WO2019060614A1 - Composition aqueuse de revêtement - Google Patents

Composition aqueuse de revêtement Download PDF

Info

Publication number
WO2019060614A1
WO2019060614A1 PCT/US2018/052051 US2018052051W WO2019060614A1 WO 2019060614 A1 WO2019060614 A1 WO 2019060614A1 US 2018052051 W US2018052051 W US 2018052051W WO 2019060614 A1 WO2019060614 A1 WO 2019060614A1
Authority
WO
WIPO (PCT)
Prior art keywords
aqueous coating
coating composition
weight
carbosiloxane dendrimer
vinyl copolymer
Prior art date
Application number
PCT/US2018/052051
Other languages
English (en)
Inventor
Pierre Leger
Original Assignee
Dow Silicones Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Silicones Corporation filed Critical Dow Silicones Corporation
Publication of WO2019060614A1 publication Critical patent/WO2019060614A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • 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
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
    • C09D155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications

Definitions

  • the present invention relates to an aqueous coating composition such as a water- based paint, using a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition.
  • the present invention further relates to the use of a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition as a water-based paint additive, particularly but not exclusively to decrease the surfactant leaching of an aqueous coating composition.
  • Various silicone-grafted vinyl copolymer emulsion compositions comprising a vinyl monomer and a carbosiloxane dendrimer are known from EP 1 095 953 A2.
  • the emulsion composition is characterized by excellent storage stability and by the ability to form a film or coating that exhibits an excellent water repellency.
  • carbosiloxane dendrimer non-emulsion additives for a coating agent which exhibit a compatibility with resins and which comprise a co-polymer that contains a hydroxyl group and a group having a carbosiloxane dendrimer structure, as set out in WO 2012/091178 A1.
  • Surfactant leaching is sometimes called a ‘snail trail of resistance’ or just‘snail trail’.
  • Such leaching occurs on both interior and exterior walls, where vertical marks are seen on the paint, and which are usually sufficiently visually unsightly as to require re-painting.
  • the marks occur as paint is drying, and the atmosphere is cold, or is humid, or there is a heavy dew fall, or there is rain.
  • Surfactants in the dried or drying paint migrate (or leach) to the wall’s surface towards the wetness or dampness, and then dry on the surface. The migration of salts causes the vertical marks or streaks, which then typically follow a gravitational direction to form vertical marks.
  • An object of the present invention is to provide an aqueous coating composition with reduced surfactant leaching.
  • a further object of the present invention is to provide a use and a method of decreasing the surfactant leaching of an aqueous coating composition.
  • Another object of the present invention is to provide an aqueous coating composition with improved stain resistance.
  • a further object of the present invention is to provide a use and a method of increasing the stain resistance of an aqueous coating composition.
  • an aqueous coating composition comprising:
  • the active content of the carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition is 2.0 weight % or more of the aqueous coating composition.
  • the problem is also solved by a method of decreasing the surfactant leaching, or of increasing the stain resistance, of an aqueous coating composition, comprising at least the step of adding a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition comprising 2.0 weight % or more active content of carbosiloxane dendrimer-grafted vinyl copolymer to the aqueous coating composition.
  • aqueous coating composition of the present invention is described in detail below.
  • the aqueous coating composition may comprise any paint or other coating agent which is‘water-based’, which includes one or more of the group comprising: organic binder emulsion (typically acrylic or styrene acrylic copolymer), dispersants, fillers and pigments, defoamers, thickeners, coalescent solvent, water, biocides, pH modifiers, etc.
  • organic binder emulsion typically acrylic or styrene acrylic copolymer
  • dispersants typically acrylic or styrene acrylic copolymer
