WO2013072769A1 - Systèmes liants aqueux et leur utilisation dans la production de compositions de revêtement - Google Patents

Systèmes liants aqueux et leur utilisation dans la production de compositions de revêtement Download PDF

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WO2013072769A1
WO2013072769A1 PCT/IB2012/002859 IB2012002859W WO2013072769A1 WO 2013072769 A1 WO2013072769 A1 WO 2013072769A1 IB 2012002859 W IB2012002859 W IB 2012002859W WO 2013072769 A1 WO2013072769 A1 WO 2013072769A1
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ethylenically unsaturated
monomers
acid
total amount
monomer
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PCT/IB2012/002859
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English (en)
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Christoph Deller
Thomas Fichtner
Stephan Krieger
Marc Ratering
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Celanese Emulsions Gmbh
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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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to aqueous binder systems, their production and their use in the production of coating compositions,
  • Aqueous binder systems composed of a polymer dispersion and colloidal silica are useful in the production of coating compositions, such as plasters, renders and paints, having low soiling tendency, high water vapor permeability, good adhesive properties and high weathering stability.
  • U.S. Published Patent Application No. 2010/0144925 discloses a composition containing a) a mineral filler, b) pigment, c) colloidal silica and d) aqueous plastics dispersion which contains a copolymer which is prepared by emulsion polymerization and is derived from A) at least 40% by weight, based on the total amount of monomer, of esters of ⁇ , ⁇ -unsaturated carboxylic acids, vinyl esters of saturated carboxylic acids, vinylaromatic monomers or combinations of two or more of these monomers, B) from 0.1 to 10% by weight, based on the total amount of monomers, of ⁇ , ⁇ -ethylenically unsaturated mono- and/or dicarboxylic acids and/or of ⁇ , ⁇ -ethylenically unsaturated sulfonic acids and/or of ⁇ , ⁇ -ethylenically unsaturated phosphoric acids and/or of ⁇ , ⁇ - ethy
  • Patent No. 7,144,944 discloses a coating composition for an ink jet recording medium comprising: i) colloidal silica; and ii) a synthetic resin emulsion composition having two or more glass transition (Tg) points, wherein said emulsion composition includes a) a first polymeric portion which includes the residues of a radical- polymerizable unsaturated monomer having a silyl group, and another radical polymerizable unsaturated monomer; and b) a second polymeric portion which also includes the residues of a radical polymerizable unsaturated monomer having a silyl group, and another radical polymerizable unsaturated monomer, wherein the first polymeric portion is constituted to provide the emulsion composition with a first Tg point, and the second polymeric portion is constituted to provide the emulsion composition with a second Tg point which is dissimilar from the first Tg point, and wherein the first polymeric portion and second polymeric portion are separately emulsion polymerized in the presence of
  • an aqueous binder mixture comprising:
  • A colloidal silica
  • B an aqueous copolymer dispersion which is prepared by emulsion polymerization of a monomer mixture comprising:
  • the alkoxy-substituted polysiloxane is present in an at least partially hydrolyzed form.
  • the alkoxy-substituent of the polysiloxane has 1 to 5 carbon atoms, and preferably comprises an ethoxy group.
  • the binder mixture comprises from 0.1 to 5 wt %, based on the solids content of the mixture, of the alkoxy-substituted polysiloxane.
  • the binder mixture comprises from 30 to 95 wt %, based on the solids content of the mixture, of said copolymer.
  • the copolymer has a Tg from 0 to 50 °C, preferably from 10 to 30 °C.
  • the momoner mixture further comprises (iv) from 0.1 to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated surface-active monomer containing at least one anionic and/or nonionic emulsifying group.
  • the momoner mixture further comprises (v) from 0.1 to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated monomer containing at least one functional group selected from a hydroxyl group, an epoxy group and a carbonyl group.
  • the colloidal silica has a particle size of 2 to 100 nanometers.
