion had a solids content of 35.5% by weight, based on the total weight of the aqueous composite-particle dispersion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention porte sur l'utilisation d'une dispersion aqueuse de particules constituées d'un polymère et d'une matière solide inorganique fine (dispersion aqueuse de particules composites) en tant que liant dans des revêtements élastiques, tels que des peintures, en particulier des peintures pour façades. Lors de la préparation de la dispersion aqueuse de particules composites, on répartit des monomères à insaturation éthylénique dans un milieu aqueux pour obtenir une dispersion, et, avec au moins un amorceur de polymérisation radicalaire, on polymérise ces monomères en présence d'au moins une matière solide inorganique fine et répartie pour obtenir une dispersion, ayant une granulométrie moyenne = 100 nm, ainsi que d'au moins un dispersant, par le procédé de polymérisation radicalaire en émulsion aqueuse, où l'on utilise en tant que monomères à insaturation éthylénique un mélange de monomères qui contient des monomères A à insaturation éthylénique et éventuellement de 0 à = 10 % en poids d'un monomère B à insaturation éthylénique, comportant un groupe époxyde (monomère époxy).
EP09782463A 2008-09-02 2009-09-01 Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques Withdrawn EP2324084A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09782463A EP2324084A1 (fr) 2008-09-02 2009-09-01 Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques

Applications Claiming Priority (3)

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EP08163496 2008-09-02
EP09782463A EP2324084A1 (fr) 2008-09-02 2009-09-01 Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques
PCT/EP2009/061281 WO2010026138A1 (fr) 2008-09-02 2009-09-01 Utilisation de dispersions aqueuses de particules composites en tant que liant dans des revêtements élastiques

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EP (1) EP2324084A1 (fr)
JP (1) JP2012501381A (fr)
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WO (1) WO2010026138A1 (fr)

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EP2147020B1 (fr) 2007-05-04 2011-04-13 Basf Se Procédé de production d'une dispersion aqueuse à particules composites
ES2402109T3 (es) 2009-04-15 2013-04-29 Basf Se Método para la producción de una dispersión acuosa de partículas de compuesto
SE1551112A1 (en) * 2015-08-27 2017-02-28 Sp Sveriges Tekniska Forskningsinstitut Ab Functionalized particles
PL3301138T5 (pl) * 2016-09-30 2022-07-04 Daw Se Wodne masy do obróbki ścian, sufitów i podłóg budynków
EP3434701A1 (fr) * 2017-07-25 2019-01-30 Arkema France Dispersions stables de polymères aqueux
CN117303911A (zh) * 2023-09-26 2023-12-29 安徽华晟新材料有限公司 坩埚及其制备方法

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US3320198A (en) * 1963-01-28 1967-05-16 Du Pont Latex paint containing benzophenone
GB1172513A (en) * 1965-11-11 1969-12-03 Ici Ltd Polymer Coated Particles
US4421660A (en) * 1980-12-15 1983-12-20 The Dow Chemical Company Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein
US4608401A (en) * 1982-09-02 1986-08-26 Union Carbide Corporation Method of encapsulating finely divided solid particles
US4647612A (en) * 1985-12-30 1987-03-03 Ppg Industries, Inc. Polymer emulsion products
JP2683548B2 (ja) * 1988-12-27 1997-12-03 出光石油化学株式会社 ポリプロピレン樹脂組成物
US4981882A (en) * 1989-03-31 1991-01-01 Union Carbide Chemicals And Plastics Company Inc. Method for enhancing encapsulation efficiency in coating particles in aqueous dispersions
DE10129537A1 (de) * 2001-06-21 2003-01-09 Basf Ag Verfahren zur Herstellung einer wässrigen Dispersion von aus Polymerisat und feinteiligem anorganischem Feststoff aufgebauten Partikeln
DE102005000918A1 (de) * 2005-01-06 2006-07-20 Basf Ag Verfahren zur Herstellung wässriger Kompositpartikel-Dispersionen
EP2147020B1 (fr) * 2007-05-04 2011-04-13 Basf Se Procédé de production d'une dispersion aqueuse à particules composites
ES2370565T3 (es) * 2007-10-24 2011-12-20 Basf Se Procedimiento para la obtención de una dispersión acuosa de partículas compuestas.

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See references of WO2010026138A1 *

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AU2009289333A1 (en) 2010-03-11
US20110207851A1 (en) 2011-08-25
WO2010026138A1 (fr) 2010-03-11
JP2012501381A (ja) 2012-01-19
CN102203193A (zh) 2011-09-28

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