  • fillers and pigments typically acrylic or styrene acrylic copolymer
  • defoamers typically acrylic or styrene acrylic copolymer
  • defoamers typically acrylic or styrene acrylic copolymer
  • thickeners typically acrylic or styrene acrylic copolymer
  • coalescent solvent water, biocides, pH modifiers, etc.
  • Water-based paints are increasingly preferred to organic solvent-based paint to avoid
  • the aqueous coating composition according to the present invention characteristically contains component (A) a water-based resin binder.
  • the water-based resin binder may be one or more of the group comprising: pure acrylic emulsions, styrene acrylic copolymer emulsions. Binders include synthetic or natural resins such as alkyds, acrylics, vinyl-acrylics, vinyl acetate/ethylene (VAE) or siloxanes.
  • the water-based binder can be exemplified by acrylic resin binders, which may comprise less than 0.5wt% alkyl phenol ethoxylates (and in some embodiments substantially free from alkyl phenol ethoxylates).
  • the acrylic resin binders may also be self-cross-linking.
  • the acrylic resin binders may have a solids content of 40- 55wt%, alternatively 40-50wt%, alternatively 43-47wt%.
  • the acrylic resin binders may pH of 7-11, alternatively 8-10.
  • the minimum film formation temperature may be -5-20°C, alternatively 0-19°C.
  • component (A) is exemplified to be a self-cross- linkable acrylic resin having a glass transition temperature (Tg) ranging from 10 to 35 °C, having a hydrophobic property derived from having a higher content for hydrophobic acrylate monomers.
  • Tg glass transition temperature
  • Such a water-based resin binder can be emulsified with any type of surfactants or combinations thereof.
  • anionic surfactants are utilized in certain embodiments to emulsify a self-cross-linkable resin into water phase.
  • Suitable acrylic resin binders include SG-380 and Primal SF-016 (both Dow Chemical, Midland, USA). Primal SF- 016 contains a higher amount of surfactant than SG-380.
  • the aqueous coating composition according to the present invention characteristically contains component (B) at least one surfactant.
  • the at least one surfactant may be for dispersing pigments in the composition.
  • the component (B) may be derived from dispersant or emulsifier for said component (A) in aqueous raw resin/paint composition, or derived from polymerization reaction material for component (A) or component (C). Needless to say, the component (B) can be independently blended to the inventive composition apart from said component (A) or component (C).
  • the at least one surfactant may be anionic or nonionic.
  • Anionic surfactants include alkyl sulfates (sodium Lauryl sulfate), Fatty Alcohol Ether Sulfates (FAES), and Alkyl Phenol Ether Sulfates (APES).
  • the alkyl sulfate may be sodium lauryl sulfate.
  • Nonionic surfactants include polyethoxylates, such as ethoxylated alkyl polyethylene glycol ethers.
  • At least one surfactant able to disperse pigment may be neutralized acid copolymers, polycarboxylic acids, polyphosphates, modified fatty acid derivatives, or amine neutralized phosphoric acid ester.
  • the surfactant can be exemplified by a polycarboxylate dispersant, such as OROTANTM 731 A ER (Dow Chemical, Midland, USA)
  • the aqueous coating composition according to the present invention characteristically contains component (C) a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition.
  • component (C) a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition.
  • Various carbosiloxane dendrimer-grafted vinyl copolymer emulsion compositions are known in the art.
  • a range of carbosiloxane dendrimer-grafted vinyl copolymer emulsion compositions are defined in EP 1 095 953 A2, which is incorporated herein by way of reference, and which describes the emulsion polymerization of:
  • Vinyl monomer (a) should contain a radically polymerizable vinyl group, but the type and properties of this monomer are not otherwise critical.
  • Vinyl monomer (a) can be exemplified by: lower alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate; lower alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate; higher acrylates such as n- butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2- ethylhexyl acrylate, octyl acrylate, lauryl acrylate, and stearyl