  • the colloidal silica is present in an amount between about 5 and about 70 wt , based on the solids content of the mixture.
  • the invention resides in a coating produced from the coating composition described herein and having a water permeability of less than 0,10 kg/m 2 h 0'5 as determined according to DIN EN ISO 1062-3 and a water vapor transmission, sd, of less than 0,15 m as determined according to DIN EN ISO 7783-2.
  • the invention resides in a method of producing an aqueous binder mixture, the method comprising:
  • aqueous binder mixture which comprises colloidal silica and a particular aqueous copolymer dispersion and which has been modified by the incorporation of an alkoxy-substituted polysiloxane. Also described herein are a method of producing the aqueous binder mixture and its use in plasters, renders and paints exhibiting both reduced water absorption and high water vapor permeability.
  • the colloidal silica employed in the present binder is preferably an aqueous colloidal dispersion or suspension of ultrafine silica particles. Typically, the particle diameter of primary silica particles in this dispersion or suspension is from 2 to 100 nm and the primary particles are spherical.
  • the colloidal silica employed is generally an amorphous silica and can be either of the anionic or of the cationic type, that is with anionic or cationic surface charges on the particles, which are compensated by corresponding counterions.
  • Preferred dispersions are those in which the particles are stabilized by anionic surface charges and contain alkali metal or ammonium counterions, in particular sodium, potassium or ammonium counterions.
  • the colloidal silica may have a monodisperse or polydisperse particle size distribution. Suitable forms of commercially available colloidal silica include, for example, those sold under the trade names Klebosol®, Kostrosol® and Levasil®.
  • the colloidal silica is present in the binder mixture in an amount from about 5 to about 70 wt , based on the solids content of the mixture.
  • the colloidal silica may be added to the binder mixture during the preparation of the aqueous copolymer dispersion. More preferably, however, the colloidal silica is added after preparation of the polymer dispersion since this generally reduces the tendency for the dispersion to coagulate, increases the storage stability of the binder mixture and allows the production of binder mixtures with higher solids content.
  • the aqueous copolymer dispersion employed in the present binder mixture is prepared by emulsion polymerization of a monomer mixture comprising (i) at least 40%, such as from 50% to 90%, by weight, based on the total amount of monomers, of at least one monomer selected from an ester of an ethylenically unsaturated carboxylic acid, a vinyl ester of an saturated carboxylic acid, and a vinylaromatic monomer; (ii) from 0.1% to 10%, such as from 1% to 6%, for example from 1% to 4%, by weight, based on the total amount of monomers, of at least one monomer selected from an ethylenically unsaturated mono- and/or dicarboxylic acid, an ethylenically unsaturated sulfonic acid, an ethylenically unsaturated phosphoric acid, an ethylenically unsaturated phosphonic acid, and an amide of an ethylenically uns
  • the monomer mixture can contain (iv) from 0.1 to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated surface- active monomer containing at least one anionic and/or nonionic emulsifying group and (v) optionally from 0.1 to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated functional monomer copolymerizable with the monomers of groups (i), (ii), (iii) and (iv).
  • esters of ethylenically unsaturated carboxylic acids having 3 to 12 carbon atoms such as esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and fumaric acid.
  • esters of ⁇ , ⁇ -unsaturated carboxylic acids include alkyl(meth)acrylates (i.e. alkyl esters of acrylic acid or of methacrylic acid).
  • alkyl esters can be used alone or in the form of a combination of two or more esters.
  • Monomer (i) can also include one or more vinyl esters of saturated carboxylic acids.