  • unsaturated group-functionalized silicone compounds such as organopolysiloxane (branched or straight-chain) bearing an acryl or methacryl group at a single terminal and polydimethylsiloxane bearing a styryl group at a single terminal; butadiene; vinyl chloride; vinylidene chloride; acrylonitrile and methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; radically polymerizable unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, as well as their alkali metal salts, ammonium salts, and organic amine salts; radically polymerizable unsaturated monomers that contain a sulfonic acid residue, e.g., styrenesulfonic acid, as well as their alkali metal salts, ammonium salts, and organic
  • multifunctional vinyl monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethylacrylate, tris(2-hydroxyethyl)isocyanurate diacrylate, tris(2- hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-but
  • Usable multifunctional vinyl monomers can also be exemplified by triethylene glycol divinyl ether, divinylbenzene, and unsaturated group-functional silicone compounds such as polydimethylsiloxane endblocked at both terminals by the styryl group and polydimethylsiloxane endblocked at both terminals by methacryloxypropyl.
  • the use in particular of vinyl monomer bearing a crosslinkable functional group makes it possible for the silicone-grafted vinyl copolymer to undergo crosslinking upon removal of the water from the composition after emulsion polymerization.
  • the crosslinkable functional group under consideration can be, for example, an amino group, epoxy group, tetrahydrofurfuryl group, carboxyl group, hydroxyl group, blocked isocyanate group, or any of various silyl groups, e.g., halogenated silyl, alkoxysilyl, and acetoxysilyl. This crosslinking serves to improve the durability and solvent resistance of the silicone-grafted vinyl copolymer.
  • the crosslinking can be of the self- crosslinking type or may be effected using a crosslinker, e.g., melamine, multifunctional epoxy, or multifunctional isocyanate.
  • a crosslinking catalyst can also be used as necessary. Since in some cases the aforementioned crosslinkable functional groups can be hydrolyzed by water, it may be necessary to effect emulsification-using techniques known in the art so as to avoid their hydrolysis.
  • an additional stabilization of the composition of the present invention can be achieved by using hydrophilic vinyl monomer for a portion of component (A), said hydrophilic vinyl monomer being exemplified by acrylic acid, methacrylic acid, 2- hydroxyethyl acrylate, dimethylaminoethyl acrylate, 2-hydroxyethyl methacrylate, and dimethylaminoethyl methacrylate.
  • the carbosiloxane dendrimer component (b) bears a radically polymerizable organic group having the following general formula:
  • Y in this general formula is a radically polymerizable organic group and can be, for example, C 2 to C 10 alkenyl or an acryl-, methacryl-, or styryl-functional organic group as defined by the following general formulas.
  • R 4 and R 6 in these formulas are hydrogen or methyl;
  • R 5 and R 8 are C 1 to C 10 alkylene;
  • R 7 is C 1 to C 10 alkyl;
  • subscript b is an integer from 0 to 4; and subscript c is 0 or 1.
  • radically polymerizable organic groups can be exemplified by acryloxymethyl, 3- acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2- propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl, 2-(3-vinylphenyl)ethyl, vinyl, allyl, methallyl, and 5-hexenyl.
  • R 1 in the preceding general formula for the carbosiloxane dendrimer (B) is C 1 to C 10 alkyl or aryl.
  • the alkyl encompassed by R 1 can be exemplified by methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl, and cyclohexyl.
  • the aryl encompassed by R 1 can be exemplified by phenyl and naphthyl. In certain embodiments, methyl and phenyl are preferred for R 1 , and methyl is particularly preferred.
  • R 1 in the preceding formula is defined as above.
  • R 2 in the preceding formula represents C 2 to C 10 alkylene and can be exemplified by ethylene, propylene, and butylene.
  • R 3 in the preceding formula is C 1 to C 10 alkyl, for example, methyl, ethyl, propyl, or butyl.
  • X i+1 is selected from the group consisting of hydrogen, C 1 to C 10 alkyl, aryl, and the above- defined silylalkyl group.
  • Subscript a i is an integer from 0 to 3.
  • the carbosiloxane dendrimer (b) has the following general formula when the number of generations i is 1:
  • the carbosiloxane dendrimer (B) has the following general formula when the number of generations i is 2:
  • the carbosiloxane dendrimer (b) has the following general formula when the number of generations i is 3:
  • Y, R 1 , R 2 , R 3 , and R 12 are defined as above; subscripts a 1 , a 2 and a 3 are defined as for a i ; and the average of the sum of the a 1 , a 2 , and a 3 values in each molecule is from 0 to 79).
  • component (b) i.e., carbosiloxane dendrimer functionalized with a radically polymerizable organic group:
  • the carbosiloxane dendrimer described above can be synthesized, for example, by the method described in Japanese Patent Application Laid Open (Kokai) Number Hei 11-1530 (1,530/1999).
  • the carbosiloxane dendrimer is synthesized by running a hydrosilylation reaction between an alkenyl-functional organosilicon compound and an SiH- functional silicon compound with the following general formula:
  • the silicon compound with this formula can be exemplified by 3-methacryloxypropyltris(dimethylsiloxy)silane, 3- acryloxypropyltris(dimethylsiloxy)silane, and 4-vinylphenyltris(dimethylsiloxy)silane.
  • the alkenyl-functional organosilicon compound referenced above can be exemplified by vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane, and 5- hexenyltris(trimethylsiloxy)silane. In general, this hydrosilylation reaction is run in the presence of a transition metal catalyst, e.g., chloroplatinic acid or a platinum-vinylsiloxane complex.
  • a transition metal catalyst e.g., chloroplatinic acid or a platinum-vinylsiloxane complex.
  • the component (a) : component (b) polymerization ratio should be in the range from 0 : 100 to 99.9 : 0.1 as the component (a) : component (b) weight ratio, and alternatively is from 50 : 50 to 95 : 5, and alternatively is from 60 : 40 to 90 : 10.
  • the characteristic properties of the carbosiloxane dendrimer structure do not appear when the component (b) blending ratio is below 0.1.
  • the surfactant (c) may be one or more surfactants typically used in the emulsion-polymerization of vinyl polymers, and the choice of such is not critical. It may be e.g., an anionic surfactant, nonionic surfactant, cationic surfactant, or amphoteric surfactant.
  • Anionic surfactants are exemplified by sodium oleate, sodium stearate, the sodium salt of dodecylbenzenesulfonic acid, salts of alkylsulfate, and the sodium salt of polyoxyethylenealkylethersulfonic acid.
  • Cationic surfactants are exemplified by quaternary ammonium salts such as dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylbenzylammonium hydroxide, dioctadecyldimethylbenzylammonium hydroxide, tallow trimethylammonium hydroxide, and coconut oil-trimethylammonium hydroxide.
  • quaternary ammonium salts such as dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylbenzylammonium hydrox
  • Nonionic surfactants are exemplified by polyoxyethylene laurylether, polyoxyethylene stearylether, polyoxyethylene nonylphenolether, polyoxyethylene monostearate, sorbitan monostearate, and polyoxyethylene sorbitan monostearate.
  • Amphoteric surfactants are exemplified by amino acid-type surfactants and betaine-type surfactants.
  • anionic surfactants, cationic surfactants or combinations of these surfactants are preferred.
  • the surfactant (c) is a radically polymerizable surfactant which enhances the water-resistance of films formed from the emulsion composition.
  • the radically polymerizable surfactant (c) should exhibit surfactancy and should be capable of undergoing radical polymerization, but its character is not otherwise critical.
  • This radically polymerizable surfactant (c) may be an anionic, nonionic, or cationic surfactant.
  • anionic types of radically polymerizable surfactant (c) may be exemplified by compounds with the following structures.
  • R is hydrogen or methyl
  • “M” denotes alkali metal
  • “AO” denotes alkylene oxide
  • subscript x is an integer from 1 to 50.
  • R is hydrogen or methyl
  • “M” denotes alkali metal
  • “AO” denotes alkylene oxide
  • subscript x is an integer from 1 to 50.
  • R 1 in the preceding structures is hydrogen or methyl
  • R 2 denotes alkylene
  • “M” denotes alkali metal
  • “AO” denotes alkylene oxide
  • subscript x is an integer from 1 to 50.
  • R is hydrogen or methyl
  • “M” denotes alkali metal
  • subscript x is an integer from 1 to 50.
  • nonionic types of the radically polymerizable surfactant (c) can be exemplified by the following compounds.