  • vinyl esters of saturated carboxylic acids having 1 to 18 carbon atoms examples include vinyl esters of carboxylic acids having 1 to 4 carbon atoms, such as, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate and vinyl 2-ethylhexanoate; vinyl esters of saturated, branched monocarboxylic acids having 9, 10 or 11 carbon atoms in the acid radical and vinyl esters of relatively long- chain, saturated and unsaturated fatty acids, for example vinyl esters of fatty acids having 8 to 18 carbon atoms, such as, for example, vinyl laurate and vinyl stearate; or vinyl esters of benzoic acid or of p-tert-butylbenzoic acid and mixtures thereof, such as, for example, mixtures of vinyl acetate and a versatic acid or of vinyl acetate and vinyl laurate
  • monomer (i) can include one or more vinylaromatic hydrocarbons, such as styrene, vinyltoluene and alpha-methylstyrene.
  • the monomer mixture employed herein also includes a monomer (ii) comprising of at least one of an ethylenically unsaturated mono- and/or dicarboxylic acid and/or an amide thereof, an ethylenically unsaturated sulfonic acid, an ethylenically unsaturated phosphoric acid and an ethylenically unsaturated phosphonic acid.
  • the acid monomers (ii) include 3 to 8 carbon atoms, such as ethylenically unsaturated C3-C8 monocarboxylic acids and ethylenically unsaturated C4-C8 dicarboxylic acids, together with the anhydrides or amides thereof and the monoesters of ethylenically unsaturated C4-C8 dicarboxylic acids.
  • Examples of ethylenically unsaturated C3-C8 monocarboxylic acids include acrylic acid, methacrylic acid and crotonic acid, and the anhydrides and amides thereof.
  • Examples of ethylenically unsaturated C4-C8 dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid, and the mono- or bisamides thereof and their monoesters with CrC 12 , preferably C1-C4, alkanols, such as, for example, monomethyl maleate and mono-n-butyl maleate.
  • Suitable ethylenically unsaturated sulfonic acids include those having 2-8 carbon atoms, such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxyethanesulfonic acid and 2-methacryloyloxyethanesulfonic acid, 2- acryloyloxy- and 3-methacryloyloxypropanesulfonic acid and vinylbenzenesulfonic acid.
  • suitable ethylenically unsaturated phosphoric acids also include those having 2-8 carbon atoms, such as vinylphosphonic acid.
  • the salts thereof preferably the alkali metal or ammonium salts thereof, particularly preferably the sodium salts thereof, such as, for example, the sodium salts of vinylsulfonic acid and of 2- acrylamidopropanesulfonic acid.
  • monomers (ii) are amides of ethylenically unsaturated carboxylic acids, in particular methacrylamide, acrylamide, crotonamide, the mono- or diamide of fumaric acid, the mono- or diamide of maleic acid, the mono- or diamide of itaconic acid and the mono- or diamide of citraconic acid.
  • amides it is also possible to use the N-functionalized derivatives thereof, such as N-alkyl- or N,N- dialkylamides. The unfunctionalized derivatives are preferred.
  • the monomer mixture employed herein also includes as monomer (iii) at least one ethylenically unsaturated monomer having at least one alkoxysilyl group.
  • the monomer mixture can contain a substance which has at least one amino, mercapto or epoxide group in addition to at least one alkoxysilyl group.
  • organoalkoxysilanes which can be used as monomer (iii) include compounds of the formula I or II:
  • R 1 is -(CH 2 ) n -NH-R 4 , -(CH 2 ) n -NH-[(CH 2 ) m -NH] 0 -R 4 or -(CH 2 ) n -0-R 5 , -(CH 2 ) n -
  • R 2 is hydrogen, -(CH 2 ) n -CH 3 or R 1 ,
  • R 3 is hydrogen, -(CH 2 ) n -CH 3 or R 2 ,
  • R 4 is hydrogen, -(CH 2 ) n -CH 3 or -CO-(CH 2 ) m -CH 3 , and
  • R 5 is hydrogen, -(CH 2 -CH 2 -0) m -R 4 or -CH 2 -CH-CH 2
  • n and m in each case independently of one another, are an integer between 0 and 12 and o is an integer between 0 and 5.