  • R is hydrogen or methyl
  • “AO” denotes alkylene oxide
  • “EO” denotes ethylene oxide
  • “PO” denotes propylene oxide
  • subscript x is an integer from 1 to 50.
  • R is hydrogen or methyl
  • “AO” denotes alkylene oxide
  • subscript x is an integer from 1 to 50.
  • R is hydrogen or methyl
  • “AO” denotes alkylene oxide
  • subscript x is an integer from 1 to 50.
  • the cationic types of the radically polymerizable surfactant (C) can be exemplified by the following compounds. [0047] Acrylic types of radically polymerizable cationic surfactant:
  • R is hydrogen or methyl
  • “X” is a halogen atom
  • R is hydrogen or methyl
  • “X” is a halogen atom
  • surfactants are preferred from among those listed above:
  • Component (c) can take the form of only a single surfactant or can be a combination of two or more surfactants.
  • Component (c) may be used at from 0.01 to 20 weight parts, and alternatively at from 0.1 to 10 weight parts, in each case per 100 weight parts of the total amount of components (a) and (b).
  • the radical polymerization initiator (d) may be selected from the radical polymerization initiators generally used for the emulsion polymerization of vinyl polymers, but its type and nature are not otherwise critical.
  • Component (d) can be exemplified by inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; organoperoxides such as tert-butyl peroxymaleic acid, succinic acid peroxide, and tert-butyl hydroperoxide; water-soluble azo-type radical initiators such as 2,2'-azobis(2-(N- benzylamidino)propane)hydrochloride, 2,2'-azobis(2-(N-2- hydroxyethylamidino)propane)hydrochloride, and 2,2'-azobis(2-methyl-N- hydroxyethyl)propionamide; oil-soluble azo-type radical initiators such as 2,2'-
  • Component (d) may be used at from 0.01 to 20 weight parts, and alternatively used at from 0.1 to 10 weight parts, in each case per 100 weight parts of the total amount of components (a) and (b).
  • the emulsion compositions of component (C) may be obtained by combining from 0.01 to 20 weight parts radically polymerizable surfactant (c) and from 0.01 to 20 weight parts radical polymerization initiator (d) with 100 weight parts of the mixture of vinyl monomer (a) and carbosiloxane dendrimer (b), producing an emulsified dispersion therefrom in an aqueous medium, and effecting emulsion polymerization therein.
  • the component (a) : component (b) weight ratio is in the range from 60 : 40 to 90 : 10.
  • component (a) is preferred to be a mixture of two or more vinyl monomers.
  • component (a) By selecting component (a) as a mixture including an alkyl-modified vinyl monomer in higher content, the flexibility and Tg for the so-obtained copolymer can also be controlled.
  • Components (a) to (d) may be emulsified and dispersed in combination with each other, or the radical polymerization initiator (d) may be added after the antecedent emulsification and dispersion process.
  • the emulsified dispersion can be prepared using the usual emulsification devices, for example, a colloid mill or a homogenizer. Polymerization may be carried out for about 2 to 8 hours after preheating the reaction system to 50 to 90°C. This polymerization can be run by dropwise addition of the emulsified dispersion or after introducing the entire emulsified dispersion in one lot. In certain embodiments, the former technique is preferred because it facilitates temperature control.
  • a chain transfer agent generally known for use in emulsion polymerizations may also be used in the present invention.
  • the chain transfer agent can be exemplified by mercaptan compounds such as 2-mercaptoethanol, butyl mercaptan, n- dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and mercaptopropyl-functional polydimethylsiloxanes; by halogen compounds such as methylene chloride, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane; and by alpha- methylstyrene dimer.
  • Surfactant lacking reactive functionality may be used ⁇ within a range that does not impair the characteristic features of the inventive composition ⁇ in combination with the surfactant (c).
  • the post-polymerization particle size of the emulsion is not critical, but viewed from the standpoints of storage stability and preventing the appearance of aggregates in various embodiments is no greater than 1.0 ⁇ m, alternatively no greater than 0.5 ⁇ m, alternatively no greater than 0.3 ⁇ m.