  • the organoalkoxysilane is a polyfunctional silane which, in addition to at least one silane group, have at least one primary, secondary or tertiary amino group, at least one alkylthio group or sulfhydryl group or at least one epoxide group. Examples of such compounds are illustrated by the compounds of the formulae III, IV, V,
  • each R 6 independently of one another, are hydrogen or Ci-C6-alkyl, preferably methyl, ethyl or propyl, R 7 is hydrogen, Ci-C6-alkyl or a glycidyl radical (1,2-epoxypropyl),
  • R 8 is hydrogen or Ci-C6-alkyl
  • R 9 and R 10 independently of one another, are hydrogen or C]-C6-alkyl and p is an integer between 1 and 12.
  • silanes of the formulae III, IV and V are the compounds:
  • Di-, tri- or oligomeric silanes can also be used.
  • silane compounds examples include Dynasylan ® (Degussa), Geniosil ® (Wacker) and Silquest ® (GE Silicones).
  • silanes are vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldiisopropoxysilane, vinylmethyldi-n-butoxysilane, viny line thyldi- sec -butoxysilane, vinylmethyldi-tert- butoxysilane, vinylmethyldi(2-methoxyisopropoxy)silane and vinylmethyldioctyloxysilane.
  • Examples of these are y-(meth)acryloyloxypropyltris(2-methoxyethoxy)-silane, y-(meth)acryloyloxypropyltrismethoxysilane, y-(meth)acryloyloxypropyltrisethoxysilane, ⁇ - (meth)acryloyloxypropyltris-n-propoxysilane, y-(meth)acryloyloxypropyltris- isopropoxysilane, y-(meth)acryloyloxypropyltrisbutoxysilane, y-acryloyloxypropyltris(2- methoxyethoxy)silane, ⁇ -acryloyloxypropyltrismethoxysilane, ⁇ - acryloyloxypropyltrisethoxysilane, ⁇ -acryloyloxypropyltris-n-propoxysilane, ⁇ - acrylo
  • the monomer mixture employed herein can optionally contain (iv) from 0.1 to 10% by weight, based on the total amount of monomers, of at least one ethylenically unsaturated surface-active monomer containing at least one anionic and/or nonionic emulsifying group.
  • emulsifiers are surfactants which may be incorporated into the copolymer during the emulsion polymerization.
  • the monomer (iv) has more than eight carbon atoms.
  • the monomer(s) (iv) has at least one hydrophilic group, which may be nonionic, for example a polyoxy ethylene or a polyoxypropylene group, or may be anionic, for example a sulfate, sulfonate, phosphate or phosphonate group. Suitable monomers may include both nonionic and anionic surfactant groups.
  • the monomer(s) (iv) additionally has at least one hydrophobic group, for example, an alkyl, cycloalkyl, alkenyl, aryl or acyl group possessing at least 9 carbon atoms.
  • hydrophobic groups include vinyl groups, allyl groups and radicals of ethylenically unsaturated acids, such as an acrylic acid, methacrylic acid, crotonic acid, itaconic acid or maleic acid radical.
  • the monomer mixture employed herein can optionally contain (v) from 0.1 to 10% by weight, such as from 0.1 to 5% by weight, based on the total amount of monomers, of at least one functional monomer copolymerizable with the monomers of groups (i), (ii), (iii) and (iv).
  • Such optional co-monomers (v) can be those which provide films and coatings of desirable properties. Such desirable film/coating properties can include, for example, enhanced adhesion to surfaces or substrates, improved wet adhesion, better resistance to removal by scrubbing or other types of weathering or abrasion, and improved resistance to solvents and chemicals.
  • the optional co-monomers useful for incorporation into the emulsion copolymers of the compositions herein are those which contain at least one polymerizable double bond along with one or more additional functional moieties selected from hydroxyl, epoxy and carbonyl groups.
  • Examples of suitable functional comonomers (v) containing hydroxyl groups includes hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate and hydroxybutyl acrylate.