  • a thickener can be added and/or the specific gravity can be adjusted when the particle size is to be made 1.0 ⁇ m or above.
  • the solids content of the inventive composition is in the range from 15 to 60 weight% based on productivity and handling considerations.
  • the obtained carbosiloxane dendrimer-grafted vinyl copolymer in this emulsion composition generally has at least some flexibility derived from its Tg (generally measured by DMA method) in the range 40 to 80°C, and an optional molecular weight (as determined by GPC-THF) in the range from 1 million to 5 million.
  • Suitable commercially available emulsion products include Dow Corning® FA 4103 Silicone Acrylate Emulsion and similar products, which can be utilized.
  • the carbosiloxane dendrimer-grafted vinyl copolymer comprises, is, or may be referred to as a carboxysiloxane dendrimer-grafted vinyl copolymer.
  • Additives such as colorants, stabilizers, fats, oils, waxes, and fillers can be added to the aqueous coating compositions of the present invention as needed.
  • a characteristic feature of the inventive aqueous coating compositions of the present invention are a high loading of active content of the carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition, in particular being above 2.0 weight %, such as being 2.5 weight % or more, 3 weight % or more, 3.5 weight % or more, 4 weight % or more, 4.5 weight % or more, 5 weight % or more, 5.5 weight % or more, 6 weight % or more, 7 weight % or more, 8 weight % or more, 9 weight % or more, or 10 weight % or more.
  • the active content may be in the range 2.0 to 20 weight % or 2.0 to 15 weight % or 2.0 to 15 weight %. Any of these ranges represent a surprising high loading of the dendrimer-grafted copolymer, whose presence may hinder the migration of water-soluble salts as the aqueous coating composition is drying.
  • active content as used herein relates to the active part of the emulsion composition, being the monomer content in the emulsion composition, typically accounting for 30% of the final composition. This is the same as the solid content of the emulsion composition.
  • One or more of the surfactants could also be defined as a‘solid component’ of the emulsion and can be separated with co-polymer by removing water, to clarify the effect of this invention, it is needed to distinguish all surfactants (in raw paints and from emulsion) from co-polymer content.
  • the co-polymer content can be calculated by the amount of monomers in emulsion polymerization.
  • the present invention further provides a use of a carbosiloxane dendrimer- grafted vinyl copolymer emulsion composition, in particular to decrease the surfactant leaching of an aqueous coating composition, especially as it dries or is drying.
  • Surfactant leaching is considered to be the mechanism through which water soluble components within the coating moves through the surface of a paint. The process usually occurs over a period of time, such as weeks, after initial drying of an aqueous coating composition is applied to a surface, and is possibly washed by rain, although it can be accelerated under certain atmospheric conditions (often in spring and in autumn time). In one example, the formation of condensation on a‘freshly painted’ exterior facade due to temperature falling below dew point will cause surfactants to migrate to surface. When the condensation subsequently dries, the surfactants are deposited on the surface of the paint, causing shiny streaks or discoloration. Surfactant leaching is visually more apparent in dark, ultra-deep colors, although it also happens for lighter colors, even for white paint, when the exudate has a tan color.
  • the present invention further provides a use of a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition to increase the water contact angle of an aqueous coating composition.
  • the amount of carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition used in an aqueous coating composition may be above 2 weight % active content, such as being 2.5 weight % or more, 3 weight % or more, 3.5 weight % or more, 4 weight % or more, 4.5 weight % or more, 5 weight % or more, 5.5 weight % or more, 6 weight % or more, 7 weight % or more, 8 weight % or more, 9 weight % or more, or 10 weight % or more. In some embodiments, the amount may be in the range 2.0 to 20 weight %.