  • Suitable functional comonomers (v) containing epoxy groups include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinyltoluenes and vinylbenzoates substituted with a glycidyl radical in the aromatic moiety.
  • Suitable adhesion-improving monomers (v) also include compounds which have one or more carbonyl groups, such as keto groups and/or aldehyde groups.
  • Examples include diacetone acrylamide, vinyl alkyl ketones having 4 to 7 carbon atoms such as vinyl methyl ketone, vinyl ethyl ketone or vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetyl acetate and butanediol- 1,4-acrylate acetyl acetate.
  • a preferred carbonyl functional co-monomer is diacetone acrylamide (DA AM).
  • Suitable carbonyl group-containing monomer (v) include those having acetoacetoxy groups and/or urea groups covalently bonded to the double bond system.
  • the first-mentioned compounds include in particular acetoacetoxyethyl(meth)acrylate and allyl acetoacetate.
  • the compounds containing urea groups include, for example, N- vinyl- and N- allylurea and derivatives of imidazolidin-2-one, such as N- vinyl- and N-allylimidazolidin-2- one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one, N-(2-(meth)acryloyloxyethyl)imidazolidin-2-one, N-(2- (meth)acryloyloxyacetamidoethyl)imidazolidin-2-one, and further adhesion promoters known to the person skilled in the art and based on urea or imidazolidin-2-one.
  • imidazolidin-2-one such as N- vinyl- and N-allylimidazolidin-2- one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acryla
  • Both bifunctional and polyfunctional monomers may be used as crosslinking monomers.
  • these are diallyl phthalate, diallyl maleate, triallyl cyanurate, tetraallyloxyethane, divinylbenzene, butanediol 1 ,4-di(meth)acrylate, triethylene glycol di(meth)acrylate, divinyladipate, allyl(meth)acrylate, vinyl crotonate, methylenebisacrylamide, hexanediol diacrylate, pentaerythrol diacrylate and trimethylolpropane triacrylate.
  • the polymer dispersion used in the present binder mixture is produced by free radical emulsion polymerization of the monomer mixture described above in an aqueous medium and normally in the presence of a free radical initiator.
  • Suitable free radical initiators include hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, isopropyl cumyl hydroperoxide, persulfates of potassium, of sodium and of ammonium, peroxides of saturated monobasic aliphatic carboxylic acids having an even number of carbon atoms and a C8-C12 chain length, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisopropyl percarbonate, azoisobutyronitrile, acetylcyclohexanesulfonyl peroxide, tert-butyl perbenzoate, tert-butyl peroctanoate, bis(3,5,5-trimethyl)hexan
  • the abovementioned compounds can also be used within a redox systems, using transition metal salts, such as iron(II) salts, or other reducing agents.
  • transition metal salts such as iron(II) salts
  • Alkali metal salts of oxymethanesulfinic acid, hydroxylamine salts, sodium dialkyldithiocarbamate, sodium bisulfite, ammonium bisulfite, sodium dithionite, diisopropyl xanthogen disulfide, ascorbic acid, tartaric acid, isoascorbic acid can also be used as reducing agents.
  • water-soluble persulfates in particular ammonium persulfate or sodium persulfate, are preferably used for initiating polymerization.
  • Any chain-transfer reagents properly chosen from among the known substances can likewise be used in the polymerization. Examples of these are, inter alia, alcohols, such as methanol, ethanol, propanol and butenol, aldehydes and ketones, such as acetone, methyl ethyl ketone, cyclohexane, acetophenone, acetaldehyde, propionaldehyde, n-butylaldehyde, furfural and benzaldehyde, and mercaptans, such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octyl thioglycolate and thioglycerol. Such chain- transfer reagents can be used alone or in the form of a combination of two or more thereof.