  • the present invention also provides a method of decreasing the surfactant leaching of an aqueous coating composition comprising at least the step of: adding 2 weight % or more active content of a carbosiloxane dendrimer-grafted vinyl copolymer emulsion composition comprising carbosiloxane dendrimer-grafted vinyl copolymer to the aqueous coating composition.
  • the range 2 weight % or more may be 2.5 weight % or more, 3 weight % or more, 3.5 weight % or more, 4 weight % or more, 4.5 weight % or more, 5 weight % or more, 5.5 weight % or more, 6 weight % or more, 7 weight % or more, 8 weight % or more, 9 weight % or more, or 10 weight % or more.
  • the active content may be in the range 2.0 to 20 weight %.
  • paint and coating surfaces can change following exposure to water, in particular exposure to rain or dew or steam, and a further characteristic of the present invention is to reduce or minimize any changes at paint surfaces following exposure to water or water vapor, which can be measured by contact angle.
  • filler (blend calcium carbonate, silica, talc– PVC ca 70%);
  • hydrophobic dispersant (ca 1.5%, i.e., a surfactant such as OROTANTM 731);
  • thickener cellulosic i.e., CELLOSIZETM QP4400, acrylic, i.e., ACRYSOLTM RM-935
  • biocide i.e., ACRYSOLTM RM-935
  • silicone antifoam silicone antifoam
  • the loadings were defined as either 10%, 5%, 2.5% and 1.25% active content
  • the active content percentages were based on the polymerized monomer fraction of the carbosiloxane dendrimer-grafted vinyl copolymer emulsion, for example 30% when residual composition being water used as dispersion medium during the emulsion polymerization process.
  • 1.25%‘active content’ corresponds to 4.17% of the Emulsion P1 as supplied, and once mixed with the paint composition.
  • the snail trail test was based on painting a surface, allowing it to dry for 24 hours at room temperature and 50% RH, followed by applying 2 ⁇ l drops of liquid H 2 O to the painted surface, leaving them for 30 minutes, removing the H 2 O by lifting up panels vertically and then evaluating the samples.
  • the water contact angle (WCA) test was based on visual appearance of the drops of H 2 O after 0 seconds and 60 seconds on the coatings.
  • a 2 ⁇ l drop of high purity water was applied to a test specimen surface using a liquid delivery system (100 ⁇ l syringe). Images of the drop in contact with the substrate were captured by a video camera at specified time intervals following deposition.
  • House hold stain resistance was evaluated by post-adding the carbosiloxane dendrimer-grafted vinyl copolymer emulsion to a‘Control’ formulation having the composition set out in Table 3 below.
  • the carbosiloxane dendrimer-grafted vinyl copolymer emulsion was added at 2% emulsion solid content, or by using the carbosiloxane dendrimer-grafted vinyl copolymer emulsion as a‘Co-binder’, in a 60/40 dry ratio between the acrylic emulsion and the carbosiloxane dendrimer-grafted vinyl copolymer emulsion (i.e., replacing 40% of dry SG- 380 with Emulsion P1).
  • the Control and Co-binder formulations are set out in Table 3 below (in parts by weight).
  • the coating formulation comprising carbosiloxane dendrimer-grafted vinyl copolymer emulsion is lower in color change degree and show better stain proof performance, reflected by the lower color difference measured through dE.
  • Such minor variations may be in the order of ⁇ 0-25, ⁇ 0-10, ⁇ 0-5, or ⁇ 0- 2.5, % of the numerical values. Further, The term“about” applies to both numerical values when associated with a range of values. Moreover, the term“about” may apply to numerical values even when not explicitly stated.
  • a hyphen“-” or dash“–” in a range of values is“to” or “through”; a“>” is“above” or“greater-than”; a“ ⁇ ” is“at least” or“greater-than or equal to”; a “ ⁇ ” is“below” or“less-than”; and a“ ⁇ ” is“at most” or“less-than or equal to.”
  • a“>” is“above” or“greater-than”
  • a“ ⁇ ” is“at least” or“greater-than or equal to”
  • a “ ⁇ ” is“below” or“less-than”
  • a“ ⁇ ” is“at most” or“less-than or equal to.”
  • any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range“of from 0.1 to 0.9” may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range“at least,”“greater than,”“less than,”“no more than,” and the like it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of“at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range“of from 1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