  • alcohols such as methanol, ethanol, propanol and butenol
  • Protective colloid and/or emulsifiers used for stabilization of polymer dispersions can likewise either be initially introduced completely at the beginning of the polymerization or partly initially introduced and partly metered or completely metered during the polymerization.
  • the polymerization temperature is typically in the range from 20 to 120 °C, such as in the range from 30 to 110 °C, for example in the range from 45 to 95 °C
  • a further, preferably chemical after treatment, in particular with redox catalysts such as, for example, combinations of the abovementioned oxidizing agents and reducing agents, can follow for demonomerization.
  • residual monomer present can be removed in a known manner, for example by physical demonomerization, i.e. removed by distillation (in particular via steam distillation) or by stripping with an inert gas.
  • a combination of physical and chemical methods which permits a reduction of the residual monomers to very low contents ( ⁇ 1000 ppm, preferably ⁇ 100 ppm) is particularly efficient.
  • the resulting copolymer typically has a Tg between 0 and 50 °C, for example between 10 and 30 °C, and generally comprises from 30 to 95 wt % of the solids content of the binder mixture.
  • the present binder mixture also includes an alkoxy-substituted polysiloxane, in addition to the ethylenically unsaturated monomer having at least one alkoxysilyl group present in and copolymerized with the monomer mixture used to produce the polymer dispersion.
  • the or each alkoxy-substituent of the polysiloxane generally has 1 to 5 carbon atoms, and preferably is an ethoxy group.
  • the alkoxy-substituted polysiloxane is present in the binder mixture present in an at least partially hydrolyzed form and in an amount from 0.1 to 5 wt , based on the solids content of the mixture.
  • the alkoxy-substituted polysiloxane can be added to the aqueous copolymer dispersion either during polymerization or after polymerization of the copolymer.
  • the polysiloxane is preferably added under conditions including a pH of less than 7 and a temperature of at least 40°C, since such conditions favor hydrolysis of the alkoxy groups on the polysiloxane.
  • emulsion polymerization is frequently conducted at a pH of less than 7, some colloidal silicas are only stable under alkaline conditions and also it is normal to neutralize acrylic dispersions to alkaline pH in order to improve stability of the polymer particles.
  • the polysiloxane is not present in the initial monomer mixture, it is preferable to add the polysiloxane during or at the end of polymerization, but before the pH is raised to stabilize the dispersion.
  • the final polymer may also contain a selected type of water-soluble cross-linking agent.
  • a cross-linking agent will react with the carbonyl functionalities of the polymer as water is removed from the coating compositions herein and as a film or coating is formed from the polymerized components.
  • a type of water-soluble cross-linking agent that can be used in the compositions herein comprises a compound which contains at least two hydrazine moieties.
  • dihydrazine compounds of aliphatic dicarboxylic acids of 2 to 10, in particular 4 to 6, carbon atoms e.g., oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide and/or itaconic acid dihydrazide.
  • Water- soluble aliphatic dihydrazines of 2 to 4 carbon atoms e.g., ethylene- 1 ,2-dihydrazine, propylene- 1,3 -dihydrazine or butylene-l,4-dihydrazine, are also suitable.
  • Adipic acid dihydrazide (ADH) is a preferred water-soluble cross-linking agent for use in the compositions herein.
  • the binder mixture described above is typically combined with one or more conventional fillers and/or pigments.
  • pigments are understood as meaning solids which have a refractive index greater than or equal to 1.75
  • fillers are understood as meaning solids which have a refractive index of less than 1.75.
  • mineral fillers are alkaline earth metal oxides, alkaline earth metal carbonates and/or silicate fillers, in particular calcium carbonate, mica, feldspar, kaolin, quartz powders and/or particulate quartz fractions and marble powders and/or particulate marble fractions.
  • the filler When used in plasters and renders, the filler generally has a particle size of at least 40 ⁇ , whereas when used in a paint, the filler typically has a size of 1 to 40 ⁇ .
  • Pigments may be any inorganic or organic pigment and may be color-imparting or opaque finely divided solids. Preferred pigments have a mean diameter for the primary particle of less than or equal to 1 ⁇ , preferably from 0.1 to 0.5 ⁇ , determined by sedimentation analysis according to DIN 66115.
  • inorganic pigments are metal oxides, such as titanium dioxide, iron oxide or zinc oxide, in particular titanium dioxide.
  • organic pigments are phthalocyanines, in particular phthalocyanine blue, or diary 1 pigments, azo pigments or quinacridone pigments.
  • auxiliaries based on anionic or non-ionic wetting agents such as preferably, for example, sodium pyrophosphate, sodium polyphosphate, naphthalenesulfonate, sodium polyacrylate, sodium polymaleinates and polyphosphonates such as sodium l-hydroxyethane-l,l-diphosphonate and sodium nitrilotris(methylenephosphonate), may be added.
  • anionic or non-ionic wetting agents such as preferably, for example, sodium pyrophosphate, sodium polyphosphate, naphthalenesulfonate, sodium polyacrylate, sodium polymaleinates and polyphosphonates such as sodium l-hydroxyethane-l,l-diphosphonate and sodium nitrilotris(methylenephosphonate).
  • Thickeners may also be added to the coating compositions described herein.
  • Thickeners which may be used include, inter alia, preferably cellulose derivates such as methylcellulose (MC), hydroxyethylcellulose (HEC) and carboxymethyl-cellulose.
  • Other thickeners which may be used include casein, gum arabic, gum tragacanth, starch, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate and water-soluble copolymers based on acrylic and methacrylic acid, such as acrylic acid/acrylamide and methacrylic acid/acrylic ester copolymers.
  • Hydrophobically-modified alkali soluble (acrylic) emulsions HASE
  • hydrophobically-modified ethoxylate (poly)urethanes HEUR
  • polyether polyols PEPO
  • Inorganic thickeners such as, for example, bentonites or hectorite, may also be used.
  • a paint coating produced from such a coating composition has a water permeability, w, of less than 0,10 kg/m 2 h 0'5 as determined according to DIN EN ISO 1062-3 and a water vapor transmission, sd, of less than 0,15 m as determined according to DIN EN ISO 7783-2.
  • a 2.5 litre reactor equipped with a condenser and anchor stirrer was filled with a pre-charge as described in Table 1 and heated to 80 °C. Subsequently 5 % of the monomer emulsion as described in Table 1 was added as fast as possible to the reactor and immediately afterwards a solution of 0.32 g ammonium persulfate in 18 grams of water was added. After 15 minutes of polymerisation, the rest of the monomer emulsion and a solution of 1.30 grams of ammonium persulfate in 72 grams of water were separately added to the reactor over 180 minutes while maintaining the temperature at 80°C.
  • Example 1 The procedure of Example 1 was repeated but immediately after completion of the feeds, 23.7 grams of ethoxy polysiloxane was added to the reactor over 15 minutes followed by a post-heating period of 60 minutes at 80°C. Then 9.4 g of ammonia (12.5%) was added over 15 minutes and the batch was cooled to room temperature. Post additions were conducted as in Example 1.
  • Example 2 The procedure of Example 1 was repeated except that 14.1 grams of ethoxy polysiloxane was included in the monomer emulsion.
  • Tylose MH 30000 YG8 is a cellulose ether available from SE Tylose GmbH & Co. KG.
  • Agitan 281 is a defoamer available from Munzing Europe.
  • Additol VXW 6208 is a dispersant available from Cytec - Liquid Coating Resins & Additives.
  • AMP 90 is an amino alcohol wetting agent available from the Dow Chemical Company.
  • Texanol ester alcohol is a coalescent available from Eastman Coatings Film Technologies.