Landscapes

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

Abstract

L'invention porte sur une composition aqueuse de revêtement. La composition aqueuse de revêtement comprend un liant formé de résine à base d'eau, au moins un tensioactif capable de disperser le liant formé de résine dans une phase aqueuse et une composition en émulsion de copolymères vinyliques greffés avec des dendrimères de carbosiloxane. La teneur en substance active de la composition en émulsion est égale ou supérieure à 2 % en poids de la composition aqueuse de revêtement. La composition aqueuse de revêtement présente une lixiviation réduite du/des tensioactifs.
PCT/US2018/052051 2017-09-22 2018-09-20 Composition aqueuse de revêtement WO2019060614A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1715402.2 2017-09-22
GB1715402.2A GB2566726A (en) 2017-09-22 2017-09-22 Aqueous coating composition

Publications (1)

Publication Number Publication Date
WO2019060614A1 true WO2019060614A1 (fr) 2019-03-28

Family

ID=60244444

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/052051 WO2019060614A1 (fr) 2017-09-22 2018-09-20 Composition aqueuse de revêtement

Country Status (2)

Country Link
GB (1) GB2566726A (fr)
WO (1) WO2019060614A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023039315A1 (fr) 2021-09-07 2023-03-16 Dow Silicones Corporation Additif polyorganosiloxane amino-fonctionnel pour compositions de revêtement aqueuses
EP4242273A1 (fr) * 2022-03-07 2023-09-13 STO SE & Co. KGaA Base de nuançage pour masses de revêtement

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1006165A2 (fr) * 1998-11-30 2000-06-07 Dow Corning Toray Silicone Company, Ltd. Composition de revêtement
EP1095953A2 (fr) * 1999-10-29 2001-05-02 Dow Corning Toray Silicone Company, Ltd. Composition d'émulsion de copolymères vinyliques greffés par des silicones
JP2001192424A (ja) * 1999-10-29 2001-07-17 Dow Corning Toray Silicone Co Ltd シリコーングラフトビニル系共重合体エマルジョン組成物
US20020120039A1 (en) * 2000-12-25 2002-08-29 Haruhiko Furukawa Vinyl copolymer emulsion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1006165A2 (fr) * 1998-11-30 2000-06-07 Dow Corning Toray Silicone Company, Ltd. Composition de revêtement
EP1095953A2 (fr) * 1999-10-29 2001-05-02 Dow Corning Toray Silicone Company, Ltd. Composition d'émulsion de copolymères vinyliques greffés par des silicones
JP2001192424A (ja) * 1999-10-29 2001-07-17 Dow Corning Toray Silicone Co Ltd シリコーングラフトビニル系共重合体エマルジョン組成物
US20020120039A1 (en) * 2000-12-25 2002-08-29 Haruhiko Furukawa Vinyl copolymer emulsion

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023039315A1 (fr) 2021-09-07 2023-03-16 Dow Silicones Corporation Additif polyorganosiloxane amino-fonctionnel pour compositions de revêtement aqueuses
EP4242273A1 (fr) * 2022-03-07 2023-09-13 STO SE & Co. KGaA Base de nuançage pour masses de revêtement

Also Published As

Publication number Publication date
GB2566726A (en) 2019-03-27
GB201715402D0 (en) 2017-11-08

Similar Documents

Publication Publication Date Title
US6534590B1 (en) Silicone-grafted vinyl copolymer emulsion composition
US7674868B2 (en) Copolymers containing nanoparticles
US8436088B2 (en) Plasters and renders and paints, copolymer dispersions and their use
US5639841A (en) Polymers containing macromonomer mixtures
JP3159234B2 (ja) 水性シリコーン変性アクリレート重合体エマルジョン
US6602949B2 (en) Vinyl copolymer emulsion
NZ527905A (en) Multistage polymer particles with select pendant groups and compositions prepared therefrom
JP4757991B2 (ja) シリコーングラフトビニル系共重合体エマルジョン組成物
CA2265218C (fr) Liants en latex pour revetements contenant un surfactif polymerisable ayant un groupe fonctionnel terminal d'amine allylique
US10487240B2 (en) Silicone based emulsion, method for making same, and waterborne co-binder resin compositions comprising such emulsions
EP0771826B1 (fr) Emulsions d'un copolymère de silicone et d'un organomonomère
WO2019060614A1 (fr) Composition aqueuse de revêtement
KR101886395B1 (ko) 안정한 신규 수성 하이브리드 결합제
US7723426B2 (en) Shelf-stable silane-modified aqueous dispersion polymers
US20120142844A1 (en) Aqueous hybrid binder for jointing mortars
JPH11217480A (ja) 耐汚染性に優れる硬化性エマルション
EP4048742A1 (fr) Composition aqueuse de microsphères polymères organiques, de particules de liant et de résine échangeuse d'ions
JPH11263936A (ja) 被覆用組成物
AU2016353049B2 (en) Coatings having improved resistance to stains and dirt
JP2000264971A (ja) 複合粒子、その分散体、分散体の製造方法、およびコーテイング材
JPH11246826A (ja) 耐汚染性水性塗料組成物
JPH11279364A (ja) 耐汚染性に優れる硬化性水性エマルション
JP2000129196A (ja) 被覆用組成物
JP2000034310A (ja) エマルションの製造方法
JP2000034308A (ja) 水性エマルションの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18788938

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18788938

Country of ref document: EP

Kind code of ref document: A1