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Abstract

L'invention porte sur un mélange liant aqueux comprenant de la silice colloïdale ; une dispersion aqueuse de copolymère ; et un polysiloxane à substitution alcoxy. La dispersion aqueuse de copolymère est préparée par polymérisation en émulsion d'un mélange de monomères comprenant (i) au moins 40 % en poids, par rapport à la quantité totale de monomères, d'au moins l'un d'un ester d'un acide carboxylique à insaturation éthylénique, d'un ester vinylique d'un acide carboxylique saturé et d'un monomère vinylaromatique ; (ii) de 0,1 à 10 % en poids, par rapport à la quantité totale de monomères, d'au moins l'un d'un acide monocarboxylique et/ou dicarboxylique à insaturation éthylénique, d'un acide sulfonique à insaturation éthylénique, d'un acide phosphorique insaturé, d'un acide phosphonique à insaturation éthylénique et d'un amide d'un acide monocarboxylique et/ou dicarboxylique à insaturation éthylénique ; et (iii) de 0,5 à 15 % en poids, par rapport à la quantité totale de monomères, d'un monomère à insaturation éthylénique ayant au moins un groupe alcoxysilyle.
PCT/IB2012/002859 2011-11-17 2012-11-13 Systèmes liants aqueux et leur utilisation dans la production de compositions de revêtement WO2013072769A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2015058344A1 (fr) 2013-10-22 2015-04-30 Dow Global Technologies Llc Composition de revêtement aqueuse et son procédé de fabrication
EP3390551A4 (fr) * 2015-12-14 2019-08-07 Dow Global Technologies LLC Composition de revêtement aqueuse et son procédé de fabrication
EP3650507A1 (fr) 2018-11-06 2020-05-13 Daw Se Composition de revêtement aqueuse
US20200200928A1 (en) * 2018-12-19 2020-06-25 Pgs Geophysical As Medetomidine Compositions Having Improved Anti-Fouling Characteristics

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EP1384596A1 (fr) * 2001-03-19 2004-01-28 Clariant International Ltd. Composition de revetement pour support d'impression a jet d'encre et support d'impression a jet d'encre
DE102006046860A1 (de) * 2006-10-02 2008-04-03 Celanese Emulsions Gmbh Putze und Farben, Copolymerdispersionen und deren Verwendung

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EP1384596A1 (fr) * 2001-03-19 2004-01-28 Clariant International Ltd. Composition de revetement pour support d'impression a jet d'encre et support d'impression a jet d'encre
US7144944B2 (en) 2001-03-19 2006-12-05 Gelanese International Corporation Coating composition for ink-jet recording medium and ink-jet recording medium
DE102006046860A1 (de) * 2006-10-02 2008-04-03 Celanese Emulsions Gmbh Putze und Farben, Copolymerdispersionen und deren Verwendung
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015058344A1 (fr) 2013-10-22 2015-04-30 Dow Global Technologies Llc Composition de revêtement aqueuse et son procédé de fabrication
CN105612222A (zh) * 2013-10-22 2016-05-25 陶氏环球技术有限责任公司 水性涂料组合物和其制造方法
EP3060611A4 (fr) * 2013-10-22 2017-07-05 Dow Global Technologies LLC Composition de revêtement aqueuse et son procédé de fabrication
EP3390551A4 (fr) * 2015-12-14 2019-08-07 Dow Global Technologies LLC Composition de revêtement aqueuse et son procédé de fabrication
US10759947B2 (en) 2015-12-14 2020-09-01 Dow Global Technologies Llc Aqueous coating composition and process of making the same
EP3650507A1 (fr) 2018-11-06 2020-05-13 Daw Se Composition de revêtement aqueuse
US20200200928A1 (en) * 2018-12-19 2020-06-25 Pgs Geophysical As Medetomidine Compositions Having Improved Anti-Fouling Characteristics
US12050293B2 (en) * 2018-12-19 2024-07-30 Pgs Geophysical As Medetomidine compositions having improved anti-fouling characteristics

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